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Sample records for higher brominated diphenyl

  1. Environmental analysis of higher brominated diphenyl ethers and decabromodiphenyl ethane.

    Science.gov (United States)

    Kierkegaard, Amelie; Sellström, Ulla; McLachlan, Michael S

    2009-01-16

    Methods for environmental analysis of higher brominated diphenyl ethers (PBDEs), in particular decabromodiphenyl ether (BDE209), and the recently discovered environmental contaminant decabromodiphenyl ethane (deBDethane) are reviewed. The extensive literature on analysis of BDE209 has identified several critical issues, including contamination of the sample, degradation of the analyte during sample preparation and GC analysis, and the selection of appropriate detection methods and surrogate standards. The limited experience with the analysis of deBDethane suggests that there are many commonalities with BDE209. The experience garnered from the analysis of BDE209 over the last 15 years will greatly facilitate progress in the analysis of deBDethane.

  2. Brominated diphenyl ethers in the sediments, porewater, and biota of the Chesapeake Bay, USA

    Energy Technology Data Exchange (ETDEWEB)

    Baker, K.; Klosterhaus, S.; Liebert, D.; Stapleton, H. [Maryland Univ., Solomons, MD (United States)

    2004-09-15

    Levels of brominated diphenyl ethers (BDEs) are rapidly increasing in the environment, and in a short time these chemicals have evolved from 'emerging contaminants' to globally-distributed organic pollutants. Recent research demonstrates BDEs are sufficiently stable to be transported long distances in the environment and to accumulate in higher trophic levels. Photolysis and metabolism appear to be dominant loss processes for the parent compounds, generating a variety of lower brominated diphenyl ethers, hydroxylated metabolites, and other products. BDEs are hydrophobic, and therefore their transport in aquatic systems is likely controlled by sorption to sediments and perhaps exchange across the air-water interface. To date, few studies have examined the geochemistry of BDEs in natural waters. In this paper, we review our recent measurements of BDEs in the Chesapeake Bay, a shallow, productive estuary in eastern North America. We focus on the distribution of BDE congeners sediment, porewater, and in faunal benthos along a contamination gradient downstream from a wastewater treatment plant and on the spatial distribution of BDEs in bottom-feeding and pelagic fish species.

  3. Fate of higher brominated PBDEs in lactating cows.

    Science.gov (United States)

    Kierkegaard, Amelie; Asplund, Lillemor; de Wit, Cynthia A; McLachlan, Michael S; Thomas, Gareth O; Sweetman, Andrew J; Jones, Kevin C

    2007-01-15

    Dietary intake studies of lower brominated diphenyl ethers (BDEs) have shown that fish and animal products are important vectors of human exposure, but almost no data exist for higher brominated BDEs. Therefore, the fate of hepta- to decaBDEs was studied in lactating cows exposed to a naturally contaminated diet by analyzing feed, feces, and milk samples from a previous mass balance study of PCB. Tissue distribution was studied in one cow slaughtered after the experiment. BDE-209 was the dominant congener in feed, organs, adipose tissues, and feces, but not in milk. In contrast to PCBs and lower brominated BDEs, concentrations of hepta- to decaBDEs in adipose tissue were 9-80 times higher than in milk fat and the difference increased with degree of bromination/log K(OW). The congener profiles in adipose tissue and feed differed; BDE-207, BDE-196, BDE-197, and BDE-182 accumulated to a surprisingly greater extent in the fat compared to their isomers, suggesting metabolic debromination of BDE-209 to these BDEs. The results indicate that meat rather than dairy product consumption may be an important human exposure route to higher brominated BDEs.

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

    Science.gov (United States)

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

    2015-09-01

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

  5. Brominated diphenyl ether levels. A comparison of tributary sediments versus biosolid material

    Energy Technology Data Exchange (ETDEWEB)

    Kolic, T.M.; MacPherson, K.A.; Reiner, E.J. [Ontario Ministry of the Environment, Laboratory Services Branch, Toronto, ON (Canada); Ho, T.; Kleywegt, S. [Ontario Ministry of the Environment, Standards Development Branch, Toronto, ON (Canada); Dove, A.; Marvin, C. [Environment Canada, Burlington, ON (Canada)

    2004-09-15

    PBDEs are persistent in the environment, have low water solubility and are known to have a tendency to bioaccumulate in wildlife and humans. There are 209 possible PBDE congeners. There has been concern over the bioaccumulation of these compounds since they have been found in mother's milk. Some of the brominated diphenyl ethers are known to metabolize into hydroxylated compounds and these metabolites are known to compete with and reduce thyroxine (T4) from binding to the thyroxine binding protein, transthyretin. This disrupts the thyroid hormone system interaction that has recently been notable amongst women in the form of hypothyroidism that can affect the fetus development in the form of neurodevelopmental deficits. There have been reports of estrogenic activities regarding PBDEs and their hydroxylated counterparts. Information such as this is indicative that PBDEs are endocrine disruptors. Due to their lipophilic nature, PBDEs have a high binding affinity to particulates and accumulate in sediments. Various reports on sediments and sludge type matrices have been reported in Austria, Switzerland, Netherlands and Canada. The following paper is a presentation of levels of PBDEs found in Tributary sediments and their comparison of levels to nearby biosolid sampling locations along Lake Ontario.

  6. Hydroxylated polybrominated diphenyl ethers exhibit different activities on thyroid hormone receptors depending on their degree of bromination.

    Science.gov (United States)

    Ren, Xiao-Min; Guo, Liang-Hong; Gao, Yu; Zhang, Bin-Tian; Wan, Bin

    2013-05-01

    Polybrominated diphenyl ethers (PBDEs) have been shown to disrupt thyroid hormone (TH) functions in experimental animals, and one of the proposed disruption mechanisms is direct binding of hydroxylated PBDE (OH-PBDE) to TH receptors (TRs). However, previous data on TH receptor binding and TH activity of OH-PBDEs were very limited and sometimes inconsistent. In the present paper, we examined the binding potency of ten OH-PBDEs with different degrees of bromination to TR using a fluorescence competitive binding assay. The results showed that the ten OH-PBDEs bound to TR with potency that correlated to their bromination level. We further examined their effect on TR using a coactivator binding assay and GH3 cell proliferation assay. Different TR activities of OH-PBDEs were observed depending on their degree of bromination. Four low-brominated OH-PBDEs (2'-OH-BDE-28, 3'-OH-BDE-28, 5-OH-BDE-47, 6-OH-BDE-47) were found to be TR agonists, which recruited the coactivator peptide and enhanced GH3 cell proliferation. However, three high-brominated OH-PBDEs (3-OH-BDE-100, 3'-OH-BDE-154, 4-OH-BDE-188) were tested to be antagonists. Molecular docking was employed to simulate the interactions of OH-PBDEs with TR and identify the structural determinants for TR binding and activity. According to the docking results, low-brominated OH-PBDEs, which are weak binders but TR agonists, bind with TR at the inner side of its binding pocket, whereas high-brominated compounds, which are potent binders but TR antagonists, reside at the outer region. These results indicate that OH-PBDEs have different activities on TR (agonistic or antagonistic), possibly due to their different binding geometries with the receptor. Copyright © 2013 Elsevier Inc. All rights reserved.

  7. Exponential increases of the brominated flame retardants, polybrominated diphenyl ethers, in the Canadian Arctic from 1981 to 2000.

    Science.gov (United States)

    Ikonomou, Michael G; Rayne, Sierra; Addison, Richard F

    2002-05-01

    A suite of 37 polybrominated diphenyl ether (PBDE) congeners and all of the homologue groups from mono- to deca-brominated were determined in ringed seal (Phoca hispida) blubber collected from subsistence hunts in the Canadian Arctic in 1981, 1991, 1996, and 2000. Total PBDE (sum(PBDE)) concentrations have increased exponentially over this period in male ringed seals aged 0-15 years. Penta- and hexa-BDEs are increasing at approximately the same rate (t2 = 4.7 and 4.3 years, respectively) and more rapidly than tetra-BDEs (t2 = 8.6 years) and tri-BDEs (t2 = infinity) in this age/sex grouping. In contrast to declining PBDE concentrations since 1997 in human milk from Sweden, sum(PBDE) concentrations in arctic ringed seals continue to increase exponentially similar to worldwide commercial penta-BDE production. PBDE congener profiles in male ringed seals aged 0-15 years from 1991 to 2000 also differ significantly from other aquatic organisms and semipermeable membrane devices collected from temperate coastal regions of British Columbia. While PBDE concentrations are 50 times lower than those of mono-ortho and non-ortho PCBs, and approxiamately 500 times higher than PCDD/Fs, our data indicate that, at current rates of bioaccumulation, PBDEs will surpass PCBs to become the most prevalent organohalogen compound in Canadian arctic ringed seals by 2050.

  8. Polybrominated diphenyl ethers and “novel” brominated flame retardants in floor and elevated surface house dust from Iraq: Implications for human exposure assessment

    Directory of Open Access Journals (Sweden)

    Layla Salih Al-Omran

    2016-03-01

    Full Text Available Concentrations of polybrominated diphenyl ethers (PBDEs and selected novel brominated flame retardants (NBFRs were measured in indoor dust from the living areas of 18 homes in Basrah, Iraq. This is the first report of contamination of the Iraqi environment with these chemicals. To evaluate the implications for human exposure, samples were collected from both the floor and from elevated surfaces like tables, shelves and chairs. When normalised for the organic carbon content of the dust sample, concentrations in elevated surface dust of BDE-99, BDE-209, pentabromoethylbenzene (PBEB, bis (2-ethylhexyl 3,4,5,6-tetrabromophthalate (BEH-TEBP, and decabromodiphenylethane (DBDPE exceeded significantly (p < 0.05 those in floor dust from the same rooms. This suggests that previous studies that base estimates of adult exposure via dust ingestion on floor dust, may underestimate exposure. Such underestimation is less likely for toddlers who are far more likely to ingest floor dust. Concentrations of PBDEs and NBFRs in indoor dust from Basrah, Iraq are at the lower end of levels reported elsewhere. The PBDE contamination pattern in our samples suggests that use in Iraq of the Deca-BDE formulation, exceeds substantially that of Penta-BDE, but that use of the Octa-BDE formulation has been higher in Iraq than in some other regions. Reassuringly, our estimates of exposure to our target BFRs via dust ingestion for the Iraqi population fall well below the relevant health-based limit values.

  9. Involvement of reactive oxygen species in brominated diphenyl ether-47-induced inflammatory cytokine release from human extravillous trophoblasts in vitro

    International Nuclear Information System (INIS)

    Park, Hae-Ryung; Kamau, Patricia W.; Loch-Caruso, Rita

    2014-01-01

    Polybrominated diphenyl ethers (PBDEs) are widely used flame retardant compounds. Brominated diphenyl ether (BDE)-47 is one of the most prevalent PBDE congeners found in human breast milk, serum and placenta. Despite the presence of PBDEs in human placenta, effects of PBDEs on placental cell function are poorly understood. The present study investigated BDE-47-induced reactive oxygen species (ROS) formation and its role in BDE-47-stimulated proinflammatory cytokine release in a first trimester human extravillous trophoblast cell line, HTR-8/SVneo. Exposure of HTR-8/SVneo cells for 4 h to 20 μM BDE-47 increased ROS generation 1.7 fold as measured by the dichlorofluorescein (DCF) assay. Likewise, superoxide anion production increased approximately 5 fold at 10 and 15 μM and 9 fold at 20 μM BDE-47 with a 1-h exposure, as measured by cytochrome c reduction. BDE-47 (10, 15 and 20 μM) decreased the mitochondrial membrane potential by 47–64.5% at 4, 8 and 24 h as assessed with the fluorescent probe Rh123. Treatment with 15 and 20 μM BDE-47 stimulated cellular release and mRNA expression of IL-6 and IL-8 after 12 and 24-h exposures: the greatest increases were a 35-fold increased mRNA expression at 12 h and a 12-fold increased protein concentration at 24 h for IL-6. Antioxidant treatments (deferoxamine mesylate, (±)α-tocopherol, or tempol) suppressed BDE-47-stimulated IL-6 release by 54.1%, 56.3% and 37.7%, respectively, implicating a role for ROS in the regulation of inflammatory pathways in HTR-8/SVneo cells. Solvent (DMSO) controls exhibited statistically significantly decreased responses compared with non-treated controls for IL-6 release and IL-8 mRNA expression, but these responses were not consistent across experiments and times. Nonetheless, it is possible that DMSO (used to dissolve BDE-47) may have attenuated the stimulatory actions of BDE-47 on cytokine responses. Because abnormal activation of proinflammatory responses can disrupt trophoblast functions

  10. Involvement of reactive oxygen species in brominated diphenyl ether-47-induced inflammatory cytokine release from human extravillous trophoblasts in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hae-Ryung, E-mail: heaven@umich.edu; Kamau, Patricia W.; Loch-Caruso, Rita

    2014-01-15

    Polybrominated diphenyl ethers (PBDEs) are widely used flame retardant compounds. Brominated diphenyl ether (BDE)-47 is one of the most prevalent PBDE congeners found in human breast milk, serum and placenta. Despite the presence of PBDEs in human placenta, effects of PBDEs on placental cell function are poorly understood. The present study investigated BDE-47-induced reactive oxygen species (ROS) formation and its role in BDE-47-stimulated proinflammatory cytokine release in a first trimester human extravillous trophoblast cell line, HTR-8/SVneo. Exposure of HTR-8/SVneo cells for 4 h to 20 μM BDE-47 increased ROS generation 1.7 fold as measured by the dichlorofluorescein (DCF) assay. Likewise, superoxide anion production increased approximately 5 fold at 10 and 15 μM and 9 fold at 20 μM BDE-47 with a 1-h exposure, as measured by cytochrome c reduction. BDE-47 (10, 15 and 20 μM) decreased the mitochondrial membrane potential by 47–64.5% at 4, 8 and 24 h as assessed with the fluorescent probe Rh123. Treatment with 15 and 20 μM BDE-47 stimulated cellular release and mRNA expression of IL-6 and IL-8 after 12 and 24-h exposures: the greatest increases were a 35-fold increased mRNA expression at 12 h and a 12-fold increased protein concentration at 24 h for IL-6. Antioxidant treatments (deferoxamine mesylate, (±)α-tocopherol, or tempol) suppressed BDE-47-stimulated IL-6 release by 54.1%, 56.3% and 37.7%, respectively, implicating a role for ROS in the regulation of inflammatory pathways in HTR-8/SVneo cells. Solvent (DMSO) controls exhibited statistically significantly decreased responses compared with non-treated controls for IL-6 release and IL-8 mRNA expression, but these responses were not consistent across experiments and times. Nonetheless, it is possible that DMSO (used to dissolve BDE-47) may have attenuated the stimulatory actions of BDE-47 on cytokine responses. Because abnormal activation of proinflammatory responses can disrupt trophoblast functions

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

    Science.gov (United States)

    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.

  12. Transformation of hydroxylated and methoxylated 2,2',4,4',5-brominated diphenyl ether (BDE-99) in plants

    Institute of Scientific and Technical Information of China (English)

    Lili Pan; Jianteng Sun; Xiaodan Wu; Zi Wei; Lizhong Zhu

    2016-01-01

    The occurrence and fate of hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) have received significant attention.However,there is limited information on the metabolism relationship between OH-pentaBDEs and MeO-pentaBDEs that were frequently detected with relatively high concentrations in the environment.In this study,the biotransformation between OH-BDE-99 and MeO-BDE-99 was investigated in rice,wheat,and soybean plants.All the three plants can metabolize OH-BDE-99 to corresponding homologous methoxylated metabolites,while the transformation from MeO-BDE-99 to OH-BDE-99 could only be found in soybean.The conversion of parent compounds was the highest in soybean,followed by wheat and rice.Transformation products were found mainly in the roots,with few metabolites being translocated to the shoots and solution after exposure.The results of this study provide valuable information for a better understanding of the accumulation and transformation of OH-PBDEs and MeO-PBDEs in different plants.

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

    Science.gov (United States)

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

    2017-11-01

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

  14. A brominated flame retardant 2,2',4,4' tetrabrominated diphenyl ether (BDE-47) leads to lipogenesis in the copepod Tigriopus japonicus.

    Science.gov (United States)

    Lee, Min-Chul; Han, Jeonghoon; Lee, Seung-Hwi; Kim, Duck-Hyun; Kang, Hye-Min; Won, Eun-Ji; Hwang, Dae-Sik; Park, Jun Chul; Om, Ae-Son; Lee, Jae-Seong

    2016-09-01

    De novo lipogenesis (DNL) is a fatty acid synthesis process that requires several genes, including sterol regulatory element binding protein (SREBP), ATP-citrate lyase (ACLY), and acetyl-CoA carboxylase (ACC). DNL up-regulation is able to induce fat accumulation through an increase in fatty acids. To investigate the relationship between DNL up-regulation and the accumulation of fatty acids and lipid droplets in response to 2,2',4,4' tetrabrominated diphenyl ether (BDE-47), we examined DNL in the copepod Tigriopus japonicus. Transcription levels of DNL-related genes were increased after exposure to 2.5μg/L BDE-47 for 24h. After exposure to 2.5μg/L BDE-47, palmitic acid was significantly increased (Pcopepod. This study provides a better understanding of the effects of BDE-47 on DNL in copepods. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Poly-brominated diphenyl-ethers (PBDEs) and other persistent organic pollutants in blood of penguins from the Ross Sea (Antarctica)

    Energy Technology Data Exchange (ETDEWEB)

    Corsolini, S.; Ademollo, N.; Mariottini, M.; Focardi, S. [Universita degli Studi di Siena, Siena (Italy)

    2004-09-15

    Polychlorobiphenyls (PCBs), hexachlorobenzene (HCB), polybrominated diphenyl ethers (PBDEs) and dichlorodiphenyl-dichloro ethane (pp'-DDE) including its isomers and metabolites are known as POPs very well. POPs are particularly hazardous to wildlife not only because they are toxic but because they are persistent and distributed on global scale. Polybrominated diphenyl ethers (PBDEs) are a class of POPs used worldwide as flame retardants with an increasing trend in the market demand (67.4 ktons in 2001), but with some restrictions in their usage in Europe. PBDEs are hydrophobic, highly soluble in lipids, resistant to biodegradation and have similar behavior to polychlorinated biphenyls (PCBs) in aquatic and terrestrial ecosystems. Their bioaccumulation and biomagnification properties, as well their global increasing presence, have already been reported by many authors. PBDEs have been detected in remote Arctic regions10 that seem to be their final sink. PBDEs show acute toxicity and a prolonged exposure can affect the function of thyroid and cause neurodevelopmental disorders and estrogenic and hepatic effects. Furthermore, a synergic effect with dioxin-like compounds or other POPs cannot be excluded. The two aims of this study are: (1) to evaluate accumulation levels and patterns of PCBs, PBDEs and chlorinated pesticides in blood samples of the Adelie penguin, Pygoscelis adeliae, the Emperor penguin, Aptenodytes forsteri and the South Polar skua, Cataracta maccormicki from three sites in the Ross Sea (Antarctica); (2) to assess the suitability of blood for the detection of POP residues in supposedly low contaminated organisms that live in protected/ecologically sensitive areas.

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

    Energy Technology Data Exchange (ETDEWEB)

    Lopez, P. [VU University Amsterdam, Institute for Environmental Studies (IVM), Amsterdam (Netherlands); Institute for Reference Materials and Measurements, European Commission, Joint Research Centre, Retieseweg 111, 2440, Geel (Belgium); Brandsma, S.A.; Leonards, P.E.G.; Boer, J. de [VU University Amsterdam, Institute for Environmental Studies (IVM), Amsterdam (Netherlands)

    2011-05-15

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

  17. Brominated dioxins/furans and hydroxylated polybrominated diphenyl ethers: Occurrences in commercial 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) and 2,4,6-tribromophenol, and formation during synthesis of BTBPE.

    Science.gov (United States)

    Ren, Man; Zeng, Hao; Peng, Ping-An; Li, Hui-Ru; Tang, Cai-Ming; Hu, Jian-Fang

    2017-07-01

    Polybrominated dibenzo-p-dioxins (PBDDs) and hydroxylated polybrominated diphenyl ethers (OH-PBDEs) can be formed from bromophenols (BPs) by thermal degradation, biosynthesis or phototransformation. However, it is unknown whether PBDDs and OH-PBDEs can be formed during the chemical production processes that utilize BPs as raw materials. 2,4,6-tribromophenol (2,4,6-TBP) is an important raw material for the synthesis of 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), a novel brominated flame retardant. In this study, PBDDs, polybrominated dibenzofurans (PBDFs) and OH-PBDEs have been identified and quantified in commercially available BTBPE and 2,4,6-TBP. Furthermore, their formation as unintentional by-products during the laboratory synthesis of BTBPE from 2,4,6-TBP and 1,2-dibromoethane in the presence of sodium carbonate has also been investigated. 2,3,7,8-substituted PBDDs and PBDFs (2,3,7,8-PBDD/Fs) were undetectable in commercial samples of BTBPE and present in low levels (nanogram per gram) in 2,4,6-TBP. Two tetrabrominated dibenzo-p-dioxins (TeBDDs), namely 1,3,6,8- and 1,3,7,9-TeBDD, and three hydroxylated pentabrominated diphenyl ethers (OH-pentaBDEs), namely 4'-OH-BDE121, 2'-OH-BDE121, and 6'-OH-BDE100, were identified or tentatively identified, and quantitatively estimated to be at concentrations in the range of undetectable to several thousands of nanograms per gram in commercial BTBPE and 2,4,6-TBP. TeBDDs and OH-pentaBDEs were formed as by-products from 2,4,6-TBP during BTBPE synthesis. Further studies need to be conducted in order to determine whether PBDD/Fs and OH-PBDEs are also formed during the industrial synthesis of other chemical compounds that utilize BPs as raw materials or intermediates. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

    NARCIS (Netherlands)

    Harju, M.; Hamers, T.; Kamstra, J.H.; Sonneveld, E.; Boon, J.P.

    2007-01-01

    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),

  19. Pollution of Lake Mjoesa by brominated flame retardants

    Energy Technology Data Exchange (ETDEWEB)

    Schlabach, M.; Gundersen, H.; Mariussen, E. [NILU, Kjeller (Norway); Fjeld, E.; Breivik, E. [NIVA, Oslo (Norway); Kjellberg, G. [NIVA, Hamar (Norway)

    2004-09-15

    The worldwide use of brominated flame retardants (BFRs) is extensive and there are significant release of these components to the environment. The last twenty years the levels of the polybrominated diphenyl ethers (PBDE) in biota have increased, and in some areas the levels are comparable or even higher to what is reported for the polychlorinated biphenyls (PCB). This study was focused on the pollution of PBDEs in Lake Mjoesa, where unusually high concentrations have been found in fish. The objective of this part of the survey was to make a broader documentation of the PBDE levels in sediments and fish, and to localize areas with point sources of PBDEs.

  20. Induced production of brominated aromatic compounds in the alga Ceramium tenuicorne.

    Science.gov (United States)

    Dahlgren, Elin; Enhus, Carolina; Lindqvist, Dennis; Eklund, Britta; Asplund, Lillemor

    2015-11-01

    In the Baltic Sea, high concentrations of toxic brominated aromatic compounds have been detected in all compartments of the marine food web. A growing body of evidence points towards filamentous algae as a natural producer of these chemicals. However, little is known about the effects of environmental factors and life history on algal production of brominated compounds. In this study, several congeners of methoxylated polybrominated diphenyl ethers (MeO-PBDEs), hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and brominated phenols (BPs) were identified in a naturally growing filamentous red algal species (Ceramium tenuicorne) in the Baltic Sea. The identified substances displayed large seasonal variations in the alga with a concentration peak in July. Production of MeO-/OH-PBDEs and BPs by C. tenuicorne was also established in isolated clonal material grown in a controlled laboratory setting. Based on three replicates, herbivory, as well as elevated levels of light and salinity in the culture medium, significantly increased the production of 2,4,6-tribromophenol (2,4,6-TBP). Investigation of differences in production between the isomorphic female, male and diploid clonal life stages of the alga grown in the laboratory revealed a significantly higher production of 2,4,6-TBP in the brackish water female gametophytes, compared to the corresponding marine gametophytes. Even higher concentrations of 2,4,6-TBP were produced by marine male gametophytes and sporophytes.

  1. Regional variation and possible sources of brominated contaminants in breast milk from Japan

    International Nuclear Information System (INIS)

    Fujii, Yukiko; Ito, Yoshiko; Harada, Kouji H.; Hitomi, Toshiaki; Koizumi, Akio; Haraguchi, Koichi

    2012-01-01

    This study focuses on the regional trends and possible sources of brominated organic contaminants accumulated in breast milk from mothers in southeastern (Okinawa) and northwestern (Hokkaido) areas of Japan. For persistent brominated flame retardants, polybrominated diphenyl ethers (PBDEs; major components, BDE-47 and BDE-153) were distributed at higher levels in mothers from Okinawa (mean, 2.1 ng/g lipid), while hexabromobenzene (HeBB) and its metabolite 1,2,4,5-tetrabromobenzene were more abundantly detected in mothers from Hokkaido (0.86 and 2.6 ng/g lipid), suggesting that there are regional differences in their exposure in Japan. We also detected naturally produced brominated compounds, one of which was identified as 2′-methoxy-2,3′,4,5′-tetrabromodiphenyl ether (2′-MeO-BDE68) at higher levels in mothers from Okinawa (0.39 ng/g lipid), while the other was identified as 3,3′,4,4′-tetrabromo-5,5′-dichloro-2,2′-dimethyl-1,1′-bipyrrole in mothers from Hokkaido (0.45 ng/g lipid). The regional variation may be caused by source differences, i.e. southern seafood for MeO-PBDEs and northern biota for halogenated bipyrroles in the Japanese coastal water. - Highlights: ► In this study, we detected brominated organic contaminants in Japanese breast milk. ► Naturally produced brominated organic contaminants were also detected. ► Northern and southern Japan showed regional differences in these contaminants. ► Exposure to the contaminants is suggested to arise from different specific sources. - Brominated organic contaminants were detected in Japanese breast milk.

  2. Bromination of Phenol

    Science.gov (United States)

    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…

  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.

    Science.gov (United States)

    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. Reproductive Effects of Two Polybrominated Diphenyl Ethers on the Rotifer Brachionus plicatilis.

    Science.gov (United States)

    Zhang, Jing; Wang, You; Zhou, Bin; Sun, Kai-Ming; Tang, Xuexi

    2016-08-01

    The effects of two polybrominated diphenyl ethers (PBDEs) on the reproduction of the rotifer Brachionus plicatilis were investigated. Results showed that sexual maturation was promoted by tetra-brominated diphenyl ether-47 (BDE-47) and deca-brominated diphenyl ether-209 (BDE-209), whereas fecundity was inhibited by BDE-47, but promoted by BDE-209. Additionally, both PBDEs affected the expression of two genes, vasa and nanos mRNA, related to rotifer reproduction. This suggests a possible regulatory molecular mechanism at the transcriptional level. Our research extends the current knowledge of the ecotoxicological mechanism induced by PBDEs and provides further essential information for assessing the risks of PBDE contamination in marine ecosystems.

  5. Preparation of bromine fluoride

    International Nuclear Information System (INIS)

    Domange, Pr; Duflo, J.

    1958-05-01

    This note addresses the preparation of bromine fluoride. It indicates the implemented process for the reaction, used products (fluorine and bromine), and column characteristics. It describes the operating mode. Apparatus drawing is provided

  6. Phytotoxicity of brominated diphenyl ether-47 (BDE-47) and its hydroxylated and methoxylated analogues (6-OH-BDE-47 and 6-MeO-BDE-47) to maize (Zea mays L.).

    Science.gov (United States)

    Xu, Xuehui; Huang, Honglin; Wen, Bei; Wang, Sen; Zhang, Shuzhen

    2015-03-16

    Polybrominated diphenyl ethers (PBDEs), methoxylated PBDEs (MeO-PBDEs), and hydroxylated PBDEs (OH-PBDEs) are widely found in various environmental media, which is of concern given their biological toxicity. In this study, the phytotoxicities of BDE-47, 6-MeO-BDE-47, and 6-OH-BDE-47 to maize (Zea mays L.) were investigated by an in vivo exposure experiment. Results showed that BDE-47, 6-MeO-BDE-47, and 6-OH-BDE-47 inhibited seed germination and seedling development, and elevated malondialdehyde (MDA), carbonyl groups, and phosphorylated histone H2AX levels in maize roots, suggesting the inducement of lipid peroxidation, protein carbonylation, and DNA damage to maize. Exposure to BDE-47, 6-MeO-BDE-47, and 6-OH-BDE-47 caused the overproduction of H2O2, O2(•-), and •OH, and elevated the activities of antioxidant enzymes in the roots. In addition, 6-OH-BDE-47 caused more severe damage and reactive oxygen species (ROS) generation in maize than did BDE-47 and 6-MeO-BDE-47. These results demonstrated the phytotoxicities of BDE-47, 6-OH-BDE-47, and 6-MeO-BDE-47 to maize, and clarified that overproduction of ROS was the key mechanism leading to toxicity. This study offers useful information for a more comprehensive understanding of the environmental behaviors and toxicities of PBDEs, MeO-PBDEs, and OH-PBDEs.

  7. Uptake, translocation, and debromination of polybrominated diphenyl ethers in maize

    Institute of Scientific and Technical Information of China (English)

    Moming Zhao; Shuzhen Zhang; Sen Wang; Honglin Huang

    2012-01-01

    Uptake,translocation and debromination of three polybrominated diphenyl ethers(PBDEs),BDE-28,-47 and-99,in maize were studied in a hydroponic experiment.Roots took up most of the PBDEs in the culture solutions and more highly brominated PBDEs had a stronger uptake capability.PBDEs were detected in the stems and leaves of maize after exposure but rarely detected in the blank control plants.Furthermore,PBDE concentrations decreased from roots to stems and then to leaves,and a very clear decreasing gradient was found in segments upwards along the stem.These altogether provide substantiating evidence for the acropetal translocation of PBDEs in maize.More highly brominated PBDEs were translocated with more difficulty.Radial translocation of PBDEs from nodes to sheath inside maize was also observed.Both acropetal and radial translocations were enhanced at higher transpiration rates,suggesting that PBDE transport was probably driven by the transpiration stream.Debromination of PBDEs occurred in all parts of the maize,and debromination patterns of different parent PBDEs and in different parts of a plant were similar but with some differences.This study for the first time provides direct evidence for the acropetal translocation of PBDEs within plants,elucidates the process of PBDE transport and clarifies the debromination products of PBDEs in maize.

  8. Protective effect of nuclear factor E2-related factor 2 on inflammatory cytokine response to brominated diphenyl ether-47 in the HTR-8/SVneo human first trimester extravillous trophoblast cell line.

    Science.gov (United States)

    Park, Hae-Ryung; Loch-Caruso, Rita

    2014-11-15

    Polybrominated diphenyl ethers (PBDEs) are widely used flame retardants, and BDE-47 is a prevalent PBDE congener detected in human tissues. Exposure to PBDEs has been linked to adverse pregnancy outcomes in humans. Although the underlying mechanisms of adverse birth outcomes are poorly understood, critical roles for oxidative stress and inflammation are implicated. The present study investigated antioxidant responses in a human extravillous trophoblast cell line, HTR-8/SVneo, and examined the role of nuclear factor E2-related factor 2 (Nrf2), an antioxidative transcription factor, in BDE-47-induced inflammatory responses in the cells. Treatment of HTR-8/SVneo cells with 5, 10, 15, and 20μM BDE-47 for 24h increased intracellular glutathione (GSH) levels compared to solvent control. Treatment of HTR-8/SVneo cells with 20μM BDE-47 for 24h induced the antioxidant response element (ARE) activity, indicating Nrf2 transactivation by BDE-47 treatment, and resulted in differential expression of redox-sensitive genes compared to solvent control. Pretreatment with tert-butyl hydroquinone (tBHQ) or sulforaphane, known Nrf2 inducers, reduced BDE-47-stimulated IL-6 release with increased ARE reporter activity, reduced nuclear factor kappa B (NF-κB) reporter activity, increased GSH production, and stimulated expression of antioxidant genes compared to non-Nrf2 inducer pretreated groups, suggesting that Nrf2 may play a protective role against BDE-47-mediated inflammatory responses in HTR-8/SVneo cells. These results suggest that Nrf2 activation significantly attenuated BDE-47-induced IL-6 release by augmentation of cellular antioxidative system via upregulation of Nrf2 signaling pathways, and that Nrf2 induction may be a potential therapeutic target to reduce adverse pregnancy outcomes associated with toxicant-induced oxidative stress and inflammation. Copyright © 2014 Elsevier Inc. All rights reserved.

  9. Polybrominated diphenyl ethers (PBDEs) in feathers of colonial water-bird species from Pakistan

    Energy Technology Data Exchange (ETDEWEB)

    Malik, Riffat Naseem, E-mail: r_n_malik2000@yahoo.co.uk [Environmental Biology Laboratory, Department of Plant Sciences, Faculty of Biological Sciences, Quaid-i-Azam University, Islamabad, PO 45320 (Pakistan); Moeckel, Claudia [Centre for Ecology and Hydrology, Lancaster Environment Centre, Library Avenue, Bailrigg, Lancaster LA1 4AP (United Kingdom); Jones, Kevin C.; Hughes, David [Centre for Chemicals Management, Lancaster Environment Centre, Lancaster University, Bailrigg, Lancaster LA1 4YQ (United Kingdom)

    2011-10-15

    Feathers of two colonial water-birds species (Bubulcus ibis, Egretta garzetta) from four heronries in the Punjab province, Pakistan were analysed for 28 Polybrominated Diphenyl Ethers (PBDEs) congeners. Median concentrations of {Sigma}PBDEs were 2.41 and 1.91 ng/g in little and cattle egrets. PBDE-47, -100, -138, -153 were abundant and detected in >70% of feather samples in both species. Species-specific differences based on dietary preferences indicated higher concentration of PBDE-47, -66, -75, -100, -153, -154, and -183 in fish eating little egret. BDE-47 and -100 were more frequent in little egrets and BDE-99 was more dominant in cattle egret which feed on terrestrial habitat. Higher {Sigma}hexa- and hepta-BDEs congeners showed larger concentrations in feathers from heronries close to water bodies which receive urban and industrial effluents whereas lower-brominated congeners (BDE-47-BDE-100) dominated in rural/agricultural regions. Hazard quotients (HQs) indicated that measured {Sigma}PBDEs pose no risk to egret population. - Highlights: > Feathers as non-destructive tool to asses Polybrominated Diphenyl Ethers (PBDEs) contamination. > PBDE-47 and -100 frequent in feathers of fish eating egrets. > BDE-99 dominant in feathers of egrets feed in terrestrial habitats. > Lower-brominated congeners (BDE-47-BDE-100) dominate in feathers from rural areas. > Greater contents of hexa- and hepta-BDEs in feathers from areas receive urban/industrial effluents. - Feathers are used as a biomonitoring tool for PBDEs contamination.

  10. Polybrominated diphenyl ethers (PBDEs) in feathers of colonial water-bird species from Pakistan

    International Nuclear Information System (INIS)

    Malik, Riffat Naseem; Moeckel, Claudia; Jones, Kevin C.; Hughes, David

    2011-01-01

    Feathers of two colonial water-birds species (Bubulcus ibis, Egretta garzetta) from four heronries in the Punjab province, Pakistan were analysed for 28 Polybrominated Diphenyl Ethers (PBDEs) congeners. Median concentrations of ΣPBDEs were 2.41 and 1.91 ng/g in little and cattle egrets. PBDE-47, -100, -138, -153 were abundant and detected in >70% of feather samples in both species. Species-specific differences based on dietary preferences indicated higher concentration of PBDE-47, -66, -75, -100, -153, -154, and -183 in fish eating little egret. BDE-47 and -100 were more frequent in little egrets and BDE-99 was more dominant in cattle egret which feed on terrestrial habitat. Higher Σhexa- and hepta-BDEs congeners showed larger concentrations in feathers from heronries close to water bodies which receive urban and industrial effluents whereas lower-brominated congeners (BDE-47-BDE-100) dominated in rural/agricultural regions. Hazard quotients (HQs) indicated that measured ΣPBDEs pose no risk to egret population. - Highlights: → Feathers as non-destructive tool to asses Polybrominated Diphenyl Ethers (PBDEs) contamination. → PBDE-47 and -100 frequent in feathers of fish eating egrets. → BDE-99 dominant in feathers of egrets feed in terrestrial habitats. → Lower-brominated congeners (BDE-47-BDE-100) dominate in feathers from rural areas. → Greater contents of hexa- and hepta-BDEs in feathers from areas receive urban/industrial effluents. - Feathers are used as a biomonitoring tool for PBDEs contamination.

  11. Protective effect of nuclear factor E2-related factor 2 on inflammatory cytokine response to brominated diphenyl ether-47 in the HTR-8/SVneo human first trimester extravillous trophoblast cell line

    International Nuclear Information System (INIS)

    Park, Hae-Ryung; Loch-Caruso, Rita

    2014-01-01

    Polybrominated diphenyl ethers (PBDEs) are widely used flame retardants, and BDE-47 is a prevalent PBDE congener detected in human tissues. Exposure to PBDEs has been linked to adverse pregnancy outcomes in humans. Although the underlying mechanisms of adverse birth outcomes are poorly understood, critical roles for oxidative stress and inflammation are implicated. The present study investigated antioxidant responses in a human extravillous trophoblast cell line, HTR-8/SVneo, and examined the role of nuclear factor E2-related factor 2 (Nrf2), an antioxidative transcription factor, in BDE-47-induced inflammatory responses in the cells. Treatment of HTR-8/SVneo cells with 5, 10, 15, and 20 μM BDE-47 for 24 h increased intracellular glutathione (GSH) levels compared to solvent control. Treatment of HTR-8/SVneo cells with 20 μM BDE-47 for 24 h induced the antioxidant response element (ARE) activity, indicating Nrf2 transactivation by BDE-47 treatment, and resulted in differential expression of redox-sensitive genes compared to solvent control. Pretreatment with tert-butyl hydroquinone (tBHQ) or sulforaphane, known Nrf2 inducers, reduced BDE-47-stimulated IL-6 release with increased ARE reporter activity, reduced nuclear factor kappa B (NF-κB) reporter activity, increased GSH production, and stimulated expression of antioxidant genes compared to non-Nrf2 inducer pretreated groups, suggesting that Nrf2 may play a protective role against BDE-47-mediated inflammatory responses in HTR-8/SVneo cells. These results suggest that Nrf2 activation significantly attenuated BDE-47-induced IL-6 release by augmentation of cellular antioxidative system via upregulation of Nrf2 signaling pathways, and that Nrf2 induction may be a potential therapeutic target to reduce adverse pregnancy outcomes associated with toxicant-induced oxidative stress and inflammation. - Highlights: • BDE-47 stimulated ARE reporter activity and GSH production. • BDE-47 resulted in differential

  12. Protective effect of nuclear factor E2-related factor 2 on inflammatory cytokine response to brominated diphenyl ether-47 in the HTR-8/SVneo human first trimester extravillous trophoblast cell line

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hae-Ryung, E-mail: heaven@umich.edu; Loch-Caruso, Rita

    2014-11-15

    Polybrominated diphenyl ethers (PBDEs) are widely used flame retardants, and BDE-47 is a prevalent PBDE congener detected in human tissues. Exposure to PBDEs has been linked to adverse pregnancy outcomes in humans. Although the underlying mechanisms of adverse birth outcomes are poorly understood, critical roles for oxidative stress and inflammation are implicated. The present study investigated antioxidant responses in a human extravillous trophoblast cell line, HTR-8/SVneo, and examined the role of nuclear factor E2-related factor 2 (Nrf2), an antioxidative transcription factor, in BDE-47-induced inflammatory responses in the cells. Treatment of HTR-8/SVneo cells with 5, 10, 15, and 20 μM BDE-47 for 24 h increased intracellular glutathione (GSH) levels compared to solvent control. Treatment of HTR-8/SVneo cells with 20 μM BDE-47 for 24 h induced the antioxidant response element (ARE) activity, indicating Nrf2 transactivation by BDE-47 treatment, and resulted in differential expression of redox-sensitive genes compared to solvent control. Pretreatment with tert-butyl hydroquinone (tBHQ) or sulforaphane, known Nrf2 inducers, reduced BDE-47-stimulated IL-6 release with increased ARE reporter activity, reduced nuclear factor kappa B (NF-κB) reporter activity, increased GSH production, and stimulated expression of antioxidant genes compared to non-Nrf2 inducer pretreated groups, suggesting that Nrf2 may play a protective role against BDE-47-mediated inflammatory responses in HTR-8/SVneo cells. These results suggest that Nrf2 activation significantly attenuated BDE-47-induced IL-6 release by augmentation of cellular antioxidative system via upregulation of Nrf2 signaling pathways, and that Nrf2 induction may be a potential therapeutic target to reduce adverse pregnancy outcomes associated with toxicant-induced oxidative stress and inflammation. - Highlights: • BDE-47 stimulated ARE reporter activity and GSH production. • BDE-47 resulted in differential

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

    Science.gov (United States)

    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 (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. 2009 Elsevier B.V. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

    Chen Shejun [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Ma Yunjuan [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Zhuhai Environmental Moniorting Center, Zhuhai 519000 (China); Wang Jing; Tian Mi [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Luo Xiaojun [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Chen Da [Department of Environmental and Aquatic Animal Health, Virginia Institute of Marine Science, College of William and Mary, Gloucester Point, VA 23062 (United States); Mai Bixian, E-mail: nancymai@gig.ac.cn [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China)

    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.

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

    International Nuclear Information System (INIS)

    Chen Shejun; Ma Yunjuan; Wang Jing; Tian Mi; Luo Xiaojun; Chen Da; Mai Bixian

    2010-01-01

    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.

  16. Contamination of U.S. butter with polybrominated diphenyl ethers from wrapping paper.

    Science.gov (United States)

    Schecter, Arnold; Smith, Sarah; Colacino, Justin; Malik, Noor; Opel, Matthias; Paepke, Olaf; Birnbaum, Linda

    2011-02-01

    Our aim was to report the first known incidence of U.S. butter contamination with extremely high levels of polybrominated diphenyl ethers (PBDEs). Ten butter samples were individually analyzed for PBDEs. One of the samples and its paper wrapper contained very high levels of higher-brominated PBDEs. Dietary estimates were calculated using the 2007 U.S. Department of Agriculture Loss-Adjusted Food Availability data, excluding the elevated sample. The highly contaminated butter sample had a total upper bound PBDE level of 42,252 pg/g wet weight (ww). Levels of brominated diphenyl ether (BDE)-206, -207, and -209 were 2,000, 2,290, and 37,600 pg/g ww, respectively. Its wrapping paper contained a total upper-bound PBDE concentration of 804,751 pg/g ww, with levels of BDE-206, -207, and -209 of 51,000, 11,700, and 614,000 pg/g, respectively. Total PBDE levels in the remaining nine butter samples ranged from 180 to 1,212 pg/g, with geometric mean of 483 and median of 284 pg/g. Excluding the outlier, total PBDE daily intake from all food was 22,764 pg/day, lower than some previous U.S. dietary intake estimates. Higher-brominated PBDE congeners were likely transferred from contaminated wrapping paper to butter. A larger representative survey may help determine how frequently PBDE contamination occurs. Sampling at various stages in food production may identify contamination sources and reduce risk.

  17. Bromine intercalated graphite for lightweight composite conductors

    KAUST Repository

    Amassian, Aram; Patole, Archana

    2017-01-01

    A method of fabricating a bromine-graphite/metal composite includes intercalating bromine within layers of graphite via liquid-phase bromination to create brominated-graphite and consolidating the brominated-graphite with a metal nanopowder via a

  18. Synthesis of hydroxylated and methoxylated polybrominated diphenyl ethers

    Institute of Scientific and Technical Information of China (English)

    ZHENG Ke-wen; GAO Li-ping; CAO Jie; YU Hai-wen; ZHANG Zhang

    2009-01-01

    Hydroxylated/methoxylated polybrominated diphenyl ethers (OH/MeO-PBDEs) are not only detected as natural products, but also regarded as metabolites formed from polybrominated diphenyl ethers (PBDEs), which are widely used as flame-retardants in various materials. The aim of the present study was to synthesize authentic OH-PBDEs and MeO-PBDEs, as reference standards for environmental exploration. Twenty OH-PBDEs and their corresponding MeO-PBDEs containing three to six bromine atoms were synthesized via a trial of reactions including coupling, oxidation, bromination, methylation, etc. The products were characterized by GC-MS and 1H-NMR spectroscopy in the work. As results show, all compounds synthesized were up to 99% on purity and be reqarded as authentic standards for detecting the chemical pollutants in the emvironment.

  19. Stable carbon isotope analysis (δ13C values) of polybrominated diphenyl ethers and their UV-transformation products

    International Nuclear Information System (INIS)

    Rosenfelder, Natalie; Bendig, Paul; Vetter, Walter

    2011-01-01

    Polybrominated diphenyl ethers (PBDEs) are frequently detected in food and environmental samples. We used compound specific isotope analysis to determine the δ 13 C values of individual PBDEs in two technical mixtures. Within the same technical product (DE-71 or DE-79), BDE congeners were the more depleted in 13 C the higher brominated they were. In contrast, the products of light-induced hydrodebromination of BDE 47 and technical DE-79 were more enriched in 13 C because of more stable bonds between 13 C and bromine. As a result, the δ 13 C values of the irradiated solution progressed diametrically compared to those of the technical synthesis. The ratio of the δ 13 C values of BDE 47 to BDE 99 and of BDE 99 to BDE 153 are thus suggested as indicators to distinguish native technical products from transformation products. Ratios 1) is typical of transformation products. - Highlights: → δ 13 C values of PBDEs were determined by means of compound specific isotope analysis. → PBDEs in technical mixtures were the more depleted in 13 C the higher they were brominated. → Solutions of individual PBDEs and technical PBDE mixtures were irradiated by UV light. → δ 13 C values of irradiated PBDEs and technical PBDEs progressed diametrically. → Ratios of the δ 13 C values were used to distinguish native from transformed PBDEs. - Diametrically progressing δ 13 C values in technical mixtures and UV-transformation products of DE-79 may be useful for source appointment of PBDEs in environmental samples

  20. Children's exposure to polybrominated diphenyl ethers (PBDEs) through mouthing toys.

    Science.gov (United States)

    Ionas, Alin C; Ulevicus, Jocelyn; Gómez, Ana Ballesteros; Brandsma, Sicco H; Leonards, Pim E G; van de Bor, Margot; Covaci, Adrian

    2016-02-01

    Polybrominated diphenyl ethers (PBDEs) have previously been detected in children toys, yet the risk of child exposure to these chemicals through the mouthing of toys or other items is still unknown. We aimed to expand on the current knowledge by investigating the impact of infants' mouthing activities on exposure to PBDEs present in toys. This was established by a leaching model for determining the amount PBDEs that can leach from toys into saliva in simulated conditions. The PBDE migration rate was at its highest for the 15 min low-exposure scenario incubations (198 pg/cm(2) × min) with the ERM EC-591 certified reference material (CRM) (0.17% w/w PBDEs). The leaching process was congener-dependent, since the percentage of lower brominated PBDE congeners that leached out was up to 4.5 times higher than for the heavier PBDEs. To study the scenario in which a child would mouth on a toy flame retarded with BDE 209 alone, a plastic item containing 7% BDE 209 (w/w) was also tested. The BDE 209 amounts leached out in only 15 min were higher than the amounts leached from the CRM after the 16 h incubation. For the Belgian population, the exposure scenario from mouthing on toys containing PBDEs in amounts similar to the REACH threshold was found to be lower than the exposure from mother's milk, but higher than the exposure through diet or even dust. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

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

    2017-11-01

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

  2. Absorption and biotransformation of polybrominated diphenyl ethers DE-71 and DE-79 in chicken (Gallus gallus), mallard (Anas platyrhynchos), American kestrel (Falco sparverius) and black-crowned night-heron (Nycticorax nycticorax) eggs

    Science.gov (United States)

    McKernan, Moira A.; Rattner, Barnett A.; Hatfield, Jeff S.; Hale, Robert C.; Ottinger, Mary Ann

    2010-01-01

    We recently reported that air cell administration of penta-brominated diphenyl ether (penta-BDE; DE-71) evokes biochemical and immunologic effects in chicken (Gallus gallus) embryos at very low doses, and impairs pipping (i.e., stage immediately prior to hatching) and hatching success at 1.8 ug g-1 egg (actual dose absorbed) in American kestrels (Falco sparverius). I n the present study, absorption of polybrominated diphenyl ether (PBDE) congeners was measured following air cell administration of a penta-BDE mixture (11.1 ug DE-71 g-1 egg) or an octa-brominated diphenyl ether mixture (octa-BDE; DE-79; 15.4 ug DE-79 g-1 egg). Uptake of PBDE congeners was measured at 24 h post-injection, midway through incubation, and at pipping in chicken, mallard (Anas platyrhynchos), and American kestrel egg contents, and at the end of incubation in black-crowned night-heron (Nycticorax nycticorax) egg contents. Absorption of penta-BDE and octa-BDE from the air cell into egg contents occurred throughout incubation; at pipping, up to 29.6% of penta-BDE was absorbed, but only 1.40-6.48% of octa-BDE was absorbed. Higher brominated congeners appeared to be absorbed more slowly than lower brominated congeners, and uptake rate was inversely proportional to the log Kow of predominant BDE congeners. Six congeners or co-eluting pairs of congeners were detected in penta-BDE-treated eggs that were not found in the dosing solution suggesting debromination in the developing embryo, extraembryonic membranes, and possibly even in the air cell membrane. This study demonstrates the importance of determining the fraction of xenobiotic absorbed into the egg following air cell administration for estimation of the lowest-observed-effect level.

  3. Polybrominated diphenyl ethers (PBDEs) in the indoor environment and associations with prenatal exposure

    DEFF Research Database (Denmark)

    Vorkamp, Katrin; Thomsen, Marianne; Frederiksen, Marie

    2011-01-01

    As part of a larger exposure study, samples of dust and indoor air were collected in the homes of 43 pregnant women living in the Copenhagen area (Denmark) and analysed for 12 polybrominated diphenyl ethers using GC-MS. A second dust sample collected after delivery was analysed for BDE-183 and BDE...... established geographical differences between continental Europe and North America. Additional octa- and nonaBDE congeners (BDE-197, BDE-203, BDE-206, BDE-207, and BDE-208) were analysed in dust and analytical issues were discussed as these congeners also can be a product of thermal degradation of BDE-209...... further in this study. For all matrices, the PBDE profile resembled that of the technical product Bromkal 70-5DE, but air contained higher percentages of the lower brominated congeners and placenta tissue was dominated by BDE-153. The predominance of BDE-153 has been described in other studies on human...

  4. Polybrominated diphenyl ethers: human tissue levels and toxicology.

    Science.gov (United States)

    Gill, Udai; Chu, Ih; Ryan, John J; Feeley, Mark

    2004-01-01

    PBDEs are being released to the environment in wastes from their production facilities, degradation, or leaching and volatilization from products that contain PBDEs during the product's useful life. Brominated diphenyl ether congeners BDE-47, -99, and -153 are ubiquitous in the environment and are regarded as the most dominant congeners present in wildlife and humans. The tetra- to hexa-BDE are most likely the congeners to which humans are exposed through food consumption. Knowledge of PBDE uptake, metabolism, elimination, and enzyme induction is restricted largely to rodents (rats and mice) in vitro and in vivo. Feeding studies have shown that excretion of higher brominated BDEs is much greater than lower brominated BDEs. Penta-BDE is more toxic than octa- and deca-BDE following oral administration (oral LD50 in rats, 0.5-5 g/kg). In rodents, repeated exposure to PBDEs results in thyroid hormone disruption, developmental neurotoxicity, some changes of fetal development, and hepatotoxic effects. The observed chronic NOELs depend upon the technical mixture type (i.e., deca-, octa-, or penta- and their congener composition), animal species, and study protocol. Values range from 0.6 to 100 mg/kg in rats and from I to 100 mg/kg in mice. PBDEs are neither mutagenic nor genotoxic. Immunotoxicity in mice is observed following exposure to BDE-47 at 18 mg/kg/d, where splenocyte number decreased. Mice exposed neonatally to a single oral dose of BDE-47(10.5 mg/kg) or BDE-99 (12 mg/kg) on Pnd10 (period of rapid brain growth and development) show permanent impairment of spontaneous motor behavior when reaching adulthood. BDE-99 also induced adverse effects on learning and memory functions of mice. The estimated daily intake based on food consumption for PBDEs ranges from 44 to 51 ng/d, with fish contributing almost one-half. The BDE-99 body burden from a human milk survey can be estimated at 0.64 microg/kg, well below the experimental body burden of 0.4 mg/kg BDE-99 associated

  5. Bromine intercalated graphite for lightweight composite conductors

    KAUST Repository

    Amassian, Aram

    2017-07-20

    A method of fabricating a bromine-graphite/metal composite includes intercalating bromine within layers of graphite via liquid-phase bromination to create brominated-graphite and consolidating the brominated-graphite with a metal nanopowder via a mechanical pressing operation to generate a bromine-graphite/metal composite material.

  6. Polybrominated diphenyl ethers in atmosphere and soil of a production area in China: levels and partitioning.

    Science.gov (United States)

    Jin, Jun; Wang, Ying; Liu, Weizhi; Yang, Congqiao; Hu, Jicheng; Cui, Jian

    2011-01-01

    Polybrominated diphenyl ethers (PBDEs) were measured in atmosphere and soil samples taken in winter and summer at a PBDE production area of Laizhou Bay in China. The concentrations of Sigma11PBDE were 0.017-1.17 ng/m3 in gaseous phase, 0.5-161.1 ng/m3 in particulate phase, and 73-2629 ng/g dry weight in soil samples. The PBDE congener pattern in the gaseous phase differed from that in the particulate phase, and the PBDE congener pattern in the particulate phase was similar with that in soil. This demonstrated that there was little difference with atmospheric particle-soil transfer efficiency among PBDE congeners. In addition, there were seasonal variations in percentages on particle for lower brominated congeners. The BDE-28 was mostly in the gaseous phase in summer (88.3%), whereas the average proportion of BDE-28 in gaseous phase in winter was 38.9%. Higher brominated congeners (i.e., BDE-206, BDE-207, BDE-208, and BDE-209) were bound to the atmospheric particulate phase, and their potentials for long-range migration were mainly affected by the environmental behavior of atmospheric particles. Results indicated that PBDE congeners in summer were closer to gas-particle partition equilibrium than in winter. Temperature should be considered the main factor causing nonequilibrium in winter.

  7. Polybrominated diphenyl ethers in atmosphere and soil of a production area in China: Levels and partitioning

    Institute of Scientific and Technical Information of China (English)

    Jun Jin; Ying Wang; Weizhi Liu; Congqiao Yang; Jicheng Hu; Jian Cui

    2011-01-01

    Polybrominated diphenyl ethers (PBDEs) were measured in atmosphere and soil samples taken in winter and summer at a PBDE production area of Laizhou Bay in China. The concentrations of ∑11 PBDE were 0.017-1.17 ng/m3 in gaseous phase, 0.5-161.1 ng/m3 in particulate phase, and 73-2629 ng/g dry weight in soil samples. The PBDE congener pattern in the gaseous phase differed from that in the particulate phase, and the PBDE congener pattern in the particulate phase was similar with that in soil. This demonstrated that there was little difference with atmospheric panicle-soil transfer efficiency among PBDE congeners. In addition, there were seasonal variations in percentages on particle for lower brominated congeners. The BDE-28 was mostly in the gaseous phase in summer (88.3%),whereas the average proportion of BDE-28 in gaseous phase in winter was 38.9%. Higher brominated congeners (i.e., BDE-206, BDE207, BDE-208, and BDE-209) were bound to the atmospheric particulate phase, and their potentials for long-range migration were mainly affected by the environmental behavior of atmospheric particles. Results indicated that PBDE congeners in summer were closer to gas-particle partition equilibrium than in winter. Temperature should be considered the main factor causing nonequilibrium in winter.

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

    International Nuclear Information System (INIS)

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

    2005-01-01

    Levels of selected sparsely investigated persistent organic pollutants (POPs) have been measured in organisms from two Arctic lakes on Bjornoya (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 Ellasjoen. In Lake Oyangen, located only 5 km north of Ellasjoen, levels of these contaminants were significantly lower. δ 15 N-values were 7-10%o higher in organisms from Ellasjoen as compared to Oyangen. 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 Ellasjoen 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. - Elevate levels of chlorobornanes, polychlorinated naphthalenes and brominated flame retardants have been measured in biota from a Norwegian Arctic lake

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

    Science.gov (United States)

    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. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Atmospheric Bromine in the Arctic

    International Nuclear Information System (INIS)

    Berg, W.W.; Sperry, P.D.; Rahn, K.A.; Gladney, E.S.

    1983-01-01

    We report the first measurements of both particulate and gas phase bromine in the Arctic troposphere. Data from continuous sampling of the Arctic aerosol over a period of 4 years (1976--1980) indicate that the bromine content in the aerosol averages 6 +- 4 ngBr/SCM (5 +- 3 pptm Br) for 9 months of every year. During the 3-month period between February 15 and May 15, however, we observed an annual sharp maximum in particulate bromine with levels exceeding 100 ngBr/SCM (82 pptm Br). The Arctic aerosol showed no bromine enrichment relative to seawater except for this 3 month peak period. During the bromine maximum, enrichment factors reached 40 with average values near 10. Calculations of the amount of excess bromine in the Arctic aerosol showed that over 90% of the peak bromine had an origin other than from direct bulk seawater injection. Total levels of gas phase bromine in the Arctic troposphere found during the peak aerosol period averaged 422 +- 48 ngBr/SCM (118 +- 14 pptv). Total bromine content during this period averaged 474 +- 49 ngBr/SCM with gas-to-particle ratios ranging from 7 to 18. A measurement under nonpeak conditions showed total bromine levels at <25 ngBr/SCM. The possibility that local contamination contributed to the seasonal development of the 3-month bromine peak was carefully considered and ruled out. Elevated particualte bromine levels, with peak values ranging from 22 to 30 ngBr/SCM, were also found at Ny-Alesund, Spitsbergen (Norway). The apparent seasonal nature of this bromine peak suggests that the large bromine maximum observed at Barrow is not an isolated or unique phenomenon characteristic of that sampling location

  11. Tracking the sources of polybrominated diphenyl ethers in birds: Foraging in waste management facilities results in higher DecaBDE exposure in males

    Energy Technology Data Exchange (ETDEWEB)

    Gentes, Marie-Line, E-mail: gentes.marie_line@courrier.uqam.ca [Centre de recherche en toxicologie de l’environnement (TOXEN), Département des sciences biologiques, Université du Québec à Montréal, P.O. Box 8888, Station Centre-ville, Montreal, QC, Canada H3C 3P8 (Canada); Mazerolle, Marc J., E-mail: Marc.Mazerolle@uqat.ca [Centre for Forest Research, Université du Québec en Abitibi-Témiscamingue, 445 boulevard de l’Université, Rouyn-Noranda, QC, Canada J9X 5E9 (Canada); Giroux, Jean-François, E-mail: giroux.jean-francois@uqam.ca [Groupe de recherche en écologie comportementale et animale, Département des sciences biologiques, Université du Québec à Montréal, P.O. Box 8888, Station Centre-ville, Montreal, QC, Canada H3C 3P8 (Canada); Patenaude-Monette, Martin [Groupe de recherche en écologie comportementale et animale, Département des sciences biologiques, Université du Québec à Montréal, P.O. Box 8888, Station Centre-ville, Montreal, QC, Canada H3C 3P8 (Canada); and others

    2015-04-15

    Differences in feeding ecology are now recognized as major determinants of inter-individual variations in contaminant profiles of free-ranging animals, but exceedingly little attention has been devoted to the role of habitat use. Marked inter-individual variations and high levels of polybrominated diphenyl ethers (PBDEs) (e.g., DecaBDE) have previously been documented in ring-billed gulls (Larus delawarensis) breeding in a colony near Montreal (QC, Canada). However, the environmental sources of these compounds, and thus the reasons causing these large inter-individual variations remain unidentified. In the present study, we used GPS-based telemetry (±5 to 10 m precision) to track ring-billed gulls from this colony to reconstruct their movements at the landscape level. We related habitat use of individual gulls (n=76) to plasma concentrations (ng/g ww) and relative contributions (percentages) to Σ{sub 38}PBDEs of major congeners in the internationally restricted PentaBDE and current-use DecaBDE mixtures. Male gulls that visited waste management facilities (WMFs; i.e., landfills, wastewater treatment plants and related facilities; 25% of all GPS-tracked males) exhibited greater DecaBDE (concentrations and percentages) and lower PentaBDE (percentages) relative to those that did not. In contrast, no such relationships were found in females. Moreover, in males, DecaBDE (concentrations and percentages) increased with percentages of time spent in WMFs (i.e., ~5% of total foraging time), while PentaBDE (percentages) decreased. No relationships between percentages of time spent in other habitats (i.e., urban areas, agriculture fields, and St. Lawrence River) were found in either sex. These findings suggest that animals breeding in the vicinity of WMFs as well as mobile species that only use these sites for short stopovers to forage, could be at risk of enhanced DecaBDE exposure. - Highlights: • The study was conducted on breeding gulls with high levels of flame

  12. Structure and functionality of bromine doped graphite.

    Science.gov (United States)

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

    2013-04-28

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

  13. Temporal Development of Brominated Flame Retardants in Peregrine Falcon (Falco peregrinus) Eggs from South Greenland (1986-2003)

    DEFF Research Database (Denmark)

    Vorkamp, K.; Thomsen, M.; Falk, K.

    2005-01-01

    A time trend between 1986 and 2003 was found for brominated flame retardants in peregrine falcon eggs from South Greenland, with significantly increasing concentrations of the polybrominated diphenyl ethers (PBDEs) 99, 100, 153, 154, and 209. For BDE-99 and -100, the concentration increased appro...

  14. Uranium hexafluoride. Bromine spectrophotometric determination

    International Nuclear Information System (INIS)

    Anon.

    Bromine determination in hydrolized uranium hexafluoride by reduction of bromates by ferrous sulfate, oxidation of bromides by potassium permanganate to give bromine which is extracted into carbon tetrachloride and transformed in eosine for spectrophotometry at 510 nm. The method is suitable for determining 5 to 150 ppm with respect to uranium [fr

  15. Sources, emissions, and fate of polybrominated diphenyl ethers and polychlorinated biphenyls indoors in Toronto, Canada.

    Science.gov (United States)

    Zhang, Xianming; Diamond, Miriam L; Robson, Matthew; Harrad, Stuart

    2011-04-15

    Indoor air concentrations of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) measured in 20 locations in Toronto ranged 0.008-16 ng·m(-3) (median 0.071 ng·m(-3)) and 0.8-130.5 ng·m(-3) (median 8.5 ng·m(-3)), respectively. PBDE and PCB air concentrations in homes tended to be lower than that in offices. Principal component analysis of congener profiles suggested that electrical equipment was the main source of PBDEs in locations with higher concentrations, whereas PUF furniture and carpets were likely sources to locations with lower concentrations. PCB profiles in indoor air were similar to Aroclors 1248, 1232, and 1242 and some exterior building sealant profiles. Individual PBDE and PCB congener concentrations in air were positively correlated with colocated dust concentrations, but total PBDE and total PCB concentrations in these two media were not correlated. Equilibrium partitioning between air and dust was further examined using log-transformed dust/air concentration ratios for which lower brominated PBDEs and all PCBs were correlated with K(OA). This was not the case for higher brominated BDEs for which the measured ratios fell below those based on K(OA) suggesting the air-dust partitioning process could be kinetically limited. Total emissions of PBDEs and PCBs to one intensively studied office were estimated at 87-550 ng·h(-1) and 280-5870 ng·h(-1), respectively, using the Multimedia Indoor Model of Zhang et al. Depending on the air exchange rate, up to 90% of total losses from the office could be to outdoors by means of ventilation. These results support the hypotheses that dominant sources of PBDEs differ according to location and that indoor concentrations and hence emissions contribute to outdoor concentrations due to higher indoor than outdoor concentrations along with estimates of losses via ventilation.

  16. Horizontal and vertical structure of reactive bromine events probed by bromine monoxide MAX-DOAS

    Directory of Open Access Journals (Sweden)

    W. R. Simpson

    2017-08-01

    aerosol extinction was higher (> 0.1 km−1; however, the presence of aerosol particles aloft was not sufficient to produce BrO aloft. Highly depleted ozone (< 1 nmol mol−1 repartitioned reactive bromine away from BrO and drove BrO events aloft in cases. This work demonstrates the interplay between atmospheric mixing and heterogeneous chemistry that affects the vertical structure and horizontal extent of reactive bromine events.

  17. Occurrence of bromine in fluidised bed combustion of solid recovered fuel

    Energy Technology Data Exchange (ETDEWEB)

    Vainikka, P.

    2011-12-15

    estimated by thermodynamic equilibrium modelling. A positive correlation was observed between the halogen (Br, Cl) and the metal (Cu, Pb, and Zn) concentrations in the lower furnace vapours when measured next to the waterwalls. Further, bromine was observed both in the wall deposits and in the corrosion front of the waterwall tubes. This was found to take place even if the bromine content in the SRF was less than 60 mg kg-1 in SRF. Laboratory scale oven tests with commercial boiler steels showed that a bromine containing salt induced a higher corrosion rate than the corresponding chloride. (orig.)

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

    Science.gov (United States)

    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.

  19. Application of non-aqueous solvents to batteries. I Physicochemical properties of propionitrile/water two-phase solvent relevant to zinc-bromine batteries

    Science.gov (United States)

    Singh, P.; White, K.; Parker, A. J.

    1983-11-01

    The properties of bromine/propionitrile solution are investigated with a view to its use as an electrolyte in zinc-bromine batteries which use circulating electrolyte. The solution, which forms a two-phase system with water, has higher conductivity than the oils formed by complexation of bromine with organic salts such as N,N-methoxymethyl methylpiperidinium bromide and N,N-ethyl methylmorpholinium bromide. The activity of bromine in the aqueous phase of the bromine-propionitrile/water, two-phase system is very low; thus, coulombic efficiencies greater than 85 percent are achieved. Zinc-bromine batteries containing this solvent system show good charge/discharge characteristics.

  20. Polybrominated diphenyl ethers in fish and sediment from river polluted by electronic waste

    Energy Technology Data Exchange (ETDEWEB)

    Luo Qian [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong (China); Croucher Institute for Environmental Sciences and Department of Biology, Hong Kong Baptist University, Kowloon Tong, Hong Kong (China); Cai Zongwei [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong (China)]. E-mail: zwcai@hkbu.edu.hk; Wong Minghung [Croucher Institute for Environmental Sciences and Department of Biology, Hong Kong Baptist University, Kowloon Tong, Hong Kong (China)]. E-mail: mhwong@hkbu.edu.hk

    2007-09-20

    The present study investigated contamination of polybrominated diphenyl ethers (PBDEs) in sediment and fish samples collected from rivers in Guiyu, China where electronic waste (e-waste) is recycled and disposed. PBDE congeners with mono-to hepta-brominated and deca-brominated substitutions were detected using {sup 13}C{sub 12} isotope dilution GC/MS/MS and GC/MS methods, respectively. The total PBDE concentrations ranged from 4434 to 16088 ng/g (dry weight) in Nanyang River bank sediment, from 55 to 445 ng/g in Nanyang River bottom sediment and 51.3 to 365 ng/g in Lianjiang River bottom sediment in Guiyu compared with those from 16.1 to 21.4 ng/g in wastewater discharged from a vehicle repairing workshop in Lo Uk Tsuen in Hong Kong. No PBDE congeners were detected in bottom sediment and fish from Mai Po Marshes in Hong Kong. The mean concentrations of total PBDEs in mixed muscles of tilapia (Oreochromis spp) from Lianjiang River were 115 ng/g wet weight (ww) and from wastewater in Hong Kong were 4.1 ng/g ww. Highest mean PBDE concentration was obtained in liver (2687 ng/g ww), followed by abdomen muscle (1088 ng/g ww) of bighead carp (Aristichthys nobilis) collected from Nanyang River. A significant correlation of concentration of each PBDE congener between sediment and muscle from Guiyu was observed. The present results of total PBDEs in sediment and fish were 10 and 1000 times higher than other studies. Open burning and dumping of e-waste are the major causes of PBDE contamination.

  1. [Indoor dust as a pathway of human exposure to polybrominated diphenyl ethers (PBDEs)].

    Science.gov (United States)

    Góralczyk, Katarzyna; Struciński, Paweł; Hernik, Agnieszka; Czaja, Katarzyna; Korcz, Wojciech; Minorczyk, Maria; Ludwicki, Jan K

    2012-01-01

    The brominated diphenyl ethers (PBDEs) belong to a class of synthetic, additive brominated flame retardants (BFRs). PBDEs are used to reduce the flammability of commercial and household products such as textiles, various plastic polymers, furnishing foam, and electronic equipment. People spend a large percentage of their life-time indoors at home, in offices and cars, etc, providing many opportunities for lengthy exposure to PBDEs from residential settings and commercial products in an indoor environment. In recent time, the foodstuffs, mainly food of animal origin, have been indicated as the main pathway of human exposure to PBDEs. However, many studies have shown that the indoor environment, mainly indoor dust, can be also a significant source of exposure to PBDEs, especially for younger children (toddlers) because of their behavioral patterns, eg. putting fingers, toys, and other items in their mouth. Numerous studies show that the median intakes of PBDEs via dust for adult range from 1.41 to 277 ng x day(-1) is lower than that via food which range from 135 to 333 ng x day-', while the median intake of these compounds via indoor dust for children range from 101 to 404 ng x day(-1) is much higher than via food: 77-190 ng x day(-1). The congener pattern observed in the indoor dust is different to that found in food. The indoor dust is dominated by the congener BDE-209 vs. food where the most dominated congeners are BDE-47 and BDE-99. Human exposure to PBDEs and other brominated flame retardants (BFRs) is widely widespread throughout the world and it depends on a country range of usage, production and legislation concerning these chemicals as well as a citizen's behavior. Generally, human exposure has been found higher in North America than in Europe and Asia. Within European countries the significant highest concentrations in dust have been found in the United Kingdom. It should be noted that many uncertainty factors such as personal habits, dietary preferences

  2. Neurotoxicity of brominated flame retardants

    Science.gov (United States)

    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...

  3. Interaction of polybrominated diphenyl ethers (PBDEs) with anaerobic mixed bacterial cultures isolated from river sediment

    Energy Technology Data Exchange (ETDEWEB)

    Yen, J H; Liao, W C; Chen, W C [Department of Agricultural Chemistry, National Taiwan University, 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan (China); Wang, Y.S., E-mail: yswang@ntu.edu.tw [Department of Agricultural Chemistry, National Taiwan University, 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan (China)

    2009-06-15

    The degradation of flame retardant polybrominated diphenyl ethers (PBDE), including tetra-brominated diphenyl ether (BDE-47), penta-brominated diphenyl ether (BDE-99 and -100), and hexa-brominated diphenyl ether (BDE-153 and -154), by anaerobic bacterial mixed cultures isolated from river sediment was investigated. The effects of PBDEs on changes of anaerobic bacterial community in sediment culture were also studied. Sediments were collected from Er-Jen River and Nan-Kan River basins, which were both heavily polluted rivers in Taiwan, and bacteria from the sediment samples were enriched before the experiment was conducted. Into the anaerobic bacterial mixed cultures, 0.1 {mu}g/mL of PBDEs was added followed by incubation under 30 deg. C for 70 days. Residues of PBDE were determined by gas chromatography with electron capture detector (GC-ECD), and the changes of bacterial community were analyzed by denaturing gradient gel electrophoresis (DGGE). Less than 20% of PBDEs were degraded after 70 days of incubation in all samples except for BDE-47 from the Nan-Kan River sediment. In that culture, BDE-47 was found to have notably degraded. In particular, after 42 days of incubation; BDE-47 was degraded, suddenly and sharply, to a negligible level on Day 70, and the result was confirmed by a repeated experiment. An interesting result was that although BDE-47 was degraded fast in the Nan-Kan River sediment, the bacterial communities did not shift significantly as we had speculated at Day 70. From UPGMA dendrograms, PBDEs changed the composition of bacterial communities, and the extents varied with the variety of PBDE congeners. By the amendment with BDE-153 or -154, bacterial communities would be changed immediately and irreversibly throughout the rest of the incubation period. No significant difference in degradation of PBDEs was observed between sediment bacteria from Er-Jen River and Nan-Kan River. However, the results verified the persistence of PBDEs in the environment.

  4. Interaction of polybrominated diphenyl ethers (PBDEs) with anaerobic mixed bacterial cultures isolated from river sediment

    International Nuclear Information System (INIS)

    Yen, J.H.; Liao, W.C.; Chen, W.C.; Wang, Y.S.

    2009-01-01

    The degradation of flame retardant polybrominated diphenyl ethers (PBDE), including tetra-brominated diphenyl ether (BDE-47), penta-brominated diphenyl ether (BDE-99 and -100), and hexa-brominated diphenyl ether (BDE-153 and -154), by anaerobic bacterial mixed cultures isolated from river sediment was investigated. The effects of PBDEs on changes of anaerobic bacterial community in sediment culture were also studied. Sediments were collected from Er-Jen River and Nan-Kan River basins, which were both heavily polluted rivers in Taiwan, and bacteria from the sediment samples were enriched before the experiment was conducted. Into the anaerobic bacterial mixed cultures, 0.1 μg/mL of PBDEs was added followed by incubation under 30 deg. C for 70 days. Residues of PBDE were determined by gas chromatography with electron capture detector (GC-ECD), and the changes of bacterial community were analyzed by denaturing gradient gel electrophoresis (DGGE). Less than 20% of PBDEs were degraded after 70 days of incubation in all samples except for BDE-47 from the Nan-Kan River sediment. In that culture, BDE-47 was found to have notably degraded. In particular, after 42 days of incubation; BDE-47 was degraded, suddenly and sharply, to a negligible level on Day 70, and the result was confirmed by a repeated experiment. An interesting result was that although BDE-47 was degraded fast in the Nan-Kan River sediment, the bacterial communities did not shift significantly as we had speculated at Day 70. From UPGMA dendrograms, PBDEs changed the composition of bacterial communities, and the extents varied with the variety of PBDE congeners. By the amendment with BDE-153 or -154, bacterial communities would be changed immediately and irreversibly throughout the rest of the incubation period. No significant difference in degradation of PBDEs was observed between sediment bacteria from Er-Jen River and Nan-Kan River. However, the results verified the persistence of PBDEs in the environment.

  5. Gridded field observations of polybrominated diphenyl ethers in soils of North China.

    Science.gov (United States)

    Liu, Di; Ma, Jin; Qiu, Xinghua; Zhao, Yifan; Lin, Yan; Yang, Qiaoyun; Gao, Zhenji; Zhu, Tong

    2014-05-01

    Polybrominated diphenyl ethers (PBDEs) were measured in 87 soil samples collected from North China. Eleven PBDE congeners (BDE28, 47, 49, 66, 99, 100, 119, 183, 196, 203, and 209) were identified with a high frequency of detection (84-100 %) in soil samples, and their frequencies were used for statistical analysis in the present study. PBDE concentrations ranged from 0.08 to 8260 ng/g with a mean of 202 ng/g, thus indicating severe pollution at these sample sites. BDE209 was the predominant congener with concentrations of 0.08-8140 ng/g (mean 188). Analysis of the spatial distribution of PBDEs in North China soils indicated that relatively high concentrations of both lower- and higher-brominated BDEs were present in Shandong Province, and a decreasing trend in PBDE concentrations from the east toward the west of North China was observed. Source identification analysis suggested that Jinghai County in Tianjin and the coastal area of Laizhou Bay, Shandong province, were the major sources in North China. The sources in Jinghai County were connected with the dismantling of electronic waste, whereas the sources in the coastal area of Laizhou Bay were connected with the production of PBDEs. Modeling results showed that the distance between the sampling sites and these point sources had a large influence on the transfer of PBDEs.

  6. Polybrominated diphenyl ethers in marine ecosystems of the American continents: foresight from current knowledge.

    Science.gov (United States)

    Shaw, Susan D; Kannan, Kurunthachalam

    2009-01-01

    Polybrominated diphenyl ethers (PBDEs) are a class of synthetic halogenated organic compounds used in commercial and household products, such as textiles, furniture, and electronics, to increase their flame ignition resistance and to meet fire safety standards. The demonstrated persistence, bioaccumulation, and toxic potential of these compounds in animals and in humans are of increasing concern. The oceans are considered global sinks for PBDEs, as higher levels are found in marine organisms than in terrestrial biota. For the past three decades, North America has dominated the world market demand for PBDEs, consuming 95% of the penta-BDE formulation. Accordingly, the PBDE concentrations in marine biota and people from North America are the highest in the world and are increasing. Despite recent restrictions on penta- and octa-BDE commercial formulations, penta-BDE containing products will remain a reservoir for PBDE release for years to come, and the deca-BDE formulation is still in high-volume use. In this paper, we review all available data on the occurrence and trends of PBDEs in the marine ecosystems (air, water, sediments, invertebrates, fish, seabirds, and marine mammals) of North and South America. We outline here our concerns about the potential future impacts of large existing stores of banned PBDEs in consumer products, and the vast and growing reservoirs of deca-BDE as well as new and naturally occurring brominated compounds on marine ecosystems.

  7. Human exposure to brominated flame retardants through dust in different indoor environments: Identifying the sources of concentration differences in hair from men and women.

    Science.gov (United States)

    Li, Junqi; Dong, Zheng; Wang, Ying; Bao, Junsong; Yan, Yijun; Liu, Anming; Jin, Jun

    2018-08-01

    Brominated flame retardants (BFRs) can accumulate in humans and are associated with adverse health effects. The study was conducted to determine the differences in Polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardant (Alt-BFR) concentrations between men and women. We analyzed hair samples from 14 male and 20 female university students, paired dust samples from their dormitories (10 for males and 8 for females), and six dust samples from university teaching buildings. The total PBDE concentrations in hair from females were significantly (three times) higher (p = 0.012) than that from males (means 372 and 109 ng/g, respectively). The mean total PBDE concentrations in classroom and dormitory dust were 36100 and 2012 ng/g, respectively. The PBDE patterns were different in the male and female hair samples, as were the patterns in the classroom and dormitory dust. There are no reports concerning human exposure to BFRs through dust that was assessed considering academic and residential environments simultaneously. The differences between BFR exposure for males and females and the differences between BFR concentrations in hair samples from males and females were consistent for 71.4% of the compounds. However, using only dormitory dust in the calculations gave consistent differences only for 28.6% of the compounds, suggesting that the BFR concentration differences in hair were mainly because females spent much more time than males in classrooms. Copyright © 2018 Elsevier Ltd. All rights reserved.

  8. Single-run determination of polybrominated diphenyl ethers (PBDEs) di- to deca-brominated in fish meal, fish oil and fish feed by isotope dilution: Application of automated sample purification and gas chromatography/ion trap tandem mass spectrometry (GC/ITMS)

    International Nuclear Information System (INIS)

    Blanco, Sonia Lucia; Vieites, Juan M.

    2010-01-01

    The present paper describes the application of automated cleanup and fractionation procedures of the Power Prep system (Fluid Management Systems) for the determination of polybrominated diphenyl ethers (PBDEs) in feeding stuffs and fish meal and oil. Gas chromatography (GC) separation followed by ion trap tandem mass spectrometry detection in EI mode (ITMS) allowed the analysis of di- to deca-BDEs in the samples matrices used in fish aquaculture. The method developed enabled the determination of 26 native PBDE congeners and 11 13 C 12 -labelled congeners, including deca-BDE 209, in a single-run analysis, using isotope dilution. The automated cleanup, consisting of a succession of multilayer silica and basic alumina columns previously applied by Wyrzykowska et al. (2009) in combustion flue gas, was succesfully applied in our complex matrices. The method allowed an increase in productivity, i.e. lower time was required to process samples, and simultaneous purification of several samples was achieved at a time, reducing analyst dedication and human error input. Average recoveries of 43-96% were obtained. GC/ITMS can overcome the complexity originating from the sample matrix, eliminating matrix effects by tandem MS, to enable the detection of congeners penta- to nona-BDEs where interferent masses were present. The provisional detection limits, estimated in the samples, were 5-30 pg for di-, tri-, tetra-, and penta-BDEs, 20-65 pg for hexa-, hepta-, octa- and nona-BDEs, and 105 pg for deca-BDE. Reduction of deca-BDE 209 blank values is of concern to ongoing research. Good accuracy was obtained by application of the whole procedure, representing an efficient, low-cost and fast alternative for routine analyses.

  9. Single-run determination of polybrominated diphenyl ethers (PBDEs) di- to deca-brominated in fish meal, fish oil and fish feed by isotope dilution: application of automated sample purification and gas chromatography/ion trap tandem mass spectrometry (GC/ITMS).

    Science.gov (United States)

    Blanco, Sonia Lucía; Vieites, Juan M

    2010-07-05

    The present paper describes the application of automated cleanup and fractionation procedures of the Power Prep system (Fluid Management Systems) for the determination of polybrominated diphenyl ethers (PBDEs) in feeding stuffs and fish meal and oil. Gas chromatography (GC) separation followed by ion trap tandem mass spectrometry detection in EI mode (ITMS) allowed the analysis of di- to deca-BDEs in the samples matrices used in fish aquaculture. The method developed enabled the determination of 26 native PBDE congeners and 11 (13)C(12)-labelled congeners, including deca-BDE 209, in a single-run analysis, using isotope dilution. The automated cleanup, consisting of a succession of multilayer silica and basic alumina columns previously applied by Wyrzykowska et al. (2009) [28] in combustion flue gas, was successfully applied in our complex matrices. The method allowed an increase in productivity, i.e. lower time was required to process samples, and simultaneous purification of several samples was achieved at a time, reducing analyst dedication and human error input. Average recoveries of 43-96% were obtained. GC/ITMS can overcome the complexity originating from the sample matrix, eliminating matrix effects by tandem MS, to enable the detection of congeners penta- to nona-BDEs where interferent masses were present. The provisional detection limits, estimated in the samples, were 5-30 pg for di-, tri-, tetra-, and penta-BDEs, 20-65 pg for hexa-, hepta-, octa- and nona-BDEs, and 105 pg for deca-BDE. Reduction of deca-BDE 209 blank values is of concern to ongoing research. Good accuracy was obtained by application of the whole procedure, representing an efficient, low-cost and fast alternative for routine analyses. Copyright 2010 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

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

    2009-10-01

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

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

    Science.gov (United States)

    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

  12. Electronic properties of bromine-doped carbon nanotubes

    CERN Document Server

    Jhi, S H; Cohen, M L

    2002-01-01

    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.

  13. Unintentional production of persistent chlorinated and brominated organic pollutants during iron ore sintering processes.

    Science.gov (United States)

    Li, Sumei; Liu, Guorui; Zheng, Minghui; Liu, Wenbin; Li, Jinhui; Wang, Mei; Li, Changliang; Chen, Yuan

    2017-06-05

    Iron ore sintering (SNT) processes are major sources of unintentionally produced chlorinated persistent organic pollutants (POPs), including polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs). However, few studies of emissions of brominated POPs, such as polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) and polybrominated diphenyl ethers (PBDEs), during SNT have been performed. Stack gas and fly ash samples from six typical SNT plants in China were collected and analyzed to determine the concentrations and profiles of PCDD/Fs, PCBs, PCNs, PBDD/Fs, and PBDEs, as well as any correlations among these compounds. The PCDD/F, PCB, PCN, PBDD/F, and PBDE emission factors were 2.47, 0.61, 552, 0.32, and 107μgt -1 , respectively (109, 4.07, 10.4, 4.41 and 0.02ng toxic equivalents t -1 , respectively). PCBs were the most abundant compounds by mass, while PCNs were the next most abundant, contributing 51% and 42% to the total POP concentration, respectively. However, PCDD/Fs were the dominant contributors to the chlorinated and brominated POP toxic equivalent concentrations, contributing 89% to the total toxic equivalent concentration. The PCDD/F and other chlorinated and brominated POP concentrations were positively correlated, indicating that chlorinated and brominated POP emissions could be synergistically decreased using the best available technologies/best environmental practices already developed for PCDD/Fs. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Microbial degradation of 4-monobrominated diphenyl ether with anaerobic sludge

    International Nuclear Information System (INIS)

    Shih, Yang-hsin; Chou, Hsi-Ling; Peng, Yu-Huei

    2012-01-01

    Highlights: ► BDE-3 was degraded with two anaerobes in different rates. ► Glucose addition augment the debromination efficiencies. ► Hydrogen gas was detected and relative microbes were identified. ► Extra-carbon source enhanced degradation partial due to H 2 -generation bacteria. - Abstract: Polybrominated diphenyl ethers (PBDEs) are widely used flame retardant additives for many plastic and electronic products. Owing to their ubiquitous distribution in the environment, multiple toxicity to humans, and increasing accumulation in the environment, the fate of PBDEs is of serious concern for public safety. In this study, the degradation of 4-monobrominated diphenyl ether (BDE-3) in anaerobic sludge and the effect of carbon source addition were investigated. BDE-3 can be degraded by two different anaerobic sludge samples. The by-products, diphenyl ether (DE) and bromide ions, were monitored, indicating the reaction of debromination within these anaerobic samples. Co-metabolism with glucose facilitated BDE-3 biodegradation in terms of kinetics and efficiency in the Jhongsing sludge. Through the pattern of amplified 16S rRNA gene fragments in denatured gradient gel electrophoresis (DGGE), the composition of the microbial community was analyzed. Most of the predominant microbes were novel species. The fragments enriched in BDE-3-degrading anaerobic sludge samples are presumably Clostridium sp. This enrichment coincides with the H 2 gas generation and the facilitation of debromination during the degradation process. Findings of this study provide better understanding of the biodegradation of brominated DEs and can facilitate the prediction of the fate of PBDEs in the environment.

  15. Measurement and modeling of diel variability of polybrominated diphenyl ethers and chlordanes in air.

    Science.gov (United States)

    Moeckel, Claudia; Macleod, Matthew; Hungerbühler, Konrad; Jones, Kevin C

    2008-05-01

    Short-term variability of concentrations of polybrominated diphenyl ethers (PBDEs) and chlordanes in air at a semirural site in England over a 5 day period is reported. Four-hour air samples were collected during a period dominated by a high pressure system that produced stable diel (24-h) patterns of meteorological conditions such as temperature and atmospheric boundary layer height. PBDE and chlordane concentrations showed clear diel variability with concentrations in the afternoon and evening being 1.9 - 2.7 times higher than in the early morning. The measurements are interpreted using a multimedia mass balance model parametrized with forcing functions representing local temperature, atmospheric boundary layer height, wind speed and hydroxyl radical concentrations. Model results indicate that reversible, temperature-controlled air-surface exchange is the primary driver of the diel concentration pattern observed for chlordanes and PBDE 28. For higher brominated PBDE congeners (47, 99 and 100), the effect of variable atmospheric mixing height in combination with irreversible deposition on aerosol particles is dominant and explains the diel patterns almost entirely. Higher concentrations of chlordanes and PBDEs in air observed at the end of the study period could be related to likely source areas using back trajectory analysis. This is the first study to clearly document diel variability in concentrations of PBDEs in air over a period of several days. Our model analysis indicates that high daytime and low nighttime concentrations of semivolatile organic chemicals can arise from different underlying driving processes, and are not necessarily evidence of reversible air-surface exchange on a 24-h time scale.

  16. Refractory concentrate gold leaching: Cyanide vs. bromine

    Science.gov (United States)

    Dadgar, Ahmad

    1989-12-01

    Gold extraction, recovery and economics for two refractory concentrates were investigated using cyanide and bromine reagents. Gold extractions for cyanide leaching (24-48 hours) and bromine leaching (six hours) were the same and ranged from 94 to 96%. Gold recoveries from bromine pregnant solutions using carbon adsorption, ion exchange, solvent extraction, and zinc and aluminum precipitation methods were better than 99.9%. A preliminary economic analysis indicates that chemical costs for cyanidation and bromine process are 11.70 and 11.60 respectively, per tonne of calcine processed.

  17. Bromine pretreated chitosan for adsorption of lead

    Indian Academy of Sciences (India)

    Pollution by heavy metals like lead (II) is responsible for health hazards and environmental degradation. Adsorption is a prevalent method applied for removal of heavy metal pollutants from water. This study explored adsorption performances of 30% bromine pretreated chitosan for lead (II) abatement from water. Bromine ...

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

    Energy Technology Data Exchange (ETDEWEB)

    Aldrian, Alexia, E-mail: alexia.aldrian@unileoben.ac.at [Chair of Waste Processing Technology and Waste Management, Montanuniversitaet Leoben, Franz-Josef-Straße 18, 8700 Leoben (Austria); Ledersteger, Alfred, E-mail: a.ledersteger@saubermacher.at [Saubermacher Dienstleistungs AG, Hans-Roth-Straße 1, 8073 Feldkirchen bei Graz (Austria); Pomberger, Roland, E-mail: roland.pomberger@unileoben.ac.at [Chair of Waste Processing Technology and Waste Management, Montanuniversitaet Leoben, Franz-Josef-Straße 18, 8700 Leoben (Austria)

    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.

  19. Occurrence, characteristics and leakage of polybrominated diphenyl ethers in leachate from municipal solid waste landfills in China

    International Nuclear Information System (INIS)

    Li, Ying; Li, Jinhui; Deng, Chao

    2014-01-01

    Raw leachate samples were collected from various municipal solid waste (MSW) landfills in a densely populated city in North China to measure the levels and compositional patterns of polybrominated diphenyl ethers (PBDEs) in leachate. The total concentration of PBDEs ranged from 4.0 to 351.2 ng/L, with an average of 73.0 ng/L. BDE-209 dominated the congeners in most of the samples, followed by BDE-47 and -99. Higher PBDEs concentrations were found in leachate from younger landfill facilities in the urban area. Pearson correlation analysis implied a potential dependence of the PBDEs level on landfill age, suspended solids and dissolved organic carbon, while the results of principal component analysis (PCA) suggested potential origins and transportation of PBDEs in leachate. The Monte Carlo method was adopted to estimate the annual leakage of PBDEs into the underground environment nationwide, based on two main scenarios: simple landfills with inadequate liner systems and composite-lined landfills with defective geomembranes. -- Highlights: • Levels and congener patterns of PBDEs in landfill leachate from China are measured. • Pollution loading of PBDEs in leachate is identified through comparative analysis. • Leachate properties perform moderate impact on the occurrence of PBDEs. • Both commercial and decomposition origins contribute to lower brominated congeners. • Leakage rate of PBDEs due to inadequate liner is estimated nationwide. -- This paper determined the levels and distribution of PBDEs in MSW landfill leachate and predicted the leakage of PBDEs from sanitary landfills into the underground environment across China

  20. Biodegradation of tert-butylphenyl diphenyl phosphate

    International Nuclear Information System (INIS)

    Heitkamp, M.A.; Freeman, J.P.; Cerniglia, C.E.

    1986-01-01

    The biodegradation of tert-butylphenyl diphenyl phosphate (BPDP) was examined in microcosms containing sediment and water from five different ecosystems as part of studies to elucidate the environmental fate of phosphate ester flame retardants. Biodegradation of [ 14 C]BPDP was monitored in the environmental microcosms by measuring the evolution of 14 CO 2 . Over 37% of BPDP was mineralized after 8 weeks in microcosms from an ecosystem which had chronic exposure to agricultural chemicals. In contrast, only 1.7% of BPDP was degraded to 14 CO 2 in samples collected from a noncontaminated site. The exposure concentration of BPDP affected the percentage which was degraded to 14 CO 2 in microcosms from the two most active ecosystems. Mineralization was highest at a concentration of 0.1 mg of BPDP and was inhibited with 10- and 100-fold higher concentrations of BPDP. The authors observed adaptive increases in both microbial populations and phosphoesterase enzymes in some sediments acclimated to BPDP. Chemical analyses of the residues in the microcosms indicated undegraded BPDP and minor amounts of phenol, tert-butylphenol, diphenyl phosphate, and triphenyl phosphate as biodegradation products. These data suggest that the microbial degradation of BPDP results from at least three catabolic processes and is highest when low concentrations of BPDP are exposed to sediment microorganisms of eutrophic ecosystems which have high phosphotri- and diesterase activities and previous exposure to anthropogenic chemicals

  1. Bioaccumulation of polybrominated diphenyl ethers and decabromodiphenyl ethane in fish from a river system in a highly industrialized area, South China

    International Nuclear Information System (INIS)

    He, Ming-Jing; Luo, Xiao-Jun; Chen, Man-Ying; Sun, Yu-Xin; Chen, She-Jun; Mai, Bi-Xian

    2012-01-01

    Polybrominated diphenyl ethers (PBDEs) and decabromodiphenyl ethane (DBDPE) were determined in water, sediment, and three fish species from the Dongjiang River, a highly polluted river by brominated flame retardants in South China due to the intensive industry activities. The stable isotope analysis was used to compare differences between the feeding ecology of the fish species. The bioaccumulations of PBDEs and DBDPE were evaluated by calculation of bioaccumulation factors (BAFs) and biota-sediment accumulation factors (BSAFs). Two potential debromination products of DBDPE were detected in sediment. The occurrence of these two compounds probably ascribed to the thermal degradation during instrumental analysis but degradation in the environment cannot be ruled out. Three fish species showed two quite different PBDE congener profiles. Two carp species were dominated by BDE47 while plecostomus were dominated by both BDE47 and BDE99. The contributions of higher brominated congeners were higher in plecostomus than in two carp species. This different PBDE congener profile can be attributed to the difference in metabolism and feeding habits among fish species. The calculated BAFs for PBDE congeners follow a bioaccumulation model. The BSAFs for all PBDE congeners except for BDE47 and BDE100 were less than unit, implying that bioavailability of PBDEs in sediments is low. Contrary to expectation, the BAFs value of DBDPE was one order of magnitude higher than that of BDE209 in fish, which can partly attributed to the absence of debromination of DBDPE in fish. The calculated BAFs for DBDPE indicated that this compound can significantly accumulate in fish. - Highlights: ►Deca-BDE had gradually substituted by DBDPE in study area. ►Two debrominated products of DBDPE were the result of thermal degradation in instrumental analysis. ►Metabolism and diet were causes for the different PBDE congener profile among fish species. ►Significant bioaccumulation of DBDPE was

  2. Dynamic dielectric properties and the γ transition of bromine doped polyacrylonitrile

    Directory of Open Access Journals (Sweden)

    2007-10-01

    Full Text Available Based on monitoring the γ process (the lowest temperature-relaxation in polyacrylonitrile (PAN by dynamic dielectric spectroscopy, new evidence for the formation of a charge transfer complex between bromine dopants and nitrile groups is presented. The experimental work is carried out on PAN and nitrile polymerized PAN with and without bromine doping and the effects of these factors on the γ process are measured. Nitrile polymerization results in diminishing of the γ process and in a 15% increase in its activation energy, whereas bromine doping produces splitting of the original γ process in PAN – coupled with a significant activation energy increase – and its complete disappearance in nitrile polymerized PAN. Both the splitting of the γ process and the higher activation energy reflect bromine-nitrile adduct formation..

  3. Distribution and accumulation of polybrominated diphenyl ethers (PBDEs) in Hong Kong mangrove sediments.

    Science.gov (United States)

    Zhu, Haowen; Wang, Ying; Wang, Xiaowei; Luan, Tiangang; Tam, Nora F Y

    2014-01-15

    Polybrominated diphenyl ethers (PBDEs) have been used extensively as brominated flame retardants in various polymers, and have become serious environmental contaminants, particularly in coastal sediments. Mangrove wetlands are important coastal ecosystems in tropical and subtropical regions, and mangrove sediments are often the pollutant sinks due to their close proximity with human activities. In Hong Kong, sediment samples collected from five mangrove swamps were found to be contaminated with PBDEs and the eight measured BDE congeners, including BDE-28, -47, -99, -100, -153, -154, -183 and -209 were detected in all mangrove sediments, indicating that these pollutants were widespread in Hong Kong mangrove wetlands. Among the five swamps, relatively high concentrations of PBDEs were recorded in Mai Po mangrove swamp in the northwestern Hong Kong, which is part of the RAMSAR site but is severely influenced by the pollution from the Pearl River Delta. The depth profile of PBDEs in sediment cores collected from Mai Po also showed the inputs of PBDEs in this mangrove swamp increased year by year. In all sediments, the concentrations of BDE-209 were 1-2 orders of magnitude higher than the other congeners in the same sediment. The concentrations of BDE-209 and ∑PBDEs (defined as the sum of seven targeted BDE congeners except BDE-209) ranged from 1.53 to 75.9 ng g(-1) and from 0.57 to 14.4 ng g(-1), respectively. Among the targeted BDE congeners except BDE-209, slightly different composition was recorded among samples collected from different locations, with BDE-153 and -183 being the pre-dominated congeners. In all mangrove swamps, except Tai O in the southwest of Hong Kong, ∑PBDEs concentrations showed a common trend of landward>seaward>mudflat. The concentrations of ∑PBDEs were significantly correlated with total organic matter (TOM) content in sediments but not with the sediment particle sizes in each mangrove swamp. © 2013.

  4. The third international interlaboratory study on brominated flame retardants

    Energy Technology Data Exchange (ETDEWEB)

    Boer, J. de [Netherlands Institute for Fisheries Research, IJmuiden (Netherlands); Wells, D. [FRS Marine Laboratory, Aberdeen (United Kingdom)

    2004-09-15

    Polybrominated diphenyl ethers (PBDEs) have been produced as brominated flame retardants (BFRs) since the early 1970s and have been found in the aquatic environment since the late 1970s. However, as a result of their detection in sperm whales from deeper Atlantic waters and in human milk, many laboratories are now measuring PBDEs in environmental samples. A first international interlaboratory study (ILS) on the analysis of PBDEs, organised by the Bromine Science and Environmental Forum (BSEF), Brussels, Belgium, in collaboration with the Netherlands Institute for Fisheries Research (RIVO) was conducted in 1999-2000. The results showed that the 18 participating laboratories produced comparable results for BDE 47 in various matrices but had analytical difficulties for other BDEs, in particular for the BDEs 99 and 209. A second study was organised in 2001-2002 by BSEF, QUASIMEME and RIVO. That study showed improvement in comparability of the participating laboratories for BDE99 and some other BDEs. However, there was no improvement for BDE209. Hexabromocyclododecane (HBCD), tetrabromobisphenol-A (TBBP-A) and the dimethyl derivative of TBBP-A (dimethyl TBBP-A) were included in the second study. However, it appeared that only two or three laboratories were able to analyse these determinands. Others laboratories were still in the development phase with their methods for these BFRs. This third study was organised as a development exercise by QUASIMEME, in collaboration with RIVO between September and December 2003. The BFRs selected were the same as in the second study. Two biota test materials, a harbor sediment, a sewage sludge, and two standard solutions were dispatched to the participants.

  5. Photolytic debromination pathway of polybrominated diphenyl ethers in hexane by sunlight

    International Nuclear Information System (INIS)

    Wei, Hua; Zou, Yonghong; Li, An; Christensen, Erik R.; Rockne, Karl J.

    2013-01-01

    The objective of this work is to identify the photolytic debromination pathways of polybrominated diphenyl ethers (PBDEs). Thirteen PBDEs (BDEs 209, 208, 207, 206, 196, 183, 154, 153, 100, 99, 85, 47 and 28) in hexane were individually exposed to sunlight for up to 64 h. A total of 180 PBDEs were screened and 74 BDE debromination products were detected. The disappearance rate constant increased exponentially with increasing number of bromines. While no evident difference in debromination preference among ortho, meta and para bromines was found for heavier congeners, the vulnerability rank order was meta ≥ ortho > para for the lighter congeners (≤8 Br). The total molar mass of PBDEs continuously decreased during sunlight exposure, indicating PBDEs were transformed to non-PBDE compounds. A stochastic least squares debromination pathway model was developed to simulate the reactions and determine the yields to extend the results beyond the experimental observations. -- Highlights: ► 74 PBDEs are identified as the products of debromination via photolysis. ► Debromination is more likely at meta than para positions for PBDEs with ≤8 bromines. ► The stochastic least squares model results agree with and expand the experimental observations. ► Mass imbalance indicates a significant loss of PBDE mass during sunlight exposure. -- The PBDE debromination products and pathways identified in this work will assist in future studies on their environmental fate

  6. Improved debromination of polybrominated diphenyl ethers by bimetallic iron–silver nanoparticles coupled with microwave energy

    International Nuclear Information System (INIS)

    Luo, Si; Yang, Shaogui; Sun, Cheng; Gu, Ji-Dong

    2012-01-01

    This study focused on the enhanced debromination of decabromodiphenyl ether (BDE-209) and 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) by Fe–Ag nano-particles under microwave radiation (Fe–Ag/MW). Fe–Ag bimetallic nano-particles were synthesized by reductive deposition of Ag on nano-iron and characterized with a number of techniques, including BET, XRD, TEM and XPS. Approximately 97% of BDE-209 or 78% of BDE-47 were rapidly transformed to its degradation products within 8 min in the Fe–Ag/MW system. The dehalogenation efficiency of polybrominated diphenyl ethers (PBDEs) was enhanced apparently by microwave radiation. Moreover, the microwave thermal energy played a significant role in accelerating the degradation reactions. Compared with nano-iron alone, the deposition of Ag also increased the rates of degradation. GC–MS and LC–MS/MS analyses of PBDEs' degradation products reveals that the possible degradation pathway proceeds through stepwise debromination from [n]-bromo- to [n-1]-bromo-DE, with bromine being substituted by hydrogen sequentially. Di- to nona-brominated congeners were formed during BDE-209 reduction, while diphenyl ether to tri-BDEs were observed during BDE-47 degradation. These results suggest that PBDEs can be debrominated rapidly by the innovative processes that may be environmentally friendly in applications. - Highlights: ► The Fe–Ag nanoparticles with a core–shell structure were successfully prepared. ► A highly efficient technology for debromination of PBDEs by Fe–Ag/MW was investigated. ► The effect of bromine's number on the stability against reduction of PBDEs was explored. ► The role of MW energy and Ag in the reactivity of the Fe–Ag/MW system was demonstrated. ► The possible degradation pathways of BDE-209 and BDE-47 were proposed.

  7. Improved debromination of polybrominated diphenyl ethers by bimetallic iron-silver nanoparticles coupled with microwave energy

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Si [College of Resources and Environment, Hunan Agricultural University, Changsha 410128 (China); State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China); Yang, Shaogui, E-mail: yangdlut@126.com [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China); Sun, Cheng, E-mail: envidean@nju.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China); Gu, Ji-Dong [College of Resources and Environment, Hunan Agricultural University, Changsha 410128 (China); Laboratory of Environmental Microbiology and Toxicology, School of Biological Sciences, The University of Hong Kong, Pokfulam Road, Hong Kong (China)

    2012-07-01

    This study focused on the enhanced debromination of decabromodiphenyl ether (BDE-209) and 2,2 Prime ,4,4 Prime -tetrabromodiphenyl ether (BDE-47) by Fe-Ag nano-particles under microwave radiation (Fe-Ag/MW). Fe-Ag bimetallic nano-particles were synthesized by reductive deposition of Ag on nano-iron and characterized with a number of techniques, including BET, XRD, TEM and XPS. Approximately 97% of BDE-209 or 78% of BDE-47 were rapidly transformed to its degradation products within 8 min in the Fe-Ag/MW system. The dehalogenation efficiency of polybrominated diphenyl ethers (PBDEs) was enhanced apparently by microwave radiation. Moreover, the microwave thermal energy played a significant role in accelerating the degradation reactions. Compared with nano-iron alone, the deposition of Ag also increased the rates of degradation. GC-MS and LC-MS/MS analyses of PBDEs' degradation products reveals that the possible degradation pathway proceeds through stepwise debromination from [n]-bromo- to [n-1]-bromo-DE, with bromine being substituted by hydrogen sequentially. Di- to nona-brominated congeners were formed during BDE-209 reduction, while diphenyl ether to tri-BDEs were observed during BDE-47 degradation. These results suggest that PBDEs can be debrominated rapidly by the innovative processes that may be environmentally friendly in applications. - Highlights: Black-Right-Pointing-Pointer The Fe-Ag nanoparticles with a core-shell structure were successfully prepared. Black-Right-Pointing-Pointer A highly efficient technology for debromination of PBDEs by Fe-Ag/MW was investigated. Black-Right-Pointing-Pointer The effect of bromine's number on the stability against reduction of PBDEs was explored. Black-Right-Pointing-Pointer The role of MW energy and Ag in the reactivity of the Fe-Ag/MW system was demonstrated. Black-Right-Pointing-Pointer The possible degradation pathways of BDE-209 and BDE-47 were proposed.

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

    Science.gov (United States)

    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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Combining Eosin Y with Selectfluor: A Regioselective Brominating System for Para-Bromination of Aniline Derivatives.

    Science.gov (United States)

    Huang, Binbin; Zhao, Yating; Yang, Chao; Gao, Yuan; Xia, Wujiong

    2017-07-21

    A mild, metal-free, and absolutely para-selective bromination of aniline derivatives has been developed in excellent yields, wherein the organic dye Eosin Y is employed as the bromine source in company with Selectfluor. Neither air nor moisture sensitive, this facile reaction proceeds smoothly at room temperature and completes within a short time. Mechanistic studies indicate a radical pathway; therefore, the existence of an in situ generated brominating reagent, "Selectbrom", is postulated, which may reasonably account for the unique regioselectivity for the para-bromination of N-acyl- as well as N-sulfonylanilines.

  10. short communication polyvinylpyrrolidone-bromine complex

    African Journals Online (AJOL)

    Preferred Customer

    Benzylic bromides were conveniently obtained in high yields via the reaction of the corresponding alcohols with crosslinked polyvinylpyrrolidone-bromine ... The traditional methods include highly toxic reagent such as HBr gas [3], BBr3 [4, ...

  11. Systematic vibration thermodynamic properties of bromine

    Science.gov (United States)

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

    2015-11-01

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

  12. Bromine accumulation in acidic black colluvial soils

    Science.gov (United States)

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

    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 (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.

  13. Polybrominated diphenyl ethers in birds of prey from Northern China.

    Science.gov (United States)

    Chen, Da; Mai, Bixian; Song, Jie; Sun, Quanhui; Luo, Yong; Luo, Xiaojun; Zeng, Eddy Y; Hale, Robert C

    2007-03-15

    Birds of prey from Northern China (Beijing area) were examined for polybrominated diphenyl ethers (PBDEs). A total of 47 specimens from eight different species were analyzed. Muscle and liver were analyzed separately for each bird. Kidneys were pooled by species. Common kestrels exhibited the highest PBDE levels (mean muscle and liver concentrations of 12300 and 12200 ng/g lipid weight, respectively), with maxima in an individual bird of 31700 in muscle and 40900 ng/g lw in liver. Congener profiles differed between some species, but were generally dominated by the more brominated congeners (e.g., BDE-153, -209, -183, -207). BDE-209 was especially elevated compared to other published reports. Interspecies differences in congener concentrations and profiles may be due to diet, behavior, or biotransformation capacities. BDE-209 was detected in 79.4% of the samples. Common kestrels contained the highest BDE-209 levels (mean/maxima of 2150/6220 in muscle and 2870/12200 ng/g lw in liver). BDE-209 was the dominant congener in tissues from some buzzards, scops owls, and long-eared owls. It was the second most abundant congener in common kestrels. The remarkable levels and dominance of BDE-209 may relate to significant production, usage, or disposal of deca-containing products in China. These observations reinforce the growing view that organisms using terrestrial food chains may have greater exposure to BDE-209.

  14. Maternal-infant transfer of polybrominated diphenyl ethers

    Energy Technology Data Exchange (ETDEWEB)

    Hirai, T.; Fujimine, Y.; Watanabe, S. [Otsuka Pharmaceutical Co., Ltd., Tokushima (Japan); Nakamura, Y. [SRL Nishinihon, Fukuoka (Japan); Shimomura, H. [Shimomura OBGY Clinic, Fukuoka (Japan); Nagayama, J. [Kyushu Univ., Fukuoka (Japan)

    2004-09-15

    Polybrominated diphenyl ethers (PBDEs) are widely used brominated flame retardants (BFRs) in plastics of automobiles, textile industry, television, personal computer, electronic appliances etc. The amount of production world-wide has reached 40,000 tons in 1992. In 1992 world-wide production of PBDEs reached 40,000 tons raising serious concern over the dangers of environmental pollution by BFRs. The toxicity of PBDEs was reported to be an antagonist of thyroid-hormone (T4) and inhibition to aryl hydrocarbon (Ah) receptor. Since PBDEs are structurally similar to PCBs and therefore they work as an antagonist. Polychlorinated biphenyl (PCBs) demonstrate biological stability and high lipophilicity. As a result, PCBs used in the past and released into the environment, have been transmitted through the food chain and accumlated in the human body over time. In Japan, approximately 58,000 tons of PCBs were produced with the grade name of Kanechlor in between 1954 and 1971. In this study, all PCB congeners and 25 PBDE congeners (17, 25, 28, 30, 32, 33, 35, 37, 47, 49, 66, 71, 75, 77, 85, 99, 100, 116, 119, 126, 138, 153, 154, 155, 166) were analyzed by the method that combines high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). The purpose of this study was to investigate whether congener-specific PCBs and PBDEs were transferred from pregnant women to their infants.

  15. Brominated flame retardants in Canadian chicken egg yolks.

    Science.gov (United States)

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

    2011-06-01

    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.

  16. Quantification of Hydroxylated Polybrominated Diphenyl Ethers (OH-BDEs), Triclosan, and Related Compounds in Freshwater and Coastal Systems.

    Science.gov (United States)

    Kerrigan, Jill F; Engstrom, Daniel R; Yee, Donald; Sueper, Charles; Erickson, Paul R; Grandbois, Matthew; McNeill, Kristopher; Arnold, William A

    2015-01-01

    Hydroxylated polybrominated diphenyl ethers (OH-BDEs) are a new class of contaminants of emerging concern, but the relative roles of natural and anthropogenic sources remain uncertain. Polybrominated diphenyl ethers (PBDEs) are used as brominated flame retardants, and they are a potential source of OH-BDEs via oxidative transformations. OH-BDEs are also natural products in marine systems. In this study, OH-BDEs were measured in water and sediment of freshwater and coastal systems along with the anthropogenic wastewater-marker compound triclosan and its photoproduct dioxin, 2,8-dichlorodibenzo-p-dioxin. The 6-OH-BDE 47 congener and its brominated dioxin (1,3,7-tribromodibenzo-p-dioxin) photoproduct were the only OH-BDE and brominated dioxin detected in surface sediments from San Francisco Bay, the anthropogenically impacted coastal site, where levels increased along a north-south gradient. Triclosan, 6-OH-BDE 47, 6-OH-BDE 90, 6-OH-BDE 99, and (only once) 6'-OH-BDE 100 were detected in two sediment cores from San Francisco Bay. The occurrence of 6-OH-BDE 47 and 1,3,7-tribromodibenzo-p-dioxin sediments in Point Reyes National Seashore, a marine system with limited anthropogenic impact, was generally lower than in San Francisco Bay surface sediments. OH-BDEs were not detected in freshwater lakes. The spatial and temporal trends of triclosan, 2,8-dichlorodibenzo-p-dioxin, OH-BDEs, and brominated dioxins observed in this study suggest that the dominant source of OH-BDEs in these systems is likely natural production, but their occurrence may be enhanced in San Francisco Bay by anthropogenic activities.

  17. Quantification of Hydroxylated Polybrominated Diphenyl Ethers (OH-BDEs, Triclosan, and Related Compounds in Freshwater and Coastal Systems.

    Directory of Open Access Journals (Sweden)

    Jill F Kerrigan

    Full Text Available Hydroxylated polybrominated diphenyl ethers (OH-BDEs are a new class of contaminants of emerging concern, but the relative roles of natural and anthropogenic sources remain uncertain. Polybrominated diphenyl ethers (PBDEs are used as brominated flame retardants, and they are a potential source of OH-BDEs via oxidative transformations. OH-BDEs are also natural products in marine systems. In this study, OH-BDEs were measured in water and sediment of freshwater and coastal systems along with the anthropogenic wastewater-marker compound triclosan and its photoproduct dioxin, 2,8-dichlorodibenzo-p-dioxin. The 6-OH-BDE 47 congener and its brominated dioxin (1,3,7-tribromodibenzo-p-dioxin photoproduct were the only OH-BDE and brominated dioxin detected in surface sediments from San Francisco Bay, the anthropogenically impacted coastal site, where levels increased along a north-south gradient. Triclosan, 6-OH-BDE 47, 6-OH-BDE 90, 6-OH-BDE 99, and (only once 6'-OH-BDE 100 were detected in two sediment cores from San Francisco Bay. The occurrence of 6-OH-BDE 47 and 1,3,7-tribromodibenzo-p-dioxin sediments in Point Reyes National Seashore, a marine system with limited anthropogenic impact, was generally lower than in San Francisco Bay surface sediments. OH-BDEs were not detected in freshwater lakes. The spatial and temporal trends of triclosan, 2,8-dichlorodibenzo-p-dioxin, OH-BDEs, and brominated dioxins observed in this study suggest that the dominant source of OH-BDEs in these systems is likely natural production, but their occurrence may be enhanced in San Francisco Bay by anthropogenic activities.

  18. Preparation and characterization of aliphatic diphenyl esters intended as precursors for polyesters

    DEFF Research Database (Denmark)

    Hvilsted, S.; Andruzzi, F.; Cerrai, P.

    1991-01-01

    An extensive number of aliphatic diphenyl esters, C6H5OOC(CH2)nCOOC6H5 (n = O,...,8,10,11,12,14), have been prepared in pure form. The crystalline melting points these esters exhibit an odd-even temperature behaviour, with the higher-melting even series (n even) displaying a minimum for n = 8 while...... based on similar data from phenyl esters, interpreted as the results of an apparent macrocyclic conformation of the larger diphenyl esters. High-performance size exclusion chromatography (s.e.c.) of diphenyl esters, phenyl esters, aromatic and linear hydrocarbons in tetrahydrofuran, toluene...

  19. Terminal elimination half-lives of the brominated flame retardants TBBPA, HBCD, and lower brominated PBDEs in humans

    Energy Technology Data Exchange (ETDEWEB)

    Geyer, H.J.; Schramm, K.W.; Feicht, E.A.; Fried, K.W.; Henkelmann, B.; Lenoir, D. [GSF-National Research Center, Institute of Ecological Chemistry, Neuherberg (Germany); Darnerud, P.O.; Aune, M. [Swedish National Food Administration, Uppsala (Sweden); Schmid, P. [Swiss Federal Laboratories for Materials Testing and Research, Laboratory of Organic Chemistry, EMPA Duebendorf (Switzerland); McDonald, T.A. [Office of Environmental Health Assessment, California EPA, Oakland, CA (United States)

    2004-09-15

    Brominated flame retardants (BFRs) are widely used in polymers and textiles and applied in electronic equipment, construction materials, and furniture for the purpose of fire prevention. BFRs with the highest production volume are tetrabromobisphenol A (TBBPA), 1,2,5,6,9,10- hexabromocyclododecanes (HBCDs: {alpha}-HBCD + {beta}-HBCD + {gamma}-HBCD), and polybrominated diphenyl ethers (PBDEs). Several BFRs are highly lipophilic persistent organic pollutants (POPs) which have been identified in the aquatic and terrestrial environment including wildlife and humans. In exposed organisms including humans toxic effects, bioaccumulation, metabolism, and pharmacokinetics (especially half-life t{sub 1/2}) are important criterions in the hazard assessment. The aim of the present study was to estimate the terminal elimination half-lives (t{sub 1/2H}) of the main BFRs from the whole body (also named body-burden half-life) and/or from the adipose tissue (fat) of adult humans. The t{sub 1/2H} data for the following BFRs were evaluated: TBBPA, HBCD, 2,2',4,4'- tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentaBDE (BDE-99), 2,2',4,4',6-pentaBDE (BDE- 100), 2,2',4,4',5,5'-hexaBDE (BDE-153), and 2,2',4,4',5,6-hexaBDE (BDE-154).

  20. Concentrations of legacy and novel brominated flame retardants in indoor dust in Melbourne, Australia: An assessment of human exposure.

    Science.gov (United States)

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

    2018-04-01

    Polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NBFR) have been used in a range of polymers to inhibit the spread of fires but also have a propensity to migrate out of consumer materials and contaminate indoor dust. In this study, a total of 57 dust samples were collected from 12 homes, eight offices and eight vehicles in Melbourne, Australia and analysed for eight PBDEs (-28, -47, -99, -100, -153, -154, -183 and -209) and seven NBFRs (PBT, PBEB, HBB, EH-TBB, BEH-TEBP, BTBPE and DBDPE) to determine human exposure risks from dust ingestion. Samples were analysed using selective pressurized liquid extraction (S-PLE) and gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Legacy and replacement flame retardants were detected in all samples with overall ∑PBDE concentrations ranging from 120 to 1700,000 ng/g (median 2100 ng/g) and ∑NBFRs ranging from 1.1 to 10,000 ng/g (median 1800 ng/g). BDE-209 and DBDPE were the dominant compounds in dust samples, followed by congeners associated with commercial Penta-BDE formulations (-47, -99, -100, -153 and -154) and then EH-TBB of the FireMaster 550 and BZ-54 products. ∑Penta-BDE concentrations were elevated in office samples compared with homes and vehicles, while EH-TBB and BDE-209 measured higher concentrations in vehicles compared with their respective levels in homes and offices. Risk assessment estimates revealed the majority of exposure to occur in the home for both adults and toddlers in the City of Melbourne. Generally, body weight adjusted exposure to PBDEs and NBFRs was predicted to be 1 to 2 orders of magnitude higher for toddlers than adults. Estimated rates of BDE-47, -99, -153 and -209 ingestion were each 2 orders of magnitude or more below the USEPA's prescribed oral reference dose values (RfDs) for typical exposure scenarios. However, exposure rates for BDE-47 and -99 reached as high as 52 and 95% of RfDs, respectively, for adults and 4.4 and 7

  1. Research status of photodegradation of polybromin-ated diphenyl ethers (PBDES)%多溴联苯醚(PBDEs)光降解研究现状∗

    Institute of Scientific and Technical Information of China (English)

    刘芃岩; 路佳良; 孙佳惠; 田燕燕; 张彦娜

    2015-01-01

    Polybrominated diphenyl ethers ( PBDEs) are a group of emerging persistent organic pollutants. They have been concerned because of widespread distribution in the environment and high accumulation in vivo. The degradation of PBDEs has also been a hot spot for researches as well. Photodegradation is one of the main degradation pathways of PBDEs in natural environment. Higher toxic polybrominated dibenzo⁃p⁃dioxins and dibenzofurans could be formed in the process of photodegradation. In this paper studies on PBDEs photodegradation were summarized, and the influence factors of the photodegradation of PBDEs ( such as: molecular structure, light source, medium, etc.) were reviewed as well as pasthways and products of photodegradation, especially the formation of brominated dioxins. This paper therefore reveals current research problems and presents opportunities for future work in this field.%多溴联苯醚( polybrominated diphenyl ethers,PBDEs)为一类新型的持久性有机污染物,因其在环境中的广泛分布和生物累积性而备受关注,环境中PBDEs 的降解也成为研究热点。光降解是自然环境中PBDEs降解的主要途径之一,而光降解过程中会形成毒性更高的溴代二英。本文在总结国内外PBDEs光降解研究的基础上,对影响PBDEs光降解的因素(诸如:分子结构、光源、介质等)、途径和产物,特别是溴代二英的形成进行了综述,对目前存在问题及进一步的研究方向进行了讨论和展望。

  2. Children's exposure to polybrominated diphenyl ethers.

    Science.gov (United States)

    Zuurbier, Moniek; Leijs, Marike; Schoeters, Greet; ten Tusscher, Gavin; Koppe, Janna G

    2006-10-01

    Polybrominated biphenyl ethers (PBDEs), a class of brominated flame retardants, are frequently used in consumer products. PBDEs levels in environmental and human samples have increased in recent decades. Children are exposed to PBDEs through diet, mainly through fish, meat and milk. Total dietary exposure of children in Europe was calculated to be 2-3 ng/kg b.w./day. For nursing infants the main source of PBDE exposure is breast milk; exposure levels are around 15 ng/kg b.w./day. PBDE exposure levels in North America are 10 to a 100 times higher. Because of their persistence and their similarity to polychlorinated biphenyls (PCBs), concern has been raised about the effects of PBDEs on human health. Exposure to penta- and octa-BDE led to learning impairment and impaired motor behaviour in rodents. Exposure to penta-, octa- and also deca-BDE caused effects on thyroid homeostasis in animals. The EU has banned the production and use of penta- and octa-BDE since 2004; however, exposure will continue during the coming decades. Based upon current toxicological evidence, human exposure to deca-BDEs is not expected to lead to health effects, but data on exposure to deca-BDE and data on toxicity of deca-BDE are scarce. Therefore, monitoring studies and toxicity studies on deca-BDEs and other BDEs should continue.

  3. A, a Brominated Flame Retardant

    Directory of Open Access Journals (Sweden)

    Tomomi Takeshita

    2013-01-01

    Full Text Available 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.

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

    International Nuclear Information System (INIS)

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

    2014-01-01

    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. - Highlights: • Decomposition of a brominated flame retardant is performed in a laboratory furnace. • Both pyrolysis and combustion at two different temperatures are studied. • Brominated organic compounds such as Br-dioxins and furans are analysed. • Main product of decomposition is HBr, accounting for ca. 50%. • Very high and dangerous levels of PBDD/Fs and precursors (bromophenols) are detected. - TBBPA mainly decomposes to give HBr and brominated hydrocarbons at high temperature, but high levels of bromophenols and polybrominated dibenzo-p-dioxins and furans are also produced

  5. Inorganic bromine in the marine boundary layer: a critical review

    Directory of Open Access Journals (Sweden)

    R. Sander

    2003-01-01

    to produce atomic Br and Cl. Subsequent transformations can destroy tropospheric ozone, oxidize dimethylsulfide (DMS and hydrocarbons in the gas phase and S(IV in aerosol solutions, and thereby potentially influence climate. The diurnal cycle of gas-phase Br and the corresponding particulate Br deficits are correlated. Higher values of Br in the gas phase during daytime are consistent with expectations based on photochemistry. We expect that the importance of inorganic Br cycling will vary in the future as a function of both increasing acidification of the atmosphere (through anthropogenic emissions and climate changes. The latter affects bromine cycling via meteorological factors including global wind fields (and the associated production of sea-salt aerosol, temperature, and relative humidity.

  6. Preparation of bromine fluoride; Preparation du fluorure de brome

    Energy Technology Data Exchange (ETDEWEB)

    Domange, Pr; Duflo, J.

    1958-05-15

    This note addresses the preparation of bromine fluoride. It indicates the implemented process for the reaction, used products (fluorine and bromine), and column characteristics. It describes the operating mode. Apparatus drawing is provided.

  7. Evaluation of hepatic biotransformation of polybrominated diphenyl ethers in the polar bear (Ursus maritimus).

    Science.gov (United States)

    Krieger, Lisa K; Szeitz, András; Bandiera, Stelvio M

    2016-03-01

    Polar bears are at the top of the Arctic marine food chain and are subject to exposure and bioaccumulation of environmental chemicals of concern such as polybrominated diphenyl ethers (PBDEs), which were widely used as flame retardants. The aim of the present study was to evaluate the in vitro oxidative metabolism of 2,2',4,4'-tetrabrominated diphenyl ether (BDE-47) and 2,2',4,4',5-pentabrominated diphenyl ether (BDE-99) by polar bear liver microsomes. The identification and quantification of the hydroxy-brominated diphenyl ethers formed were assessed using an ultra-high performance liquid chromatography-tandem mass spectrometry-based method. Incubation of BDE-47 with archived individual liver microsomes, prepared from fifteen polar bears from northern Canada, produced a total of eleven hydroxylated metabolites, eight of which were identified using authentic standards. The major metabolites were 4'-hydroxy-2,2',4,5'-tetrabromodiphenyl ether and 5'-hydroxy-2,2',4,4'-tetrabromodiphenyl ether. Incubation of BDE-99 with polar bear liver microsomes produced a total of eleven hydroxylated metabolites, seven of which were identified using authentic standards. The major metabolites were 2,4,5-tribromophenol and 4-hydroxy-2,2',3,4',5-pentabromodiphenyl ether. Among the CYP specific antibodies tested, anti-rat CYP2B was found to be the most active in inhibiting the formation of hydroxylated metabolites of both BDE-47 and BDE-99, indicating that CYP2B was the major CYP enzyme involved in the oxidative biotransformation of these two congeners. Our study shows that polar bears are capable of forming multiple hydroxylated metabolites of BDE-47 and BDE-99 in vitro and demonstrates the role of CYP2B in the biotransformation and possibly in the toxicity of BDE-47 and BDE-99 in polar bears. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Dietary accumulation and metabolism of polybrominated diphenyl ethers by juvenile carp (Cyprinus carpio).

    Science.gov (United States)

    Stapleton, Heather M; Letcher, Robert J; Li, Juliana; Baker, Joel E

    2004-08-01

    Polybrominated diphenyl ethers (PBDEs) are hydrophobic organic contaminants with properties and nomenclature similar to polychlorinated biphenyls (PCBs). While much information is available on the bioaccumulation and pharamcokinetics of PCBs, little information is available on PBDEs. In this study, juvenile carp were exposed to a diet spiked with a cocktail of four BDE congeners (2,4,4'-tribromoDE [BDE 28], 2,2',4,4'-tetrabromoDE [BDE 47], 2,2',4,4',5-pentabromoDE [BDE 99], and 2,2',4,4',5,5'hexabromoDE [BDE 153]) for 60 d followed by a 40-d depuration period. As a positive control, three PCB congeners with similar log K(ow), values (2,2',5,5'-tetrachlorobiphenyl [PCB 52], 2,2',4,4', 5,5'-hexachlorobiphenyl [PCB 153], and 2,2',3,4,4',5,5'-heptachlorobiphenyl [PCB 180]) were included in the cocktail to compare their assimilation and fate with the model BDE congeners. Concentrations of BDEs and PCBs were monitored in whole-fish tissues and liver tissues over the duration of the experiment. In addition, blood serum samples were taken and pooled among replicates to determine if any phenolic metabolites of BDE and PCBs were formed. Rapid assimilation of BDE 47 was observed relative to all other BDE and PCB congeners, whereas apparently no accumulation of BDE 99 occurred over the course of the experiment. Assimilation efficiencies for BDE 47 suggest that approximately 100% of the BDE 47 exposure was absorbed by carp tissues after 60 d. However, based on the time course of BDE 47 assimilation, it is improbable that all BDE 47 was assimilated; more likely, production of BDE 47 in carp tissues occurred as a result of debromination of higher-brominated compounds, possibly BDE 99. The net assimilation efficiencies of BDE 28 and BDE 153 were also apparently low (20 and 4%, respectively) relative to the three PCBs (40% assimilated) examined in this study. The low assimilation efficiency and high depuration rates for BDEs suggest a higher potential for biotransformation. While

  9. Current levels of primary polybrominated diphenyl ethers (PBDEs) in Norwegian seafood

    Energy Technology Data Exchange (ETDEWEB)

    Bethune, C.; Nielsen, J.; Julshamn, K. [National Institute of Nutrition and Seafood Research, Bergen (Norway)

    2004-09-15

    The brominated flame retardants (BFRs) represent major industrial chemicals whose use has increased dramatically over the past few decades. Polybrominated diphenyl ethers (PBDEs) are BFRs that are used in many types of consumer products. PBDEs have come to the attention of regulators and scientists due to their bioaccumulation, increasing exposure and persistence in the environment, and adverse health effects in animals and humans. Although PBDE contamination in marine fish was first detected in Sweden in 1979, and certain PBDEs are now banned as of this year, the European Union has yet to establish regulations on PBDE levels in either feed or seafood. The determination of these contaminants in consumer seafood is important for dietary exposure assessment and protection of human health. This study reports on the levels of 6 prominent PBDE congeners (28, 47, 99, 100, 153, and 154) in a selection of common Norwegian seafood.

  10. Particle size distribution of brominated flame retardants in house dust from Japan

    Directory of Open Access Journals (Sweden)

    Natsuko Kajiwara

    2016-06-01

    Full Text Available The present study was conducted to examine the concentrations, profiles, and mass distributions of polybrominated diphenyl ethers (PBDEs, hexabromocyclododecanes (HBCDs, and polybrominated dibenzo-p-dioxins/furans (PBDD/Fs based on the particle sizes of house dust samples from five homes in Japan. After removal of impurities from house dust from vacuum cleaner bags, selected indoor dust samples were size fractionated (>2 mm, 1–2 mm, 0.5–1 mm, 250–500 μm, 106–250 μm, 53–106 μm, and 250 μm in size and fluffy dust were included. The conclusion is that particulate dust <250 μm in size without fluffy dust should be used to analyze dust for brominated flame retardants.

  11. Occurrence and levels of polybrominated diphenyl ethers in surface sediments from the Yellow River Estuary, China

    International Nuclear Information System (INIS)

    Yuan, Zijiao; Liu, Guijian; Lam, Michael Hon Wah; Liu, Houqi; Da, Chunnian

    2016-01-01

    A total of 21 surface sediments collected from the Yellow River Estuary, China were analyzed for 40 kinds of polybrominated diphenyl ethers (PBDEs) using gas chromatography-mass spectrometry (GC–MS). Their levels, spatial distribution, congener profiles and possible sources were investigated. Only ten congeners were detected in the sediments. The total concentrations of the lower brominated BDEs (∑PBDEs_l_o_w_, PBDEs excluding BDE 209) and BDE 209 ranged from 0.482 ng/g to 1.07 ng/g and 1.16–5.40 ng/g, with an average value of 0.690 and 2.79 ng/g, respectively, which were both at the low end of the global contamination level. The congener profiles were dominated by BDE 209, with the average value accounting for 79.2% of the total PBDEs in the sediment samples. Among the nine lower brominated BDE congeners, BDE 47, 99 and 183 had high abundances. Although the commercial Penta/Octa-BDE products have been banned in most countries, the residual commercial Penta/Octa/Deca-BDE products and the debromination of highly brominated BDE compounds such as BDE 209 were still found to be the possible sources for the trace level of PBDEs in the present study area. In spite of the gradual removal of the commercial PBDEs in the world, the present research results further suggested that scientific attention should not be reduced on the issue of environmental contamination caused by these outdated chemical compounds. - Highlights: • This is the first study concentrating specifically on PBDEs in the study area. • The commercial Penta/Octa/Deca-BDE products were the possible sources. • The debromination of highly brominated PBDEs were also found to be the sources. • Scientific attention should not be reduced on these outdated chemical compounds. - The commercial Penta/Octa/Deca-BDE products and the debromination of highly brominated BDE compounds were found to be the possible sources.

  12. Natural and anthropogenically-produced brominated compounds in endemic dolphins from Western South Atlantic: Another risk to a vulnerable species

    International Nuclear Information System (INIS)

    Alonso, Mariana B.; Eljarrat, Ethel; Gorga, Marina; Secchi, Eduardo R.; Bassoi, Manuela; Barbosa, Lupércio; Bertozzi, Carolina P.; Marigo, Juliana; Cremer, Marta; Domit, Camila; Azevedo, Alexandre F.; Dorneles, Paulo R.; Torres, João Paulo M.

    2012-01-01

    Liver samples from 53 Franciscana dolphins along the Brazilian coast were analyzed for organobrominated compounds. Target substances included the following anthropogenic pollutants: polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), pentabromoethylbenzene (PBEB), hexabromobenzene (HBB), decabromodiphenylethane (DBDPE), as well as the naturally-generated methoxylated-PBDEs (MeO-PBDEs). PBDE concentrations ranged from 6 to 1797 ng/g lw (mean 166 ± 298 ng/g lw) and were similar to those observed in cetaceans from Northern Hemisphere. PBBs were found in all sampling locations (< LOQ to 57 ng/g lw). DBDPE was detected in 42% of the dolphins from the most industrialized Brazilian state and the concentrations ranging from < LOQ to 352 ng/g lw. Franciscana dolphins from the tropical Brazilian shore presented the highest MeO-PBDE concentrations ever reported for coastal cetaceans (up to 14 μg/g lw). Eight MeO-PBDE congeners were detected and the present investigation constituted the first record of occurrence of six of them in marine mammal livers. - Highlights: ► PBDE, emerging BFR and MeO-PBDE levels in Franciscana dolphin from Brazil were reported. ► Six MeO-PBDEs were detected for the first time in marine mammals. ► PBDE contamination was similar than those from other industrialized areas around the world. ► MeO-PBDEs presented the higher concentrations found in coastal biota worldwide. - Concentrations and accumulation profiles of PBDEs, MeO-PBDEs and emerging brominated compounds in livers of dolphins from South Atlantic.

  13. Children's exposure to polybrominated diphenyl ethers.

    NARCIS (Netherlands)

    Zuurbier, M.; Leijs, M.; Schoeters, G.; Tusscher, G. Ten; Koppe, J.G.

    2006-01-01

    Background: Polybrominated biphenyl ethers (PBDEs), a class of brominated flame retardants, are frequently used in consumer products. PBDEs levels in environmental and human samples have increased in recent decades. Children are exposed to PBDEs through diet, mainly through fish, meat and milk.

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

    NARCIS (Netherlands)

    Brandsma, S.H.; Leonards, P.E.G.; Leslie, H.A.; de Boer, J.

    2015-01-01

    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

  15. Brominated flame retardants and endocrine disruption

    NARCIS (Netherlands)

    Vos, J.G.; Becher, G.; Berg, van den M.; Boer, de J.; Leonards, P.E.G.

    2003-01-01

    From an environmental point of view, an increasing important group of organohalogen compounds are the brominated flame retardants (BFRs), which are widely used in polymers and textiles and applied in construction materials, furniture, and electronic equipment. BFRs with the highest production volume

  16. Brominated flame retardants and endocrine disruption

    NARCIS (Netherlands)

    Vos, Joseph G.; Becher, Georg; Van Den Berg, Martin; Leonards, Pim E G

    2003-01-01

    From an environmental point of view, an increasing important group of organo-halogen compounds are the brominated flame retardants (BFRs), which are widely used in polymers and textiles and applied in construction materials, furniture, and electronic equipment. BFRs with the highest production

  17. short communication polyvinylpyrrolidone-bromine complex

    African Journals Online (AJOL)

    Preferred Customer

    2011-06-15

    2Department of Organic-Polymer Chemistry, Mazandaran University, Babolsar, Iran. (Received June 15, 2011; revised January 11, 2012). ABSTRACT. Benzylic bromides were conveniently obtained in high yields via the reaction of the corresponding alcohols with crosslinked polyvinylpyrrolidone-bromine complex ...

  18. Solid-state one-way photoisomerisation of Z,E,Z-1,6-(4,4'-diphenyl)hexa-1,3,5-triene dicarboxylate examined using higher-order derivative spectra and powder XRD patterns.

    Science.gov (United States)

    Sonoda, Yoriko; Goto, Midori; Ichimura, Kunihiro

    2018-03-14

    Higher order derivative spectra were applied at first to one-way ZEZ-to-EEE photoisomerisation of dimethyl ester (ZEZ-DPH1) of the titled compound in a methylcyclohexane solution. Many common crossing points emerged in UV-induced derivative-spectral changes to reveal the direct ZEZ-to-EEE photoisomerisation without the transient formation of an intermediate to suggest the bicycle-pedal mechanism. The solid-state photoisomerisation was subsequently monitored by tracing changes in the fourth-order derivatives of absorption spectra of a thin crystalline layer of ZEZ-DPH1 prepared by the drop-casting method, because the distortion of absorption spectra due to light scattering is cancelled. It was suggested that the solid-state photochemical event consists of three steps: fast ZEZ-to-EEE photoisomerisation, a subsequent slow ZEZ-to-EEE photoisomerisation and very slow disappearance of the EEE-isomer. Studies on powder XRD were also carried out for a drop-cast solid layer of ZEZ-DPH1 to disclose the coexistence of a crystal form other than the original one, and the former exhibited faster ZEZ-to-EEE photoisomerisation when compared with the original crystal form. The results revealed by XRD analysis are in line with those obtained by higher-order derivative spectra, confirming the solid-state one-way photoisomerisation to take place through the bicycle-pedal process.

  19. Depositional characteristics of atmospheric polybrominated diphenyl ethers on tree barks

    Directory of Open Access Journals (Sweden)

    Man Young Chun

    2014-07-01

    Full Text Available Objectives This study was conducted to determine the depositional characteristics of several tree barks, including Ginkgo (Ginkgo biloba, Pine (Pinus densiflora, Platanus (Platanus, and Metasequoia (Metasequoia glyptostroboides. These were used as passive air sampler (PAS of atmospheric polybrominated diphenyl ethers (PBDEs. Methods Tree barks were sampled from the same site. PBDEs were analyzed by highresolution gas chromatography/high-resolution mass spectrometer, and the lipid content was measured using the gravimetric method by n-hexane extraction. Results Gingko contained the highest lipid content (7.82 mg/g dry, whereas pine (4.85 mg/g dry, Platanus (3.61 mg/g dry, and Metasequoia (0.97 mg/g dry had relatively lower content. The highest total PBDEs concentration was observed in Metasequoia (83,159.0 pg/g dry, followed by Ginkgo (53,538.4 pg/g dry, Pine (20,266.4 pg/g dry, and Platanus (12,572.0 pg/g dry. There were poor correlations between lipid content and total PBDE concentrations in tree barks (R2=0.1011, p =0.682. Among the PBDE congeners, BDE 206, 207 and 209 were highly brominated PBDEs that are sorbed to particulates in ambient air, which accounted for 90.5% (84.3-95.6% of the concentration and were therefore identified as the main PBDE congener. The concentrations of particulate PBDEs deposited on tree barks were dependent on morphological characteristics such as surface area or roughness of barks. Conclusions Therefore, when using the tree barks as the PAS of the atmospheric PBDEs, samples belonging to same tree species should be collected to reduce errors and to obtain reliable data.

  20. Depositional characteristics of atmospheric polybrominated diphenyl ethers on tree barks.

    Science.gov (United States)

    Chun, Man Young

    2014-07-17

    This study was conducted to determine the depositional characteristics of several tree barks, including Ginkgo (Ginkgo biloba), Pine (Pinus densiflora), Platanus (Platanus), and Metasequoia (Metasequoia glyptostroboides). These were used as passive air sampler (PAS) of atmospheric polybrominated diphenyl ethers (PBDEs). Tree barks were sampled from the same site. PBDEs were analyzed by highresolution gas chromatography/high-resolution mass spectrometer, and the lipid content was measured using the gravimetric method by n-hexane extraction. Gingko contained the highest lipid content (7.82 mg/g dry), whereas pine (4.85 mg/g dry), Platanus (3.61 mg/g dry), and Metasequoia (0.97 mg/g dry) had relatively lower content. The highest total PBDEs concentration was observed in Metasequoia (83,159.0 pg/g dry), followed by Ginkgo (53,538.4 pg/g dry), Pine (20,266.4 pg/g dry), and Platanus (12,572.0 pg/g dry). There were poor correlations between lipid content and total PBDE concentrations in tree barks (R(2)=0.1011, p =0.682). Among the PBDE congeners, BDE 206, 207 and 209 were highly brominated PBDEs that are sorbed to particulates in ambient air, which accounted for 90.5% (84.3-95.6%) of the concentration and were therefore identified as the main PBDE congener. The concentrations of particulate PBDEs deposited on tree barks were dependent on morphological characteristics such as surface area or roughness of barks. Therefore, when using the tree barks as the PAS of the atmospheric PBDEs, samples belonging to same tree species should be collected to reduce errors and to obtain reliable data.

  1. The environmental fate of polybrominated diphenyl ethers in the Great Lakes Basin

    Science.gov (United States)

    Gouin, Todd William

    Semi-volatile organic compounds, such as the polybrominated diphenyl ethers (PBDEs) have the potential to undergo long-range atmospheric transport (LRAT) to remote locations, which can increase the exposure of sensitive ecosystems to potentially harmful substances. Regulatory instruments, such as the Stockholm Convention on persistent organic pollutants (POPs), have been implemented to limit and/or prevent this exposure. Through the acquisition of scientific data, knowledge can be gained about the environmental fate and human exposure of chemical substances, and the risks associated with using those substances assessed. PBDEs are a class of flame retardants that are used in a wide range of commercial products. In response to growing concern over the detection of PBDEs in remote regions, a number of regulatory bodies have implemented measures to restrict the use of PBDEs. Using a suite of environmental fate models it is shown that PBDEs will most likely partition to organic carbon in soil and sediment, and that their persistence in the environment will be strongly influenced by their reactivity in those compartments. The transport potential of the PBDEs is investigated using the transport and persistence level III model TaPL3, using model environments with and without vegetation. It is suggested that the LRAT potential of the PBDEs is likely to be greater for the more volatile lower brominated congeners than for the higher brominated congeners, and that the LRAT may be sensitive to seasonal changes in the environment, such as temperature, vegetation and changes in precipitation. Furthermore, model results suggest that the PBDEs may be subject to a "spring pulse" effect, whereby concentrations are elevated in air during the early spring. Field studies support the theory of a "spring pulse" effect, where concentrations were observed to be five times greater during the period between snowmelt and bud burst than the average concentration before and after, but conclude

  2. Riverine inputs of polybrominated diphenyl ethers from the Pearl River Delta (China) to the coastal ocean.

    Science.gov (United States)

    Guan, Yu-Feng; Wang, Ji-Zhong; Ni, Hong-Gang; Luo, Xiao-Jun; Mai, Bi-Xian; Zeng, Eddy Y

    2007-09-01

    Riverine runoff is an important mode to transport anthropogenic pollutants from terrestrial sources to oceans. Polybrominated diphenyl ethers (PBDEs) were measured in riverine runoff samples from the eight major outlets within the Pearl River Delta (PRD), China, an economically fast developing region housing a vast number of electronics manufacturing and assembling plants. The sigma 17PBDEs (sum of 17 BDE congeners, i.e., BDE-28, -47, -66, -85, -99, -100, -138, -153, -154, -183, -196, -197, -203, -206, -207, -208, and -209) concentrations varied from 344 to 68,000 pg/L, with those of BDE-209, BDE-47, and BDE-99 being 335-65200, 3-143, and production of brominated fire retardants (approximately 10000 metric tons/year) and the annual riverine input of total PBDEs from the PRD, suggesting that the majority of PBDEs inventory has been accumulated from importation of e-wastes. Because of the continuous importation of e-wastes and strong demand for brominated fire retardants, the impact of PBDEs on China's and the world's environments is expected to persist for many years to come.

  3. Characteristics of Polybrominated Diphenyl Ethers Released from Thermal Treatment and Open Burning of E-Waste.

    Science.gov (United States)

    Li, Ting-Yu; Zhou, Jun-Feng; Wu, Chen-Chou; Bao, Lian-Jun; Shi, Lei; Zeng, Eddy Y

    2018-04-17

    Primitive processing of e-waste potentially releases abundant organic contaminants to the environment, but the magnitudes and mechanisms remain to be adequately addressed. We conducted thermal treatment and open burning of typical e-wastes, that is, plastics and printed circuit boards. Emission factors of the sum of 39 polybrominated diphenyl ethers (∑ 39 PBDE) were 817-1.60 × 10 5 ng g -1 in thermal treatment and nondetected-9.14 × 10 4 ng g -1 , in open burning. Airborne particles (87%) were the main carriers of PBDEs, followed by residual ashes (13%) and gaseous constituents (0.3%), in thermal treatment, while they were 30%, 43% and 27% in open burning. The output-input mass ratios of ∑ 39 PBDE were 0.12-3.76 in thermal treatment and 0-0.16 in open burning. All PBDEs were largely affiliated with fine particles, with geometric mean diameters at 0.61-0.83 μm in thermal degradation and 0.57-1.16 μm in open burning from plastic casings, and 0.44-0.56 and nondetected- 0.55 μm, from printed circuit boards. Evaporation and reabsorption may be the main emission mechanisms for lightly brominated BDEs, but heavily brominated BDEs tend to affiliate with particles from heating or combustion. The different size distributions of particulate PBDEs in emission sources and adjacent air implicated a noteworthy redisposition process during atmospheric dispersal.

  4. Algae form brominated organic compounds in surface waters

    Energy Technology Data Exchange (ETDEWEB)

    Huetteroth, A; Putschew, A; Jekel, M [Tech. Univ. Berlin (Germany)

    2004-09-15

    Monitoring of organic halogen compounds, measured as adsorbable organic bromine (AOBr) revealed seasonal high concentrations of organic bromine compounds in a surface water (Lake Tegel, Berlin, Germany). Usually, in late summer, concentrations are up to five times higher than during the rest of the year. The AOBr of the lake inflows (throughout the year less then 6 {mu}g/L) were always lower then those in the lake, which indicates a production of AOBr in the lake. A correlation of the AOBr and chlorophyll-a concentration (1) in the lake provides first evidence for the influence of phototrophic organisms. The knowledge of the natural production of organohalogens is relatively recent. Up to now there are more then 3800 identified natural organohalogen compounds that have been detected in marine plants, animals, and bacteria and also in terrestrial plants, fungi, lichen, bacteria, insects, some higher animals, and humans. Halogenated organic compounds are commonly considered to be of anthropogenic origin; derived from e.g. pharmaceuticals, herbicides, fungicides, insecticides, flame retardants, intermediates in organic synthesis and solvents. Additionally they are also produced as by-products during industrial processes and by waste water and drinking water disinfection. Organohalogen compounds may be toxic, persistent and/or carcinogenic. In order to understand the source and environmental relevance of naturally produced organobromine compounds in surface waters, the mechanism of the formation was investigated using batch tests with lake water and algae cultures.

  5. Reductive debromination of polybrominated diphenyl ethers in anaerobic sediment and a biomimetic system.

    Science.gov (United States)

    Tokarz, John A; Ahn, Mi-Youn; Leng, June; Filley, Timothy R; Nies, Loring

    2008-02-15

    Because of the bioaccumulation of penta- and tetrapolybrominated diphenyl ether (PBDE) flame retardants in biota,the environmental biotransformation of decabromodiphenyl ether (BDE-209) is of interest. BDE-209 accounts for more than 80% by mass of PBDE production and is the dominant PBDE in sediments. Most sediments are anaerobic and reports of microbial reductive dehalogenation of hydrophobic persistent organohalogen pollutants are numerous. Reductive debromination of BDE-209 in the environment could provide a significant source of lesser-brominated PBDEs to biota. Moreover, a recent study showed that BDE-209 debrominates in sewage sludge, and another demonstrated that some halorespiring bacteria will debrominate BDE-209. To determine whether reductive debromination of BDE-209 occurs in sediments, parallel experiments were conducted using anaerobic sediment microcosms and a cosolvent-enhanced biomimetic system. In the biomimetic system, reductive debromination occurred at rates corresponding to bromine substitution levels with a BDE-209 half-life of only 18 s compared with a halflife of almost 60 days for 2,2',4,4'-tetrabromodiphenyl ether. In sediment, the measured debromination half-life of BDE-209 was well over a decade and was in good agreement with the predicted value obtained from the biomimetic experiment. Product congeners were predominantly double para-substituted. BDE-209 debrominated in sediment with a corresponding increase in nona-, octa-, hepta-, and hexa-PBDEs. Nine new PBDE congeners appeared in sediment from reductive debromination. Given the very large BDE-209 burden already in sediments globally, it is important to determine whether this transformation is a significant source of lesser-brominated PBDEs to the environment.

  6. Occurrence and levels of polybrominated diphenyl ethers in surface sediments from the Yellow River Estuary, China.

    Science.gov (United States)

    Yuan, Zijiao; Liu, Guijian; Lam, Michael Hon Wah; Liu, Houqi; Da, Chunnian

    2016-05-01

    A total of 21 surface sediments collected from the Yellow River Estuary, China were analyzed for 40 kinds of polybrominated diphenyl ethers (PBDEs) using gas chromatography-mass spectrometry (GC-MS). Their levels, spatial distribution, congener profiles and possible sources were investigated. Only ten congeners were detected in the sediments. The total concentrations of the lower brominated BDEs (∑PBDEslow, PBDEs excluding BDE 209) and BDE 209 ranged from 0.482 ng/g to 1.07 ng/g and 1.16-5.40 ng/g, with an average value of 0.690 and 2.79 ng/g, respectively, which were both at the low end of the global contamination level. The congener profiles were dominated by BDE 209, with the average value accounting for 79.2% of the total PBDEs in the sediment samples. Among the nine lower brominated BDE congeners, BDE 47, 99 and 183 had high abundances. Although the commercial Penta/Octa-BDE products have been banned in most countries, the residual commercial Penta/Octa/Deca-BDE products and the debromination of highly brominated BDE compounds such as BDE 209 were still found to be the possible sources for the trace level of PBDEs in the present study area. In spite of the gradual removal of the commercial PBDEs in the world, the present research results further suggested that scientific attention should not be reduced on the issue of environmental contamination caused by these outdated chemical compounds. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Using disposable solid-phase microextraction (SPME) to determine the freely dissolved concentration of polybrominated diphenyl ethers (PBDEs) in sediments

    International Nuclear Information System (INIS)

    Jia Fang; Cui Xinyi; Wang Wei; Delgado-Moreno, Laura; Gan, Jay

    2012-01-01

    Polybrominated diphenyl ethers (PBDEs) are brominated flame retardants (BFRs). The ubiquity and persistence of PBDEs in sediment have raised concerns over their environmental fate and ecological risks. Due to strong affinity for sediment organic matter, environmental fate and bioavailability of PBDEs closely depend on their phase distribution. In this study, disposable polydimethylsiloxane (PDMS) fiber was used to derive the freely dissolved concentration (C free ) of PBDEs in sediment porewater as a measurement of bioavailability. The PDMS-to-water partition coefficient (log K PDMS ) was 5.46–5.83 for BDE 47, 99, and 153. In sediments, PBDEs were predominantly sorbed to the sediment phase, with C free accounting for free of PBDEs decreased as their bromination or sediment organic carbon content increased. The strong association with dissolved organic matter (DOM) implies a potential for facilitated offsite transport and dispersion in the environment that depends closely on the stability of sediment aggregates. - Highlights: ► A disposable SPME method was developed for measuring C free of PBDEs in sediment. ► C free decreased with increasing congener bromination or sediment OC content. ► C free of PBDEs accounted for DOC values suggest a high probability for DOM-facilitated offsite transport. - A SPME method based on disposable PDMS fibers was developed for measuring the freely dissolved concentration of PBDEs (C free ) in sediment porewater.

  8. Excited States and Photodebromination of Selected Polybrominated Diphenyl Ethers: Computational and Quantitative Structure—Property Relationship Studies

    Directory of Open Access Journals (Sweden)

    Jin Luo

    2015-01-01

    Full Text Available This paper presents a density functional theory (DFT/time-dependent DFT (TD-DFT study on the lowest lying singlet and triplet excited states of 20 selected polybrominateddiphenyl ether (PBDE congeners, with the solvation effect included in the calculations using the polarized continuum model (PCM. The results obtained showed that for most of the brominated diphenyl ether (BDE congeners, the lowest singlet excited state was initiated by the electron transfer from HOMO to LUMO, involving a π–σ* excitation. In triplet excited states, structure of the BDE congeners differed notably from that of the BDE ground states with one of the specific C–Br bonds bending off the aromatic plane. In addition, the partial least squares regression (PLSR, principal component analysis-multiple linear regression analysis (PCA-MLR, and back propagation artificial neural network (BP-ANN approaches were employed for a quantitative structure-property relationship (QSPR study. Based on the previously reported kinetic data for the debromination by ultraviolet (UV and sunlight, obtained QSPR models exhibited a reasonable evaluation of the photodebromination reactivity even when the BDE congeners had same degree of bromination, albeit different patterns of bromination.

  9. Brominated flame retardants in black plastic kitchen utensils: Concentrations and human exposure implications.

    Science.gov (United States)

    Kuang, Jiangmeng; Abdallah, Mohamed Abou-Elwafa; Harrad, Stuart

    2018-01-01

    Concerns exist that restricted brominated flame retardants (BFRs) present in waste polymers may have, as a result of recycling, inadvertently contaminated items not required to meet flame retardancy regulations (e.g. plastic kitchen utensils). To investigate the extent to which kitchen utensils are contaminated with BFRs and the potential for resultant human exposure, we collected 96 plastic kitchen utensils and screened for Br content using a hand-held X-ray fluorescence (XRF) spectrometer. Only 3 out of 27 utensils purchased after 2011 contained detectable concentrations of Br (≥3μg/g). In contrast, Br was detected in 31 out of the 69 utensils purchased before 2011. Eighteen utensils with Br content higher than 100μg/g, and 12 new utensils were selected for GC-MS analysis of BFRs. BFRs targeted were polybrominated diphenyl ethers (PBDEs) BDE-28, 47, 99, 100, 153, 154, 183 and 209, and novel BFRs (NBFRs) pentabromoethylbenzene (PBEB), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (BEH-TEBP) and decabromodiphenyl ethane (DBDPE). The ability of XRF to act as a surrogate metric of BFR concentration was indicated by a significant (Spearman coefficient=0.493; p=0.006) positive relationship between Br and ΣBFR concentration. Measurements of ΣBFRs were always exceeded by those of Br. This may be due partly to the presence of BFRs not targeted in our study and also to reduced extraction efficiency of BFRs from utensils. Of our target BFRs, BDE-209 was the most abundant one in most samples, but an extremely high concentration (1000μg/g) of BTBPE was found in one utensil. Simulated cooking experiments were conducted to investigate BFR transfer from selected utensils (n=10) to hot cooking oil, with considerable transfer (20% on average) observed. Estimated median exposure via cooking with BFR contaminated utensils was 60ng/day for total BFRs. In contrast, estimated

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

    Science.gov (United States)

    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.

  11. Concentrations and speciation of polybrominated diphenyl ethers in human amniotic fluid

    Science.gov (United States)

    Miller, Mark F.; Chernyak, Sergei M.; Domino, Steven E.; Batterman, Stuart A.; Loch-Caruso, Rita

    2012-01-01

    Polybrominated diphenyl ethers (PBDEs) are persistent organic chemicals used as flame retardants in textiles, plastics, and consumer products. Although PBDE accumulation in humans has been noted since the 1970s, few studies have investigated PBDEs within the gestational compartment, and none to date has identified levels in amniotic fluid. The present study reports congener-specific brominated diphenyl ether (BDE) concentrations in second-trimester clinical amniotic fluid samples collected in 2009 from fifteen women in southeast Michigan, USA. Twenty-one BDE congeners were measured by GC/MS/NCI. The average total PBDE concentration was 3795 pg/ml amniotic fluid (range: 337 – 21842 pg/ml). BDE-47 and BDE-99 were identified in all samples. Based on median concentrations, the dominant congeners were BDE-208, 209, 203, 206, 207, and 47 representing 23, 16, 12, 10, 9 and 6%, respectively, of the total detected PBDEs. PBDE concentrations were identified in all amniotic fluid samples from southeast Michigan, supporting a need for further investigations of fetal exposure pathways and potential impacts on perinatal health. PMID:22236635

  12. Fate of polybrominated diphenyl ethers in the environment of the Pearl River Estuary, South China

    International Nuclear Information System (INIS)

    Guan Yufeng; Sojinu, O.S. Samuel; Li Shaomeng; Zeng, Eddy Y.

    2009-01-01

    Ninety-six riverine runoff samples collected at eight major outlets in the Pearl River Delta (PRD), South China, during 2005-2006 were analyzed for 17 brominated diphenyl ether (BDE) congeners (defined as Σ 17 PBDE). Fourteen and 15 congeners were detected, respectively, in the dissolved and particulate phases. These data were further used to elucidate the partitioning behavior of BDE congeners in riverine runoff. Several related fate processes, i.e. air-water exchange, dry and wet deposition, degradation, and sedimentation, within the Pearl River Estuary (PRE), were examined to estimate the inputs of Σ 10 PBDE (sum of the target BDE congeners, BDE-28, -47, -66, -85, -99, -100, -138, -153, -154, and -183) and BDE-209 from the PRD to the coastal ocean based on mass balance considerations. The results showed that annual outflows of Σ 10 PBDE and BDE-209 were estimated at 126 and 940 kg/year, respectively from the PRE to coastal ocean. Besides sedimentation and degradation, the majority of Σ 10 PBDE and BDE-209 discharged into the PRE via riverine runoff was transported to the coastal ocean. - Fate of polybrominated diphenyl ethers in the environment the Pearl River Estuary, South China.

  13. Comparative environmental analysis of waste brominated plastic thermal treatments

    International Nuclear Information System (INIS)

    Bientinesi, M.; Petarca, L.

    2009-01-01

    The aim of this research activity is to investigate the environmental impact of different thermal treatments of waste electric and electronic equipment (WEEE), applying a life cycle assessment methodology. Two scenarios were assessed, which both allow the recovery of bromine: (A) the co-combustion of WEEE and green waste in a municipal solid waste combustion plant, and (B) the staged-gasification of WEEE and combustion of produced syngas in gas turbines. Mass and energy balances on the two scenarios were set and the analysis of the life cycle inventory and the life cycle impact assessment were conducted. Two impact assessment methods (Ecoindicator 99 and Impact 2002+) were slightly modified and then used with both scenarios. The results showed that scenario B (staged-gasification) had a potentially smaller environmental impact than scenario A (co-combustion). In particular, the thermal treatment of staged-gasification was more energy efficient than co-combustion, and therefore scenario B performed better than scenario A, mainly in the impact categories of 'fossil fuels' and 'climate change'. Moreover, the results showed that scenario B allows a higher recovery of bromine than scenario A; however, Br recovery leads to environmental benefits for both the scenarios. Finally the study demonstrates that WEEE thermal treatment for energy and matter recovery is an eco-efficient way to dispose of this kind of waste

  14. Membrane-less hydrogen bromine flow battery

    Science.gov (United States)

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

    2013-08-01

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

  15. Symproportionation versus Disproportionation in Bromine Redox Systems

    International Nuclear Information System (INIS)

    Toporek, Marcin; Michałowska-Kaczmarczyk, Anna M.; Michałowski, Tadeusz

    2015-01-01

    Graphical abstract: Display Omitted -- Highlights: • The disproportionation and symproportionation of bromine in different media is presented. • All the redox systems are elaborated according to the principles of the generalized approach to electrolytic redox systems (GATES/GEB). • All physicochemical knowledge is involved in the algorithm applied for this purpose. • The graphical representation of the systems is the basis of gaining the detailed physicochemical knowledge on the systems in question. -- Abstract: The paper refers to dynamic (titration) redox systems where symproportionation or disproportionation of bromine species occur. The related systems are modeled according to principles assumed in the Generalized Approach to Electrolytic Redox Systems (GATES), with Generalized Electron Balance (GEB) concept involved in the GATES/GEB software. The results obtained from calculations made with use of iterative computer programs prepared according to MATLAB computational software, are presented graphically, as 2D and 3D graphs

  16. Membrane-less hydrogen bromine flow battery

    OpenAIRE

    Braff, W. A.; Bazant, M. Z.; Buie, C. R.

    2014-01-01

    In order for the widely discussed benefits of flow batteries for electrochemical energy storage to be applied at large scale, the cost of the electrochemical stack must come down substantially. One promising avenue for reducing stack cost is to increase the system power density while maintaining efficiency, enabling smaller stacks. Here we report on a membrane-less, hydrogen bromine laminar flow battery as a potential high power density solution. The membrane-less design enables power densiti...

  17. 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.

    Science.gov (United States)

    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. Copyright © 2012 Elsevier Ltd. All rights reserved.

  18. Hydrogen-bromine fuel cell advance component development

    Science.gov (United States)

    Charleston, Joann; Reed, James

    1988-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Windham, Gayle C., E-mail: gayle.windham@cdph.ca.gov [CA Department of Public Health, DEODC, 850 Marina Bay Pkwy, Bldg. P, Richmond, CA 94804 (United States); Pinney, Susan M. [University of Cincinnati College of Medicine, Cincinnati, OH 45267 (United States); Sjodin, Andreas [Centers for Disease Control and Prevention, Atlanta, GA 30341 (United States); Lum, Raymond [Impact Assessment Inc., San Diego, CA (United States); Jones, Richard S.; Needham, Larry L. [Centers for Disease Control and Prevention, Atlanta, GA 30341 (United States); Biro, Frank M. [University of Cincinnati College of Medicine, Cincinnati, OH 45267 (United States); Hiatt, Robert A. [University of California Medical School, San Francisco, CA (United States); Kushi, Lawrence H. [Kaiser Permanente Northern California, Oakland, CA 94612 (United States)

    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

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

    International Nuclear Information System (INIS)

    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.

    2010-01-01

    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

  1. Simultaneous Determination of Methoxylated Polybrominated Diphenyl Ethers and Polybrominated Diphenyl Ethers in Water, Soil and Sediment from China by GC-MS.

    Science.gov (United States)

    Hu, Xiaozhong; Hu, Decong; Chen, Wei; Wu, Bin; Lin, Changjun

    2015-09-01

    Polybrominated diphenyl ethers (PBDEs) are widely used brominated flame retardants, which are increasingly reported in the environment. Methoxylated polybrominated diphenyl ethers (MeO-PBDEs) are structural analogs to PBDEs and reported as natural products and novel pollutants present in the environment. First, a new isotopic dilution GC-MS method was developed in this study to simultaneously determine 13 PBDEs and 8 MeO-PBDEs in water, soil and sediment. Liquid/liquid extraction, pressurized liquid extraction and multi-layer silica gel column chromatography cleanup were used, and some important steps and crucial parameters were modified and intensified compared with the other literatures. Besides, the conditions of GC and MS were also optimized. The limits of quantitation values of 0.005-0.1 and 0.02-0.1 µg L(-1) in water were calculated for PBDEs and MeO-PBDEs, respectively; so did 0.25-5 and 1-5 µg kg(-1) dry weight in soil and sediment. In addition, good repeatability and accuracy of the whole method were achieved. Moreover, 60 water and 30 sediment samples for aquaculture crayfish and freshwater fish collected from aquatic products production base, 40 soil samples collected from agricultural products production base and also 20 Yangtze River water samples and 20 Hanjiang River water samples collected from different sampling situations near Wuhan, Hubei province along the Yangtze River and the Hanjiang River were analyzed to determine whether they are contaminated by PBDEs and MeO-PBDEs. Using the established methods, it was found that PBDEs or MeO-PBDEs emerged in 4 of 60 water samples for aquatic products, 3 of 40 soils, and 2 of 30 sediments and in low µg kg(-1) dry weight for soil and sediments and low µg L(-1) for water. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  2. Legacy and novel brominated flame retardants in interior car dust – Implications for human exposure

    International Nuclear Information System (INIS)

    Besis, Athanasios; Christia, Christina; Poma, Giulia; Covaci, Adrian; Samara, Constantini

    2017-01-01

    Brominated flame retardants (BFRs) are organobromine compounds with an inhibitory effect on combustion chemistry tending to reduce the flammability of products. Concerns about health effects and environmental threats have led to phase-out or restrictions in the use of Penta-, Octa- and Deca-BDE technical formulations, increasing the demand for Novel BFRs (NBFRs) as replacements for the banned formulations. This study examined the occurrence of legacy and NBFRs in the dust from the interior of private cars in Thessaloniki, Greece, aged from 1 to 19 years with variable origin and characteristics. The determinants included 20 Polybrominated Diphenyl Ethers (PBDEs) (Di-to Deca-BDEs), four NBFRs such as Decabromodiphenylethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB), and bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (TBPH), three isomers of hexabromocyclododecane (HBCD), and tetrabromobisphenol A (TBBPA). The concentrations of ∑ 20 PBDE ranged from 132 to 54,666 ng g −1 being dominated by BDE-209. The concentrations of ∑ 4 NBFRs ranged from 48 to 7626 ng g −1 and were dominated by DBDPE, the major substitute of BDE-209. HBCDs ranged between <5 and 1745 ng g −1 , with alpha-HBCD being the most prevalent isomer Finally, the concentrations of TBBPA varied from <10 to 1064 ng g −1 . The concentration levels and composition profiles of BFRs were investigated in relation to the characteristics of cars, such as year of manufacture, country of origin, and interior equipment (type of car seats, electronic and electrical components, ventilation, etc.). The average daily intakes of selected BFRs (BDE-47, BDE-99, BDE-153, BDE-209, TBB, BTBPE, TBPH, DBDPE, HBCDs and TBBPA) via ingestion and dermal absorption were estimated for adults and toddlers. The potential health risk due to BFRs was found to be several orders of magnitude lower than their corresponding reference dose (RfD) values. - Highlights:

  3. Model for Photodegradation of Polybrominated Diphenyl Ethers

    Czech Academy of Sciences Publication Activity Database

    Veselý, M.; Vajglová, Zuzana; Kotas, Petr; Křišťál, Jiří; Ponec, Robert; Jiřičný, Vladimír

    2015-01-01

    Roč. 22, č. 7 (2015), s. 4949-4963 ISSN 0944-1344 R&D Projects: GA ČR GA104/09/0880; GA ČR(CZ) GAP105/12/0664 Institutional support: RVO:67985858 ; RVO:67179843 Keywords : polybrominated diphenyl ethers * photodegradation model * quantum chemical calculation Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.760, year: 2015

  4. Uranium hexafluoride and uranyl nitrate. Ionometric determination of bromine

    International Nuclear Information System (INIS)

    Anon.

    Bromine was determined in uranium hexafluoride. The method is suitable for determining 2 to 20 ppm with respect to uranium. Bromides are oxidized by potassium permanganate to give bromine which is extracted into carbon tetrachloride, reduced by ascorbic acid and determined by ionometry [fr

  5. Brominated flame retardants: occurrence, dietary intake and risk assessment

    NARCIS (Netherlands)

    Winter-Sorkina R de; Bakker MI; Wolterink G; Zeijlmaker MJ; SIR

    2006-01-01

    Brominated flame retardants have entered the human food chain. For the time being the occurrence of these chemicals in Dutch food does not pose a human health risk. However, this might easily change at increasing contents of flame retardants in Dutch food. The monitoring of brominated flame

  6. Peroxometal-mediated oxidation of bromine leading to ...

    Indian Academy of Sciences (India)

    Administrator

    Peroxometal-mediated oxidation of bromine leading to environmentally favourable protocol for selective bromination of organic substrates: Implications for vanadium bromo peroxidase (VBrPO). SIDDHARTHA D DHAR and MIHIR K CHAUDHURI. Department of Chemistry, Indian Institute of Technology,. Guwahati 781 001 ...

  7. Promoting environmentally sound management of polybrominated diphenyl ethers in Asia.

    Science.gov (United States)

    Li, Jinhui; Zhao, Nana; Liu, Xue; Wu, Xiaoyang

    2014-06-01

    Polybrominated diphenyl ethers with persistent organic pollutant properties are required to be controlled by the Stockholm Convention. Recently, polybrominated diphenyl ether contamination has become widespread in Asia, mainly because of the disposal and recycling processes of polybrominated diphenyl ether-containing wastes. The management status, production, usage, import/export, treatment, and disposal, as well as implementation deficiencies for the environmentally sound management of polybrominated diphenyl ethers and polybrominated diphenyl ether-containing materials in ten Asian countries were investigated and assessed in this study. This information could help the participating countries implement the Stockholm Convention and could promote the regional environmentally sound management of polybrominated diphenyl ether-containing articles and products. The results obtained were as follows. (1) Most of the countries studied lacked environmental policies and regulations, or even standards of polybrominated diphenyl ether pollution management and emission control actions. Accurate data on the consumption and importation of polybrominated diphenyl ether-containing materials, however, were not available for all the participating countries. In addition, there were no special treatment or disposal systems for polybrominated diphenyl ether-containing materials, or emission-cutting measures for the treatment of waste in these countries, owing to the lack of sufficient funding or technologies. (2) The improper dismantling of e-waste is a major source of polybrominated diphenyl ether emissions in these countries. (3) Proper e-waste management could result in a breakthrough in the environmentally sound management of this major polybrominated diphenyl ether-containing material flow, and could significantly reduce polybrominated diphenyl ether emissions. Finally, based on the study results, this article puts forward some recommendations for improving the environmentally

  8. Bromine-doped DWNTs: A Molecular Faraday Cage

    Science.gov (United States)

    Chen, Gugang; Margine, Roxana; Gupta, Rajeev; Crespi, Vincent; Eklund, Peter; Sumanasekera, Gamini; Bandow, Shunji; Iijima, S.

    2003-03-01

    Raman scattering is used to probe the charge transfer distribution in Bromine-doped double-walled carbon nanotubes (DWNT). Using 1064 nm and 514.5 nm laser excitation we are able to study the charge-transfer sensitive phonons in the inner ( (5,5)) and outer ( (10,10)) tubes of the double-walled pair. The experimental results are compared to our tight binding band structure calculations that include a self-consistent electrostatic term sensitive to the average net charge density on each tube. Upon doping, the nanotube tangential and radial Raman bands from the outer (primary) tubes were observed to shift dramatically to higher frequencies, consistent with a C-C bond contraction driven by the acceptor-doping. The peak intensities of these bands significantly decreased with increasing doping exposure, and they eventually vanished, consistent with a deep depression in the Fermi energy that extinguishes the resonant Raman effect. Interestingly, at the same time, we observed little or no change for the tangential and radial Raman features identified with the inner (secondary) tubes during the bromine doping. Our electronic structure calculations show that the charge distribution between the outer and inner tubes depends on doping level and also, to some extent, on specific tube chirality combinations. In general, in agreement with experiment, the calculations find a very small net charge on the inner tube, consistent with a "Molecular Faraday Effect", e.g., a DWNT of (10, 10)/ (5, 5) configuration that exhibits 0.5 holes/Å total charge transfer, has only 0.04 holes/Å on the inner (secondary) tube.

  9. Levels of polybrominated diphenyl-ethers and polybrominated dioxins in fish, total diet study food groups, and Japanese meals

    Energy Technology Data Exchange (ETDEWEB)

    Ashizuka, Y.; Nakagawa, R.; Hori, T.; Tobiishi, K.; Iida, T. [Fukuoka Inst. of Health and Environmental Sciences, Dazaifu (Japan)

    2004-09-15

    Since they were found in mother's milk and blood in several studies, the polybrominated diphenyl-ethers (PBDEs) and other polybrominated flame-retardants (BFRs) that are used in plastics, electrical appliances, and textiles have been recognized as ubiquitous pollutants. BFRs are precursors of polybrominated dibenzo-p-dioxins/ polybrominated dibenzofurans (PBDD/Fs). Recently, 2,3,7,8-TBDD/Fs and PBDEs have been detected in adipose tissue and blood in Japanese people. Food is naturally suspected. However, there is very few information on food contamination with those brominated compounds in Japan. Therefore, we measured the levels of PBDEs and PBDD/Fs in various fish samples, meal samples, and total diet study (TDS) food groups and estimated Japanese people's dietary intake of PBDD/Fs and PBDEs.

  10. Metabolism of polybrominated diphenyl ethers and tetrabromobisphenol A by fish liver subcellular fractions in vitro.

    Science.gov (United States)

    Shen, Mengnan; Cheng, Jie; Wu, Ruohan; Zhang, Shenghu; Mao, Liang; Gao, Shixiang

    2012-06-15

    Polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA) are two major flame retardants that accumulate in fish tissues and are potentially toxic. Their debrominated and oxidated derivatives were also reported in fish tissues although the sources of theses derivatives were unidentified. Our study was to determine whether PBDEs and TBBPA could be metabolized by fish liver subcellular fractions in vitro and to identify what types of metabolites were formed. Liver microsomes and S9 fractions of crucian carp (Carassius auratus) were exposed to 4,4'-dibromodiphenyl ether (BDE 15), 2,2',4,4'-tetrabromodiphenyl ether (BDE 47) or TBBPA solutions for 4h. Exposure of liver subcellular fractions to BDE 15 resulted in the formation of bromophenol and two monohydroxylated dibromodiphenyl ether metabolites. Neither in microsomes nor in S9 studies has revealed the presence of hydroxylated metabolites with BDE 47 exposure which indicated that the oxidation reactions in vitro were hindered by the increased number of bromine substituents on the PBDEs. TBBPA underwent an oxidative cleavage near the central carbon of the molecule, which led to the production of 2,6-dibromo-4-isopropyl-phenol and three unidentified metabolites. Another metabolite of TBBPA characterized as a hexa-brominated compound with three aromatic rings was also found in the liver subcellular fractions. These results suggest that the biotransformation of BDE 15 and TBBPA in fish liver is mediated by cytochrome P450 (CYP450) enzymes, as revealed by the formation of hydroxylated metabolites and oxidative bond cleavage products. Moreover, further studies on the identification of specific CYP450 isozymes involved in the biotransformation revealed that CYP1A was the major enzyme responsible for the biotransformation of BDE 15 and TBBPA in fish liver subcellular fractions and CYP3A4 also played a major role in metabolism of TBBPA. Copyright © 2012 Elsevier B.V. All rights reserved.

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

    International Nuclear Information System (INIS)

    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-, 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. - Highlights: ► Brominated flame retardants (BFRs) including PBDEs and alternates were measured. ► Exposure to BFRs is characterized from concentrations in participant vacuum bag dust. ► Exposure to PBDEs and

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

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Paula I. [Department of Environmental Health Sciences, University of Michigan, 1415 Washington Heights, Ann Arbor, MI 48109 (United States); Stapleton, Heather M. [Nicholas School of the Environment, Box 90328, Duke University, Durham, NC 27708 (United States); Mukherjee, Bhramar [Department of Biostatistics, University of Michigan, 1415 Washington Heights, Ann Arbor, MI 48109 (United States); Hauser, Russ [Department of Environmental Health, Harvard School of Public Health, 677 Huntington Ave., Boston, MA 02115 (United States); Meeker, John D., E-mail: meekerj@umich.edu [Department of Environmental Health Sciences, University of Michigan, 1415 Washington Heights, Ann Arbor, MI 48109 (United States)

    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. - Highlights: ► Brominated flame retardants (BFRs) including PBDEs and alternates were measured. ► Exposure to BFRs is characterized from concentrations in participant vacuum bag dust. ► Exposure to PBDEs and

  13. Detection of novel brominated flame retardants (NBFRs in the urban soils of Melbourne, Australia

    Directory of Open Access Journals (Sweden)

    Thomas J. McGrath

    2017-03-01

    Full Text Available A range of brominated flame retardants (BFRs have been incorporated into polymeric materials like plastics, electronic equipment, foams and textiles to prevent fires. The most common of these, polybrominated diphenyl ethers (PBDEs, have been subject to legislated bans and voluntary withdrawal by manufacturers in North America, Europe and Australia over the past decade due to long-range atmospheric transport, persistence in the environment, and toxicity. Evidence has shown that replacement novel brominated flame retardants (NBFRs are released to the environment by the same mechanisms as PBDEs and share similar hazardous properties. The objective of the current research was to characterize soil contamination by NBFRs in the urban soils of Melbourne, Australia. A variety of industrial and non-industrial land-uses were investigated with the secondary objective of determining likely point sources of pollution. Six NBFRs; pentabromotoluene (PBT, pentabromoethylbenzene (PBEB, hexabromobenzene (HBB, 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB, 1,2-bis(2,4,6-tribromophenoxyethane (BTBPE and decabromodiphenyl ethane (DBDPE were measured in 30 soil samples using selective pressurized liquid extraction (S-PLE and gas chromatography coupled to triple quadrupole mass spectrometry (GC-MS/MS. NBFRs were detected in 24/30 soil samples with Σ5NBFR concentrations ranging from nd-385 ng/g dw. HBB was the most frequently detected compound (14/30, while the highest concentrations were observed for DBDPE, followed by BTBPE. Electronic waste recycling and polymer manufacturing appear to be key contributors to NBFR soil contamination in the city of Melbourne. A significant positive correlation between Σ8PBDEs and Σ5NBFR soil concentrations was observed at waste disposal sites to suggest that both BFR classes are present in Melbourne's waste streams, while no association was determined among manufacturing sites. This research provides the first account of NBFRs

  14. Direct Vapor-Phase Bromination of Multiwall Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Ilya Mazov

    2012-01-01

    Full Text Available We present the simple procedure of the vapor-phase bromination of multiwall carbon nanotubes (MWNTs at moderate temperatures. MWNTs with average diameter 9±3 nm were treated with Br2 vapors at 250°C to produce Br-functionalized product. Transmission electron microscopy analysis was used to prove low damage of MWNT walls during bromination. X-ray photoelectron spectroscopy (XPS and differential thermal analysis (DTA were used to investigate chemical composition of the surface of initial and brominated nanotubes. The experimental results show that the structure of MWNTs is not affected by the bromination process and the total amount of Br-containing surface functions reaches 2.5 wt. %. Electrophysical properties of initial and brominated MWNTs were investigated showing decrease of conductivity for functionalized sample. Possible mechanism of the vapor-phase bromination via surface defects and oxygen-containing functional groups was proposed according to data obtained. Additional experiments with bromination of annealed low-defected MWNTs were performed giving Br content a low as 0.75 wt. % proving this hypothesis.

  15. An Exposure Assessment of Polybrominated Diphenyl Ethers ...

    Science.gov (United States)

    EPA announced the availability of the final report, An Exposure Assessment of Polybrominated Diphenyl Ethers. This report provides a comprehensive assessment of the exposure of Americans to this class of persistent organic pollutants. Individual chapters in this document address: the production, use, and lifecycle of PBDEs; environmental fate; environmental levels; and human exposure. This final report addresses the exposure assessment needs identified in the OPBDE Workgroup project plan. It provides a comprehensive assessment of the exposure of Americans to this class of persistent organic pollutants. Individual chapters in this document address: the production, use, and lifecycle of PBDEs; environmental fate; environmental levels; and human exposure.

  16. Hydrogen-Bromine Flow Battery: Hydrogen Bromine Flow Batteries for Grid Scale Energy Storage

    Energy Technology Data Exchange (ETDEWEB)

    None

    2010-10-01

    GRIDS Project: LBNL is designing a flow battery for grid storage that relies on a hydrogen-bromine chemistry which could be more efficient, last longer and cost less than today’s lead-acid batteries. Flow batteries are fundamentally different from traditional lead-acid batteries because the chemical reactants that provide their energy are stored in external tanks instead of inside the battery. A flow battery can provide more energy because all that is required to increase its storage capacity is to increase the size of the external tanks. The hydrogen-bromine reactants used by LBNL in its flow battery are inexpensive, long lasting, and provide power quickly. The cost of the design could be well below $100 per kilowatt hour, which would rival conventional grid-scale battery technologies.

  17. An experimental and theoretical method for determination of standard electrode potential for the redox couple diphenyl sulfone/diphenyl sulfide

    Science.gov (United States)

    Song, Y. Z.; Wei, K. X.; Lv, J. S.

    2013-12-01

    DFT calculations were performed for diphenyl sulfide and diphenyl sulfone. The electrochemistry of diphenyl sulfide on the gold electrode was investigated by cyclic voltammety and the results show that standard electrode potential for redox couple diphenyl sulfone/diphenyl sulfide is 1.058 V, which is consistent with that of 1.057 calculated at B3LYP/6-31++G( d, p)-IEFPCM level. The front orbit theory and Mulliken charges of molecular explain well on the oxidation of diphenyl sulfide in oxidative desulfurization. According to equilibrium theory the experimental equilibrium constant in the oxidative desulfurization of H2O2, is 1.17 × 1048, which is consistent with the theoretical equilibrium constant is 2.18 × 1048 at B3LYP/6-31++G( d, p)-IEFPCM level.

  18. Temporal trends of polychlorinated biphenyls, polybrominated diphenyl ethers, and perfluorinated compounds in Chinese sturgeon (Acipenser sinensis) eggs (1984-2008).

    Science.gov (United States)

    Jianxian, Sun; Hui, Peng; Jianying, Hu

    2015-02-03

    Because investigation on the temporal trends of persistent halogenated compounds (PHCs) is necessary to predict their future impacts on the environment and human health and evaluate the effectiveness of regulations on their production and usage, it is of concern to investigate annual temporal trends of PHCs in biota samples. This study examined the temporal trends of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and perfluorinated compounds (PFCs) in Chinese sturgeon (Acipenser sinensis) eggs over a period of 25 years (1984-2008), and 62 PCBs (19.2-1030 ng/g dw for total PCBs), 16 PBDEs (4.7-572 ng/g dw for total PBDEs), and 14 PFCs (26-46 ng/g dw for total PFCs) were detected. Although a decreasing temporal trend was observed for total PCBs with annual reduction rate of 3.4% (ρ = 0.005), a clear break point was observed around 1991, indicating their continuing emission in the 1980s in China. All major PBDEs showed increasing temporal trends, with annual change rates at 3.5-10.2% over the 25 years, but a sharp decreasing trend was observed after 2006, indicating a rapid response to the banning of PBDE usage in China in 2004. The greatest annual rate of increase was observed for BDE-28 (10.2%) followed by BDE-100 (7.7%), which would be due to metabolism input from higher brominated PBDEs. Significantly increasing temporal trends were observed for all PFCs, and the annual rates of increase were 7.9% and 5.9% for total perfluorinated carboxylic acids and perfluorooctanesulfonate (PFOS), respectively. A peak concentration for PFOS was observed in 1989, which may be related to the import history of PFCs in China. The present study is the first report of systematic temporal trends of PHCs in biota samples from China and shows that regulatory policy is needed to reduce their potential health and ecological risk in China considering the increasing temporal trends of PBDEs and PFCs.

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

    Science.gov (United States)

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

    2006-09-01

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

  20. 对称多溴代二苯醚类化合物的精确合成%Accurate synthesis of symmetrical polybrominated diphenyl ethers

    Institute of Scientific and Technical Information of China (English)

    崔凯; 沈宏; 苏长会; 马洁洁; 丁志远

    2016-01-01

    A series of symmetrical polybrominated diphenyliodonium trifluoromethanesulfonic were synthesized from brominated io-dobenzene and brominated benzene catalyzed by m-chloroperoxybenzoic acid and trifluoromethanesulfonic acid. Then Corresponding symmetrical polybrominated diphenyl ethers were accurately synthesized with them and brominated phenol in alkaline condition. The advantages of the procedure were:mild reaction condition,easy operation,simple after-treatment,high yield and purity of products.%用间氯过氧苯甲酸和三氟甲磺酸做酸性氧化体系,以溴代碘苯及溴苯合成了对称的溴代二苯基碘盐。再以其同溴代苯酚在碱性条件下反应,精确合成对称的多溴代二苯醚。此法合成目标化合物方法简便,反应条件温和,后处理简单,产品纯度好,收率高。

  1. Chlorine and bromine contents in tobacco and tobacco smoke

    International Nuclear Information System (INIS)

    Haesaenen, E.; Manninen, P.K.G.; Himberg, K.; Vaeaetaeinen, V.

    1990-01-01

    The chlorine and bromine contents in tobacco and tobacco smoke in both the particulate and gaseous phases were studied by neutron activation analysis. Eleven popular brands of western filter cigarettes were tested. Methyl chloride and methyl bromide concentrations were measured in the gaseous phase in two leading brands in Finland. The results suggest that the mainstream smoke from one cigarette conveys into the lungs about 150 μg chlorine and about 5 μg bromine. Probably most of the chlorine and bromine is in the form of organic compounds and the main components are methyl chloride and methyl bromide. (author) 14 refs.; 1 tab

  2. (Development of Bromine-77 from the LAMPF facility)

    Energy Technology Data Exchange (ETDEWEB)

    1989-01-01

    The objective of the work was to conduct the necessary studies required to evaluate the efficacy, potential benefit and role of bromine-77 labeled steroids in the detection and evaluation of treatment for hormone-dependent tumors. This report presents progress on the following tasks: An initial investigation concentrating on the radiobromination at carbon-6 or carbon-7 in selected simple steroids utilizing the nuclides, bromine-82 and bromine-77, analytical spectroscopy of radiolabeled compounds, and investigating the biodistribution, toxicology and tumor affinity of labeled agents.

  3. Formation of brominated phenolic contaminants from natural manganese oxides-catalyzed oxidation of phenol in the presence of Br(.).

    Science.gov (United States)

    Lin, Kunde; Song, Lianghui; Zhou, Shiyang; Chen, Da; Gan, Jay

    2016-07-01

    Brominated phenolic compounds (BPCs) are a class of persistent and potentially toxic compounds ubiquitously present in the aquatic environment. However, the origin of BPCs is not clearly understood. In this study, we investigated the formation of BPCs from natural manganese oxides (MnOx)-catalyzed oxidation of phenol in the presence of Br(-). Experiments at ambient temperature clearly demonstrated that BPCs were readily produced via the oxidation of phenol by MnOx in the presence of Br(-). In the reaction of MnOx sand with 0.213 μmol/L phenol and 0.34 mmol/L Br(-) for 10 min, more than 60% of phenol and 56% of Br(-) were consumed to form BPCs. The yield of BPCs increased with increasing concentrations of phenol and Br(-). Overall, a total of 14 BPCs including simple bromophenols (4-bromophenol, 2,4-dibromophenol, and 2,4,6-tribromophenol), hydroxylated polybrominated diphenyl ethers (OH-PBDEs), and hydroxylated polybrominated biphenyls (OH-PBBs) were identified. The production of BPCs increased with increasing concentrations of Br(-) or phenol. It was deduced that Br(-) was first oxidized to form active bromine, leading to the subsequent bromination of phenol to form bromophenols. The further oxidation of bromophenols by MnOx resulted in the formation of OH-PBDEs and OH-PBBs. In view of the ubiquity of phenol, Br(-), and MnOx in the environment, MnOx-mediated oxidation may play a role on the natural production of BPCs. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Accumulation of chlorinated and brominated persistent toxic substances (PTS) and their relationship to testosterone suppression in Norway rats from Japan

    Energy Technology Data Exchange (ETDEWEB)

    Takasuga, T.; Senthilkumar, K. [Shimadzu Techno-Research Inc. (Japan); Ishizuka, M.; Fujita, S. [Graduate School of Veterinary Medicine, Hokkaido Univ. (Japan); Tanikawa, R. [Inst. of Tech., Ikari Corp. (Japan)

    2004-09-15

    Contamination of chlorinated/brominated persistent toxic substances (PTS) such as polychlorinated, -dibenzo-p-dioxins (PCDDs), -dibenzofurans (PCDFs), -biphenyls (PCBs), - organochlorine pesticides (OCPs) {l_brace}e.g., aldrin, dieldrin, endrin, chlordane compounds [cis/transchlordane, cis/trans-nonachlor, oxychlordane, heptachlor, heptachlor epoxide], hexachlorobenzene (HCB), 2,2-bis(p-chlorophenyl)-1,1,1-trichloroethane (DDTs) and its metabolities [o,p/p,p'-DDD and DDE] and hexachlorocyclohexane (HCHs){r_brace} and -brominated diphenyl ethers (PBDEs) are considered to important class of chemicals due to persistence in nature, bioaccumulation potential and adverse health effects in wildlife and humans. Among South East Asian countries, Japan reported to contaminated with aforesaid chemicals with considerable amounts. There is no document reports contamination of PTS in wild animals, which in-habit near humans. Norway rat (NR) inhabits not only near human environment but also distributed worldwide. Especially, NR feeds on human waste and shelter in and around human environment and thus exposure of toxic contaminants in this animal considered to similar with those in humans. In addition, rats have unique physiology that match with humans (e.g., they have similar pathogens as humans have). Therefore, analysis of toxic contaminants in NR considered as indirect measure in humans. Considering those facts, in this study, we analyzed NR collected from urban area, rural area, waste dumping or land fill site and isolated remote island from Japan. Particularly several chlorinated and brominated organic contaminants such as PCDDs, PCDFs, PCBs, DDTs, HCHs, chlordane compounds, heptachlor, heptachlor epoxide, HCB, aldrin, dieldrin, endrin and PBDEs were analyzed in rat livers by isotope dilution technique using HRGC-HRMS. In addition, laboratory Wistar rats (WR) were used as control.

  5. Synthesis and characterization of sulfonated bromo-poly(2,6-dimethyl-1,4-phenylene oxide)-co-(2,6-diphenyl-1,4-phenylene oxide) copolymer as proton exchange membrane

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Young-Gi; Seo, Dong-Wan; Lim, Young-Don; Jin, Hyun-Mi; Islam Mollah, M.S. [Department of Applied Chemistry, Konkuk University/RIC-ReSEM Chungju, 322 Danwol-dong, Chungbuk 380-701 (Korea, Republic of); Ur, Soon-Chul [Department of Materials Science and Engineering/RIC-ReSEM, Chungju National University, Chungju, Chungbuk 380-702 (Korea, Republic of); Pyun, Sang-Yong [Department of Chemistry, Pukyong National University, Pusan 608-737 (Korea, Republic of); Kim, Whan-Gi, E-mail: wgkim@kku.ac.k [Department of Applied Chemistry, Konkuk University/RIC-ReSEM Chungju, 322 Danwol-dong, Chungbuk 380-701 (Korea, Republic of)

    2010-01-25

    Novel polymer electrolyte membranes containing the sulfonic acid groups attached on polymer backbone and side group simultaneously were synthesized. The bromo-poly(2,6-dimethyl-1,4-phenylene oxide)-co-(2,6-diphenyl-1,4-phenylene oxide) copolymer (BrcoPPO) was prepared by oxidative coupling polymerization with 2,6-dimethyl phenol, 2,6-diphenyl phenol, CuCl(I) and pyridine, and followed by bromination with bromine. Copolymer was maintained in 2,6-diphenyl phenol 10 mol% and 2,6-dimethyl phenol 90 mol%. Sulfonation of BrcoPPO (S-BrcoPPO) was carried out in a chlorobenzene solvent using chlorosulfonic acid. The polymeric membranes were cast from dimethylsulfoxide solution. The membranes were studied by nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymers with water and methanol. S-BrcoPPO membranes exhibited proton conductivities from 2.3 x 10{sup -3} to 1.4 x 10{sup -2} S/cm, water uptake from 7.00 to 49.43%, IEC from 0.58 to 1.38 mequiv./g, methanol permeability from 1.9 x 10{sup -7} to 3.5 x 10{sup -7} cm{sup 2}/S.

  6. Magnetic trapping of cold bromine atoms.

    Science.gov (United States)

    Rennick, C J; Lam, J; Doherty, W G; Softley, T P

    2014-01-17

    Magnetic trapping of bromine atoms at temperatures in the millikelvin regime is demonstrated for the first time. The atoms are produced by photodissociation of Br2 molecules in a molecular beam. The lab-frame velocity of Br atoms is controlled by the wavelength and polarization of the photodissociation laser. Careful selection of the wavelength results in one of the pair of atoms having sufficient velocity to exactly cancel that of the parent molecule, and it remains stationary in the lab frame. A trap is formed at the null point between two opposing neodymium permanent magnets. Dissociation of molecules at the field minimum results in the slowest fraction of photofragments remaining trapped. After the ballistic escape of the fastest atoms, the trapped slow atoms are lost only by elastic collisions with the chamber background gas. The measured loss rate is consistent with estimates of the total cross section for only those collisions transferring sufficient kinetic energy to overcome the trapping potential.

  7. Tetrameric DABCO™-Bromine: an Efficient and Versatile Reagent ...

    African Journals Online (AJOL)

    NJD

    Reagent for Bromination of Various Organic Compounds. Majid M. Heravi,a* ... aDepartment of Chemistry, School of Sciences, Azzahra University, Vanak, Tehran, Iran. bChemistry ... Synthesis of "-bromo ketones and nitriles has also been ...

  8. Bromine pretreated chitosan for adsorption of lead (II) from water

    Indian Academy of Sciences (India)

    isotherm and maximum sorption capacity of 30% bromine pretreated chitosan sorbent was 1·755 g/kg with 85–. 90% lead .... C by applying Lagergren first ... Lead (II) ions concentrations were determined by using an .... following equation.

  9. The bromine content of some Dutch crops and fruits

    International Nuclear Information System (INIS)

    Admiraal, P.; Kok, H.A.; Das, H.A.; Hoede, D.; Zonderhuis, J.

    1975-09-01

    The natural bromine-content of Dutch potatoes, vegetables and fruits was determined by instrumental neutron activation analysis. Results are given for 348 samples divided over 20 crops and fruits. The data are compared to values published in the literature

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

    Energy Technology Data Exchange (ETDEWEB)

    Sühring, Roxana, E-mail: roxana.suehring@hzg.de [Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research, Institute of Coastal Research, Department for Environmental Chemistry, Max-Planck-Strasse 1, 21502 Geesthacht (Germany); Leuphana University Lüneburg, Institute of Sustainable and Environmental Chemistry, Scharnhorststraße 1, 21335 Lüneburg (Germany); Freese, Marko [Thünen Institute of Fisheries Ecology, Palmaille 9, 22767 Hamburg (Germany); Schneider, Mandy [Leuphana University Lüneburg, Institute of Sustainable and Environmental Chemistry, Scharnhorststraße 1, 21335 Lüneburg (Germany); Schubert, Sophia; Pohlmann, Jan-Dag [Thünen Institute of Fisheries Ecology, Palmaille 9, 22767 Hamburg (Germany); Alaee, Mehran [Water Science and Technology Directorate, Environment Canada, Burlington, Ontario, L7R4A6 Canada (Canada); Wolschke, Hendrik [Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research, Institute of Coastal Research, Department for Environmental Chemistry, Max-Planck-Strasse 1, 21502 Geesthacht (Germany); Leuphana University Lüneburg, Institute of Sustainable and Environmental Chemistry, Scharnhorststraße 1, 21335 Lüneburg (Germany); Hanel, Reinhold [Thünen Institute of Fisheries Ecology, Palmaille 9, 22767 Hamburg (Germany); Ebinghaus, Ralf [Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research, Institute of Coastal Research, Department for Environmental Chemistry, Max-Planck-Strasse 1, 21502 Geesthacht (Germany); Marohn, Lasse [Thünen Institute of Fisheries Ecology, Palmaille 9, 22767 Hamburg (Germany)

    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{sup −1} ww for sum Dechlorane metabolites (DPMA, aCL{sub 10}DP, aCl{sub 11}DP) to 2.1 ng g{sup −1} ww for TBA in eggs, 0.001 ng g{sup −1} ww for Dechlorane metabolites to 9.4 ng g{sup −1} ww for TBA in gonads and 0.002 ng g{sup −1} ww for Dechlorane metabolites to 54 ng g{sup −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

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

    International Nuclear Information System (INIS)

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

    2015-01-01

    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, aCL 10 DP, aCl 11 DP) 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

  12. Brominated flame retardants and organochlorine pollutants in eggs of little owls (Athene noctua) from Belgium

    International Nuclear Information System (INIS)

    Jaspers, Veerle; Covaci, Adrian; Maervoet, Johan; Dauwe, Tom; Voorspoels, Stefan; Schepens, Paul; Eens, Marcel

    2005-01-01

    Residues of brominated diphenylethers (PBDEs), organochlorinated pesticides (OCPs) and polychlorinated biphenyls (PCBs) were measured in 40 eggs of little owls (Athene noctua), a terrestrial top predator from Belgium. The major organohalogens detected were PCBs (median 2,600 ng/g lipid, range 790-23000 ng/g lipid). PCB 153,138/163, 170, 180 and 187 were the predominant congeners and constituted 71% of total sum PCBs. PBDEs were measurable in all samples, but their concentrations were much lower than for PCBs, with a range from 29-572 ng/g lipid (median 108 ng/g lipid). The most prevalent PBDE congeners in little owl egg samples were BDE 47, 99 and 153. This profile differs from the profile in marine bird species, for which BDE 47 was the dominant congener, indicating that terrestrial birds may be more exposed to higher brominated BDE congeners than marine birds. The fully brominated BDE 209 could be detected in one egg sample (17 ng/g lipid), suggesting that higher brominated BDEs may accumulate in terrestrial food chains. Brominated biphenyl (BB) 153 was determined in all egg samples, with levels ranging from 0.6 to 5.6 ng/g lipid (median 1.3 ng/g lipid). Additionally, hexabromocyclododecane (HBCD) could be identified and quantified in only two eggs at levels of 20 and 50 ng/g lipid. OCPs were present at low concentrations, suggesting a rather low contamination of the sampled environment with OCPs (median concentrations of sum DDTs: 826 ng/g lipid, sum chlordanes: 1,016 ng/g lipid, sum HCHs: 273 ng/g lipid). Hexachlorobenzene (HCB) and octachlorostyrene (OCS) were also found at low median levels of 134 and 3.4 ng/g lipid, respectively. Concentrations of most analytes were significantly higher in eggs collected from deserted nests in comparison to addled (unhatched) eggs, while eggshell thickness did not differ between deserted and addled eggs. No significant correlations were found between eggshell thickness and the analysed organohalogens. - PBDEs are measurable

  13. Induction of Adipocyte Differentiation by Polybrominated Diphenyl Ethers (PBDEs) in 3T3-L1 Cells

    Science.gov (United States)

    Tung, Emily W. Y.; Boudreau, Adèle; Wade, Michael G.; Atlas, Ella

    2014-01-01

    Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants that were extensively used in commercial products. PBDEs are ubiquitous environmental contaminants that are both lipophilic and bioaccumulative. Effects of PBDEs on adipogenesis were studied in the 3T3-L1 preadipocyte cell model in the presence and absence of a known adipogenic agent, dexamethasone (DEX). A PBDE mixture designed to mimic body burden of North Americans was tested, in addition to the technical mixture DE-71 and the individual congener BDE-47. The mixture, DE-71, and BDE-47 all induced adipocyte differentiation as assessed by markers for terminal differentiation [fatty acid binding protein 4 (aP2) and perilipin] and lipid accumulation. Characterization of the differentiation process in response to PBDEs indicated that adipogenesis induced by a minimally effective dose of DEX was enhanced by these PBDEs. Moreover, C/EBPα, PPARγ, and LXRα were induced late in the differentiation process. Taken together, these data indicate that adipocyte differentiation is induced by PBDEs; they act in the absence of glucocorticoid and enhance glucocorticoid-mediated adipogenesis. PMID:24722056

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

    Science.gov (United States)

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

    2013-03-01

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

  15. A study of the presence of brominated flame retardants in Australian fauna

    Energy Technology Data Exchange (ETDEWEB)

    Symons, R.; Burniston, D.; Piro, N.; Stevenson, G.; Yates, A. [Australian Government Analytical Laboratories, Sydney (Australia)

    2004-09-15

    Brominated flame retardants, in particular polybrominated diphenyl ethers (PBDEs) gained prominence in the late nineties when Noren et al. reported an exponential increase in PBDE levels found in Swedish mothers milk over a quarter of a century period with an associated decrease in levels of dioxin-like compounds. PBDEs have since become exceptionally widely studied being detected in most environmental compartments and food as well as human tissues. Only limited information on the distribution if PBDEs is available for the Southern Hemisphere, however, elevated levels of PBDEs in pork fat were detected during the routine screening for organochlorine pesticide residues. More recently an investigation of breast milk for PBDE levels also demonstrated that levels were comparable with those in the Northern Hemisphere. BFRs are not manufactured in Australia but it has been estimated that over 500 tonnes are imported yearly of which 340 tonnes are PBDEs. In addition, the amount of PBDEs that are contained in imported articles used both in domestic and industrial applications is unknown. In this paper, we report levels of PBDEs in a range of different Australian fauna that show that these POPs have indeed become widely distributed both in terms of the types of the fauna but also the levels determined.

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

    Science.gov (United States)

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

    2016-12-20

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

  17. Occupational exposure to polybrominated diphenyl ethers (PBDEs) and other flame retardant foam additives at gymnastics studios: Before, during and after the replacement of pit foam with PBDE-free foams.

    Science.gov (United States)

    Ceballos, Diana M; Broadwater, Kendra; Page, Elena; Croteau, Gerry; La Guardia, Mark J

    2018-07-01

    Coaches spend long hours training gymnasts of all ages aided by polyurethane foam used in loose blocks, mats, and other padded equipment. Polyurethane foam can contain flame retardant additives such as polybrominated diphenyl ethers (PBDEs), to delay the spread of fires. However, flame retardants have been associated with endocrine disruption and carcinogenicity. The National Institute for Occupational Safety and Health (NIOSH) evaluated employee exposure to flame retardants in four gymnastics studios utilized by recreational and competitive gymnasts. We evaluated flame retardant exposure at the gymnastics studios before, during, and after the replacement of foam blocks used in safety pits with foam blocks certified not to contain several flame retardants, including PBDEs. We collected hand wipes on coaches to measure levels of flame retardants on skin before and after their work shift. We measured flame retardant levels in the dust on window glass in the gymnastics areas and office areas, and in the old and new foam blocks used throughout the gymnastics studios. We found statistically higher levels of 9 out of 13 flame retardants on employees' hands after work than before, and this difference was reduced after the foam replacement. Windows in the gymnastics areas had higher levels of 3 of the 13 flame retardants than windows outside the gymnastics areas, suggesting that dust and vapor containing flame retardants became airborne. Mats and other padded equipment contained levels of bromine consistent with the amount of brominated flame retardants in foam samples analyzed in the laboratory. New blocks did not contain PBDEs, but did contain the flame retardants 2-ethylhexyl 2,3,4,5-tetrabromobenzoate and 2-ethylhexyl 2,3,4,5-tetrabromophthalate. We conclude that replacing the pit foam blocks eliminated a source of PBDEs, but not 2-ethylhexyl 2,3,4,5-tetrabromobenzoate and 2-ethylhexyl 2,3,4,5-tetrabromophthalate. We recommend ways to further minimize employee exposure

  18. Role of heme in bromine-induced lung injury

    Science.gov (United States)

    Lam, Adam; Vetal, Nilam; Matalon, Sadis; Aggarwal, Saurabh

    2016-01-01

    Bromine (Br2) gas inhalation poses an environmental and occupational hazard resulting in high morbidity and mortality. In this review, we underline the acute lung pathology (within 24 hours of exposure) and potential therapeutic interventions that may be utilized to mitigate Br2-induced human toxicity. We will discuss our latest published data, which suggests that an increase in heme-dependent tissue injury underlies the pathogenesis of Br2 toxicity. Our study was based on previous findings that demonstrated that Br2 upregulates the heme-degrading enzyme heme oxygenase-1 (HO-1), which converts toxic heme into billiverdin. Interestingly, following Br2 inhalation, heme levels were indeed elevated in bronchoalveolar lavage fluid, plasma, and whole lung tissue in C57BL/6 mice. High heme levels correlated with increased lung oxidative stress, lung inflammation, respiratory acidosis, lung edema, higher airway resistance, and mortality. However, therapeutic reduction of heme levels, by either scavenging with hemopexin or degradation by HO-1, improved lung function and survival. Therefore, heme attenuation may prove a useful adjuvant therapy to treat patients after Br2 exposure. PMID:27244263

  19. Dietary exposure assessment of Chinese population to tetrabromobisphenol-A, hexabromocyclododecane and decabrominated diphenyl ether: Results of the 5th Chinese Total Diet Study

    International Nuclear Information System (INIS)

    Shi, Zhixiong; Zhang, Lei; Zhao, Yunfeng; Sun, Zhiwei; Zhou, Xianqing; Li, Jingguang; Wu, Yongning

    2017-01-01

    Based on the 5th Chinese Total Diet Study (TDS) carried out in 2011, the dietary exposure of Chinese population to three currently used brominated flame retardants (BFRs), tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD) and decabrominated diphenyl ether (BDE-209), was estimated and the related health risks were assessed. Levels of the three BFRs were determined in 80 composite samples from four animal-origin food groups. The average levels of BFRs in various food groups ranged from 0.671 to 5.76 ng/g lipid weight (lw). The levels of TBBPA were lower than those of HBCD but higher than those of BDE-209. Moreover, average contamination levels of TBBPA and HBCD in TDS 2011 were found to be 3 to 30 times higher than those observed in TDS 2007 in the four food groups, indicating an increase in TBBPA and HBCD in the environment during 2007–2011. The average estimated daily intakes (EDIs) of TBBPA, HBCD and BDE-209 via food consumption for a “standard Chinese man” were 1.34, 1.51 and 0.96 ng/kg bw/day, respectively. Meat and meat products were found to be the major contributor to the daily dietary intake because the consumption of meat and meat products were significantly higher than that of other food groups in China. In comparison, the levels and EDIs of BFRs in this study were found to be higher than those in most studies worldwide. However, the large margin of exposure (MOE), with at least 1.1 × 10 5 calculated following the European Food Safety Authority (EFSA) approach, indicates that the estimated dietary exposure to these three BFRs is unlikely to raise significant health concerns. In addition, a comparison between the contamination levels of TBBPA, HBCD, BDE-209 and some novel BFRs in food samples from TDS 2011 indicated an obvious shift in the industrial production and usage pattern between PBDE and non-PBDE BFRs in China. - Highlights: • In a national survey, TBBPA, HBCD and BDE-209 were measured in food composites collected from 20

  20. AIRBORNE POLYBROMINATED DIPHENYL ETHERS IN A COMPUTER CLASSROOM OF COLLEGE IN TAIWAN

    Directory of Open Access Journals (Sweden)

    F. H. Chang ، C. R. Yang ، C. Y. Tsai ، W. C. Lin

    2009-04-01

    Full Text Available This study characterized the airborne exposure of students to thirty polybrominated diphenyl ether congeners inside and outside a computer classroom in a southern Taiwan college. Arithmetic mean values of total indoor and outdoor polybrominated diphenyl ether concentrations were 125.0 pg/m3 (89.8 to 203.9 pg/m3 and 110.3 pg/m3 (83.5 to 157.0 pg/m3, respectively. Total indoor polybrominated diphenyl ether concentrations were one order of magnitude lower than those detected in homes in Birmingham, United Kingdom and in Ottawa, Canada but were several times higher than those measured in the ambient air in Ottawa, Canada and from the Bohai Sea to the Arctic. The five highest indoor concentrations of polybrominated diphenyl ether congeners were decabromodiphenyl ether (23.0 pg/m3, 4,4’-dibromodiphenyl ether (15.9 pg/m3, 2,2’,3,4,4’,5,5’,6-octabromodiphenyl ether (10.6 pg/m3, 2,4-dibromodiphenyl ether (10.3 pg/m3 and 2,2’,3,4,4’,5’,6-heptabromodiphenyl ether (10.0 pg/m3. Although indoor and outdoor total polybrominated diphenyl ether concentrations did not significantly differ, the indoor concentrations of 2,4-dibromodiphenyl ether, 2,2’,4-tribromodiphenyl ether, 2,4,4’-tribromodiphenyl ether, 2,2’,4,5’-tetrabromodiphenyl ether and 2,3’,4’,6-tetrabromodiphenyl ether were significantly higher than their outdoor concentrations. This study suggests the following measures: 1 to increase the air exchange rate and open classroom doors and windows for several minutes before classes to reduce indoor PBDE concentrations; 2 to reduce polybrominated diphenyl ether emissions from new devices, it’s better to use computer-related products that meet the Restriction of Hazardous Substances Directive adopted by the European Union.

  1. Sorption-desorption behavior of polybrominated diphenyl ethers in soils

    International Nuclear Information System (INIS)

    Olshansky, Yaniv; Polubesova, Tamara; Vetter, Walter; Chefetz, Benny

    2011-01-01

    Polybrominated diphenyl ethers (PBDEs) are flame retardants that are commonly found in commercial and household products. These compounds are considered persistent organic pollutants. In this study, we used 4,4'-dibromodiphenyl ether (BDE-15) as a model compound to elucidate the sorption and desorption behavior of PBDEs in soils. The organic carbon-normalized sorption coefficient (K OC ) of BDE-15 was more than three times higher for humin than for bulk soils. However, pronounced desorption hysteresis was obtained mainly for bulk soils. For humin, increasing concentration of sorbed BDE-15 resulted in decreased desorption. Our data illustrate that BDE-15 and probably other PBDEs exhibit high sorption affinity to soils. Moreover, sorption is irreversible and thus PBDEs can potentially accumulate in the topsoil layer. We also suggest that although humin is probably a major sorbent for PBDEs in soils, other humic materials are also responsible for their sequestration. - Highlights: → BDE-15 exhibited pronounced desorption hysteresis. → BDE-15 sowed higher sorption affinity to humin as compared to the bulk soils. → Sequestration of PBDEs depends on soil organic matter constitutes other than humin. - Pronounced desorption hysteresis was observed for BDE-15 in natural soils.

  2. Spatial trends of polybrominated diphenyl ether (PBDE) congeners

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Spatial trends of polybrominated diphenyl ether (PBDE) congeners were analyzed in young of the year bluefish collected along the U.S. Atlantic coastline from...

  3. The geochemistry of stable chlorine and bromine isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Eggenkamp, Hans [Onderzock and Beleving, Bussum (Netherlands)

    2014-11-01

    First book solely dedicated to the geochemistry of chlorine and bromine isotopes. Detailed description of analytical techniques, including their advantages and disadvantages. Indication of research fields where measurement of these isotopes is especially useful. This book provides detailed information on the history, analysis and applications of chlorine and bromine isotope geochemistry. Chlorine and bromine are geochemically unique as they prefer to exist as single charged negative ions. For this reason isotope fractionation reflects mostly processes that are not related to changes in the redox state and this fractionation is generally modest. The book will describe the processes that are most easily detected using these isotopes. Also isotope variations, and processes that cause them, measured in oxidised species such as perchlorates and in organic molecules will be described in this book.

  4. Sodium, Iodine and Bromine in Polar Ice Cores

    DEFF Research Database (Denmark)

    Maffezzoli, Niccolo

    Abstract: This research focuses on sodium, bromine and iodine in polar ice cores, with the aim of reviewing and advancing their current understanding with additional measurements and records, and investigating the connections of these tracers with sea ice and their feasibility as sea ice indicators...... with a description of the main analytic al techniques used to measure ionic and elemental species in ice cores. Chapter 4 introduces sodium, bromine and iodine with a theoretical perspective and a particular focus on their connections with sea ice. Some of the physical and chemical properties that are believed...... back trajectory analyses of the past 17 years. The results identify the aerosol source area influencing the Renland ice cap, a result necessary for the interpretation of impurity records obtained from the ice core. Chapter 6 reviews the published ice/snow measurements of bromine and iodine at polar...

  5. PIXE analysis of remaining bromine in fumigated old manuscripts and books

    International Nuclear Information System (INIS)

    Kohno, M.; Yoshida, K.; Moritani, K.; Naito, M.; Enami, K.; Kasajima, H.; Takada, J.; Matsushita, R.

    1999-01-01

    Buddhist scriptures in Reeky University Library have been fumigated regularly for protecting them from vermin. Methyl bromide (CH 3 Br) had been used there till 1985. In order to examine whether the chemical remains on the fumigated objects or not, paper fragments of old manuscripts and books, modern paper placed together with them, and non-fumigated ones were analyzed by PIXE. The bromine concentration of fumigated paper was more than from several tens to several hundreds times higher than non-fumigated ones. (author)

  6. An Efficient and Facile Methodology for Bromination of Pyrimidine and Purine Nucleosides with Sodium Monobromoisocyanurate (SMBI

    Directory of Open Access Journals (Sweden)

    Roger Stromberg

    2013-10-01

    Full Text Available An efficient and facile strategy has been developed for bromination of nucleosides using sodium monobromoisocyanurate (SMBI. Our methodology demonstrates bromination at the C-5 position of pyrimidine nucleosides and the C-8 position of purine nucleosides. Unprotected and also several protected nucleosides were brominated in moderate to high yields following this procedure.

  7. Brominated flame retardants in the Arctic. An overview of spatial and temporal trends

    Energy Technology Data Exchange (ETDEWEB)

    Wit, C de [Institute of Applied Environmental Research, Stockholm (Sweden); Alaee, M; Muir, D [National Water Research Institute, Burlington, MA (United States)

    2004-09-15

    The Stockholm Convention on Persistent Organic Pollutants (POPs), which entered into force on May 17, 2004, includes wording that chemicals with the characteristics of POPs are those found in locations ''distant from sources'' and those for which ''monitoring data showing that long-range environmental transport of the chemical may have occurred''. Thus, the Arctic has become an important indicator region for assessment of persistence and bioaccumulation. The Arctic environment is well suited as a region in which to evaluate POPs. Some regions of thee Arctic, particularly the Barents Sea area north of Norway and western Russia are relatively close to source regions of POPs. Cold conditions favor persistence of POPs relative to temperate or tropical environments. The presence of fourth level carnivores (e.g. polar bears and seabirds), and storage of lipid as an energy source, make Arctic food webs vulnerable to bioaccumulative chemicals. Indigenous people in the Arctic utilizing a traditional diet, which is high in nutritionally beneficial fat, results in their elevated exposure to some POPs. The first indication that brominated flame retardants (BFRs) were reaching the Arctic was the detection by Jansson et al. of lower molecular weight polybrominated diphenyl ethers (PBDEs) in Svalbard Brunnichfs guillemots (130 ng/g lipid weight) and ringed seals (40 ng/g lw) collected in 1981. Whitefish collected from Lake Storvindeln in 1986, a pristine mountain lake in the Swedish mountains near Ammarnas, had {sigma}PBDE levels of 26 ng/g lw. Despite these early findings, only recently have the spatial and temporal trends of BFRs been studied in detail in the Arctic. The purpose of this paper is to review the new data on BFRs in the Arctic and assess whether this information supports the view that PBDEs and other BFRs of similar molecular weight are POPs and potential global pollutants. This review is based on a recent assessment of POPs in the Arctic combined with newer data

  8. Brominated flame retardants in the Arctic. An overview of spatial and temporal trends

    Energy Technology Data Exchange (ETDEWEB)

    Wit, C. de [Institute of Applied Environmental Research, Stockholm (Sweden); Alaee, M.; Muir, D. [National Water Research Institute, Burlington, MA (United States)

    2004-09-15

    The Stockholm Convention on Persistent Organic Pollutants (POPs), which entered into force on May 17, 2004, includes wording that chemicals with the characteristics of POPs are those found in locations ''distant from sources'' and those for which ''monitoring data showing that long-range environmental transport of the chemical may have occurred''. Thus, the Arctic has become an important indicator region for assessment of persistence and bioaccumulation. The Arctic environment is well suited as a region in which to evaluate POPs. Some regions of thee Arctic, particularly the Barents Sea area north of Norway and western Russia are relatively close to source regions of POPs. Cold conditions favor persistence of POPs relative to temperate or tropical environments. The presence of fourth level carnivores (e.g. polar bears and seabirds), and storage of lipid as an energy source, make Arctic food webs vulnerable to bioaccumulative chemicals. Indigenous people in the Arctic utilizing a traditional diet, which is high in nutritionally beneficial fat, results in their elevated exposure to some POPs. The first indication that brominated flame retardants (BFRs) were reaching the Arctic was the detection by Jansson et al. of lower molecular weight polybrominated diphenyl ethers (PBDEs) in Svalbard Brunnichfs guillemots (130 ng/g lipid weight) and ringed seals (40 ng/g lw) collected in 1981. Whitefish collected from Lake Storvindeln in 1986, a pristine mountain lake in the Swedish mountains near Ammarnas, had {sigma}PBDE levels of 26 ng/g lw. Despite these early findings, only recently have the spatial and temporal trends of BFRs been studied in detail in the Arctic. The purpose of this paper is to review the new data on BFRs in the Arctic and assess whether this information supports the view that PBDEs and other BFRs of similar molecular weight are POPs and potential global pollutants. This review is based on a recent assessment of POPs

  9. Developmental exposure to low concentrations of two brominated flame retardants, BDE-47 and BDE-99, causes life-long behavioral alterations in zebrafish.

    Science.gov (United States)

    Glazer, Lilah; Wells, Corinne N; Drastal, Meghan; Odamah, Kathryn-Ann; Galat, Richard E; Behl, Mamta; Levin, Edward D

    2018-05-01

    Polybrominated diphenyl ethers (PBDEs) were widely used as flame retardants until the early 2000s, mainly in home furnishings and electronics. The persistence of PBDEs in the environment leads to continued ubiquitous exposure to low levels, with infants and children experiencing higher exposures than adults. Accumulating evidence suggest that low-level exposures during early life stages can affect brain development and lead to long-term behavioral impairments. We investigated the effects of zebrafish exposure to low doses of the two prominent PBDEs; 2,2',4,4',5,-Pentabromodiphenyl ether (BDE-99) and 2,2',4,4',-Tetrabromodiphenyl ether (BDE-47), during embryo-development on short- and long-term behavioral endpoints. We included the organophosphate pesticide chlorpyrifos (CPF) due to its well documented neurotoxicity across species from zebrafish to humans. Zebrafish embryos were exposed to the following individual treatments; 0.1% DMSO (vehicle control); 0.3μM CPF; 0.01, 0.03, 0.1, 0.3μM BDE-47; 0.003, 0.03, 0.3, 1, 3, 10, 20μM BDE-99 from 5 until 120h post fertilization (hpf). Low exposure levels were determined as those not causing immediate overt toxicity, and behavior assays were conducted in the low-level range. At 144 hpf the larvae were tested for locomotor activity. At approximately 6 months of age adult zebrafish were tested in a behavioral battery including assays for anxiety-related behavior, sensorimotor response and habituation, social interaction, and predator avoidance. In the short-term, larval locomotor activity was reduced in larvae treated with 0.3μM CPF and 0.1μM BDE-47. BDE-99 treatment caused non-monotonic dose effects, with 0.3μM causing hyperactivity and 1μM or higher causing hypoactivity. In the long-term, adult anxiety-related behavior was reduced in all treatments as measured in both the novel tank dive test and tap test. We show that exposure of zebrafish embryos to low concentrations of the brominated flame retardants BDE-47 and

  10. Phthalates and polybrominated diphenyl ethers in retail stores

    Science.gov (United States)

    Xu, Ying; Liang, Yirui; Urquidi, Jorge R.; Siegel, Jeffrey A.

    2014-04-01

    Retail stores contain a wide range of products that can emit a variety of indoor pollutants. Among these chemicals, phthalate esters and polybrominated diphenyl ethers (PBDEs) are two important categories, because they are extensively used as additives in consumer products and associated with serious health concerns. This study measured six phthalate and 14 PBDE compounds inside of 12 retail stores in Texas and Pennsylvania, U.S. Phthalates and PBDEs were widely found in the retail environment, indicating that they are ubiquitous indoor air pollutants. DEP, DnBP, and DEHP were the most abundant phthalates, with DnBP showing the highest concentration (0.23 ± 0.36 μg m-3). PBDEs were dominated by BDE-28, -99, and -209, having concentrations as high as 0.85 ± 1.99 ng m-3 (BDE-99). The levels of phthalates and PBDEs measured in this study are comparable to concentrations found in previous investigations of residential buildings, with phthalates showing lower concentrations and PBDEs exhibiting higher concentrations in retail stores. The potential co-occurrence of phthalates was not as strong as that of PBDEs, suggesting that phthalates might have more diverse sources. Whole building emission rates were calculated and showed similar patterns of variations as indoor air concentrations, suggestion the diversity of indoor sources of phthalates and PBDEs in retail environments.

  11. Body burdens of polybrominated diphenyl ethers among urban anglers.

    Science.gov (United States)

    Morland, Kimberly B; Landrigan, Philip J; Sjödin, Andreas; Gobeille, Alayne K; Jones, Richard S; McGahee, Ernest E; Needham, Larry L; Patterson, Donald G

    2005-12-01

    Polybrominated diphenyl ethers (PBDEs) have been widely used in the United States and worldwide as flame retardants. Recent PBDE production figures show that worldwide use has increased. To determine whether fish consumption is a source of PBDE exposure for humans, a cross-sectional epidemiologic study of New York and New Jersey urban anglers was conducted during the summers of 2001-2003. Frequency of local fish consumption was assessed by questionnaire, and blood samples for PBDE analysis were collected from 94 anglers fishing from piers on the lower Hudson River and Newark Bay. We analyzed PBDEs by gas chromatography-isotope dilution-high-resolution mass spectrometry. The congeners found in anglers' serum at the highest concentrations were, by International Union of Pure and Applied Chemistry numbers, BDE-47, BDE-153, and BDE-99. Anglers reporting consumption of local fish had higher, but nonstatistically significantly different, concentrations of PBDEs than did anglers who did not eat local fish. For some congeners (BDE-100 and BDE-153), we observed moderate dose-response relationships between serum PBDE levels and frequency of reported fish intake. These findings suggest that consumption of locally caught fish is not a major route of human exposure for this study population.

  12. Sex difference in polybrominated diphenyl ether concentrations of walleyes

    Science.gov (United States)

    Madenjian, Charles P.; Trombka, Autumn W.; Rediske, Richard R.; Jude, David J.; O'Keefe, James P.

    2012-01-01

    Polybrominated diphenyl ether (PBDE) concentrations were determined for mature male and mature female walleyes (Sander vitreus) sampled from the Saginaw Bay population during 2007. PBDE concentrations in prey fish caught in the Saginaw River, the primary tributary to Saginaw Bay, and in Saginaw Bay during 2005 and 2007 also were determined. Mature male and mature female walleyes averaged 70.3 ng/g and 24.8 ng/g, respectively, in ΣPBDE, which was equal to the sum of concentrations of six PBDE congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, and BDE-154). This sex difference was likely due to males spending more time in the Saginaw River system than females. Prey fish captured in the Saginaw River were roughly ten times higher in ΣPBDE than those caught in Saginaw Bay. BDE-47 was the predominant congener in both walleyes and prey fish, and this congener contributed about 50%, on average, to ΣPBDE. Congener profiles differed significantly between the two sexes of walleyes. In contrast, congener profiles of the prey fish did not differ significantly between the river-caught fish and the bay-caught fish. One plausible explanation for these congener profile results was that net trophic transfer efficiencies of PBDEs to walleyes from their prey were similar for all congeners except BDE-28, and that diet composition differed between the two sexes of walleyes.

  13. Nitrogenous disinfection byproducts in English drinking water supply systems: Occurrence, bromine substitution and correlation analysis.

    Science.gov (United States)

    Bond, Tom; Templeton, Michael R; Mokhtar Kamal, Nurul Hana; Graham, Nigel; Kanda, Rakesh

    2015-11-15

    Despite the recent focus on nitrogenous disinfection byproducts in drinking water, there is limited occurrence data available for many species. This paper analyses the occurrence of seven haloacetonitriles, three haloacetamides, eight halonitromethanes and cyanogen chloride in 20 English drinking water supply systems. It is the first survey of its type to compare bromine substitution factors (BSFs) between the haloacetamides and haloacetonitriles. Concentrations of the dihalogenated haloacetonitriles and haloacetamides were well correlated. Although median concentrations of these two groups were lower in chloraminated than chlorinated surface waters, median BSFs for both in chloraminated samples were approximately double those in chlorinated samples, which is significant because of the higher reported toxicity of the brominated species. Furthermore, median BSFs were moderately higher for the dihalogenated haloacetamides than for the haloacetonitriles. This indicates that, while the dihalogenated haloacetamides were primarily generated from hydrolysis of the corresponding haloacetonitriles, secondary formation pathways also contributed. Median halonitromethane concentrations were remarkably unchanging for the different types of disinfectants and source waters: 0.1 μg · mgTOC(-1) in all cases. Cyanogen chloride only occurred in a limited number of samples, yet when present its concentrations were higher than the other N-DBPs. Concentrations of cyanogen chloride and the sum of the halonitromethanes were not correlated with any other DBPs. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

    International Nuclear Information System (INIS)

    Canton, Rocio F.; Sanderson, J. Thomas; Nijmeijer, Sandra; Bergman, Ake; Letcher, Robert J.; Berg, Martin van den

    2006-01-01

    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 3 O) metabolites or analogues), TBBPA and brominated phenols (BPs) on the combined 17α-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 3 O group eliminated this cytotoxic effect, but CYP17 activity measured as DHEA production was still significantly inhibited. Other OH- or CH 3 O-PBDE analogues were used to elucidate possible structural properties behind this CYP17 inhibition and associated cytotoxicity, but no distinct structure activity relationship could be determined. These in vitro results indicate that OH and CH 3 O-PBDEs have potential to interfere with CYP17 activity for which the in vivo

  15. Levels of brominated flame retardants and other pesistent organic pollutants in breast milk samples from Limpopo province, South Africa

    Energy Technology Data Exchange (ETDEWEB)

    Darnerud, Per Ola, E-mail: poda@slv.se [Toxicology Division, National Food Administration, P.O. Box 622, SE-751 26 Uppsala (Sweden); Aune, Marie; Larsson, Lotta [Chemistry Division 2, National Food Administration, P.O. Box 622, SE-751 26 Uppsala (Sweden); Lignell, Sanna [Toxicology Division, National Food Administration, P.O. Box 622, SE-751 26 Uppsala (Sweden); Mutshatshi, Tshinanne; Okonkwo, Jonathan; Botha, Ben [Faculty of Science, Tshwane University of Technology, Pretoria (South Africa); Agyei, Nana [Department of Chemistry, Limpopo University, Medunsa (South Africa)

    2011-09-01

    The non-occupational exposure to brominated flame retardants, and other persistent organic pollutants (POPs) was studied by collecting human breast milk samples from mothers residing in Thohoyandou area, a rural district in the Limpopo Province, northern part of South Africa (SA). Of all collected samples to be analysed (n = 28), those with large enough milk volumes, (n = 14) were quantified for polybrominated diphenyl ethers (PBDEs) (9 congeners: BDE-28, 47, 66, 99, 100, 138, 153, 154, and 183) and hexabromocyclododecane (HBCD) on a GC equipped with dual capillary columns and dual electron-capture detectors (ECD). The levels of PBDE congeners (median sumBDE 1.3 ng/g of lipids) and of HBCD were not far from levels generally found in European studies, and this study may be the first report on the presence of PBDEs and HBCD in SA breast milk. On a congener basis, the finding of comparably high BDE-183 levels suggests a specific PBDE usage, or contamination situation in SA. Apart from BFRs, the high DDT levels found in the breast milk from this area (median and maximum sumDDT levels of about 4 600 and over 20 000 ng/g of lipids, respectively; n = 28) have earlier been reported. In addition, other POPs (PCBs, HCB and HCHs) were found in SA breast milk, at relatively low levels. To conclude, measurable levels of PBDEs and HBCD, and a specific BDE congener pattern, were found in breast milk from the Limpopo province, SA. A number of other POPs, including DDTs in high levels, were also present. - Highlights: {yields} Persistent organic pollutants (POPs) were analysed in South African breast milk. {yields} Focus of interest were brominated flame retardants (BRFs). {yields} Sampling area was the rural Limpopo Province, northern SA. {yields} Probably the first reported African data on BFRs (PBDEs, HBCD) in breast milk. {yields} Reported BFR data similar to European levels.

  16. A study of oxidative stress induced by two polybrominated diphenyl ethers in the rotifer Brachionus plicatilis.

    Science.gov (United States)

    Zhang, Jing; Wang, You; Sun, Kai-Ming; Fang, Kuan; Tang, Xuexi

    2016-12-15

    Polybrominated diphenyl ethers (PBDEs) are widely dispersed persistent organic pollutants in the marine ecosystem. However, their toxic mechanisms in marine organisms, especially invertebrates, remain poorly understood. Two common congeners of PBDEs, tetrabrominated diphenyl ether-47 (BDE-47) and decabrominated diphenyl ether-209 (BDE-209), were investigated. Their toxic mechanisms, with a focus on oxidative stress, were examined in rotifer Brachionus plicatilis. Overproduction of reactive oxygen species (ROS) was induced by two PBDEs. The expression of superoxide dismutase (SOD) mRNA was increased, suggesting SOD play a main role in ROS-scavenging. The intercellular concentrations of calcium ([Ca 2+ ] in ) and the expression of calmodulin (CaM) mRNA were increased. This indicates the calcium ion (Ca 2+ ) signaling channel is involved in PBDEs stress. Further analysis showed that the reproductive system might be the target site for toxicity of PBDEs. Moreover, high value of detection indexes in BDE-47 experimental groups suggested BDE-47 might cause higher oxidative damage than BDE-209 in rotifers. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

    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. Copyright © 2014. Published by Elsevier Ltd.

  18. Brominated Dioxins: Little-Known New Health Hazards - A Review

    Directory of Open Access Journals (Sweden)

    Piskorska-Pliszczyńska Jadwiga

    2014-10-01

    Full Text Available This article reviews the present state of the science concerning the polybrominated dibenzo-p-dioxins (PBDDs and dibenzofurans (PBDFs. Everywhere in the world people are exposed to anthropogenic origin chemicals. Some of them are long-lived organic compounds, which persist over the years in the environment. Persistent organic pollutants, such as organohalogen compounds, accumulate in environmental and biological compartments and have adverse effects on the health of humans and animals. Little is known about the brominated and mixed chloro/bromo dioxin and furans. Existing literature suggests that brominated dioxins and furans have similar toxicity profiles to their chlorinated analogues. The exposure data are extremely limited, showing a major data gap in estimating the potential environmental and health risk of these chemicals. The rapid increase in the use of brominated flame retardants (the main source of these pollutants has raised the level of concern over environmental and health damage from brominated dioxins and furans. It is likely that human as well as wildlife exposure to these contaminants will increase with their greater use. The findings reported here present strong evidence of the PBDDs and PBDFs as an emerging new class of contaminants.

  19. Ecotoxicity and biodegradability of new brominated flame retardants: A review

    Czech Academy of Sciences Publication Activity Database

    Ezechiáš, Martin; Covino, Stefano; Cajthaml, Tomáš

    2014-01-01

    Roč. 110, č. 2 (2014), s. 153-167 ISSN 0147-6513 R&D Projects: GA MŠk(CZ) EE2.3.30.0003; GA TA ČR TE01020218 Institutional support: RVO:61388971 Keywords : Ecotoxicity * brominated flame retardants * biodegradation * review Subject RIV: EE - Microbiology, Virology Impact factor: 2.762, year: 2014

  20. Novel and simple synthesis of brominated 1,10-phenanthrolines

    Czech Academy of Sciences Publication Activity Database

    Výprachtický, Drahomír; Kaňková, Dana; Pokorná, Veronika; Kmínek, Ivan; Dzhabarov, Vagif; Cimrová, Věra

    2014-01-01

    Roč. 67, č. 6 (2014), s. 915-921 ISSN 0004-9425 R&D Projects: GA ČR GAP106/12/0827; GA ČR(CZ) GA13-26542S Institutional support: RVO:61389013 Keywords : 1,10-phenanthroline * electrophilic aromatic substitution * bromination Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.558, year: 2014

  1. Self-assembled growth of nanostructural Ge islands on bromine ...

    Indian Academy of Sciences (India)

    bromine-passivated Si(111) surfaces at room temperature. AMAL K DAS1 ... Both the islands and the layer are nanocrystalline. This appears ..... coworkers estimated an activation energy of 0.59 ±0.1 eV for Ge diffusion on Si(100) and 0.45 eV ...

  2. Estimation of the residual bromine concentration after disinfection of cooling water by statistical evaluation.

    Science.gov (United States)

    Megalopoulos, Fivos A; Ochsenkuehn-Petropoulou, Maria T

    2015-01-01

    A statistical model based on multiple linear regression is developed, to estimate the bromine residual that can be expected after the bromination of cooling water. Make-up water sampled from a power plant in the Greek territory was used for the creation of the various cooling water matrices under investigation. The amount of bromine fed to the circuit, as well as other important operational parameters such as concentration at the cooling tower, temperature, organic load and contact time are taken as the independent variables. It is found that the highest contribution to the model's predictive ability comes from cooling water's organic load concentration, followed by the amount of bromine fed to the circuit, the water's mean temperature, the duration of the bromination period and finally its conductivity. Comparison of the model results with the experimental data confirms its ability to predict residual bromine given specific bromination conditions.

  3. Occurrence of polybrominated diphenyl ethers (PBDEs) in brown trout bile and liver from Swiss rivers

    Energy Technology Data Exchange (ETDEWEB)

    Hartmann, Paul C. [Eawag, Swiss Federal Institute of Aquatic Science and Technology, Ueberlandstrasse 133, P.O. Box 611, 8600 Duebendorf (Switzerland); Burkhardt-Holm, Patricia [Department of Environmental Science, University of Basel, Vesalgasse 1, 4051 Basel (Switzerland)]. E-mail: patricia.holm@unibas.ch; Giger, Walter [Eawag, Swiss Federal Institute of Aquatic Science and Technology, Ueberlandstrasse 133, P.O. Box 611, 8600 Duebendorf (Switzerland)]. E-mail: giger@eawag.ch

    2007-03-15

    The ranges of total polybrominated diphenyl ethers (PBDEs) in fish from four Swiss rivers were 0.8-240 ng/g in the bile and 16-7400 ng/g lipid in the liver. PBDE concentrations varied within each river and among the various rivers. Female fish tended to have higher concentrations in the liver, while the male fish had higher concentrations in the bile. From the resulting PBDE concentrations in fish it could not be infered that these contaminants contribute to the causes of the observed fish catch decline in Swiss rivers. - PBDEs with the most abundant BDE-47 were determined in brown trout bile and liver from Swiss rivers.

  4. Occurrence of polybrominated diphenyl ethers (PBDEs) in brown trout bile and liver from Swiss rivers

    International Nuclear Information System (INIS)

    Hartmann, Paul C.; Burkhardt-Holm, Patricia; Giger, Walter

    2007-01-01

    The ranges of total polybrominated diphenyl ethers (PBDEs) in fish from four Swiss rivers were 0.8-240 ng/g in the bile and 16-7400 ng/g lipid in the liver. PBDE concentrations varied within each river and among the various rivers. Female fish tended to have higher concentrations in the liver, while the male fish had higher concentrations in the bile. From the resulting PBDE concentrations in fish it could not be infered that these contaminants contribute to the causes of the observed fish catch decline in Swiss rivers. - PBDEs with the most abundant BDE-47 were determined in brown trout bile and liver from Swiss rivers

  5. Effects of polybrominated diphenyl ethers on steroidogenesis in rat Leydig cells.

    Science.gov (United States)

    Wang, Kai-Lee; Hsia, Shih-Min; Mao, I-Fang; Chen, Mei-Lien; Wang, Shyi-Wu; Wang, Paulus S

    2011-08-01

    Polybrominated diphenyl ethers (PBDEs) are brominated flame retardants that have been defined as major environmental pollutants. While previous studies have found that PBDEs may enhance the levels of sex-steroid hormones, their effects on testosterone secretion from rat Leydig cells are unclear. This study investigated the effects and mechanisms of PBDE-710, a mixture of tetra- and penta-PBDEs, on testosterone biosynthesis in rat Leydig cells. Leydig cells from adult male rats were challenged with different concentrations of PBDE-710 (0.5-15 ng/ml) to evaluate the effects on testosterone steroidogenesis. Concentrations of testosterone and of cAMP and pregnenolone in medium were measured by radioimmunoassay (RIA) and by enzyme-linked immunosorbent assay, respectively. Nuclear translocation of protein kinase A α (PKAα) was determined by immunofluorence assay and western blot assay, and the mRNA expression of steroidogenic acute regulatory protein (StAR) was analyzed by quantitative real-time polymerase chain reaction. In this in vitro study, PBDE-710 (5 or 15 ng/ml) increased basal testosterone secretion and cAMP production by 3- and 2-fold, respectively. The stimulatory effect was abolished by adenylyl cyclase inhibitor. Enzyme activity of CYP11A1, as determined by the pregnenolone concentration, was stimulated by PBDE-710 treatment. Furthermore, nuclear translocation of PKAα was increased by 20% and StAR gene expression was elevated by 4-fold after PBDE-710 treatment. These results suggest that low concentrations of PBDE-710 could stimulate testosterone secretion by acting directly on Leydig cells to activate the cAMP pathway and increase expression of StAR.

  6. Adsorption and sequential degradation of polybrominated diphenyl ethers with zerovalent iron

    International Nuclear Information System (INIS)

    Peng, Yu-Huei; Chen, Mei-kuei; Shih, Yang-hsin

    2013-01-01

    Highlights: • A detailed analysis in the removal mechanism of PBDEs by MZVI was conducted. • 13% of DBDE and 24% of BDE-3 in average were adsorbed on the surface of MZVI. • The adsorbed PBDEs on MZVI were also confirmed by FTIR spectroscopy. • MZVI continues the reductive debromination of PBDEs even after one month. •MZVI has great longevity to adsorb and degrade PBDE in the environment. -- Abstract: The widely used flame retardants, polybrominated diphenyl ethers (PBDEs), have been regulated owing to their persistence and toxicity. However, the high and increasing accumulation amount of PBDEs in the environment raises a big concern for public safety. In this study, the removal processes of decabromodiphenyl ether (BDE-209) and monobromodiphenyl ether (BDE-3) with microscale zerovalent iron (MZVI) were investigated to get better understandings for the removal mechanism based upon adsorption and degradation. The removal kinetics of both compounds was analyzed and revealed two-step kinetics: a fast removal step at the beginning of the reaction and a follow-up slow removal step. By-products generated during the entire process followed a stepwise sequence. The content of brominated compounds on the surface of MZVI was measured. About 10–20% of BDE-209 and 15–30% of BDE-3 were adsorbed on MZVI. The adsorption of BDE-209 and BDE-3 on MZVI was confirmed through the Fourier transform infrared spectroscopy. Surface adsorption of PBDEs on MZVI dominates the removal mechanism in the beginning and further debromination with MZVI was found. Finally, about 70% of BDE-209 and 60% of BDE-3 was degraded by MZVI within about one month. Our findings provide evidences for understanding the removal mechanism of PBDEs with MZVI and its great longevity on the PBDE degradation, which can facilitate the remediation design

  7. Separation of polybrominated diphenyl ethers in fish for compound-specific stable carbon isotope analysis

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Yan-Hong [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Graduate University of Chinese Academy of Sciences, Beijing, 100049 (China); Luo, Xiao-Jun, E-mail: luoxiaoj@gig.ac.cn [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Chen, Hua-Shan; Wu, Jiang-Ping; Chen, She-Jun; Mai, Bi-Xian [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China)

    2012-05-15

    A separation and isotopic analysis method was developed to accurately measure the stable carbon isotope ratios of polybrominated diphenyl ethers (PBDEs) with three to six substituted bromine atoms in fish samples. Sample extracts were treated with concentrated sulfuric acid to remove lipids, purified using complex silica gel column chromatography, and finally processed using alumina/silica (Al/Si) gel column chromatography. The purities of extracts were verified by gas chromatography and mass spectrometry (GC-MS) in the full-scan mode. The average recoveries of all compounds across the purification method were between 60% and 110%, with the exception of BDE-154. The stable carbon isotopic compositions of PBDEs can be measured with a standard deviation of less than 0.5 Per-Mille-Sign . No significant isotopic fraction was found during the purification of the main PBDE congeners. A significant change in the stable carbon isotope ratio of BDE-47 was observed in fish carcasses compared to the original isotopic signatures, implying that PBDE stable carbon isotopic compositions can be used to trace the biotransformation of PBDEs in biota. - Highlights: Black-Right-Pointing-Pointer A method for the purification of PBDEs for CSIA was developed. Black-Right-Pointing-Pointer The {delta}{sup 13}C of PBDE congeners can be measured with a standard deviation of less than 0.5 Per-Mille-Sign . Black-Right-Pointing-Pointer Common carp were exposed to a PBDE mixture to investigate debromination. Black-Right-Pointing-Pointer Ratios of the {delta}{sup 13}C values can be used to trace the debromination of PBDE in fish.

  8. Distribution of polybrominated diphenyl ethers in Japanese autopsy tissue and body fluid samples.

    Science.gov (United States)

    Hirai, Tetsuya; Fujimine, Yoshinori; Watanabe, Shaw; Nakano, Takeshi

    2012-09-01

    Brominated flame retardants are components of many plastics and are used in products such as cars, textiles, televisions, and personal computers. Human exposure to polybrominated diphenyl ether (PBDE) flame retardants has increased exponentially during the last three decades. Our objective was to measure the body burden and distribution of PBDEs and to determine the concentrations of the predominant PBDE congeners in samples of liver, bile, adipose tissue, and blood obtained from Japanese autopsy cases. Tissues and body fluids obtained from 20 autopsy cases were analyzed. The levels of 25 PBDE congeners, ranging from tri- to hexa-BDEs, were assessed. The geometric means of the sum of the concentrations of PBDE congeners having detection frequencies >50 % (ΣPBDE) in the blood, liver, bile, and adipose tissue were 2.4, 2.6, 1.4, and 4.3 ng/g lipid, respectively. The most abundant congeners were BDE-47 and BDE-153, followed by BDE-100, BDE-99, and BDE-28+33. These concentrations of PBDE congeners were similar to other reports of human exposure in Japan but were notably lower than concentrations than those reported in the USA. Significant positive correlations were observed between the concentrations of predominant congeners and ΣPBDE among the samples analyzed. The ΣPBDE concentration was highest in the adipose tissue, but PBDEs were distributed widely among the tissues and body fluids analyzed. The PBDE levels observed in the present study are similar to those reported in previous studies in Japan and significantly lower than those reported in the USA.

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

    Science.gov (United States)

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

    2017-10-01

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

  10. Design and synthesis of novel diphenyl oxalamide and diphenyl acetamide derivatives as anticonvulsants.

    Science.gov (United States)

    Nikalje, Anna Pratima G; Ghodke, Mangesh; Girbane, Amol

    2012-01-01

    A series of novel N(1) -substituted-N(2) ,N(2) -diphenyl oxalamides 3a-l were synthesized in good yield by stirring diphenylcarbamoyl formyl chloride (2) and various substituted aliphatic, alicyclic, aromatic, heterocyclic amines in DMF and K(2) CO(3) . Also 2-substituted amino-N,N-diphenylacetamides 5a-m were designed by pharmacophore generation and synthesized by stirring 2-chloro-N,N-diphenylacetamide (4) and various substituted amines in acetone using triethyl amine as a catalyst. All the synthesized compounds were screened for anticonvulsant activity in Swiss albino mice by MES and ScPTZ induced seizure tests. Neurotoxicity screening and behavioral testing was also carried out. Some of the synthesized test compounds were found to be more potent than the standard drug. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Oxidative transformation of polybrominated diphenyl ether congeners (PBDEs) and of hydroxylated PBDEs (OH-PBDEs).

    Science.gov (United States)

    Moreira Bastos, Patricia; Eriksson, Johan; Vidarson, Jenny; Bergman, Ake

    2008-10-01

    The historical and widespread use of polybrominated diphenyl ethers (PBDEs) as flame retardants in consumer products worldwide has caused PBDEs to now be regarded as pervasive environmental contaminants. Most recently, hydroxylated PBDEs (OH-PBDEs) and methoxylated PBDEs (MeO-PBDEs) have emerged as environmentally relevant due to reports of their natural production and metabolism. An important parameter for assessing the environmental impact of a chemical substance is persistence. By formulating the concept that persistence is the result of the substance's physicochemical properties and chemical reactivity, Green and Bergman have proposed a new methodology to determine the inherent persistence of a chemical. If persistence could be predicted by straightforward methods, substances with this quality could be screened out before large-scale production/manufacturing begins. To provide data to implement this concept, we have developed new methodologies to study chemical transformations through photolysis; hydrolysis, substitution, and elimination; and via oxidation. This study has focused on adapting an oxidative reaction method to be applicable to non-water soluble organic pollutants. PBDEs and one MeO-PBDE were dissolved in tetrahydrofuran/methanol and then diluted in alkaline water. The OH-PBDEs were dissolved in alkaline water prior to reaction. The oxidation degradation reaction was performed at 50 degrees C using potassium permanganate as described elsewhere. The pH was maintained at 7.6 with disodium hydrogen phosphate and barium hydrogen phosphate, the latter also serving as a trapping agent for manganate ions. The oxidation reactions were monitored by high-performance liquid chromatography and reaction rates were calculated. The OH-PBDEs have very fast oxidative transformation rates compared to the PBDEs. The reaction rates seem to be primarily dependent on substitution pattern of the pi-electron-donating bromine substituents and of bromine content. There are

  12. Bromine measurements in ozone depleted air over the Arctic Ocean

    Directory of Open Access Journals (Sweden)

    J. A. Neuman

    2010-07-01

    Full Text Available In situ measurements of ozone, photochemically active bromine compounds, and other trace gases over the Arctic Ocean in April 2008 are used to examine the chemistry and geographical extent of ozone depletion in the arctic marine boundary layer (MBL. Data were obtained from the NOAA WP-3D aircraft during the Aerosol, Radiation, and Cloud Processes affecting Arctic Climate (ARCPAC study and the NASA DC-8 aircraft during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS study. Fast (1 s and sensitive (detection limits at the low pptv level measurements of BrCl and BrO were obtained from three different chemical ionization mass spectrometer (CIMS instruments, and soluble bromide was measured with a mist chamber. The CIMS instruments also detected Br2. Subsequent laboratory studies showed that HOBr rapidly converts to Br2 on the Teflon instrument inlets. This detected Br2 is identified as active bromine and represents a lower limit of the sum HOBr + Br2. The measured active bromine is shown to likely be HOBr during daytime flights in the arctic. In the MBL over the Arctic Ocean, soluble bromide and active bromine were consistently elevated and ozone was depleted. Ozone depletion and active bromine enhancement were confined to the MBL that was capped by a temperature inversion at 200–500 m altitude. In ozone-depleted air, BrO rarely exceeded 10 pptv and was always substantially lower than soluble bromide that was as high as 40 pptv. BrCl was rarely enhanced above the 2 pptv detection limit, either in the MBL, over Alaska, or in the arctic free troposphere.

  13. Effects of diphenyl and p-chloro-diphenyl diselenides on feeding behavior of rats.

    Science.gov (United States)

    Bortolatto, Cristiani F; Heck, Suélen O; Gai, Bibiana M; Zborowski, Vanessa A; Neto, José S S; Nogueira, Cristina W

    2015-07-01

    The searching for safe and effective antiobesity drugs has been the subject of intense research. Previous studies have shown several pharmacological applications of organoselenium compounds; however, their possible anorectic-like actions have not been investigated. This study aims to investigate the effects of (PhSe)2 and (p-ClPhSe)2 on feeding behavior of rats and their potential as weight-reducing agents. The effects of intraperitoneal administration of diselenides were investigated through the microstructural pattern of feeding behavior, behavioral satiety sequence (BSS), hypothalamic serotonin (5-HT) uptake, body weight, and epididymal fat content of male rats. Our findings demonstrated that food intake of fasted rats was reduced by both diselenides (1 and 10 mg/kg). Diphenyl diselenide [(PhSe)2] (1 mg/kg) and p-chloro-diphenyl diselenide [(p-ClPhSe)2] (10 mg/kg) decreased the frequency, mean duration, and mean size of meals compared with the control treatment. The BSS structure was preserved when organoselenium compounds (1 mg/kg) were administered, and it was associated to a displacement to the left when the resting period started indicating a satiating action. Inhibition of 5-HT uptake in the hypothalamus (∼20 %) was also found in rats treated with low doses of (PhSe)2 and (p-ClPhSe)2 (1 mg/kg). Treatments with a high dose of both diselenides (10 mg/kg) carried out for 7 days induced weight loss and epididymal fat reduction in sated rats. This study suggests that diselenides caused a satiating action in rats that could be partially explained by the inhibition of hypothalamic 5-HT uptake. These organoselenium compounds were potential weight-reducing agents when repeatedly administered.

  14. Occurrence of organochlorine pesticides (OCPs) and their enantiomeric signatures, and concentrations of polybrominated diphenyl ethers (PBDEs) in the Adelie penguin food web, Antarctica

    International Nuclear Information System (INIS)

    Corsolini, Simonetta; Covaci, Adrian; Ademollo, Nicoletta; Focardi, Silvano; Schepens, Paul

    2006-01-01

    Concentrations and enantiomeric signatures of organochlorine pesticides were determined in Antarctic krill, emerald rockcod and Adelie penguin from the Ross Sea, Antarctica. HCB and DDTs were prevalent contaminants in penguin eggs. The highest concentrations of ΣHCHs (1.35 ± 0.72 ng/g) were found in the rockcod muscle, where γ-HCH (1.23 ± 0.67 ng/g) was the principal isomer. The ratio γ-HCH/α-HCH was evaluated. Enantioselective gas chromatography was used for the evaluation of enantiomeric fractions (EFs) for α-HCH and oxychlordane. An increase of 14% in the (+)α-HCH enantiomer was found from krill through penguin, suggesting the enantioselective biotrasformation increased proportionately with trophic level. Polybrominated diphenyl ethers (PBDEs) were measured and their concentrations were 5.6 ± 1.12, 5.81 ± 2.32, 4.57 ± 0.17 and 3.06 ± 3.27 ng/g lipids in krill, rockcod muscle, rockcod homogenate and penguin eggs, respectively. The detection of BDE28, BDE47, BDE99 and BDE100 in Antarctic organisms confirmed their global transport and distribution; the detection of lower brominated congeners suggested a potential long-range transport. - Enantiomeric signature and accumulation of polybrominated diphenyl ethers in the Adelie Penguin food chain are discussed

  15. Oxidative treatment of bromide-containing waters: formation of bromine and its reactions with inorganic and organic compounds--a critical review.

    Science.gov (United States)

    Heeb, Michèle B; Criquet, Justine; Zimmermann-Steffens, Saskia G; von Gunten, Urs

    2014-01-01

    Bromide (Br(-)) is present in all water sources at concentrations ranging from ≈ 10 to >1000 μg L(-1) in fresh waters and about 67 mg L(-1) in seawater. During oxidative water treatment bromide is oxidized to hypobromous acid/hypobromite (HOBr/OBr(-)) and other bromine species. A systematic and critical literature review has been conducted on the reactivity of HOBr/OBr(-) and other bromine species with inorganic and organic compounds, including micropollutants. The speciation of bromine in the absence and presence of chloride and chlorine has been calculated and it could be shown that HOBr/OBr(-) are the dominant species in fresh waters. In ocean waters, other bromine species such as Br2, BrCl, and Br2O gain importance and may have to be considered under certain conditions. HOBr reacts fast with many inorganic compounds such as ammonia, iodide, sulfite, nitrite, cyanide and thiocyanide with apparent second-order rate constants in the order of 10(4)-10(9)M(-1)s(-1) at pH 7. No rate constants for the reactions with Fe(II) and As(III) are available. Mn(II) oxidation by bromine is controlled by a Mn(III,IV) oxide-catalyzed process involving Br2O and BrCl. Bromine shows a very high reactivity toward phenolic groups (apparent second-order rate constants kapp ≈ 10(3)-10(5)M(-1)s(-1) at pH 7), amines and sulfamides (kapp ≈ 10(5)-10(6)M(-1)s(-1) at pH 7) and S-containing compounds (kapp ≈ 10(5)-10(7)M(-1)s(-1) at pH 7). For phenolic moieties, it is possible to derive second-order rate constants with a Hammett-σ-based QSAR approach with [Formula in text]. A negative slope is typical for electrophilic substitution reactions. In general, kapp of bromine reactions at pH 7 are up to three orders of magnitude greater than for chlorine. In the case of amines, these rate constants are even higher than for ozone. Model calculations show that depending on the bromide concentration and the pH, the high reactivity of bromine may outweigh the reactions of chlorine during

  16. Associations between urinary diphenyl phosphate and thyroid function.

    Science.gov (United States)

    Preston, Emma V; McClean, Michael D; Claus Henn, Birgit; Stapleton, Heather M; Braverman, Lewis E; Pearce, Elizabeth N; Makey, Colleen M; Webster, Thomas F

    2017-04-01

    Triphenyl phosphate (TPHP) is a commonly used organophosphate flame retardant and plasticizer with widespread human exposure. Data on health effects of TPHP are limited. Recent toxicological studies suggest TPHP may alter thyroid function. We used repeated measures to assess the temporal variability in urinary concentrations of the TPHP metabolite, diphenyl phosphate (DPHP), and to examine relationships between DPHP concentrations and thyroid hormones. We sampled 51 adults at months 1, 6, and 12 from 2010 to 2011. Urine samples were analyzed for DPHP. Serum samples were analyzed for free and total thyroxine (fT 4 , TT 4 ), total triiodothyronine (TT 3 ), and thyroid stimulating hormone (TSH). We assessed variability in DPHP using intraclass correlation coefficients (ICCs) and kappa statistics. We used linear mixed-effects models to examine associations between DPHP and thyroid hormones. DPHP was detected in 95% of urine samples. Mean DPHP concentrations were 43% higher in women than men. DPHP showed high within-subject variability (ICC range, 0.13-0.39; kappa range, 0.16-0.39). High versus low (≥2.65 vs. <2.65ng/mL) DPHP in all participants was associated with a 0.43μg/dL (95% confidence interval: 0.15, 0.72) increase in mean TT 4 levels. In sex-stratified analyses, high versus low DPHP was associated with a 0.91μg/dL (95% CI: 0.47, 1.36) increase in mean TT 4 in women. The association was attenuated in men (βeta=0.19; 95% CI: -0.15, 0.52). We found no significant associations between DPHP and fT 4 , TT 3 , or TSH. We found evidence that TPHP exposure may be associated with increased TT 4 levels, especially in women. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. The mercury species and their association with carbonaceous compositions, bromine and iodine in PM2.5 in Shanghai.

    Science.gov (United States)

    Duan, Lian; Xiu, Guangli; Feng, Ling; Cheng, Na; Wang, Chenggang

    2016-03-01

    PM2.5 samples were collected in south Shanghai from November 2013 to October 2014. The species of particulate bounded mercury (PBM), including hydrochloric soluble particle-phase mercury (HPM), element soluble particle-phase mercury (EPM) and residual soluble particle-phase mercury (RPM), were determined in PM2.5. The chemical composition of PM2.5 including organic carbon (OC) and elemental carbon (EC), total bromine and iodine were also analyzed. The results showed that the annual average concentration of PBM was 0.30 ± 0.31 ng m(-3) and 0.34 ± 0.32 ng m(-3) in winter, 0.31 ± 0.19 ng m(-3) in spring, 0.30 ± 0.45 ng m(-3) in fall and 0.28 ± 0.17 ng m(-3) in summer. HPM took the highest fraction 51.2% in PBM, followed by RPM 27.7% and EPM 21.1%. EC positively correlated to particle mercury, especially in winter (r = 0.70), the same for OC in winter (r = 0.72), which indicated that the carbonaceous composition may affect the transformation of Hg in the atmosphere. Mercury species showed different correlations with bromine and iodine in the four seasons. The strongest correlation between bromine, iodine and mercury was found in spring and fall, respectively. Bromine showed the stronger correlation with total mercury and speciated particle mercury than iodine. In addition, the days were classified into haze and non-haze days based on the visibility and relative humidity, while the ratio of HPM in haze days was much higher than that in non-haze days. EC strongly correlated with PBM during haze and non-haze days while OC only positively correlated with PBM in non-haze days, this may indicate that the different carbonaceous part may affect PBM differently. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Concentration of polybrominated diphenyl ethers (PBDEs) in sediment cores of Sundarban mangrove wetland, northeastern part of Bay of Bengal (India)

    Energy Technology Data Exchange (ETDEWEB)

    Binelli, Andrea [Department of Biology, University of Milan, Via Celoria 26, 20133 Milan (Italy)]. E-mail: andrea.binelli@unimi.it; Sarkar, Santosh Kumar [Department of Marine Science, University of Calcutta, 35 Ballygunge Circular Road, Calcutta 700 019 (India); Chatterjee, Mousumi [Department of Marine Science, University of Calcutta, 35 Ballygunge Circular Road, Calcutta 700 019 (India); Riva, Consuelo [Department of Biology, University of Milan, Via Celoria 26, 20133 Milan (Italy); Parolini, Marco [Department of Biology, University of Milan, Via Celoria 26, 20133 Milan (Italy); Bhattacharya, Bhaskar deb [Department of Marine Science, University of Calcutta, 35 Ballygunge Circular Road, Calcutta 700 019 (India); Bhattacharya, Asok Kumar [Department of Marine Science, University of Calcutta, 35 Ballygunge Circular Road, Calcutta 700 019 (India); Satpathy, Kamala Kanta [Indira Gandhi Center for Atomic Research, Environmental and Industrial Safety Section, Safety Group, Kalpakkam 603 102, Tamil Nadu (India)

    2007-08-15

    The paper presents the first comprehensive survey of congener profiles (12 congeners) of polybrominated diphenyl ethers (PBDEs) in core sediment samples (<63 {mu}m) covering seven sites in Sundarban mangrove wetland (India). Gas-chromatographic analyses were carried out in GC-Ms/Ms for tri- to hepta- brominated congeners. Results pointed out a non-homogenous contamination of the wetland with {sigma}{sub 12} PBDE values ranging from 0.08 to 29.03 ng g{sup -1}, reflecting moderate to low contamination closely in conformity to other Asian aquatic environments. The general order of decreasing congener contribution to the total load was: BDE 47 > 99 > 100 > 154, similar to the distribution pattern worldwide. Although tetrabromodiphenyl ether BDE 47 was found in all samples followed by hexabromodiphenyl ether BDE-154, they were not necessarily the dominant congeners. No uniform temporal trend on PBDE levels was recorded probably due to particular hydrological characteristics of the wetland and/on non-homologous inputs from point sources (untreated municipal wastewater and local industries, electronic wastes from the dump sites, etc.) of these compounds. Because of the propensity of PBDEs to accumulate in various compartments of wildlife and human food webs, evaluation of biological tissues should be undertaken as a high priority.

  19. Polybrominated diphenyl ethers in surface sediments of the Yangtze River Delta: Levels, distribution and potential hydrodynamic influence

    International Nuclear Information System (INIS)

    Chen Shejun; Gao Xiaojiang; Mai Bixian; Chen Zhuomin; Luo Xiaojun; Sheng Guoying; Fu Jiamo; Zeng, Eddy Y.

    2006-01-01

    A total of 32 surface sediments collected from the Yangtze River Estuary, Hangzhou Bay and the Qiantang River were analyzed for polybrominated diphenyl ethers (PBDEs). The concentrations of ΣPBDEs (sum of 12 PBDE congeners without BDE 209) and BDE 209 varied from n.d. to 0.55 and from 0.16 to 94.6 ng/g, respectively. The spatial variability of ΣPBDEs concentrations indicated that waste discharge from the urban areas might been the main source of PBDEs in the Yangtze River Delta. BDE 209 was the predominant congener (∼90-100%) detected among the 13 congeners, consistent with the fact that technical deca-BDE mixtures are presently the dominant technical PBDE mixtures used in China. Compared to published data acquired from other locales, PBDE congeners with less than four bromines were more abundant in the present study area. The hydrodynamic conditions may likely be a significant factor in dictating the observed levels and congener distribution patterns of PBDEs. - This study discussed the possible effects of hydrodynamic conditions on the distribution of PBDEs in estuarine and marine boundary

  20. Polybrominated diphenyl ethers in sewage sludge and effluents of sewage plants from a central region of Germany

    Energy Technology Data Exchange (ETDEWEB)

    Hamm, S. [eurofins/GfA, Muenster (Germany)

    2004-09-15

    Polybrominated Diphenyl Ethers (PBDEs) belong to the group of bromine-containing flame retardants. They are added to materials such as plastics, resins and textiles in percent concentrations to make them flameproof. While in former times also Penta and OctaBDE formulations were used, today mainly the technical DecaBDE is applied throughout Europe. Meanwhile PBDEs have been found in partly increasing concentrations in a number of aquatic environmental compartments such as river and marine sediments, river water, fishes and mussels. Here, mostly the same PBDE components which are present in the technical mixtures are found in the environment. PBDE emissions can punctually take place during the manufacture or processing of the flame retardants and during the disposal and recycling of flame-retarded materials. This, as a rule, should lead to local contamination but cannot explain the meanwhile wide spread of these flame retardants in the aquatic environment. Therefore, we have to have a closer look at possible further sources. Thus, the sewage sludges and suspended matter from the effluents of 8 municipal sewage treatment plants from a central region of Germany were examined for their PBDE content. The analyses included the quantitation of Tri to DecaBDE under congener-specific determination of components which are typically present in technical PBDE products. This paper reports on the applied method of analysis and presents the PBDE data for the sewage sludges and the respective sewage plant effluents.

  1. Polybrominated diphenyl ethers (PBDEs) in US meat and poultry: 2012-13 levels, trends and estimated consumer exposures.

    Science.gov (United States)

    Lupton, Sara J; Hakk, Heldur

    2017-09-01

    Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants whose use has contaminated foods and caused subsequent human exposures. To address the issue of possible human exposure, samples from a 2012-13 US meat and poultry (beef, pork, chicken, turkey) study were analysed for seven PBDEs. The mean summed concentrations of the seven BDE congeners (ΣPBDE) from beef, pork, chicken and turkey were 0.40, 0.36, 0.19, and 0.76 ng g -1 lipid weight (lw). The range of ΣPBDEs for all meat classes was 0.01-15.78 ng g -1 lw. A comparison of this study with a 2007-08 study revealed a decline in the median ΣPBDEs for all four meat classes, a reduction of 25.9% to 70.0%, with pork, chicken and turkey PBDE residues being statistically lower relative to the 2007-08 study. BDEs 47 and 99 contributed the most to the ΣPBDE concentrations, indicating likely animal exposures to the penta-BDE formulation. Based on the reported data an estimate of US consumer daily intake of PBDEs from meat and poultry was 6.42 ng day -1 .

  2. Polybrominated diphenyl ethers (PBDEs) in the indoor and outdoor environments – A review on occurrence and human exposure

    International Nuclear Information System (INIS)

    Besis, Athanasios; Samara, Constantini

    2012-01-01

    Polybrominated diphenyl ethers (PBDEs) constitute an important group of brominated flame retardants that have been massively produced and extensively used in numerous everyday products, providing longer escape times in case of fire and thus saving lives, as well as reducing the damage of property. In recent years, PBDEs have been recognized as significant pollutants of the indoor environment. This article provides a synthesis and critical evaluation of the state of the knowledge about the occurrence of PBDEs in the indoor environment (air and dust in homes, workplaces and cars) in different countries in Europe, North America, Asia and Australia, as well as about the human exposure via indoor air inhalation and dust ingestion in comparison to outdoor air inhalation and dietary intake. - Although dietary intake is major human exposure route to PBDEs, there is sufficient body of evidence for the ubiquitous presence of these compounds in indoor air and dust, therefore for the potential for significant exposure at work, at home, as well as in closed means of transport.

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

    Science.gov (United States)

    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. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

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

    2014-09-01

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

  5. Brominated flame retardants and perfluorinated chemicals, two groups of persistent contaminants in Belgian human blood and milk

    Energy Technology Data Exchange (ETDEWEB)

    Roosens, Laurence [Toxicological Centre, Department of Pharmaceutical Sciences, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk (Belgium); D' Hollander, Wendy; Bervoets, Lieven [Laboratory for Ecophysiology, Biochemistry and Toxicology, Department of Biology, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp (Belgium); Reynders, Hans; Van Campenhout, Karen [Environment and Health Unit, Department of Environment, Nature and Energy, Flemish Government - Koning Albert II-laan 20, Bus 8, 1000 Brussels (Belgium); Cornelis, Christa; Van Den Heuvel, Rosette; Koppen, Gudrun [Unit Environmental Risk and Health, Flemish Institute of Technological Research (VITO), Boeretang 200, 2400 Mol (Belgium); Covaci, Adrian, E-mail: adrian.covaci@ua.ac.b [Toxicological Centre, Department of Pharmaceutical Sciences, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk (Belgium); Laboratory for Ecophysiology, Biochemistry and Toxicology, Department of Biology, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp (Belgium)

    2010-08-15

    We assessed the exposure of the Flemish population to brominated flame retardants (BFRs) and perfluorinated compounds (PFCs) by analysis of pooled cord blood, adolescent and adult serum, and human milk. Levels of polybrominated diphenyl ethers (PBDEs) in blood (range 1.6-6.5 ng/g lipid weight, lw) and milk (range 2.0-6.4 ng/g lw) agreed with European data. Hexabromocyclododecane ranged between <2.1-5.7 ng/g lw in milk. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) dominated in blood and ranged between 1 and 171 ng/mL and <0.9-9.5 ng/mL, respectively. Total PFC levels in milk ranged between <0.5-29 ng/mL. A significant increase in PBDE concentrations was detected from newborns (median 2.1) to the adolescents and adults (medians 3.8 and 4.6 ng/g lw, respectively). An identical trend was observed for PFOS, but not for PFOA. We estimated that newborn exposure to BFRs and PFCs occurs predominantly post-natally, whereas placental transfer has a minor impact on the body burden. - The exposure to BFRs and PFCs of general Flemish population has been assessed throughout several age groups.

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

    Science.gov (United States)

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

    2017-03-01

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

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

    Science.gov (United States)

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

    2017-03-10

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

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

    Science.gov (United States)

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

    2013-09-01

    Brominated flame retardants were determined in adipose tissues from 294 polar bears (Ursus maritimus) sampled in East Greenland in 23 of the 28years between 1983 and 2010. Significant linear increases were found for sum polybrominated diphenyl ether (ΣPBDE), BDE100, BDE153, and hexabromocyclododecane (HBCD). Average increases of 5.0% per year (range: 2.9-7.6%/year) were found for the subadult polar bears. BDE47 and BDE99 concentrations did not show a significant linear trend over time, but rather a significant non-linear trend peaking between 2000 and 2004. The average ΣPBDE concentrations increased 2.3 fold from 25.0ng/g lw (95% C.I.: 15.3-34.7ng/g lw) in 1983-1986 to 58.5ng/g lw (95% C.I.: 43.6-73.4ng/g lw) in 2006-2010. Similar but fewer statistically significant trends were found for adult females and adult males likely due to smaller sample size and years. Analyses of δ(15)N and δ(13)C stable isotopes in hair revealed no clear linear temporal trends in trophic level or carbon source, respectively, and non-linear trends differed among sex and age groups. These increasing concentrations of organobromine contaminants contribute to complex organohalogen mixture, already causing health effects to the East Greenland polar bears. Copyright © 2012 Elsevier Ltd. All rights reserved.

  9. Bromine and water quality – Selected aspects and future perspectives

    International Nuclear Information System (INIS)

    Winid, Bogumiła

    2015-01-01

    Bromine is a microelement present in waters, both in inorganic and in a wide range of organic compounds, though at lower concentrations. Typically, concentrations of organobromine compounds in waters are several orders of magnitude lower than of bromides. Two issues are addressed in the paper: the influence of bromides on the quality of treated waters and organobromines as contaminants of natural waters. Bromide presence in treated water gives rise to formation of potentially mutagenic disinfection by-products (DBPs). Registered amounts of DBPs in potable waters, exceeding the admissible levels, and the published data on DBPs in waters used for leisure and recreation activities, clearly indicate the health risk. Major sources are identified and registered concentrations of EDB, DBCB, methyl bromide, bromacil and PBDEs in the aquatic environment are summarized. The effects of bromide on DBPs formation and numerous examples of organobromine contamination of the aquatic environment indicate that the presence of bromides and organobromine compounds in the aquatic environment will have to be given more consideration, for several reasons. Firstly, larger amounts of bromide are present in saline and contaminated waters and the proportion of such waters being handled is increasing. Similarly, the processes of water purification, treatment and disinfection are now playing a major role. Secondly, emissions from manufacturing of bromine-containing materials growing, due to, inter alia, intensive development of the electronic industry and the plastic manufacturing sector. Thirdly, bromine compounds are also used as medicine ingredients. There is now a growing awareness of the presence of pharmaceuticals in the aquatic environment. Fourth, low bromide concentrations in hypergene zones may be modified in the future, partly because of the climate changes, which may give rise to difficulties with water treatment systems. Water quality standards having relevance to water used for

  10. Thermodynamic properties of 4-tert-butyl-diphenyl oxide

    International Nuclear Information System (INIS)

    Druzhinina, A.I.; Pimenova, S.M.; Tarazanov, S.V.; Nesterova, T.N.; Varushchenko, R.M.

    2015-01-01

    Highlights: • The sample of the 4-tert-butyl-diphenyl oxide was synthesized and purified. • Heat capacities, energy of combustion, saturation vapor pressures were measured. • The temperature, the enthalpy and the entropy of fusion were determined. • The enthalpy of sublimation at T = 298.15 K was derived. • The main thermodynamic functions and functions of formation were computed. - Abstract: The main thermodynamic functions (changes of the entropy, enthalpy, and Gibbs free energy) and functions of formation at T = 298.15 K of 4-tert-butyl-diphenyl oxide in condensed and ideal gas states were computed on the basis of experimental results obtained. The heat capacities of 4-tert-butyl-diphenyl oxide was measured by vacuum adiabatic calorimetry over the temperature range (8 to 371) K. The temperature, the enthalpy and the entropy of fusion were determined. The energy of combustion of the sample was determined by static-bomb combustion calorimetry. The saturation vapor pressures of the substance were measured by dynamic transpiration method over the temperature and pressure intervals (298 to 325) K and (0.05 to 1.2) Pa. The enthalpy of sublimation at T = 298.15 K was derived. The contribution of O-(2C b ) group (where C b is the carbon atom in a benzene ring) into the absolute entropies of diphenyl oxide derivatives was assessed

  11. O interactions in 1,3-diphenyl-urea

    Indian Academy of Sciences (India)

    The synthesis, X-ray structure and role of intermolecular interactions have been studied in case of 1,3-diphenyl-urea, owing to its medicinal importance. The compound crystallizes in orthorhombic crystal system (space group, 21) with unit cell parameters, = 9.118(3), = 10.558(2), = 11.780(3) Å and = 4.

  12. Competition between Halogen, Hydrogen and Dihydrogen Bonding in Brominated Carboranes

    Czech Academy of Sciences Publication Activity Database

    Fanfrlík, Jindřich; Holub, Josef; Růžičková, Z.; Řezáč, Jan; Lane, P. D.; Wann, D. A.; Hnyk, Drahomír; Růžička, A.; Hobza, Pavel

    2016-01-01

    Roč. 17, č. 21 (2016), s. 3373-3376 ISSN 1439-4235 R&D Projects: GA ČR(CZ) GBP208/12/G016; GA ČR(CZ) GA15-05677S Institutional support: RVO:61388963 ; RVO:61388980 Keywords : bromine * carboranes * halogen bonds * sigma holes * X-ray crystal structure Subject RIV: CF - Physical ; Theoretical Chemistry; CA - Inorganic Chemistry (UACH-T) Impact factor: 3.075, year: 2016

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

    DEFF Research Database (Denmark)

    Pivnenko, Kostyantyn; Granby, Kit; Eriksson, Eva

    2017-01-01

    ,4,6-TBP)), hexabromocyclododecane stereoisomers (α-, β-, and γ-HBCD), as well as selected polybrominated diphenyl ethers (PBDEs) in samples of household waste plastics, virgin and recycled plastics. A considerable number of samples contained BFRs, with highest concentrations associated with acrylonitrile...

  14. Polybrominated diphenyl ethers (PBDEs) and thyroid hormones in cord blood

    International Nuclear Information System (INIS)

    Ding, Guodong; Yu, Jing; Chen, Limei; Wang, Caifeng; Zhou, Yijun; Hu, Yi; Shi, Rong; Zhang, Yan; Cui, Chang; Gao, Yu; Tian, Ying; Liu, Fang

    2017-01-01

    Human exposure to polybrominated diphenyl ethers (PBDEs) has been increasing over the last three decades in China and around the world. Animal studies suggest that PBDEs could reduce blood levels of thyroid hormones, but it is unclear whether PBDEs disrupt thyroid function in humans. We used data from a prospective birth cohort of 123 pregnant women who were enrolled between September 2010 and March 2011 in Shandong, China. We measured the concentrations of eight PBDE congeners (n = 106) and five thyroid hormones (n = 107) in cord serum samples. We examined the relationship between prenatal exposure to PBDEs and thyroid function (n = 90). Median concentrations of BDEs 47, 99, 100, and 153 (detection frequencies > 75%) were 3.96, 8.27, 3.31, and 1.89 ng/g lipid, respectively. A 10-fold increase in BDE-99 and Σ 4 PBDEs (the sum of BDEs 47, 99, 100, and 153) concentrations was associated with a 0.41 μg/dL (95% confidence interval [CI]: 0.10 to 0.72) and 0.37 μg/dL (95% CI: 0.06 to 0.68) increase in total thyroxine levels (TT 4 ), respectively. No associations were found between other individual congeners and any of the five thyroid hormones. Our study suggests that prenatal exposure to PBDEs may be associated with higher TT 4 in cord blood. Given the inconsistent findings across existing studies, our results need to be confirmed in additional studies. - Highlights: • Human exposure to PBDEs has been increased over recent decades in China. • PBDEs reduce thyroid hormones in animal studies, but it is unclear in humans. • We examined the relation of PBDE levels with thyroid hormones in cord blood. • Prenatal exposure to PBDEs is associated with higher total thyroxine levels. • The findings may have implications for fetal development. - Exposure to PBDEs is associated with higher total thyroxine levels in cord blood, and the findings may have implications for fetal development.

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

    LENUS (Irish Health Repository)

    Pratt, Iona

    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

  16. Observations of Inland Snowpack-driven Bromine Chemistry near the Brooks Range, Alaska

    Science.gov (United States)

    Peterson, P.; Pöhler, D.; Sihler, H.; Zielcke, J.; S., General; Friess, U.; Platt, U.; Simpson, W. R.; Nghiem, S. V.; Shepson, P. B.; Stirm, B. H.; Pratt, K.

    2017-12-01

    The snowpack produces high amounts of reactive bromine in the polar regions during spring. The resulting atmospheric bromine chemistry depletes boundary layer ozone to near-zero levels and alters oxidation of atmospheric pollutants, particularly elemental mercury. To improve our understanding of the spatial extent of this bromine chemistry in Arctic coastal regions, the Purdue Airborne Laboratory for Atmospheric Research (ALAR), equipped with the Heidelberg Imaging differential optical absorption spectroscopy (DOAS) instrument, measured the spatial distribution of BrO, an indicator of active bromine chemistry, over northern Alaska during the March 2012 BRomine Ozone Mercury Experiment (BROMEX). Here we show that this bromine chemistry, commonly associated with snow-covered sea ice regions in the Arctic Ocean, is active 200 km inland in the foothills of the Brooks Range. Profiles retrieved from limb-viewing measurements show this event was located near the snowpack surface, with measured BrO mole ratios of 20 pmol mol-1 in a 500 m thick layer. This observed bromine chemistry is likely enabled by deposition of transported sea salt aerosol or gas phase bromine species from prior activation events to the snowpack. These observations of halogen activation hundreds of km from the coast suggest the impacts of this springtime bromine chemistry are not restricted to sea ice regions and directly adjacent coastal regions.

  17. New insight into photo-bromination processes in saline surface waters: The case of salicylic acid

    International Nuclear Information System (INIS)

    Tamtam, Fatima; Chiron, Serge

    2012-01-01

    It was shown, through a combination of field and laboratory observations, that salicylic acid can undergo photo-bromination reactions in sunlit saline surface waters. Laboratory-scale experiments revealed that the photochemical yields of 5-bromosalicylic acid and 3,5-dibromosalicylic acid from salicylic acid were always low (in the 4% range at most). However, this might be of concern since these compounds are potential inhibitors of the 20α-hydroxysteroid dehydrogenase enzyme, with potential implications in endocrine disruption processes. At least two mechanisms were involved simultaneously to account for the photo-generation of brominated substances. The first one might involve the formation of reactive brominated radical species (Br·, Br 2 · − ) through hydroxyl radical mediated oxidation of bromide ions. These ions reacted more selectively than hydroxyl radicals with electron-rich organic pollutants such as salicylic acid. The second one might involve the formation of hypobromous acid, through a two electron oxidation of bromine ions by peroxynitrite. This reaction was catalyzed by nitrite, since these ions play a crucial role in the formation of nitric oxide upon photolysis. This nitric oxide further reacts with superoxide radical anions to yield peroxynitrite and by ammonium through the formation of N-bromoamines, probably due to the ability of N-bromoamines to promote the aromatic bromination of phenolic compounds. Field measurements revealed the presence of salicylic acid together with 5-bromosalicylic and 3,5-dibromosalicylic acid in a brackish coastal lagoon, thus confirming the environmental significance of the proposed photochemically induced bromination pathways. -- Highlights: ► Brominated derivatives of salicylic acid were detected in a brackish lagoon. ► A photochemical pathway was hypothesized to account for bromination of salicylic acid. ► Radical bromine species are partly responsible for the bromination process. ► Hypobromous acid

  18. Functionalization and migration of bromine adatoms on zigzag graphene nanoribbons: A first-principles study

    Science.gov (United States)

    Jaiswal, Neeraj K.; Kumar, Amit; Patel, Chandrabhan

    2018-05-01

    Tailoring the electronic band gap of graphene nanoribbons (GNR) through edge functionalization and understanding the adsorption of guest adatoms on GNR is crucial for realization of upcoming organic devices. In the present work, we have investigated the structural stability and electronic property of bromine (Br) termination at the edges of zigzag GNR (ZGNR). The migration pathways of Br adatom on ZGNR have also been discussed along four different diffusion paths. It is revealed that Br termination induces metallicity in ZGNR and caused upward shifting of Fermi level. Further, the migration is predicted to take place preferable along the ribbon edges whereas across the ribbon width, migration is least probable to take place due to sufficiently higher migration barrier of ˜160 meV.

  19. Superior bactericidal activity of N-bromine compounds compared to their N-chlorine analogues can be reversed under protein load.

    Science.gov (United States)

    Gottardi, W; Klotz, S; Nagl, M

    2014-06-01

    To investigate and compare the bactericidal activity (BA) of active bromine and chlorine compounds in the absence and presence of protein load. Quantitative killing tests against Escherichia coli and Staphylococcus aureus were performed both in the absence and in the presence of peptone with pairs of isosteric active chlorine and bromine compounds: hypochlorous and hypobromous acid (HOCl and HOBr), dichloro- and dibromoisocyanuric acid, chlorantine and bromantine (1,3-dibromo- and 1,3 dichloro-5,5-dimethylhydantoine), chloramine T and bromamine T (N-chloro- and N-bromo-4-methylbenzenesulphonamide sodium), and N-chloro- and N-bromotaurine sodium. To classify the bactericidal activities on a quantitative basis, an empirical coefficient named specific bactericidal activity (SBA), founded on the parameters of killing curves, was defined: SBA= mean log reductions/(mean exposure times x concentration) [mmol 1(-1) min (-1)]. In the absence of peptone, tests with washed micro-organisms revealed a throughout higher BA of bromine compounds with only slight differences between single substances. This was in contrast to chlorine compounds, whose killing times differed by a factor of more than four decimal powers. As a consequence, also the isosteric pairs showed according differences. In the presence of peptone, however, bromine compounds showed an increased loss of BA, which partly caused a reversal of efficacy within isosteric pairs. In medical practice, weakly oxidizing active chlorine compounds like chloramines have the highest potential as topical anti-infectives in the presence of proteinaceous material (mucous membranes, open wounds). Active bromine compounds, on the other hand, have their chance at insensitive body regions with low organic matter, for example skin surfaces. The expected protein load is one of the most important parameters for selection of a suited active halogen compound. © 2014 The Society for Applied Microbiology.

  20. Dioxin-like activity of brominated dioxins as individual compounds or mixtures in in vitro reporter gene assays with rat and mouse hepatoma cell lines.

    Science.gov (United States)

    Suzuki, G; Nakamura, M; Michinaka, C; Tue, N M; Handa, H; Takigami, H

    2017-10-01

    In vitro reporter gene assays detecting dioxin-like compounds have been developed and validated since the middle 1990's, and applied to the determination of dioxin-like activities in various samples for their risk management. Data on characterizing the potency of individual brominated dioxins and their activity in mixture with chlorinated dioxins are still limited on the cell-based assay. This study characterized the dioxin-like activities of the 32 brominated dioxins, such as polybrominated dibenzo-p-dioxins, polybrominated dibenzofurans (PBDFs), coplanar polybrominated biphenyls, mixed halogenated dibenzo-p-dioxins and dibenzofurans (PXDFs), as a sole component or in a mixture by DR-CALUX (dioxin-responsive chemically activated luciferase expression) using the rat hepatoma H4IIE cell line and XDS-CALUX (xenobiotic detection systems-chemically activated luciferase expression) assays using the mouse hepatoma H1L6.1 cell line. The 2,3,7,8-TCDD-relative potencies (REPs) of most of the brominated dioxins were within a factor of 10 of the WHO toxicity equivalency factor (WHO-TEF) for the chlorinated analogues. The REPs of a few PXDFs were an order of magnitude higher than the corresponding WHO-TEFs, indicating their toxicological importance. Results with reconstituted mixtures suggest that the activity of brominated and chlorinated dioxins in both CALUX assays was dose-additive. Thus, obtained results indicated the applicability of the CALUX assays as screening tools of brominated dioxins together with their chlorinated analogues. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Distribution of bromine in mixed iodide-bromide organolead perovskites and its impact on photovoltaic performance

    NARCIS (Netherlands)

    Zhou, Yang; Wang, Feng; Fang, Hong-Hua; Loi, Maria Antonietta; Xie, Fang-Yan; Zhao, Ni; Wong, Ching-Ping

    2016-01-01

    Mixed iodide-bromide (I-Br) organolead perovskites are of great interest for both single junction and tandem solar cells since the optical bandgap of the materials can be tuned by varying the bromine to iodine ratio. Yet, it remains unclear how bromine incorporation modifies the properties of the

  2. Control of fouling organisms in estuarine cooling water systems by chlorine and bromine chloride

    International Nuclear Information System (INIS)

    Burton, D.T.; Margrey, S.L.

    1979-01-01

    The study described was initiated to evaluate the antifouling effectiveness of chlorine and bromine chloride in low velocity flow areas where estuarine waters are used for cooling purposes. The relative antifouling effectiveness of chlorine and bromine chloride under intermittent and continuous modes of application in low velocity flow areas was evaluated at an estuarine power plant located on the Chesapeake Bay

  3. A Multistep Synthesis Incorporating a Green Bromination of an Aromatic Ring

    Science.gov (United States)

    Cardinal, Pascal; Greer, Brandon; Luong, Horace; Tyagunova, Yevgeniya

    2012-01-01

    Electrophilic aromatic substitution is a fundamental topic taught in the undergraduate organic chemistry curriculum. A multistep synthesis that includes a safer and greener method for the bromination of an aromatic ring than traditional bromination methods is described. This experiment is multifaceted and can be used to teach students about…

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

    Science.gov (United States)

    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…

  5. New fast organic scintillators using intramolecular bromine quenching

    International Nuclear Information System (INIS)

    Berlman, I.B.; Lutz, S.S.; Flournoy, J.M.; Ashford, C.B.; Franks, L.A.

    1984-01-01

    Organic scintillator solutions with decay times as fast as 500 ps and with relatively high conversion efficiencies have been developed. The intramolecular quenching was achieved through the novel approach of adding a bromine atom to the 3- or 4-position of para-oligophenylenes, the fluorescent solutes in these binary solutions. The bromine serves to enhance singlet-to-triplet intersystem crossing in the chromophore, causing a reduction in the scintillation yield and a concomitant reduction in the decay time. The very fast value given above probably also involves some intermolecular self-quenching at high concentration. In addition, the bromine reduces the symmetry of the molecules, thereby increasing their solubility. Finally, an alkyl chain on the opposite para position further increases the solubility and also increases the immunity of the chromophore to quenching. The decay times for binary liquid solutions in toluene (at the indicated concentrations) were 0.51 ns for 4-BHTP (0.14 M), 0.75 ns for 3-BHTP (0.14 M), 0.57 ns for 3-BTP (0.14 M), and 1.3 ns for 4-BHQP (0.06 M). Binary plastics with 4-BHTP as the solute in concentrations up to 0.14 M were cast in polystyrene. The shortest decay time, 0.40 ns, was measured for the 0.14 M concentration. A plastic scintillator containing 3-BTP (0.11 M in polystyrene) had a decay time of 0.85 ns. These results compare favorably with the plastic scintillator BC-422 whose decay time is about 1.4 ns. (orig./HSI)

  6. Inhibition of human placental aromatase activity by hydroxylated polybrominated diphenyl ethers (OH-PBDEs).

    Science.gov (United States)

    Cantón, Rocío F; Scholten, Deborah E A; Marsh, Göran; de Jong, Paul C; van den Berg, Martin

    2008-02-15

    Polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants in many different polymers, resins and substrates. Due to their widespread production and use, their high binding affinity to particles, and their lipophilic properties, several PBDE congeners can bioaccumulate in the environment. As a result, PBDEs and their hydroxylated metabolites (OH-PBDEs) have been detected in humans and various wildlife samples, such as birds, seals, and whales. Furthermore, certain OH-PBDEs and their methoxylated derivatives (MeO-PBDEs) are natural products in the marine environment. Recently, our laboratory focused on the possible effects on steroidogenesis of PBDEs and OH-PBDEs, e.g. in the human adrenocortical carcinoma (H295R) cell line indicating that some OH-PBDEs can significantly influence steroidogenic enzymes like CYP19 (aromatase) and CYP17. In the present study, human placental microsomes have been used to study the possible interaction of twenty two OH-PBDEs and MeO-PBDEs with aromatase, the enzyme that mediates the conversion of androgens into estrogens. All OH-PBDE derivates showed significant inhibition of placental aromatase activity with IC(50) values in the low micromolar range, while the MeO-PBDEs did not have any effect on this enzyme activity. Enzyme kinetics studies indicated that two OH-PBDEs, 5-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (5-OH-BDE47) and 6-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (6-OH-BDE47), had a mixed-type inhibition of aromatase activity with apparent K(i)/K(i)' of 7.68/0,02 microM and 5.01/0.04 microM respectively. For comparison, some structurally related compounds, a dihydroxylated polybrominated biphenyl, which is a natural product (2,2'-dihyroxy-3,3',5,5'-tetrabromobiphenyl (2,2'-diOH-BB80)) and its non-bromo derivative were also included in the study. Again inhibition of aromatase activity could be measured, but their potency was significantly less than those observed for the OH-PBDEs. These results show that a

  7. Inhibition of human placental aromatase activity by hydroxylated polybrominated diphenyl ethers (OH-PBDEs)

    International Nuclear Information System (INIS)

    Canton, Rocio F.; Scholten, Deborah E.A.; Marsh, Goeran; Jong, Paul C. de; Berg, Martin van den

    2008-01-01

    Polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants in many different polymers, resins and substrates. Due to their widespread production and use, their high binding affinity to particles, and their lipophilic properties, several PBDE congeners can bioaccumulate in the environment. As a result, PBDEs and their hydroxylated metabolites (OH-PBDEs) have been detected in humans and various wildlife samples, such as birds, seals, and whales. Furthermore, certain OH-PBDEs and their methoxylated derivatives (MeO-PBDEs) are natural products in the marine environment. Recently, our laboratory focused on the possible effects on steroidogenesis of PBDEs and OH-PBDEs, e.g. in the human adrenocortical carcinoma (H295R) cell line indicating that some OH-PBDEs can significantly influence steroidogenic enzymes like CYP19 (aromatase) and CYP17. In the present study, human placental microsomes have been used to study the possible interaction of twenty two OH-PBDEs and MeO-PBDEs with aromatase, the enzyme that mediates the conversion of androgens into estrogens. All OH-PBDE derivates showed significant inhibition of placental aromatase activity with IC 50 values in the low micromolar range, while the MeO-PBDEs did not have any effect on this enzyme activity. Enzyme kinetics studies indicated that two OH-PBDEs, 5-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (5-OH-BDE47) and 6-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (6-OH-BDE47), had a mixed-type inhibition of aromatase activity with apparent K i /K i ' of 7.68/0,02 μM and 5.01/0.04 μM respectively. For comparison, some structurally related compounds, a dihydroxylated polybrominated biphenyl, which is a natural product (2,2'-dihyroxy-3,3',5,5'-tetrabromobiphenyl (2,2'-diOH-BB80)) and its non-bromo derivative were also included in the study. Again inhibition of aromatase activity could be measured, but their potency was significantly less than those observed for the OH-PBDEs. These results show that a wide

  8. Polybrominated diphenyl ethers (PBDEs) in leachates from selected landfill sites in South Africa.

    Science.gov (United States)

    Odusanya, David O; Okonkwo, Jonathan O; Botha, Ben

    2009-01-01

    The last few decades have seen dramatic growth in the scale of production and the use of polybrominated diphenyl ethers (PBDEs) as flame retardants. Consequently, PBDEs such as BDE -28, -47, -66, -71, -75, -77, -85, -99, -100, -119, -138, -153, -154, and -183 have been detected in various environmental matrices. Generally, in South Africa, once the products containing these chemicals have outlived their usefulness, they are discarded into landfill sites. Consequently, the levels of PBDEs in leachates from landfill sites may give an indication of the general exposure and use of these compounds. The present study was aimed at determining the occurrence and concentrations of most common PBDEs in leachates from selected landfill sites. The extraction capacities of the solvents were also tested. Spiked landfill leachate samples were used for the recovery tests. Separation and determination of the PBDE congeners were carried out with a gas chromatograph equipped with Ni63 electron capture detector. The mean percentage recoveries ranged from 63% to 108% (n=3) for landfill leachate samples with petroleum ether giving the highest percentage extraction. The mean concentrations of PBDEs obtained ranged from ND to 2670pgl(-1), ND to 6638pgl(-1), ND to 7230pgl(-1), 41 to 4009pgl(-1), 90 to 9793pgl(-1) for the Garankuwa, Hatherly, Kwaggarsrand, Soshanguve and Temba landfill sites, respectively. Also BDE -28, -47, -71 and BDE-77 were detected in the leachate samples from all the landfill sites; and all the congeners were detected in two of the oldest landfill sites. The peak concentrations were recorded for BDE-47 at three sites and BDE-71 and BDE-75 at two sites. The highest concentration, 9793+/-1.5pgl(-1), was obtained for the Temba landfill site with the highest BOD value. This may suggest some influence of organics on the level of PBDEs. Considering the leaching characteristics of brominated flame retardants, there is a high possibility that with time these compounds may

  9. Polybrominated diphenyl ethers (PBDEs) in leachates from selected landfill sites in South Africa

    International Nuclear Information System (INIS)

    Odusanya, David O.; Okonkwo, Jonathan O.; Botha, Ben

    2009-01-01

    The last few decades have seen dramatic growth in the scale of production and the use of polybrominated diphenyl ethers (PBDEs) as flame retardants. Consequently, PBDEs such as BDE -28, -47, -66, -71, -75, -77, -85, -99, -100, -119, -138, -153, -154, and -183 have been detected in various environmental matrices. Generally, in South Africa, once the products containing these chemicals have outlived their usefulness, they are discarded into landfill sites. Consequently, the levels of PBDEs in leachates from landfill sites may give an indication of the general exposure and use of these compounds. The present study was aimed at determining the occurrence and concentrations of most common PBDEs in leachates from selected landfill sites. The extraction capacities of the solvents were also tested. Spiked landfill leachate samples were used for the recovery tests. Separation and determination of the PBDE congeners were carried out with a gas chromatograph equipped with Ni 63 electron capture detector. The mean percentage recoveries ranged from 63% to 108% (n = 3) for landfill leachate samples with petroleum ether giving the highest percentage extraction. The mean concentrations of PBDEs obtained ranged from ND to 2670 pg l -1 , ND to 6638 pg l -1 , ND to 7230 pg l -1 , 41 to 4009 pg l -1 , 90 to 9793 pg l -1 for the Garankuwa, Hatherly, Kwaggarsrand, Soshanguve and Temba landfill sites, respectively. Also BDE -28, -47, -71 and BDE-77 were detected in the leachate samples from all the landfill sites; and all the congeners were detected in two of the oldest landfill sites. The peak concentrations were recorded for BDE-47 at three sites and BDE-71 and BDE-75 at two sites. The highest concentration, 9793 ± 1.5 pg l -1 , was obtained for the Temba landfill site with the highest BOD value. This may suggest some influence of organics on the level of PBDEs. Considering the leaching characteristics of brominated flame retardants, there is a high possibility that with time these

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

    Science.gov (United States)

    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. Differences in neonatal neurotoxicity of brominated flame retardants, PBDE 99 and TBBPA, in mice

    International Nuclear Information System (INIS)

    Viberg, Henrik; Eriksson, Per

    2011-01-01

    Highlights: → Neonatal exposure to PBDE 99, but not TBBPA, causes changes in the neonatal brain. → CaMKII increases in neonatal hippocampus after PBDE 99 exposure. → CaMKII, GAP-43 and synaptophysin increase in neonatal cortex after PBDE 99 exposure. → CaMKII increase in hippocampus has earlier been seen to proceed behavioral changes. → Neonatal exposure to PBDE 99, but not TBBPA, is known to cause behavioral deficits. -- Abstract: Flame retardants such as polybrominated diphenyl ethers (PBDE) and tetrabromobisphenol A are used as flame retardants and detected in the environmental, wildlife species and human tissues. Exposure to PBDEs during the neonatal development of the brain has been shown to affect behavior and learning and memory in adult mice, while neonatal exposure to TBBPA (another brominated flame retardant) did not affect behavioral variables in the adult. In this study, we hypothesized that the effects of these compounds could be reflected by changes in biochemical substrates and cholinergic receptors and have examined the levels of four proteins involved in maturation of the brain, neuronal growth and synaptogenesis and the densities of both muscarinic and nicotinic cholinergic receptors. We measured the levels of radioactivity in the brain after administration of 14 C-labelled TBBPA at different time points and saw that levels of TBBA peaked earlier and decreased faster than the earlier reported levels of PBDE 99. The protein analysis in the neonatal brain showed changes in the levels of calcium/calmodulin-dependent protein kinase II (CaMKII), growth associated protein-43 (GAP-43) and synaptophysin following neonatal exposure to PBDE 99 (21 μmol/kg body weight), but not following exposure TBBPA. Furthermore, neonatal exposure to PBDE 99 and TBBPA caused a decrease in binding sites of the nicotinic ligand cytisine in frontal cortex. These results confirm earlier reported data that PBDE 99 can act as a developmental neurotoxicant, possibly

  12. Theoretical performance of hydrogen-bromine rechargeable SPE fuel cell

    Science.gov (United States)

    Savinell, Robert F.; Fritts, S. D.

    1987-01-01

    A mathematical model was formulated to describe the performance of a hydrogen-bromine fuel cell. Porous electrode theory was applied to the carbon felt flow-by electrode and was coupled to theory describing the solid polymer electrolyte (SPE) system. Parametric studies using the numerical solution to this model were performed to determine the effect of kinetic, mass transfer, and design parameters on the performance of the fuel cell. The results indicate that the cell performance is most sensitive to the transport properties of the SPE membrane. The model was also shown to be a useful tool for scale-up studies.

  13. Deriving an atmospheric budget of total organic bromine using airborne in-situ measurements of brominated hydrocarbons in the Western Pacific during SHIVA

    Science.gov (United States)

    Sala, Stephan; Bönisch, Harald; Keber, Timo; Oram, Dave; Mills, Graham; Engel, Andreas

    2014-05-01

    Halogenated hydrocarbons play a major role as precursors for stratospheric ozone depletion. Released from the surface in the troposphere, the halocarbons reach the stratosphere via transport through the tropical tropopause layer. The contribution of the so called very short lived species (VSLS), having atmospheric lifetimes of less than half a year as sources gases for stratospheric bromine is significant. Source gas observations of long-lived bromine compounds and VSLS have so far not been able to explain the amount of bromine derived in the stratosphere from observations of BrO and modeling of the ratio of BrO to total bromine. Due to the short lifetimes and the high atmospheric variability, the representativeness of the available observations of VSLS source gases remains unclear, as these may vary with region and display seasonal variability. During the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) project an extensive dataset with over 700 samples of ambient air of all halogen species relevant for the atmospheric budget of total organic bromine (long lived halocarbons: H-1301, H-1211, H-1202, H-2402 and CH3Br, very short lived substances: CHBr3, CH2Br2, CHBr2Cl, CHBrCl2 and CHBrCl) have been collected from onboard the FALCON aircraft in the West Pacific region. Measurements were performed with the newly developed fully-automated in-situ instrument GHOST-MS (Gas chromatograph for the Observation of Tracers - coupled with a Mass Spectrometer) by the Goethe University of Frankfurt and with the onboard whole-air sampler WASP with subsequent ground based state-of-the-art GC/MS analysis by the University of East Anglia. We will present the datasets, compare these to other observation, derive a bromine budget for the West Pacific and derive an estimate of the amount of bromine from VSLS reaching the stratosphere. Using the mean mixing ratios in the upper troposphere of the halocarbons mentioned above, the calculated budget of the total organic

  14. Research on the phenomenon of graphitization. Crystallographic study - Study of bromine sorption

    International Nuclear Information System (INIS)

    Maire, Jacques

    1967-01-01

    This research thesis reports the study of the mechanism of graphitization of carbon by using X-ray diffraction analysis and the physical and chemical study of lamellar reactions between carbon and bromine. The author first presents generalities and results of preliminary studies (meaning of graphitization, presentation of the various carbon groups and classes), and then reports the study of the graphitization of compact carbons (soft carbons). More precisely, he reports the crystallographic study of partially graphitized carbons: methods and principles, experimental results and their analysis, discussion of the graphitization mechanism. In the next part, the author reports the study of bromine sorption on carbons: experimental method, isotherms of a natural graphite and of a graphitized carbon, structure of carbon-bromine complexes, isotherms of graphitizable carbons and of all other carbons, distribution of bromine layers in partially graphitized carbons, bromine sorption and Fermi level

  15. Effects of bromine on mitosis in root-tips of Allium cepa

    Energy Technology Data Exchange (ETDEWEB)

    Chury, J; Slouka, V

    1949-01-01

    The root-tips of Allium cepa, 1.5-2 cm. long, were exposed to pure bromine vapor for five minutes. The root-tips were then washed for ten minutes in water, and kept in fresh-water at a temperature of 20-24/sup 0/C. Squash preparations were made and stained according to the method of Darlington and La Cour. Bromine acting for five minutes on the root-tips of Allium has a specific effect on the cell nucleus in the resting stage. The effects induced are shown thirty-six hours after treatment by spindle abnormalities in metaphase and anaphase, and result in polyploidy in a large number of cells. Bromine produces chromosome and chromatid fragmentation; the latter may be followed by reunion. The effect of the bromine is cumulative and depends on the time which elapses between treatment and fixation. The cytological effects induced by bromine strongly suggest that it is another specific mutafacient chemical.

  16. Labeling of receptor ligands with bromine radionuclides. Progress report, March 1, 1981-February 28, 1982

    International Nuclear Information System (INIS)

    Welch, M.J.

    1981-10-01

    In recent years there has been an interest in the use of various radioisotopes of bromine as labels for radiopharmaceuticals. Although radioisotopes of iodine have been used extensively as radiopharmaceutical labels, there are several advantages associated with the use of radiobromine as a label, due primarily to increased stability of bonds to the radiohalide and smaller steric perturbation resulting from substitution of the radiohalide. Methods of attaching radiobromine to receptor ligands with the potential of mapping estrogen receptors in mammary tumors and uteri were studied. Two ligands were studied extensively in vitro and in animal models; preliminary studies were also carried out in humans. To date, the only radioisotope of bromine used was bromine-77. In addition, a series of model compounds were labeled with bromine-77 using a recently described method for rapid bromination; the scope and limitations of this new rapid radiobromination technique were evaluated

  17. Levels and distribution of polybrominated diphenyl ethers in various tissues of birds of prey

    International Nuclear Information System (INIS)

    Voorspoels, Stefan; Covaci, Adrian; Lepom, Peter; Jaspers, Veerle L.B.; Schepens, Paul

    2006-01-01

    In the present study, concentrations and tissue distribution of polybrominated diphenyl ethers (PBDEs; IUPAC nos. 28, 47, 99, 100, 153, 154, 183, and 209) were examined in brain, adipose tissue, liver, muscle, and serum of birds of prey. Median ΣPBDE levels (BDE 28-183) in the tissues of sparrowhawks ranged from 360 to 1900 ng/g lipid weight (lw), which was in general one order of magnitude higher than in the tissues of common buzzards (26-130 ng/g lw). There were no differences in PBDE congener patterns between the various tissues within individuals of a certain species. Inter-species differences in PBDE patterns and in particular the percentage of BDE 99, 100 and 153 were, however, pronounced between sparrowhawk and common buzzard. BDE 209 was detected in nearly all serum and in some liver samples, but not in any other tissues. This observation suggests that exposure to BDE 209 is low or that this congener is poorly accumulated. Passive (lipid content related) diffusion could not completely describe the PBDE tissue distribution, e.g. the lowest PBDE-load was measured in brain, a fairly lipid rich tissue. - Distribution of polybrominated diphenyl ethers in birds of prey is tissue dependent

  18. Dietary exposure of juvenile common sole (Solea solea L.) to polybrominated diphenyl ethers (PBDEs): Part 1. Bioaccumulation and elimination kinetics of individual congeners and their debrominated metabolites

    International Nuclear Information System (INIS)

    Munschy, C.; Heas-Moisan, K.; Tixier, C.; Olivier, N.; Gastineau, O.; Le Bayon, N.; Buchet, V.

    2011-01-01

    The uptake and elimination of six PBDE congeners (BDE-28, -47, -99, -100, -153, -209) were studied in juvenile common sole (Solea solea L.) exposed to spiked contaminated food over a three-month period, then depurated over a five-month period. The results show that all of the studied PBDEs accumulate in fish tissues, including the higher brominated congener BDE-209. Several additional PBDE congeners were identified in the tissues of exposed fish, revealing PBDE transformation, mainly via debromination. The identified congeners originating from PBDE debromination include BDE-49 and BDE-202 and a series of unidentified tetra-, penta-, and hepta- BDEs. Contaminant assimilation efficiencies (AEs) were related to their hydrophobicity (log K ow ) and influenced by PBDE biotransformation. Metabolism via debromination appears to be a major degradation route of PBDEs in juvenile sole in comparison to biotransformation into hydroxylated metabolites. - Juvenile sole exposed to artificially-contaminated food accumulate PBDEs, including the higher brominated congeners, and have a debromination capacity.

  19. Improved electrolyte for zinc-bromine flow batteries

    Science.gov (United States)

    Wu, M. C.; Zhao, T. S.; Wei, L.; Jiang, H. R.; Zhang, R. H.

    2018-04-01

    Conventional zinc bromide electrolytes offer low ionic conductivity and often trigger severe zinc dendrite growth in zinc-bromine flow batteries. Here we report an improved electrolyte modified with methanesulfonic acid, which not only improves the electrolyte conductivity but also ameliorates zinc dendrite. Experimental results also reveal that the kinetics and reversibility of Zn2+/Zn and Br2/Br- are improved in this modified electrolyte. Moreover, the battery's internal resistance is significantly reduced from 4.9 to 2.0 Ω cm2 after adding 1 M methanesulfonic acid, thus leading to an improved energy efficiency from 64% to 75% at a current density of 40 mA cm-2. More impressively, the battery is capable of delivering an energy efficiency of about 78% at a current density of as high as 80 mA cm-2 when the electrode is replaced by a thermally treated one. Additionally, zinc dendrite growth is found to be effectively suppressed in methanesulfonic acid supported media, which, as a result, enables the battery to be operated for 50 cycles without degradation, whereas the one without methanesulfonic acid suffers from significant decay after only 40 cycles, primarily due to severe zinc dendrite growth. These superior results indicate methanesulfonic acid is a promising supporting electrolyte for zinc-bromine flow batteries.

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

    Science.gov (United States)

    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.

  1. One-pot oxidation and bromination of 3,4-diaryl-2,5-dihydrothiophenes using Br2: synthesis and application of 3,4-diaryl-2,5-dibromothiophenes.

    Science.gov (United States)

    Dang, Yizhe; Chen, Yi

    2007-08-31

    A class of 3,4-diaryl-2,5-dibromothiophenes (1b-5b) was synthesized by a one-pot reaction of 3,4-diaryl-2,5-dihydrothiophenes with Br2 reagent in excellent yield (83-92%). It was found that Br2 performed a double function (oxidation and bromination) during the conversion of 3,4-diaryl-2,5-dihydrothiophenes to 3,4-diaryl-2,5-dibromothiophenes. The application of 3,4-diaryl-2,5-dibromothiophenes used as building blocks was also investigated. Employing 3,4-diphenyl-2,5-dibromothiophene (1b) as a template, a class of 2,3,4,5-tetraarylthiophenes was prepared by the Suzuki coupling reaction. This provided a new and simple approach to the preparation of 2,3,4,5-tetraarylthiophenes.

  2. Bromine species fluxes from Lake Constance’s catchment, and a preliminary lake mass balance

    Science.gov (United States)

    Gilfedder, B. S.; Petri, M.; Wessels, M.; Biester, H.

    2011-06-01

    Bromine was historically termed a cyclic salt in terrestrial freshwater environments due to its perceived conservative cycling between the oceans and the continents. This basic assumption has been challenged recently, with evidence that bromine is involved in dynamic chemical cycles in soils and freshwaters. We present here a study on dissolved bromine species (bromide, organically bound bromine, DOBr) concentrations and fluxes as well as sediment trap bromine levels and fluxes in Lake Constance, a large lake in southern Germany. Water samples were obtained from all major and some minor inflows and outflows over one year, where-after dissolved bromine species were measured by a combination of ICP-MS and ion chromatography coupled to an ICP-MS (IC-ICP-MS). Sediment traps were deployed at two locations for two years with Br, Ti and Zr levels being measured by μ-XRF. 190 t yr -1 of total dissolved bromine (TDBr) was delivered to the lake via 14 rivers and precipitation, with the rivers Alpenrhein (84 t TDBr yr -1) and the Schussen (50 t TDBr yr -1) providing the largest sources. The estimated particulate bromine flux contributed an extra 24-26 t Br yr -1. In comparison, only 40 t TDBr yr -1 was deposited to the lake's catchment by precipitation, and thus ˜80% of the riverine TDBr flux came from soils and rocks. Bromide was the dominant species accounting for, on average, 78% of TDBr concentrations and 93% of TDBr flux to the lake. Despite some high concentrations in the smaller lowland rivers, DOBr was only a minor component of the total riverine bromine flux (˜12 t yr -1, 7%), most of which came from the rivers Schussen, Bregenzer Ach and Argen. In contrast, most of the bromine in the sediment traps was bound to organic matter, and showed a clear seasonal pattern in concentrations, with a maximum in winter and minimum in summer. The summer minimum is thought to be due to dilution of a high Br autochthonous component by low bromine mineral and organic material from

  3. Estimating persistence of brominated and chlorinated organic pollutants in air, water, soil, and sediments with the QSPR-based classification scheme.

    Science.gov (United States)

    Puzyn, T; Haranczyk, M; Suzuki, N; Sakurai, T

    2011-02-01

    We have estimated degradation half-lives of both brominated and chlorinated dibenzo-p-dioxins (PBDDs and PCDDs), furans (PBDFs and PCDFs), biphenyls (PBBs and PCBs), naphthalenes (PBNs and PCNs), diphenyl ethers (PBDEs and PCDEs) as well as selected unsubstituted polycyclic aromatic hydrocarbons (PAHs) in air, surface water, surface soil, and sediments (in total of 1,431 compounds in four compartments). Next, we compared the persistence between chloro- (relatively well-studied) and bromo- (less studied) analogs. The predictions have been performed based on the quantitative structure-property relationship (QSPR) scheme with use of k-nearest neighbors (kNN) classifier and the semi-quantitative system of persistence classes. The classification models utilized principal components derived from the principal component analysis of a set of 24 constitutional and quantum mechanical descriptors as input variables. Accuracies of classification (based on an external validation) were 86, 85, 87, and 75% for air, surface water, surface soil, and sediments, respectively. The persistence of all chlorinated species increased with increasing halogenation degree. In the case of brominated organic pollutants (Br-OPs), the trend was the same for air and sediments. However, we noticed that the opposite trend for persistence in surface water and soil. The results suggest that, due to high photoreactivity of C-Br chemical bonds, photolytic processes occurring in surface water and soil are able to play significant role in transforming and removing Br-OPs from these compartments. This contribution is the first attempt of classifying together Br-OPs and Cl-OPs according to their persistence, in particular, environmental compartments.

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

    Science.gov (United States)

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

    2013-05-24

    A capillary poly(trimethyl-2-methacroyloxyethylammonium chloride-co-ethylene glycol dimethacrylate) monolith was in situ synthesized by thermally initiated free radical co-polymerization using trimethyl-2-methacroyloxyethylammonium chloride (MATE) and ethylene glycol dimethacrylate (EGDMA) as functional monomer and cross-linker, respectively. N,N-dimethylformamide and polyethylene glycol 6000 were used as solvent and porogen, respectively. The morphology and porous structure of the resulting monoliths were assessed by scanning electron microscope. In order to prepare practically useful poly(MATE-co-EGDMA) monoliths with low flow resistance and good mechanical strength, some parameters such as PEG-6000 to DMF ratio, total monomer to porogen ratio, and crosslinker to monomer ratio were optimized systematically. Moreover, the extraction mechanism was evaluated using two series of compounds, alkylbenzenes and weak acids, as model compounds on poly(MATE-co-EGDMA) monoliths as liquid chromatographic stationary phase. Finally, the monoliths were applied as the solid phase microextraction medium, and a simple off-line method for simultaneous determination of three brominated flame retardants, 2,4,6-tribromophenol (TBP), tetrabromobisphenol A (TBBPA) and 4,4'-dibrominated diphenyl ether (DBDPE), in environmental waters was developed by coupling the polymer monolith microextraction to HPLC with UV detection. The regression equations for these three brominated flame retardants showed good linearity from their limit of quantification to 5000ng/mL. The limits of detection were 0.20, 0.15 and 0.10ng/mL for TBP, TBBPA and DBDPE, respectively. The recovery of the proposed method was 78.7-106.1% with intra-day relative standard deviation of 1.3-4.4%. Copyright © 2013 Elsevier B.V. All rights reserved.

  5. Pulse radiolysis studies of the reactions of bromine atoms and dimethyl sulfoxide bromine atom complexes with alcohols

    Science.gov (United States)

    Sumiyoshi, Takashi; Fujiyoshi, Ryoko; Katagiri, Miho; Sawamura, Sadashi

    2007-05-01

    Dimethylsulfoxide (DMSO)-Br complexes were generated by pulse radiolysis of DMSO/bromomethane mixtures and the formation mechanism and spectral characteristics of the formed complexes were investigated in detail. The rate constant for the reaction of bromine atoms with DMSO and the extinction coefficient of the complex were obtained to be 4.6×10 9 M -1 s -1 and 6300 M -1 cm -1 at the absorption maximum of 430 nm. Rate constants for the reaction of bromine atoms with a series of alcohols were determined in CBrCl 3 solutions applying a competitive kinetic method using the DMSO-Br complex as the reference system. The obtained rate constants were ˜10 8 M -1 s -1, one or two orders larger than those reported for highly polar solvents. Rate constants of DMSO-Br complexes with alcohols were determined to be ˜ 10 7 M -1 s -1. A comparison of the reactivities of Br atoms and DMSO-Br complexes with those of chlorine atoms and chlorine atom complexes which are ascribed to hydrogen abstracting reactants strongly indicates that hydrogen abstraction from alcohols is not the rate determining step in the case of Br atoms and DMSO-Br complexes.

  6. Deriving an atmospheric budget of total organic bromine using airborne in-situ measurements from the Western Pacific during SHIVA

    Science.gov (United States)

    Sala, S.; Bönisch, H.; Keber, T.; Oram, D. E.; Mills, G.; Engel, A.

    2014-02-01

    During the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) project an extensive dataset of all halogen species relevant for the atmospheric budget of total organic bromine has been collected in the West Pacific region using the FALCON aircraft operated by the German Aerospace agency DLR (Deutsches Zentrum für Luft- und Raumfahrt) covering a vertical range from the planetary boundary layer up to the ceiling altitude of the aircraft of 13 km. In total, more than 700 measurements were performed with the newly developed fully-automated in-situ instrument GHOST-MS (Gas cHromatograph for the Observation of Tracers - coupled with a Mass Spectrometer) by the Goethe University of Frankfurt (GUF) and with the onboard whole-air sampler WASP with subsequent ground based state-of-the-art GC/MS analysis by the University of East Anglia (UEA). Both instruments yield good agreement for all major (CHBr3 and CH2Br2) and minor (CHBrCl, CHBrCl2 and CHBr2Cl) VSLS (very short-lived substances), at least at the level of their 2 σ measurement uncertainties. In contrast to the suggestion that the Western Pacific could be a major source region for VSLS (Pyle et al., 2011), we found only slightly enhanced mixing ratios of brominated halogen source gases relative to the levels reported in Montzka et al. (2011) for other tropical regions. A budget for total organic bromine, including all four halons,CH3Br and the VSLS, is derived for the upper troposphere, the input region for the TTL and thus also for the stratosphere, compiled from the SHIVA dataset. With exception of the two minor VSLS CHBrCl2 and CHBr2Cl, excellent agreement with the values reported in Montzka et al. (2011) is found, while being slightly higher than previous studies from our group based on balloon-borne measurements.

  7. Polybrominated Diphenyl Ethers (PBDEs) in Surface Soils across Five Asian Countries: Levels, Spatial Distribution, and Source Contribution.

    Science.gov (United States)

    Li, Wen-Long; Ma, Wan-Li; Jia, Hong-Liang; Hong, Wen-Jun; Moon, Hyo-Bang; Nakata, Haruhiko; Minh, Nguyen Hung; Sinha, Ravindra Kumar; Chi, Kai Hsien; Kannan, Kurunthachalam; Sverko, Ed; Li, Yi-Fan

    2016-12-06

    A total of 23 polybrominated diphenyl ether (PBDE) congeners were measured in soil samples collected in areas with no known point source [urban/rural/background (U/R/B) sites] and in areas with known point source [brominated flame retardant (BFR)-related industrial sites (F sites) and e-waste recycling sites (E sites)] across five Asian countries. The highest PBDE concentrations were found in BFR-related industrial and e-waste recycling sites. The concentrations of PBDEs in U/R/B sites decreased in the following order: urban > rural > background sites. Total PBDE concentrations were dominated by BDE-209, while BDE-17, -85, -138, -191, -204, and -205 were the least abundant compounds. In both urban sites and rural sites, the mean concentrations of total PBDEs (∑ 23 BDEs) in soils decreased in the following order: Japan > China > South Korea > India > Vietnam. The concentrations of PBDEs in soils were comparable with those reported in other studies. Among the three commercial PBDE mixtures, relatively large contributions of commercial penta-BDE were observed in Vietnam, whereas deca-BDE was the dominant form in mixtures contributing from 55.8 ± 2.5 to 100.0 ± 1.2% of the total PBDEs in soils collected from other four countries. Regression analysis suggested that local population density (PD) is a good indicator of PBDEs in soils of each country. Significant and positive correlation between soil organic content and PBDE level was observed in Chinese soil for most nondeca-BDE homologues with their usage stopped 10 years ago, indicating its important role in controlling the revolatilization of PBDEs from soil and changing the spatial trend of PBDE in soil from the primary distribution pattern to the secondary distribution pattern, especially when primary emission is ceased.

  8. The environmental fate of polybrominated diphenyl ethers in the centre of Stockholm - Assessment using a multimedia fugacity model

    Energy Technology Data Exchange (ETDEWEB)

    Palm, Anna

    2001-01-01

    A local-scale assessment of the environmental fate of three congeners of polybrominated diphenyl ethers (PBDEs) has been performed for the centre of Stockholm. The partitioning properties and main transport processes of these congeners in Stockholm are identified using a site-specific multimedia fugacity model, called CeStoc, that was developed and parameterized for the area of interest. CeStoc was based on level III and IV fugacity models. Five compartments were included: air, water, soil, sediment and an organic film covering the impervious surfaces in the city. The model was satisfactory calibrated with the PAH fluoranthene, before it was run for the compounds of interest. Validation with environmental levels of PBDEs was made where possible, showing reasonable agreement with model results. According to the CeStoc results, the majority of the PBDEs emitted are transported out of the region through air advection, implying that Stockholm may act as a source for chemical release to other regions. The largest sink for PBDEs in Stockholm is soil, closely followed by sediment, the two compartments together accounting for about 98 % of the total amount remaining in the system. The degree of bromination does not seem to have a large impact on the environmental distribution in this area, but further research on e.g. physical-chemical properties is necessary before this can be finally concluded. Predicted concentrations of individual PBDE congeners in sediment and water lie in the same range as measured levels of individual PCB-congeners, indicating that PBDEs could have an environmental impact of about the same size as the PCBs.

  9. Diphenyl-phosphinyl-morpholide (DPPM) lanthanide trifluoroacetate adducts

    International Nuclear Information System (INIS)

    Carvalho, L.R.F. de; Kim, D.J.

    1984-01-01

    Preparation and properties of adducts of lanthanide salts and diphenyl-phosphinyl-morpholide (DPPM) have been described in the literature. Addition compounds containing lanthanide nitrates, isothiocyanates, perchlorates, chlorides, bromides with DPPM have been obtained. In this article, the preparation and characterization of the addition compounds of lanthanide trifluoroacetates (TFA) with DPPM are reported. The compounds of general formula Ln (TFA) 3 . 3DPPM, Ln= La-Lu, Y were characterized by elemental analysis, melting ranges, infrared spectra, absorption and emission visible spectra, X-ray powder patterns. (Author) [pt

  10. Polybrominated diphenyl ether flame retardants in Virginia freshwater fishes (USA).

    Science.gov (United States)

    Hale, R C; La Guardia, M J; Harvey, E P; Mainor, T M; Duff, W H; Gaylor, M O

    2001-12-01

    Polybrominated diphenyl ethers (PBDEs) were examined in fish fillets collected from two large Virginia watersheds. Emphasis was on the tetra- to hexabrominated congeners since these exhibit the greatest bioaccumulation and toxicological potentials. These congeners are dominant constituents of Penta-, a commercial PBDE product used to flame retard polyurethane foam. In 1999, North America accounted for98% of global Penta-demand. Concentrations of total tetra- to hexabrominated congeners in fillets ranged from furniture and textile manufacturing, although polyurethane foam production here has been limited.

  11. Evaluation of long-range transport potential of selected brominated flame retardants with measured 1-octanol-air partition coefficients

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Hyun Jeong; Kwon, Jung Hwan [Div. of Environmental Science and Ecological Engineering, Korea University, Seoul (Korea, Republic of)

    2016-10-15

    Various alternative flame retardants are used in many countries since polybrominated diphenyl ethers (PBDEs) were classified as persistent organic pollutants (POPs). However, difficulties in the evaluation of the long-range transport potential (LRTP) of the alternatives are related to the lack of information on their physicochemical properties, which govern their environmental fates and transport. Based on the simulation of LRTP using OECD P{sub OV} and LRTP Screening Tool, five alternative brominated flame retardants (BFRs) (hexabromobenzene [HBB], 2,3,4,5,6-pentabromotoluene [PBT], 2,3,4,5,6-pentabromoethylbenzene [PBEB], 2-ethylhexyl 2,3,4,5-tetrabromobenzoate [TBB], and 1,2,4,5-tetrabromo-3,6-dimethylbenzene [TBX]), and 3 PBDEs (BDE-28, BDE-47, and BDE-99) were chosen to perform a refined assessment. This was done using an experimentally measured 1-octanol–air partition coefficient (K{sub OA}) for the calculation of the air–water partition coefficient (K{sub AW}) required for the model. The four selected alternative BFRs (HBB, PBT, PBEB, TBX) have K{sub OA} values close to the in silico estimation used in the screening evaluation. On the other hand, the measured K{sub OA} value for TBB was two orders of magnitude lower than the estimated value used in the screening simulation. The refined simulation showed that characteristic travel distance (CTD) and transfer efficiency (TE) for HBB, PBT, PBEB, and TBX were greater than those for BDE-28, whereas CTD and TE for TBB were lower than those for BDE-28. This suggested that TBB has a lower LRTP than BDE-28, considering the refined partition coefficients.

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

    Energy Technology Data Exchange (ETDEWEB)

    Qi, Hong; Li, Wen-Long; Liu, Li-Yan; Song, Wei-Wei; Ma, Wan-Li, E-mail: mawanli002@163.com; Li, Yi-Fan, E-mail: ijrc_pts_paper@yahoo.com

    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{sup 3} and 180 pg/m{sup 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 (logK{sub p}) for most low molecular weight BFRs were highly temperature dependent as well. Gas–particle partitioning coefficients (logK{sub p}) also correlated with the sub-cooled liquid vapor pressure (logP{sub L}{sup o}). Our results indicated that absorption into organic matter is the main control mechanism for the gas–particle partitioning of atmospheric PBDEs. - Highlights: • Both PBDEs and alternative BFRs were analyzed in the atmosphere of Northeast China. • Partial pressure of BFRs was significantly correlated with the ambient temperature. • A strong temperature dependence of gas-particle partitioning was found. • Absorption into organic matter was the control mechanism for G-P partitioning.

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

    Science.gov (United States)

    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. Copyright © 2016 Elsevier Ltd. All rights reserved.

  14. Standard test method for determination of bromine and chlorine in UF6 and uranyl nitrate by X-Ray fluorescence (XRF) spectroscopy

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2001-01-01

    1.1 This method covers the determination of bromine (Br) and chlorine (Cl) in uranium hexafluoride (UF6) and uranyl nitrate solution. The method as written covers the determination of bromine in UF6 over the concentration range of 0.2 to 8 μg/g, uranium basis. The chlorine in UF6 can be determined over the range of 4 to 160 μg/g, uranium basis. Higher concentrations may be covered by appropriate dilutions. The detection limit for Br is 0.2 μg/g uranium basis and for Cl is 4 μg/g uranium basis. 1.2 This standard may involve hazardous materials, operations and equipment. This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

  15. The chemistry of bromine in the stratosphere: Influence of a new rate constant for the reaction BrO + HO2

    Science.gov (United States)

    Pirre, Michel; Marceau, Francois J.; Lebras, Georges; Maguin, Francoise; Poulet, Gille; Ramaroson, Radiela

    1994-01-01

    The impact of new laboratory data for the reaction BrO + HO2 yields HOBr + O2 in the depletion of global stratospheric ozone has been estimated using a one-dimensional photochemical model taking into account the heterogeneous reaction on sulphate aerosols which converts N2O5 into HNO3. Assuring an aerosol loading 2 times as large as the 'background' and a reaction probability of 0.1 for the above heterogeneous reaction, the 6 fold increase in the measured rate constant for the reaction of BrO with HO2 increases the computed depletion of global ozone produced by 20 ppt of total bromine from 2.01 percent to 2.36 percent. The use of the higher rate constant increases the HOBr mixing ratio and makes the bromine partitioning and the ozone depletion very sensitive to the branching ratio of the potential channel forming HBr in the BrO + HO2 reaction.

  16. Kinetics and Pathways for the Debromination of Polybrominated Diphenyl Ethers by Bimetallic and Nanoscale Zerovalent Iron: Effects of Particle Properties and Catalyst

    Science.gov (United States)

    Zhuang, Yuan; Jin, Luting; Luthy, Richard G.

    2012-01-01

    Polybrominated diphenyl ethers (PBDEs) are recognized as a new class of widely-distributed and persistent contaminants for which effective treatment and remediation technologies are needed. In this study, two kinds of commercially available nanoscale Fe° slurries (Nanofer N25 and N25S), a freeze-dried laboratory-synthesized Fe° nanoparticle (nZVI), and their palladized forms were used to investigate the effect of particle properties and catalyst on PBDE debromination kinetics and pathways. Nanofers and their palladized forms were found to debrominate PBDEs effectively. The laboratory-synthesized Fe° nanoparticles also debrominated PBDEs, but were slower due to deactivation by the freeze-drying and stabilization processes in the laboratory synthesis. An organic modifier, polyacrylic acid (PAA), bound on N25S slowed PBDE debromination by a factor of three to four compared to N25. The activity of palladized nZVI (nZVI/Pd) was optimized at 0.3 Pd/Fe wt% in our system. N25 could debrominate selected environmentally-abundant PBDEs, including BDE 209, 183, 153, 99, and 47, to end products di-BDEs, mono-BDEs and diphenyl ether (DE) in one week, while nZVI/Pd (0.3 Pd/Fe wt%) mainly resulted in DE as a final product. Step-wise major PBDE debromination pathways by unamended and palladized Fe° are described and compared. Surface precursor complex formation is an important limiting factor for palladized Fe° reduction as demonstrated by PBDE pathways where steric hindrance and rapid sequential debromination of adjacent bromines play an important role. PMID:22732301

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

    Science.gov (United States)

    Kikuchi, Ryunosuke; Gerardo, Romeu; Gorbacheva, Tamara

    2010-05-01

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

  18. Occurrence of polybrominated diphenyl ethers (PBDEs) in foodstuffs in Italy and implications for human exposure.

    Science.gov (United States)

    Martellini, Tania; Diletti, Gianfranco; Scortichini, Giampiero; Lolini, Meri; Lanciotti, Eudes; Katsoyiannis, Athanasios; Cincinelli, Alessandra

    2016-03-01

    Polybrominated diphenyl ethers (PBDEs) were determined in various foodstuffs in Italy and the dietary intake was estimated. PBDEs were detected in all analysed samples at concentrations that spanned over five orders of magnitude. The most abundant congeners were the BDE-209, followed by BDE-47 and BDE-99. Fish oil and milk samples showed the highest PBDE concentrations among all samples. The daily dietary intake values were found to be in good agreement or higher to literature values, impacted mainly from the contribution of the analysed dairy products. The cancer risk values estimated for BDE-209 indicated that this specific risk associated with the studied foodstuffs is limited. Italy is one of the world-leading countries in the production of furniture and clothes and has extremely developed medium enterprise industrial sector, where PBDEs were historically used suggesting that their occurrence may be linked to these activities. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Determination of polybrominated diphenyl ethers in environmental standard reference materials

    Energy Technology Data Exchange (ETDEWEB)

    Stapleton, Heather M.; Schantz, Michele M.; Wise, Stephen A. [National Institute of Standards and Technology, Analytical Chemistry Division, Gaithersburg, MD (United States); Keller, Jennifer M.; Kucklick, John R. [National Institute of Standards and Technology, Analytical Chemistry Division, Hollings Marine Laboratory, Charleston, SC (United States); Leigh, Stefan D. [National Institute of Standards and Technology, Statistical Engineering Division, Gaithersburg, MD (United States)

    2007-04-15

    Standard reference materials (SRMs) are valuable tools in developing and validating analytical methods to improve quality assurance standards. The National Institute of Standards and Technology (NIST) has a long history of providing environmental SRMs with certified concentrations of organic and inorganic contaminants. Here we report on new certified and reference concentrations for 27 polybrominated diphenyl ether (PBDE) congeners in seven different SRMs: cod-liver oil, whale blubber, fish tissue (two materials), mussel tissue and sediment (two materials). PBDEs were measured in these SRMs, with the lowest concentrations measured in mussel tissue (SRM 1974b) and the highest in sediment collected from the New York/New Jersey Waterway (SRM 1944). Comparing the relative PBDE congener concentrations within the samples, we found the biota SRMs contained primarily tetrabrominated and pentabrominated diphenyl ethers, whereas the sediment SRMs contained primarily decabromodiphenyl ether (BDE 209). The cod-liver oil (SRM 1588b) and whale blubber (SRM 1945) materials were also found to contain measurable concentrations of two methoxylated PBDEs (MeO-BDEs). Certified and reference concentrations are reported for 12 PBDE congeners measured in the biota SRMs and reference values are available for two MeO-BDEs. Results from a sediment interlaboratory comparison PBDE exercise are available for the two sediment SRMs (1941b and 1944). (orig.)

  20. Developmental toxicity of diphenyl ether herbicides in nestling American kestrels.

    Science.gov (United States)

    Hoffman, D J; Spann, J W; LeCaptain, L J; Bunck, C M; Rattner, B A

    1991-11-01

    Beginning the day after hatching, American kestrel (Falco sparverius) nestlings were orally dosed for 10 consecutive days with 5 microliters/g of corn oil (controls) or one of the diphenyl ether herbicides (nitrofen, bifenox, or oxyfluorfen) at concentrations of 10, 50, 250, or 500 mg/kg in corn oil. At 500 mg/kg, nitrofen resulted in complete nestling mortality, bifenox in high (66%) mortality, and oxyfluorfen in no mortality. Nitrofen at 250 mg/kg reduced nestling growth as reflected by decreased body weight, crown-rump length, and bone lengths including humerus, radius-ulna, femur, and tibiotarsus. Bifenox at 250 mg/kg had less effect on growth than nitrofen, but crown-rump, humerus, radius-ulna, and femur were significantly shorter than controls. Liver weight as a percent of body weight increased with 50 and 250 mg/kg nitrofen. Other manifestations of impending hepatotoxicity following nitrofen ingestion included increased hepatic GSH peroxidase activity in all nitrofen-treated groups, and increased plasma enzyme activities for ALT, AST, and LDH-L in the 250-mg/kg group. Bifenox ingestion resulted in increased hepatic GSH peroxidase activity in the 50- and 250-mg/kg groups. Nitrofen exposure also resulted in an increase in total plasma thyroxine (T4) concentration. These findings suggest that altricial nestlings are more sensitive to diphenyl ether herbicides than young or adult birds of precocial species.

  1. Brominated methanes as photoresponsive molecular storage of elemental Br2.

    Science.gov (United States)

    Kawakami, Kazumitsu; Tsuda, Akihiko

    2012-10-01

    The photochemical generation of elemental Br(2) from brominated methanes is reported. Br(2) was generated by the vaporization of carbon oxides and HBr through oxidative photodecomposition of brominated methanes under a 20 W low-pressure mercury lamp, wherein the amount and situations of Br(2) generation were photochemically controllable. Liquid CH(2)Br(2) can be used not only as an organic solvent but also for the photoresponsive molecular storage of Br(2), which is of great technical benefit in a variety of organic syntheses and in materials science. By taking advantage of the in situ generation of Br(2) from the organic solvent itself, many organobromine compounds were synthesized in high practical yields with or without the addition of a catalyst. Herein, Br(2) that was generated by the photodecomposition of CH(2)Br(2) retained its reactivity in solution to undergo essentially the same reactions as those that were carried out with solutions of Br(2) dissolved in CH(2)Br(2) that were prepared without photoirradiation. Furthermore, HBr, which was generated during the course of the photodecomposition of CH(2)Br(2), was also available for the substitution of the OH group for the Br group and for the preparation of the HBr salts of amines. Furthermore, the photochemical generation of Br(2) from CH(2)Br(2) was available for the area-selective photochemical bleaching of natural colored plants, such as red rose petals, wherein Br(2) that was generated photochemically from CH(2)Br(2) was painted onto the petal to cause radical oxidations of the chromophoric anthocyanin molecules. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. “One-shot” analysis of polybrominated diphenyl ethers and their hydroxylated and methoxylated analogs in human breast milk and serum using gas chromatography-tandem mass spectrometry

    International Nuclear Information System (INIS)

    Butryn, Deena M.; Gross, Michael S.; Chi, Lai-Har; Schecter, Arnold; Olson, James R.; Aga, Diana S.

    2015-01-01

    The presence of polybrominated diphenyl ethers (PBDEs) and their hydroxylated (OH-BDE) and methoxylated (MeO-BDE) analogs in humans is an area of high interest to scientists and the public due to their neurotoxic and endocrine disrupting effects. Consequently, there is a rise in the investigation of the occurrence of these three classes of compounds together in environmental matrices and in humans in order to understand their bioaccumulation patterns. Analysis of PBDEs, OH-BDEs, and MeO-BDEs using liquid chromatography-mass spectrometry (LC-MS) can be accomplished simultaneously, but detection limits for PBDEs and MeO-BDEs in LC-MS is insufficient for trace level quantification. Therefore, fractionation steps of the phenolic (OH-BDEs) and neutral (PBDEs and MeO-BDEs) compounds during sample preparation are typically performed so that different analytical techniques can be used to achieve the needed sensitivities. However, this approach involves multiple injections, ultimately increasing analysis time. In this study, an analytical method was developed for a “one-shot” analysis of 12 PBDEs, 12 OH-BDEs, and 13 MeO-BDEs using gas chromatography with tandem mass spectrometry (GC-MS/MS). This overall method includes simultaneous extraction of all analytes via pressurized liquid extraction followed by lipid removal steps to reduce matrix interferences. The OH-BDEs were derivatized using N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide (TBDMS-MTFA), producing OH-TBDMS derivatives that can be analyzed together with PBDEs and MeO-BDEs by GC-MS/MS in “one shot” within a 25-min run time. The overall recoveries were generally higher than 65%, and the limits of detection ranged from 2 to 14 pg in both breast milk and serum matrices. The applicability of the method was successfully validated on four paired human breast milk and serum samples. The mean concentrations of total PBDEs, OH-BDEs, and MeO-BDEs in breast milk were 59, 2.2, and 0.57 ng g −1 lipid

  3. “One-shot” analysis of polybrominated diphenyl ethers and their hydroxylated and methoxylated analogs in human breast milk and serum using gas chromatography-tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Butryn, Deena M.; Gross, Michael S. [Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, NY 14260 (United States); Chi, Lai-Har [Department of Pharmacology and Toxicology, University at Buffalo, The State University of New York, Buffalo, NY 14214 (United States); Department of Epidemiology and Environmental Health, University at Buffalo, The State University of New York, Buffalo, NY 14214 (United States); Schecter, Arnold [Department of Pharmacology and Toxicology, University of Louisville College of Medicine, Louisville, KY 40202 (United States); Olson, James R. [Department of Pharmacology and Toxicology, University at Buffalo, The State University of New York, Buffalo, NY 14214 (United States); Department of Epidemiology and Environmental Health, University at Buffalo, The State University of New York, Buffalo, NY 14214 (United States); Aga, Diana S., E-mail: dianaaga@buffalo.edu [Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, NY 14260 (United States)

    2015-09-10

    The presence of polybrominated diphenyl ethers (PBDEs) and their hydroxylated (OH-BDE) and methoxylated (MeO-BDE) analogs in humans is an area of high interest to scientists and the public due to their neurotoxic and endocrine disrupting effects. Consequently, there is a rise in the investigation of the occurrence of these three classes of compounds together in environmental matrices and in humans in order to understand their bioaccumulation patterns. Analysis of PBDEs, OH-BDEs, and MeO-BDEs using liquid chromatography-mass spectrometry (LC-MS) can be accomplished simultaneously, but detection limits for PBDEs and MeO-BDEs in LC-MS is insufficient for trace level quantification. Therefore, fractionation steps of the phenolic (OH-BDEs) and neutral (PBDEs and MeO-BDEs) compounds during sample preparation are typically performed so that different analytical techniques can be used to achieve the needed sensitivities. However, this approach involves multiple injections, ultimately increasing analysis time. In this study, an analytical method was developed for a “one-shot” analysis of 12 PBDEs, 12 OH-BDEs, and 13 MeO-BDEs using gas chromatography with tandem mass spectrometry (GC-MS/MS). This overall method includes simultaneous extraction of all analytes via pressurized liquid extraction followed by lipid removal steps to reduce matrix interferences. The OH-BDEs were derivatized using N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide (TBDMS-MTFA), producing OH-TBDMS derivatives that can be analyzed together with PBDEs and MeO-BDEs by GC-MS/MS in “one shot” within a 25-min run time. The overall recoveries were generally higher than 65%, and the limits of detection ranged from 2 to 14 pg in both breast milk and serum matrices. The applicability of the method was successfully validated on four paired human breast milk and serum samples. The mean concentrations of total PBDEs, OH-BDEs, and MeO-BDEs in breast milk were 59, 2.2, and 0.57 ng g{sup −1} lipid

  4. Preparation of radioactive labelled compounds Pt.1. 82Br labelled organic bromine compounds

    International Nuclear Information System (INIS)

    Otto, R.

    1988-05-01

    A simple method allowing the preparation of 82 Br labelled organic bromine compounds from olefins with chemical and radiochemical yields between 75 and 95% and the specific activities required, is described [fr

  5. Theoretical study of the reaction kinetics of atomic bromine with tetrahydropyran

    KAUST Repository

    Giri, Binod; Lo, John M H; Roscoe, John M.; Alquaity, Awad; Farooq, Aamir

    2015-01-01

    A detailed theoretical analysis of the reaction of atomic bromine with tetrahydropyran (THP, C5H10O) was performed using several ab initio methods and statistical rate theory calculations. Initial geometries of all species involved in the potential

  6. Bromine determination by neutron activation analysis and its distribution in the atmosphere

    International Nuclear Information System (INIS)

    Iturbe Garcia, J.L.; Lopez Munoz, B.E.

    2002-01-01

    Bromine, one of the main participants in ozone layer destruction, is 10 to 100 times more effective than chlorine. There are two principal sources of methyl bromide emissions: the oceans and some pesticides that are used in farming. Bromine was detected in 'premium' and 'magna sin' gasolines (2.86±0.96 and 1.54±0.38 ppm, respectively) as well as in condensed water found in exhaust pipes of vehicles. In addition, samples of rainwater were also analyzed to determine atmospheric bromine concentration. In water samples Br concentrations ranging from 2.09 to 0.06 ppm were found. The techniques utilised were neutron activation analysis and high voltage electrophoresis, the latter to determine the chemical form of bromine in condensed water samples. Finally, suspended particles from rainwater were also analysed by scanning electron microscopy (SEM). (author)

  7. Bromine and iodine in Chinese medical herbs determined via epithermal neutron activation analysis

    International Nuclear Information System (INIS)

    Chien-Yi Chen; Yuan-Yaw Wei; Sheng-Pin ChangLai; Lung-Kwang Pan

    2003-01-01

    Nineteen natural herbs and two prescriptions prepared from mixed herbs were analyzed via epithermal neutron activation analysis (ENAA) to evaluate their bromine and iodine concentration. Traditional medical doctors prescribed the samples presented in this work to most Taiwanese children for strengthening their immune systems. Empirical results indicated a wide diversity of bromine in the samples. Yet, the iodine concentration was only around one to tenth or twentieth of the bromine. The maximum daily intake (MDI) for various medical herbs was also widely diversified from one to tenfold on the basis of various criteria. The minimum detectable concentration (MDC) of bromine and iodine found was 0.42±0.14 ppm and 0.067±0.016 ppm, respectively. Compared to that from conventional thermal neutron activation analysis (NAA) for a similar evaluation, the extremely low MDC obtained here was attributed to the large amount of thermal neutron absorption during sample irradiation. (author)

  8. Molecular dynamics simulations and thermochemistry of reactive ion etching of silicon by chlorine, chlorine dimer, bromine, and bromine dimer cations

    Energy Technology Data Exchange (ETDEWEB)

    Valone, S.M.; Hanson, D.E.; Kress, J.D.

    1998-05-08

    Simulations of Cl plasma etch of Si surfaces with MD techniques agree reasonably well with the available experimental information on yields and surface morphologies. This information has been supplied to a Monte Carlo etch profile resulting in substantial agreement with comparable inputs provided through controlled experiments. To the extent that more recent measurements of etch rates are more reliable than older ones, preliminary MD simulations using bond-order corrections to the atomic interactions between neighboring Si atoms on the surface improves agreement with experiment through an increase in etch rate and improved agreement with XPS measurements of surface stoichiometry. Thermochemical and geometric analysis of small Si-Br molecules is consistent with the current notions of the effects of including brominated species in etchant gases.

  9. New insight into photo-bromination processes in saline surface waters: The case of salicylic acid

    Energy Technology Data Exchange (ETDEWEB)

    Tamtam, Fatima; Chiron, Serge, E-mail: serge.chiron@msem.univ-montp2.fr

    2012-10-01

    It was shown, through a combination of field and laboratory observations, that salicylic acid can undergo photo-bromination reactions in sunlit saline surface waters. Laboratory-scale experiments revealed that the photochemical yields of 5-bromosalicylic acid and 3,5-dibromosalicylic acid from salicylic acid were always low (in the 4% range at most). However, this might be of concern since these compounds are potential inhibitors of the 20{alpha}-hydroxysteroid dehydrogenase enzyme, with potential implications in endocrine disruption processes. At least two mechanisms were involved simultaneously to account for the photo-generation of brominated substances. The first one might involve the formation of reactive brominated radical species (Br{center_dot}, Br{sub 2}{center_dot}{sup -}) through hydroxyl radical mediated oxidation of bromide ions. These ions reacted more selectively than hydroxyl radicals with electron-rich organic pollutants such as salicylic acid. The second one might involve the formation of hypobromous acid, through a two electron oxidation of bromine ions by peroxynitrite. This reaction was catalyzed by nitrite, since these ions play a crucial role in the formation of nitric oxide upon photolysis. This nitric oxide further reacts with superoxide radical anions to yield peroxynitrite and by ammonium through the formation of N-bromoamines, probably due to the ability of N-bromoamines to promote the aromatic bromination of phenolic compounds. Field measurements revealed the presence of salicylic acid together with 5-bromosalicylic and 3,5-dibromosalicylic acid in a brackish coastal lagoon, thus confirming the environmental significance of the proposed photochemically induced bromination pathways. -- Highlights: Black-Right-Pointing-Pointer Brominated derivatives of salicylic acid were detected in a brackish lagoon. Black-Right-Pointing-Pointer A photochemical pathway was hypothesized to account for bromination of salicylic acid. Black

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

    Science.gov (United States)

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

    2017-02-15

    The concentrations and distributions of PBDEs and novel brominated flame retardants (NBFRs) in dissolved phase of surface seawater near a coastal mariculture area of the Bohai Sea were investigated. The total concentrations of PBDE and NBFRs were in the range of 15.4-65.5 and 2.12-13.6ng/L, respectively. The highest concentration was discovered in the water near an anchorage ground, whereas concentrations in water samples from offshore cage-culture area were not elevated. Relatively high concentrations of BDE28, 99, and 100 were discovered in the medium range of distance from shore, where is the path of tidal or coastal current. This suggested that inputs from ships or through tidal current rather than mariculture activities may be the main sources of BFRs in this area. BDE209, BDE47, hexabromobenzene (HBB), and 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) were the most abundant BFR congeners. Relatively high proportions of these BFRs may originate from discharge of wastewater nearby or degradation from higher brominated PBDEs. No correlations were found between BFR concentrations and water dissolved organic carbon, suggesting that concentrations and distributions of BFRs in this area were source-dependent. The relatively high concentrations in this study emphasized the importance of monitoring and managing BFR contaminations in mariculture areas of China. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. DETERMINATION OF ALKYLATED & SULFONATED DIPHENYL OXIDE SULFACTANT BY HIGH PERFORMANCE LIQUID CHROMATOGRAPHY

    Science.gov (United States)

    Methods for the determination of the anionic surfactant Dowfax 8390 are described. Dowfax is a complex mixture of various alkylated and sulfonated diphenyl oxides. The primary component of Dowfax is monoalkylated disulfonated diphenyl oxide (MADS). This work uses ion pairing chro...

  12. 40 CFR 721.2565 - Alkylated sulfonated diphenyl oxide, alkali and amine salts.

    Science.gov (United States)

    2010-07-01

    ..., alkali and amine salts. 721.2565 Section 721.2565 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.2565 Alkylated sulfonated diphenyl oxide, alkali and... substances identified as alkylated sulfonated diphenyl oxide, alkali salt (PMN P-93-352) and alkylated...

  13. Determination of arsenic and bromine in hot spring waters by neutron activation analysis

    International Nuclear Information System (INIS)

    Kikawada, Y.; Kawai, S.; Oi, T.

    2004-01-01

    Concentrations of arsenic and bromine dissolved in hot spring waters have been determined by neutron activation analysis using 0.5 cm 3 of sample waters without any chemical pretreatment. The samples prepared for neutron irradiation were simply pieces of filter papers which were infiltrated with samples. With the results of satisfactorily high accuracy and precision, this analytical method was found to be very convenient for the determinations of arsenic and bromine dissolved in water at ppm to sub-ppm levels. (author)

  14. Global assessment of polybrominated diphenyl ethers in farmed and wild salmom

    Energy Technology Data Exchange (ETDEWEB)

    Hites, R. [Indiana Univ., Bloomington, IN (United States); Foran, J. [Midwest Center for Environmental Science, Milwaukee, WI (United States); Schwager, S.; Knuth, B. [Cornell Univ., Ithaca, NY (United States); Hamilton, C. [AXYS Analytical, Sydney (Australia); Carpenter, D. [Albany Univ., NY (United States)

    2004-09-15

    Despite their societal benefits, polybrominated diphenyl ethers (PBDEs) seem to be migrating from the products in which they are used and entering the environment and people. PBDEs are now ubiquitous; they can be found in air, water, fish, birds, marine mammals, and people, and in most cases, the concentrations of these compounds have increased dramatically over the last 20 years. One source of PBDEs in people is their food supply, and an increasingly important food is salmon, which is nutritious and high in beneficial fats. Between 1987 and 1999, salmon consumption increased annually at a rate of 10-20%. Currently, over half the salmon sold globally is farm-raised in Northern Europe, Chile, Canada, and the United States, and the annual global production of farmed salmon (predominantly Atlantic salmon) has risen from {proportional_to}27,000 to over 1 million metric tons during the past two decades. The health benefits of eating fish such as salmon have been well documented. However, salmon are relatively fatty, carnivorous fish that feed high in the food web, and as such, they bioaccumulate contaminants. In a previous study, we reported that levels of persistent, bioaccumulative contaminants (such as PCBs, dioxins, and several chlorinated pesticides) are significantly higher in farm-raised salmon than in wild salmon and that salmon raised on European farms have significantly greater toxic contaminant loads than those raised on North and South American farms. In this report, we provide results on polybrominated diphenyl ether concentrations in salmon purchased from farms in eight major salmon farming regions, in five species of wild Pacific salmon, and in salmon fillets purchased at supermarkets in North America and Europe.

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

    Science.gov (United States)

    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.

  16. Polybrominated diphenyl ethers in Mississippi River suspended sediment

    Energy Technology Data Exchange (ETDEWEB)

    Raff, J.; Hites, R. [Indiana Univ., Bloomington, IN (United States)

    2004-09-15

    The Mississippi River Basin drains water from 41% of the conterminous U.S. and is a valuable resource that supplies food, transportation, and irrigation to more than 95 million people of the region. Discharge and runoff from industry, agriculture, and population centers have increased the loads of anthropogenic organic compounds in the river. There has been growing concern over the rising levels of polybrominated diphenyl ethers (PBDEs) in air, sediment, biota, and humans, but there have been no studies to measure the concentrations of these chemicals in North America's largest river system. The goal of this study was to investigate the occurrence of PBDEs (15 congeners including BDE-209) and to identify possible sources within the Mississippi River Basin. We found PBDEs to be widespread throughout the region, rivaling PCBs in their extent and magnitude of contamination. We have also calculated the total amount of PBDEs released to the Gulf of Mexico in 2002.

  17. Substance Flow Analysis of Wastes Containing Polybrominated Diphenyl Ethers

    DEFF Research Database (Denmark)

    Vyzinkarova, Dana; Brunner, Paul H.

    2013-01-01

    materials. Therefore, end-of-life (EOL) plastic materials used for construction must be separated and properly treated, for example, in a state-of-the-art municipal solid waste (MSW) incinerator. In the case of cOctaBDE, the main flows are waste electrical and electronic equipment (WEEE) and, possibly......The present article examines flows and stocks of Stockholm Convention regulated pollutants, commercial penta- and octabrominated diphenyl ether (cPentaBDE, cOctaBDE), on a city level. The goals are to (1) identify sources, pathways, and sinks of these compounds in the city of Vienna, (2) determine...... the fractions that reach final sinks, and (3) develop recommendations for waste management to ensure their minimum recycling and maximum transfer to appropriate final sinks. By means of substance flow analysis (SFA) and scenario analysis, it was found that the key flows of cPentaBDE stem from construction...

  18. Photochemical Formation of Hydroxylated Polybrominated Diphenyl Ethers (OH-PBDEs) from Polybrominated Diphenyl Ethers (PBDEs) in Aqueous Solution under Simulated Solar Light Irradiation.

    Science.gov (United States)

    Zhao, Qian; Zhao, Huimin; Quan, Xie; He, Xin; Chen, Shuo

    2015-08-04

    Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) are of great concern due to their higher toxicity compared to PBDEs. However, the abiologic process whereby PBDEs are converted to OH-PBDEs in the aquatic environment is not well understood. To explore the possibility of OH-PBDEs photoformation in natural water, the photohydroxylation of BDE-47 has been investigated in aqueous Fe(III) and/or fulvic acid (FA) solutions and in natural lake water under simulated solar light irradiation. The results showed that 6-OH-BDE-47 and 2'-OH-BDE-68 were generated from BDE-47 under these conditions. Based on the identification of derivatives and reactive radicals, OH-PBDEs formation can be ascribed to an addition reaction of ortho-tetra-BDE radical and hydroxyl radical ((•)OH), with or without a subsequent Smiles rearrangement reaction. Since the ortho-tetra-BDE radical could be readily produced by the photolysis of BDE-47, even in pure water, (•)OH production was considered as critical for the photoformation of OH-PBDEs. Thus, it is reasonable to deduce that the photoreactive components (Fe(III), FA) in aqueous solution played an important role through influencing (•)OH generation. Although the yields of OH-PBDEs did not increase regularly with increasing concentration of these photoreactive components in solution, this study suggests a possible abiotic origin of OH-PBDEs formation in the aquatic environment.

  19. Fluorination of uranium compounds by gaseous bromine trifluoride and a bromine-fluorine mixture

    International Nuclear Information System (INIS)

    Sakurai, Tsutomu

    1976-03-01

    This report summarizes the studies of fluorination of uranium compounds by gaseous BrF 3 and a Br 2 -F 2 mixture, which were carried out in Fluorine Chemistry Laboratory of JAERI in connection with the reprocessing method of nuclear fuels. Although thermodynamically more stable than F 2 , BrF 3 has higher reactivity at relatively low temperatures: fluorination of uranium compounds can be carried out at 100 0 -- 200 0 C by using gaseous BrF 3 . This fluorination temperature is lower than those of F 2 , BrF 5 , ClF and SF 4 , and close to that of ClF 3 . The usage of BrF 3 has however the drawbacks that it requires additional devices to heat the corrosive liquid and to remove Br 2 produced as a byproduct. In order to eliminate the difficulties indicated, a new method of fluorination was developed - the use of a Br 2 -F 2 mixture. Addition of small amounts of Br 2 to the fluorine flow (about 6% in relation to the fluorine concentration) gives marked effects on the rate of fluorination. (auth.)

  20. An exemplary case of a bromine explosion event linked to cyclone development in the Arctic

    Directory of Open Access Journals (Sweden)

    A.-M. Blechschmidt

    2016-02-01

    Full Text Available Intense, cyclone-like shaped plumes of tropospheric bromine monoxide (BrO are regularly observed by GOME-2 on board the MetOp-A satellite over Arctic sea ice in polar spring. These plumes are often transported by high-latitude cyclones, sometimes over several days despite the short atmospheric lifetime of BrO. However, only few studies have focused on the role of polar weather systems in the development, duration and transport of tropospheric BrO plumes during bromine explosion events. The latter are caused by an autocatalytic chemical chain reaction associated with tropospheric ozone depletion and initiated by the release of bromine from cold brine-covered ice or snow to the atmosphere. In this manuscript, a case study investigating a comma-shaped BrO plume which developed over the Beaufort Sea and was observed by GOME-2 for several days is presented. By making combined use of satellite data and numerical models, it is shown that the occurrence of the plume was closely linked to frontal lifting in a polar cyclone and that it most likely resided in the lowest 3 km of the troposphere. In contrast to previous case studies, we demonstrate that the dry conveyor belt, a potentially bromine-rich stratospheric air stream which can complicate interpretation of satellite retrieved tropospheric BrO, is spatially separated from the observed BrO plume. It is concluded that weather conditions associated with the polar cyclone favoured the bromine activation cycle and blowing snow production, which may have acted as a bromine source during the bromine explosion event.

  1. Observations of bromine monoxide transport in the Arctic sustained on aerosol particles

    Directory of Open Access Journals (Sweden)

    P. K. Peterson

    2017-06-01

    Full Text Available The return of sunlight in the polar spring leads to the production of reactive halogen species from the surface snowpack, significantly altering the chemical composition of the Arctic near-surface atmosphere and the fate of long-range transported pollutants, including mercury. Recent work has shown the initial production of reactive bromine at the Arctic surface snowpack; however, we have limited knowledge of the vertical extent of this chemistry, as well as the lifetime and possible transport of reactive bromine aloft. Here, we present bromine monoxide (BrO and aerosol particle measurements obtained during the March 2012 BRomine Ozone Mercury EXperiment (BROMEX near Utqiaġvik (Barrow, AK. The airborne differential optical absorption spectroscopy (DOAS measurements provided an unprecedented level of spatial resolution, over 2 orders of magnitude greater than satellite observations and with vertical resolution unable to be achieved by satellite methods, for BrO in the Arctic. This novel method provided quantitative identification of a BrO plume, between 500 m and 1 km aloft, moving at the speed of the air mass. Concurrent aerosol particle measurements suggest that this lofted reactive bromine plume was transported and maintained at elevated levels through heterogeneous reactions on colocated supermicron aerosol particles, independent of surface snowpack bromine chemistry. This chemical transport mechanism explains the large spatial extents often observed for reactive bromine chemistry, which impacts atmospheric composition and pollutant fate across the Arctic region, beyond areas of initial snowpack halogen production. The possibility of BrO enhancements disconnected from the surface potentially contributes to sustaining BrO in the free troposphere and must also be considered in the interpretation of satellite BrO column observations, particularly in the context of the rapidly changing Arctic sea ice and snowpack.

  2. Material and orientation dependent activity for heterogeneously catalyzed carbon-bromine bond homolysis

    Energy Technology Data Exchange (ETDEWEB)

    Walch, Hermann; Gutzler, Rico; Sirtl, Thomas; Eder, Georg; Lackinger, Markus [LMU Munich, Section Crystallography (Germany)

    2010-07-01

    Adsorption of the organic molecule 1,3,5-tris(4-bromophenyl)benzene on different metallic substrates, namely Cu(111), Ag(111) and Ag(110) has been studied by variable temperature Scanning Tunneling Microscopy (STM). Depending on substrate temperature, material and orientation, we observe a surface-catalyzed dehalogenation reaction. Deposition onto the catalytically active substrates Cu(111) and Ag(110) held at room temperature leads to cleavage of the carbon-bromine bonds and subsequent formation of protopolymers, i.e radical metal coordination complexes. However upon deposition on Ag(111) no such reaction has been observed. Instead, various self-assembled ordered structures based on intact molecules could be identified. Also sublimation onto either substrate held at 80 K did not result in any dehalogenation, thereby exemplifying that the dehalogenation reaction is thermally activated. We explain the differences in catalytic activity by charge transfer into unoccupied molecular orbitals and subsequent destabilization of the C-Br bond, whereby enhanced molecule-substrate interaction leads to an increasing magnitude of charge transfer. The interaction strength follows the general reactivity order Cu>Ag>Au for (111) faces and is generally enhanced on higher corrugated surfaces as the (110) facet in case of fcc substrates.

  3. A quorum sensing-disrupting brominated thiophenone with a promising therapeutic potential to treat luminescent vibriosis.

    Directory of Open Access Journals (Sweden)

    Tom Defoirdt

    Full Text Available Vibrio harveyi is amongst the most important bacterial pathogens in aquaculture. Novel methods to control this pathogen are needed since many strains have acquired resistance to antibiotics. We previously showed that quorum sensing-disrupting furanones are able to protect brine shrimp larvae against vibriosis. However, a major problem of these compounds is that they are toxic toward higher organisms and therefore, they are not safe to be used in aquaculture. The synthesis of brominated thiophenones, sulphur analogues of the quorum sensing-disrupting furanones, has recently been reported. In the present study, we report that these compounds block quorum sensing in V. harveyi at concentrations in the low micromolar range. Bioluminescence experiments with V. harveyi quorum sensing mutants and a fluorescence anisotropy assay indicated that the compounds disrupt quorum sensing in this bacterium by decreasing the ability of the quorum sensing master regulator LuxR to bind to its target promoter DNA. In vivo challenge tests with gnotobiotic brine shrimp larvae showed that thiophenone compound TF310, (Z-4-((5-(bromomethylene-2-oxo-2,5-dihydrothiophen-3-ylmethoxy-4-oxobutanoic acid, completely protected the larvae from V. harveyi BB120 when dosed to the culture water at 2.5 µM or more, whereas severe toxicity was only observed at 250 µM. This makes TF310 showing the highest therapeutic index of all quorum sensing-disrupting compounds tested thus far in our brine shrimp model system.

  4. Is cloud seeding in coastal Antarctica linked to bromine and nitrate variability in snow?

    Energy Technology Data Exchange (ETDEWEB)

    Antony, Runa; Thamban, Meloth; Krishnan, K P; Mahalinganathan, K, E-mail: runa@ncaor.or [National Centre for Antarctic and Ocean Research, Headland Sada, Vasco-da-Gama, Goa-403 804 (India)

    2010-01-15

    Considering the significance of methanesulfonate (MSA) in the sulfur cycle and global climate, we analyzed MSA and other ionic species in snow from the coastal Larsemann Hills, East Antarctica. MSA concentrations recorded were high (0.58 +- 0.7 {mu}M) with ice-cap regions showing significantly higher concentrations (df = 10, p < 0.001) than ice-free regions. High nutrient concentration in ice-cap snow appears to have favored algal growth (7.6 x 10{sup 2} cells l{sup -1}) with subsequent production of brominated compounds. The consequent elevated Br{sup -} (3.2 +- 2.2 {mu}M) in the ice-cap region could result in the release of Br atoms through photoactivated reactions on aerosols and the snow surface. Activated Br atoms in the atmosphere could react with ozone leading to BrO enhancement with subsequent dimethylsulfide (DMS) oxidation and production of sulfur aerosols. Since BrO based DMS oxidation is much faster than the OH/NO{sub 3} pathway, elevated Br{sup -} in ice-cap snow could contribute more than ice-free sites towards formation of cloud condensation nuclei at the expense of ozone.

  5. A quorum sensing-disrupting brominated thiophenone with a promising therapeutic potential to treat luminescent vibriosis.

    Science.gov (United States)

    Defoirdt, Tom; Benneche, Tore; Brackman, Gilles; Coenye, Tom; Sorgeloos, Patrick; Scheie, Anne Aamdal

    2012-01-01

    Vibrio harveyi is amongst the most important bacterial pathogens in aquaculture. Novel methods to control this pathogen are needed since many strains have acquired resistance to antibiotics. We previously showed that quorum sensing-disrupting furanones are able to protect brine shrimp larvae against vibriosis. However, a major problem of these compounds is that they are toxic toward higher organisms and therefore, they are not safe to be used in aquaculture. The synthesis of brominated thiophenones, sulphur analogues of the quorum sensing-disrupting furanones, has recently been reported. In the present study, we report that these compounds block quorum sensing in V. harveyi at concentrations in the low micromolar range. Bioluminescence experiments with V. harveyi quorum sensing mutants and a fluorescence anisotropy assay indicated that the compounds disrupt quorum sensing in this bacterium by decreasing the ability of the quorum sensing master regulator LuxR to bind to its target promoter DNA. In vivo challenge tests with gnotobiotic brine shrimp larvae showed that thiophenone compound TF310, (Z)-4-((5-(bromomethylene)-2-oxo-2,5-dihydrothiophen-3-yl)methoxy)-4-oxobutanoic acid, completely protected the larvae from V. harveyi BB120 when dosed to the culture water at 2.5 µM or more, whereas severe toxicity was only observed at 250 µM. This makes TF310 showing the highest therapeutic index of all quorum sensing-disrupting compounds tested thus far in our brine shrimp model system.

  6. Extended analysis of fifth spectrum of bromine: Br V

    Science.gov (United States)

    Riyaz, A.; Tauheed, A.; Rahimullah, K.

    2014-11-01

    The fifth spectrum of bromine (Br V) has been studied in the 200-2400 Å wavelength region. The spectrum was photographed on a 3-m normal incidence vacuum spectrograph at the St. Francis Xavier University, Antigonish (Canada) and 6.65-m grazing incidence spectrograph at the Zeeman laboratory (Amsterdam). The light sources used were a triggered spark and sliding spark. The ground configuration of Br V is 4s24p. The excited configurations 4s4p2+4s2(4d+5d+5s+6s+7s+5g+6g)+4s4p(5p+4f)+4p24d in the even parity system and the 4p3+4s2(5p+6p+7p+4f)+4s4p4d+4s4p5s configurations in the odd parity system have been studied. Relativistic Hartree-Fock (HFR) and least squares fitted (LSF) parametric calculations have been used to interpret the observed spectrum. 99 levels of Br V have now been established, 43 being new. Among 394 classified spectral lines, 181 are newly classified. The level 4s27s 2S1/2 is revised. We estimate the accuracy of our measured wavelengths for sharp and unblended lines to be±0.005 Å. The ionization limit is determined as 479,657±200 cm-1 (59.470±0.025 eV).

  7. Brominated flame retardants in Belgian little owl (Athene noctua) eggs

    Energy Technology Data Exchange (ETDEWEB)

    Jaspers, V.; Covaci, A.; Maervoet, J.; Dauwe, T.; Schepens, P.; Eens, M. [Antwerp Univ. (Belgium)

    2004-09-15

    Since the 1960s, polybrominated diphenylethers (PBDEs), a class of brominated flame retardants (BFRs), are widely used in textiles, plastics, electronic equipment and other materials. Their massive use has led to the ubiquitous presence of PBDEs in the environment and in biota in which the PBDE levels seem to increase rapidly. High concentrations of some congeners may cause adverse effects in both wildlife and in human populations1 and this has led to the growing concern of scientists over the last decade and to the need for more data on environmental levels of PBDEs. The little owl (Athene noctua) is a small sedentary predator, which makes it a very suitable biomonitoring species. This owl species feeds on a variety of preys, including small mammals and birds, reptiles, amphibians, earthworms and beetles, depending on the season and the local circumstances. Because very limited information is available about contamination levels in the little owl, a study was conducted to determine the concentrations of PBDEs, polybrominated biphenyls (PBBs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in deserted or addled eggs of little owls in Belgium. Eggs have been used successfully as a monitoring tool for persistent organic pollutants (POPs) in several studies. Although the analysis of POPs in deserted or addled eggs has clear limitations, these can be partially avoided by analysing only highly persistent components, for which the original composition will not change due to 'posthatching' microbiological degradation.

  8. Measurement-based modeling of bromine chemistry in the boundary layer: 1. Bromine chemistry at the Dead Sea

    Science.gov (United States)

    Tas, E.; Peleg, M.; Pedersen, D. U.; Matveev, V.; Pour Biazar, A.; Luria, M.

    2006-12-01

    The Dead Sea is an excellent natural laboratory for the investigation of Reactive Bromine Species (RBS) chemistry, due to the high RBS levels observed in this area, combined with anthropogenic air pollutants up to several ppb. The present study investigated the basic chemical mechanism of RBS at the Dead Sea using a numerical one-dimensional chemical model. Simulations were based on data obtained from comprehensive measurements performed at sites along the Dead Sea. The simulations showed that the high BrO levels measured frequently at the Dead Sea could only partially be attributed to the highly concentrated Br- present in the Dead Sea water. Furthermore, the RBS activity at the Dead Sea cannot solely be explained by a pure gas phase mechanism. This paper presents a chemical mechanism which can account for the observed chemical activity at the Dead Sea, with the addition of only two heterogeneous processes: the "Bromine Explosion" mechanism and the heterogeneous decomposition of BrONO2. Ozone frequently dropped below a threshold value of ~1 to 2 ppbv at the Dead Sea evaporation ponds, and in such cases, O3 became a limiting factor for the production of BrOx (BrO+Br). The entrainment of O3 fluxes into the evaporation ponds was found to be essential for the continuation of RBS activity, and to be the main reason for the jagged diurnal pattern of BrO observed in the Dead Sea area, and for the positive correlation observed between BrO and O3 at low O3 concentrations. The present study has shown that the heterogeneous decomposition of BrONO2 has a great potential to affect the RBS activity in areas influenced by anthropogenic emissions, mainly due to the positive correlation between the rate of this process and the levels of NO2. Further investigation of the influence of the decomposition of BrONO2 may be especially important in understanding the RBS activity at mid-latitudes.

  9. Measurement-based modeling of bromine chemistry in the boundary layer: 1. Bromine chemistry at the Dead Sea

    Directory of Open Access Journals (Sweden)

    E. Tas

    2006-01-01

    Full Text Available The Dead Sea is an excellent natural laboratory for the investigation of Reactive Bromine Species (RBS chemistry, due to the high RBS levels observed in this area, combined with anthropogenic air pollutants up to several ppb. The present study investigated the basic chemical mechanism of RBS at the Dead Sea using a numerical one-dimensional chemical model. Simulations were based on data obtained from comprehensive measurements performed at sites along the Dead Sea. The simulations showed that the high BrO levels measured frequently at the Dead Sea could only partially be attributed to the highly concentrated Br− present in the Dead Sea water. Furthermore, the RBS activity at the Dead Sea cannot solely be explained by a pure gas phase mechanism. This paper presents a chemical mechanism which can account for the observed chemical activity at the Dead Sea, with the addition of only two heterogeneous processes: the "Bromine Explosion" mechanism and the heterogeneous decomposition of BrONO2. Ozone frequently dropped below a threshold value of ~1 to 2 ppbv at the Dead Sea evaporation ponds, and in such cases, O3 became a limiting factor for the production of BrOx (BrO+Br. The entrainment of O3 fluxes into the evaporation ponds was found to be essential for the continuation of RBS activity, and to be the main reason for the jagged diurnal pattern of BrO observed in the Dead Sea area, and for the positive correlation observed between BrO and O3 at low O3 concentrations. The present study has shown that the heterogeneous decomposition of BrONO2 has a great potential to affect the RBS activity in areas influenced by anthropogenic emissions, mainly due to the positive correlation between the rate of this process and the levels of NO2. Further investigation of the influence of the decomposition of BrONO2 may be especially important in understanding the RBS activity at mid-latitudes.

  10. [Atmospheric Polybrominated Diphenyl Ethers in Eight Cities of China: Pollution Characteristics and Human Exposure].

    Science.gov (United States)

    Lin, Hai-tao; Li, Qi-lu; Zhang, Gan; Li, Jun

    2016-01-15

    The gas and particle samples of eight cities were collected by high flow active air sampler in the Eastern and Western China and eight congeners of polybrominated diphenyl ethers were analyzed. The results showed that the concentration of BDE-28 (tri-BDE) in the gas-phase (three bromide components) was the highest, which was different from previous studies where BDE-99 and-47 were the predominant homologues in the gas-phase while the concentration of BDE-209 [(25.4 ± 124) pg · m⁻³] in particle-phase was the highest. The atmospheric concentrations of PBDEs in Beijing and Guangzhou were relatively higher, especially the BDE-209 concentration in particle phases of Guangzhou was two orders higher than those of other cities. However, the atmospheric concentrations of PBDEs declined significantly when compared with the data from previous studies. Meanwhile, the results indicated that the gas-phase concentrations decreased slowly and the particle-phase concentrations decreased rapidly. Combined with the results of correlation analysis, this phenomenon might be ascribed to the ceased commercial production of penta- and octa-BDE, the light degradation of high bromide components and reduced concentrations of atmospheric particles in urban area. Inhalation exposure for infants was about 2-3 times higher than that of adults. This reflected that the potential health risk of atmospheric PBDEs in city for residents, especially infants and young children, should not be ignored.

  11. Modification of nylon-6 with semi-rigid poly (p-diphenyl oxide terephthalamide)

    International Nuclear Information System (INIS)

    Lin, M.F.; Wang, H.H.; Shu, Y.C.

    1994-01-01

    In this study, the flexible nylon-6 was reinforced by the semi-rigid aromatic polyamide, poly (p-diphenyl oxide terephthalamide) (POA), through physical polybending and chemical copolymerization using p-aminophenylacetic acid (P-APA) as a coupling agent. From the DSC measurements, it was shown that Tg of the polyblends was increased with the increase of POA content. The Tg and Tm of multiblock copolyamides were found to be higher than those of polyblends and triblock copolyamides. From the Rheovibron measurements, it was shown that the POA with nylon-6 poy-blends exhibited higher E' and Tg value than that of nylon-6, which increased with the increase of POA content. The Tg and E' values of multiblock copolyamides were higher than those of polyblends triblock copolyamides. Scanning electron microscopy revealed that the polyblends were a dispersed phase structure, although the multiblock copolyamides exhibited a homogeneous texture rather than an aggregated one. From the wide-angle x-ray diffraction pattern, the triblock copolyamides and polyblends had two diffraction peaks, i.e., 2 θ = 20.5 degrees and 24 degrees. However, the multiblock had only one at 2 θ = 20 degrees, which indicates that a different crystal structure of multiblock copolyamides. For the mechanical properties, it was found that the multiblock copolyamides had a more significant reinforcing effect than those of polyblends and triblock copolyamides. 21 refs., 11 figs., 5 tabs

  12. Brominated flame retardants in end-of-life management not problematic regarding formation of brominated dioxins/furans (PBDD/F)

    Energy Technology Data Exchange (ETDEWEB)

    Drohmann, D. [Great Lakes Chemical, Bergisch Gladbach (Germany); Tange, L. [Eurobrom B.V., Rijswijk (Netherlands); Rothenbacher, K. [Bromine Science and Environmental Forum, Brussels (Belgium)

    2004-09-15

    Bromine is used as the building block for some of the most effective flame retarding agents available to the plastics industry today. They are used to protect against the risk of accidental fires in a wide range of products. Brominated flame retardants (BFRs), as all flame retardants, act to decrease the risk of fire by increasing the fire resistance of the materials in which they are applied. There is a perception that BFRs affect adversely the end-of-life management of plastics through formation of brominated dioxins and furans (PBDD/F). In fact, there exists a wide range of data and practical experience demonstrating that the end-of-life management of plastics containing BFRs are fully compliant with legislation setting the strictest limit values for PBDD/F and is fully compatible with an integrated waste management concept. Furthermore, all existing EU Risk Assessments on BFRs according to the European Existing Substance Regulations include an assessment of the potential formation of dioxins and furans. All assessments conclude that the risks along the life-cycle of the chemicals for human health and the environment associated with the potential formation of PBDD/F are negligible. Moreover, two recent Swedish studies found, that consumer products with BFRs emit less pollutants than the same products without any FRs. This paper summarises available studies and presents the latest results regarding potential formation of brominated dioxins and furans in end-of-life management of plastics containing brominated flame retardants. Additionally, before BFR products enter the market they are tested for PBDD/F according to the ''German Dioxin Ordinance''. Depending on the substitution pattern the limit values for PBDD/F are set at <1{mu}g/kg (ppb) respectively <5{mu}g/kg (ppb).

  13. Release of chlorinated, brominated and mixed halogenated dioxin-related compounds to soils from open burning of e-waste in Agbogbloshie (Accra, Ghana).

    Science.gov (United States)

    Tue, Nguyen Minh; Goto, Akitoshi; Takahashi, Shin; Itai, Takaaki; Asante, Kwadwo Ansong; Kunisue, Tatsuya; Tanabe, Shinsuke

    2016-01-25

    Although complex mixtures of dioxin-related compounds (DRCs) can be released from informal e-waste recycling, DRC contamination in African e-waste recycling sites has not been investigated. This study examined the concentrations of DRCs including chlorinated, brominated, mixed halogenated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs, PBDD/Fs, PXDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in surface soil samples from the Agbogbloshie e-waste recycling site in Ghana. PCDD/F and PBDD/F concentrations in open burning areas (18-520 and 83-3800 ng/g dry, respectively) were among the highest reported in soils from informal e-waste sites. The concentrations of PCDFs and PBDFs were higher than those of the respective dibenzo-p-dioxins, suggesting combustion and PBDE-containing plastics as principal sources. PXDFs were found as more abundant than PCDFs, and higher brominated analogues occurred at higher concentrations. The median total WHO toxic equivalent (TEQ) concentration in open burning soils was 7 times higher than the U.S. action level (1000 pg/g), with TEQ contributors in the order of PBDFs>PCDD/Fs>PXDFs. DRC emission to soils over the e-waste site as of 2010 was estimated, from surface soil lightness based on the correlations between concentrations and lightness, at 200mg (95% confidence interval 93-540 mg) WHO-TEQ over three years. People living in Agbogbloshie are potentially exposed to high levels of not only chlorinated but also brominated DRCs, and human health implications need to be assessed in future studies. Copyright © 2015 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

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

    2010-03-01

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

  15. Sea ice and pollution-modulated changes in Greenland ice core methanesulfonate and bromine

    Science.gov (United States)

    Maselli, Olivia J.; Chellman, Nathan J.; Grieman, Mackenzie; Layman, Lawrence; McConnell, Joseph R.; Pasteris, Daniel; Rhodes, Rachael H.; Saltzman, Eric; Sigl, Michael

    2017-01-01

    Reconstruction of past changes in Arctic sea ice extent may be critical for understanding its future evolution. Methanesulfonate (MSA) and bromine concentrations preserved in ice cores have both been proposed as indicators of past sea ice conditions. In this study, two ice cores from central and north-eastern Greenland were analysed at sub-annual resolution for MSA (CH3SO3H) and bromine, covering the time period 1750-2010. We examine correlations between ice core MSA and the HadISST1 ICE sea ice dataset and consult back trajectories to infer the likely source regions. A strong correlation between the low-frequency MSA and bromine records during pre-industrial times indicates that both chemical species are likely linked to processes occurring on or near sea ice in the same source regions. The positive correlation between ice core MSA and bromine persists until the mid-20th century, when the acidity of Greenland ice begins to increase markedly due to increased fossil fuel emissions. After that time, MSA levels decrease as a result of declining sea ice extent but bromine levels increase. We consider several possible explanations and ultimately suggest that increased acidity, specifically nitric acid, of snow on sea ice stimulates the release of reactive Br from sea ice, resulting in increased transport and deposition on the Greenland ice sheet.

  16. Brominated Skeletal Components of the Marine Demosponges, Aplysina cavernicola and Ianthella basta: Analytical and Biochemical Investigations

    Directory of Open Access Journals (Sweden)

    Eike Brunner

    2013-04-01

    Full Text Available Demosponges possess a skeleton made of a composite material with various organic constituents and/or siliceous spicules. Chitin is an integral part of the skeleton of different sponges of the order Verongida. Moreover, sponges of the order Verongida, such as Aplysina cavernicola or Ianthella basta, are well-known for the biosynthesis of brominated tyrosine derivates, characteristic bioactive natural products. It has been unknown so far whether these compounds are exclusively present in the cellular matrix or whether they may also be incorporated into the chitin-based skeletons. In the present study, we therefore examined the skeletons of A. cavernicola and I. basta with respect to the presence of bromotyrosine metabolites. The chitin-based-skeletons isolated from these sponges indeed contain significant amounts of brominated compounds, which are not easily extractable from the skeletons by common solvents, such as MeOH, as shown by HPLC analyses in combination with NMR and IR spectroscopic measurements. Quantitative potentiometric analyses confirm that the skeleton-associated bromine mainly withstands the MeOH-based extraction. This observation suggests that the respective, but yet unidentified, brominated compounds are strongly bound to the sponge skeletons, possibly by covalent bonding. Moreover, gene fragments of halogenases suggested to be responsible for the incorporation of bromine into organic molecules could be amplified from DNA isolated from sponge samples enriched for sponge-associated bacteria.

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

    International Nuclear Information System (INIS)

    Zhang, Cong-Cong; Zhang, Fu-Shen

    2012-01-01

    Highlights: ► A process for brominated flame retardants (BFRs) removal in plastic was established. ► The plastic became bromine-free with the structure maintained after this treatment. ► BFRs transferred into alcohol solvent were easily debrominated by metallic copper. - Abstract: Brominated flame retardants (BFRs) in electrical and electronic (E and 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, 2 h 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Cong-Cong [Research Center For Eco-Environmental Sciences, Chinese Academy of Sciences, 18 Shuangqing Road, Beijing 100085 (China); Zhang, Fu-Shen, E-mail: fszhang@rcees.ac.cn [Research Center For Eco-Environmental Sciences, Chinese Academy of Sciences, 18 Shuangqing Road, Beijing 100085 (China)

    2012-06-30

    Highlights: Black-Right-Pointing-Pointer A process for brominated flame retardants (BFRs) removal in plastic was established. Black-Right-Pointing-Pointer The plastic became bromine-free with the structure maintained after this treatment. Black-Right-Pointing-Pointer BFRs transferred into alcohol solvent were easily debrominated by metallic copper. - Abstract: Brominated flame retardants (BFRs) in electrical and electronic (E and 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 Degree-Sign C, 2 h 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.

  19. Occurrence, profiles, and toxic equivalents of chlorinated and brominated polycyclic aromatic hydrocarbons in E-waste open burning soils.

    Science.gov (United States)

    Nishimura, Chiya; Horii, Yuichi; Tanaka, Shuhei; Asante, Kwadwo Ansong; Ballesteros, Florencio; Viet, Pham Hung; Itai, Takaaki; Takigami, Hidetaka; Tanabe, Shinsuke; Fujimori, Takashi

    2017-06-01

    We conducted this study to assess the occurrence, profiles, and toxicity of chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) and brominated polycyclic aromatic hydrocarbons (Br-PAHs) in e-waste open burning soils (EOBS). In this study, concentrations of 15 PAHs, 26 Cl-PAHs and 14 Br-PAHs were analyzed in EOBS samples. We found that e-waste open burning is an important emission source of Cl-PAHs and Br-PAHs as well as PAHs. Concentrations of total Cl-PAHs and Br-PAHs in e-waste open burning soil samples ranged from 21 to 2800 ng/g and from 5.8 to 520 ng/g, respectively. Compared with previous studies, the mean of total Cl-PAH concentrations of the EOBS samples in this study was higher than that of electronic shredder waste, that of bottom ash, and comparable to fly ash from waste incinerators in Korea and Japan. The mean of total Br-PAH concentrations of the EOBS samples was generally three to four orders of magnitude higher than those in incinerator bottom ash and comparable to incinerator fly ash, although the number of Br-PAH congeners measured differed among studies. We also found that the Cl-PAH and Br-PAH profiles were similar among all e-waste open burning soil samples but differed from those in waste incinerator fly ash. The profiles and principal component analysis results suggested a unique mechanism of Cl-PAH and Br-PAH formation in EOBS. In addition, the Cl-PAHs and Br-PAHs showed high toxicities equivalent to PCDD/Fs measured in same EOBS samples when calculated based on their relative potencies to benzo[a]pyrene. Along with chlorinated and brominated dioxins and PAHs, Cl-PAHs and Br-PAHs are important environmental pollutants to investigate in EOBS. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. Metals and polybrominated diphenyl ethers leaching from electronic waste in simulated landfills

    Energy Technology Data Exchange (ETDEWEB)

    Kiddee, Peeranart [Centre for Environmental Risk Assessment and Remediation, University of South Australia, Mawson Lakes Campus, Adelaide, 5095 (Australia); Cooperative Research Centre for Contamination Assessment and Remediation of the Environment, Mawson Lakes Campus, Adelaide, 5095 (Australia); Naidu, Ravi, E-mail: ravi.naidu@crccare.com [Centre for Environmental Risk Assessment and Remediation, University of South Australia, Mawson Lakes Campus, Adelaide, 5095 (Australia); Cooperative Research Centre for Contamination Assessment and Remediation of the Environment, Mawson Lakes Campus, Adelaide, 5095 (Australia); Wong, Ming H. [Croucher Institute for Environmental Sciences, and Department of Biology, Hong Kong Baptist University, Kowloon Tong (China)

    2013-05-15

    Highlights: • Simulated landfill columns provided realistic results than lab based column study. • Column leachates showed significant seasonal effect on toxic substances. • Toxic substances in the landfill leachates pose environmental and health hazards. • A better management of e-waste is urgently needed. -- Abstract: Landfills established prior to the recognition of potential impacts from the leaching of heavy metals and toxic organic compounds often lack appropriate barriers and pose significant risks of contamination of groundwater. In this study, bioavailable metal(oids) and polybrominated diphenyl ethers (PBDEs) in leachates from landfill columns that contained intact or broken e-waste were studied under conditions that simulate landfills in terms of waste components and methods of disposal of e-wastes, and with realistic rainfall. Fourteen elements and PBDEs were analysed in leachates over a period of 21 months. The results demonstrate that the average concentrations of Al, Ba, Be, Cd, Co, Cr, Cu, Ni, Pb, Sb and V in leachates from the column that contained broken e-waste items were significantly higher than the column without e-waste. BDE-153 was the highest average PBDEs congener in all columns but the average of ∑PBDEs levels in columns that contained intact e-waste were (3.7 ng/l) and were not significantly higher than that in the leachates from the control column.

  1. Estimating stepwise debromination pathways of polybrominated diphenyl ethers with an analogue Markov Chain Monte Carlo algorithm.

    Science.gov (United States)

    Zou, Yonghong; Christensen, Erik R; Zheng, Wei; Wei, Hua; Li, An

    2014-11-01

    A stochastic process was developed to simulate the stepwise debromination pathways for polybrominated diphenyl ethers (PBDEs). The stochastic process uses an analogue Markov Chain Monte Carlo (AMCMC) algorithm to generate PBDE debromination profiles. The acceptance or rejection of the randomly drawn stepwise debromination reactions was determined by a maximum likelihood function. The experimental observations at certain time points were used as target profiles; therefore, the stochastic processes are capable of presenting the effects of reaction conditions on the selection of debromination pathways. The application of the model is illustrated by adopting the experimental results of decabromodiphenyl ether (BDE209) in hexane exposed to sunlight. Inferences that were not obvious from experimental data were suggested by model simulations. For example, BDE206 has much higher accumulation at the first 30 min of sunlight exposure. By contrast, model simulation suggests that, BDE206 and BDE207 had comparable yields from BDE209. The reason for the higher BDE206 level is that BDE207 has the highest depletion in producing octa products. Compared to a previous version of the stochastic model based on stochastic reaction sequences (SRS), the AMCMC approach was determined to be more efficient and robust. Due to the feature of only requiring experimental observations as input, the AMCMC model is expected to be applicable to a wide range of PBDE debromination processes, e.g. microbial, photolytic, or joint effects in natural environments. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Quantitative structure-property relationships for octanol-water partition coefficients of polybrominated diphenyl ethers.

    Science.gov (United States)

    Li, Linnan; Xie, Shaodong; Cai, Hao; Bai, Xuetao; Xue, Zhao

    2008-08-01

    Theoretical molecular descriptors were tested against logK(OW) values for polybrominated diphenyl ethers (PBDEs) using the Partial Least-Squares Regression method which can be used to analyze data with many variables and few observations. A quantitative structure-property relationship (QSPR) model was successfully developed with a high cross-validated value (Q(cum)(2)) of 0.961, indicating a good predictive ability and stability of the model. The predictive power of the QSPR model was further cross-validated. The values of logK(OW) for PBDEs are mainly governed by molecular surface area, energy of the lowest unoccupied molecular orbital and the net atomic charges on the oxygen atom. All these descriptors have been discussed to interpret the partitioning mechanism of PBDE chemicals. The bulk property of the molecules represented by molecular surface area is the leading factor, and K(OW) values increase with the increase of molecular surface area. Higher energy of the lowest unoccupied molecular orbital and higher net atomic charge on the oxygen atom of PBDEs result in smaller K(OW). The energy of the lowest unoccupied molecular orbital and the net atomic charge on PBDEs oxygen also play important roles in affecting the partition of PBDEs between octanol and water by influencing the interactions between PBDEs and solvent molecules.

  3. Human exposure to polybrominated diphenyl ethers at production area, China.

    Science.gov (United States)

    Jin, Jun; Wang, Ying; Yang, Congqiao; Hu, Jicheng; Liu, Weizhi; Cui, Jian

    2010-05-01

    The concentrations of polybrominated diphenyl ethers (PBDEs) were detected in air and aquatic products in PBDEs production areas which are located at the south coast area of Laizhou Bay, Shandong province, China in this study. Concentrations of SigmaPBDEs in the air ranged from 0.47 ng/m3 to 161 ng/m3. In aquatic products, concentrations of SigmaPBDEs ranged from 2.7 ng/g wet weight to 42 ng/g wet weight. The mean dietary intake of SigmaPBDEs via aquatic products consumption in this study was 218 ng/day. Daily intake of SigmaPBDEs via inhalation in this study was 612 ng for men and 455 ng for women. With a contribution of 80%, BDE-209 was predominant in the total intake. Dietary intake and breathing inhalation contributed 29 and 71%, respectively, to the total PBDEs intake. The results indicate that breathing inhalation also plays a very significant pathway for the population of the PBDEs production area. Compared with similar studies in other countries, human exposure to PBDEs via diet and inhalation in this study was the highest in the world. Copyright (c) 2010 SETAC.

  4. Comparison between Two Bromine Containing Free Radical Initiators in PRESAGE®

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hyeonsuk; Ryu, Dongmin; Ye, Sung-Joon [Seoul National University, Seoul (Korea, Republic of)

    2016-10-15

    PRESAGE® is an optically clear 3-D polyurethane dosimeter which contains a halogenated carbon as a free radical initiator and leucomalachite dye. The change of the optical density is known to be linear with respect to the absorbed dose and the sensitivity is related to the carbon–halogen bond dissociation energy of the free radical initiator. Although there are some studies regarding free radical initiators and dye materials, there’s a lack of reports about the effect of other elements like LMG solvent which can be added when there’s a difficulty mixing materials. Also, there are some studies about comparison between free radicals with different kind of halogen atoms but there’s a lack of studies of comparison between initiators with the same halogen atom. In this experiments, two kinds of halocarbon free radical initiator with the same halogen atom (bromine) as well as the effect of the LMG solvent were studied to use the dosimeter as a therapeutic purpose. Effective atomic numbers were also calculated. The initiators with the same halogen atom, CBr{sub 4} and C{sub 2}H{sub 2}Br{sub 4}, reacted totally differently. CBr{sub 4} was more sensitive to the radiation and emitted maximum 4 times more free radicals upon irradiation with no additional effective atomic number but the absorbance after irradiation was highly variable with time. For stable measurement, C{sub 2}H{sub 2}Br{sub 4} would be more appropriate as a free radical initiator.

  5. Extended analysis of fifth spectrum of bromine: Br V

    International Nuclear Information System (INIS)

    Riyaz, A.; Tauheed, A.; Rahimullah, K.

    2014-01-01

    The fifth spectrum of bromine (Br V) has been studied in the 200–2400 Å wavelength region. The spectrum was photographed on a 3-m normal incidence vacuum spectrograph at the St. Francis Xavier University, Antigonish (Canada) and 6.65-m grazing incidence spectrograph at the Zeeman laboratory (Amsterdam). The light sources used were a triggered spark and sliding spark. The ground configuration of Br V is 4s 2 4p. The excited configurations 4s4p 2 +4s 2 (4d+5d+5s+6s+7s+5g+6g)+4s4p(5p+4f)+4p 2 4d in the even parity system and the 4p 3 +4s 2 (5p+6p+7p+4f)+4s4p4d+4s4p5s configurations in the odd parity system have been studied. Relativistic Hartree–Fock (HFR) and least squares fitted (LSF) parametric calculations have been used to interpret the observed spectrum. 99 levels of Br V have now been established, 43 being new. Among 394 classified spectral lines, 181 are newly classified. The level 4s 2 7s 2 S 1/2 is revised. We estimate the accuracy of our measured wavelengths for sharp and unblended lines to be±0.005 Å. The ionization limit is determined as 479,657±200 cm −1 (59.470±0.025 eV). - Highlights: • The spectrum of Br was recorded on a 3-m spectrograph with triggered spark source. • Atomic transitions for Br V were identified to established new energy levels. • CI calculations with relativistic corrections were made for theoretical predictions. • Weighted oscillator strength (gf) and transition probabilities (gA) were calculated. • Ionization potential of Br V was determined experimentally

  6. Brominated flame retardants in birds of prey from Flanders, Belgium

    Energy Technology Data Exchange (ETDEWEB)

    Voorspoels, S.; Covaci, A.; Schepens, P. [Antwerp Univ., Wilrijk (Belgium). Toxicological Centre

    2004-09-15

    Since their introduction on the market, environmental levels of polybrominated diphenyl ethers (PBDEs) are continuously increasing. This is caused by spillage and emission during production and use, but also by improper disposal at the end-of-life of the products in which they are used. These chemicals are highly persistent and lipophilic which results in bioaccumulation in fatty tissues of biota and biomagnification throughout the food chain. Because PBDEs have a high toxicological potential, this biomagnification can have serious health consequences for top-predators, such as birds of prey. Data about PBDE concentrations in terrestrial biota, especially in birds of prey, is scarce. A rapid increase of PBDE concentrations has been seen in pooled guillemot (Uria algae) eggs from the Baltic proper7 during the late 1970's and early 1980's, followed by a decrease during the 1990's8. In herring gull eggs from the Great Lakes, the PBDE concentrations increased exponentially from 1981 to 2000. Most of the studies look at concentrations in eggs, while less is known about tissue levels and distribution of these pollutants in birds of prey.

  7. An XPS study of bromine in methanol etching and hydrogen peroxide passivation treatments for cadmium zinc telluride radiation detectors

    International Nuclear Information System (INIS)

    Babar, S.; Sellin, P.J.; Watts, J.F.; Baker, M.A.

    2013-01-01

    Highlights: ► CdZnTe single crystal etched in bromine-in-methanol and passivated in H 2 O 2 . ► XPS depth used to accurately determine enriched Te layer and TeO 2 thickness. ► For 0.2 and 2.0 (v/v) % bromine-in-methanol treatments, enriched Te layer thickness determined to be 1.3 and 1.8 nm, respectively. ► After passivation in 30 wt.% H 2 O 2 , the oxide thickness varies between 1.0 and 1.25 nm depending on the calculation method. - Abstract: The performance of single crystal CdZnTe radiation detectors is dependent on both the bulk and the surface properties of the material. After single crystal fabrication and mechanical polishing, modification of the surface to remove damage and reduce the surface leakage current is generally achieved through chemical etching followed by a passivation treatment. In this work, CdZnTe single crystals have been chemically etched using a bromine in methanol (BM) treatment. The BM concentrations employed were 0.2 and 2.0 (v/v) % and exposure times varied between 5 and 120 s. Angle resolved XPS and sputter depth profiling has been employed to characterize the surfaces for the different exposure conditions. A Te rich surface layer was formed for all exposures and the layer thickness was found to be independent of exposure time. The enriched Te layer thickness was accurately determined by calibrating the sputter rate against a CdTe layer of known thickness. For BM concentrations of 0.2 (v/v) % and 2 (v/v) %, the Te layer thickness was determined to be 1.3 ± 0.2 and 1.8 ± 0.2 nm, respectively. The BM etched surfaces have subsequently been passivated in a 30 wt.% H 2 O 2 solution employing exposure time of 15 s. The oxide layer thickness has been calculated using two standard XPS methodologies, based on the Beer–Lambert expression. The TeO 2 thickness calculated from ARXPS data are slightly higher than the thickness obtained by the simplified Beer–Lambert expression. For BM exposures of 30–120 s followed by a passivation

  8. Deriving an atmospheric budget of total organic bromine using airborne in situ measurements from the western Pacific area during SHIVA

    Science.gov (United States)

    Sala, S.; Bönisch, H.; Keber, T.; Oram, D. E.; Mills, G.; Engel, A.

    2014-07-01

    During the recent SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) project an extensive data set of all halogen species relevant for the atmospheric budget of total organic bromine was collected in the western Pacific region using the Falcon aircraft operated by the German Aerospace agency DLR (Deutsches Zentrum für Luft- und Raumfahrt) covering a vertical range from the planetary boundary layer up to the ceiling altitude of the aircraft of 13 km. In total, more than 700 measurements were performed with the newly developed fully automated in situ instrument GHOST-MS (Gas chromatograph for the Observation of Tracers - coupled with a Mass Spectrometer) by the Goethe University of Frankfurt (GUF) and with the onboard whole-air sampler WASP with subsequent ground-based state-of-the-art GC / MS analysis by the University of East Anglia (UEA). Both instruments yield good agreement for all major (CHBr3 and CH2Br2) and minor (CH2BrCl, CHBrCl2 and CHBr2Cl) VSLS (very short-lived substances), at least at the level of their 2σ measurement uncertainties. In contrast to the suggestion that the western Pacific could be a region of strongly increased atmospheric VSLS abundance (Pyle et al., 2011), we found only in the upper troposphere a slightly enhanced amount of total organic bromine from VSLS relative to the levels reported in Montzka and Reimann et al. (2011) for other tropical regions. From the SHIVA observations in the upper troposphere, a budget for total organic bromine, including four halons (H-1301, H-1211, H-1202, H-2402), CH3Br and the VSLS, is derived for the level of zero radiative heating (LZRH), the input region for the tropical tropopause layer (TTL) and thus also for the stratosphere. With the exception of the two minor VSLS CHBrCl2 and CHBr2Cl, excellent agreement with the values reported in Montzka and Reimann et al. (2011) is found, while being slightly higher than previous studies from our group based on balloon-borne measurements.

  9. Bromine-77-labeled estrogen receptor-binding radiopharmaceuticals for breast tumor imaging

    International Nuclear Information System (INIS)

    McElvany, K.D.

    1985-01-01

    Two derivatives of 16α-bromoestradiol, both with and without an 11β-methoxy substituent, have been labeled with bromine-77 and evaluated as potential breast tumor imaging agents. Extensive characterization of these radiotracers in animal models has demonstrated their effective concentration in estrogen target tissues. Preliminary clinical studies have demonstrated the potential of radiolabeled estrogens for breast tumor imaging; however, the suboptimal decay properties of bromine-77 limit the utility of these agents in imaging studies. These results with 77 -Br-labeled estrogens suggest that estrogen derivatives labeled with other radionuclides should provide enhanced image resolution with various imaging devices. Although the decay characteristics of bromine-77 are such that it is not ideally suited to imaging with conventional gamma cameras, it may be a useful radionuclide for therapeutic applications

  10. Determination by neutron activation analysis of loss of arsenic, antimony, bromine and mercury during lyophilization

    International Nuclear Information System (INIS)

    Carlson, M.; Litman, R.

    1978-01-01

    Neutron activation analysis has been used to monitor the loss of arsenic, as dimethylarsinic acid, (CH 3 ) 2 AsOOH, or as sodium arsenate (Na 2 HAsO 4 .7H 2 O), antimony (as potassium antimony, tartrate, KSbC 4 O 7 .1/2H 2 O) and bromine (as bromide ion) during lyophilization of acidified and neutral aqueous synthetic and environmental samples. Losses of Sb and As ranged from zero to 60%, while losses of bromine were constant (at 91%) in acidic solutions. The variable losses of As and Sb were due solely to the presence of and partial decomposition of the (CH 3 ) 2 AsOOH. Electrochemical oxidation of Br - to Br 2 is responsible for the high losses of bromine. In addition losses of mercury (as methylmercuric chloride) were 1O0% in both acidic and neutral aqueous synthetic samples during lyophilization. (author)

  11. Use of bromine as biocide in cooling waters (Preprint No. CA-19)

    Energy Technology Data Exchange (ETDEWEB)

    Sriraman, A K [Bhabha Atomic Research Centre, Bombay (India). Water Chemistry Div.

    1989-04-01

    In all fresh water circuits, the slime forming bacteria develop an insulating layer on the condenser surfaces. If these bacteria are not controlled, they induce bacterial promoted corrosion of the materials in contact with cooling water. Chlorination is effective against slime forming bacteria, fungi and algae. The algistatic nature of the chlorine is partly compensated by the use of other non-oxidisable biocides. Amongst the various alternative biocides such as bromine, methyl bis-isocyanate, sodium pentachlorophenate etc, bromine is the most simple biocide, which is being increasingly used in cooling water systems. In this context, the chemistry of bromination and its bactericidal properties is examined along with those of chlorination. (author). 7 refs., 3 tabs., 2 figs.

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

    International Nuclear Information System (INIS)

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

    2016-01-01

    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. - Highlights: • Airborne particle and residue ash are two major emissions from burns of plastic waste. • Mass unbalance showed formation of PBDE occurred during burning process. • Open burning of plastic waste is major source of PBDE compared to industrial sources. • BFRs in residual ash of waste combustion would be

  13. Complete Reductive Dehalogenation of Brominated Biphenyls by Anaerobic Microorganisms in Sediment

    Science.gov (United States)

    Bedard, Donna L.; Van Dort, Heidi M.

    1998-01-01

    We sought to determine whether microorganisms from the polychlorinated biphenyl (PCB)-contaminated sediment in Woods Pond (Lenox, Mass.) could dehalogenate brominated biphenyls. The PCB dechlorination specificities for the microorganisms in this sediment have been well characterized. This allowed us to compare the dehalogenation specificities for brominated biphenyls and chlorinated biphenyls within a single sediment. Anaerobic sediment microcosms were incubated separately at 25°C with 16 different mono- to tetrabrominated biphenyls (350 μM) and disodium malate (10 mM). Samples were extracted and analyzed by gas chromatography with an electron capture detector and a mass spectrometer detector at various times for up to 54 weeks. All of the tested brominated biphenyls were dehalogenated. For most congeners, including 2,6-dibromobiphenyl (26-BB) and 24-25-BB, the dehalogenation began within 1 to 2 weeks. However, for 246-BB and 2-2-BB, debromination was first observed at 7 and 14 weeks, respectively. Most intermediate products did not persist, but when 2-2-BB was produced as a dehalogenation product, it persisted for at least 15 weeks before it was dehalogenated to 2-BB and then to biphenyl. The dehalogenation specificities for brominated and chlorinated biphenyls were similar: meta and para substituents were generally removed first, and ortho substituents were more recalcitrant. However, the brominated biphenyls were better dehalogenation substrates than the chlorinated biphenyls. All of the tested bromobiphenyls, including those with ortho and unflanked meta and para substituents, were ultimately dehalogenated to biphenyl, whereas their chlorinated counterparts either were not dehalogenation substrates or were only partially dehalogenated. Our data suggest that PCB-dechlorinating microorganisms may be able to dehalogenate brominated biphenyls and may exhibit a relaxed specificity for these substrates. PMID:16349530

  14. Bromination of Marine Dissolved Organic Matter following Full Scale Electrochemical Ballast Water Disinfection.

    Science.gov (United States)

    Gonsior, Michael; Mitchelmore, Carys; Heyes, Andrew; Harir, Mourad; Richardson, Susan D; Petty, William Tyler; Wright, David A; Schmitt-Kopplin, Philippe

    2015-08-04

    An extensively diverse array of brominated disinfection byproducts (DBPs) were generated following electrochemical disinfection of natural coastal/estuarine water, which is one of the main treatment methods currently under consideration for ballast water treatment. Ultra-high-resolution mass spectrometry revealed 462 distinct brominated DBPs at a relative abundance in the mass spectra of more than 1%. A brominated DBP with a relative abundance of almost 22% was identified as 2,2,4-tribromo-5-hydroxy-4-cyclopentene-1,3-dione, which is an analogue to several previously described 2,2,4-trihalo-5-hydroxy-4-cyclopentene-1,3-diones in drinking water. Several other brominated molecular formulas matched those of other known brominated DBPs, such as dibromomethane, which could be generated by decarboxylation of dibromoacetic acid during ionization, dibromophenol, dibromopropanoic acid, dibromobutanoic acid, bromohydroxybenzoic acid, bromophenylacetic acid, bromooxopentenoic acid, and dibromopentenedioic acid. Via comparison to previously described chlorine-containing analogues, bromophenylacetic acid, dibromooxopentenoic acid, and dibromopentenedioic acid were also identified. A novel compound at a 4% relative abundance was identified as tribromoethenesulfonate. This compound has not been previously described as a DBP, and its core structure of tribromoethene has been demonstrated to show toxicological implications. Here we show that electrochemical disinfection, suggested as a candidate for successful ballast water treatment, caused considerable production of some previously characterized DBPs in addition to novel brominated DBPs, although several hundred compounds remain structurally uncharacterized. Our results clearly demonstrate that electrochemical and potentially direct chlorination of ballast water in estuarine and marine systems should be approached with caution and the concentrations, fate, and toxicity of DBP need to be further characterized.

  15. Waste water treatment plants as sources of polyfluorinated compounds, polybrominated diphenyl ethers and musk fragrances to ambient air

    International Nuclear Information System (INIS)

    Weinberg, Ingo; Dreyer, Annekatrin; Ebinghaus, Ralf

    2011-01-01

    To investigate waste water treatment plants (WWTPs) as sources of polyfluorinated compounds (PFCs), polybrominated diphenyl ethers (PBDEs) and synthetic musk fragrances to the atmosphere, air samples were simultaneously taken at two WWTPs and two reference sites using high volume samplers. Contaminants were accumulated on glass fiber filters and PUF/XAD-2/PUF cartridges, extracted compound-dependent by MTBE/acetone, methanol, or hexane/acetone and detected by GC-MS or HPLC-MS/MS. Total (gas + particle phase) concentrations ranged from 97 to 1004 pg m -3 (neutral PFCs), -3 (ionic PFCs), 5781 to 482,163 pg m -3 (musk fragrances) and -3 (PBDEs) and were usually higher at WWTPs than at corresponding reference sites, revealing that WWTPs can be regarded as sources of musk fragrances, PFCs and probably PBDEs to the atmosphere. Different concentrations at the two WWTPs indicated an influence of WWTP size or waste water origin on emitted contaminant amounts. - Waste water treatment plants can be regarded as sources of musk fragrances, polyfluorinated compounds (PFCs) and polybrominated diphenyl ethers (PBDEs) to the atmosphere

  16. Characterization of bromine-76-labelled 5-bromo-6-nitroquipazine for PET studies of the serotonin transporter

    Energy Technology Data Exchange (ETDEWEB)

    Lundkvist, Camilla E-mail: Lundkvis@shfj.cea.fr; Loc' h, Christian; Halldin, Christer; Bottlaender, Michel; Ottaviani, Michele; Coulon, Christine; Fuseau, Chantal; Mathis, Chester; Farde, Lars; Maziere, Bernard

    1999-07-01

    The development of suitable radioligands for brain imaging of the serotonin transporter is of great importance for the study of depression and other affective disorders. The potent and selective serotonin transporter ligand, 5-iodo-6-nitro-2-piperazinylquinoline, has been labelled with iodine-123 and used as a radioligand for single photon emission computerized tomography. To evaluate the potential of the bromine-76-labelled analogue, 5-bromo-6-nitroquipazine, as a radioligand for positron emission tomography (PET), its brain distribution and binding characteristics were examined in rats. In vivo brain distribution and ex vivo autoradiography demonstrated that [{sup 76}Br]5-bromo-6-nitroquipazine enters the brain rapidly. The regional brain distribution of [{sup 76}Br]5-bromo-6-nitroquipazine was consistent with the known distribution of serotonin transporters in the midbrain, pons, thalamus, striatum, and neocortex. Specific binding was inhibited by the selective serotonin reuptake inhibitor citalopram. The peripheral metabolism in plasma was rapid, but more than 90% of the radioactivity in brain represented unchanged radioligand 2 h postinjection (p.i.). A preliminary PET study was also performed in a baboon. Following the intravenous injection of [{sup 76}Br]5-bromo-6-nitroquipazine in a baboon, there was a conspicuous accumulation of radioactivity in thalamus, striatum, and pons. The radioactivity in these brain regions was 1.5 times higher than in the cerebellum at 3 h and 2.5-4 times higher at 24 h. A rapid metabolism of the radioligand in plasma was observed (38% unchanged after 5 min). The results indicate that [{sup 76}Br]5-bromo-6-nitroquipazine has potential for PET imaging of the serotonin transporter.

  17. In vitro effects of selected brominated flame retardants on the adreno cortical enzyme (CYP17). A novel endocrine mechanism of action?

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez Canton, R.; Sanderson, T.; Nijmeijer, S.; Berg, M. van den [Utrecht Univ. (NL). Inst. for Risk Assessment Sciences (IRAS); Berkman, Aa. [Stockholm Univ. (Sweden). Dept. of Environmental Chemistry and Analytical Chemistry

    2004-09-15

    Fire incidents have decreased over the last 20 years partly due to regulations requiring addition of flame retardants (FRs) to materials. These compounds can be divided into different chemical classes: inorganic, nitrogen, phosphorus and halogen containing flame retardants (usually brominated or chlorinated). Not surprisingly, the use of brominated flame retardants (BFRs) in a variety of commercial and household products has increased over the years due to their low cost and high effectiveness. Consequence of the high production of BFRs is that these compounds are now readily detectable in air, water, birds, fish, marine mammals, and in human adipose tissue and blood. The five major BFRs are hexabromocyclododecane (HBCD), tetrabromobisphenol-A (TBBPA) and three commercial mixtures of polybrominated diphenyl ethers (PBDEs) (penta, octa, deca), which are extensively used as FRs at high production volume levels. In addition, concentrations of PBDEs concentration have been rapidly increasing during the last 10 years in human breast milk from European and American women and a number of endocrine (in vitro) effects have been reported. Consequently, the concern about BFRs and their metabolites with respect to their potential as endocrine disruptors (EDs) has been growing. Studies in our laboratory are focused on potential interactions of a wide range of BFRs with sex hormone synthesis and metabolism. Previous results from our research group, showed inhibitory and inductive effects on aromatase (CYP19) (the key enzyme that converts androgens to estrogens) by certain BFRs, in particular the hydroxylated PBDEs and several bromophenols. In the present study, the effects of ten of these BFRs on CYP17 activity were investigated. This enzyme also catalyzes an important step in the sex steroidogenesis and is responsible for the biosynthesis of dehydroepiandrosterone (DHEA). DHEA, produced in the adrenal gland, is the most abundant sex steroid hormone in human blood and has been

  18. The role of diet on long-term concentration and pattern trends of brominated and chlorinated contaminants in western Hudson Bay polar bears, 1991-2007

    International Nuclear Information System (INIS)

    McKinney, Melissa A.; Stirling, Ian; Lunn, Nick J.; Peacock, Elizabeth; Letcher, Robert J.

    2010-01-01

    Adipose tissue was sampled from the western Hudson Bay (WHB) subpopulation of polar bears at intervals from 1991 to 2007 to examine temporal trends of PCB and OCP levels both on an individual and sum-(Σ-)contaminant basis. We also determined levels and temporal trends of emerging polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), polybrominated biphenyls (PBBs) and other current-use brominated flame retardants. Over the 17-year period, Σ DDT (and p,p'-DDE, p,p'-DDD, p,p'-DDT) decreased (-8.4%/year); α-hexachlorocyclohexane (α-HCH) decreased (-11%/year); β-HCH increased (+ 8.3%/year); and Σ PCB and Σ chlordane (CHL), both contaminants at highest concentrations in all years (> 1 ppm), showed no distinct trends even when compared to previous data for this subpopulation dating back to 1968. Some of the less persistent PCB congeners decreased significantly (-1.6%/year to -6.3%/year), whereas CB153 levels tended to increase (+ 3.3%/year). Parent CHLs (c-nonachlor, t-nonachlor) declined, whereas non-monotonic trends were detected for metabolites (heptachlor epoxide, oxychlordane). Σ chlorobenzene, octachlorostyrene, Σ mirex, Σ MeSO 2 -PCB and dieldrin did not significantly change. Increasing Σ PBDE levels (+ 13%/year) matched increases in the four consistently detected congeners, BDE47, BDE99, BDE100 and BDE153. Although no trend was observed, total-(α)-HBCD was only detected post-2000. Levels of the highest concentration brominated contaminant, BB153, showed no temporal change. As long-term ecosystem changes affecting contaminant levels may also affect contaminant patterns, we examined the influence of year (i.e., aging or 'weathering' of the contaminant pattern), dietary tracers (carbon stable isotope ratios, fatty acid patterns) and biological (age/sex) group on congener/metabolite profiles. Patterns of PCBs, CHLs and PBDEs were correlated with dietary tracers and biological group, but only PCB and CHL patterns were correlated with year

  19. Bioaccumulation and biotransformation of brominated and chlorinated contaminants and their metabolites in ringed seals (Pusa hispida) and polar bears (Ursus maritimus) from East Greenland.

    Science.gov (United States)

    Letcher, Robert J; Gebbink, Wouter A; Sonne, Christian; Born, Erik W; McKinney, Melissa A; Dietz, Rune

    2009-11-01

    We report on the comparative bioaccumulation, biotransformation and/or biomagnification from East Greenland ringed seal (Pusa hispida) blubber to polar bear (Ursus maritimus) tissues (adipose, liver and brain) of various classes and congeners of persistent chlorinated and brominated contaminants and metabolic by-products: polychlorinated biphenyls (PCBs), chlordanes (CHLs), hydroxyl (OH-) and methylsulfonyl (MeSO(2)-) PCBs, polybrominated biphenyls (PBBs), OH-PBBs, polybrominated diphenyl ether (PBDE) and hexabromocyclododecane (HBCD) flame retardants and OH- and methoxyl (MeO-) PBDEs, 2,2-dichloro-bis(4-chlorophenyl)ethene (p,p'-DDE), 3-MeSO(2)-p,p'-DDE, pentachlorophenol (PCP) and 4-OH-heptachlorostyrene (4-OH-HpCS). We detected all of the investigated contaminants in ringed seal blubber with high frequency, the main diet of East Greenland bears, with the exception of OH-PCBs and 4-OH-HpCS, which indicated that these phenolic contaminants were likely of metabolic origin and formed in the bears from accumulated PCBs and octachlorostyrene (OCS), respectively, rather than being bioaccumulated from a seal blubber diet. For all of the detectable sum of classes or individual organohalogens, in general, the ringed seal to polar bear mean BMFs for SigmaPCBs, p,p'-DDE, SigmaCHLs, SigmaMeSO(2)-PCBs, 3-MeSO(2)-p,p'-DDE, PCP, SigmaPBDEs, total-(alpha)-HBCD, SigmaOH-PBDEs, SigmaMeO-PBDEs and SigmaOH-PBBs indicated that these organohalogens bioaccumulate, and in some cases there was tissue-specific biomagnification, e.g., BMFs for bear adipose and liver ranged from 2 to 570. The blood-brain barrier appeared to be effective in minimizing brain accumulation as BMFs were bear tissues appeared to be mainly accumulated from the seal blubber rather than being metabolic formed from PBDEs in the bears. In vitro PBDE depletion assays using polar bear hepatic microsomes, wherein the rate of oxidative metabolism of PBDE congeners was very slow, supported the probability that accumulation

  20. Polybrominated diphenyl ethers: occurrence, dietary exposure, and toxicology.

    Science.gov (United States)

    Darnerud, P O; Eriksen, G S; Jóhannesson, T; Larsen, P B; Viluksela, M

    2001-03-01

    Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in plastics (concentration, 5--30%) and in textile coatings. Commercial products consist predominantly of penta-, octa-, and decabromodiphenyl ether mixtures, and global PBDE production is about 40,000 tons per year. PBDEs are bioaccumulated and biomagnified in the environment, and comparatively high levels are often found in aquatic biotopes from different parts of the world. During the mid-1970--1980s there was a substantial increase in the PBDE levels with time in both sediments and aquatic biota, whereas the latest Swedish data (pike and guillemot egg) may indicate that levels are at steady state or are decreasing. However, exponentially increasing PBDE levels have been observed in mother's milk during 1972--1997. Based on levels in food from 1999, the dietary intake of PBDE in Sweden has been estimated to be 0.05 microg per day. Characteristic end points of animal toxicity are hepatotoxicity, embryotoxicity, and thyroid effects as well as maternal toxicity during gestation. Recently, behavioral effects have been observed in mice on administration of PBDEs during a critical period after birth. Based on the critical effects reported in available studies, we consider the lowest-observed-adverse-effect level (LOAEL) value of the PBDE group to be 1 mg/kg/day (primarily based on effects of pentaBDEs). In conclusion, with the scientific knowledge of today and based on Nordic intake data, the possible consumer health risk from PBDEs appears limited, as a factor of over 10(6) separates the estimated present mean dietary intake from the suggested LOAEL value. However, the presence of many and important data gaps, including those in carcinogenicity, reproduction, and developmental toxicity, as well as additional routes of exposure, make this conclusion only preliminary. Moreover, the time trend of PBDEs in human breast milk is alarming for the future.

  1. Effect of polybrominated diphenyl ether congeners on placental cytokine production.

    Science.gov (United States)

    Arita, Yuko; Yeh, Corinne; Thoma, Theodosia; Getahun, Darios; Menon, Ramkumar; Peltier, Morgan R

    2018-02-01

    Polybrominated diphenyl ethers (PBDEs) are pollutants that may increase the risk of preterm birth. In previous studies, we found that a mixture of PBDEs altered the expression of biomarkers for preterm birth by the placenta. However, there are 209 different PBDE congeners with different tissue distributions. How these different congeners may alter the production of immunomodulators by the placenta that help to maintain the survival of the fetal allograft is unclear. Therefore, we compared the effects 5 common congeners on basal and bacteria-stimulated cytokine production by the placenta. Placental explant cultures were incubated with 20 μM of PBDE congeners 47, 99, 100, 153, 209 or vehicle in the presence and absence of Escherichia coli for 20 h. Conditioned medium was harvested and concentrations of IL-1β, TNF-α, IL-6, sgp130, HO-1, IL-10, BDNF, and 8-IsoP quantified. For unstimulated cultures, all congeners, except for PBDE-47, reduced the production of IL-1β and IL-6 production was enhanced by PBDE-153. BDNF concentrations tended to be reduced by most PBDE congeners and IL-10 production was enhanced by PBDE-99, -153, and -209. 8-IsoP production was enhanced by PBDE-153, but not the other congeners. For bacteria-stimulated cultures, PBDE-47 increased IL-1β production and PBDE-47, -153, and -209 tended to reduce TNF-α production. IL-6 production was enhanced by all PBDEs except 153. IL-10 production was enhanced by all congeners except for PBDE-47. All congeners significantly enhanced BDNF and 8-IsoP. These results suggest that PBDEs can alter the expression of placental biomarkers in a congener and infection-dependent manner. Copyright © 2018 Elsevier B.V. All rights reserved.

  2. Synthesis and physicochemical properties of polyhydroxylated diphenyl ethers

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Fu; Zhang, Xuesheng; Qu, Ruijuan; Shi, Jiaqi; Wang, Zunyao, E-mail: wangzun315cn@163.com

    2013-09-20

    Highlights: • The experimental pK{sub a1} values of five synthesized PHODEs were determined. • The hydrogen bonds existed in PHODEs were investigated. • There exist close relationships between the thermodynamic properties and N{sub PHOS}. • The relative stability order of PHODE congeners was theoretically proposed. - Abstract: Five polyhydroxylated diphenyl ethers (PHODEs) were synthesized. The first ionization constants (pK{sub a1}) of the synthesized compounds and seven phenolic compounds were determined using potentiometric titration experiments, together with the software ACD/Labs pK{sub a} DB program (version 6.0). The compared results showed that the software could be used to predict the pK{sub a1} of all 209 PHODEs. The thermodynamic properties of 209 PHODEs were calculated using density functional theory (DFT) at the B3LYP/6-311G** level with Gaussian 09 program. The standard enthalpy of formation (Δ{sub f}H{sup θ}) and the standard Gibbs energy of formation (Δ{sub f}G{sup θ}) were obtained. Two types of hydrogen bond were found to exist in the PHODEs’ molecules. The intramolecular hydrogen bond energies were discussed. The relative stability of PHODEs isomers was proposed theoretically with the relative standard Gibbs energy of formation (Δ{sub f}G{sub R}{sup θ}). The relationships of S{sup θ}, Δ{sub f}H{sup θ} and Δ{sub f}G{sup θ} to the number and position of the hydroxyl substitution (N{sub PHOS}) were studied.

  3. Levels and pattern of polybrominated diphenyl ethers in eggs of Antarctic seabirds: Endemic versus migratory species

    Energy Technology Data Exchange (ETDEWEB)

    Yogui, G.T. [Geochemical and Environmental Research Group, College of Geosciences, Texas A and M University, 833 Graham Road, College Station, TX 77845 (United States)], E-mail: gtyogui@ocean.tamu.edu; Sericano, J.L. [Geochemical and Environmental Research Group, College of Geosciences, Texas A and M University, 833 Graham Road, College Station, TX 77845 (United States)], E-mail: jsericano@gerg.tamu.edu

    2009-03-15

    Chinstrap and gentoo penguins are endemic species that live year round south of the Antarctic Convergence. South polar skua is a migratory seabird that can be observed in Antarctica during the breeding season (i.e., austral summer). This study compares concentration and pattern of polybrominated diphenyl ethers (PBDEs) in eggs of seabirds breeding at King George Island, Antarctic Peninsula. PBDEs in south polar skua eggs are approximately 20 times higher than in penguin eggs suggesting that skuas are more exposed to contaminants during the non-breeding season when they migrate to waters of the northern hemisphere. The pattern of PBDE congeners also differs between south polar skua and penguin eggs. The latter exhibited a pattern similar to that found in the local biota. In contrast, the congener pattern in south polar skua eggs suggests that birds breeding at King George Island may winter in the northwestern Pacific Ocean. - Skua and penguin eggs collected at King George Island have different concentration and pattern of PBDEs.

  4. Uptake of polybrominated diphenyl ethers by carrot and lettuce crops grown in compost-amended soils.

    Science.gov (United States)

    Bizkarguenaga, E; Iparraguirre, A; Oliva, E; Quintana, J B; Rodil, R; Fernández, L A; Zuloaga, O; Prieto, A

    2016-02-01

    The uptake of polybrominated diphenyl ethers (PBDEs) by carrot and lettuce was investigated. Degradation of PBDEs in soil in the absence of the plants was discarded. Different carrot (Nantesa and Chantenay) and lettuce (Batavia Golden Spring and Summer Queen) varieties were grown in fortified or contaminated compost-amended soil mixtures under greenhouse conditions. After plant harvesting, roots (core and peel) and leaves were analyzed separately for carrot, while for lettuce, leaves and hearts were analyzed together. The corresponding bioconcentration factors (BCFs) were calculated. In carrots, a concentration gradient of 2,2',3,4,4',5'-hexabromodiphenyl ether (BDE-138) became evident that decreased from the root peel via root core to the leaves. For decabromodiphenyl ether (BDE-209) at the low concentration level (7 and 20 ng g(-1)), the leaves incorporated the highest concentration of the target substance. For lettuce, a decrease in the BCF value (from 0.24 to 0.02) was observed the higher the octanol-water partition coefficient, except in the case of BDE-183 (BCF = 0.51) and BDE-209 (BCF values from 0.41 to 0.74). Significant influence of the soils and crop varieties on the uptake could not be supported. Metabolic debromination, hydroxylation or methylation of the target PBDEs in the soil-plant system was not observed.

  5. Polybrominated diphenyl ethers in pinnipeds stranded along the southern California coast

    International Nuclear Information System (INIS)

    Meng Xiangzhou; Blasius, Mary Ellen; Gossett, Richard W.; Maruya, Keith A.

    2009-01-01

    Little to no information exists for polybrominated diphenyl ethers (PBDEs) in marine mammals frequenting the highly urbanized southern California (USA) coast. Fourteen PBDE congeners were determined by GC-ECNI-MS in blubber of pinnipeds stranded locally between 1994 and 2006. Total PBDE concentrations (ΣPBDE) in California sea lion (n = 63) ranged from 0.04 to 33.7 μg/g wet weight (mean: 5.24 μg/g). To our knowledge, these are the highest reported PBDE levels in marine mammals to date. By comparison, mean ΣPBDE in Pacific harbor seals (n = 9) and northern elephant seals (n = 16) were 0.96 and 0.09 μg/g, respectively. PBDEs in adult males were higher than for adult females, however, no age class differences or temporal trends were observed. As the first PBDE data reported for marine mammals in this region, the elevated levels underscore the need for additional studies on the sources, temporal trends, and potential effects of PBDEs in highly urbanized coastal zones. - Levels of PBDEs in pinnipeds found stranded along the southern California coast (USA) between 1994 and 2006 are the highest reported to date for marine mammals.

  6. Polybrominated diphenyl ethers in pinnipeds stranded along the southern California coast

    Energy Technology Data Exchange (ETDEWEB)

    Meng Xiangzhou [Southern California Coastal Water Research Project, 3535 Harbor Blvd, Suite 110, Costa Mesa, CA 92626 (United States); Blasius, Mary Ellen; Gossett, Richard W. [Institute for Integrated Research in Materials, Environments and Society (IIRMES), California State University, Long Beach, 1250 Bellflower Blvd, Long Beach, CA 90840 (United States); Maruya, Keith A., E-mail: keithm@sccwrp.or [Southern California Coastal Water Research Project, 3535 Harbor Blvd, Suite 110, Costa Mesa, CA 92626 (United States)

    2009-10-15

    Little to no information exists for polybrominated diphenyl ethers (PBDEs) in marine mammals frequenting the highly urbanized southern California (USA) coast. Fourteen PBDE congeners were determined by GC-ECNI-MS in blubber of pinnipeds stranded locally between 1994 and 2006. Total PBDE concentrations (SIGMAPBDE) in California sea lion (n = 63) ranged from 0.04 to 33.7 mug/g wet weight (mean: 5.24 mug/g). To our knowledge, these are the highest reported PBDE levels in marine mammals to date. By comparison, mean SIGMAPBDE in Pacific harbor seals (n = 9) and northern elephant seals (n = 16) were 0.96 and 0.09 mug/g, respectively. PBDEs in adult males were higher than for adult females, however, no age class differences or temporal trends were observed. As the first PBDE data reported for marine mammals in this region, the elevated levels underscore the need for additional studies on the sources, temporal trends, and potential effects of PBDEs in highly urbanized coastal zones. - Levels of PBDEs in pinnipeds found stranded along the southern California coast (USA) between 1994 and 2006 are the highest reported to date for marine mammals.

  7. Levels and pattern of polybrominated diphenyl ethers in eggs of Antarctic seabirds: Endemic versus migratory species

    International Nuclear Information System (INIS)

    Yogui, G.T.; Sericano, J.L.

    2009-01-01

    Chinstrap and gentoo penguins are endemic species that live year round south of the Antarctic Convergence. South polar skua is a migratory seabird that can be observed in Antarctica during the breeding season (i.e., austral summer). This study compares concentration and pattern of polybrominated diphenyl ethers (PBDEs) in eggs of seabirds breeding at King George Island, Antarctic Peninsula. PBDEs in south polar skua eggs are approximately 20 times higher than in penguin eggs suggesting that skuas are more exposed to contaminants during the non-breeding season when they migrate to waters of the northern hemisphere. The pattern of PBDE congeners also differs between south polar skua and penguin eggs. The latter exhibited a pattern similar to that found in the local biota. In contrast, the congener pattern in south polar skua eggs suggests that birds breeding at King George Island may winter in the northwestern Pacific Ocean. - Skua and penguin eggs collected at King George Island have different concentration and pattern of PBDEs

  8. Passive air sampling of polychlorinated biphenyls, organochlorine compounds, and polybrominated diphenyl ethers across Asia.

    Science.gov (United States)

    Jaward, Foday M; Zhang, Gan; Nam, Jae Jak; Sweetman, Andrew J; Obbard, Jeffrey P; Kobara, Yuso; Jones, Kevin C

    2005-11-15

    Asia is of global importance economically, yet data on ambient persistent organic pollutant levels are still sparse for the region, despite international efforts under the Stockholm Convention to identify and reduce emissions. A large-scale passive air sampling survey was therefore conducted in Asia, specifically in China, Japan, South Korea, and Singapore. Polyurethane foam disks were deployed simultaneously at 77 sites, between Sept 21 and Nov 16, 2004, and analyzed for polychlorinated biphenyls (PCBs), organochlorine compounds (hexachlorobenzene (HCB), dichlorodiphenyltrichloroethanes (DDTs), chlordane), and polybrominated diphenyl ethers (PBDEs). The meteorological conditions prevailing in the region at this time facilitated the assessment of local/regional differences in atmospheric emissions, because large-scale advection effects due to monsoons or dust storms did not occur. Air concentrations estimated assuming an average sampler uptake rate of 3.5 m3/day ranged as follows (pg m(-3)): PCBs, 5-340; HCB, 10-460; DDTs, 0.4-1800; chlordanes, 1-660; PBDEs, < 0.13-340. South Korea and Singapore generally had regionally low concentrations. Elevated concentrations of PCBs, DDTs, and HCB occurred at sites in China, higher than reported in a similar recent sampling campaign in Europe. Chlordane was highest in samples from Japan (which also had elevated levels of PCBs and DDTs) and was also elevated in some Chinese locations. PBDE levels were generally low in the region.

  9. Landfills as sources of polyfluorinated compounds, polybrominated diphenyl ethers and musk fragrances to ambient air

    Science.gov (United States)

    Weinberg, Ingo; Dreyer, Annekatrin; Ebinghaus, Ralf

    2011-02-01

    In order to investigate landfills as sources of polyfluorinated compounds (PFCs), polybrominated diphenyl ethers (PBDEs) and synthetic musk fragrances to the atmosphere, air samples were simultaneously taken at two landfills (one active and one closed) and two reference sites using high volume air samplers. Contaminants were accumulated on glass fiber filters (particle phase) and PUF/XAD-2/PUF cartridges (gas phase), extracted by methyl-tert butyl ether/acetone (neutral PFCs), methanol (ionic PFCs) or hexane/acetone (PBDEs, musk fragrances), and detected by GC-MS (neutral PFCs, PBDEs, musk fragrances) or HPLC-MS/MS (ionic PFCs). Total concentrations ranged from 84 to 706 pg m -3 (volatile PFCs, gas phase), from fragrances, gas + particle phase) and from 1 to 11 pg m -3 (PBDEs, gas + particle phase). Observed sum concentrations of PFCs and synthetic musk fragrances and partly PBDE concentrations were elevated at landfill sites compared to corresponding reference sites. Concentrations determined at the active landfill were higher than those of the inactive landfill. Overall, landfills can be regarded as a source of synthetic musk fragrances, several PFCs and potentially of PBDEs to ambient air.

  10. Polychlorinated biphenyls and polybrominated diphenyl ethers in the North American atmosphere

    International Nuclear Information System (INIS)

    Shen Li; Wania, Frank; Lei, Ying D.; Teixeira, Camilla; Muir, Derek C.G.; Xiao, Hang

    2006-01-01

    To assess the spatial concentration variability of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in the atmosphere on a large continental scale, their annually integrated air concentrations were determined in 2000/2001 using XAD-based passive air samplers (PAS). The network included 40 stations in Canada, the United States, Mexico, Belize and Costa Rica, and covered 72 degrees of latitude and longitude. Total concentrations of PCB and PBDE congeners ranged from below the detection limit to 130 ng PAS -1 and 24 ng PAS -1 , respectively. PCBs displayed a large variation between urban, rural and remote sites, whereas PBDEs did not follow such a pattern. Open burning of 'Penta'-containing waste may have contributed to the PBDEs detected in the air samples from rural and remote areas. Air from the Canadian Arctic had a relatively higher percentage of lighter PCB congeners than air sampled in the tropical region, which is interpreted as evidence for global fractionation. - A continental passive air sampling network reveals atmospheric distribution patterns of two classes of industrial chemicals

  11. Polybrominated diphenyl ethers (PBDEs) in marine mammals from Arctic and North Atlantic regions, 1986-2009.

    Science.gov (United States)

    Rotander, Anna; van Bavel, Bert; Polder, Anuschka; Rigét, Frank; Auðunsson, Guðjón Atli; Gabrielsen, Geir Wing; Víkingsson, Gísli; Bloch, Dorete; Dam, Maria

    2012-04-01

    A selection of PBDE congeners was analyzed in pooled blubber samples of pilot whale (Globicephala melas), ringed seal (Phoca hispida), minke whale (Balaenoptera acutorostrata), fin whale (Balaenoptera physalus), harbor porpoise (Phocoena phocoena), hooded seal (Cystophora cristata) and Atlantic white-sided dolphin (Lagenorhynchus acutus), covering a time period of more than 20 years (1986-2009). The analytes were extracted and cleaned-up using open column extraction and multi-layer silica gel column chromatography, and the analysis was performed on a GC-MS system operating in the NCI mode. The highest PBDE levels were found in the toothed whale species pilot whale and white-sided dolphin, and the lowest levels in fin whales and ringed seals. One-sided analyses of variance (ANOVA) followed by Tukey comparisons of means were applied to test for differences between years and sampling areas. Due to inter-year sampling variability, only general comparisons of PBDE concentrations between different sampling areas could be made. Differences in PBDE concentrations between three sampling periods, from 1986 to 2007, were evaluated in samples of pilot whales, ringed seals, white-sided dolphins and hooded seals. The highest PBDE levels were found in samples from the late 1990s or beginning of 2000, possibly reflecting the increase in the global production of technical PBDE mixtures in the 1990s. The levels of BDE #153 and #154 increased relative to the total PBDE concentration in some of the species in recent years, which may indicate an increased relative exposure to higher brominated congeners. In order to assess the effect of measures taken in legally binding international agreements, it is important to continuously monitor POPs such as PBDEs in sub-Arctic and Arctic environments. Copyright © 2011 Elsevier Ltd. All rights reserved.

  12. High-performance liquid chromatographic method to evaluate the hydrogen atom transfer during reaction between 1,1-diphenyl-2-picryl-hydrazyl radical and antioxidants

    International Nuclear Information System (INIS)

    Boudier, Ariane; Tournebize, Juliana; Bartosz, Grzegorz; El Hani, Safae; Bengueddour, Rachid; Sapin-Minet, Anne; Leroy, Pierre

    2012-01-01

    Highlights: ► Both 1,1-diphenyl-2-picrylhydrazyl radical and its product measurement by HPLC. ► Lowest limit of detection by monitoring 1,1-diphenyl-2-picryl-hydrazine. ► Adsorption problem of the radical on HPLC parts have been pointed out. - Abstract: 1,1-Diphenyl-2-picrylhydrazyl (DPPH·) is a stable nitrogen centred radical widely used to evaluate direct radical scavenging properties of various synthetic or natural antioxidants (AOs). The bleaching rate of DPPH· absorbance at 515 nm is usually monitored for this purpose. In order to avoid the interference of complex coloured natural products used as antioxidant supplements or cosmetics, HPLC systems have been reported as alternative techniques to spectrophotometry. They also rely upon measurement of DPPH· quenching rate and none of them permits to identify and measure 1,1-diphenyl-2-picryl-hydrazine (DPPH-H), the reduced product of DPPH· resulting from hydrogen atom transfer (HAT), which is the main mechanism of the reaction between DPPH· and AOs. We presently report an HPLC method devoted to the simultaneous measurement of DPPH· and DPPH-H. Both were fully separated on a C18 column eluted with acetonitrile–10 mM ammonium citrate buffer pH 6.8 (70:30, v/v) and detected at 330 nm. Adsorption process of DPPH· onto materials of the HPLC system was pointed out. Consequently, the linearity range observed for DPPH· was restricted, thus a much lower limit of detection was obtained for DPPH-H than for DPPH· using standards (0.02 and 14 μM, respectively). The method was applied to three commonly used AOs, i.e. Trolox ® , ascorbic acid and GSH, and compared with spectrophotometry. Further application to complex matrices (cell culture media, vegetal extracts) and nanomaterials demonstrated (i) its usefulness because of higher selectivity than colorimetry, and (ii) its help to investigate the mechanisms occurring with the free radical.

  13. Mortality of workers potentially exposed to organic and inorganic brominated chemicals, DBCP, TRIS, PBB, and DDT

    Energy Technology Data Exchange (ETDEWEB)

    Wong, O; Brocker, W; Davis, H V; Nagle, G S

    1984-02-01

    A historical prospective mortality study was conducted on 3579 white male workers employed between 1935 and 1976 with potential exposures to brominated compounds including 1,2-dibromo-3-chloropropane (DBCP), Tris (2,3-dibromopropyl) phosphate, polybrominated biphenyls (PBB), various organic and inorganic bromides, and DDT. Death certificates were obtained for 541 deaths (94% of all deaths). The mortality experience of the entire cohort and several subcohorts was compared with that of United States white men adjusted for age and calendar time. The comparison statistic was the commonly used standardised mortality ratio (SMR). Historical industrial hygiene data were not available, and the workers were classified by their work areas or departments in order to estimate their potential exposures. Overall mortality for the entire cohort and several subgroups was significantly lower than expected. For the entire cohort, significant mortality deficits were observed in diseases of the circulatory system, non-malignant respiratory disease, and diseases of the digestive system. On the other hand, mortality from diabetes mellitus was significantly raised for the cohort. No significant overall or cause-specific mortality excess was detected among employees potentially exposed to either TRIS or DDT. A significant mortality excess due to diseases of the circulatory system was observed among workers potentially exposed to DBCP. Mortality from testicular cancer was significantly higher than expected among those potentially exposed to other organic bromides. The common potential exposure of those who had died of testicular cancer was methyl bromide. Owing to the lack of accurate historical exposure information and the fact that many workers were potentially exposed to a multitude of chemicals, it is difficult to draw definitive statements on the causations of the observed mortality excesses.

  14. Polybrominated diphenyl ethers and their hydroxylated and methoxylated derivatives in seafood obtained from Puget Sound, WA

    Energy Technology Data Exchange (ETDEWEB)

    Cade, Sara E.; Kuo, Li-Jung; Schultz, Irvin R.

    2018-03-07

    Synthetic polybrominated diphenyl ethers (PBDEs) are ubiquitous environmental contaminants and known to occur in most food items. Consumer fish products have been identified as having some of the highest PBDE levels found in USA food sources. Natural formation of hydroxylated (OH-) and methoxylated (MeO-) PBDEs are also known to occur in simple marine organisms, which may be bioaccumulated by seafood. In this study, we report findings of an initial survey of PBDE, OH-PBDE and MeO-PBDE content in common seafood items available to residents living in the Puget Sound region of Washington State. Seafood samples were either purchased from local grocery stores or caught off the coast of SE Alaska and in Puget Sound. The edible portions of the seafood were analyzed, which for finfish was white muscle (skinless fillets) and for shellfish, either the entire soft tissue (bivalves) or processed meat (calamari, shrimp and scallops). Results indicated that finfish typically had higher levels of PBDEs compared to shellfish with BDE-47 and BDE-99 as the most common congeners detected. Among shellfish, bivalves (clams and mussels) were notable for having much higher levels of OH- and MeO-PBDEs compared to other types of seafood with 6'-OH-BDE-47 and 2'-MeO-BDE-68 being the more common OH- and MeO- congeners, respectively. Based on our results and recent updates to daily fish consumption rates, estimated intake rates for Washington State residents will be between 34 and 644 ng PBDEs/day, depending on species consumed. For the OH- and MeO- forms, daily exposure is much more variable but typically would range between 15 and 90 ng/day for most seafood types. If shellfish are primarily consumed, OH-PBDE intake could be as high as 350 ng/day. These daily intake rates for PBDEs are higher than most dietary intake rates calculated for populations in other world regions.

  15. Summer atmospheric polybrominated diphenyl ethers in urban and rural areas of northern China

    International Nuclear Information System (INIS)

    Wang Chen; Li Wei; Chen Jiwei; Wang Hongqijie; Li Tongchao; Shen Guofeng; Shen Huizhong; Huang Ye; Wang Rong; Wang Bin; Zhang Yanyan; Tang Jianhui; Liu Wenxin; Wang Xilong; Tao Shu

    2012-01-01

    High levels of polybrominated diphenyl ethers (PBDEs) have been extensively reported in urban areas and at e-waste recycling sites in coastal China. However, data are scarce in northern China and are not available in rural areas at all. In addition, it is often believed that air concentrations in rural areas are lower than those in urban areas without distinguishing rural residential areas and open fields. In this study, air samples were collected at 17 sites covering urban and rural (residential and open field) areas in northern China using active samplers. With BDE-209 dominated in all congeners, the average concentrations of BDE-209 (41 ± 72 pg/m 3 ) and other 13 PBDEs (16 ± 12 pg/m 3 ) were significantly lower than those found in south China, such as in Guangzhou or Hong Kong. On average, the total PBDE concentrations at the urban sites were 2.2 and 2.9 times of those at the rural residential and field sites, respectively. - Graphical abstract: Concentration of PBDEs at each site of the studied area. Highlights: ► High levels of PBDEs with BDE-209 domination were detected in air in northern China. ► PBDE concentrations in rural residential areas were significantly higher than those in rural open fields. ► Proportions of BDE-209 in urban areas were higher than those in rural areas. ► PBDE concentrations were correlated to local population density and Gross Domestic Production. - In northern China, PBDEs in air in rural residential areas were significantly higher than those in open fields.

  16. Interaction of chelate cyclopentadienyl compounds of zirconium and hafnium with bromine

    International Nuclear Information System (INIS)

    Brajnina, Eh.M.; Minacheva, M.Kh.

    1975-01-01

    Interaction of bromine with Zr and Hf dibenzoylmethane (DBM) compounds of following type: (DBM) 4 M, CpM(DBM) 3 and Cp 2 M(DBM) 2 leads to the formation of (DBM) 2 MBr 2 , (DBM) 3 MBr and CpZr(DBM) 2 Br in the rations which depend on the conditions of the reaction (Cp=C 5 H 5 )

  17. XAS AND XPS CHARACTERIZATION OF MERCURY BINDING ON BROMINATED ACTIVATED CARBON

    Science.gov (United States)

    Brominated powdered activated carbon sorbents have been shown to e quite effective for mercury capture when injected into the flue gas duct at coal-fired power plants and are especially useful when buring Western low-chlorine subbituminous coals. X-ray absorption spectroscopy (X...

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

    Science.gov (United States)

    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. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. Preparation of radioactive labelled compounds. Pt. 2. 82Br labelled organic bromine compounds by isotopic exchange

    International Nuclear Information System (INIS)

    Otto, R.

    1988-05-01

    Studies on isotopic exchange between organic bromine compounds and 82 Br labelled dioxane dibromide in the presence of AlCl 3 are described. The results obtained enable to develop a simple and quick preparation method for the labelling with 82 Br [fr

  20. Bromine content in some seaweeds of Goa (Central West Coast of India)

    Digital Repository Service at National Institute of Oceanography (India)

    Naqvi, S.W.A.; Mittal, P.K.; Kamat, S.Y.; Solimabi; Reddy, C.V.G.

    in chloroform at 400 and 650 nm. The bromine content, on a dry dry weight basis, varied from 0.024 to 0.024% for the green algae, from 0.020 to 0.400% for the algae, and from 0.015 to 0.054% for the brown algae. Only two species @iChondria armata@@ and @i...

  1. Brominated Flame Retardants and their metabolites: Novel insights into endocrine disruptive properties.

    NARCIS (Netherlands)

    Fernández Cantón, R.|info:eu-repo/dai/nl/304831530

    2008-01-01

    Brominated flame retardants (BFRs) are chemicals that are added to materials to inhibit or suppress ignition and are incorporated during the manufacture of e.g. electronic equipment, furniture, construction materials and textiles. BFRs have become an increasingly important group of organohalogen

  2. Relationship among iodine, bromine and chlorine concentrations in cow's milk in Japan

    International Nuclear Information System (INIS)

    Ohno, Shigeru; Itoh, Takashi; Morishima, Hiroshige; Honda, Yoshihide.

    1989-01-01

    In order to know the relationship among some elements in biological materials, iodine, bromine and chlorine concentrations in cow's milk samples in Japan were determined by the thermal neutron activation analysis using a low power research reactor and a Van de Graaff accelerator. The iodine contents in cow's milk samples ranged from 0.041 to 0.316 ppm with an average of 0.096 ppm. The bromine and chlorine in these samples ranged from 2.3 to 11.1 ppm and from 475 to 1650 ppm, respectively. The average concentration of the bromine was calculated to be 5.6 ppm and that of the chlorine was 853 ppm. The relationship among iodine, bromine and chlorine concentrations in cow's milk samples in Japan was studied with a regression analysis. It was suggested that the correlation has a power function as follows; Y = K(Z) -A where, Y is elemental concentration in ppm, Z is atomic number of element, A (=7.4) is exponent and K (=14.7) is a constant. (author)

  3. Ullmann-type coupling of brominated tetrathienoanthracene on copper and silver

    Czech Academy of Sciences Publication Activity Database

    Gutzler, R.; Cardenas, L.; Lipton-Duffin, J.; El Garah, M.; Dinca, L.E.; Szakacs, C.E.; Fu, Ch.; Gallagher, M.; Vondráček, Martin; Rybachuk, M.; Perepichka, D.F.; Rosei, F.

    2014-01-01

    Roč. 6, č. 5 (2014), 2660-2668 ISSN 2040-3364 R&D Projects: GA MŠk(CZ) LM2011029 Institutional support: RVO:68378271 Keywords : Ullmann reaction * brominated tetrathienoanthracene * high resolution photoemission * STM Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 7.394, year: 2014

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

    NARCIS (Netherlands)

    Kotterman, M.J.J.; Veen, van der I.; Hesselingen, van J.M.; Leonards, P.E.G.; Osinga, R.; Boer, de J.

    2003-01-01

    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

  5. Kinetics of aerobic cometabolic biodegradation of chlorinated and brominated aliphatic hydrocarbons: A review.

    Science.gov (United States)

    Jesus, João; Frascari, Dario; Pozdniakova, Tatiana; Danko, Anthony S

    2016-05-15

    This review analyses kinetic studies of aerobic cometabolism (AC) of halogenated aliphatic hydrocarbons (HAHs) from 2001-2015 in order to (i) compare the different kinetic models proposed, (ii) analyse the estimated model parameters with a focus on novel HAHs and the identification of general trends, and (iii) identify further research needs. The results of this analysis show that aerobic cometabolism can degrade a wide range of HAHs, including HAHs that were not previously tested such as chlorinated propanes, highly chlorinated ethanes and brominated methanes and ethanes. The degree of chlorine mineralization was very high for the chlorinated HAHs. Bromine mineralization was not determined for studies with brominated aliphatics. The examined research period led to the identification of novel growth substrates of potentially high interest. Decreasing performance of aerobic cometabolism were found with increasing chlorination, indicating the high potential of aerobic cometabolism in the presence of medium- and low-halogenated HAHs. Further research is needed for the AC of brominated aliphatic hydrocarbons, the potential for biofilm aerobic cometabolism processes, HAH-HAH mutual inhibition and the identification of the enzymes responsible for each aerobic cometabolism process. Lastly, some indications for a possible standardization of future kinetic studies of HAH aerobic cometabolism are provided. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Biodegradation of brominated aromatics by cultures and laccase of Trametes versicolor

    Czech Academy of Sciences Publication Activity Database

    Uhnáková, Bronislava; Petříčková, Alena; Biedermann, David; Homolka, Ladislav; Vejvoda, Vojtěch; Bednář, P.; Papoušková, B.; Šulc, Miroslav; Martínková, Ludmila

    2009-01-01

    Roč. 76, č. 6 (2009), s. 826-832 ISSN 0045-6535 R&D Projects: GA MŠk 2B06151 Institutional research plan: CEZ:AV0Z50200510 Keywords : Brominated phenols * Tetrabromobisphenol A * Laccase Subject RIV: CE - Biochemistry Impact factor: 3.253, year: 2009

  7. The distribution of lignin in white birch wood as determined by bromination with TEM-EDXA

    International Nuclear Information System (INIS)

    Saka, S.; Goring, D.A.I.

    1988-01-01

    Ultraviolet absorbance and bromine uptake were measured on various morphological regions of birch wood. To facilitate precise comparison, observations were made on identical locations in successive cross sections. From the data, the concentration of lignin and the ratio of the guaiacyl to syringyl residues were determined. The results obtained were then compared with the previous findings from the use of UV microscopy alone

  8. Laboratory Studies of Stratospheric Bromine Chemistry: Kinetics of the Reactions of Bromine Monoxide with Nitrogen Dioxide and Atomic Oxygen.

    Science.gov (United States)

    Thorn, Robert Peyton, Jr.

    interferences from production of vibrationally or electronically excited O_2 are discussed. The effect of the faster reaction rate coefficients that are reported for the rm BrO + NO_2 + M and BrO + O(^3P) reactions upon bromine partitioning and ozone depletion in the stratosphere is discussed.

  9. Effects of polybrominated diphenyl ethers (PBDEs) and their derivatives on protein disulfide isomerase activity and growth hormone release of GH3 cells.

    Science.gov (United States)

    Hashimoto, Shoko; Yoshimura, Hiromi; Okada, Kazushi; Uramaru, Naoto; Sugihara, Kazumi; Kitamura, Shigeyuki; Imaoka, Susumu

    2012-03-19

    Polybrominated diphenyl ethers (PBDEs) have been used in a variety of consumer products such as flame retardants and recently have been known to be widespread environmental pollutants, which probably affect biological functions of mammalian cells. However, the risk posed by PBDE metabolites has not been clarified. Our previous study suggested that bisphenol A (BPA), an endocrine-disrupting chemical, binds to protein disulfide isomerase (PDI) and inhibits its activity. PDI is an isomerase enzyme in the endoplasmic reticulum and facilitates the formation or cleavage of disulfide bonds. PDI consists of a, b, b', and a' domains and the c region, with the a and a' domains having isomerase active sites. In the present study, we tested the effects of 10 kinds of PBDE compounds and their metabolites on PDI. OH-PBDEs specifically inhibited the isomerase activity of PDI, with 4'-OH-PBDE more effective than 2' (or 2)-OH-PBDEs. 4'-OH-PBDE inhibited the isomerase activity of the b'a'c fragment but not that of ab and a'c, suggesting that the b' domain of PDI is essential for the inhibition by 4'-OH-PBDE. We also investigated the effects of these chemicals on the production of growth hormone (GH) in GH3 cells. In GH3 cells, levels of mRNA and protein of GH stimulated by T(3) were reduced by 4'-OH-PBDE and 4'-MeO-PBDE. The reduction in GH expression caused by these compounds was not changed by the overexpression or knockdown of PDI in GH3 cells, while these manipulations of PDI levels significantly suppressed the expression of GH. These results suggest that the biological effects of PBDEs differed depending on their brominated and hydroxylated positions. © 2011 American Chemical Society

  10. Placental transfer of the polybrominated diphenyl ethers BDE-47, BDE-99 and BDE-209 in a human placenta perfusion system: an experimental study

    Directory of Open Access Journals (Sweden)

    Frederiksen Marie

    2010-07-01

    Full Text Available Abstract Background Polybrominated diphenyl ethers (PBDEs have been widely used as flame retardants in consumer products. PBDEs may affect thyroid hormone homeostasis, which can result in irreversible damage of cognitive performance, motor skills and altered behaviour. Thus, in utero exposure is of very high concern due to critical windows in fetal development. Methods A human ex vivo placenta perfusion system was used to study the kinetics and extent of the placental transfer of BDE-47, BDE-99 and BDE-209 during four-hour perfusions. The PBDEs were added to the maternal circulation and monitored in the maternal and fetal compartments. In addition, the perfused cotyledon, the surrounding placental tissue as well as pre-perfusion placental tissue and umbilical cord plasma were also analysed. The PBDE analysis included Soxhlet extraction, clean-up by adsorption chromatography and GC-MS analysis. Results and Discussion Placental transfer of BDE-47 was faster and more extensive than for BDE-99. The fetal-maternal ratios (FM-ratio after four hours of perfusion were 0.47 and 0.25 for BDE-47 and BDE-99, respectively, while the indicative permeability coefficient (IPC measured after 60 minutes of perfusion was 0.26 h-1 and 0.10 h-1, respectively. The transport of BDE-209 seemed to be limited. These differences between the congeners may be related to the degree of bromination. Significant accumulation was observed for all congeners in the perfused cotyledon as well as in the surrounding placental tissue. Conclusion The transport of BDE-47 and BDE-99 indicates in utero exposure to these congeners. Although the transport of BDE-209 was limited, however, possible metabolic debromination may lead to products which are both more toxic and transportable. Our study demonstrates fetal exposure to PBDEs, which should be included in risk assessment of PBDE exposure of women of child-bearing age.

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

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Mingbao; Qu, Ruijuan; Wang, Chao; Wang, Liansheng; Wang, Zunyao, E-mail: wangzun315cn@163.com

    2013-09-15

    Highlights: •A combined experimental and theoretical approach was used for risk assessments of six BFRs in fish. •Oxidative stress biomarkers were measured for toxicity identification. •Toxicity order was proposed via the integrated biomarker response. •Theoretical calculations were performed to analyze the BFRs toxicity. -- Abstract: 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 100 mg/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

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

    International Nuclear Information System (INIS)

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

    2013-01-01

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Mengmei [State key laboratory of clean energy utilisation, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou (China); Buekens, Alfons [State key laboratory of clean energy utilisation, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou (China); Formerly with Chemical Engineering department, Vrije Universiteit Brussel, Brussels (Belgium); Li, Xiaodong, E-mail: lixd@zju.edu.cn [State key laboratory of clean energy utilisation, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou (China)

    2016-03-05

    Highlights: • BFRs (PBDEs, HBCD and TBBP-A) are the main sources of PBDD/Fs in combustion process. • Precursor formation is the most relevant pathway for PBDD/Fs formation. • Adding bromine into combustion system can enhance the formation of PCDD/Fs. • Primitive recycling of e-waste produces the largest amounts of PBDD/Fs. - Abstract: 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 (Br{sub 2}) 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.

  14. Global atmospheric model for mercury including oxidation by bromine atoms

    Directory of Open Access Journals (Sweden)

    C. D. Holmes

    2010-12-01

    Full Text Available Global models of atmospheric mercury generally assume that gas-phase OH and ozone are the main oxidants converting Hg0 to HgII and thus driving mercury deposition to ecosystems. However, thermodynamic considerations argue against the importance of these reactions. We demonstrate here the viability of atomic bromine (Br as an alternative Hg0 oxidant. We conduct a global 3-D simulation with the GEOS-Chem model assuming gas-phase Br to be the sole Hg0 oxidant (Hg + Br model and compare to the previous version of the model with OH and ozone as the sole oxidants (Hg + OH/O3 model. We specify global 3-D Br concentration fields based on our best understanding of tropospheric and stratospheric Br chemistry. In both the Hg + Br and Hg + OH/O3 models, we add an aqueous photochemical reduction of HgII in cloud to impose a tropospheric lifetime for mercury of 6.5 months against deposition, as needed to reconcile observed total gaseous mercury (TGM concentrations with current estimates of anthropogenic emissions. This added reduction would not be necessary in the Hg + Br model if we adjusted the Br oxidation kinetics downward within their range of uncertainty. We find that the Hg + Br and Hg + OH/O3 models are equally capable of reproducing the spatial distribution of TGM and its seasonal cycle at northern mid-latitudes. The Hg + Br model shows a steeper decline of TGM concentrations from the tropics to southern mid-latitudes. Only the Hg + Br model can reproduce the springtime depletion and summer rebound of TGM observed at polar sites; the snowpack component of GEOS-Chem suggests that 40% of HgII deposited to snow in the Arctic is transferred to the ocean and land reservoirs, amounting to a net deposition flux to the Arctic of 60 Mg a−1. Summertime events of depleted Hg0 at Antarctic sites due to subsidence are much better simulated by

  15. Synthesis of heterocyclic chalcone derivatives and their radical scavenging ability toward 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radicals

    International Nuclear Information System (INIS)

    Hwang, Kijun; Kim, Hoseok; Kim, Beomtae; Han, Incheol

    2012-01-01

    A series of heterocyclic chalcone derivatives bearing heterocycles such as thiophene or furan ring as an isostere of benzene ring were carefully prepared, and the influence of heterocycles on 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activities was systematically investigated. Structure-activity relationships (SAR) analysis showed that the activities of thiophene ring-containing chalcones were higher than those of furan ring containing chalcones, and the presence of methyl substituent of heterocyclic ring distinctly affected the activities compared with non-substituted heterocycles in an opposite manner, with the 4'-methyl group of thiophene ring increasing activity and the 3'-methyl group of the furan ring decreasing activity. The distinct isosteric effect of heterocycles (i.e., thiophene or furan ring) on radical scavenging activities of heterocyclic chalcones was distinctly demonstrated in our work

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

    Science.gov (United States)

    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 (pwebs. The relative high PFR levels in several fish species suggest high emissions and substantial exposure of organisms to PFRs in the Western Scheldt. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Triclosan and Hydroxylated Polybrominated Diphenyl Ethers in Lake and Esturaine Sediments

    Science.gov (United States)

    Arnold, W. A.; Kerrigan, J. F.; McNeill, K.; Erickson, P. R.; Grandbois, M.

    2014-12-01

    Halogenated diphenyl ethers are a class of emerging contaminants that includes the antibacterial compound triclosan and the flame retardant polybrominated diphenyl ethers (PBDEs). Both triclosan and hydroxylated polybrominated diphenyl ethers (OH-BDEs) are known to form dioxins when exposed to sunlight in aqueous solution. Thus, it is important to understand the sources and presence of these compounds in the environment, especially because OH-BDEs are breakdown products of PBDEs and also naturally produced compounds. In this work, the levels of OH-BDEs were determined in lake sediments from Minnesota and esturaine sediments from San Francisco Bay. Both surface sediments over a broad spatial area and sediment cores were collected and analyzed. Triclosan was used as a marker of wastewater as a source of the targeted emerging contaminants. The relationship between triclosan and OH-BDE levels provides insight into the importance of natural and anthropogenic influences on the levels of OH-BDEs.

  18. Induced production of halogenated diphenyl ethers from the marine-derived fungus Penicillium chrysogenum.

    Science.gov (United States)

    Yang, Guohua; Yun, Keumja; Nenkep, Viviane N; Choi, Hong Dae; Kang, Jung Sook; Son, Byeng Wha

    2010-11-01

    Manipulation of the fermentation of the marine-derived fungus Penicillium chrysogenum by addition of CaBr(2) resulted in induced production of bromodiphenyl ether analogs. Two new free-radical-scavenging polybrominated diphenyl ethers, 1 and 2, and three known diphenyl ethers, 3,3'-dihydroxy-5,5'-dimethyldiphenyl ether (3), and an inseparable mixture of violacerol-I (4) and violacerol-II (5) were isolated. The structures of the two new polybromodiphenyl ethers 1 and 2 were assigned by combined spectroscopic-data analysis, including deuterium-induced isotope effect. Compounds 1-3, and a mixture of 4 and 5 exhibited radical-scavenging activities against 1,1-diphenyl-2-picrylhydrazyl with IC(50) values of 18, 15, 42, and 6 μM, respectively. With the exception of 3, the compounds were, therefore, more active than the positive control, ascorbic acid (IC(50) 20 μM).

  19. Characteristics of the trace elements and arsenic, iodine and bromine species in snow in east-central China

    Science.gov (United States)

    Gao, Yunchuan; Yang, Chao; Ma, Jin; Yin, Meixue

    2018-02-01

    Fifty-five snow samples were collected from 11 cities in east-central China. These sampling sites cover the areas with the most snowfall in 2014, there were only two snowfalls from June 2013 to May 2014 in east-central China. Twenty-three trace elements in the filtered snow samples were measured with inductively coupled plasma-mass spectrometry (ICP-MS). Statistical analysis of the results show that the total concentrations of elements in the samples from different cities are in the order of SJZ > LZ > XA > ZZ > GD > NJ > QD > JX > WH > HZ > LA, which are closely related to the levels of AQI, PM2.5 and PM10 in these cities, and their correlation coefficients are 0.93, 0.76 and 0.93. The concentration of elements in snow samples is highly correlated with air pollution and reflects the magnitude of the local atmospheric deposition. The concentrations of Fe, Al, Zn, Ba, and P are over 10.0 μg/L, the concentrations of Mn, Cu, Pb, As, Br and I are between 1.0 μg/L to 10.0 μg/L, the concentrations of V, Cr, Co, Ni, Se, Mo, Cd and Sb are less than 1.0 μg/L in snow samples in east-central China, and Rh, Pd, Pt, Hg were not detected. Iodine and bromine species in all samples and arsenic species (As(III), As(V), dimethylarsinic acid (DMA) and monomethyl arsenic (MMA)) in some samples were separated and measured successfully by HPLC-ICP-MS. The majority of arsenic in the snow samples is inorganic arsenic, and the concentration of As(III) (0.104-1.400 μg/L) is higher than that of As(V) (0.012-0.180 μg/L), while methyl arsenicals, such as DMA and MMA, were almost not detected. The concentration of I- (Br-) is much higher than that of IO3- (BrO3-). The mean concentration of soluble organic iodine (SOI) (1.64 μg/L) is higher than that of I- (1.27 μg/L), however the concentration of Br- (5.58 μg/L) is higher than that of soluble organic bromine (SOBr) (2.90 μg/L). The data presented here shows that SOI is the most abundant species and the majority of the total bromine is

  20. Rigid-rod polyamides and polyimides derived from 4,3 ''-diamino-2 ',6 '-diphenyl- or di(4-biphenylyl)-p-terphenyl and 4-amino-4 ''-carboxy-2 ',6 '-diphenyl-p-terphenyl

    NARCIS (Netherlands)

    Spiliopoulos, IK; Mikroyannidis, JA; Tsivgoulis, GM

    1998-01-01

    4,3 "-Diamino-2',6'-diphenyl- or di(4-biphenylyl)p-terphenyl (3a or 3b) and 4-amino-4 "-carboxy-2',6'-diphenyl-p-terphenyl (6) were synthesized through pyrylium salts and used for the preparation of rigid-rod polyamides and polyimides. The polymers were characterized by inherent viscosity, elemental

  1. Evaluation of diphenyl and dowtherm-A's thermal cross sections and their application to reactor calculation

    International Nuclear Information System (INIS)

    Florido, P.C.; Gillette, V.H.; Granada, J.R.; Patino, N.E.

    1990-01-01

    This work applies a scattering synthetic approximation to represent diphenyl and dowtherm-A dispersion laws on typical ranges of interest regarding temperature. The present formalism is based on a previous model of benzene molecule formerly validated. The results obtained from diphenyl agree with laboratory measurements, but those regarding dowtherm-A present some variations with respect to the available information. The result of the application of this model to the measurements made in Wrenlingen (Switzerland) to measure the vacuum coefficient of the cells charasteristic of high conversion reactors, are also presented, experimentally simulating said vacuum using dowtherm-A instead of H 2 O. (Author) [es

  2. Comparative study of the formation of brominated disinfection byproducts in UV/persulfate and UV/H2O2 oxidation processes in the presence of bromide.

    Science.gov (United States)

    Wang, Lu; Ji, Yuefei; Lu, Junhe; Kong, Deyang; Yin, Xiaoming; Zhou, Quansuo

    2017-10-01

    The objective of this research was to compare the transformation of Br - and formation of brominated byproducts in UV/persulfate (PS) and UV/H 2 O 2 processes. It was revealed that Br - was efficiently transformed to free bromine which reacted with humic acid (HA) or dihydroxybenzoic acid resulting in the formation of brominated byproducts such as bromoacetic acids (BAAs) in UV/PS system. In contrast, no free bromine and brominated byproducts could be detected in UV/H 2 O 2 system, although the oxidization of Br - was evident. We presumed that the oxidation of Br - by hydroxyl radicals led to the formation of bromine radicals. However, the bromine radical species could be immediately reduced back to Br - by H 2 O 2 before coupling to each other to form free bromine, which explains the undetection of free bromine and BAAs in UV/H 2 O 2 . In addition to free bromine, we found that the phenolic functionalities in HA molecules, which served as the principal reactive sites for free chlorine attack, could be in situ generated when HA was exposed to free radicals. This study demonstrates that UV/H 2 O 2 is more suitable than UV/PS for the treatment of environmental matrices containing Br - . Graphical abstract Graphical abstract.

  3. Prenatal Exposure to Organohalogens, Including Brominated Flame Retardants, Influences Motor, Cognitive, and Behavioral Performance at School Age

    NARCIS (Netherlands)

    Roze, Elise; Meijer, Lisethe; Bakker, Attie; Van Braeckel, Koenraad N. J. A.; Sauer, Pieter J. J.; Bos, Arend F.

    2009-01-01

    BACKGROUND: Organohalogen compounds (OHCs) are known to have neurotoxic effects on the developing brain. OBJECTIVE: We investigated the influence of prenatal exposure to OHCs, including brominated flame retardants, on motor, cognitive, and behavioral outcome in healthy children of school age.

  4. Concentrations of Polybrominated Diphenyl Ethers (PBDEs) and 2,4,6-Tribromophenol in Human Placental Tissues

    Science.gov (United States)

    Leonetti, Christopher; Butt, Craig M.; Hoffman, Kate; Miranda, Marie Lynn; Stapleton, Heather M.

    2015-01-01

    Legacy environmental contaminants such as polybrominated diphenyl ethers (PBDEs) are widely detected in human tissues. However, few studies have measured PBDEs in placental tissues, and there are no reported measurements of 2,4,6-tribromophenol (2,4,6-TBP) in placental tissues. Measurements of these contaminants are important for understanding potential fetal exposures, as these compounds have been shown to alter thyroid hormone regulation in vitro and in vivo. In this study, we measured a suite of PBDEs and 2,4,6-TBP in 102 human placental tissues collected between 2010–2011 in Durham County, North Carolina, USA. The most abundant PBDE congener detected was BDE-47, with a mean concentration of 5.09 ng/g lipid (range: 0.12–141 ng/g lipid; detection frequency 91%); however, 2,4,6-TBP was ubiquitously detected and present at higher concentrations with a mean concentration of 15.4 ng/g lipid (range:1.31–316 ng/g lipid; detection frequency 100%). BDE-209 was also detected in more than 50% of the samples, and was significantly associated with 2,4,6-TBP in placental tissues, suggesting they may have a similar source, or that 2,4,6-TBP may be a degradation product of BDE-209. Interestingly, BDE-209 and 2,4,6-TBP were negatively associated with age (rs=−0.16; p=0.10 and rs=−0.17; p=0.08, respectively). The results of this work indicate that PBDEs and 2,4,6-TBP bioaccumulate in human placenta tissue and likely contribute to prenatal exposures to these environmental contaminants. Future studies are needed to determine if these joint exposures are associated with any adverse health measures in infants and children. PMID:26700418

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

    Science.gov (United States)

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

    1999-08-01

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

  6. Measurement of the flame retardants polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) in house dust

    Energy Technology Data Exchange (ETDEWEB)

    Stapleton, H.; Dodder, N.; Schantz, M.; Wise, S. [National Institute of Standards and Technology, Gaithersburg, MD (United States)

    2004-09-15

    Current monitoring of polybrominated diphenyl ethers (PBDEs) has shown that concentrations are increasing in the environment very rapidly with doubling times as short as three to five years. North America consumes a large percentage of the global market demand for PBDEs, and as a result, concentrations of PBDEs in human milk and serum are an order of magnitude higher in women from North America relative to Europe. Within sampled populations, PBDE levels in human serum have been shown to range over an order of magnitude, and high levels cannot always be attributed to occupational exposure, age or diet. One source that may be responsible for these observations is exposure in the home. These compounds are liberally applied to many common household items such as furniture, mattresses, computers and TVs to retard or hinder the outbreak of fire. Over time, these flame retardants may leach out into the home environment, where they may be inhaled or ingested, resulting in elevated levels in human serum. Very few studies have examined PBDE levels within the home and only one study has measured the concentrations of two PBDE congeners in house dust. The present study was undertaken to measure a suite PBDE congeners in house dust from a variety of homes and to assess the contribution of the three commercial PBDE mixtures (penta-, octa- and decaBDE) to the house dust composition. In addition, we also measured the concentrations of hexabromocyclododecane (HBCDD), another flame retardant. Correlations with properties of the houses such as year of construction, square footage, carpeting coverage and number of computers in the house were also examined for any positive influences.

  7. Occurrence of polybrominated diphenyl ethers in floor and elevated surface house dust from Shanghai, China.

    Science.gov (United States)

    Niu, Dong; Qiu, Yanling; Li, Li; Zhou, Yihui; Du, Xinyu; Zhu, Zhiliang; Chen, Ling; Lin, Zhifen

    2018-04-24

    House dust is the main source of human exposure to flame retardants by ingestion. This study investigated the occurrence of polybrominated diphenyl ethers (PBDEs) in indoor dust from 22 houses in Shanghai, China. House dust was separately collected from the floor and elevated furnishings surface (mostly between 0.5 and 2 m height) for comparison. The concentrations of ∑ 22 PBDEs ranged from 19.4 to 3280 ng/g (with a geometric mean of 203 ng/g) and from 55.1 to 792 ng/g (with a geometric mean of 166 ng/g) in floor dust (FD) and elevated surface dust (ESD), respectively. BDE-209 was the predominant congener, accounting for about 73.1% of total PBDE burdens. In terms of congener profiles, the comparison of FD and ESD revealed no significant differences except for the ratio of BDE-47/BDE-99. ESD samples displayed a ratio of BDE-47/BDE-99 very similar to commercial penta-BDE products DE-71 while the ratio in FD was exceptionally higher. Significant correlation was found between concentrations of commercial penta-BDE compositions in FD and ESD (p house dust exhibited temporal stability. Human exposure to PBDEs via dust ingestion was estimated. The highest daily intake of PBDEs was for toddlers by using 95th percentile concentrations of PBDEs via high dust ingestion in FD (23.07 ng/kg bw/day). About 20-fold difference in exposure estimates between toddlers and adults supports that toddlers are facing greater risk from indoor floor dust. Expectedly, this study highlighted the point that residents in Shanghai were exposed to low doses of PBDEs in house dust.

  8. Ozone Formation Induced by the Impact of Reactive Bromine and Iodine Species on Photochemistry in a Polluted Marine Environment.

    Science.gov (United States)

    Shechner, M; Tas, E

    2017-12-19

    Reactive iodine and bromine species (RIS and RBS, respectively) are known for altering atmospheric chemistry and causing sharp tropospheric ozone (O 3 ) depletion in polar regions and significant O 3 reduction in the marine boundary layer (MBL). Here we use measurement-based modeling to show that, unexpectedly, both RIS and RBS can lead to enhanced O 3 formation in a polluted marine environment under volatile organic compound (VOC)-limited conditions associated with high nitrogen oxide (NO X = [NO] + [NO 2 ]) concentrations. Under these conditions, the daily average O 3 mixing ratio increased to ∼44 and ∼28% for BrO and IO mixing ratios of up to ∼6.8 and 4.7 ppt, respectively. The increase in the level of O 3 was partially induced by enhanced ClNO 3 formation for higher Br 2 and I 2 emission flux. The increase in the level of O 3 was associated with an increased mixing ratio of hydroperoxyl radical to hydroxyl radical ([HO 2 ]/[OH]) and increased [NO 2 ]/[NO] with higher levels of RBS and/or RIS. NO X -rich conditions are typical of the polluted MBL, near coastlines and ship plumes. Considering that O 3 is toxic to humans, plants, and animals and is a greenhouse gas, our findings call for adequate updating of local and regional air-quality models with the effects of activities of RBS and RIS on O 3 mixing ratios in the polluted MBL.

  9. Determination of organic-bound chlorine and bromine in human body fluids by neutron activation analysis

    International Nuclear Information System (INIS)

    McKinney, J.D.; Abusamra, A.; Reed, J.H.

    1983-01-01

    The levels of organic-bound chlorine and bromine in human milk and serum are determined by neutron activation analysis. Desalted milk and serum fractions are irradiated with neutrons in a nuclear reactor and the resulting γ-rays of 38 Cl and 80 Br are measured. The desalting procedure, achieved by using Bio-Gel molecular sieves, virtually removes all ionic chloride and bromides from milk and serum. Radioactive tracer studies with polychlorinated biphenyl- 14 C indicate a recovery of 90% through the Bio-Gel column. The total organic chlorine in 2.2-(4-chlorophenyl)-1,1-dichloroethane spiked milk and heptachlor spiked milk, determined after being desalted and irradiated according to this procedure, substantiates a good recovery of the added spike. The lower limits of detection of organic-bound chlorine and bromine in milk or serum are 50 and 5 parts per billion (ppb), respectively

  10. The Determination of Bromine in Wheat, Flour and Bread by Neutron Activation Analysis. RCN Report

    International Nuclear Information System (INIS)

    Das, H.A.; Hoede, D.; Zonderhuis, J.

    1969-07-01

    Gaseous germicides are commonly used to improve the tenability of wheat. The bulk material is exposed to a gas which is highly poisonous to fungi. Methylene and ethylene dibromide are often used for this purpose. Traces of these compounds in wheat, flour and bread are dangerous. Consequently, the persistence of these gases should be determined experimentally. This implies that sensitive methods to detect traces of methylene and ethylene dibromide must be available. Neutron activation analysis can be used to determine the total amount of bromine present in the sample. This datum is a useful addition to the gaschromato-graphic determinations of the compounds involved. A routine method for the determination of bromine in corn, flour and bread has been developed and is described in the text

  11. A Quaternized Polysulfone Membrane for Zinc-Bromine Redox Flow Battery

    Directory of Open Access Journals (Sweden)

    Mingqiang Li

    2014-01-01

    Full Text Available A quaternized polysulfone (QNPSU composite membrane is fabricated for zinc-bromine redox flow battery. The structure of the membrane is examined by FT-IR spectra and SEM. The conductivity of the membrane is tested by electrochemical analyzer. After a zinc-bromine battery with this composite membrane is operated at different voltage while charging and at different current while discharging to examine the performance of the membrane, it is found that the discharge voltage was 0.9672 V and the power density was 6 mW/cm2 at a current of 0.1 A, which indicated that the novel composite membrane is a promising material for the flow battery.

  12. The Effect of Representing Bromine from VSLS on the Simulation and Evolution of Antarctic Ozone

    Science.gov (United States)

    Oman, Luke D.; Douglass, Anne R.; Salawitch, Ross J.; Canty, Timothy P.; Ziemke, Jerald R.; Manyin, Michael

    2016-01-01

    We use the Goddard Earth Observing System Chemistry Climate Model (GEOSCCM), a contributor to both the 2010 and 2014 WMO Ozone Assessment Reports, to show that inclusion of 5 parts per trillion (ppt) of stratospheric bromine(Br(sub y)) from very short lived substances (VSLS) is responsible for about a decade delay in ozone hole recovery. These results partially explain the significantly later recovery of Antarctic ozone noted in the 2014 report, as bromine from VSLS was not included in the 2010 Assessment. We show multiple lines of evidence that simulations that account for VSLS Br(sub y) are in better agreement with both total column BrO and the seasonal evolution of Antarctic ozone reported by the Ozone Monitoring Instrument (OMI) on NASAs Aura satellite. In addition, the near zero ozone levels observed in the deep Antarctic lower stratospheric polar vortex are only reproduced in a simulation that includes this Br(sub y) source from VSLS.

  13. Simulation of dual carbon-bromine stable isotope fractionation during 1,2-dibromoethane degradation.

    Science.gov (United States)

    Jin, Biao; Nijenhuis, Ivonne; Rolle, Massimo

    2018-06-01

    We performed a model-based investigation to simultaneously predict the evolution of concentration, as well as stable carbon and bromine isotope fractionation during 1,2-dibromoethane (EDB, ethylene dibromide) transformation in a closed system. The modelling approach considers bond-cleavage mechanisms during different reactions and allows evaluating dual carbon-bromine isotopic signals for chemical and biotic reactions, including aerobic and anaerobic biological transformation, dibromoelimination by Zn(0) and alkaline hydrolysis. The proposed model allowed us to accurately simulate the evolution of concentrations and isotope data observed in a previous laboratory study and to successfully identify different reaction pathways. Furthermore, we illustrated the model capabilities in degradation scenarios involving complex reaction systems. Specifically, we examined (i) the case of sequential multistep transformation of EDB and the isotopic evolution of the parent compound, the intermediate and the reaction product and (ii) the case of parallel competing abiotic pathways of EDB transformation in alkaline solution.

  14. Study of reactivity of p-cymene ruthenium(II) dimer towards diphenyl ...

    Indian Academy of Sciences (India)

    Unknown

    The reaction of [{(η6-p-cymene)Ru(µ-Cl)}2Cl2] with functionalized phosphine viz, diphenyl-. 2-pyridylphosphine ... ing from the displacement of the p-cymene ligand. ... The structures of complexes 1 and 2 have been confirmed by single crystal.

  15. A National Probabilistic Study of Polybrominated Diphenyl Ethers in Fish from US Lakes and Reservoirs

    Science.gov (United States)

    National estimates were developed for polybrominated diphenyl ethers (PBDEs) in fish from lakes and reservoirs of the conterminous United States (excluding the Laurentian Great Lakes and Great Salt Lake) using an unequal probability design. Predator (fillet) and bottom-dweller (w...

  16. In vitro estrogenicity of polybrominated diphenyl ethers, hydroxylated PBDEs, and polybrominated bisphenol A compounds

    NARCIS (Netherlands)

    Meerts, I.A.T.M.; Letcher, R.J.; Hoving, S.; Marsh, G.; Bergman, A.; Lemmen, J.G.; Burg, van der B.; Brouwer, A.

    2001-01-01

    Polybrominated diphenyl ethers (PBDEs) are used in large quantities as additive flame retardants in plastics and textile materials. PBDEs are persistent compounds and have been detected in wildlife and in human adipose tissue and plasma samples. In this study, we investigated the (anti)estrogenic

  17. Photosynthesis involvement in the mechanism of action of diphenyl ether herbicides.

    Science.gov (United States)

    Ensminger, M P; Hess, F D

    1985-05-01

    Photosynthesis is not required for the toxicity of diphenyl ether herbicides, nor are chloroplast thylakoids the primary site of diphenyl ether herbicide activity. Isolated spinach (Spinacia oleracea L.) chloroplast fragments produced malonyl dialdehyde, indicating lipid peroxidation, when paraquat (1,1'-dimethyl-4,4'-bipyridinium ion) or diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] were added to the medium, but no malonyl dialdehyde was produced when chloroplast fragments were treated with the methyl ester of acifluorfen (methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid), oxyfluorfen [2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene], or MC15608 (methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-chlorobenzoate). In most cases the toxicity of acifluorfen-methyl, oxyfluorfen, or MC15608 to the unicellular green alga Chlamydomonas eugametos (Moewus) did not decrease after simultaneous treatment with diuron. However, diuron significantly reduced cell death after paraquat treatment at all but the highest paraquat concentration tested (0.1 millimolar). These data indicate electron transport of photosynthesis is not serving the same function for diphenyl ether herbicides as for paraquat. Additional evidence for differential action of paraquat was obtained from the superoxide scavenger copper penicillamine (copper complex of 2-amino-3-mercapto-3-methylbutanoic acid). Copper penicillamine eliminated paraquat toxicity in cucumber (Cucumis sativus L.) cotyledons but did not reduce diphenyl ether herbicide toxicity.

  18. Photosynthesis Involvement in the Mechanism of Action of Diphenyl Ether Herbicides 1

    Science.gov (United States)

    Ensminger, Michael P.; Hess, F. Dan

    1985-01-01

    Photosynthesis is not required for the toxicity of diphenyl ether herbicides, nor are chloroplast thylakoids the primary site of diphenyl ether herbicide activity. Isolated spinach (Spinacia oleracea L.) chloroplast fragments produced malonyl dialdehyde, indicating lipid peroxidation, when paraquat (1,1′-dimethyl-4,4′-bipyridinium ion) or diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] were added to the medium, but no malonyl dialdehyde was produced when chloroplast fragments were treated with the methyl ester of acifluorfen (methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid), oxyfluorfen [2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene], or MC15608 (methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-chlorobenzoate). In most cases the toxicity of acifluorfen-methyl, oxyfluorfen, or MC15608 to the unicellular green alga Chlamydomonas eugametos (Moewus) did not decrease after simultaneous treatment with diuron. However, diuron significantly reduced cell death after paraquat treatment at all but the highest paraquat concentration tested (0.1 millimolar). These data indicate electron transport of photosynthesis is not serving the same function for diphenyl ether herbicides as for paraquat. Additional evidence for differential action of paraquat was obtained from the superoxide scavenger copper penicillamine (copper complex of 2-amino-3-mercapto-3-methylbutanoic acid). Copper penicillamine eliminated paraquat toxicity in cucumber (Cucumis sativus L.) cotyledons but did not reduce diphenyl ether herbicide toxicity. PMID:16664206

  19. Study of the liquid vapor equilibrium in the bromine-hydrobromic acid-water system

    Science.gov (United States)

    Benizri, R.; Lessart, P.; Courvoisier, P.

    1984-01-01

    A glass ebullioscope was built and at atmospheric pressure, liquid-vapor equilibria relative to the Br2-HBr-H2O system, in the concentration range of interest for evaluation of the Mark 13 cycle was studied. Measurements were performed for the brome-azeotrope (HBr-H2O) pseudo-binary system and for the ternary system at temperatures lower than 125 C and in the bromine concentration range up to 13% wt.

  20. Hydrostatic pressure study of MBE CdMnTe doped bromine

    Energy Technology Data Exchange (ETDEWEB)

    Szczytko, J.; Wasek, D.; Przybytek, J.; Baj, M. [Institute of Experimental Physics, Warsaw University, Warsaw (Poland); Waag, A. [Physikalisches Institut, Universitaet Wuerzburg, Wuerzburg (Germany)

    1995-12-31

    We present Hall effect and resistivity measurements as a function of pressure performed on MBE-grown Cd{sub 1-x}Mn{sub x}Te (with x=0.14) layer doped with bromine. The experimental data were analysed using positive and negative U model of Br centers. We found that both models could reproduce the experimental points, but in the case of positive U modes - only under assumption that the sample was completely uncompensated. (author). 6 refs, 3 figs.

  1. Hydrostatic pressure study of MBE CdMnTe doped bromine

    International Nuclear Information System (INIS)

    Szczytko, J.; Wasek, D.; Przybytek, J.; Baj, M.; Waag, A.

    1995-01-01

    We present Hall effect and resistivity measurements as a function of pressure performed on MBE-grown Cd 1-x Mn x Te (with x=0.14) layer doped with bromine. The experimental data were analysed using positive and negative U model of Br centers. We found that both models could reproduce the experimental points, but in the case of positive U modes - only under assumption that the sample was completely uncompensated. (author)

  2. Assessing oestrogenic effects of brominated flame retardants Hexabromocyclododecane and Tetrabromobisphenol A on MCF-7 cells

    Czech Academy of Sciences Publication Activity Database

    Dorosh, Andriy; Děd, Lukáš; Elzeinová, Fatima; Pěknicová, Jana

    2010-01-01

    Roč. 56, - (2010), s. 35-39 ISSN 0015-5500 R&D Projects: GA MŠk(CZ) 1M06011; GA MŠk(CZ) 2B06151 Institutional research plan: CEZ:AV0Z50520701 Keywords : endocrine disruptors * BRF - brominated flame retardant * MCF-7 cells * TFF1 - trefoil factor Subject RIV: DN - Health Impact of the Environment Quality Impact factor: 0.729, year: 2010

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

    International Nuclear Information System (INIS)

    Kajiwara, Natsuko; Noma, Yukio; Takigami, Hidetaka

    2011-01-01

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

  4. Evaluation of Soxhlet extraction, accelerated solvent extraction and microwave-assisted extraction for the determination of polychlorinated biphenyls and polybrominated diphenyl ethers in soil and fish samples

    International Nuclear Information System (INIS)

    Wang Pu; Zhang Qinghua; Wang Yawei; Wang Thanh; Li Xiaomin; Ding Lei; Jiang Guibin

    2010-01-01

    Three commonly applied extraction techniques for persistent organic chemicals, Soxhlet extraction (SE), accelerated solvent extraction (ASE) and microwave-assisted extraction (MAE), were applied on soil and fish samples in order to evaluate their performances. For both PCBs and PBDEs, the two more recent developed techniques (ASE and MAE) were in general capable of producing comparable extraction results as the classical SE, and even higher extraction recoveries were obtained for some PCB congeners with large octanol-water partitioning coefficients (K ow ). This relatively uniform extraction results from ASE and MAE indicated that elevated temperature and pressure are favorable to the efficient extraction of PCBs from the solid matrices. For PBDEs, difference between the results from MAE and ASE (or SE) suggests that the MAE extraction condition needs to be carefully optimized according to the characteristics of the matrix and analyte to avoid degradation of higher brominated BDE congeners and improve the extraction yields.

  5. Evaluation of Soxhlet extraction, accelerated solvent extraction and microwave-assisted extraction for the determination of polychlorinated biphenyls and polybrominated diphenyl ethers in soil and fish samples

    Energy Technology Data Exchange (ETDEWEB)

    Wang Pu [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, 18 Shuangqing Road, Beijing 100085 (China); Zhang Qinghua, E-mail: qhzhang@rcees.ac.cn [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, 18 Shuangqing Road, Beijing 100085 (China); Wang Yawei; Wang Thanh; Li Xiaomin; Ding Lei; Jiang Guibin [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, 18 Shuangqing Road, Beijing 100085 (China)

    2010-03-17

    Three commonly applied extraction techniques for persistent organic chemicals, Soxhlet extraction (SE), accelerated solvent extraction (ASE) and microwave-assisted extraction (MAE), were applied on soil and fish samples in order to evaluate their performances. For both PCBs and PBDEs, the two more recent developed techniques (ASE and MAE) were in general capable of producing comparable extraction results as the classical SE, and even higher extraction recoveries were obtained for some PCB congeners with large octanol-water partitioning coefficients (K{sub ow}). This relatively uniform extraction results from ASE and MAE indicated that elevated temperature and pressure are favorable to the efficient extraction of PCBs from the solid matrices. For PBDEs, difference between the results from MAE and ASE (or SE) suggests that the MAE extraction condition needs to be carefully optimized according to the characteristics of the matrix and analyte to avoid degradation of higher brominated BDE congeners and improve the extraction yields.

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

    DEFF Research Database (Denmark)

    Abbasi, Naeem Akhtar; Eulaers, Igor; Jaspers, Veerle Leontina Bernard

    2017-01-01

    The exposure to legacy polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs) and unrestricted 1,2-bis (2,4,6-tribromophenoxy) ethane (BTBPE), bis (2-ethylhexyl)-2,3,4,5-tetrabromophthalate (BEH-TEBP) and 2-ethylhexyl-2,3,4,5-tetrabromo-benzoate (EH-TBB) was examined in tail fea...

  7. High Performance Hydrogen/Bromine Redox Flow Battery for Grid-Scale Energy Storage

    Energy Technology Data Exchange (ETDEWEB)

    Cho, KT; Ridgway, P; Weber, AZ; Haussener, S; Battaglia, V; Srinivasan, V

    2012-01-01

    The electrochemical behavior of a promising hydrogen/bromine redox flow battery is investigated for grid-scale energy-storage application with some of the best redox-flow-battery performance results to date, including a peak power of 1.4 W/cm(2) and a 91% voltaic efficiency at 0.4 W/cm(2) constant-power operation. The kinetics of bromine on various materials is discussed, with both rotating-disk-electrode and cell studies demonstrating that a carbon porous electrode for the bromine reaction can conduct platinum-comparable performance as long as sufficient surface area is realized. The effect of flow-cell designs and operating temperature is examined, and ohmic and mass-transfer losses are decreased by utilizing a flow-through electrode design and increasing cell temperature. Charge/discharge and discharge-rate tests also reveal that this system has highly reversible behavior and good rate capability. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.018211jes] All rights reserved.

  8. Bromine incorporation into five DBP classes upon chlorination of water with extremely low SUVA values.

    Science.gov (United States)

    Hong, Huachang; Yan, Xiaoqing; Song, Xuhui; Qin, Yanyan; Sun, Hongjie; Lin, Hongjun; Chen, Jianrong; Liang, Yan

    2017-07-15

    The main objective of this study was to assess the effects of disinfection conditions on bromine incorporation into disinfection by-products (DBPs) during chlorination of water with low specific UV absorbance (SUVA). Five classes of DBPs were included: trihalomethanes (THMs), dihaloacetic acids (di-HAAs), trihaloacetic acids (tri-HAAs), dihaloacetonitriles (DHANs) and trihalonitromethanes (THNMs). Results showed that the bromine utilization in DBPs formation was positive related with reaction time, pH and temperature. On the other hand, the bromine substitution factors (BSFs) of DBPs were generally increased with pH (except tri-HAAs) and bromide concentration, but decreased with the reaction time, temperature and chlorine dose. Moreover, the BSFs values varied with DBP classes with the ranking being as following: THNMs≫DHANs≫tri-HAAs>THM≈di-HAAs. These results were mostly similar with the references, yet the pH effect on BSFs as well as the rank of BSFs for different DBP classes may differ with the specific UV absorbance of organic matter. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Mechanochemical conversion of brominated POPs into useful oxybromides: a greener approach

    Science.gov (United States)

    Cagnetta, Giovanni; Liu, Han; Zhang, Kunlun; Huang, Jun; Wang, Bin; Deng, Shubo; Wang, Yujue; Yu, Gang

    2016-06-01

    Brominated organic pollutants are considered of great concern for their adverse effect on human health and the environment, so an increasing number of such compounds are being classified as persistent organic pollutants (POPs). Mechanochemical destruction is a promising technology for POPs safe disposal because it can achieve their complete carbonization by solvent-free high energy ball milling at room temperature. However, a large amount of co-milling reagent usually is necessary, so a considerable volume of residue is produced. In the present study a different approach to POPs mechanochemical destruction is proposed. Employing stoichiometric quantities of Bi2O3 or La2O3 as co-milling reagent, brominated POPs are selectively and completely converted into their corresponding oxybromides (i.e. BiOBr and LaOBr), which possess very peculiar properties and can be used for some actual and many more potential applications. In this way, bromine is beneficially reused in the final product, while POPs carbon skeleton is safely destroyed to amorphous carbon. Moreover, mechanochemical destruction is employed in a greener and more sustainable manner.

  10. Integration of Bromine and Cyanogen Bromide Generators for the Continuous-Flow Synthesis of Cyclic Guanidines.

    Science.gov (United States)

    Glotz, Gabriel; Lebl, René; Dallinger, Doris; Kappe, C Oliver

    2017-10-23

    A continuous-flow process for the in situ on-demand generation of cyanogen bromide (BrCN) from bromine and potassium cyanide that makes use of membrane-separation technology is described. In order to circumvent the handling, storage, and transportation of elemental bromine, a continuous bromine generator using bromate-bromide synproportionation can optionally be attached upstream. Monitoring and quantification of BrCN generation was enabled through the implementation of in-line FTIR technology. With the Br 2 and BrCN generators connected in series, 0.2 mmol BrCN per minute was produced, which corresponds to a 0.8 m solution of BrCN in dichloromethane. The modular Br 2 /BrCN generator was employed for the synthesis of a diverse set of biologically relevant five- and six-membered cyclic amidines and guanidines. The set-up can either be operated in a fully integrated continuous format or, where reactive crystallization is beneficial, in semi-batch mode. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. 母乳中溴代/氯代阻燃剂及其代谢产物的分析检测方法%Determination of Chlorinated/Brominated Flame Retardants and their Metabolites in Breast Milk

    Institute of Scientific and Technical Information of China (English)

    贲玉婕; 李龙; 王文月; 李兴红; 田媛; 徐晓白

    2013-01-01

    A method was developed for the determination of trace-amount chlorinated/brominated flame, retardants and their metabolites in breast milk by gas chromatography combined with mass spectrum in negative chemical ionization mode (GC/NCI-LRMS ). Chlorinated/brominated flame retardants and their metabolites were classified into netural and phenolic fractions. Neutral targets included eight brominated diphenyl ether (BDE) congeners (including BDE-209) , five MeO-BDE congeners and other new flame retardants or the metabolites. Phenolic targets referred to nine OH-BDEs congeners. The efficient separation of various neutral targets was obtained on a 30-m column (RTX-1614) and that of phenolic targets was achieved on a 30-m column ( DB-5 ) in the optimized GC condition. In the extraction and clean-up procedures, before supersonic extracting, surrogate/internal standards were required spiking into breast milk, then the samples were separated into neutral and phenolic fractions by a liquid-liquid extraction methods. The extracts were cleaned-up further to remove other co-extracts by sulfuric acid silica prior to injection. It was noticeable that phenolic fractions required to be further derived by diazomethane before clean-up. The recoveries of decabrominated diphenyl ethers, other polybrominated diphenyl ethers, methoxyl-polybrominated diphenyl ethers, dechlorane plus and dechlorinated products, other flame retardants, hydroxylated polybrominated diphenyl ethers were 66.5% -75.4% , 84.2% -126.4% , 60.9% -115.1% , 86.7% -104.9% , 42.9% -113. 8% and 64.7% -129. 5% , respectively. The RSD of neutral targets were all below 22% , and those of the phenolic targets were all below 30%. The method was used for the determination of targets in breast milk collected from an e-waste dismantling area. The results of quality control showed the method was reliable investigation.%建立了低分辨气相色谱-负化学源质谱法(GC/NCI-LRMS)定性与定量检测母乳中的溴代/氯代

  12. Synthesis of 2-phenyl- and 2,3-diphenyl-quinolin-4-carboxylic acid derivatives

    International Nuclear Information System (INIS)

    Elhadi, S. A.

    2004-09-01

    Quinolin derivatives are a group of compounds known to possess a wide range of biological activities. The chemistry of quinolines together with their corresponding aldehydes were dealt with in chapter one of this study. Special emphasis was given to the chemistry of benzaldehyde. Twenty five 2-phenyl- and 2,3-diphenyl-quinolin-4-carboxylic acid derivatives together with their corresponding intermediates were prepared in this work. Basically, the synthetic design of these compounds arise from the appropriate disconnections of the target 2-phenyl and 2,3-diphenyl-quinolin-4-carboxylic acids. The retro synthesis analysis of these compounds reveals pyruvic acid, aromatic amine and benzaldehyde or phenyl pyruvic acid, aromatic amine and benzaldehyde as possible logical precursors for 2-phenyl-and 2,3-diphenyl- quinoline-4-carboxylic acids respectively. The purity and identities of the synthesized compounds were elucidated through chromatographic and spectroscopic techniques. The compounds were heavily subjected to spectroscopic analysis (UV, IR, GC/MS, 1 H-and 13 C- NMR). The appropriate disconnections and the mechanisms of the corresponding reactions were given and discussed in chapter three. The spectral data were interpreted and correlated with the target structures. The prepared 2-phenyl- and 2,3-diphenyl-quinoline-4-carboxylic acid derivatives were screened for their antibacterial activity. The compounds were tested against the standard bacterial organisms B. subtilis, S. aureus, E. coli and P. vulgaris. Some of these compounds were devoid of antibacterial activity against S. aureus and P. vulgaris, while others showed moderate activity. All of the tested compounds showed an activity against B. subtilis and E. coli. 2,3-diphenyl -6-sulphanilamide-quinolin-4-carboxylic acid showed the highest activity against the four standard tested organisms.(Author)

  13. Synthesis of 2-phenyl- and 2,3-diphenyl-quinolin-4-carboxylic acid derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Elhadi, S A [Department of Chemistry, Faculty of Education, University of Khartoum, Khartoum (Sudan)

    2004-09-01

    Quinolin derivatives are a group of compounds known to possess a wide range of biological activities. The chemistry of quinolines together with their corresponding aldehydes were dealt with in chapter one of this study. Special emphasis was given to the chemistry of benzaldehyde. Twenty five 2-phenyl- and 2,3-diphenyl-quinolin-4-carboxylic acid derivatives together with their corresponding intermediates were prepared in this work. Basically, the synthetic design of these compounds arise from the appropriate disconnections of the target 2-phenyl and 2,3-diphenyl-quinolin-4-carboxylic acids. The retro synthesis analysis of these compounds reveals pyruvic acid, aromatic amine and benzaldehyde or phenyl pyruvic acid, aromatic amine and benzaldehyde as possible logical precursors for 2-phenyl-and 2,3-diphenyl- quinoline-4-carboxylic acids respectively. The purity and identities of the synthesized compounds were elucidated through chromatographic and spectroscopic techniques. The compounds were heavily subjected to spectroscopic analysis (UV, IR, GC/MS, {sup 1}H-and {sup 13}C- NMR). The appropriate disconnections and the mechanisms of the corresponding reactions were given and discussed in chapter three. The spectral data were interpreted and correlated with the target structures. The prepared 2-phenyl- and 2,3-diphenyl-quinoline-4-carboxylic acid derivatives were screened for their antibacterial activity. The compounds were tested against the standard bacterial organisms B. subtilis, S. aureus, E. coli and P. vulgaris. Some of these compounds were devoid of antibacterial activity against S. aureus and P. vulgaris, while others showed moderate activity. All of the tested compounds showed an activity against B. subtilis and E. coli. 2,3-diphenyl -6-sulphanilamide-quinolin-4-carboxylic acid showed the highest activity against the four standard tested organisms.(Author)

  14. Bromine monoxide / sulphur dioxide ratios in relation to volcanological observations at Mt. Etna 2006–2009

    Directory of Open Access Journals (Sweden)

    G. Giuffrida

    2012-12-01

    Full Text Available Over a 3-yr period, from 2006 to 2009, frequent scattered sunlight DOAS measurements were conducted at Mt. Etna at a distance of around 6 km downwind from the summit craters. During the same period and in addition to these measurements, volcanic observations were made by regularly visiting various parts of Mt. Etna. Here, results from these measurements and observations are presented and their relation is discussed. The focus of the investigation is the bromine monoxide/sulphur dioxide (BrO / SO2 ratio, and its variability in relation to volcanic processes. That the halogen/sulphur ratio can serve as a precursor or indicator for the onset of eruptive activity was already proposed by earlier works (e.g. Noguchi and Kamiya 1963; Menyailov, 1975; Pennisi and Cloarec, 1998; Aiuppa et al., 2002. However, there is still a limited understanding today because of the complexity with which halogens are released, depending on magma composition and degassing conditions. Our understanding of these processes is far from complete, for example of the rate and mechanism of bubble nucleation, growth and ascent in silicate melts (Carroll and Holloway, 1994, the halogen vapour-melt partitioning and the volatile diffusivity in the melt (Aiuppa et al., 2009. With this study we aim to add one more piece to the puzzle of what halogen/sulphur ratios might tell about volcanic activities. Our data set shows an increase of the BrO / SO2 ratio several weeks prior to an eruption, followed by a decline before and during the initial phase of eruptive activities. Towards the end of activity or shortly thereafter, the ratio increases to baseline values again and remains more or less constant during quiet phases. To explain the observed evolution of the BrO / SO2 ratio, a first empirical model is proposed. This model suggests that bromine, unlike chlorine and fluorine, is less soluble in the magmatic melt than sulphur. By using the DOAS method to determine SO2, we actually

  15. Bromine doping of CdTe and CdMnTe epitaxial layers grown by molecular beam epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Waag, A. (Physikalisches Inst. der Univ. Wuerzburg (Germany)); Scholl, S. (Physikalisches Inst. der Univ. Wuerzburg (Germany)); Schierstedt, K. von (Physikalisches Inst. der Univ. Wuerzburg (Germany)); Hommel, D. (Physikalisches Inst. der Univ. Wuerzburg (Germany)); Landwehr, G. (Physikalisches Inst. der Univ. Wuerzburg (Germany)); Bilger, G. (Zentrum fuer Sonnenenergie und Wasserstoff-Forschung, Stuttgart (Germany))

    1993-03-01

    We report on the n-type doping of CdTe and CdMnTe with bormine as a novel dopant material. /the thin films were grown by molecular beam epitaxy. ZnBr[sub 2] was used as a source material for the n-type doping. Free carrier concentrations at room temperature of up to 2.8x10[sup 18] cm[sup -3] could be readily obtained for both CdTe as well as CdMnTe thin films with Mn concentrations below 10%. This is to our knowledge the highest value ever obtained for the dilute magnetic semiconductor CdMnTe. For ZnBr[sub 2] source temperatures up to 60 C - corresponding to a free carrier concentration of (2-3)x10[sup 18] cm[sup -3] - the free carrier concentration of the epitaxial film increases with ZnBr[sub 2] source temperature. For higher ZnBr[sub 2] source temperatures compensation becomes dominant, which is indicated by a steep decrease of the free carrier concentration with increasing ZnBr[sub 2] source temperature. In addition the carrier mobility decreases drastically for such high dopant fluxes. A model of bromine incorporation is proposed. (orig.)

  16. Prenatal and postnatal polybrominated diphenyl ether exposure and visual spatial abilities in children

    Energy Technology Data Exchange (ETDEWEB)

    Vuong, Ann M. [Division of Epidemiology, Department of Environmental Health, University of Cincinnati College of Medicine, Cincinnati, OH (United States); Braun, Joseph M. [Department of Epidemiology, Brown University School of Public Health, Providence, RI (United States); Yolton, Kimberly [Division of General and Community Pediatrics, Department of Pediatrics, Cincinnati Children' s Hospital Medical Center, Cincinnati, OH (United States); Xie, Changchun [Division of Biostatistics and Bioinformatics, Department of Environmental Health, University of Cincinnati College of Medicine, Cincinnati, OH (United States); Webster, Glenys M. [BC Children' s Hospital Research Institute, Simon Fraser University, Vancouver, British Columbia (Canada); Sjödin, Andreas [Division of Laboratory Sciences, National Center for Environmental Health, Centers for Disease Control and Prevention, Atlanta, GA (United States); Dietrich, Kim N. [Division of Epidemiology, Department of Environmental Health, University of Cincinnati College of Medicine, Cincinnati, OH (United States); Lanphear, Bruce P. [BC Children' s Hospital Research Institute, Simon Fraser University, Vancouver, British Columbia (Canada); Chen, Aimin, E-mail: aimin.chen@uc.edu [Division of Epidemiology, Department of Environmental Health, University of Cincinnati College of Medicine, Cincinnati, OH (United States)

    2017-02-15

    Polybrominated diphenyl ethers (PBDEs) are associated with impaired visual spatial abilities in toxicological studies, but no epidemiologic study has investigated PBDEs and visual spatial abilities in children. The Health Outcomes and Measures of the Environment Study, a prospective birth cohort (2003–2006, Cincinnati, OH), was used to examine prenatal and childhood PBDEs and visual spatial abilities in 199 children. PBDEs were measured at 16±3 weeks gestation and at 1, 2, 3, 5, and 8 years using gas chromatography/isotope dilution high-resolution mass spectrometry. We used the Virtual Morris Water Maze to measure visual spatial abilities at 8 years. In covariate-adjusted models, 10-fold increases in BDE-47, −99, and −100 at 5 years were associated with shorter completion times by 5.2 s (95% Confidence Interval [CI] −9.3, −1.1), 4.5 s (95% CI −8.1, −0.9), and 4.7 s (95% CI −9.0, −0.3), respectively. However, children with higher BDE-153 at 3 years had longer completion times (β=5.4 s, 95% CI −0.3, 11.1). Prenatal PBDEs were associated with improved visual spatial memory retention, with children spending a higher percentage of their search path in the correct quadrant. Child sex modified some associations between PBDEs and visual spatial learning. Longer path lengths were observed among males with increased BDE-47 at 2 and 3 years, while females had shorter paths. In conclusion, prenatal and postnatal BDE-28, −47, −99, and −100 at 5 and 8 years were associated with improved visual spatial abilities, whereas a pattern of impairments in visual spatial learning was noted with early childhood BDE-153 concentrations. - Highlights: • The VMWM test was used to assess visual spatial abilities in children at 8 years. • BDE-153 at 3 years was adversely associated with visual spatial learning. • BDE-47, −99, and −100 at 5 years was associated with better visual spatial learning. • Prenatal PBDEs were associated with improved visual

  17. Prenatal and postnatal polybrominated diphenyl ether exposure and visual spatial abilities in children

    International Nuclear Information System (INIS)

    Vuong, Ann M.; Braun, Joseph M.; Yolton, Kimberly; Xie, Changchun; Webster, Glenys M.; Sjödin, Andreas; Dietrich, Kim N.; Lanphear, Bruce P.; Chen, Aimin

    2017-01-01

    Polybrominated diphenyl ethers (PBDEs) are associated with impaired visual spatial abilities in toxicological studies, but no epidemiologic study has investigated PBDEs and visual spatial abilities in children. The Health Outcomes and Measures of the Environment Study, a prospective birth cohort (2003–2006, Cincinnati, OH), was used to examine prenatal and childhood PBDEs and visual spatial abilities in 199 children. PBDEs were measured at 16±3 weeks gestation and at 1, 2, 3, 5, and 8 years using gas chromatography/isotope dilution high-resolution mass spectrometry. We used the Virtual Morris Water Maze to measure visual spatial abilities at 8 years. In covariate-adjusted models, 10-fold increases in BDE-47, −99, and −100 at 5 years were associated with shorter completion times by 5.2 s (95% Confidence Interval [CI] −9.3, −1.1), 4.5 s (95% CI −8.1, −0.9), and 4.7 s (95% CI −9.0, −0.3), respectively. However, children with higher BDE-153 at 3 years had longer completion times (β=5.4 s, 95% CI −0.3, 11.1). Prenatal PBDEs were associated with improved visual spatial memory retention, with children spending a higher percentage of their search path in the correct quadrant. Child sex modified some associations between PBDEs and visual spatial learning. Longer path lengths were observed among males with increased BDE-47 at 2 and 3 years, while females had shorter paths. In conclusion, prenatal and postnatal BDE-28, −47, −99, and −100 at 5 and 8 years were associated with improved visual spatial abilities, whereas a pattern of impairments in visual spatial learning was noted with early childhood BDE-153 concentrations. - Highlights: • The VMWM test was used to assess visual spatial abilities in children at 8 years. • BDE-153 at 3 years was adversely associated with visual spatial learning. • BDE-47, −99, and −100 at 5 years was associated with better visual spatial learning. • Prenatal PBDEs were associated with improved visual

  18. Antifungal activities of diphenyl diselenide and ebselen against echinocandin-susceptible and -resistant strains of Candida parapsilosis.

    Science.gov (United States)

    Chassot, Francieli; Pozzebon Venturini, Tarcieli; Baldissera Piasentin, Fernanda; Morais Santurio, Janio; Estivalet Svidzinski, Terezinha Inez; Hartz Alves, Sydney

    2016-10-01

    We evaluated the in vitro antifungal activity of diphenyl diselenide and ebselen against echinocandin-susceptible and -resistant strains of Candida parapsilosis using the broth microdilution method. Diphenyl diselenide (MIC range =1-8 µg/mL) and ebselen (MIC range =0.25-4 µg/mL) showed in vitro activity against echinocandin-susceptible isolates. However, ebselen also showed the highest antifungal activity against echinocandin-resistant strains (MIC range =0.06-4 µg/mL). This study demonstrated that the antifungal potential of diphenyl diselenide and ebselen deserves further investigation using in vivo experimental protocols.

  19. Gas to liquid to solid transition in halogen hot atom chemistry. II. Systematics of bromine reactions activated by radiative neutron capture and isomeric transition with halomethanes

    International Nuclear Information System (INIS)

    Berg, M.E.; Grauer, W.M.; Helton, R.W.; Rack, E.P.

    1975-01-01

    Bromine reactions activated by 79 Br(n,γ) 80 Br, 81 Br(n,γ)/sup 82m/Br + 82 Br, and /sup 82m/Br(I.T.) 82 Br nuclear transformations were studied in halomethanes as functions of mole fraction of Br 2 , phase, density, and intermolecular distance. Gas phase systematics coupled with the density and mole fraction of Br 2 studies demonstrate the existence of systematic trends in the condensed phases as evidenced by the Richardson--Wolfgang effect. A definitive difference due to activation that is independent of system and suggests the importance of caging at higher densities is shown by the variation of total and individual organic product yields with density. The study of total organic product yield vs. intermolecular distance provides both a means of separating cage and molecular reactions and suggests the importance of molecular properties in the caging event. (U.S.)

  20. Solvent effects on the kinetics of the chlorine isotopic exchange reaction between chloride ion and O,O-diphenyl phosphorochloridate or O,O-diphenyl phosphorchloridothioate

    International Nuclear Information System (INIS)

    Mikolajczyk, M.; Slebocka-Tilk, H.; Reimschussel, W.

    1982-01-01

    The effect of solvent on the kinetics of the chlorine isotopic exchange reaction between 36 Cl- ions and O,O-diphenyl phosphorochloridate or O,O-diphenyl phosphorochloridothioate has been investigated in nitromethane, acetonitrile, propylene carbonate, benzonitrile, nitrobenzene, and hexamethyl-phosphoric triamide. The rate constants decrease with increasing electrophilicity of the solvent. A good correlation between the logarithm of the rate constants and acceptor number (AN) of the solvent was obtained with identical slopes for reactions with phosphoryl and thiophosporyl compounds. The slopes for the dependence of ΔH or TΔS vs. AN for chlorine isotopic exchange in (PHO) 2 pace are opposite those for the exchange reaction in (PHO) 2 PSCl, so a constant ratio of k/sub p=O//k/sub p=s/ is observed, resulting from compensation of ΔH by ΔS. The effect of solvent on the initial state (from solubility measurements) and the transition state of the reaction between (PhO) 2 PSCl and the Cl- ion was evaluated. Changes of solvation of (PHO) 2 PSCE have practically no effect on the kinetics of the reactions. Changes of solvation of the chloride ion and of the transition state primarily influence the rate constants and activation parameters of the investigated isotopic-exchange reaction

  1. Polybrominated diphenyl ethers and polychlorinated biphenyls in human adipose tissue from New York.

    Science.gov (United States)

    Johnson-Restrepo, Boris; Kannan, Kurunthachalam; Rapaport, David P; Rodan, Bruce D

    2005-07-15

    Human adipose tissue samples (n=52) collected in New York City during 2003-2004 were analyzed for the presence of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs). Concentrations of PBDEs in adipose tissues ranged from 17 to 9630 ng/g, lipid wt (median: 77; mean: 399 ng/g, lipid wt; sum all di- through hexaBDE congeners). Average PBDE concentrations in human adipose tissues from New York City were 10- to 100-times greater than those reported for European countries. A concentration of 9630 ng/g, lipid wt, found in a sample of adipose tissue, is one of the highest concentrations reported to date. PBDE 47 (2,2',4,4'-tetraBDE) was the major congener detected in human tissues, followed by PBDE congeners #99 (2,2',4,4',5-penta BDE), 100 (2,2',4,4',6-pentaBDE), and 153 (2,2',4,4',5,5'-hexaBDE). A few individuals contained PBDE 153 as the predominant congener in total PBDE concentrations, suggesting alternative exposure sources, possibly occupational. Principal component analysis of PBDE congener composition in human adipose tissues revealed the presence of five clusters, each characterized by varying composition. No significant difference was found in the concentrations of PBDEs between gender. Concentrations of PBDEs were, on average, similar to those for PCBs in human adipose tissues, and substantially higher when PBDE outliers were retained. PBDE and PCB concentrations were not correlated. PBDE concentrations did not increase with increasing age of the subjects, whereas concentrations of PCBs increased with increasing age in males but not in females in this study. These results suggest differences between PBDEs and PCBs in their sources or time course of exposure and disposition. The presence of comparable or greater concentrations of PBDEs, relative to PCBs, highlights the importance of recentvoluntary and regulatory effortsto cease production of commercial penta- and octa-BDE in North America, although these efforts do not address

  2. Levels of dechloranes and polybrominated diphenyl ethers (PBDEs) in human serum from France.

    Science.gov (United States)

    Brasseur, Catherine; Pirard, Catherine; Scholl, Georges; De Pauw, Edwin; Viel, Jean-François; Shen, Li; Reiner, Eric J; Focant, Jean-François

    2014-04-01

    Human exposure to dechloranes has been evaluated in Western Europe (France) with the analysis of Dechlorane Plus (DP), Dechloranes (Dec) 602, 603 and 604, Chlordene Plus (CP) and Mirex in 48 serum samples collected between 2003 and 2005. While no production source has been identified in Europe until now, detection frequencies for all investigated dechloranes were high, except for Dec 604 which was below detection limit for all samples. The mean DP concentration was 1.40±1.40ng/g lipid weight (lw), lower than levels reported in serum from Chinese population, but higher than levels reported in Canadian human milk. To the best of our knowledge, this is the first time that ∑5dechlorane levels are reported for human serum. A specific pattern of contamination was found (Dec 603>DP>Mirex>Dec 602>CP) compared to other biota samples that have been analyzed from Europe, with Dec 603 as the most abundant dechlorane (mean level: 2.61±2.63ng/g lw). Dec 603 and CP levels were correlated with age and with levels of some bioaccumulative organochlorine pesticides (OCPs). These results indicate that bioaccumulation properties should be further investigated and taken in consideration when assessing human exposure to dechloranes. For comparison purposes, polybrominated diphenyl ether (PBDE) levels were also measured for BDE-47, -99, -100, -153 and -154 in the serum samples. As expected, BDE-47 and BDE-153 were the major congeners with mean levels of 2.06±1.80ng/g lw and 1.39±0.97ng/g lw, respectively. The mean ∑5PBDE levels (4.32±2.99ng/g lw) were in the range typical of Western Europe levels, but lower than the mean ∑5dechlorane levels (6.24±4.16ng/g lw). These results indicate that the attention to dechloranes should be continued if research indicates toxicological concerns. Copyright © 2013 Elsevier Ltd. All rights reserved.

  3. High-performance liquid chromatographic method to evaluate the hydrogen atom transfer during reaction between 1,1-diphenyl-2-picryl-hydrazyl radical and antioxidants

    Energy Technology Data Exchange (ETDEWEB)

    Boudier, Ariane; Tournebize, Juliana [CITHEFOR - EA 3452, Faculte de Pharmacie, Nancy-Universite, 5 Rue Albert Lebrun, BP 80403, 54001 Nancy Cedex (France); Bartosz, Grzegorz [Department of Molecular Biophysics, University of Lodz, Lodz (Poland); El Hani, Safae; Bengueddour, Rachid [Laboratoire de Nutrition et Sante, Biology Department, Faculty of Sciences, Ibn Tofail University, Kenitra (Morocco); Sapin-Minet, Anne [CITHEFOR - EA 3452, Faculte de Pharmacie, Nancy-Universite, 5 Rue Albert Lebrun, BP 80403, 54001 Nancy Cedex (France); Leroy, Pierre, E-mail: pierre.leroy@pharma.uhp-nancy.fr [CITHEFOR - EA 3452, Faculte de Pharmacie, Nancy-Universite, 5 Rue Albert Lebrun, BP 80403, 54001 Nancy Cedex (France)

    2012-01-20

    Highlights: Black-Right-Pointing-Pointer Both 1,1-diphenyl-2-picrylhydrazyl radical and its product measurement by HPLC. Black-Right-Pointing-Pointer Lowest limit of detection by monitoring 1,1-diphenyl-2-picryl-hydrazine. Black-Right-Pointing-Pointer Adsorption problem of the radical on HPLC parts have been pointed out. - Abstract: 1,1-Diphenyl-2-picrylhydrazyl (DPPH{center_dot}) is a stable nitrogen centred radical widely used to evaluate direct radical scavenging properties of various synthetic or natural antioxidants (AOs). The bleaching rate of DPPH{center_dot} absorbance at 515 nm is usually monitored for this purpose. In order to avoid the interference of complex coloured natural products used as antioxidant supplements or cosmetics, HPLC systems have been reported as alternative techniques to spectrophotometry. They also rely upon measurement of DPPH{center_dot} quenching rate and none of them permits to identify and measure 1,1-diphenyl-2-picryl-hydrazine (DPPH-H), the reduced product of DPPH{center_dot} resulting from hydrogen atom transfer (HAT), which is the main mechanism of the reaction between DPPH{center_dot} and AOs. We presently report an HPLC method devoted to the simultaneous measurement of DPPH{center_dot} and DPPH-H. Both were fully separated on a C18 column eluted with acetonitrile-10 mM ammonium citrate buffer pH 6.8 (70:30, v/v) and detected at 330 nm. Adsorption process of DPPH{center_dot} onto materials of the HPLC system was pointed out. Consequently, the linearity range observed for DPPH{center_dot} was restricted, thus a much lower limit of detection was obtained for DPPH-H than for DPPH{center_dot} using standards (0.02 and 14 {mu}M, respectively). The method was applied to three commonly used AOs, i.e. Trolox{sup Registered-Sign }, ascorbic acid and GSH, and compared with spectrophotometry. Further application to complex matrices (cell culture media, vegetal extracts) and nanomaterials demonstrated (i) its usefulness because of

  4. Bromine-80m-labeled estrogens: Auger-electron emitting, estrogen receptor-directed ligands with potential for therapy of estrogen receptor positive cancers

    International Nuclear Information System (INIS)

    DeSombre, E.R.; Mease, R.C.; Hughes, A.; Harper, P.V.; DeJesus, O.T.; Friedman, A.M.

    1988-01-01

    A triphenylbromoethylene, 1,1-bis(p-hydroxyphenyl)-2-bromo-2-phenylethylene, Br-BHPE, and a bromosteroidal estrogen, 17α- bromovinylestradiol, BrVE 2 , were labeled with the Auger electron emitting nuclide bromine-80m, prepared by the [p,n] reaction with 80 Se. To assess their potential as estrogen receptor (ER) directed therapeutic substrates the bromine-80m labeled estrogens were injected into immature female rats and the tissue distribution studied at 0.5 and 2 hours. Both radiobromoestrogens showed substantial diethylstilbesterol (DES)-inhibitable localization in the ER rich tissues, uterus, pituitary, ovary and vagina at both time points. While the percent dose per gram tissue was higher for the Br-BHPE, the BrVE 2 showed higher tissue to blood ratios, especially at 2 hr, reflecting the lower blood concentrations of radiobromine following administration of the steroidal bromoestrogen. Comparing intraperitoneal, intravenous and subcutaneous routes of administration for the radiobromine labeled Br-BHPE, the intraperitoneal route was particularly advantageous to provide maximum, DES-inhibitable concentrations in the peritoneal, ER-rich target organs, the uterus, ovary and vagina. While uterine concentrations after BrBHPE were from 10--48% dose/g and after BrVE 2 were 15--25% dose/g, similar treatment with /sup 80m/Br as sodium bromide showed uniform low concentrations in all tissues at about the levels seen in blood. The effective specific activity of [/sup 80m/Br]BrBHPE, assayed by specific binding to ER in rat uterine cytosol, was 8700 Ci/mmole. 23 refs., 9 figs., 2 tabs

  5. Polymerization of 5-alkyl δ-lactones catalyzed by diphenyl phosphate and their sequential organocatalytic polymerization with monosubstituted epoxides

    KAUST Repository

    Zhao, Junpeng

    2015-02-04

    Organocatalytic ring-opening polymerization (ROP) reactions of three renewable 5-alkyl δ-lactones, namely δ-hexalactone (HL), δ-nonalactone (NL) and δ-decalactone (DL), using diphenyl phosphate (DPP) were investigated. Room temperature, together with a relatively high monomer concentration (≥3 M), was demonstrated to be suitable for achieving a living ROP behavior, a high conversion of the lactone, a controlled molecular weight and a low dispersity of the polyester. HL, containing a 5-methyl substituent, showed a much higher reactivity (polymerization rate) and a slightly higher equilibrium conversion than the compounds with longer alkyl substituents (NL and DL). The effectiveness of DPP-catalyzed ROP of 5-alkyl δ-lactones facilitated the one-pot performance following the t-BuP4-promoted ROP of monosubstituted epoxides. It has been shown in an earlier study that substituted polyethers acted as "slow initiators" for non-substituted lactones. However, efficient initiations were observed in the present study as substituted lactones were polymerized from the substituted polyethers. Therefore, this reinforces the previously developed "catalyst switch" strategy, making it a more versatile tool for the synthesis of well-defined polyether-polyester block copolymers from a large variety of epoxide and lactone monomers. © The Royal Society of Chemistry 2015.

  6. Polybrominated diphenyl ethers in soils, sediments, and human hair in a plastic waste recycling area: a neglected heavily polluted area.

    Science.gov (United States)

    Tang, Zhenwu; Huang, Qifei; Cheng, Jiali; Yang, Yufei; Yang, Jun; Guo, Wei; Nie, Zhiqiang; Zeng, Ning; Jin, Lu

    2014-01-01

    The release of pollutants during the recycling of contaminated plastics is a problem which has drawn worldwide attention; however, little information on the transfer of polybrominated diphenyl ethers (PBDEs) in these processes is available. We conducted a survey of PBDEs in soils, sediments, and human hair in a typical plastic waste recycling area in northern China. The total concentrations (ng/g) of 21 PBDEs were 1.25-5504 (average 600), 18.2-9889 (average 1619), and 1.50-861 (average 112) in soils, sediments, and hair, respectively. The PBDE concentrations were comparable to concentrations observed in e-waste recycling areas; however, the concentrations in soils and sediments were 1-3 orders of magnitude higher than in other areas, and the concentrations in hair were much higher than in other areas. This indicates that this area is highly polluted with PBDEs. BDE-209 was the dominant congener (representing 91.23%, 92.3%, and 91.5% of the total PBDEs observed in soils, sediments, and hair, respectively), indicating that the commercial deca-BDE product was dominant. The commercial penta- and octa-BDE products made small contributions to the total PBDE concentrations, unlike what has been found in some e-waste recycling areas. Our results show that crude plastic waste processing is a major contributor of PBDEs to the environment and humans, which should be of great concern.

  7. Transgenic rice plants expressing a Bacillus subtilis protoporphyrinogen oxidase gene are resistant to diphenyl ether herbicide oxyfluorfen.

    Science.gov (United States)

    Lee, H J; Lee, S B; Chung, J S; Han, S U; Han, O; Guh, J O; Jeon, J S; An, G; Back, K

    2000-06-01

    Protoporphyrinogen oxidase (Protox), the penultimate step enzyme of the branch point for the biosynthetic pathway of Chl and hemes, is the target site of action of diphenyl ether (DPE) herbicides. However, Bacillus subtilis Protox is known to be resistant to the herbicides. In order to develop the herbicide-resistant plants, the transgenic rice plants were generated via expression of B. subtilis Protox gene under ubiquitin promoter targeted to the cytoplasm or to the plastid using Agrobacterium-mediated gene transformation. The integration and expression of the transgene were investigated at T0 generation by DNA and RNA blots. Most transgenic rice plants revealed one copy transgene insertion into the rice genome, but some with 3 copies. The expression levels of B. subtilis Protox mRNA appeared to correlate with the copy number. Furthermore, the plastidal transgenic lines exhibited much higher expression of the Protox mRNA than the cytoplasmic transgenic lines. The transgenic plants expressing the B. subtilis Protox gene at T0 generation were found to be resistant to oxyfluorfen when judged by cellular damage with respect to cellular leakage, Chl loss, and lipid peroxidation. The transgenic rice plants targeted to the plastid exhibited higher resistance to the herbicide than the transgenic plants targeted to the cytoplasm. In addition, possible resistance mechanisms in the transgenic plants to DPE herbicides are discussed.

  8. Polybrominated Diphenyl Ethers and Perfluoroalkyl Substances in Serum of Pregnant Women

    DEFF Research Database (Denmark)

    Vorkamp, Katrin; Nielsen, Flemming; Kyhl, Henriette Boye

    2014-01-01

    Polybrominated diphenyl ethers (PBDEs), a group of flame retardants, and perfluoroalkyl substances (PFASs) were analysed in serum samples of pregnant women from Denmark to provide information about their exposure and to study indications of common exposure pathways. The main BDE congener was the ...... of exposure and/or pharmacokinetic and metabolisation processes. PBDE and PFAS concentrations were in the range associated with adverse effects in some epidemiological studies....

  9. Photochemical Degradation of Polybrominated Diphenyl Ethers in Micro Photo-Reactor

    Czech Academy of Sciences Publication Activity Database

    Vajglová, Zuzana; Veselý, M.; Křišťál, Jiří; Vychodilová, Hana; Tříska, Jan; Jiřičný, Vladimír

    2012-01-01

    Roč. 42, SI (2012), s. 1378-1382 E-ISSN 1877-7058. [International Congress of Chemical and Process Engineering CHISA 2012 and 15th Conference PRES 2012 /20./. Prague, 25.08.2012-29.08.2012] R&D Projects: GA ČR GA104/09/0880 Institutional support: RVO:67985858 ; RVO:67179843 Keywords : polybrominated diphenyl ethers * micro photo reactor * debromination Subject RIV: CI - Industrial Chemistry, Chemical Engineering

  10. Absorption and translocation of polybrominated diphenyl ethers (PBDEs) by plants from contaminated sewage sludge

    Czech Academy of Sciences Publication Activity Database

    Vrkoslavová, J.; Demnerová, K.; Macková, M.; Zemanová, T.; Macek, Tomáš; Hajšlová, J.; Pulkrabová, J.; Hrádková, P.; Stiborová, H.

    2010-01-01

    Roč. 81, č. 3 (2010), s. 381-386 ISSN 0045-6535 R&D Projects: GA MŠk 2B06151 Grant - others:GA ČR(CZ) GP104/08/P188 Institutional research plan: CEZ:AV0Z40550506 Keywords : polybrominated diphenyl ethers * contaminated sewage sludge * plant uptake * bioconcentration factors * Nicotiana tabacum Subject RIV: EI - Biotechnology ; Bionics Impact factor: 3.155, year: 2010

  11. Assessment of PCDD/F and PBDD/F Emissions from Coal-fired Power Plants during Injection of Brominated Activated Carbon for Mercury Control

    Science.gov (United States)

    The effect of the injection of brominated powdered activated carbon (Br-PAC) on the emission of brominated and chlorinated dioxins and furans in coal combustion flue gas has been evaluated. The tests were performed at two U.S. Department of Energy (DOE) demonstration sites where ...

  12. Bromine cycle in subduction zones through in situ Br monitoring in diamond anvil cells

    Science.gov (United States)

    Bureau, Hélène; Foy, Eddy; Raepsaet, Caroline; Somogyi, Andrea; Munsch, Pascal; Simon, Guilhem; Kubsky, Stefan

    2010-07-01

    The geochemical partitioning of bromine between hydrous haplogranitic melts, initially enriched with respect to Br and aqueous fluids, has been continuously monitored in situ during decompression. Experiments were carried out in diamond anvil cells from 890 °C to room temperature and from 1.7 GPa to room pressure, typically from high P, T conditions corresponding to total miscibility (presence of a supercritical fluid). Br contents were measured in aqueous fluids, hydrous melts and supercritical fluids. Partition coefficients of bromine were characterized at pressure and temperature between fluids, hydrous melts and/or glasses, as appropriate: DBrfluid/melt = (Br) fluid/(Br) melt, ranges from 2.18 to 9.2 ± 0.5 for conditions within the ranges 0.66-1.7 GPa, 590-890 °C; and DBrfluid/glass = (Br) fluid/(Br) glass ranges from 60 to 375 at room conditions. The results suggest that because high pressure melts and fluids are capable of accepting high concentrations of bromine, this element may be efficiently removed from the slab to the mantle source of arc magmas. We show that Br may be highly concentrated in subduction zone magmas and strongly enriched in subduction-related volcanic gases, because its mobility is strongly correlated with that of water during magma degassing. Furthermore, our experimental results suggest that a non negligible part of Br present in the subducted slab may remain in the down-going slab, being transported toward the transition zone. This indicates that the Br cycle in subduction zones is in fact divided in two related but independent parts: (1) a shallower one where recycled Br may leave the slab with a water and silica-bearing "fluid" leading to enriched arc magmas that return Br to the atmosphere. (2) A deeper cycle where Br may be recycled back to the mantle maybe to the transition zone, where it may be present in high pressure water-rich metasomatic fluids.

  13. Determination of the total amount of organically bound chlorine, bromine and iodine in environmental samples by instrumental neutron activation analysis

    Energy Technology Data Exchange (ETDEWEB)

    Gether, J; Lunde, G [Central Institute for Industrial Research, Oslo (Norway); Steinnes, E [Institutt for Atomenergi, Kjeller (Norway)

    1979-07-01

    The determination of chlorine, bromine and iodine present as non-polar, hydrophobic hydrocarbons in environmental samples is reported. The organohalogen compounds are seprated from water into an organic phase by on-site liquid-liquid extraction, and form biological material by procedures based on lipid phase extraction and codistillation. After removal of inorganic halides by washing with water and concentration of the sample by evaporation of the solvent, the resulting extracts are analyzed for their chlorine, bromine and iodine contents by instrumental neutron activation analysus. Strict attention is paid to the possibility of contamination in every step of the procedure. Background values in routine analysis are approximately 100-200 ng of chlorine, <5 ng of bromine and <3 ng of iodine.

  14. Reaction modelling of Iron Oxide Bromination in the UT-3 thermochemical cycle for Hydrogen production from water

    International Nuclear Information System (INIS)

    Amir-Rusli

    1996-01-01

    Analysis modelling of the iron oxide bromination had been carried out using experiment data from the iron oxide bromination in the UT-3 thermochemical cycle. Iron oxide in the form of pellets were made of the calcination of the mixture of iron oxide, silica, graphite and cellulose at 1473 K. Thermobalance reactor was used to study the kinetic reactions of the iron oxide bromination at a temperature of 473 K for 2 - 6 hours. The data collected from the experiments were used as input for the common models. However, none of these models could not explain the result of the experiments. A new model, a combination of two kinetic reactions : exposed particle and coated particle was created and worked successfully

  15. Magnetically enhanced triode etching of large area silicon membranes in a molecular bromine plasma

    International Nuclear Information System (INIS)

    Wolfe, J.C.; Sen, S.; Pendharkar, S.V.; Mauger, P.; Shimkunas, A.R.

    1992-01-01

    The optimization of a process for etching 125 mm silicon membranes formed on 150 mm wafers and bonded to Pyrex rings is discussed. A magnetically enhanced triode etching system was designed to provide an intense, remote plasma surrounding the membrane while, at the same time, suppressing the discharge over the membrane itself. For the optimized molecular bromine process, the silicon etch rate is 40 nm/min and the selectivity relative to SiO 2 is 160:1. 14 refs., 6 figs

  16. Bromine-quenched high temperature G-M tube with passivated cathode

    International Nuclear Information System (INIS)

    Mitrofanov, N.

    1975-01-01

    A bromine doped self-quenching Geiger-Mueller tube having an operational life expectancy in excess of 1,200 hours at a temperature of 315 0 C is described. The tube comprises a passivated metal coated cathode which is conditioned or aged for operation at room temperature, thus obviating the necessity of thermally cycling the tube at progressively elevated temperatures. Useful metal coatings for the cathode include chromium, platinum, and nickel-copper alloys deposited in a layer less than about 1 mil thick. A method for passivating the metal coated cathode and subsequently conditioning the tube and its contents is disclosed. (auth)

  17. Synthesis of the omega-brominated alpha-trifluoroacetylcycloalkanones and their isoxazole derivatives

    Directory of Open Access Journals (Sweden)

    Flores Alex F. C.

    2006-01-01

    Full Text Available The reactions of a serie of the 2-trifluoroacetyl-1-methoxy-1-cycloalkenes (1a-1e and 2-trifluoroacetylcycloalkanones (2a-2e with molecular bromine to obtain omega-bromo-alpha-trifluoroacetylcycloalkanones (3a-3e, 4a is reported. Was determined that 2-trifluoroacetyl group have established the C-omega as reactive site. The 2-trifluoroacetylcycloalkanones and omega-bromo-alpha-trifluoroacetylcycloalkanones were reacted with hydroxylamine hydrochloride leading to respective 5-trifluoromethyl-5-hydroxy-4,5-dihydro-3,4-polimethyleneisoxazole derivatives (5c-5e and 6c-6e.

  18. Reactive bromine in the low troposphere of Antarctica. Estimations at two research sites

    OpenAIRE

    Prados-Roman, Cristina; Gómez-Martín, Laura; Puentedura, Olga; Navarro-Comas, Mónica; Iglesias, Javier; Mingo, José Ramón; Pérez, Manuel; Ochoa, Héctor; Barlasina, María Elena; Carbajal, Gerardo; Yela, Margarita

    2018-01-01

    For decades, reactive halogen species (RHS) have been subject of detailed scientific research due to their influence on the oxidizing capacity of the atmosphere and on the climate. From the RHS, those containing bromine are of particular interest in the polar troposphere as a result of their link to ozone depletion events (ODEs) and to the perturbation of the cycle of e.g. the toxic mercury. Given its remoteness and related limited accessibility compared to the Arctic region, the RHS in the A...

  19. Production of krypton isotopes by (p,xn) reactions on bromine

    International Nuclear Information System (INIS)

    Chiengmai, S.N.; Hans, L.; Petter, M.

    1976-06-01

    Radioactive isotopes of the halogens are of great importance when preparing radiopharmaceuticals. 77 Br has mainly been produced by a direct reaction 75 As(α,2n) 77 Br. Recently an indirect way, producing 77 Kr which then decays to 77 Br, has been suggested. Since this provides a convenient method of separation this work develops this idea further making use of high energy protons on bromine Br(p,xn) 77 Kr→ 77 Br. The production cross-section for this reaction has been studied in the proton-energy interval of 20-80 MeV and the optimal production procedures considered. (Auth.)

  20. Introduction of iodine 131 and bromine 82 in antibiotics of tetracycline group

    International Nuclear Information System (INIS)

    Mironov, V.P.; Kudryashov, V.P.; Grushevich, L.E.; Kuz'mina, T.S.

    1983-01-01

    Chloline- and oxytetracycline reactions with iodide-131-and bromide-82-ions in methanol and acetone are studied. It is established that labelled compounds reveal tetracycline (TC) properties in pharmacokinetic experiments on laboratory animals for 20-25 hours after synthesis; the yield of purposeful preparations for radioactive isotopes is 90-95%. Kinetic dependences of iodine-131 and bromine-82-TC yield on acidity and temperature of medium are presented. TC radiation resistance in solutions and in solid state at different temperatures in the range of absorbed doses of 1-10 Mrad is investigated. The possibility of TC radiation sterilization is shown

  1. Theoretical performance of hydrogen-bromine rechargeable SPE fuel cell. [Solid Polymer Electrolyte

    Science.gov (United States)

    Savinell, R. F.; Fritts, S. D.

    1988-01-01

    A mathematical model was formulated to describe the performance of a hydrogen-bromine fuel cell. Porous electrode theory was applied to the carbon felt flow-by electrode and was coupled to theory describing the solid polymer electrolyte (SPE) system. Parametric studies using the numerical solution to this model were performed to determine the effect of kinetic, mass transfer, and design parameters on the performance of the fuel cell. The results indicate that the cell performance is most sensitive to the transport properties of the SPE membrane. The model was also shown to be a useful tool for scale-up studies.

  2. Antifungal activities of diphenyl diselenide and ebselen alone and in combination with antifungal agents against Fusarium spp.

    Science.gov (United States)

    Venturini, Tarcieli Pozzebon; Chassot, Francieli; Loreto, Érico Silva; Keller, Jéssica Tairine; Azevedo, Maria Izabel; Zeni, Gilson; Santurio, Janio Morais; Alves, Sydney Hartz

    2016-07-01

    Herein, we describe the in vitro activity of a combination of the organoselenium compounds diphenyl diselenide and ebselen alone and in combination with amphotericin B, caspofungin, itraconazole, and voriconazole against 25 clinical isolates of Fusarium spp. For this analysis, we used the broth microdilution method based on the M38-A2 technique and checkerboard microdilution method. Diphenyl diselenide (MIC range = 4-32 μg/ml) and ebselen (MIC range = 2-8 μg/ml) showed in vitro activity against the isolates tested. The most effective combinations were (synergism rates): ebselen + amphotericin B (88%), ebselen + voriconazole (80%), diphenyl diselenide + amphotericin B (72%), and diphenyl diselenide + voriconazole (64%). Combination with caspofungin resulted in low rates of synergism: ebselen + caspofungin, 36%, and diphenyl diselenide + caspofungin, 28%; combination with itraconazole demonstrated indifferent interactions. Antagonistic effects were not observed for any of the combinations tested. Our findings suggest that the antifungal potential of diphenyl diselenide and ebselen deserves further investigation in in vivo experimental models, especially in combination with amphotericin B and voriconazole. © The Author 2016. Published by Oxford University Press on behalf of The International Society for Human and Animal Mycology. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  3. Polybrominated diphenyl ethers, polychlorinated dibenzo-dioxins, -furans, and -biphenyls in three species of Antarctic penguins.

    Science.gov (United States)

    Corsolini, Simonetta; Borghesi, Nicoletta; Schiamone, Alessandra; Focardi, Silvano

    2007-09-01

    Fish-eating seabirds are recognized to be at risk of accumulating toxic contaminants due to their high position in the trophic web and to their low ability to metabolize xenobiotic compounds. Penguins are widely distributed in Antarctica and represent an important fraction of the Antarctic biomass. They feed mainly on krill and, depending on krill availability, also on fish. It has been reported that predators may be a sink for volatile and toxic chemicals and this may pose a serious environmental problem. Polybrominated diphenyl ethers (PBDEs), polychlorinated dibenzo-dioxins (PCDDs), -furans (PCDFs), and -biphenyls (PCBs), including non-ortho congeners, hexachlorobenzene (HCB) and p,p'-DDE, were quantified in three species of Antarctic Pygoscelids in order to evaluate their accumulation patterns. The potential toxicity of twenty-two dioxin-like congeners was assessed and expressed as 2,3,7,8-tetraCDD equivalents (TEQs). Differences between males and females were investigated. Blood samples of the Adélie penguin Pygoscelis adeliae, Chinstrap penguin Pygoscelis antarctica and Gentoo penguin Pygoscelis papua were collected at Admiralty Bay, King George Is (62 degrees 10'39" S, 58 degrees 26'46" W) in February 2004. Halogenated hydrocarbons were identified and quantified using gas chromatography coupled with gas chromatography mass spectrometry analyses. Results are expressed on a wet weight basis. HCB, p,p'-DDE and sigmaPCBs were higher in Adélie penguins (6.7 +/- 6.1, 8.2 +/- 3.3 and 9.8 +/- 3.8 ng/g, respectively) than in Chinstrap and Gentoo penguins, both of which showed values in the same order of magnitude, but approximately 40% lower than Adélie penguins. Hexa-CBs ranged 35-45% of the residue. Low-chlorinated PCBs (nos. 70+76+95+ 56+60+101) accounted for 40-60% in the three species. PCB101 made up 15% of the residue in Adélie penguins. PBDEs were 291 +/- 477, 107 +/- 104 and 116 +/- 108 pg/g in Adélie, Chinstrap and Gentoo penguins, respectively; the

  4. Characterization of Some Real Mixed Plastics from WEEE: A Focus on Chlorine and Bromine Determination by Different Analytical Methods

    Directory of Open Access Journals (Sweden)

    Beatrice Beccagutti

    2016-10-01

    Full Text Available Bromine and chlorine are almost ubiquitous in waste of electrical and electronic equipment (WEEE and the knowledge of their content in the plastic fraction is an essential step for proper end of life management. The aim of this study is to compare the following analytical methods: energy dispersive X-ray fluorescence spectroscopy (ED-XRF, ion chromatography (IC, ion-selective electrodes (ISEs, and elemental analysis for the quantitative determination of chlorine and bromine in four real samples taken from different WEEE treatment plants, identifying the best analytical technique for waste management workers. Home-made plastic standard materials with known concentrations of chlorine or bromine have been used for calibration of ED-XRF and to test the techniques before the sample analysis. Results showed that IC and ISEs, based upon dissolution of the products of the sample combustion, have not always achieved a quantitative absorption of the analytes in the basic solutions and that bromine could be underestimated since several oxidation states occur after combustion. Elemental analysis designed for chlorine determination is subjected to strong interference from bromine and required frequent regeneration and recalibration of the measurement cell. The most reliable method seemed to be the non-destructive ED-XRF. Calibration with home-made standards, having a similar plastic matrix of the samples, enabled us to carry out quantitative determinations, which have been revealed to be satisfactorily accurate and precise. In all the analyzed samples a total concentration of chlorine and/or bromine between 0.6 and 4 w/w% was detected, compromising the feasibility of a mechanical recycling and suggesting the exploration of an alternative route for managing these plastic wastes.

  5. Modeling the inorganic bromine partitioning in the tropical tropopause layer over the eastern and western Pacific Ocean

    Directory of Open Access Journals (Sweden)

    M. A. Navarro

    2017-08-01

    Full Text Available The stratospheric inorganic bromine (Bry burden arising from the degradation of brominated very short-lived organic substances (VSLorg and its partitioning between reactive and reservoir species is needed for a comprehensive assessment of the ozone depletion potential of brominated trace gases. Here we present modeled inorganic bromine abundances over the Pacific tropical tropopause based on aircraft observations of VSLorg from two campaigns of the Airborne Tropical TRopopause EXperiment (ATTREX 2013, carried out over the eastern Pacific, and ATTREX 2014, carried out over the western Pacific and chemistry-climate simulations (along ATTREX flight tracks using the specific meteorology prevailing. Using the Community Atmosphere Model with Chemistry (CAM-Chem we model that BrO and Br are the daytime dominant species. Integrated across all ATTREX flights, BrO represents ∼ 43 and 48 % of daytime Bry abundance at 17 km over the western and eastern Pacific, respectively. The results also show zones where Br / BrO > 1 depending on the solar zenith angle (SZA, ozone concentration, and temperature. On the other hand, BrCl and BrONO2 were found to be the dominant nighttime species with ∼  61 and 56 % of abundance at 17 km over the western and eastern Pacific, respectively. The western-to-eastern differences in the partitioning of inorganic bromine are explained by different abundances of ozone (O3, nitrogen dioxide (NO2, total inorganic chlorine (Cly, and the efficiency of heterogeneous reactions of bromine reservoirs (mostly BrONO2 and HBr occurring on ice crystals.

  6. Levels of persistent fluorinated, chlorinated and brominated compounds in human blood collected in Sweden in 1997-2000

    Energy Technology Data Exchange (ETDEWEB)

    Lindstroem, G.; Kaerrman, A.; Bavel, B. van [MTM Research Centre, Oerebro Univ. (Sweden); Hardell, L. [Dept. of Oncology, Univ. Hospital, Oerebro (Sweden); Hedlund, B. [Environmental Monitoring Section, Swedish EPA, Stockholm (Sweden)

    2004-09-15

    Levels of persistent fluorinated, chlorinated and brominated compounds in blood collected from the Swedish population have been determined in connection with several exposure and monitoring studies at the MTM Research Centre. A data base with 631 individual congener specific measurements on halogenated POPs such as dioxins, PCBs, HCB, DDE, chlordanes, PBDEs and PFAs including information on residency, age, BMI, diet, occupation, number of children, smoking habits, immunological status etc. has been compiled from samples collected between 1994 and 2004. A brief overview focusing on levels of some persistent chlorinated, brominated and fluorinated, compounds in blood collected in a background population group (n=83) in 1997-2000 is given here.

  7. Treatment of sewage from iodo-bromine industrial plants from the second group cations using carboxyl cationnites

    International Nuclear Information System (INIS)

    Kononova, G.N.; Dolbysheva, A.G.; Ksenzenko, V.I.; Ryazantseva, Zh.I.

    1977-01-01

    Effectiveness has been shown of purifying sewage from iodo-bromine plants from the second Group cations on a carboxyl cationite KB-4P. For strongly mineralized waters as industrial waters from iodo-bromine plants, the selectivity decreases in the series: Ca 2+ > Sr 2+ > Mg 2+ . It has been shown that the determining stage is an outside diffusion. SH nitric acid has been used for regeneration of cationite. The second Group cations are washed off with nitric acid simultaneously and at a high rate. Strontium can be separated from the eluate obtained by the halurgical method

  8. Synchrotron X-ray fluorescence studies of a bromine-labelled cyclic RGD peptide interacting with individual tumor cells

    International Nuclear Information System (INIS)

    Sheridan, Erin J.; Austin, Christopher J. D.; Aitken, Jade B.; Vogt, Stefan; Jolliffe, Katrina A.; Harris, Hugh H.; Rendina, Louis M.

    2013-01-01

    The first example of synchrotron X-ray fluorescence imaging of cultured mammalian cells in cyclic peptide research is reported. The study reports the first quantitative analysis of the incorporation of a bromine-labelled cyclic RGD peptide and its effects on the biodistribution of endogenous elements (for example, K and Cl) within individual tumor cells. The first example of synchrotron X-ray fluorescence imaging of cultured mammalian cells in cyclic peptide research is reported. The study reports the first quantitative analysis of the incorporation of a bromine-labelled cyclic RGD peptide and its effects on the biodistribution of endogenous elements (for example, K and Cl) within individual tumor cells

  9. Development of Zinc/Bromine Batteries for Load-Leveling Applications: Phase 2 Final Report

    Energy Technology Data Exchange (ETDEWEB)

    CLARK,NANCY H.; EIDLER,PHILLIP

    1999-10-01

    This report documents Phase 2 of a project to design, develop, and test a zinc/bromine battery technology for use in utility energy storage applications. The project was co-funded by the U.S. Department of Energy Office of Power Technologies through Sandia National Laboratories. The viability of the zinc/bromine technology was demonstrated in Phase 1. In Phase 2, the technology developed during Phase 1 was scaled up to a size appropriate for the application. Batteries were increased in size from 8-cell, 1170-cm{sup 2} cell stacks (Phase 1) to 8- and then 60-cell, 2500-cm{sup 2} cell stacks in this phase. The 2500-cm{sup 2} series battery stacks were developed as the building block for large utility battery systems. Core technology research on electrolyte and separator materials and on manufacturing techniques, which began in Phase 1, continued to be investigated during Phase 2. Finally, the end product of this project was a 100-kWh prototype battery system to be installed and tested at an electric utility.

  10. Electrospun Nafion®/Polyphenylsulfone Composite Membranes for Regenerative Hydrogen Bromine Fuel Cells

    Science.gov (United States)

    Park, Jun Woo; Wycisk, Ryszard; Pintauro, Peter N.; Yarlagadda, Venkata; Van Nguyen, Trung

    2016-01-01

    The regenerative H2/Br2-HBr fuel cell, utilizing an oxidant solution of Br2 in aqueous HBr, shows a number of benefits for grid-scale electricity storage. The membrane-electrode assembly, a key component of a fuel cell, contains a proton-conducting membrane, typically based on the perfluorosulfonic acid (PFSA) ionomer. Unfortunately, the high cost of PFSA membranes and their relatively high bromine crossover are serious drawbacks. Nanofiber composite membranes can overcome these limitations. In this work, composite membranes were prepared from electrospun dual-fiber mats containing Nafion® PFSA ionomer for facile proton transport and an uncharged polymer, polyphenylsulfone (PPSU), for mechanical reinforcement, and swelling control. After electrospinning, Nafion/PPSU mats were converted into composite membranes by softening the PPSU fibers, through exposure to chloroform vapor, thus filling the voids between ionomer nanofibers. It was demonstrated that the relative membrane selectivity, referenced to Nafion® 115, increased with increasing PPSU content, e.g., a selectivity of 11 at 25 vol% of Nafion fibers. H2-Br2 fuel cell power output with a 65 μm thick membrane containing 55 vol% Nafion fibers was somewhat better than that of a 150 μm Nafion® 115 reference, but its cost advantage due to a four-fold decrease in PFSA content and a lower bromine species crossover make it an attractive candidate for use in H2/Br2-HBr systems. PMID:28773268

  11. Levelized cost of energy and sensitivity analysis for the hydrogen-bromine flow battery

    Science.gov (United States)

    Singh, Nirala; McFarland, Eric W.

    2015-08-01

    The technoeconomics of the hydrogen-bromine flow battery are investigated. Using existing performance data the operating conditions were optimized to minimize the levelized cost of electricity using individual component costs for the flow battery stack and other system units. Several different configurations were evaluated including use of a bromine complexing agent to reduce membrane requirements. Sensitivity analysis of cost is used to identify the system elements most strongly influencing the economics. The stack lifetime and round-trip efficiency of the cell are identified as major factors on the levelized cost of electricity, along with capital components related to hydrogen storage, the bipolar plate, and the membrane. Assuming that an electrocatalyst and membrane with a lifetime of 2000 cycles can be identified, the lowest cost market entry system capital is 220 kWh-1 for a 4 h discharge system and for a charging energy cost of 0.04 kWh-1 the levelized cost of the electricity delivered is 0.40 kWh-1. With systems manufactured at large scales these costs are expected to be lower.

  12. Inorganic bromine in organic molecular crystals: Database survey and four case studies

    Science.gov (United States)

    Nemec, Vinko; Lisac, Katarina; Stilinović, Vladimir; Cinčić, Dominik

    2017-01-01

    We present a Cambridge Structural Database and experimental study of multicomponent molecular crystals containing bromine. The CSD study covers supramolecular behaviour of bromide and tribromide anions as well as halogen bonded dibromine molecules in crystal structures of organic salts and cocrystals, and a study of the geometries and complexities in polybromide anion systems. In addition, we present four case studies of organic structures with bromide, tribromide and polybromide anions as well as the neutral dibromine molecule. These include the first observed crystal with diprotonated phenazine, a double salt of phenazinium bromide and tribromide, a cocrystal of 4-methoxypyridine with the neutral dibromine molecule as a halogen bond donor, as well as bis(4-methoxypyridine)bromonium polybromide. Structural features of the four case studies are in the most part consistent with the statistically prevalent behaviour indicated by the CSD study for given bromine species, although they do exhibit some unorthodox structural features and in that indicate possible supramolecular causes for aberrations from the statistically most abundant (and presumably most favourable) geometries.

  13. Iodine-123 and bromine-75 production and development program at Juelich

    International Nuclear Information System (INIS)

    Stoecklin, G.

    1985-01-01

    The iodine-123 and bromine-75 production and development program at the Nuclear Research Center in Juelich as of 1982 is described, and examples of recent 123 I- and 75 Br-analogue tracers that have been developed to the level of clinical trial are given. Iodine-123 is produced via the 127 I(d,6n) 123 Xe → 123 I process and by the 124 Te(p,2n) 123 I and 122 Te(d,n) 123 I reactions. These production methods are critically reviewed. Bromine-75-labeled benzodiazenes have been prepared for in vivo mapping of benzodiazepine receptor sites. The 7-( 75 Br)-5-(2-fluorophenyl)-1-methyl-1,3-dihydro-2H-1,4-benzodiazepine-2-one (BFB) was prepared with a specific activity of > 10 4 Ci/mmole. Finally, preparation and applications of the halogenated amino acid L-3-( 123 I)-iodo-α-methyltyrosine (IMT) and the analogous 75 Br compound (BMT) are reported. Both IMT and BMT have been successfully applied for pancreas imaging and tomography, and IMT has been used for imaging both melanotic and amelanotic malignant melanoma of the eye

  14. Specific role of taurine in the 8-brominated-2'-deoxyguanosine formation.

    Science.gov (United States)

    Asahi, Takashi; Nakamura, Yoshimasa; Kato, Yoji; Osawa, Toshihiko

    2015-11-15

    At the sites of inflammation, hypohalous acids, such as hypochlorous acid and hypobromous acid (HOBr), are produced by myeloperoxidase. These hypohalous acids rapidly react with the primary amino groups to produce haloamines, which are relatively stable and can diffuse long distances and cross the plasma membrane. In this study, we examined the effects of taurine, the most abundant free amino acid in the leukocyte cytosol, on the hypohalous acid-dependent formation of 8-chloro-2'-deoxyguanosine (8-CldG) and 8-bromo-2'-deoxyguanosine (8-BrdG). The reaction of taurine with HOBr yielded taurine bromamine, which is the most stable among other bromamines of amino acids. Taurine also enhanced the bromination of only dG among the four 2'-deoxynucleosides, whereas it inhibited the 8-CldG formation. The specificity of taurine for the enhanced formation of halogenated dG is completely different from that of nicotine, an enhancer of chlorination. The amount of dibrominated taurine (taurine dibromamine) closely correlated with the formation of 8-BrdG, suggesting that taurine dibromamine might be a plausible mediator for the dG bromination in vivo. Copyright © 2015 Elsevier Inc. All rights reserved.

  15. Synthesis of α-Bromine- Terminated Polystyrene Macroinitiator and Its Initiation of MMA Polymerization by ATRP

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    In the present paper the synthesis of block copolymers via the transformation from living anionic polymerization (LAP) to atom transfer radical polymerization (ATRP) was described. Α-Bromine-terminated polystyrenes(PStBr) in the LAP step was prepared by using n-BuLi as initiator, tetrahydrofuran (THF) as the activator, α-methylstyrene (α-MeSt) as the capping group and liquid bromine (Br2) as the bromating agent. The effects of reaction conditions such as the amounts of α-MeSt, THF, and Br2 as well as molecular weight of polystyrene on the bromating efficiency (BE) and coupling extent (CE) were examined. The present results show that the yield of PStBr obtained was more than 93.8% and the coupling reaction was substantially absent. PStBr was further used as the macroinitiator in the polymerization of methyl-methacrylate(MMA) in the presence of copper(Ⅰ) halogen and 2,2-bipyridine(bpy) complexes. It was found that the molecular weight of the resulted PSt-b-PMMA increased linearly with the increase of the conversion of MMA and the polydispersity was 1.2-1.6. The structures of PStBr and P(St-b-MMA) were characterized by 1H NMR spectra.

  16. Stable bromine isotopic composition of methyl bromide released from plant matter

    Science.gov (United States)

    Horst, Axel; Holmstrand, Henry; Andersson, Per; Thornton, Brett F.; Wishkerman, Asher; Keppler, Frank; Gustafsson, Örjan

    2014-01-01

    Methyl bromide (CH3Br) emitted from plants constitutes a natural source of bromine to the atmosphere, and is a component in the currently unbalanced global CH3Br budget. In the stratosphere, CH3Br contributes to ozone loss processes. Studies of stable isotope composition may reduce uncertainties in the atmospheric CH3Br budget, but require well-constrained isotope fingerprints of the source end members. Here we report the first measurements of stable bromine isotopes (δ81Br) in CH3Br from abiotic plant emissions. Incubations of both KBr-fortified pectin, a ubiquitous cell-stabilizing macromolecule, and of a natural halophyte (Salicornia fruticosa), yielded an enrichment factor (ε) of -2.00 ± 0.23‰ (1σ, n = 8) for pectin and -1.82 ± 0.02‰ (1σ, n = 4) for Salicornia (the relative amount of the heavier 81Br was decreased in CH3Br compared to the substrate salt). For short incubations, and up to 10% consumption of the salt substrate, this isotope effect was similar for temperatures from 30 up to 300 °C. For longer incubations of up to 90 h at 180 °C the δ81Br values increased from -2‰ to 0‰ for pectin and to -1‰ for Salicornia. These δ81Br source signatures of CH3Br formation from plant matter combine with similar data for carbon isotopes to facilitate multidimensional isotope diagnostics of the CH3Br budget.

  17. Tropospheric Bromine Chemistry: Implications for Present and Pre-industrial Ozone and Mercury

    Science.gov (United States)

    Parella, J. P.; Jacob, D. J.; Liang, Q.; Zhang, Y.; Mickley, L. J.; Miller, B.; Evans, M. J.; Yang, X.; Pyle, J. A.; Theys, N.; hide

    2012-01-01

    We present a new model for the global tropospheric chemistry of inorganic bromine (Bry) coupled to oxidant-aerosol chemistry in the GEOS-Chem chemical transport model (CTM). Sources of tropospheric Bry include debromination of sea-salt aerosol, photolysis and oxidation of short-lived bromocarbons, and transport from the stratosphere. Comparison to a GOME-2 satellite climatology of tropospheric BrO columns shows that the model can reproduce the observed increase of BrO with latitude, the northern mid-latitudes maximum in winter, and the Arctic maximum in spring. This successful simulation is contingent on the HOBr + HBr reaction taking place in aqueous aerosols and ice clouds. Bromine chemistry in the model decreases tropospheric ozone mixing ratios by mercury against oxidation by Br. This suggests that historical anthropogenic mercury emissions may have mostly deposited to northern mid-latitudes, enriching the corresponding surface reservoirs. The persistent rise in background surface ozone at northern mid-latitudes during the past decades could possibly contribute to the observations of elevated mercury in subsurface waters of the North Atlantic.

  18. Electrospun Nafion®/Polyphenylsulfone Composite Membranes for Regenerative Hydrogen Bromine Fuel Cells.

    Science.gov (United States)

    Park, Jun Woo; Wycisk, Ryszard; Pintauro, Peter N; Yarlagadda, Venkata; Van Nguyen, Trung

    2016-02-29

    The regenerative H₂/Br₂-HBr fuel cell, utilizing an oxidant solution of Br₂ in aqueous HBr, shows a number of benefits for grid-scale electricity storage. The membrane-electrode assembly, a key component of a fuel cell, contains a proton-conducting membrane, typically based on the perfluorosulfonic acid (PFSA) ionomer. Unfortunately, the high cost of PFSA membranes and their relatively high bromine crossover are serious drawbacks. Nanofiber composite membranes can overcome these limitations. In this work, composite membranes were prepared from electrospun dual-fiber mats containing Nafion ® PFSA ionomer for facile proton transport and an uncharged polymer, polyphenylsulfone (PPSU), for mechanical reinforcement, and swelling control. After electrospinning, Nafion/PPSU mats were converted into composite membranes by softening the PPSU fibers, through exposure to chloroform vapor, thus filling the voids between ionomer nanofibers. It was demonstrated that the relative membrane selectivity, referenced to Nafion ® 115, increased with increasing PPSU content, e.g., a selectivity of 11 at 25 vol% of Nafion fibers. H₂-Br₂ fuel cell power output with a 65 μm thick membrane containing 55 vol% Nafion fibers was somewhat better than that of a 150 μm Nafion ® 115 reference, but its cost advantage due to a four-fold decrease in PFSA content and a lower bromine species crossover make it an attractive candidate for use in H₂/Br₂-HBr systems.

  19. Electrospun Nafion®/Polyphenylsulfone Composite Membranes for Regenerative Hydrogen Bromine Fuel Cells

    Directory of Open Access Journals (Sweden)

    Jun Woo Park

    2016-02-01

    Full Text Available The regenerative H2/Br2-HBr fuel cell, utilizing an oxidant solution of Br2 in aqueous HBr, shows a number of benefits for grid-scale electricity storage. The membrane-electrode assembly, a key component of a fuel cell, contains a proton-conducting membrane, typically based on the perfluorosulfonic acid (PFSA ionomer. Unfortunately, the high cost of PFSA membranes and their relatively high bromine crossover are serious drawbacks. Nanofiber composite membranes can overcome these limitations. In this work, composite membranes were prepared from electrospun dual-fiber mats containing Nafion® PFSA ionomer for facile proton transport and an uncharged polymer, polyphenylsulfone (PPSU, for mechanical reinforcement, and swelling control. After electrospinning, Nafion/PPSU mats were converted into composite membranes by softening the PPSU fibers, through exposure to chloroform vapor, thus filling the voids between ionomer nanofibers. It was demonstrated that the relative membrane selectivity, referenced to Nafion® 115, increased with increasing PPSU content, e.g., a selectivity of 11 at 25 vol% of Nafion fibers. H2-Br2 fuel cell power output with a 65 μm thick membrane containing 55 vol% Nafion fibers was somewhat better than that of a 150 μm Nafion® 115 reference, but its cost advantage due to a four-fold decrease in PFSA content and a lower bromine species crossover make it an attractive candidate for use in H2/Br2-HBr systems.

  20. Estimation of the source strength of polybrominated diphenyl ethers based on their diel variability in air in Zurich, Switzerland.

    Science.gov (United States)

    Moeckel, Claudia; Gasic, Bojan; MacLeod, Matthew; Scheringer, Martin; Jones, Kevin C; Hungerbühler, Konrad

    2010-06-01

    Diel (24-h) concentration variations of polybrominated diphenyl ethers (PBDEs) in air were measured in the center of Zurich, Switzerland, and on Uetliberg, a hill about 5 km from the city center. Air samples were collected simultaneously at both sites over 4 h time periods for 3 consecutive days during a stable high pressure system in August 2007. Higher PBDE concentrations in the city compared to the Uetliberg site indicate that Zurich is a likely source of PBDEs to the atmosphere. A multimedia mass balance model was used to (i) explain the diel cycling pattern of PBDE concentrations observed at both sites in terms of dominant processes and (ii) estimate emission rates of PBDEs from the city to the atmosphere. We estimate that Zurich emits 0.4, 6.2, 1.6, and 0.4 kg year(-1) of the PBDE congeners 28, 47, 99, and 100, respectively. On a per-capita basis, these estimates are within the range or somewhat above those obtained in other studies using approaches based on emission factors (EF) and PBDE production, usage, and disposal data, or concentration measurements. The present approach complements emission estimates based on the EF approach and can also be applied to source areas where EFs and PBDE material flows are poorly characterized or unknown, such as electronic waste processing plants.

  1. Synthesis, X-ray crystal structure and optical properties research of novel diphenyl sulfone-based bis-pyrazoline derivatives

    International Nuclear Information System (INIS)

    Gong Zhongliang; Zheng Liangwen; Zhao Baoxiang

    2012-01-01

    A series of novel bis-pyrazoline derivatives were synthesized by the reaction of chalcone and (sulfonylbis(3,1-phenylene))bis(hydrazine) in 20–34% yields. The structures of the compounds were determined by IR, 1 H NMR, HRMS spectra, and a representative compound 3b was confirmed based on the X-ray crystallographic analysis. Absorption and fluorescence spectra of these compounds in dichloromethane solution were investigated. The results showed that the emission maxima varied from 415 to 444 nm mainly depending on C3 substituents of pyrazoline moiety. The compounds had higher quantum yields, when C3 substituent was an electron-withdrawing p-chlorophenyl group. Moreover, absorption spectra and emission spectra exhibited a blue-shift and a red-shift with increasing the polarity of solvents, respectively. Fluorescent molecules happened to collide with each other and resulted in quench of the fluorescence when the concentration increased over to 10 −5 M. - Highlights: ► A series of novel diphenyl sulfone-based bis-pyrazoline derivatives were designed and synthesized. ► Their UV–vis absorption and fluorescence emission spectra were investigated. ► The relationship of substituents and the optical properties were discussed. ► With increasing the solvent polarity, fluorescence emission displayed a red-shift and fluorescence quantum yields decreased. ► Fluorescence was quenched when the concentration increased over to 10 −5 M.

  2. Contamination of phthalate esters, organochlorine pesticides and polybrominated diphenyl ethers in agricultural soils from the Yangtze River Delta of China.

    Science.gov (United States)

    Sun, Jianteng; Pan, Lili; Zhan, Yu; Lu, Hainan; Tsang, Daniel C W; Liu, Wenxin; Wang, Xilong; Li, Xiangdong; Zhu, Lizhong

    2016-02-15

    To reveal the pollution status associated with rapid urbanization and economic growth, extensive areas of agricultural soils (approximately 45,800 km(2)) in the Yangtze River Delta of China were investigated with respect to selected endocrine disruptor compounds (EDCs), including phthalate esters (PAEs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs). The residues of sum of 15 PAEs, sum of 15 OCPs and sum of 13 PBDEs were in the range of 167-9370 ng/g, 1.0-3520 ng/g, and usage and recent input. Agricultural plastic film was considered to be an important source of PAEs. Discharge from furniture industry was potential major source of PBDEs in this region. The selected pollutants showed quite different spatial distributions within the studied region. It is worth noting that much higher concentrations of the EDCs were found on the borders between Shanghai and the two neighboring provinces, where agriculture and industry developed rapidly in recent years. Contaminants from both agricultural and industrial activities made this area a pollution hotspot, which should arouse more stringent regulation to safeguard the environment and food security. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. An exposure study with polybrominated diphenyl ethers (PBDEs) in female European starlings (Sturnus vulgaris): Toxicokinetics and reproductive effects

    International Nuclear Information System (INIS)

    Steen, Evi van den; Eens, Marcel; Covaci, Adrian; Dirtu, Alin C.; Jaspers, Veerle L.B.; Neels, Hugo; Pinxten, Rianne

    2009-01-01

    We exposed female European starlings to a pentabromodiphenyl ether (Penta-BDE) mixture through subcutaneous implants, and examined levels and profiles of polybrominated diphenyl ethers (PBDEs) together with reproductive effects. Sum PBDE levels increased significantly in the serum of the exposed females from 218 ± 43 to 23,400 ± 2035 pg/ml. Sum PBDE concentrations in the eggs of the exposed group ranged from 130 ± 12 to 220 ± 37 ng/g wet weight (ww). The profile in serum after egg laying was very similar to that in eggs. There were no detectable levels of HO-PBDEs in both serum and eggs. Fewer females of the exposed group initiated egg laying compared to the control group, although the difference was not significant. In addition, egg weight and volume were significantly higher in the exposed group. These results suggest that, at the investigated exposure levels (150 μg sum PBDEs/bird), PBDEs may have a negative effect on reproductive performance. - Exposure to an environmentally relevant concentration of PBDEs may result in adverse reproductive effects in a terrestrial songbird species, the European starling

  4. Age and seasonal variability of polybrominated diphenyl ethers in free-ranging East Greenland polar bears (Ursus maritimus)

    International Nuclear Information System (INIS)

    Dietz, Rune; Riget, Frank F.; Sonne, Christian; Letcher, Robert J.; Backus, Sean; Born, Erik W.; Kirkegaard, Maja; Muir, Derek C.G.

    2007-01-01

    Polybrominated diphenyl ethers (PBDEs) were analysed in adipose tissue from 92 East Greenland polar bears (Ursus maritimus) sampled during 1999-2001. Mean ΣPBDE concentrations were 70 ng/g lipid weight (lw) (range: 22-192 ng/g lw) and showed no relationship with age or sex. Of the 32 analysed PBDE congeners; BDE47, BDE153, BDE99 and BDE100 dominated, and comprised 99.6% of the ΣPBDE concentration. The ΣPBDE concentration had a highly significant correlation with ΣPCB, ΣCHL, dieldrin, HCB and ΣHCH concentrations. We found a seasonal pattern of median ΣPBDE concentration with 1.2 to 1.8 times higher concentrations in March to July than the rest of the year. The seasonal variation also provides a clue to the seasonal exposure, bio-availability, toxic exposure and degradation. We suggest that future geographical PBDE data comparisons may not need corrections for sex or age, but such data sets should be corrected for seasonal variability, using the presented correctional trigonometric regression. - Mean ΣPBDE concentrations of East Greenland polar bears (Ursus maritimus) were 69.5 ng/g lw (range: 21.7-192 ng/g lw) and showed a seasonal pattern with no relationship with age and sex

  5. Temporal trend studies on tetra- and pentabrominated diphenyl ethers and hexabromocyclododecane in guillemot egg from the Baltic Sea.

    Science.gov (United States)

    Sellström, Ulla; Bignert, Anders; Kierkegaard, Amelie; Häggberg, Lisbeth; de Wit, Cynthia A; Olsson, Mats; Jansson, Bo

    2003-12-15

    Guillemot eggs from the Baltic Sea, sampled between 1969 and 2001, were analyzed for tetra- and pentabromodiphenyl ethers (2,2',4,4'-tetraBDE (BDE-47), 2,2',4,4',5-pentaBDE (BDE-99), and 2,2',4,4',6-pentaBDE (BDE-100)), and hexabromocyclododecane (HBCD). This temporal trend study indicates that the concentrations of the polybrominated diphenyl ether compounds increased from the 1970s to the 1980s, peaking around the mid- to the late-1980s. These peaks are then followed by a rapid decrease in concentrations during the rest of the study period, with the concentrations of the major BDE congener below 100 ng/g lipid weight at the end of the period. This corresponds to less than 10% of its peak values. The concentrations of HBCD show a different pattern over time. After a peak in the middle of the 1970s followed by a decrease, the concentrations increased during the latter part of the 1980s. During the recent 10-yr period no significant change has occurred, and the annual mean concentrations are more or less stable at a higher level as compared to the beginning of the study period.

  6. Toxicity and physiological effects of brominated flame retardant PBDE-47 on two life stages of grass shrimp, Palaemonetes pugio.

    Science.gov (United States)

    Key, Peter B; Chung, Katy W; Hoguet, Jennifer; Shaddrix, Brian; Fulton, Michael H

    2008-07-25

    This study examined the effects of a polybrominated diphenyl ether (PBDE) compound, PBDE-47, on adult and larval stages of the estuarine grass shrimp (Palaemonetes pugio). The 96-h LC50 test resulted in an estimate of 23.60 microg/L (95% confidence interval=14.51-38.37 microg/L) for larval shrimp. Adult shrimp had a higher 96-h LC50 of 78.07 microg/L (95% CI=65.1-93.63 microg/L). Four physiological biomarkers glutathione (GSH), lipid peroxidation (LPx), cholesterol (CHL) and acetylcholinesterase (AChE) were then assessed to study the sublethal effects of PBDE-47 exposure. GSH, LPx and AChE levels in both adults and larvae were not affected by PBDE-47 at concentrations up to 50 microg/L for 96 h. CHL levels were elevated in adults and larvae at the lowest exposure concentrations tested, but significant differences were found only in adult exposures. Effects associated with PBDE-47 aqueous exposures were observed at levels well above those reported in the environment.

  7. Serum concentrations of polybrominated diphenyl ethers (PBDEs) and a polybrominated biphenyl (PBB) in men from Greenland, Poland and Ukraine

    DEFF Research Database (Denmark)

    Lenters, Virissa; Thomsen, Cathrine; Smit, Lidwien A M

    2013-01-01

    in Inuit men from across Greenland, and in men from Warsaw, Poland and Kharkiv, Ukraine. Serum was sampled between 2002 and 2004 from men 19 to 50years of age. 299 samples were analyzed for BDE-28, 47, 99, 100, 153, 154 and 183 and the brominated biphenyl BB-153 using gas chromatography-high resolution...

  8. The detection of some halogenated phenols and nitrophenols in thin-layer chromatography by means of bromine

    NARCIS (Netherlands)

    Tadema, G.; Batelaan, P.H.

    1968-01-01

    A method is described for the detection of halogeno- and nitro-phenols in sub-microgram quantities. Theses compounds are made visible by exposure of the developed thin layer plates to bromine vapour and subsequent spraying with an aqueous solution of potassium iodide or an ethanolic solution of

  9. Bromine isotopic signature facilitates de novo sequencing of peptides in free-radical-initiated peptide sequencing (FRIPS) mass spectrometry.

    Science.gov (United States)

    Nam, Jungjoo; Kwon, Hyuksu; Jang, Inae; Jeon, Aeran; Moon, Jingyu; Lee, Sun Young; Kang, Dukjin; Han, Sang Yun; Moon, Bongjin; Oh, Han Bin

    2015-02-01

    We recently showed that free-radical-initiated peptide sequencing mass spectrometry (FRIPS MS) assisted by the remarkable thermochemical stability of (2,2,6,6-tetramethyl-piperidin-1-yl)oxyl (TEMPO) is another attractive radical-driven peptide fragmentation MS tool. Facile homolytic cleavage of the bond between the benzylic carbon and the oxygen of the TEMPO moiety in o-TEMPO-Bz-C(O)-peptide and the high reactivity of the benzylic radical species generated in •Bz-C(O)-peptide are key elements leading to extensive radical-driven peptide backbone fragmentation. In the present study, we demonstrate that the incorporation of bromine into the benzene ring, i.e. o-TEMPO-Bz(Br)-C(O)-peptide, allows unambiguous distinction of the N-terminal peptide fragments from the C-terminal fragments through the unique bromine doublet isotopic signature. Furthermore, bromine substitution does not alter the overall radical-driven peptide backbone dissociation pathways of o-TEMPO-Bz-C(O)-peptide. From a practical perspective, the presence of the bromine isotopic signature in the N-terminal peptide fragments in TEMPO-assisted FRIPS MS represents a useful and cost-effective opportunity for de novo peptide sequencing. Copyright © 2015 John Wiley & Sons, Ltd.

  10. Bromination of Aromatic Compounds by Residual Bromide in Sodium Chloride Matrix Modifier Salt During Heated Headspace GC/MS Analysis

    Science.gov (United States)

    Analytical artifacts attributed to the bromination of toluene, xylenes, and trimethylbenzenes were found during the heated headspace gas chromatography/mass spectrometry (GC/MS) analysis of aqueous samples. The aqueous samples were produced from Fenton-like chemical oxidation rea...

  11. Accumulation of organochlorines and brominated flame retardants in estuarine and marine food chains: Field measurements and model calculations

    NARCIS (Netherlands)

    Veltman, K.; Hendriks, J.; Huijbregts, M.; Leonards, P.E.G.; Heuvel-Greve, van den M.J.; Vethaak, D.

    2005-01-01

    Food chain accumulation of organochlorines and brominated flame retardants in estuarine and marine environments is compared to model estimations and fresh water field data. The food chain consists of herbivores, detritivores and primary and secondary carnivores i.e. fish, fish-eating birds and

  12. Dehydrohalogenation during pyrolysis of brominated flame retardant containing high impact polystyrene (HIPS-Br) mixed with polyvinylchloride (PVC)

    Energy Technology Data Exchange (ETDEWEB)

    Uddin, M.A.; Bhaskar, T.; Kaneko, J.; Muto, A.; Sakata, Y.; Matsui, T. [Okayama University, Okayama (Japan). Dept. of Applied Chemistry, Faculty of Engineering

    2002-09-01

    Dehydrohalogenation during pyrolysis of brominated flame retardant containing polystyrene (brominated high impact polystyrene (HIPS-Br)) mixed with polyvinylchloride (PVC) was carried out in a laboratory scale batch process. Thermal and catalytic degradation of HIPS-Br mixed with PVBC on carbon composite of iron oxide (TR-00301) catalyst was investigated. The thermal degradation of waste plastics (HIPS-Br/PVC) yielded liquid products with 55,000 ppm bromine and 4300 ppm chlorine content in oil. Catalytic degradation (4 g; TR-00301) of HIPS-Br/PVC waste plastics at 430{degree}C produced halogen-free clean oil, which can be used as a fuel oil or chemical feedstock. The main liquid products during catalytic degradation were benzene, toluene, styrene, ethyl benzene, {alpha}-methyl styrene, butyl benzene, 1,2-dimethyl benzene etc. The average carbon number of the liquid products produced during catalytic degradation (9.3) of waste plastics was less than that of the thermal degradation (10.4) and the density of liquid products was found to be lower during the catalytic degradation than the thermal degradation. The possibility of a single step catalytic process for the conversion of halogenated waste plastics into fuel oil with the simultaneous removal of chlorine and bromine content form the oil was demonstrated. 21 refs., 7 figs., 2 tabs.

  13. A Novel Brominated Triazine-based Flame Retardant (TTBP-TAZ) in Plastic Consumer Products and Indoor Dust

    NARCIS (Netherlands)

    Ballesteros Gomez, A.M.; de Boer, J.; Leonards, P.E.G.

    2014-01-01

    The presence of a novel brominated flame retardant named 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ) is reported for the first time in plastic parts of consumer products and indoor dust samples. TTBP-TAZ was identified by untargeted screening and can be a replacement of the banned

  14. Rapid Formation of Molecular Bromine from Deliquesced NaBr Aerosol in the Presence of Ozone and UV Light

    Science.gov (United States)

    The formation of gas-phase bromine from aqueous sodium bromide aerosols is investigated through a combination of chamber experiments and chemical kinetics modeling. Experiments show that Br2(g) is produced rapidly from deliquesced NaBr aerosols in the presence of OH radicals prod...

  15. Gram-Scale Synthesis and Highly Regioselective Bromination of 1,1,9,9-Tetramethyl[9](2,11)teropyrenophane

    Czech Academy of Sciences Publication Activity Database

    Unikela, K. S.; Roemmele, T. L.; Houska, Václav; McGrath, K. E.; Tobin, D. M.; Dawe, L. N.; Boeré, R. T.; Bodwell, G. J.

    2018-01-01

    Roč. 57, č. 6 (2018), s. 1707-1711 ISSN 1433-7851 Institutional support: RVO:61388963 Keywords : aromaticity * bromination * cyclophanes * EPR spectroscopy * structure elucidation Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 11.994, year: 2016

  16. Corrosion mechanism of 13Cr stainless steel in completion fluid of high temperature and high concentration bromine salt

    International Nuclear Information System (INIS)

    Liu, Yan; Xu, Lining; Lu, Minxu; Meng, Yao; Zhu, Jinyang; Zhang, Lei