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Sample records for toxic halogenated aromatics

  1. Removal of Intermediate Aromatic Halogenated DBPs by Activated Carbon Adsorption: A New Approach to Controlling Halogenated DBPs in Chlorinated Drinking Water.

    Science.gov (United States)

    Jiang, Jingyi; Zhang, Xiangru; Zhu, Xiaohu; Li, Yu

    2017-03-21

    During chlorine disinfection of drinking water, chlorine may react with natural organic matter (NOM) and bromide ion in raw water to generate halogenated disinfection byproducts (DBPs). To mitigate adverse effects from DBP exposure, granular activated carbon (GAC) adsorption has been considered as one of the best available technologies for removing NOM (DBP precursor) in drinking water treatment. Recently, we have found that many aromatic halogenated DBPs form in chlorination, and they act as intermediate DBPs to decompose and form commonly known DBPs including trihalomethanes and haloacetic acids. In this work, we proposed a new approach to controlling drinking water halogenated DBPs by GAC adsorption of intermediate aromatic halogenated DBPs during chlorination, rather than by GAC adsorption of NOM prior to chlorination (i.e., traditional approach). Rapid small-scale column tests were used to simulate GAC adsorption in the new and traditional approaches. Significant reductions of aromatic halogenated DBPs were observed in the effluents with the new approach; the removals of total organic halogen, trihalomethanes, and haloacetic acids by the new approach always exceeded those by the traditional approach; and the effluents with the new approach were considerably less developmentally toxic than those with the traditional approach. Our findings indicate that the new approach is substantially more effective in controlling halogenated DBPs than the traditional approach.

  2. Limitations of the toxic equivalency factor (TEF) approach for risk assessment of halogenated aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Safe, S. [Texas A and M Univ., College Station, TX (United States). Dept. of Veterinary Physiology and Pharmacology

    1995-12-31

    2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) and related halogenated aromatic hydrocarbons (HAHs) are present as complex mixtures of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs) in most environmental matrices. Risk management of these mixtures utilize the toxic equivalency factor (TEF) approach in which the TCDD (dioxin) or toxic equivalents of a mixture is a summation of the congener concentration (Ci) times TEF{sub i} (potency relative to TCDD) where. TEQ{sub mixture} = {Sigma}[Cil] {times} TEF{sub i}. TEQs are determined only for those HAHs which are aryl hydrocarbon (Ah) receptor agonists and this approach assumes that the toxic or biochemical effects of individual compounds in a mixture are additive. Several in vivo and in vitro laboratory and field studies with different HAH mixtures have been utilized to validate the TEF approach. For some responses, the calculated toxicities of PCDD/PCDF and PCB mixtures predict the observed toxic potencies. However, for fetal cleft palate and immunotoxicity in mice, nonadditive (antagonistic) responses are observed using complex PCB mixtures or binary mixtures containing an Ah receptor agonist with 2,2{prime},4,4{prime},5,5{prime}-hexachlorobiphenyl (PCB153). The potential interactive effects of PCBs and other dietary Ah receptor antagonist suggest that the TEF approach for risk management of HAHs requires further refinement and should be used selectively.

  3. Process for removing halogenated aliphatic and aromatic compounds from petroleum products

    Science.gov (United States)

    Googin, J.M.; Napier, J.M.; Travaglini, M.A.

    1983-09-20

    A process is described for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 1 fig.

  4. Effects of halogenated aromatics/aliphatics and nitrogen(N)-heterocyclic aromatics on estimating the persistence of future pharmaceutical compounds using a modified QSAR model.

    Science.gov (United States)

    Lim, Seung Joo; Fox, Peter

    2014-02-01

    The effects of halogenated aromatics/aliphatics and nitrogen(N)-heterocyclic aromatics on estimating the persistence of future pharmaceutical compounds were investigated using a modified half life equation. The potential future pharmaceutical compounds investigated were approximately 2000 pharmaceutical drugs currently undergoing the United States Food and Drug Administration (US FDA) testing. EPI Suite (BIOWIN) model estimates the fates of compounds based on the biodegradability under aerobic conditions. While BIOWIN considered the biodegradability of a compound only, the half life equation used in this study was modified by biodegradability, sorption and cometabolic oxidation. It was possible that the potential future pharmaceutical compounds were more accurately estimated using the modified half life equation. The modified half life equation considered sorption and cometabolic oxidation of halogenated aromatic/aliphatics and nitrogen(N)-heterocyclic aromatics in the sub-surface, while EPI Suite (BIOWIN) did not. Halogenated aliphatics in chemicals were more persistent than halogenated aromatics in the sub-surface. In addition, in the sub-surface environment, the fates of organic chemicals were much more affected by halogenation in chemicals than by nitrogen(N)-heterocyclic aromatics. © 2013.

  5. Process for removing halogenated aliphatic and aromatic compounds from petroleum products. [Polychlorinated biphenyls; methylene chloride; perchloroethylene; trichlorofluoroethane; trichloroethylene; chlorobenzene

    Science.gov (United States)

    Googin, J.M.; Napier, J.M.; Travaglini, M.A.

    1982-03-31

    A process for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contracting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible polyhydroxy compound, such as, water, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds in the low polar or nonpolar solvent by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered for recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 2 tables.

  6. Molecular recognition of halogen-tagged aromatic VOCs at the air-silicon interface.

    Science.gov (United States)

    Condorelli, Guglielmo G; Motta, Alessandro; Favazza, Maria; Gurrieri, Ettore; Betti, Paolo; Dalcanale, Enrico

    2010-01-14

    Selective and reversible complexation of halogen-tagged aromatic VOCs by a quinoxaline cavitand-decorated Si surface is demonstrated. The specific host-guest interactions of the Si-bonded receptors are proved to be responsible of the surface recognition properties, while extracavity non specific adsorptions are totally suppressed compared to the bulk material.

  7. Four groups of new aromatic halogenated disinfection byproducts: effect of bromide concentration on their formation and speciation in chlorinated drinking water.

    Science.gov (United States)

    Pan, Yang; Zhang, Xiangru

    2013-02-05

    Bromide is naturally present in source waters worldwide. Chlorination of drinking water can generate a variety of chlorinated and brominated disinfection byproducts (DBPs). Although substantial efforts have been made to examine the effect of bromide concentration on the formation and speciation of halogenated DBPs, almost all previous studies have focused on trihalomethanes and haloacetic acids. Given that about 50% of total organic halogen formed in chlorination remains unknown, it is still unclear how bromide concentration affects the formation and speciation of the new/unknown halogenated DBPs. In this study, chlorinated drinking water samples with different bromide concentrations were prepared, and a novel approach-precursor ion scan using ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry-was adopted for the detection and identification of polar halogenated DBPs in these water samples. With this approach, 11 new putative aromatic halogenated DBPs were identified, and they were classified into four groups: dihalo-4-hydroxybenzaldehydes, dihalo-4-hydroxybenzoic acids, dihalo-salicylic acids, and trihalo-phenols. A mechanism for the formation of the four groups of new aromatic halogenated DBPs was proposed. It was found that increasing the bromide concentration shifted the entire polar halogenated DBPs as well as the four groups of new DBPs from being less brominated to being more brominated; these new aromatic halogenated DBPs might be important intermediate DBPs formed in drinking water chlorination. Moreover, the speciation of the four groups of new DBPs was modeled: the speciation patterns of the four groups of new DBPs well matched those determined from the model equations, and the reactivity differences between HOBr and HOCl in reactions forming the four groups of new DBPs were larger than those in reactions forming trihalomethanes and haloacetic acids.

  8. Polycyclic’ Aromatic Hydrocarbon Induced Intracellular Signaling and Lymphocyte Apoptosis

    DEFF Research Database (Denmark)

    Schneider, Alexander M.

    The aryl hydrocarbon (dioxin) receptor (AhR) is a transcription factor possessing high affinity to potent environmental pollutants, polycyclic aromatic hydrocarbons (PAH) and related halogenated hydrocarbons (e.g. dioxins). Numerous research attribute toxicity of these compounds to the receptor...

  9. The effect of halogen hetero-atoms on the vapor pressures and thermodynamics of polycyclic aromatic compounds measured via the Knudsen effusion technique

    International Nuclear Information System (INIS)

    Goldfarb, Jillian L.; Suuberg, Eric M.

    2008-01-01

    Knowledge of vapor pressures of high molar mass organics is essential to predicting their behavior in combustion systems as well as their fate and transport within the environment. This study involved polycyclic aromatic compounds (PACs) containing halogen hetero-atoms, including bromine and chlorine. The vapor pressures of eight PACs, ranging in molar mass from (212 to 336) g . mol -1 , were measured using the isothermal Knudsen effusion technique over the temperature range of (296 to 408) K. These compounds included those with few or no data available in the literature, namely: 1,4-dibromonaphthalene, 5-bromoacenaphthene, 9-bromoanthracene, 1,5-dibromoanthracene, 9,10-dibromoanthracene, 2-chloroanthracene, 9,10-dichloroanthracene, and 1-bromopyrene. Enthalpies of sublimation of these compounds were determined via application of the Clausius-Clapeyron equation. An analysis is presented on the effects of the addition of halogen hetero-atoms to pure polycyclic aromatic hydrocarbons using these data as well as available literature data. As expected, the addition of halogens onto these PACs increases their enthalpies of sublimation and decreases their vapor pressures as compared to the parent compounds

  10. Halogenating reaction activity of aromatic organic compounds during disinfection of drinking water

    International Nuclear Information System (INIS)

    Guo Gaimei; Chen Xiaodong

    2009-01-01

    The halogenating reactions of five aromatic organic compounds (AOCs) with aqueous chlorine (HOCl/OCl - ) and aqueous bromine (HOBr/OBr - ) were studied with an aim to compare the formation properties of haloacetic acids (HAAs) for the corresponding chlorination or bromination reactions of AOCs, respectively. The experiment results indicated that the HAAs substitution efficiency for the bromination reactions of AOCs was greater than that for the chlorination reactions, and the formation of HAAs had a strong dependence on the chemical structure of AOCs. The chlorination or bromination reaction activities for the AOCs with electron donating functional groups were higher than that for them with electron withdrawing functional groups. The kinetic experiments indicated that the reactions of aqueous bromine with phenol were faster than those of aqueous chlorine with phenol and the halogen consumption exhibited rapid initial and slower consumption stages for the reactions of phenol with aqueous chlorine and bromine, respectively. In addition, the HAAs production for the chlorination reaction of phenol decreased with the increase of pH. These conclusions could provide the valuable information for the effective control of the disinfection by-products during drinking water treatment operation

  11. N-Chloro and N-bromosaccharins: valuable reagents for halogenation of electron rich aromatics and cohalogenation of alkenes

    Directory of Open Access Journals (Sweden)

    Souza Soraia P. L. de

    2003-01-01

    Full Text Available N-Chloro- and N-bromosaccharins react with electron rich aromatic compounds (anisole, acetanilide, N,N-dimethylaniline producing halogenated compounds. The reaction with N-bromosaccharin gives para- substituted compounds only, whereas N-chlorosaccharin produces orto and para mixtures (para isomer predominantly, ca. 4-5 : 1. The reactions of the N-halosaccharins with alkenes (cyclohexene, styrene, a-methylstyrene, and 1-hexene give the corresponding halohydrins.

  12. [Pollution of Halogenated Polycyclic Aromatic Hydrocarbons in Atmospheric Particulate Matters of Shenzhen].

    Science.gov (United States)

    Sun, Jian-lin; Chang, Wen-jing; Chen, Zheng-xia; Zeng, Hui

    2015-05-01

    Concentrations of halogenated polycyclic aromatic hydrocarbons ( HPAHs) in atmospheric PM10 and PM2.5 samples collected from Shenzhen were determined using GC-MS. Total concentrations of nine HPAHs in atmospheric PM10 and PM2.5 samples ranged from 118 to 1,476 pg · m(-3) and 89 to 407 pg · m(-3), respectively. In PM10 and PM(2.5) samples, the concentration of 9-BrAnt was the highest, followed by 7-BrBaA and 9, 10-Br2Ant. Seasonal levels of total HPAHs in atmospheric PM10 and PM2.5 samples in Shenzhen decreased in the following order: winter > autumn > spring > summer, whereas concentrations of individual HPAHs showed different seasonal levels. Meteorological conditions, including temperature, precipitation, and relative humidity, might be important factors affecting the seasonal levels of HPAHs in atmospheric PM10 and PM2.5 In addition, there were significant correlations between concentrations of HPAHs and parent PAHs. Finally, the toxic equivalency quotients (TEQs) of HPAHs were estimated. The TEQs of HPAHs in atmospheric PM10 and PM2.5 samples ranged from 17.6 to 86.2 pg · m(-3) and 14.6 to 70.4 pg · m(-3), respectively. Among individual HPAHs, 7-BrBaA contributed greatly to the total TEQs of HPAHs. Our results indicated that the total TEQs of HPAHs were lower than parent PAHs in atmospheric PM10 and PM2.5 samples in Shenzhen.

  13. Control of aliphatic halogenated DBP precursors with multiple drinking water treatment processes: Formation potential and integrated toxicity.

    Science.gov (United States)

    Zhang, Yimeng; Chu, Wenhai; Yao, Dechang; Yin, Daqiang

    2017-08-01

    The comprehensive control efficiency for the formation potentials (FPs) of a range of regulated and unregulated halogenated disinfection by-products (DBPs) (including carbonaceous DBPs (C-DBPs), nitrogenous DBPs (N-DBPs), and iodinated DBPs (I-DBPs)) with the multiple drinking water treatment processes, including pre-ozonation, conventional treatment (coagulation-sedimentation, pre-sand filtration), ozone-biological activated carbon (O 3 -BAC) advanced treatment, and post-sand filtration, was investigated. The potential toxic risks of DBPs by combing their FPs and toxicity values were also evaluated. The results showed that the multiple drinking water treatment processes had superior performance in removing organic/inorganic precursors and reducing the formation of a range of halogenated DBPs. Therein, ozonation significantly removed bromide and iodide, and thus reduced the formation of brominated and iodinated DBPs. The removal of organic carbon and nitrogen precursors by the conventional treatment processes was substantially improved by O 3 -BAC advanced treatment, and thus prevented the formation of chlorinated C-DBPs and N-DBPs. However, BAC filtration leads to the increased formation of brominated C-DBPs and N-DBPs due to the increase of bromide/DOC and bromide/DON. After the whole multiple treatment processes, the rank order for integrated toxic risk values caused by these halogenated DBPs was haloacetonitriles (HANs)≫haloacetamides (HAMs)>haloacetic acids (HAAs)>trihalomethanes (THMs)>halonitromethanes (HNMs)≫I-DBPs (I-HAMs and I-THMs). I-DBPs failed to cause high integrated toxic risk because of their very low FPs. The significant higher integrated toxic risk value caused by HANs than other halogenated DBPs cannot be ignored. Copyright © 2017. Published by Elsevier B.V.

  14. In vitro toxicity of polycyclic aromatic hydrocarbons and halogenated aromatic hydrocarbons to cetacean cells and tissues

    Energy Technology Data Exchange (ETDEWEB)

    Carvan, M.J. III.

    1993-01-01

    Cetaceans bioaccumulate high aromatic hydrocarbon tissue residues, and elevated levels of PCB residues in tissues are proposed to have occurred concurrently with recent epizootic deaths of dolphins. The objectives of this study were: (1) to develop and characterize an epithelial cell line derived from dolphin tissues, (2) to investigate the effects of hydrocarbon pollutants on those cells, and (3) to analyze the toxicity of hydrocarbon pollutants on cetacean tissues in vitro. An epithelial cell line, Carvan dolphin kidney (CDK), isolated from a spontaneously aborted female bottlenose dolphin, Tursiops truncatus, grew rapidly. These cells were neither transformed nor immortal. Velocity sedimentation analysis showed CDK cells contained nuclear aryl hydrocarbon receptor, suggestive of cytochrome P450 inducibility. BaP inhibited mitosis in CDK cells in a dose-dependent manner. Data indicate that CDK cells metabolize BaP, that BaP metabolites bind to cellular DNA initiating unscheduled DNA synthesis, and that the inhibition of cytochrome P450 metabolism decrease the BaP-associated inhibition of mitosis in dolphin cells. The data also suggest that TCDD acts synergistically to increase the levels of DNA damage by the procarcinogen BaP. Cetacean liver microsomes was isolated and evaluated for the presence of cytochrome P450 proteins by SDS-PAGE, apparent minimum molecular weight determination, and immunoblot analysis. P450 activity was induced in cetacean tissue samples and CDK cells by exposure in vitro to one of several cytochrome P450-inducing chemicals. The data suggest that cetacean tissues and cells can be utilized to study the in vitro induction of cytochrome P450, resultant metabolism of xenobiotic contaminants, and the subsequent cellular and molecular responses. However, the identity of specific P450 isozymes involved in this process will remain undetermined until monoclonal antibodies that recognize cetacean P450s can be generated.

  15. Parent and halogenated polycyclic aromatic hydrocarbons in rice and implications for human health in China

    International Nuclear Information System (INIS)

    Ding Chao; Ni Honggang; Zeng Hui

    2012-01-01

    Rice is the staple food for approximate two thirds of the Chinese population. However, human exposure to parent and halogenated polycyclic aromatic hydrocarbons (PAHs) via rice consumption is still not clear for Chinese people so far. The goals of this work are to assess human exposure to PAHs and halogenated PAHs (HPAHs) via rice ingestion and the cancer risk for Chinese population. 16 PAHs and eight HPAHs were determined in rice samples collected from 18 provinces in China. In general terms, the general population in China was exposed to higher levels of PAHs via rice ingestion in comparison to that via cereals for other countries. The cancer risk values induced by exposure to PAHs and HPAHs for male and female on each age group were between the priority risk level (10 −4 ) and the acceptable risk level (10 −6 ). Children faced the highest cancer risk, followed by adolescents and adults. - Highlights: ► Dietary exposure to PAHs via rice ingestion for Chinese population was higher than that via cereals in other countries. ► The cancer risk induced by PAHs and HPAHs intakes via rice consumption were between 10 −6 and 10 −4 . ► Children faced the highest cancer risk, followed by adolescents and adults. ► Given all exposure routes were considered, the real cancer risk for Chinese people would be greater. - Human exposure to parent and halogenated PAHs via rice ingestion and the cancer risk for Chinese population were assessed.

  16. The reproductive and developmental toxicity of High Flash Aromatic Naphtha.

    Science.gov (United States)

    McKee, R H; Wong, Z A; Schmitt, S; Beatty, P; Swanson, M; Schreiner, C A; Schardein, J L

    1990-01-01

    Catalytic reforming is a refining process that converts naphthenes to aromatics by dehydrogenation to make higher octane gasoline blending components. A portion of this wide boiling range hydrocarbon stream can be separated by distillation and used for other purposes. One such application is a mixture of predominantly 9-carbon aromatic molecules (C9 aromatics, primarily isomers of ethyltoluene and trimethylbenzene), which is removed and used as a solvent--High Flash Aromatic Naphtha. A program was initiated to assess the toxicological properties of High Flash Aromatic Naphtha since there may be human exposure through inhalation or external body contact. The current study was conducted to assess the potential for developmental toxicity in the mouse and for reproductive toxicity in the rat. In the developmental toxicity study in CD-1 mice, exposure of dams by inhalation to near lethal levels (1500 ppm) resulted in fetal mortality, reduced weight, delayed ossification, and an increased incidence of cleft palate. At 500 ppm, a level at which maternal weight gain was slightly reduced, fetal weight gain was also reduced, but there was no other evidence of developmental effects. The lowest exposure level (100 ppm) did not cause any maternal or developmental toxicity. There was no consistent evidence of reproductive toxicity in rats, even at exposure levels which resulted in significantly reduced parental weight gain. In addition, when parental exposure was stopped on GD (gestation day) 20, birth weights as well as postnatal survival were generally similar to control values, even in the 1500 ppm exposure group. Postnatal weight gain was also similar to controls early in weaning, but, if maternal exposure was reinitiated, weight gain was reduced in the high exposure group. However, when exposure was continued until delivery, pups in the high exposure group exhibited reduced litter size, birth weight and poor survival. Thus it was likely that the reduction in fetal weight

  17. Toxic Potential of Carcinogenic Polycyclic Aromatic Hydrocarbons ...

    African Journals Online (AJOL)

    Toxic Potential of Carcinogenic Polycyclic Aromatic Hydrocarbons (cPAHs) and Heavy Metal in Crude Oil from Gokana Area, Rivers State, Nigeria. ... Considerable caution should be applied in exploration, exposure and distribution of the crude oil through protected and well maintained pipelines to avoid the possible ...

  18. Enzymatic Halogenation and Dehalogenation Reactions: Pervasive and Mechanistically Diverse.

    Science.gov (United States)

    Agarwal, Vinayak; Miles, Zachary D; Winter, Jaclyn M; Eustáquio, Alessandra S; El Gamal, Abrahim A; Moore, Bradley S

    2017-04-26

    Naturally produced halogenated compounds are ubiquitous across all domains of life where they perform a multitude of biological functions and adopt a diversity of chemical structures. Accordingly, a diverse collection of enzyme catalysts to install and remove halogens from organic scaffolds has evolved in nature. Accounting for the different chemical properties of the four halogen atoms (fluorine, chlorine, bromine, and iodine) and the diversity and chemical reactivity of their organic substrates, enzymes performing biosynthetic and degradative halogenation chemistry utilize numerous mechanistic strategies involving oxidation, reduction, and substitution. Biosynthetic halogenation reactions range from simple aromatic substitutions to stereoselective C-H functionalizations on remote carbon centers and can initiate the formation of simple to complex ring structures. Dehalogenating enzymes, on the other hand, are best known for removing halogen atoms from man-made organohalogens, yet also function naturally, albeit rarely, in metabolic pathways. This review details the scope and mechanism of nature's halogenation and dehalogenation enzymatic strategies, highlights gaps in our understanding, and posits where new advances in the field might arise in the near future.

  19. Extending Halogen-based Medicinal Chemistry to Proteins: IODO-INSULIN AS A CASE STUDY.

    Science.gov (United States)

    El Hage, Krystel; Pandyarajan, Vijay; Phillips, Nelson B; Smith, Brian J; Menting, John G; Whittaker, Jonathan; Lawrence, Michael C; Meuwly, Markus; Weiss, Michael A

    2016-12-30

    Insulin, a protein critical for metabolic homeostasis, provides a classical model for protein design with application to human health. Recent efforts to improve its pharmaceutical formulation demonstrated that iodination of a conserved tyrosine (Tyr B26 ) enhances key properties of a rapid-acting clinical analog. Moreover, the broad utility of halogens in medicinal chemistry has motivated the use of hybrid quantum- and molecular-mechanical methods to study proteins. Here, we (i) undertook quantitative atomistic simulations of 3-[iodo-Tyr B26 ]insulin to predict its structural features, and (ii) tested these predictions by X-ray crystallography. Using an electrostatic model of the modified aromatic ring based on quantum chemistry, the calculations suggested that the analog, as a dimer and hexamer, exhibits subtle differences in aromatic-aromatic interactions at the dimer interface. Aromatic rings (Tyr B16 , Phe B24 , Phe B25 , 3-I-Tyr B26 , and their symmetry-related mates) at this interface adjust to enable packing of the hydrophobic iodine atoms within the core of each monomer. Strikingly, these features were observed in the crystal structure of a 3-[iodo-Tyr B26 ]insulin analog (determined as an R 6 zinc hexamer). Given that residues B24-B30 detach from the core on receptor binding, the environment of 3-I-Tyr B26 in a receptor complex must differ from that in the free hormone. Based on the recent structure of a "micro-receptor" complex, we predict that 3-I-Tyr B26 engages the receptor via directional halogen bonding and halogen-directed hydrogen bonding as follows: favorable electrostatic interactions exploiting, respectively, the halogen's electron-deficient σ-hole and electronegative equatorial band. Inspired by quantum chemistry and molecular dynamics, such "halogen engineering" promises to extend principles of medicinal chemistry to proteins. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

  20. Halogenated and parent polycyclic aromatic hydrocarbons in vegetables: Levels, dietary intakes, and health risk assessments.

    Science.gov (United States)

    Wang, Li; Li, Chunmei; Jiao, Bining; Li, Qiwan; Su, Hang; Wang, Jing; Jin, Fen

    2018-03-01

    Halogenated polycyclic aromatic hydrocarbons (HPAHs) are attracting increasing concern because of their greater toxicity than their corresponding parent PAHs. However, human exposure to HPAHs via food consumption is not fully understood. In this study, daily intake via vegetable ingestion of 11 HPAHs and 16 PAHs and subsequent cancer risk were assessed for population in Beijing. A total of 80 vegetable samples were purchased from markets, including five leafy vegetables and three root vegetables. The concentrations of total HPAHs (∑HPAHs) were 0.357-0.874ng/g in all vegetables, lower than that of total PAHs (∑PAHs, 10.6-47.4ng/g). ∑HPAHs and ∑PAHs concentrations in leafy vegetables were higher than those in root vegetables, suggesting that the atmospheric deposition might be the dominant source of PAHs and HPAHs in leafy vegetables. Among the HPAH congeners, 2-BrFle and 9-ClFle were the predominant compounds and frequently detected in the vegetable samples. HPAHs and PAHs were also found in certificated vegetables at the concentrations of 0.466-0.751ng/g and 10.6-38.9ng/g, respectively, which were lower than those in non-certificated vegetables except for spinach. For leafy vegetables from local farms, the ∑PAHs and ∑HPAHs levels in the rape and Chinese cabbage samples significantly decreased with increasing the distance away from the incineration plant. The incremental lifetime cancer risks of HPAHs were below the acceptable risk level (10 -6 ), suggesting that there might be little or no risk to consumers from these compounds in vegetables. For all population groups, children were the most sensitive population to PAHs and HPAHs, and their health issues should be paid more attention. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. SYNTHESIS AND CHARACTERIZATION OF NEW HALOGENATED CURCUMINOIDS

    Directory of Open Access Journals (Sweden)

    Eugenio Torres

    2013-12-01

    Full Text Available In this work a novel procedure of synthesis of compounds analogues to curcumin with halogens atoms in its structure is described, which can increase its solubility and biological activity. Four halogenated curcuminoids were obtained with great pharmacological interest, none of them reported in literature before. Synthesis was carried out by means of the aldol condensation assisted by microwaves of halogenated aromatic aldehydes and acetylacetona, using morpholine as basic catalyst, in absence of solvent, and the reaction just needed 1 min. The products were purified by treatment of the reaction mixture with methanol under ultrasound irradiation, followed by chromatographic column. All obtained compounds were characterized by infrared spectroscopy, nuclear magnetic resonance, quantitative elementary analysis and high resolution mass spectrometry. The RMN-1H data demonstrate in all structures of synthesized curcuminoids the enol form is the most favored.

  2. Quantitative structure-activity relationships for toxicity and genotoxicity of halogenated aliphatic compounds: wing spot test of Drosophila melanogaster.

    Science.gov (United States)

    Chroust, Karel; Pavlová, Martina; Prokop, Zbynek; Mendel, Jan; Bozková, Katerina; Kubát, Zdenek; Zajícková, Veronika; Damborský, Jiri

    2007-02-01

    Halogenated aliphatic compounds were evaluated for toxic and genotoxic effects in the somatic mutation and recombination test employing Drosophila melanogaster. The tested chemicals included chlorinated, brominated and iodinated; mono-, di- and tri-substituted; saturated and unsaturated alkanes: 1,2-dibromoethane, 1-bromo-2-chloroethane, 1-iodopropane, 2,3-dichloropropene, 3-bromo-1-propene, epibromohydrin, 2-iodobutane, 3-chloro-2-methylpropene, 1,2,3-trichloropropane, 1,2-dichloroethane, 1,2-dichlorobutane, 1-chloro-2-methylpropane, 1,3-dichloropropane, 1,2-dichloropropane, 2-chloroethymethylether, 1-bromo-2-methylpropane and 1-chloropentane. N-methyl-N-nitrosourea served as the positive and distilled water as the negative control. The set of chemicals for the toxicological testing was selected by the use of statistical experiment design. Group of unsaturated aliphatic hydrocarbons were generally more toxic than saturated analogues. The genotoxic effect was observed with 14 compounds in the wing spot test, while 3 substances did not show any genotoxicity by using the wing spot test at 50% lethal concentration. The highest number of wing spots was observed in genotoxicity assay with 1-bromo-2-chloroethane, 1,2-dichloroethane, 1,2-dibromoethane and 1-iodopropane. Nucleophilic superdelocalizability calculated by quantum mechanics appears to be a good parameter for prediction of both toxicity and genotoxicity effects of halogenated aliphatic compounds.

  3. Acute and chronic aquatic toxicity of aromatic extracts. Summary of relevant test data

    Energy Technology Data Exchange (ETDEWEB)

    Comber, M.I.H.; Den Haan, K.; Djemel, N.; Eadsforth, C.V.; King, D.; Parkerton, T.; Leon Paumen, M.; Dmytrasz, B.; Del Castillo, F.

    2013-09-15

    This report describes the experimental procedures and the results obtained in acute and chronic ecotoxicity tests on several aromatic extracts samples. The samples were tested for toxicity to the rainbow trout (Oncorhynchus mykiss), the crustacean zooplankter, Daphnia magna and the algae, Selenastrum capricornutum using water accommodated fractions. These results assist in determining the environmental hazard posed by aromatic extracts.

  4. Comparative toxicity of ten organic chemicals to four earthworm species

    Energy Technology Data Exchange (ETDEWEB)

    Neuhauser, E.F.; Durkin, P.R.; Malecki, M.R.; Anatra, M.

    1986-01-01

    Ten organic chemicals were tested for toxicity to four earthworm species: Allolobophora tuberculata, Eisenia fetida, Eudrilus eugeniae and Perionyx excavatus, using the European Economic Community's (EEC) earthworm artificial soil and contact testing procedure. The phenols were the most toxic chemicals tested, followed by the amine, substituted benzenes, halogenated aliphatic hydrocarbon, polycyclic aromatic hydrocarbon and phthalate as the least toxic chemical tested. Correlations among species within each type of test for a given chemical were extremely high, suggesting that the selection of earthworm test species does not markedly affect the assessment of a chemical's toxicity. The correlation between the two tests was low for all test species. The contact test LC50 for a given chemical cannot be directly correlated to an artificial soil test LC50 for the same earthworm species.

  5. Bacterial Degradation of Aromatic Compounds

    Directory of Open Access Journals (Sweden)

    Qing X. Li

    2009-01-01

    Full Text Available Aromatic compounds are among the most prevalent and persistent pollutants in the environment. Petroleum-contaminated soil and sediment commonly contain a mixture of polycyclic aromatic hydrocarbons (PAHs and heterocyclic aromatics. Aromatics derived from industrial activities often have functional groups such as alkyls, halogens and nitro groups. Biodegradation is a major mechanism of removal of organic pollutants from a contaminated site. This review focuses on bacterial degradation pathways of selected aromatic compounds. Catabolic pathways of naphthalene, fluorene, phenanthrene, fluoranthene, pyrene, and benzo[a]pyrene are described in detail. Bacterial catabolism of the heterocycles dibenzofuran, carbazole, dibenzothiophene, and dibenzodioxin is discussed. Bacterial catabolism of alkylated PAHs is summarized, followed by a brief discussion of proteomics and metabolomics as powerful tools for elucidation of biodegradation mechanisms.

  6. Development of non-halogen cables for nuclear power stations

    Energy Technology Data Exchange (ETDEWEB)

    Yagyu, Hideki; Yamamoto, Yasuaki; Onishi, Takao (Hitachi Cable, Ltd., Tokyo (Japan))

    1983-12-01

    The non-halogen fire-resistant cables for nuclear power stations which never generate halogen gas, have been developed. The cables comprise the insulator of EP rubber and the sheath of polyolefine containing non-halogen inorganic fire-retardant. The results of the environmental test and fire-resistance test are described. In the environmental test, the cables were subjected to the heating, gamma-irradiation and steam exposure successively, according to IEEE specification 323,383, and subsequently the change in the appearance, tensile strength and electrical performance of the cables was measured. In the fire-resistance test, the vertical tray fire test according to the IEEE specification 383 was adopted, and other tests including the vertical fire test on insulator cores, oxygen index, the generation of corrosive gas, copper mirror corrosion test, gas toxicity test and optical smoke density test were carried out. It became clear that the cables did not generate halogen gas on burning, and brought about reduced toxicity, corrosion and smoke, and that the safety against fire is greatly improved by using the cables.

  7. Development of non-halogen cables for nuclear power stations

    International Nuclear Information System (INIS)

    Yagyu, Hideki; Yamamoto, Yasuaki; Onishi, Takao

    1983-01-01

    The non-halogen fire-resistant cables for nuclear power stations which never generate halogen gas, have been developed. The cables comprise the insulator of EP rubber and the sheath of polyolefine containing non-halogen inorganic fire-retardant. The results of the environmental test and fire-resistance test are described. In the environmental test, the cables were subjected to the heating, gamma-irradiation and steam exposure successively, according to IEEE specification 323,383, and subsequently the change in the appearance, tensile strength and electrical performance of the cables was measured. In the fire-resistance test, the vertical tray fire test according to the IEEE specification 383 was adopted, and other tests including the vertical fire test on insulator cores, oxygen index, the generation of corrosive gas, copper mirror corrosion test, gas toxicity test and optical smoke density test were carried out. It became clear that the cables did not generate halogen gas on burning, and brought about reduced toxicity, corrosion and smoke, and that the safety against fire is greatly improved by using the cables. (Yoshitake, I.)

  8. Symmetric and asymmetric halogen-containing metallocarboranylporphyrins and uses thereof

    Science.gov (United States)

    Miura, Michiko; Wu, Haitao

    2013-05-21

    The present invention is directed to low toxicity boronated compounds and methods for their use in the treatment, visualization, and diagnosis of tumors. More specifically, the present invention is directed to low toxicity halogenated, carborane-containing 5,10,15,20-tetraphenylporphyrin compounds and methods for their use particularly in boron neutron capture therapy (BNCT) and photodynamic therapy (PDT) for the treatment of tumors of the brain, head and neck, and surrounding tissue. The invention is also directed to using these halogenated, carborane-containing tetraphenylporphyrin compounds in methods of tumor imaging and/or diagnosis such as MRI, SPECT, or PET.

  9. Toxicity of selected organic chemicals to the earthworm Eisenia fetida

    Energy Technology Data Exchange (ETDEWEB)

    Neuhauser, E.F.; Loehr, R.C.; Malecki, M.R.; Milligan, D.L.; Durkin, P.R.

    A number of methods recently have been developed to biologically evaluate the impact of man's activities on soil ecosystems. Two test methods, the 2-d contact test and the 14-d artificial soil test, were used to evaluate the impact of six major classes of organic chemicals on the earthworm Eisenia fetida (Savigny). Of the organic chemicals tested, phenols and amines were the most toxic to the worms, followed in descending order of toxicity by the substituted aromatics, halogenated aliphatics, polycyclic aromatic hydrocarbons, and phthalates. No relationship was found between earthworm toxicity as determined by the contact test and rat, Rattus norvegicus Berkenhout and mouse, Mus musculus L. LD/sub 50/ values. The physicochemical parameters of water solubility, vapor pressure, and octanol/water partition coefficient for the chemicals tested in the contact test did not show a significant relationship to the E. fetida LC/sub 50/ values. These studies indicate that: (i) earthworms can be a suitable biomonitoring tool to assist in measuring the impact of organic chemicals in wastes added to soils and (ii) contact and artificial soil tests can be useful in measuring biological impacts.

  10. Development of Halogen-free flame-retardant cable for nuclear power plant

    International Nuclear Information System (INIS)

    Ishii, Nobuhisa; Morii, Akira; Fujimura, Shunichi

    1992-01-01

    Conventional flame-retardant cables release a large volume of corrosive and toxic gases as well as smoke while combusted. Cables covered with halogen-free flame-retardant material, containing no halogen in it, have been developed to reduce generation of such gases and smoke, and have already been used in telecommunication service, subway and shipboard applications. However, for cables for nuclear power plant, covering materials should also have radiation resistance and other properties, including long-term physical stability. We have developed halogen-free flame-retardant cables for BWR nuclear power plant with sufficient flame retardancy radiation resistance and environmental resistance including steam-exposure resistance all of which are in accordance with Japanese specifications for BWR nuclear cables and have such characteristics as low corrosiveness, low toxicity and low smoke emission. (author)

  11. Development of halogen-free flame-retardant cable for nuclear power plant

    International Nuclear Information System (INIS)

    Ishii, Nobuhisa; Morii, Akira; Fujimura, Shunichi

    1991-01-01

    Conventional flame-retardant cables release a large amount of corrosive and toxic gases and also smoke during combustion on fire. Cables covered with halogen-free flame-retardant material, containing no halogen in it, have been developed to reduce generation of such gases and smoke, and already used in telecommunication plant, subway and shipboard applications. In the case of nuclear power plant application, cable covering materials should also have radiation resistance and other properties including long-term physical stability. We have developed halogen-free flame-retardant cables for nuclear power plant with sufficient flame retardancy, radiation resistance, and environmental resistance including steam-exposure resistance, all of which are in accordance with Japanese specifications for nuclear cables, and with characteristics as low corrosiveness, low toxicity, and low smoke evolution. (author)

  12. Chronic toxicity of selected polycyclic aromatic hydrocarbons to algae and crustaceans using passive dosing.

    Science.gov (United States)

    Bragin, Gail E; Parkerton, Thomas F; Redman, Aaron D; Letinksi, Daniel J; Butler, Josh D; Paumen, Miriam Leon; Sutherland, Cary A; Knarr, Tricia M; Comber, Mike; den Haan, Klaas

    2016-12-01

    Because of the large number of possible aromatic hydrocarbon structures, predictive toxicity models are needed to support substance hazard and risk assessments. Calibration and evaluation of such models requires toxicity data with well-defined exposures. The present study has applied a passive dosing method to generate reliable chronic effects data for 8 polycyclic aromatic hydrocarbons (PAHs) on the green algae Pseudokirchneriella subcapitata and the crustacean Ceriodaphnia dubia. The observed toxicity of these substances on algal growth rate and neonate production were then compared with available literature toxicity data for these species, as well as target lipid model and chemical activity-based model predictions. The use of passive dosing provided well-controlled exposures that yielded more consistent data sets than attained by past literature studies. Results from the present study, which were designed to exclude the complicating influence of ultraviolet light, were found to be well described by both target lipid model and chemical activity effect models. The present study also found that the lack of chronic effects for high molecular weight PAHs was consistent with the limited chemical activity that could be achieved for these compounds in the aqueous test media. Findings from this analysis highlight that variability in past literature toxicity data for PAHs may be complicated by both poorly controlled exposures and photochemical processes that can modulate both exposure and toxicity. Environ Toxicol Chem 2016;35:2948-2957. © 2016 SETAC. © 2016 SETAC.

  13. Toxicity assessment of volatile organic compounds and polycyclic aromatic hydrocarbons in motorcycle exhaust.

    Science.gov (United States)

    Chang, Chang-Tang; Chen, Bor-Yann

    2008-05-30

    This study investigates the toxicity of various pollutant species from motorcycle exhaust via dose-response analysis and margin of safety using Escherichia coli DH5 alpha. The toxicity evaluation of the major components of motorcycle exhaust volatile organic compounds (VOCs), collected with impinger, and polycyclic aromatic hydrocarbons (PAHs), collected with filter and XAD-2, is essential to determine emission standards for motorcycles. The toxicity of benzene (B), toluene (T), ethyl benzene (E) and xylene (X) was selected for comparison as standard VOCs emitted from motorcycles. In addition, three types of reformulated gasoline (high oxygenate and high benzene content (No. 1), low oxygen and high benzene (No. 2), and low oxygen and low benzene (No. 3) were prepared to reveal combined toxicity of individual compositions. Motorcycle exhaust is significantly more toxic than BTEX due to the highly toxic VOCs generated from incomplete combustion. Overall toxicity evaluation showed that the toxicity, indicated as EC50, was approximately as follows: PAHs>two-stroke engines>four-stroke engines>BTEX.

  14. Toxicity assessment of volatile organic compounds and polycyclic aromatic hydrocarbons in motorcycle exhaust

    International Nuclear Information System (INIS)

    Chang, C.-T.; Chen, B.-Y.

    2008-01-01

    This study investigates the toxicity of various pollutant species from motorcycle exhaust via dose-response analysis and margin of safety using Escherichia coli DH5α. The toxicity evaluation of the major components of motorcycle exhaust volatile organic compounds (VOCs), collected with impinger, and polycyclic aromatic hydrocarbons (PAHs), collected with filter and XAD-2, is essential to determine emission standards for motorcycles. The toxicity of benzene (B), toluene (T), ethyl benzene (E) and xylene (X) was selected for comparison as standard VOCs emitted from motorcycles. In addition, three types of reformulated gasoline (high oxygenate and high benzene content (No. 1), low oxygen and high benzene (No. 2), and low oxygen and low benzene (No. 3) were prepared to reveal combined toxicity of individual compositions. Motorcycle exhaust is significantly more toxic than BTEX due to the highly toxic VOCs generated from incomplete combustion. Overall toxicity evaluation showed that the toxicity, indicated as EC 50 , was approximately as follows: PAHs > two-stroke engines > four-stroke engines > BTEX

  15. Presence, origin and importance of toxic substances in drinking water

    Energy Technology Data Exchange (ETDEWEB)

    Seemayer, N H

    1980-01-01

    The ubiquitous, environmental toxic substances representing a risk to health, and of importance with respect to the production of drinking water, largely belong to the following groups: cancerogenic, polycyclic, aromatic hydrocarbons, aromatic amines, N-nitroso compounds, pesticides. In addition the following substances: polychlorinated biphenyls, hormones, antibiotics, halogen hydrocarbons and heavy metals such as mercury, cadmium, lead, vanadium, chromium etc. Today, there is full appreciation of the qualitative aspects associated with the burdening of the environmental factor 'water' with toxic substances. However, as to the quantitative aspects, especially those relating to a combined effect of toxic substances adding to the total burden of man with noxious environmental agents, data are still lacking. The assessment of the chronic action exercised by minute and very minute concentrations of potentially toxic, cancerogenic or mutagenic substances possess a particularly complex problem for the environmental and water hygiene. Nowadays, there are basically 3 possibilities of solving this problem: epidemiological-statistical analyses, long-term animal experiments and in-vitro short-term tests. The epidemiological-statistical analysis can make a valuable contribution to the evaluation of the risk to human health of polluted drinking water and may also furnish the first clues to an incipient danger. However, it has to be considered that epidemiological studies deal with multifactorial events and that a monocausality is difficult to establish.

  16. Nucleophilic Aromatic Substitution Between Halogenated Benzene Dopants and Nucleophiles in Atmospheric Pressure Photoionization.

    Science.gov (United States)

    Kauppila, Tiina J; Haack, Alexander; Kroll, Kai; Kersten, Hendrik; Benter, Thorsten

    2016-03-01

    In a preceding work with dopant assisted-atmospheric pressure photoionization (DA-APPI), an abundant ion at [M + 77](+) was observed in the spectra of pyridine and quinoline with chlorobenzene dopant. This contribution aims to reveal the identity and route of formation of this species, and to systematically investigate structurally related analytes and dopants. Compounds containing N-, O-, and S-lone pairs were investigated with APPI in the presence of fluoro-, chloro-, bromo-, and iodobenzene dopants. Computational calculations on a density functional theory (DFT) level were carried out to study the reaction mechanism for pyridine and the different halobenzenes. The experimental and computational results indicated that the [M + 77](+) ion was formed by nucleophilic aromatic ipso-substitution between the halobenzene radical cation and nucleophilic analytes. The reaction was most efficient for N-heteroaromatic compounds, and it was weakened by sterical effects and enhanced by resonance stabilization. The reaction was most efficient with chloro-, bromo-, and iodobenzenes, whereas with fluorobenzene the reaction was scarcely observed. The calculated Gibbs free energies for the reaction between pyridine and the halobenzenes were shown to increase in the order I < Br < Cl < F. The reaction was found endergonic for fluorobenzene due to the strong C-F bonding, and exergonic for the other halobenzenes. For fluoro- and chlorobenzenes the reaction was shown to proceed through an intermediate state corresponding to [M + dopant](+), which was highly stable for fluorobenzene. For the bulkier bromine and iodine, this intermediate did not exist, but the halogens were shown to detach already during the approach by the nucleophile.

  17. Thermodynamic and aromaticity studies for the assessment of the halogen⋯cyano interactions on Iodobenzonitrile

    International Nuclear Information System (INIS)

    Rocha, Inês M.; Ribeiro da Silva, Maria D.M.C.; Ribeiro da Silva, Manuel A.V.

    2013-01-01

    Highlights: • Vapour pressure study of the iodobenzonitrile isomers by Knudsen effusion technique. • Enthalpies of formation of the iodobenzonitrile isomers by combustion calorimetry. • NICS, HOMA, SA indices used as aromaticity criteria for iodobenzonitrile isomers. • QTAIMs properties, HOMO–LUMO gap, UV–Vis spectra of iodobenzonitriles. • Bromo and fluorobenzonitriles are taken as references for the aromaticity analysis. -- Abstract: The standard (p° = 0.1 MPa) molar enthalpies of formation, in the gaseous phase, of the 2-, 3- and 4-iodobenzonitrile isomers were derived from the combination of the corresponding standard molar enthalpies of formation, in the condensed phase, at T = 298.15 K, and the standard molar enthalpies of sublimation, at the same temperature, calculated respectively from the standard molar energies of combustion in oxygen, measured by rotating-bomb calorimetry, and from the vapour-pressure study of the referred compounds, measured by mass-loss Knudsen effusion technique. The strength of the halogen-halogen and the halogen-cyano intermolecular interactions, in the crystal, are evaluated by the enthalpies and entropies of phase transition of the iodobenzonitrile derived from mass-loss Knudsen technique and differential scanning calorimetry measurements and compared with those reported to fluorobenzonitrile and bromobenzonitrile isomers. The computational calculations complement the experimental work, using different aromaticity criteria (HOMA, NICS, Shannom Aromaticity, PDI and ATI) for the analysis of the electronic behaviour of each iodobenzonitrile isomer

  18. Peculiarities of the photoinitiator-free photopolymerization of pentabrominated and pentafluorinated aromatic acrylates and methacrylates.

    Science.gov (United States)

    Daikos, Olesya; Naumov, Sergej; Knolle, Wolfgang; Heymann, Katja; Scherzer, Tom

    2016-11-30

    Pentabrominated and fluorinated aromatic (meth)acrylates as well as their non-halogenated counterparts have been studied with the aim to avoid conventional photoinitiators and to overcome some negative consequences related to their use. Therefore, RTIR spectroscopy, laser flash photolysis and GC/MS were utilized. Even low concentrations (1 to 5 wt%) of brominated (meth)acrylates in the model varnish lead to initiation of a photopolymerization reaction under exposure to UV light with λ > 300 nm. This is due to the fact that excitation of the aryl moiety leads to the homolysis of bromine-phenyl bonds with a high quantum yield of ∼0.15-0.3. Both, bromine radicals released from either ortho, meta or para position as well as the corresponding tetrabromoaryl radicals, may initiate the polymerization of brominated aromatic (meth)acrylates. In contrast, fluorinated aromatic (meth)acrylates undergo α-cleavage of the carboxyl group (as in the case of non-halogenated aromatic (meth)acrylates), if excitation of the acrylic double bonds is done with UV-C light (λ fluorinated) and 0.16-0.36 (non-halogenated compounds), despite the different pathway of fragmentation. Thus, in all cases the efficiency of initiation is comparable to conventional photoinitiators. Quantum chemical calculations of orbitals involved and of the Gibbs free energy of transients and products support the suggested reaction pathway.

  19. Do 16 Polycyclic Aromatic Hydrocarbons Represent PAH Air Toxicity?

    Science.gov (United States)

    Samburova, Vera; Zielinska, Barbara; Khlystov, Andrey

    2017-08-15

    Estimation of carcinogenic potency based on analysis of 16 polycyclic aromatic hydrocarbons (PAHs) ranked by U.S. Environmental Protection Agency (EPA) is the most popular approach within scientific and environmental air quality management communities. The majority of PAH monitoring projects have been focused on particle-bound PAHs, ignoring the contribution of gas-phase PAHs to the toxicity of PAH mixtures in air samples. In this study, we analyzed the results of 13 projects in which 88 PAHs in both gas and particle phases were collected from different sources (biomass burning, mining operation, and vehicle emissions), as well as in urban air. The aim was to investigate whether 16 particle-bound U.S. EPA priority PAHs adequately represented health risks of inhalation exposure to atmospheric PAH mixtures. PAH concentrations were converted to benzo(a)pyrene-equivalent (BaPeq) toxicity using the toxic equivalency factor (TEF) approach. TEFs of PAH compounds for which such data is not available were estimated using TEFs of close isomers. Total BaPeq toxicities (∑ 88 BaPeq) of gas- and particle-phase PAHs were compared with BaPeq toxicities calculated for the 16 particle-phase EPA PAH (∑ 16EPA BaPeq). The results showed that 16 EPA particle-bound PAHs underrepresented the carcinogenic potency on average by 85.6% relative to the total (gas and particle) BaPeq toxicity of 88 PAHs. Gas-phase PAHs, like methylnaphthalenes, may contribute up to 30% of ∑ 88 BaPeq. Accounting for other individual non-EPA PAHs (i.e., benzo(e)pyrene) and gas-phase PAHs (i.e., naphthalene, 1- and 2-methylnaphthalene) will make the risk assessment of PAH-containing air samples significantly more accurate.

  20. Understanding the toxic potencies of xenobiotics inducing TCDD/TCDF-like effects.

    Science.gov (United States)

    Şahin, A D; Saçan, M T

    2018-02-01

    Toxic potencies of xenobiotics such as halogenated aromatic hydrocarbons inducing 2,3,7,8-tetrachlorodibenzo-p-dioxin/2,3,7,8-tetrachlorodibenzofuran (TCDD/TCDF)-like effects were investigated by quantitative structure-toxicity relationships (QSTR) using their aryl hydrocarbon receptor (AhR) binding affinity data. A descriptor pool was created using the SPARTAN 10, DRAGON 6.0 and ADMET 8.0 software packages, and the descriptors were selected using QSARINS (v.2.2.1) software. The QSTR models generated for AhR binding affinities of chemicals with TCDD/TCDF-like effects were internally and externally validated in line with the Organization of Economic Co-operation and Development (OECD) principles. The TCDD-based model had six descriptors from DRAGON 6.0 and ADMET 8.0, whereas the TCDF-based model had seven descriptors from DRAGON 6.0. The predictive ability of the generated models was tested on a diverse group of chemicals including polychlorinated/brominated biphenyls, dioxins/furans, ethers, polyaromatic hydrocarbons with fused heterocyclic rings (i.e. phenoxathiins, thianthrenes and dibenzothiophenes) and polyaromatic hydrocarbons (i.e. halogenated naphthalenes and phenanthrenes) with no AhR binding data. For the external set chemicals, the structural coverage of the generated models was 90% and 89% for TCDD and TCDF-like effects, respectively.

  1. Structure-Energy Relationships of Halogen Bonds in Proteins.

    Science.gov (United States)

    Scholfield, Matthew R; Ford, Melissa Coates; Carlsson, Anna-Carin C; Butta, Hawera; Mehl, Ryan A; Ho, P Shing

    2017-06-06

    The structures and stabilities of proteins are defined by a series of weak noncovalent electrostatic, van der Waals, and hydrogen bond (HB) interactions. In this study, we have designed and engineered halogen bonds (XBs) site-specifically to study their structure-energy relationship in a model protein, T4 lysozyme. The evidence for XBs is the displacement of the aromatic side chain toward an oxygen acceptor, at distances that are equal to or less than the sums of their respective van der Waals radii, when the hydroxyl substituent of the wild-type tyrosine is replaced by a halogen. In addition, thermal melting studies show that the iodine XB rescues the stabilization energy from an otherwise destabilizing substitution (at an equivalent noninteracting site), indicating that the interaction is also present in solution. Quantum chemical calculations show that the XB complements an HB at this site and that solvent structure must also be considered in trying to design molecular interactions such as XBs into biological systems. A bromine substitution also shows displacement of the side chain, but the distances and geometries do not indicate formation of an XB. Thus, we have dissected the contributions from various noncovalent interactions of halogens introduced into proteins, to drive the application of XBs, particularly in biomolecular design.

  2. Bacterial degradation of monocyclic aromatic amines

    Directory of Open Access Journals (Sweden)

    Pankaj Kumar Arora

    2015-08-01

    Full Text Available Aromatic amines are an important group of industrial chemicals, which are widely used for manufacturing of dyes, pesticides, drugs, pigments, and other industrial products. These compounds have been considered highly toxic to human beings due to their carcinogenic nature. Three groups of aromatic amines have been recognized: monocyclic, polycyclic and heterocyclic aromatic amines. Bacterial degradation of several monocyclic aromatic compounds has been studied in a variety of bacteria, which utilizes monocyclic aromatic amines as their sole source of carbon and energy. Several degradation pathways have been proposed and the related enzymes and genes have also been characterized. Many reviews have been reviewed toxicity of monocyclic aromatic amines; however, there is lack of review on biodegradation of monocyclic aromatic amines. The aim of this review is to summarize bacterial degradation of monocyclic aromatic amines. This review will increase our current understanding of biochemical and molecular basis of bacterial degradation of monocyclic aromatic amines.

  3. Toxicity of Aromatic Ketone to Yeast Cell and Improvement of the Asymmetric Reduction of Aromatic Ketone Catalyzed by Yeast Cell with the Introduction of Resin Adsorption

    Directory of Open Access Journals (Sweden)

    Zhong-Hua Yang

    2008-01-01

    Full Text Available Asymmetric reduction of the prochiral aromatic ketone catalyzed by yeast cells is one of the most promising routes to produce its corresponding enantiopure aromatic alcohol, but the space-time yield does not meet people’s expectations. Therefore, the toxicity of aromatic ketone and aromatic alcohol to the yeast cell is investigated in this work. It has been found that the aromatic compounds are poisonous to the yeast cell. The activity of yeast cell decreases steeply when the concentration of acetophenone (ACP is higher than 30.0 mmol/L. Asymmetric reduction of acetophenone to chiral S-α-phenylethyl alcohol (PEA catalyzed by the yeast cell was chosen as the model reaction to study in detail the promotion effect of the introduction of the resin adsorption on the asymmetric reduction reaction. The resin acts as the substrate reservoir and product extraction agent in situ. It has been shown that this reaction could be remarkably improved with this technique when the appropriate kind of resin is applied. The enantioselectivity and yield are acceptable even though the initial ACP concentration reaches 72.2 mmol/L.

  4. Comparative chronic toxicity of homo- and heterocyclic aromatic compounds to benthic and terrestrial invertebrates: Generalizations and exceptions.

    NARCIS (Netherlands)

    Leon Paumen, M.; de Voogt, P.; van Gestel, C.A.M.; Kraak, M.H.S.

    2009-01-01

    The aim of the present study was to elucidate consistent patterns in chronic polycyclic aromatic compound (PAC) toxicity to soil and sediment inhabiting invertebrates. Therefore we examined our experimental dataset, consisting of twenty-one chronic effect concentrations for two soil invertebrates

  5. Comparative chronic toxicity of homo- and heterocyclic aromatic compounds to benthic and terrestrial invertebrates: Generalizations and exceptions

    NARCIS (Netherlands)

    León Paumen, M.; de Voogt, P.; van Gestel, C.A.M.; Kraak, M.H.S.

    2009-01-01

    The aim of the present study was to elucidate consistent patterns in chronic polycyclic aromatic compound (PAC) toxicity to soil and sediment inhabiting invertebrates. Therefore we examined our experimental dataset, consisting of twenty-one chronic effect concentrations for two soil invertebrates

  6. Assessing Photoinduced Toxicity of Polycyclic Aromatic Hydrocarbons in an Urbanized Estuary

    Directory of Open Access Journals (Sweden)

    M. Vo

    2004-12-01

    Full Text Available Increases in contaminants associated with urban sprawl are a particular concern in the rapidly developing coastal areas of the southeastern United States. Polycyclic aromatic hydrocarbons (PAHs are contaminants associated with vehicle emissions and runoff from impervious surfaces. Increased vehicular traffic and more impervious surfaces lead to an increased loading of PAHs into coastal estuarine systems. The phototoxic effect of PAH-contaminated sediments on a sediment-dwelling meiobenthic copepod, Amphiascus tenuiremis, was estimated in Murrells Inlet, a small, high-salinity estuary with moderate urbanization located in Georgetown and Horry Counties, South Carolina, USA. Field-determined solar ultraviolet radiation (UV and UV extinction coefficients were incorporated into laboratory toxicity experiments, and a model was developed to predict areas of specific hazard to A. tenuiremis in the estuary. The model incorporated laboratory toxicity data, UV extinction coefficients, and historical sediment chemistry and bathymetric data within a spatial model of sedimentary areas of the estuary. The model predicted that approximately 8-16% of the total creek habitat suitable for meiobenthic copepods is at risk to photoinduced PAH toxicity. This area is in the northern, more developed part of Murrells Inlet.

  7. Passive dosing of polycyclic aromatic hydrocarbon (PAH) mixtures to terrestrial springtails: Linking mixture toxicity to chemical activities, equilibrium lipid concentrations, and toxic units

    DEFF Research Database (Denmark)

    Schmidt, Stine Nørgaard; Holmstrup, Martin; Smith, Kilian E. C.

    2013-01-01

    treatments, containing the polycyclic aromatic hydrocarbons (PAHs) naphthalene, phenanthrene, and pyrene. Springtail lethality was then linked to sum chemical activities (∑a), sum equilibrium lipid concentrations (∑Clipid eq.), and sum toxic units (∑TU). In each case, the effects of all 12 mixture treatments...... could be fitted to one sigmoidal exposure-response relationship. The effective lethal chemical activity (La50) of 0.027 was well within the expected range for baseline toxicity of 0.01-0.1. Linking the effects to the lipid-based exposure parameter yielded an effective lethal concentration (LClipid eq...

  8. Forms of polycyclic aromatic hydrocarbon in the formation of sewage sludge toxicity to Heterocypris incongruens

    International Nuclear Information System (INIS)

    Oleszczuk, Patryk

    2008-01-01

    The aim of the present study was to evaluate to what degree polycyclic aromatic hydrocarbon (PAH) determines sewage sludge toxicity in relation to Heterocypris incongruens. Six differing sewage sludges with increasing contents of polycyclic aromatic hydrocarbons were selected for the present study. As well as total PAH content, the content of the potentially bioavailable fraction was also determined in the sewage sludges using a method of mild-solvent extraction (with n-butanol). The PAH content was also calculated in the sewage sludge pore water by the equilibrium partitioning method. The total PAH content in the sewage sludges studied were in the range 3.60 to 27.95 mg kg -1 . The contribution of the n-butanol extracted fraction was in the range 38.7 to 75.4%. In the group of individual PAHs, 4- and 5-ring compounds had the highest content in the potentially bioavailable group. H. incongruens mortality in the range 6.7 to 100%, depending both on the sewage sludge and the dose applied. An increase of the sewage sludge dose usually resulted in an increase in toxicity. At the highest dose, a 100% mortality of H. incongruens was found in half of the sludges. The lowest dose, irrespective of the sludge type, caused over 40% growth inhibition. However, the results obtained did not allow for the establishing of an unambiguous relationship between various sludge toxicity levels and the content of potentially bio-available PAHs. In some cases only, the extraction using n-butanol explained the high difference in toxicity despite a slight differentiation in the PAH content

  9. Halogenated fatty acids

    DEFF Research Database (Denmark)

    Mu, Huiling; Sundin, Peter; Wesén, Clas

    1997-01-01

    Halogenated fatty acids are the major contributors to organohalogen compounds in lipids of marine mammals, fish, and bivalves. For the initial characterization of these recently noticed compounds, a determination of the halogen concentration has usually been combined with some lipid isolation......), atomic emission spectrometry, and mass spectrometry. For most environmental samples, chlorinated FAMEs must be enriched prior to GC. ELCD is a useful detection method for indicating halogenated FAMEs in the chromatograms, and tentative identification of the halogenated species can be obtained...

  10. Iodine and tritium labelling of curarizing and cardiotoxic agents. Study of the conformation of toxic polypeptides extracted from snake venom

    International Nuclear Information System (INIS)

    Menez, Andre.

    1977-01-01

    A short review of present-day knowledge on the action mechanism of toxic snake venom polypeptides is followed by a study of the radioactive labelling of some toxic compounds. Those dealt with more especially are Naja nigricollis α toxin and Laticauda semifasciata b erabutoxin, then (+) tubocurarin, a non-peptidic curarizing alkaloid, and two cardiotoxic polypeptides: cytotoxin II and cardiotoxin γ extracted from the venom of Naja naja and Naja nigricollis respectively. The labelling principle is based on the specific fixation of one or more iodine atoms then tritium substitution of the halogen by catalytic hydrogenolysis. As predicted from titration of the aromatic groups the halogenation process, obtained by addition of iodine monochloride, takes place sometimes on the phenolic nuclei and sometimes on the imidazole nuclei, the position of which targets within each sequence has been identified. From results of the study of reactivity towards iodine combined with those of basic titration, the accessibility of several aromatic nuclei has also been defined. Each iodinated polypeptide is then hydrogenolysed in the presence of tritium gas giving a specific activity between 4 and 27 Ci/mmole according to the compound treated. In all cases the biological potential and physical properties of the radioactive material obtained by the above titration process remained intact. An example of the bonding kinetics of short toxins with the partially purified choligenic receptor is given in the special case of tritiated b erabutoxin. The affinity of this toxin for its receptor target is strong, though slightly less so than that of tritiated Naja nigricollis α toxin [fr

  11. Development of halogen-free flame-retardant cable for nuclear power plant. 2

    International Nuclear Information System (INIS)

    Matsumoto, Tetsuo; Kimura, Hitoshi; Ishii, Nobuhisa

    1997-01-01

    Halogen-free flame-retardant cables were developed for PWR nuclear power stations. It was confirmed that the developed cables possess flame retardant property, corrosion resistance, low toxicity and low smoke generation, and withstand the normal operation in the environment in PWR containment vessels for 60 years and loss of coolant accident. In the advancement of LWR technology, it is important to improve the reliability of machinery and equipment, to extend the period of continuous operation, to optimize the operation cycle and to improve the maintenance of plants. By improving halogen-free flame-retardant material and applying it to the cables for nuclear power stations, it can contribute to the above purposes. The required characteristics of these cables are explained, and the targets of development are power cables, control cables, instrumentation cables and insulated wires which do not contain halogen. The basic material is polyolefin, in which flame retardant magnesium hydroxide and the agent for improving radiation resistance are mixed. The corrosive property and toxicity of gases, smoke generation and the prevention of spread of flame when the cables burn and the durability in environment were evaluated. (K.I.)

  12. Using quantitative structure-activity relationships (QSAR) to predict toxic endpoints for polycyclic aromatic hydrocarbons (PAH).

    Science.gov (United States)

    Bruce, Erica D; Autenrieth, Robin L; Burghardt, Robert C; Donnelly, K C; McDonald, Thomas J

    2008-01-01

    Quantitative structure-activity relationships (QSAR) offer a reliable, cost-effective alternative to the time, money, and animal lives necessary to determine chemical toxicity by traditional methods. Additionally, humans are exposed to tens of thousands of chemicals in their lifetimes, necessitating the determination of chemical toxicity and screening for those posing the greatest risk to human health. This study developed models to predict toxic endpoints for three bioassays specific to several stages of carcinogenesis. The ethoxyresorufin O-deethylase assay (EROD), the Salmonella/microsome assay, and a gap junction intercellular communication (GJIC) assay were chosen for their ability to measure toxic endpoints specific to activation-, induction-, and promotion-related effects of polycyclic aromatic hydrocarbons (PAH). Shape-electronic, spatial, information content, and topological descriptors proved to be important descriptors in predicting the toxicity of PAH in these bioassays. Bioassay-based toxic equivalency factors (TEF(B)) were developed for several PAH using the quantitative structure-toxicity relationships (QSTR) developed. Predicting toxicity for a specific PAH compound, such as a bioassay-based potential potency (PP(B)) or a TEF(B), is possible by combining the predicted behavior from the QSTR models. These toxicity estimates may then be incorporated into a risk assessment for compounds that lack toxicity data. Accurate toxicity predictions are made by examining each type of endpoint important to the process of carcinogenicity, and a clearer understanding between composition and toxicity can be obtained.

  13. Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms.

    Science.gov (United States)

    Carter, Korey P; Kalaj, Mark; Surbella, Robert G; Ducati, Lucas C; Autschbach, Jochen; Cahill, Christopher L

    2017-11-02

    Engaging the nominally terminal oxo atoms of the linear uranyl (UO 2 2+ ) cation in non-covalent interactions represents both a significant challenge and opportunity within the field of actinide hybrid materials. An approach has been developed for promoting oxo atom participation in a range of non-covalent interactions, through judicious choice of electron donating equatorial ligands and appropriately polarizable halogen-donor atoms. As such, a family of uranyl hybrid materials was generated based on a combination of 2,5-dihalobenzoic acid and aromatic, chelating N-donor ligands. Delineation of criteria for oxo participation in halogen bonding interactions has been achieved by preparing materials containing 2,5-dichloro- (25diClBA) and 2,5-dibromobenzoic acid (25diBrBA) coupled with 2,2'-bipyridine (bipy) (1 and 2), 1,10-phenanthroline (phen) (3-5), 2,2':6',2''-terpyridine (terpy) (6-8), or 4'-chloro-2,2':6',2''-terpyridine (Cl-terpy) (9-10), which have been characterized through single crystal X-ray diffraction, Raman, Infrared (IR), and luminescence spectroscopy, as well as through density functional calculations of electrostatic potentials. Looking comprehensively, these results are compared with recently published analogues featuring 2,5-diiodobenzoic acid which indicate that although inclusion of a capping ligand in the uranyl first coordination sphere is important, it is the polarizability of the selected halogen atom that ultimately drives halogen bonding interactions with the uranyl oxo atoms. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Photocatalytic oxidation of polycyclic aromatic hydrocarbons: Intermediates identification and toxicity testing

    International Nuclear Information System (INIS)

    Woo, O.T.; Chung, W.K.; Wong, K.H.; Chow, Alex T.; Wong, P.K.

    2009-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are hydrophobic pollutants and their low water solubility limits their degradation in aqueous solution. The presence of water-miscible solvent such as acetone can increase the water solubility of PAHs, however acetone will also affect the degradation of PAH. In this study the effects of acetone on the photocatalytic degradation efficiency and pathways of 5 selected PAHs, namely naphthalene (2 rings), acenaphthylene (3 rings), phenanthrene (3 rings), anthracene (3 rings) and benzo[a]anthracene (4 rings) were investigated. The Microtox toxicity test was used to determine whether the PCO system can completely detoxify the parental PAHs and its intermediates. The addition of 16% acetone can greatly alter the degradation pathway of naphthalene and anthracene. Based on intermediates identified from degradation of the 5 PAHs, the location of parental PAHs attacked by reactive free radicals can be correlated with the localization energies of different positions of the compound. For toxicity analysis, irradiation by UV light was found to induce acute toxicity by generating intermediates/degradation products from PAHs and possibly acetone. Lastly, all PAHs (10 mg l -1 ) can be completely detoxified by titanium dioxide (100 mg l -1 ) within 24 h under UVA irradiation (3.9 mW cm -2 ).

  15. An Acetyltransferase Conferring Tolerance to Toxic Aromatic Amine Chemicals

    Science.gov (United States)

    Martins, Marta; Rodrigues-Lima, Fernando; Dairou, Julien; Lamouri, Aazdine; Malagnac, Fabienne; Silar, Philippe; Dupret, Jean-Marie

    2009-01-01

    Aromatic amines (AA) are a major class of environmental pollutants that have been shown to have genotoxic and cytotoxic potentials toward most living organisms. Fungi are able to tolerate a diverse range of chemical compounds including certain AA and have long been used as models to understand general biological processes. Deciphering the mechanisms underlying this tolerance may improve our understanding of the adaptation of organisms to stressful environments and pave the way for novel pharmaceutical and/or biotechnological applications. We have identified and characterized two arylamine N-acetyltransferase (NAT) enzymes (PaNAT1 and PaNAT2) from the model fungus Podospora anserina that acetylate a wide range of AA. Targeted gene disruption experiments revealed that PaNAT2 was required for the growth and survival of the fungus in the presence of toxic AA. Functional studies using the knock-out strains and chemically acetylated AA indicated that tolerance of P. anserina to toxic AA was due to the N-acetylation of these chemicals by PaNAT2. Moreover, we provide proof-of-concept remediation experiments where P. anserina, through its PaNAT2 enzyme, is able to detoxify the highly toxic pesticide residue 3,4-dichloroaniline in experimentally contaminated soil samples. Overall, our data show that a single xenobiotic-metabolizing enzyme can mediate tolerance to a major class of pollutants in a eukaryotic species. These findings expand the understanding of the role of xenobiotic-metabolizing enzyme and in particular of NATs in the adaptation of organisms to their chemical environment and provide a basis for new systems for the bioremediation of contaminated soils. PMID:19416981

  16. Environmental levels and toxicological potencies of a novel mixed halogenated carbazole

    Directory of Open Access Journals (Sweden)

    Miren Pena-Abaurrea

    2016-09-01

    Full Text Available The present work involves an extensive analytical and toxicological description of a recently identified mixed halogenated carbazole found in sediment samples, 1,8-dibromo-3,6-dichloro-9H-carbazole (BCCZ. Concentrations and the relative effect potency (REP were calculated for the target BCCZ in a set of stream sediments collected in 2008 in Ontario, Canada. The levels calculated for BCCZ as compared to those previously assessed for legacy persistent organic pollutants (POPs in the same samples revealed a significant contribution of BCCZ to the total organic chemical contamination (<1%–95%; average 37%. The corresponding dioxin toxic equivalencies (TEQs of BCCZ in the sediment extracts were estimated from experimental REP data. The experimental data presented supports the classification of this emerging halogenated chemical as a contaminant of emerging environmental concern. Although potential emission sources could not be identified, this study highlights the importance of on-going research for complete characterization of halogenated carbazoles and related compounds.

  17. Passive dosing of polycyclic aromatic hydrocarbon (PAH) mixtures to terrestrial springtails: linking mixture toxicity to chemical activities, equilibrium lipid concentrations, and toxic units.

    Science.gov (United States)

    Schmidt, Stine N; Holmstrup, Martin; Smith, Kilian E C; Mayer, Philipp

    2013-07-02

    A 7-day mixture toxicity experiment with the terrestrial springtail Folsomia candida was conducted, and the effects were linked to three different mixture exposure parameters. Passive dosing from silicone was applied to tightly control exposure levels and compositions of 12 mixture treatments, containing the polycyclic aromatic hydrocarbons (PAHs) naphthalene, phenanthrene, and pyrene. Springtail lethality was then linked to sum chemical activities (∑a), sum equilibrium lipid concentrations (∑C(lipid eq.)), and sum toxic units (∑TU). In each case, the effects of all 12 mixture treatments could be fitted to one sigmoidal exposure-response relationship. The effective lethal chemical activity (La50) of 0.027 was well within the expected range for baseline toxicity of 0.01-0.1. Linking the effects to the lipid-based exposure parameter yielded an effective lethal concentration (LC(lipid eq 50)) of 133 mmol kg(-1) lipid in good correspondence with the lethal membrane burden for baseline toxicity (40-160 mmol kg(-1) lipid). Finally, the effective lethal toxic unit (LTU50) of 1.20 was rather close to the expected value of 1. Altogether, passive dosing provided tightly controlled mixture exposure in terms of both level and composition, while ∑a, ∑C(lipid eq.), and ∑TU allowed baseline toxicity to be linked to mixture exposure.

  18. Atmospheric polycyclic aromatic hydrocarbons in the urban environment: Occurrence, toxicity and source apportionment.

    Science.gov (United States)

    Mishra, Nitika; Ayoko, Godwin A; Morawska, Lidia

    2016-01-01

    Polycyclic Aromatic Hydrocarbons (PAHs) represent a major class of toxic pollutants because of their carcinogenic and mutagenic characteristics. People living in urban areas are regularly exposed to PAHs because of abundance of their emission sources. Within this context, this study aimed to: (i) identify and quantify the levels of ambient PAHs in an urban environment; (ii) evaluate their toxicity; and (iii) identify their sources as well as the contribution of specific sources to measured concentrations. Sixteen PAHs were identified and quantified in air samples collected from Brisbane. Principal Component Analysis - Absolute Principal Component Scores (PCA-APCS) was used in order to conduct source apportionment of the measured PAHs. Vehicular emissions, natural gas combustion, petrol emissions and evaporative/unburned fuel were the sources identified; contributing 56%, 21%, 15% and 8% of the total PAHs emissions, respectively, all of which need to be considered for any pollution control measures implemented in urban areas. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Development of halogen-free cables for nuclear power plants

    International Nuclear Information System (INIS)

    Yamamoto, Mitsuo; Ito, Kazumi; Yaji, Takeo; Yoshida, Shin; Sakurai, Takako; Matsushita, Shigetoshi.

    1990-01-01

    On the occasion where serious fire accidents were experienced in the past, the need for making flame-retardant wire and cable incombustible took place and has since been generalizing. Various sorts of flame-retardant cables have already been developed and been actually used. From the viewpoint of avoiding the interference with the evacuation and fire-fighting activity in case of fire or the secondary accidents such as corrosion of the distributing panel, etc., the demand for non-halogen flame-retardant cable has rapidly been increasing in recent years in some fields of general industries, because this specific cable would generate the least amount of toxic smoke or corrosive gas even when it should burn. Similar demand has been increasing also for the cable used for nuclear power plants. In this field, earnest desire has been made for the development of non-halogen flame-retardant cable having specific environmental resistance specially required at nuclear power plants in addition to the properties and capacities required in general industries. The authors have continued examinations on the anti-environmental properties of the materials for cable such as long heat resistance, radiation resistance, steam resistance and succeeded in completing various sorts of non-halogen flame-retardant cable for nuclear power plants. In this report, we will introduce various features of the cable we have developed this time as well as the long-term reliability of non-halogen flame-retardant materials. (author)

  20. The use of quantum chemically derived descriptors for QSAR modelling of reductive dehalogenation of aromatic compounds

    NARCIS (Netherlands)

    Rorije E; Richter J; Peijnenburg WJGM; ECO; IHE Delft

    1994-01-01

    In this study, quantum-chemically derived parameters are developed for a limited number of halogenated aromatic compounds to model the anaerobic reductive dehalogenation reaction rate constants of these compounds. It is shown that due to the heterogeneity of the set of compounds used, no single

  1. Computational Methods to Predict the Regioselectivity of Electrophilic Aromatic Substitution Reactions of Heteroaromatic Systems

    DEFF Research Database (Denmark)

    Kruszyk, Monika; Jessing, Mikkel; Kristensen, Jesper L

    2016-01-01

    The validity of calculated NMR shifts to predict the outcome of electrophilic aromatic substitution reactions on different heterocyclic compounds has been examined. Based on an analysis of >130 literature examples it was found that the lowest calculated 13C and/or 1H chemical shift of a heterocycle...... correlates qualitatively with the regiochemical outcome of halogenation reactions in >80% of the investigated cases. In the remaining cases, the site of electrophilic aromatic substitution can be explained by the calculated HOMO orbitals obtained using density functional theory. Using a combination...

  2. Apparatus for washing out halogens

    Energy Technology Data Exchange (ETDEWEB)

    Pier, M; Hahn, J; Kroenig, W

    1941-03-26

    An apparatus is described for washing out of halogens and the like or liquid halogen compounds from the products, which are formed on pressure hydrogenation or splitting of carbon-containing material in the presence of halogens or halogen compounds, consisting of a washing apparatus installed between the reaction vessel and the hot separator, which is inclined in relatively small space for steam regulation and contains, with the steam, arranged baffles, especially spirals.

  3. A copper-mediated reverse aromatic Finkelstein reaction in ionic liquid

    Directory of Open Access Journals (Sweden)

    Anh T.H. Nguyen

    2018-03-01

    Full Text Available We have developed a general method for reverse aromatic Finkelstein reactions. Good reaction yields were obtained when aryl iodides or aryl bromides were treated with copper halide salts as promoters in a 1-butyl-3-methylimidazolium bromide ([BMIM]Br ionic liquid (IL solvent at 140 °C for 8 h. Preliminary investigation supported that the copper salts were also the halide sources in halogen exchange reactions. The optimized conditions are applicable to a variety of substrates and have excellent functional group tolerance. Additionally, the [BMIM]Br solvent showed good stability for at least 10 consecutive runs. Results indicated that the [BMIM]Br solvent was recyclable for reverse aromatic Finkelstein reactions.

  4. Decomposition of halogenated organic chemicals in ionic liquid by ionizing radiation

    International Nuclear Information System (INIS)

    Kimura, A.; Taguchi, M.; Kojima, T.; Nagaishi, R.; Hiratsuka, H.

    2006-01-01

    as electron scavenger under γ-ray irradiation. CP in RTILs, therefore, is considered to be reduced to phenol by solvated electron. Formation yields of phenol estimated by the ratios of G(Phenol)/G(-CP) are 17 to 82% in the alcohols, which differ by the position of chlorine on aromatic ring. On the contrary, the yields are 66% to 73% in RTILs for all types of CP. Dimers of CP were observed after irradiation in methanol but not in RTILs. These results can be explained in terms of the stabilization of solvated electron and the cage effect related to high polarity and high viscosity of RTIL, leading the longer lifetime of solvated electron. Decompositions of CP were investigated in aromatic RTILs having different viscosity. Both G(-CP) and G(Phenol) in aromatic RTILs was lower than those in alphatic ones. Decomposition of CP, therefore, is suppressed by the aromatic group scavenging the solvated electron. The G(Phenol) increased in ascending order of their viscosities.. Advanced reduction technique combined ionizing radiation with RTILs should be a promising method for halogenated organic chemicals treatment. (authors)

  5. Genetic architecture of evolved tolerance to PCBs in the estuarine fish Fundulus heteroclitus

    Science.gov (United States)

    Populations of Atlantic killifish (F. heteroclitus) resident to coastal estuarine habitats contaminated with halogenated aromatic hydrocarbons (HAHs) exhibit heritable resistance to the early life-stage toxicity associated with these compounds. Beyond our knowledge of the aryl hy...

  6. Is halogen content the most important factor in the removal of halogenated trace organics by MBR treatment?

    Science.gov (United States)

    Hai, Faisal I; Tadkaew, Nichanan; McDonald, James A; Khan, Stuart J; Nghiem, Long D

    2011-05-01

    This study investigated the relationship between physicochemical properties (namely halogen content and hydrophobicity) of halogenated trace organics and their removal efficiencies by a laboratory scale membrane bioreactor (MBR) under stable operating conditions. The reported results demonstrated a combined effect of halogen content and hydrophobicity on the removal. Compounds with high halogen content (>0.3) were well removed (>85%) when they possessed high hydrophobicity (Log D>3.2), while those with lower Log D values were also well removed if they had low halogen content (BIOWIN index (which is based on only biodegradation) or a more specific index such as the halogen content (which captures a chemical aspect) appeared insufficient to predict the removal efficiency of halogenated compounds in MBR. Experimental data confirmed that the ratio of halogen content and Log D, which incorporates two important physico-chemical properties, is comparatively more suitable. Copyright © 2011 Elsevier Ltd. All rights reserved.

  7. The Influence of Multiwalled Carbon Nanotubes on Polycyclic Aromatic Hydrocarbon (PAH) Bioavailability and Toxicity to Soil Microbial Communities in Alfalfa Rhizosphere

    Science.gov (United States)

    Carbon nanotubes (CNTs) may affect bioavailability and toxicity of organic contaminants due to their adsorption properties. Recent studies have observed the influence of multiwalled carbon nanotubes (MWNTs) on the fate of polycyclic aromatic hydrocarbons (PAHs) and other organic contaminants. Greenh...

  8. Estrogenicity of halogenated bisphenol A: in vitro and in silico investigations.

    Science.gov (United States)

    Zhang, Jie; Li, Tiezhu; Wang, Tuoyi; Yuan, Cuiping; Zhong, Shuning; Guan, Tianzhu; Li, Zhuolin; Wang, Yongzhi; Yu, Hansong; Luo, Quan; Wang, Yongjun; Zhang, Tiehua

    2018-03-01

    The binding interactions of bisphenol A (BPA) and its halogenated derivatives (halogenated BPAs) to human estrogen receptor α ligand binding domain (hERα-LBD) was investigated using a combined in vitro and in silico approach. First, the recombinant hERα-LBD was prepared as a soluble protein in Escherichia coli BL21(DE3)pLysS. A native fluorescent phytoestrogen, coumestrol, was employed as tracer for the fluorescence polarization assay. The results of the in vitro binding assay showed that bisphenol compounds could bind to hERα-LBD as the affinity ligands. All the tested halogenated BPAs exhibited weaker receptor binding than BPA, which might be explained by the steric effect of substituents. Molecular docking studies elucidated that the halogenated BPAs adopted different conformations in the flexible hydrophobic ligand binding pocket (LBP), which is mainly dependent on their distinct halogenation patterns. The compounds with halogen substituents on the phenolic rings and on the bridging alkyl moiety acted as agonists and antagonists for hERα, respectively. Interestingly, all the compounds in the agonist conformation of hERα formed a hydrogen bond with His524, while the compounds in the antagonist conformation formed a hydrogen bond with Thr347. These docking results suggested a pivotal role of His524/Thr347 in maintaining the hERα structure in the biologically active agonist/antagonist conformation. Comparison of the calculated binding energies vs. experimental binding affinities yielded a good correlation, which might be applicable for the structure-based design of novel bisphenol compounds with reduced toxicities and for environmental risk assessment. In addition, based on hERα-LBD as a recognition element, the proposed fluorescence polarization assay may offer an alternative to chromatographic techniques for the multi-residue determination of bisphenol compounds.

  9. The Effects of Water Spray Cooling in Conjunction with Halogenated Extinguishants on Hydrogen Fluoride Generation and Decay

    National Research Council Canada - National Science Library

    Burch, Ian

    2007-01-01

    The halogenated extinguishants Halon 1301, HFC-227ea (FM200) and NAF-S-III used within Royal Australian Navy vessels for total flooding fire suppression applications have hydrogen fluoride (HF) toxicity concerns...

  10. Halogenated arsenenes as Dirac materials

    International Nuclear Information System (INIS)

    Tang, Wencheng; Sun, Minglei; Ren, Qingqiang; Wang, Sake; Yu, Jin

    2016-01-01

    Highlights: • We have revealed the presence of Dirac cone in fully-halogenated arsenene compounds. • All fully-halogenated arsenene except As_2I_2 would spontaneously form and stable in defending the thermal fluctuation in room temperature. - Abstract: Arsenene is the graphene-like arsenic nanosheet, which has been predicted very recently [S. Zhang, Z. Yan, Y. Li, Z. Chen, and H. Zeng, Angewandte Chemie, 127 (2015) 3155–3158]. Using first-principles calculations, we systematically investigate the structures and electronic properties of fully-halogenated arsenenes. Formation energy analysis reveals that all the fully-halogenated arsenenes except iodinated arsenene are energetically favorable and could be synthesized. We have revealed the presence of Dirac cone in fully-halogenated arsenene compounds. They may have great potential applications in next generation of high-performance devices.

  11. Singlet oxygen production by combining erythrosine and halogen light for photodynamic inactivation of Streptococcus mutans.

    Science.gov (United States)

    Fracalossi, Camila; Nagata, Juliana Yuri; Pellosi, Diogo Silva; Terada, Raquel Sano Suga; Hioka, Noboru; Baesso, Mauro Luciano; Sato, Francielle; Rosalen, Pedro Luiz; Caetano, Wilker; Fujimaki, Mitsue

    2016-09-01

    Photodynamic inactivation of microorganisms is based on a photosensitizing substance which, in the presence of light and molecular oxygen, produces singlet oxygen, a toxic agent to microorganisms and tumor cells. This study aimed to evaluate singlet oxygen quantum yield of erythrosine solutions illuminated with a halogen light source in comparison to a LED array (control), and the photodynamic effect of erythrosine dye in association with the halogen light source on Streptococcus mutans. Singlet oxygen quantum yield of erythrosine solutions was quantified using uric acid as a chemical-probe in an aqueous solution. The in vitro effect of the photodynamic antimicrobial activity of erythrosine in association with the halogen photopolimerizing light on Streptococcus mutans (UA 159) was assessed during one minute. Bacterial cultures treated with erythrosine alone served as negative control. Singlet oxygen with 24% and 2.8% degradation of uric acid in one minute and a quantum yield of 0.59 and 0.63 was obtained for the erythrosine samples illuminated with the halogen light and the LED array, respectively. The bacterial cultures with erythrosine illuminated with the halogen light presented a decreased number of CFU mL(-1) in comparison with the negative control, with minimal inhibitory concentrations between 0.312 and 0.156mgmL(-1). The photodynamic response of erythrosine induced by the halogen light was capable of killing S. mutans. Clinical trials should be conducted to better ascertain the use of erythrosine in association with halogen light source for the treatment of dental caries. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Dissociative Photoionization of 1-Halogenated Silacyclohexanes: Silicon Traps the Halogen.

    Science.gov (United States)

    Bodi, Andras; Sigurdardottir, Katrin Lilja; Kvaran, Ágúst; Bjornsson, Ragnar; Arnason, Ingvar

    2016-11-23

    The threshold photoelectron spectra and threshold photoionization mass spectra of 1-halogenated-1-silacyclohexanes, for the halogens X = F, Cl, Br, and I, have been obtained using synchrotron vacuum ultraviolet radiation and photoelectron photoion coincidence spectroscopy. As confirmed by a similar ionization onset and density functional theory molecular orbitals, the ionization to the ground state is dominated by electron removal from the silacyclohexane ring for X = F, Cl, and Br, and from the halogen lone pair for X = I. The breakdown diagrams show that the dissociative photoionization mechanism is also different for X = I. Whereas the parent ions decay by ethylene loss for X = F to Br in the low-energy regime, the iodine atom is lost for X = I. The first step is followed by a sequential ethylene loss at higher internal energies in each of the compounds. It is argued that the tendency of silicon to lower bond angles stabilizes the complex cation in which C 2 H 4 is η 2 -coordinated to it, and which precedes ethylene loss. Together with the relatively strong silicon-halogen bonds and the increased inductive effect of the silacyclohexane ring in stabilizing the cation, this explains the main differences observed in the fragmentation of the halogenated silacyclohexane and halogenated cyclohexane ions. The breakdown diagrams have been modeled taking into account slow dissociations at threshold and the resulting kinetic shift. The 0 K appearance energies have been obtained to within 0.08 eV for the ethylene loss for X = F to Br (10.56, 10.51, and 10.51 eV, respectively), the iodine atom loss for X = I (10.11 eV), the sequential ethylene loss for X = F to I (12.29, 12.01, 11.94, and 11.86 eV, respectively), and the minor channels of H loss for X = F (10.56 eV) and propylene loss in X = Cl (also at 10.56 eV). The appearance energies for the major channels likely correspond to the dissociative photoionization reaction energy.

  13. Organic halogen compounds and surface water pollution; Composti organoalogenati alifatici e contaminazione delle acque superficiali

    Energy Technology Data Exchange (ETDEWEB)

    Cocchioni, M.; Pellegrini, M. G.; Grappasonni, I.; Nacciarriti, L.; Bernacchia, G. [Camerino, Univ. (Italy). Dipt. di Scienze Igienistiche e Sanitarie-Ambientali

    1997-03-01

    A brief review of the effects of halogenated organic compounds on the fluvial ecosystem is followed by results from a detailed monitoring of these substances in all the Marches Region rivers. The results show generally modest concentrations, except for sporadic peaks for chloroform. Sites revealing significant concentrations of halogenated organic compounds also manifested a worsening of the biological quality of the waters with lessening of E.B.I. Attention is drawn to the negative effects of indiscriminate chlorination of purification plant outputs, as this practice often fails to resolve infective problems and in itself adds toxicity to the watercourse.

  14. Boiling points of halogenated ethanes: an explanatory model implicating weak intermolecular hydrogen-halogen bonding.

    Science.gov (United States)

    Beauchamp, Guy

    2008-10-23

    This study explores via structural clues the influence of weak intermolecular hydrogen-halogen bonds on the boiling point of halogenated ethanes. The plot of boiling points of 86 halogenated ethanes versus the molar refraction (linked to polarizability) reveals a series of straight lines, each corresponding to one of nine possible arrangements of hydrogen and halogen atoms on the two-carbon skeleton. A multiple linear regression model of the boiling points could be designed based on molar refraction and subgroup structure as independent variables (R(2) = 0.995, standard error of boiling point 4.2 degrees C). The model is discussed in view of the fact that molar refraction can account for approximately 83.0% of the observed variation in boiling point, while 16.5% could be ascribed to weak C-X...H-C intermolecular interactions. The difference in the observed boiling point of molecules having similar molar refraction values but differing in hydrogen-halogen intermolecular bonds can reach as much as 90 degrees C.

  15. Yellow phosphorus process to convert toxic chemicals to non-toxic products

    Science.gov (United States)

    Chang, S.G.

    1994-07-26

    The present invention relates to a process for generating reactive species for destroying toxic chemicals. This process first contacts air or oxygen with aqueous emulsions of molten yellow phosphorus. This contact results in rapid production of abundant reactive species such as O, O[sub 3], PO, PO[sub 2], etc. A gaseous or liquid aqueous solution organic or inorganic chemicals is next contacted by these reactive species to reduce the concentration of toxic chemical and result in a non-toxic product. The final oxidation product of yellow phosphorus is phosphoric acid of a quality which can be recovered for commercial use. A process is developed such that the byproduct, phosphoric acid, is obtained without contamination of toxic species in liquids treated. A gas stream containing ozone without contamination of phosphorus containing species is also obtained in a simple and cost-effective manner. This process is demonstrated to be effective for destroying many types of toxic organic, or inorganic, compounds, including polychlorinated biphenyls (PCB), aromatic chlorides, amines, alcohols, acids, nitro aromatics, aliphatic chlorides, polynuclear aromatic compounds (PAH), dyes, pesticides, sulfides, hydroxyamines, ureas, dithionates and the like. 20 figs.

  16. Evidence for Interfacial Halogen Bonding.

    Science.gov (United States)

    Swords, Wesley B; Simon, Sarah J C; Parlane, Fraser G L; Dean, Rebecca K; Kellett, Cameron W; Hu, Ke; Meyer, Gerald J; Berlinguette, Curtis P

    2016-05-10

    A homologous series of donor-π-acceptor dyes was synthesized, differing only in the identity of the halogen substituents about the triphenylamine (TPA; donor) portion of each molecule. Each Dye-X (X=F, Cl, Br, and I) was immobilized on a TiO2 surface to investigate how the halogen substituents affect the reaction between the light-induced charge-separated state, TiO2 (e(-) )/Dye-X(+) , with iodide in solution. Transient absorption spectroscopy showed progressively faster reactivity towards nucleophilic iodide with more polarizable halogen substituents: Dye-F < Dye-Cl < Dye-Br < Dye-I. Given that all other structural and electronic properties for the series are held at parity, with the exception of an increasingly larger electropositive σ-hole on the heavier halogens, the differences in dye regeneration kinetics for Dye-Cl, Dye-Br, and Dye-I are ascribed to the extent of halogen bonding with the nucleophilic solution species. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Tropospheric Halogen Chemistry

    Science.gov (United States)

    von Glasow, R.; Crutzen, P. J.

    2003-12-01

    Halogens are very reactive chemicals that are known to play an important role in anthropogenic stratospheric ozone depletion chemistry, first recognized by Molina and Rowland (1974). However, they also affect the chemistry of the troposphere. They are of special interest because they are involved in many reaction cycles that can affect the oxidation power of the atmosphere indirectly by influencing the main oxidants O3 and its photolysis product OH and directly, e.g., by reactions of the Cl radical with hydrocarbons (e.g., CH4).Already by the middle of the nineteenth century, Marchand (1852) reported the presence of bromine and iodine in rain and other natural waters. He also mentions the benefits of iodine in drinking water through the prevention of goitres and cretinism. In a prophetic monograph "Air and Rain: The Beginnings of a Chemical Climatology," Smith (1872) describes measurements of chloride in rain water, which he states to originate partly from the oceans by a process that he compares with the bursting of "soap bubbles" which produces "small vehicles" that transfer small spray droplets of seawater to the air. From deviations of the sulfate-to-chloride ratio in coastal rain compared to seawater, Smith concluded that chemical processes occur once the particles are airborne.For almost a century thereafter, however, atmospheric halogens received little attention. One exception was the work by Cauer (1939), who reported that iodine pollution has been significant in Western and Central Europe due to the inefficient burning of seaweed, causing mean gas phase atmospheric concentrations as high as or greater than 0.5 μg m-3. In his classical textbook Air Chemistry and Radioactivity, Junge (1963) devoted less than three pages to halogen gas phase chemistry, discussing chlorine and iodine. As reviewed by Eriksson (1959a, b), the main atmospheric source of halogens is sea salt, derived from the bursting of bubbles of air which are produced by ocean waves and other

  18. Modulation of human α4β2 nicotinic acetylcholine receptors by brominated and halogen-free flame retardants as a measure for in vitro neurotoxicity

    NARCIS (Netherlands)

    Hendriks, H.S.; van Kleef, R.G.D.M.; Westerink, R.H.S.

    2012-01-01

    Brominated flame retardants (BFRs) are abundant persistent organic pollutants with well-studied toxicity. The toxicological and ecological concern associated with BFRs argues for replacement by safer alternatives. However, the (neuro)toxic potential of alternative halogen-free flame retardants

  19. Halogen bond: a long overlooked interaction.

    Science.gov (United States)

    Cavallo, Gabriella; Metrangolo, Pierangelo; Pilati, Tullio; Resnati, Giuseppe; Terraneo, Giancarlo

    2015-01-01

    Because of their high electronegativity, halogen atoms are typically considered, in most of their derivatives, as sites of high electron density and it is commonly accepted that they can form attractive interactions by functioning as the electron donor site (nucleophilic site). This is the case when they work as hydrogen bond acceptor sites. However, the electron density in covalently bound halogens is anisotropically distributed. There is a region of higher electron density, accounting for the ability of halogens to function as electron donor sites in attractive interactions, and a region of lower electron density where the electrostatic potential is frequently positive (mainly in the heavier halogens). This latter region is responsible for the ability of halogen atoms to function as the electron-acceptor site (electrophilic site) in attractive interactions formed with a variety of lone pair-possessing atoms, anions, and π-systems. This ability is quite general and is shown by a wide diversity of halogenated compounds (e.g., organohalogen derivatives and dihalogens). According to the definition proposed by the International Union of Pure and Applied Chemistry, any attractive interactions wherein the halogen atom is the electrophile is named halogen bond (XB). In this chapter, it is discussed how the practice and the concept of XB developed and a brief history of the interaction is presented. Papers (either from the primary or secondary literature) which have reported major experimental findings in the field or which have given important theoretical contributions for the development of the concept are recollected in order to trace how a unifying and comprehensive categorization emerged encompassing all interactions wherein halogen atoms function as the electrophilic site.

  20. Assessment of the toxicity of a substance under Canadian environmental protection act, a case study. Polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Nadon, B.; Germain, A.; Coillie, R. van [Environment Canada, Montreal (Canada)

    1995-12-31

    The Canadian Environmental Protection Act (CEPA) proclaimed in 1988 requires the Canadian Ministers of the Environment and of National Health and Welfare to assess the toxicity of different substances. A Priority Substances List containing 44 substances was developed and their assessments had to determine if they were `toxic`, according to the CEPA definition. This definition states that `a substance is toxic if it is entering or may enter the environment in a quantity or concentration or under conditions (a) having or that may have an immediate or long-term harmful effect on the environment, (b) constituting or that may constitute a danger to the environment on which human life depends; or (c) constituting or that may constitute a danger in Canada to human life of health.` This presentation use the assessment of the polycyclic aromatic hydrocarbons (PAHs) as an example of this procedure. (author)

  1. Assessment of the toxicity of a substance under Canadian environmental protection act, a case study. Polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Nadon, B; Germain, A; Coillie, R van [Environment Canada, Montreal (Canada)

    1996-12-31

    The Canadian Environmental Protection Act (CEPA) proclaimed in 1988 requires the Canadian Ministers of the Environment and of National Health and Welfare to assess the toxicity of different substances. A Priority Substances List containing 44 substances was developed and their assessments had to determine if they were `toxic`, according to the CEPA definition. This definition states that `a substance is toxic if it is entering or may enter the environment in a quantity or concentration or under conditions (a) having or that may have an immediate or long-term harmful effect on the environment, (b) constituting or that may constitute a danger to the environment on which human life depends; or (c) constituting or that may constitute a danger in Canada to human life of health.` This presentation use the assessment of the polycyclic aromatic hydrocarbons (PAHs) as an example of this procedure. (author)

  2. Halogen bonding in solution: thermodynamics and applications.

    Science.gov (United States)

    Beale, Thomas M; Chudzinski, Michael G; Sarwar, Mohammed G; Taylor, Mark S

    2013-02-21

    Halogen bonds are noncovalent interactions in which covalently bound halogens act as electrophilic species. The utility of halogen bonding for controlling self-assembly in the solid state is evident from a broad spectrum of applications in crystal engineering and materials science. Until recently, it has been less clear whether, and to what extent, halogen bonding could be employed to influence conformation, binding or reactivity in the solution phase. This tutorial review summarizes and interprets solution-phase thermodynamic data for halogen bonding interactions obtained over the past six decades and highlights emerging applications in molecular recognition, medicinal chemistry and catalysis.

  3. Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms

    Directory of Open Access Journals (Sweden)

    J. Ofner

    2012-07-01

    Full Text Available Reactive halogen species (RHS, such as X·, X2 and HOX containing X = chlorine and/or bromine, are released by various sources like photo-activated sea-salt aerosol or from salt pans, and salt lakes. Despite many studies of RHS reactions, the potential of RHS reacting with secondary organic aerosol (SOA and organic aerosol derived from biomass-burning (BBOA has been neglected. Such reactions can constitute sources of gaseous organohalogen compounds or halogenated organic matter in the tropospheric boundary layer and can influence physicochemical properties of atmospheric aerosols.

    Model SOA from α-pinene, catechol, and guaiacol was used to study heterogeneous interactions with RHS. Particles were exposed to molecular chlorine and bromine in an aerosol smog-chamber in the presence of UV/VIS irradiation and to RHS, released from simulated natural halogen sources like salt pans. Subsequently, the aerosol was characterized in detail using a variety of physicochemical and spectroscopic methods. Fundamental features were correlated with heterogeneous halogenation, which results in new functional groups (FTIR spectroscopy, changes UV/VIS absorption, chemical composition (ultrahigh resolution mass spectroscopy (ICR-FT/MS, or aerosol size distribution. However, the halogen release mechanisms were also found to be affected by the presence of organic aerosol. Those interaction processes, changing chemical and physical properties of the aerosol are likely to influence e.g. the ability of the aerosol to act as cloud condensation nuclei, its potential to adsorb other gases with low-volatility, or its contribution to radiative forcing and ultimately the Earth's radiation balance.

  4. Biosynthesis of polybrominated aromatic organic compounds by marine bacteria

    Science.gov (United States)

    Agarwal, Vinayak; El Gamal, Abrahim A.; Yamanaka, Kazuya; Poth, Dennis; Kersten, Roland D.; Schorn, Michelle; Allen, Eric E.; Moore, Bradley S.

    2014-01-01

    Polybrominated diphenyl ethers (PBDEs) and polybrominated bipyrroles are natural products that bioaccumulate in the marine food chain. PBDEs have attracted widespread attention due to their persistence in the environment and potential toxicity to humans. However, the natural origins of PBDE biosynthesis are not known. Here we report marine bacteria as producers of PBDEs and establish a genetic and molecular foundation for their production that unifies paradigms for the elaboration of bromophenols and bromopyrroles abundant in marine biota. We provide biochemical evidence of marine brominase enzymes revealing decarboxylative-halogenation enzymology previously unknown among halogenating enzymes. Biosynthetic motifs discovered in our study were used to mine sequence databases to discover unrealized marine bacterial producers of organobromine compounds. PMID:24974229

  5. Organic halogens in landfill leachates

    DEFF Research Database (Denmark)

    Grøn, C.; Christensen, J. B.; Jensen, Dorthe Lærke

    2000-01-01

    Using a group parameter, total organic halogens (TOX), high TOX concentrations were found in leachates and leachate contaminated groundwaters at two Danish mixed sanitary and hazardous waste sites. With commonly used screening procedures for organic contaminants, the individual halogenated organi...

  6. Atmospheric polycyclic aromatic hydrocarbons in the urban environment: Occurrence, toxicity and source apportionment

    International Nuclear Information System (INIS)

    Mishra, Nitika; Ayoko, Godwin A.; Morawska, Lidia

    2016-01-01

    Polycyclic Aromatic Hydrocarbons (PAHs) represent a major class of toxic pollutants because of their carcinogenic and mutagenic characteristics. People living in urban areas are regularly exposed to PAHs because of abundance of their emission sources. Within this context, this study aimed to: (i) identify and quantify the levels of ambient PAHs in an urban environment; (ii) evaluate their toxicity; and (iii) identify their sources as well as the contribution of specific sources to measured concentrations. Sixteen PAHs were identified and quantified in air samples collected from Brisbane. Principal Component Analysis – Absolute Principal Component Scores (PCA-APCS) was used in order to conduct source apportionment of the measured PAHs. Vehicular emissions, natural gas combustion, petrol emissions and evaporative/unburned fuel were the sources identified; contributing 56%, 21%, 15% and 8% of the total PAHs emissions, respectively, all of which need to be considered for any pollution control measures implemented in urban areas. - Highlights: • PAHs represent a major group of outdoor air pollutants. • Concentration levels of PAHS in urban schools ranged from 1.2 to 38 ng/m"3. • PCA–APCS technique used to identify sources of PAHs and their contributions. • Vehicular emissions (56%) were found to be the prominent sources of PAHs.

  7. Biogeochemistry of Halogenated Hydrocarbons

    Science.gov (United States)

    Adriaens, P.; Gruden, C.; McCormick, M. L.

    2003-12-01

    Halogenated hydrocarbons originate from both natural and industrial sources. Whereas direct anthropogenic emissions to the atmosphere and biosphere are often easy to assess, particularly when they are tied to major industrial activities, the attribution of emissions to other human activities (e.g., biomass burning), diffuse sources (e.g., atmospheric discharge, run off), and natural production (e.g., soils, fungi, algae, microorganisms) are difficult to quantify. The widespread occurrence of both alkyl and aryl halides in groundwater, surface water, soils, and various trophic food chains, even those not affected by known point sources, suggests a substantial biogeochemical cycling of these compounds (Wania and Mackay, 1996; Adriaens et al., 1999; Gruden et al., 2003). The transport and reactive fate mechanisms controlling their reactivity are compounded by the differences in sources of alkyl-, aryl-, and complex organic halides, and the largely unknown impact of biogenic processes, such as enzymatically mediated halogenation of organic matter, fungal production of halogenated hydrocarbons, and microbial or abiotic transformation reactions (e.g., Asplund and Grimvall, 1991; Gribble, 1996; Watling and Harper, 1998; Oberg, 2002). The largest source may be the natural halogenation processes in the terrestrial environment, as the quantities detected often exceed the amount that can be explained by human activities in the surrounding areas ( Oberg, 1998). Since biogeochemical processes result in the distribution of a wide range of halogenated hydrocarbon profiles, altered chemical structures, and isomer distributions in natural systems, source apportionment (or environmental forensics) can often only be resolved using multivariate statistical methods (e.g., Goovaerts, 1998; Barabas et al., 2003; Murphy and Morrison, 2002).This chapter will describe the widespread occurrence of halogenated hydrocarbons, interpret their distribution and biogeochemical cycling in light of

  8. Studies on halogen quenching through the Stern-Volmer plot

    International Nuclear Information System (INIS)

    Takiue, Makoto; Ishikawa, Hiroaki.

    1978-01-01

    The quenching effect for halogenated benzenes, methanes and ethanes have been investigated. The halogen quenching was accurately measured using the internal conversion electrons emitted from 113 Sn-sup(113m)In. From the quenching constants determined by the Stern-Volmer plots with respect to various halogen quenchers, the following results have been obtained. (1) The quenching constants increase with the number of halogen substituents, so as linearly in halogenated benzenes and exponentially in halogenated methanes and ethanes. Even the isomers of halogenides have different quenching constants. (2) There is a linearity between logarithm of the quenching constant and a polarographic half-wave reduction potential. (3) Electron excitation provides larger quenching constants than UV excitation for halogenated methanes. Based on these results, the mechanism of halogen quenching have been discussed in connection with the exciplex formation. (auth.)

  9. Independent Evolution of Six Families of Halogenating Enzymes.

    Science.gov (United States)

    Xu, Gangming; Wang, Bin-Gui

    2016-01-01

    Halogenated natural products are widespread in the environment, and the halogen atoms are typically vital to their bioactivities. Thus far, six families of halogenating enzymes have been identified: cofactor-free haloperoxidases (HPO), vanadium-dependent haloperoxidases (V-HPO), heme iron-dependent haloperoxidases (HI-HPO), non-heme iron-dependent halogenases (NI-HG), flavin-dependent halogenases (F-HG), and S-adenosyl-L-methionine (SAM)-dependent halogenases (S-HG). However, these halogenating enzymes with similar biological functions but distinct structures might have evolved independently. Phylogenetic and structural analyses suggest that the HPO, V-HPO, HI-HPO, NI-HG, F-HG, and S-HG enzyme families may have evolutionary relationships to the α/β hydrolases, acid phosphatases, peroxidases, chemotaxis phosphatases, oxidoreductases, and SAM hydroxide adenosyltransferases, respectively. These halogenating enzymes have established sequence homology, structural conservation, and mechanistic features within each family. Understanding the distinct evolutionary history of these halogenating enzymes will provide further insights into the study of their catalytic mechanisms and halogenation specificity.

  10. Bio-Based Aromatic Epoxy Monomers for Thermoset Materials

    Directory of Open Access Journals (Sweden)

    Feifei Ng

    2017-01-01

    Full Text Available The synthesis of polymers from renewable resources is a burning issue that is actively investigated. Polyepoxide networks constitute a major class of thermosetting polymers and are extensively used as coatings, electronic materials, adhesives. Owing to their outstanding mechanical and electrical properties, chemical resistance, adhesion, and minimal shrinkage after curing, they are used in structural applications as well. Most of these thermosets are industrially manufactured from bisphenol A (BPA, a substance that was initially synthesized as a chemical estrogen. The awareness on BPA toxicity combined with the limited availability and volatile cost of fossil resources and the non-recyclability of thermosets implies necessary changes in the field of epoxy networks. Thus, substitution of BPA has witnessed an increasing number of studies both from the academic and industrial sides. This review proposes to give an overview of the reported aromatic multifunctional epoxide building blocks synthesized from biomass or from molecules that could be obtained from transformed biomass. After a reminder of the main glycidylation routes and mechanisms and the recent knowledge on BPA toxicity and legal issues, this review will provide a brief description of the main natural sources of aromatic molecules. The different epoxy prepolymers will then be organized from simple, mono-aromatic di-epoxy, to mono-aromatic poly-epoxy, to di-aromatic di-epoxy compounds, and finally to derivatives possessing numerous aromatic rings and epoxy groups.

  11. Characterization of halogenated DBPs and identification of new DBPs trihalomethanols in chlorine dioxide treated drinking water with multiple extractions.

    Science.gov (United States)

    Han, Jiarui; Zhang, Xiangru; Liu, Jiaqi; Zhu, Xiaohu; Gong, Tingting

    2017-08-01

    Chlorine dioxide (ClO 2 ) is a widely used alternative disinfectant due to its high biocidal efficiency and low-level formation of trihalomethanes and haloacetic acids. A major portion of total organic halogen (TOX), a collective parameter for all halogenated DBPs, formed in ClO 2 -treated drinking water is still unknown. A commonly used pretreatment method for analyzing halogenated DBPs in drinking water is one-time liquid-liquid extraction (LLE), which may lead to a substantial loss of DBPs prior to analysis. In this study, characterization and identification of polar halogenated DBPs in a ClO 2 -treated drinking water sample were conducted by pretreating the sample with multiple extractions. Compared to one-time LLE, the combined four-time LLEs improved the recovery of TOX by 2.3 times. The developmental toxicity of the drinking water sample pretreated with the combined four-time LLEs was 1.67 times higher than that pretreated with one-time LLE. With the aid of ultra-performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry, a new group of polar halogenated DBPs, trihalomethanols, were detected in the drinking water sample pretreated with multiple extractions; two of them, trichloromethanol and bromodichloromethanol, were identified with synthesized standard compounds. Moreover, these trihalomethanols were found to be the transformation products of trihalomethanes formed during ClO 2 disinfection. The results indicate that multiple LLEs can significantly improve extraction efficiencies of polar halogenated DBPs and is a better pretreatment method for characterizing and identifying new polar halogenated DBPs in drinking water. Copyright © 2017. Published by Elsevier B.V.

  12. QSTR with extended topochemical atom (ETA) indices. 14. QSAR modeling of toxicity of aromatic aldehydes to Tetrahymena pyriformis

    Energy Technology Data Exchange (ETDEWEB)

    Roy, Kunal, E-mail: kunalroy_in@yahoo.com [Drug Theoretics and Cheminformatics Laboratory, Division of Medicinal and Pharmaceutical Chemistry, Department of Pharmaceutical Technology, Jadavpur University, Kolkata 700 032 (India); Das, Rudra Narayan [Drug Theoretics and Cheminformatics Laboratory, Division of Medicinal and Pharmaceutical Chemistry, Department of Pharmaceutical Technology, Jadavpur University, Kolkata 700 032 (India)

    2010-11-15

    Aldehydes are a toxic class of chemicals causing severe health hazards. In this background, quantitative structure-toxicity relationship (QSTR) models have been developed in the present study using Extended Topochemical Atom (ETA) indices for a large group of 77 aromatic aldehydes for their acute toxicity against the protozoan ciliate Tetrahymena pyriformis. The ETA models have been compared with those developed using various non-ETA topological indices. Attempt was also made to include the n-octanol/water partition coefficient (log K{sub o/w}) as an additional descriptor considering the importance of hydrophobicity in toxicity prediction. Thirty different models were developed using different chemometric tools. All the models have been validated using internal validation and external validation techniques. The statistical quality of the ETA models was found to be comparable to that of the non-ETA models. The ETA models have shown the important effects of steric bulk, lipophilicity, presence of electronegative atom containing substituents and functionality of the aldehydic oxygen to the toxicity of the aldehydes. The best ETA model (without using log K{sub o/w}) shows encouraging statistical quality (Q{sub int}{sup 2}=0.709,Q{sub ext}{sup 2}=0.744). It is interesting to note that some of the topological models reported here are better in statistical quality than previously reported models using quantum chemical descriptors.

  13. Passivation of quartz for halogen-containing light sources

    Science.gov (United States)

    Falkenstein, Zoran

    1999-01-01

    Lifetime of halogen containing VUV, UV, visible or IR light sources can be extended by passivating the quartz or glass gas containers with halogens prior to filling the quartz with the halogen and rare gas mixtures used to produce the light.

  14. Role of the Ah locus in suppression of cytotoxic T lymphocyte activity by halogenated aromatic hydrocarbons (PCBs and TCDD): Structure-activity relationships and effects in C57Bl/6 mice congenic at the Ah locus

    International Nuclear Information System (INIS)

    Kerkvliet, N.I.; Baecher-Steppan, L.; Smith, B.B.; Youngberg, J.A.; Henderson, M.C.; Buhler, D.R.

    1990-01-01

    Previous studies have shown that the generation of cytotoxic T lymphocytes (CTL) following allogeneic tumor challenge is suppressed in Ah-responsive C57Bl/6 mice treated with a single oral dose of the toxic, Ah receptor-binding 3,4,5,3',4',5'-hexachlorobiphenyl (HxCB). The present studies have examined the specific role of the Ah receptor in this immunotoxic response by utilizing HxCB isomers of known, varied affinity for the Ah receptor as well as by comparing effects of high-affinity Ah receptor ligands (3,4,5,3',4',5'-HxCB and 2,3,7,8-tetrachlorodibenzo-p-dioxin [TCDD]) on the CTL response of mice that differ only at the Ah locus, that is, Ah-responsive (Ahbb) and Ah-nonresponsive (Ahdd) congenic C57Bl/6 mice. Correlative changes in thymic weight, serum corticosterone (CS) levels, and spleen cellularity were also measured. The potency of HxCB congeners (3,4,5,3',4',5'-; 2,3,4,5,3',4'-; 2,4,5,2',4',5'-) and 2,3,7,8-TCDD to suppress the CTL response, to reduce spleen cellularity, to cause thymic atrophy, and to elevate serum CS levels was directly correlated with the binding affinity of the congener for the Ah receptor. Furthermore, these parameters of immunotoxicity in Ahdd C57Bl/6 mice were significantly more resistant to alterations induced by either 3,4,5,3',4',5'-HxCB or 2,3,7,8-TCDD as compared to Ahbb C57Bl/6 mice. These results strongly support an Ah receptor-dependent immunotoxic mechanism in suppression of the CTL response following acute exposure to halogenated aromatic hydrocarbons

  15. METHOD FOR PRODUCING ISOTOPIC METHANES AND PARTIALLY HALOGENATED DERIVATIVES THEROF

    Science.gov (United States)

    Frazer, J.W.

    1959-08-18

    A method is given for producing isotopic methanes and/ or partially halogenated derivatives. Lithium hydride, deuteride, or tritide is reacted with a halogenated methane or with a halogenated methane in combination with free halogen. The process is conveniently carried out by passing a halogenated methane preferably at low pressures or in an admixture with an inert gas through a fixed bed of finely divided lithium hydride heated initially to temperatures of 100 to 200 deg C depending upon the halogenated methane used.

  16. Organic halogens in spruce forest throughfall

    DEFF Research Database (Denmark)

    Öberg, G.; Johansen, C.; Grøn, C.

    1998-01-01

    . No relationship between the position of the collectors and the forest edge or dominating wind-direction was found, suggesting that dry deposition was not a major source. The concentration of organic halogens was related to that of organic carbon and decreased from the tree-trunk and outwards. In addition......, the concentrations were higher during the growing season than during the dormant season. This indicates that the major part of the organic carbon and organic halogens in spruce forest throughfall originates from canopy leachates or other internal sources. (C) 1998 Elsevier Science Ltd.......Deposition of dissolved organic halogens by throughfall was determined in a small spruce forest site in Denmark (56 degrees 28'N, 8 degrees 24'E). The mean annual deposition of dissolved organic halogens was 377 g ha(-1)yr(-1), and larger than the general deposition by precipitation...

  17. New Type of Halogen Bond: Multivalent Halogen Interacting with π- and σ-Electrons

    Directory of Open Access Journals (Sweden)

    Sławomir J. Grabowski

    2017-12-01

    Full Text Available MP2/aug-cc-pVTZ calculations were performed for complexes of BrF3 and BrF5 acting as Lewis acids through the bromine centre, with species playing a role of Lewis base: dihydrogen, acetylene, ethylene, and benzene. The molecular hydrogen donates electrons by its σ-bond, while in remaining moieties—in complexes of hydrocarbons; such an electron transfer follows from π-electrons. The complexes are linked by a kind of the halogen bond that is analyzed for the first time in this study, i.e., it is the link between the multivalent halogen and π or σ-electrons. The nature of such a halogen bond is discussed, as well as various dependencies and correlations are presented. Different approaches are applied here, the Quantum Theory of Atoms in Molecules, Natural Bond Orbital method, the decomposition of the energy of interaction, the analysis of electrostatic potentials, etc.

  18. Survey of benzene and aromatics in Canadian Gasoline - 1994

    International Nuclear Information System (INIS)

    Tushingham, M.

    1996-01-01

    A comprehensive database of the benzene and aromatics levels of gasoline produced in or imported into Canada during 1994, was presented. Environment Canada conducted a survey that requested refineries and importers to report quarterly on benzene and aromatics levels in gasoline. Benzene, which has been declared toxic by the Canadian Environmental Protection Act, is found in gasoline and is formed during the combustion of the aromatic components of gasoline. It was shown that benzene and aromatics levels differ regionally and seasonally. There are also variations in benzene levels between batches of gasoline produced at any one refinery. This report listed the responses to the benzene/aromatics survey. It also described the analytical procedures used to measure benzene and aromatics levels in gasoline, and provided guidelines for reporting gasoline benzene and total aromatics data. 7 tabs., 21 figs

  19. Experimental and computational evidence of halogen bonds involving astatine

    Science.gov (United States)

    Guo, Ning; Maurice, Rémi; Teze, David; Graton, Jérôme; Champion, Julie; Montavon, Gilles; Galland, Nicolas

    2018-03-01

    The importance of halogen bonds—highly directional interactions between an electron-deficient σ-hole moiety in a halogenated compound and an acceptor such as a Lewis base—is being increasingly recognized in a wide variety of fields from biomedicinal chemistry to materials science. The heaviest halogens are known to form stronger halogen bonds, implying that if this trend continues down the periodic table, astatine should exhibit the highest halogen-bond donating ability. This may be mitigated, however, by the relativistic effects undergone by heavy elements, as illustrated by the metallic character of astatine. Here, the occurrence of halogen-bonding interactions involving astatine is experimentally evidenced. The complexation constants of astatine monoiodide with a series of organic ligands in cyclohexane solution were derived from distribution coefficient measurements and supported by relativistic quantum mechanical calculations. Taken together, the results show that astatine indeed behaves as a halogen-bond donor—a stronger one than iodine—owing to its much more electrophilic σ-hole.

  20. Transition from metal-ligand bonding to halogen bonding involving a metal as halogen acceptor a study of Cu, Ag, Au, Pt, and Hg complexes

    Science.gov (United States)

    Oliveira, Vytor; Cremer, Dieter

    2017-08-01

    Utilizing all-electron Dirac-exact relativistic calculations with the Normalized Elimination of the Small Component (NESC) method and the local vibrational mode approach, the transition from metal-halide to metal halogen bonding is determined for Au-complexes interacting with halogen-donors. The local stretching force constants of the metal-halogen interactions reveal a smooth transition from weak non-covalent halogen bonding to non-classical 3-center-4-electron bonding and finally covalent metal-halide bonding. The strongest halogen bonds are found for dialkylaurates interacting with Cl2 or FCl. Differing trends in the intrinsic halogen-metal bond strength, the binding energy, and the electrostatic potential are explained.

  1. Photoinduced toxicity of three polycyclic aromatic hydrocarbons (fluoranthene, pyrene, and naphthalene) to the duckweed Lemna gibba L. G-3

    International Nuclear Information System (INIS)

    Ren, L.; Huang, X.D.; McConkey, B.J.; Dixon, D.G.; Greenberg, B.M.

    1994-01-01

    The authors recently demonstrated that light dramatically enhances the hazards of three polycyclic aromatic hydrocarbons (PAHs), anthracene, phenanthrene, and benzo[a]pyrene, to the duckweed Lemna gibba L. G-3 (X.-D. Huang, D. G. Dixon, and B. M. Greenberg, 1993, Environ. Toxicol. Chem., 12, 1067-1077). To extend this research, growth and chlorosis were used as end points to assess the photoinduced toxicity of three additional PAHs, fluoranthene, pyrene, and naphthalene, to L. gibba in the presence of simulated solar radiation (a light source with a UV-B: UV-A:visible light ratio equivalent to that of sunlight). The phytotoxicity of these three PAHs was photoactivated, with ultraviolet radiation being the only spectral region that enhanced the harmful effects of the chemicals. Dose-response curves based on chemical concentration and light intensity revealed that the order of phytotoxic strength was fluoranthene > pyrene > naphthalene. To explore whether photomodification (in addition to photosensitization) of fluoranthene, pyrene, and naphthalene could contribute to photoinduced toxicity, the chemicals were irradiated prior to (as opposed to simultaneously with) application to the plans. The rates of photomodification of the three PAHs were rapid enough for the photooxidized compounds to contribute to toxicity, and the photomodified PAHs were more toxic than the parent compounds. As well, toxicity could be correlated to photomodification; impacts increased in parallel with the extent of photomodification

  2. The halogen bond: Nature and applications

    Science.gov (United States)

    Costa, Paulo J.

    2017-10-01

    The halogen bond, corresponding to an attractive interaction between an electrophilic region in a halogen (X) and a nucleophile (B) yielding a R-X⋯B contact, found applications in many fields such as supramolecular chemistry, crystal engineering, medicinal chemistry, and chemical biology. Their large range of applications also led to an increased interest in their study using computational methods aiming not only at understanding the phenomena at a fundamental level, but also to help in the interpretation of results and guide the experimental work. Herein, a succinct overview of the recent theoretical and experimental developments is given starting by discussing the nature of the halogen bond and the latest theoretical insights on this topic. Then, the effects of the surrounding environment on halogen bonds are presented followed by a presentation of the available method benchmarks. Finally, recent experimental applications where the contribution of computational chemistry was fundamental are discussed, thus highlighting the synergy between the lab and modeling techniques.

  3. Molecular activation analysis for organo-halogen contaminants in yogurt

    International Nuclear Information System (INIS)

    Zhang Hong; Chai Zhifang

    2004-01-01

    The concentrations of total halogen (TX), extractable organo-halogen (EOX), extractable persistent organo-halogen (EPOX), organo-chlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in 18 different yogurt specimens of 14 brands from Beijing, Tianjin, Shanghai, Guangzhou and Shijiazhuang were determined by epithermal neutron activation analysis (ENAA), molecular activation analysis (MAA) and GC-Mass Spectrometry (GC-MS), respectively. The results indicated that the halogen in yogurt mainly existed as inorganic species and non-extractable organo-halogen compounds. About 1/3 to 1/4 of EOX was EPOX. Further, EOCl and EPOCl were the main organo-halogen species in yogurt. The average concentration of the unknown organo-chlorine was 96% of the EPOCl. HCHs and DDTs were still the main contaminants of OCPs in the yogurt of interest. Also, PCB202, PCB103 and PCB208 were the main contaminants of PCBs. (authors)

  4. FIELD SCREENING FOR HALOGENATED VOLATILE ORGANIC COMPOUNDS

    Energy Technology Data Exchange (ETDEWEB)

    John F. Schabron; Joseph F. Rovani Jr.; Theresa M. Bomstad

    2002-06-01

    Western Research Institute (WRI) initiated exploratory work towards the development of new field screening methodology and a test kit to measure halogenated volatile organic compounds (VOCs) in the field. Heated diode and corona discharge sensors are commonly used to detect leaks of refrigerants from air conditioners, freezers, and refrigerators. They are both selective to the presence of carbon-halogen bonds. Commercially available heated diode and corona discharge leak detectors were procured and evaluated for halogenated VOC response. The units were modified to provide a digital readout of signal related to VOC concentration. Sensor response was evaluated with carbon tetrachloride and tetrachloroethylene (perchloroethylene, PCE), which represent halogenated VOCs with and without double bonds. The response characteristics were determined for the VOCs directly in headspace in Tedlar bag containers. Quantitation limits in air were estimated. Potential interferences from volatile hydrocarbons, such as toluene and heptane, were evaluated. The effect of humidity was studied also. The performance of the new devices was evaluated in the laboratory by spiking soil samples and monitoring headspace for halogenated VOCs. A draft concept of the steps for a new analytical method was outlined. The results of the first year effort show that both devices show potential utility for future analytical method development work towards the goal of developing a portable test kit for screening halogenated VOCs in the field.

  5. Halogens in chondritic meteorites and terrestrial accretion

    Science.gov (United States)

    Clay, Patricia L.; Burgess, Ray; Busemann, Henner; Ruzié-Hamilton, Lorraine; Joachim, Bastian; Day, James M. D.; Ballentine, Christopher J.

    2017-11-01

    Volatile element delivery and retention played a fundamental part in Earth’s formation and subsequent chemical differentiation. The heavy halogens—chlorine (Cl), bromine (Br) and iodine (I)—are key tracers of accretionary processes owing to their high volatility and incompatibility, but have low abundances in most geological and planetary materials. However, noble gas proxy isotopes produced during neutron irradiation provide a high-sensitivity tool for the determination of heavy halogen abundances. Using such isotopes, here we show that Cl, Br and I abundances in carbonaceous, enstatite, Rumuruti and primitive ordinary chondrites are about 6 times, 9 times and 15-37 times lower, respectively, than previously reported and usually accepted estimates. This is independent of the oxidation state or petrological type of the chondrites. The ratios Br/Cl and I/Cl in all studied chondrites show a limited range, indistinguishable from bulk silicate Earth estimates. Our results demonstrate that the halogen depletion of bulk silicate Earth relative to primitive meteorites is consistent with the depletion of lithophile elements of similar volatility. These results for carbonaceous chondrites reveal that late accretion, constrained to a maximum of 0.5 ± 0.2 per cent of Earth’s silicate mass, cannot solely account for present-day terrestrial halogen inventories. It is estimated that 80-90 per cent of heavy halogens are concentrated in Earth’s surface reservoirs and have not undergone the extreme early loss observed in atmosphere-forming elements. Therefore, in addition to late-stage terrestrial accretion of halogens and mantle degassing, which has removed less than half of Earth’s dissolved mantle gases, the efficient extraction of halogen-rich fluids from the solid Earth during the earliest stages of terrestrial differentiation is also required to explain the presence of these heavy halogens at the surface. The hydropilic nature of halogens, whereby they track

  6. Organic halogen compounds in the environment

    International Nuclear Information System (INIS)

    1979-07-01

    There are 20 research reports on selected problems concerning the analysis, the occurence, and the behaviour of a wide spectrum of organic halogen compounds. The work was carried out in the framework of the project 'Organic Halogen Compounds in the Environment', financed by the BMFT, between 1975 and 1978. (orig.) [de

  7. Base catalyzed decomposition of toxic and hazardous chemicals

    International Nuclear Information System (INIS)

    Rogers, C.J.; Kornel, A.; Sparks, H.L.

    1991-01-01

    There are vast amounts of toxic and hazardous chemicals, which have pervaded our environment during the past fifty years, leaving us with serious, crucial problems of remediation and disposal. The accumulation of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), ''dioxins'' and pesticides in soil sediments and living systems is a serious problem that is receiving considerable attention concerning the cancer-causing nature of these synthetic compounds.US EPA scientists developed in 1989 and 1990 two novel chemical Processes to effect the dehalogenation of chlorinated solvents, PCBs, PCDDs, PCDFs, PCP and other pollutants in soil, sludge, sediment and liquids. This improved technology employs hydrogen as a nucleophile to replace halogens on halogenated compounds. Hydrogen as nucleophile is not influenced by steric hinderance as with other nucleophile where complete dehalogenation of organohalogens can be achieved. This report discusses catalyzed decomposition of toxic and hazardous chemicals

  8. Continuous flow bioassay method to evaluate the effects of outboard motor exhausts and selected aromatic toxicants on fish. [Carassius auratus

    Energy Technology Data Exchange (ETDEWEB)

    Brenniman, G. (Univ. of Illinois, Chicago); Hartung, R.; Weber, W.J. Jr.

    1976-01-01

    A continuous flow bioassay system was designed to measure the effects of outboard motor exhaust (OME) emissions and selected volatile and evaporative aromatic toxicants on goldfish (Carassius auratus). Continuous flow bioassays were run for 24, 48, 72, 96, and 720 h to determine lethal concentrations for 50 percent of individuals (LC 50's) for leaded OME, non-leaded OME, toluene, xylene, and 1,3,5 trimethylbenzene, the three individual compounds having been identified as significant aromatic components of OME. The 96 h LC-50's for these substances were found to be 171, 168, 23, 17, and 13 ppm, respectively. The values of 171 and 168 ppm for the two OME's are given in terms of gallons of fuel burned per million gallons of water. The continuous flow bioassay method was demonstrated to be a more reliable indicator of the effects of OME pollutants on aquatic organisms than is the static bioassay method.

  9. Assessment of the radiation resistance of some aromatic polyesters

    International Nuclear Information System (INIS)

    Choi, E.J.; Hill, D.J.T.; Kim, K.Y.

    1998-01-01

    Full text: For many applications, polyesters have more useful properties than vinyl polymers, and they can be degraded to their monomer components and recycled. In addition, aromatic polyesters are known to display a resistance to high temperatures and high-energy ionizing radiation. Recently, we have reported the γ-radiolysis for some aromatic polyesters at low radiation dose; The G-values of radical formation at 77 K were determined to be in the range 0.38∼0.46 for the polyesters of bisphenol A with fluorine substitution at isopropylidene units and in the range 0.71∼1.18 for the polyesters of halogenated bisphenol A with decamethylene segments. While the radiation sensitivities of the latter polymers were dependent on the position and content of halogen substitution, those of the former polymers were slightly dependent on these factors as assessed by the G-values at 77 K. We also have studied the radiolysis of the commercial aromatic polyesters (UP) and polycarbonate (PC). UP has been found to be more radiation stable than PC with respect to the total yield of radicals formed. The G-values for radical formation at 77K was determined to be 0.31 and 0.5 for UP and PC, respectively. In this work, we have prepared poly(ethylene-, butylene- or decalene-terephthalate)s (PET, PBT or PDT) and poly(ethylene-, buthylene- or decalene-2,6-naphthalenedicarboxylate)s (PEN, PBN or PDN) by standard melt polymerization methods, and have examined their γ-radiolysis at 77 K or room temperature, and in vacuum or air, through the applications of ESR spectroscopy and thermal analysis. Inherent viscosities of the polyesters used for the radiation studies were in the range of 0.16∼0.69 dL/g. The values of G(R) indicates that PEN-related polymers have more radiation stable than PET-related polymers and the E, B and D order is one of decreasing stability as one might expect. The significant decrease in the G(R)-values of the polyester being in the range of 0.1∼0.41 at 77 K by

  10. Process for removal of hydrogen halides or halogens from incinerator gas

    Science.gov (United States)

    Huang, H.S.; Sather, N.F.

    1987-08-21

    A process for reducing the amount of halogens and halogen acids in high temperature combustion gas and through their removal, the formation of halogenated organics at lower temperatures, with the reduction being carried out electrochemically by contacting the combustion gas with the negative electrode of an electrochemical cell and with the halogen and/or halogen acid being recovered at the positive electrode.

  11. Polycyclic aromatic hydrocarbons (PAHs) degradation by laccase ...

    African Journals Online (AJOL)

    PRECIOUS

    2009-11-02

    Nov 2, 2009 ... Full Length Research Paper. Polycyclic aromatic ... production of paper, feeds, chemicals and fuels there is ... microbes with the production of lignin-modifying enzymes ... enable white rot fungi to degrade a variety of toxic.

  12. Computational Tools To Model Halogen Bonds in Medicinal Chemistry.

    Science.gov (United States)

    Ford, Melissa Coates; Ho, P Shing

    2016-03-10

    The use of halogens in therapeutics dates back to the earliest days of medicine when seaweed was used as a source of iodine to treat goiters. The incorporation of halogens to improve the potency of drugs is now fairly standard in medicinal chemistry. In the past decade, halogens have been recognized as direct participants in defining the affinity of inhibitors through a noncovalent interaction called the halogen bond or X-bond. Incorporating X-bonding into structure-based drug design requires computational models for the anisotropic distribution of charge and the nonspherical shape of halogens, which lead to their highly directional geometries and stabilizing energies. We review here current successes and challenges in developing computational methods to introduce X-bonding into lead compound discovery and optimization during drug development. This fast-growing field will push further development of more accurate and efficient computational tools to accelerate the exploitation of halogens in medicinal chemistry.

  13. Contribution to the study of radio toxicity of aromatic and medicinal plants using solid state nuclear track detectors

    International Nuclear Information System (INIS)

    Mortassim, A.; Misdaq, M.A.; Naaman, A

    2009-01-01

    The concentrations of uranium (238 U), thorium (232 Th), radon (222 Rn) and thoron (220 Rn) were measured in twenty aromatic and medicinal plants in f ind a new method based on using solid state nuclear track detectors type Cr-39 and Rs-115. He emerges from this study that the verbena and salvia have higher levels of uranium (radon) higher than that of other plants while the leaves of olive and saturja have concentrations of thorium (thoron) higher than other plants therefore radio toxicity of these plants is higher than that of others and may pose a radiological hazard if the masses are incorporated by consumers high. [fr

  14. Effects of sulfur and aromatic contents in gasoline on motorcycle emissions

    Science.gov (United States)

    Yao, Yung-Chen; Tsai, Jiun-Horng; Chang, An-Lin; Jeng, Fu-Tien

    By investigating the effect of sulfur and aromatic contents in gasoline on the criteria pollutant emissions [CO, total hydrocarbons (THCs), and NO x] and on air toxics in the exhaust from a non-catalyst four-stroke motorcycle engine, inferences can be made concerning the effect of fuel composition on motorcycle emissions. The fuels were blended with different contents of sulfur (40 and 150 ppmw) and aromatics (20 and 30 vol%). The data indicate that the sulfur content does not correlate with the emissions of the criteria pollutants from the catalyst free engine. Instead, lowering aromatic content in gasoline reduced the THC emission by over 30%, especially in the cruising test. The NO x emission, however, showed an inverse correlation with the aromatic content in gasoline. While a reduction of aromatic content in gasoline may decrease emissions of benzene and toluene, it will increase the emission of aldehyde. Since the percentage changes of emission factor of THC and air toxics in the motorcycle were larger than those in passenger cars, the benefit of emission reduction due to fuel composition changes in motorcycles may have significant impacts in health risk analysis.

  15. Ozone Depletion in Tropospheric Volcanic Plumes: From Halogen-Poor to Halogen-Rich Emissions

    Directory of Open Access Journals (Sweden)

    Tjarda J. Roberts

    2018-02-01

    Full Text Available Volcanic halogen emissions to the troposphere undergo a rapid plume chemistry that destroys ozone. Quantifying the impact of volcanic halogens on tropospheric ozone is challenging, only a few observations exist. This study presents measurements of ozone in volcanic plumes from Kīlauea (HI, USA, a low halogen emitter. The results are combined with published data from high halogen emitters (Mt Etna, Italy; Mt Redoubt, AK, USA to identify controls on plume processes. Ozone was measured during periods of relatively sustained Kīlauea plume exposure, using an Aeroqual instrument deployed alongside Multi-Gas SO2 and H2S sensors. Interferences were accounted for in data post-processing. The volcanic H2S/SO2 molar ratio was quantified as 0.03. At Halema‘uma‘u crater-rim, ozone was close to ambient in the emission plume (at 10 ppmv SO2. Measurements in grounding plume (at 5 ppmv SO2 about 10 km downwind of Pu‘u ‘Ō‘ō showed just slight ozone depletion. These Kīlauea observations contrast with substantial ozone depletion reported at Mt Etna and Mt Redoubt. Analysis of the combined data from these three volcanoes identifies the emitted Br/S as a strong but non-linear control on the rate of ozone depletion. Model simulations of the volcanic plume chemistry highlight that the proportion of HBr converted into reactive bromine is a key control on the efficiency of ozone depletion. This underlines the importance of chemistry in the very near-source plume on the fate and atmospheric impacts of volcanic emissions to the troposphere.

  16. Retention of Halogenated Solutes on Stationary Phases Containing Heavy Atoms

    Directory of Open Access Journals (Sweden)

    Toshio Miwa

    2013-05-01

    Full Text Available To examine the effects of weak intermolecular interactions on solid-phase extraction (SPE and chromatographic separation, we synthesized some novel stationary phases with a heavy atom effect layer by immobilizing halogenated aromatic rings and hydroxyl groups onto the surface of a hydrophilic base polymer. Using SPE cartridges packed with the functionalized materials, we found that the heavy atom stationary phases could selectively retain halophenols in organic solvents, such as 1-propanol which blocks the hydrogen bonding, or acetonitrile which blocks the p-p interaction. The extraction efficiency of the materials toward the halophenols depended on the dipole moments of phenoxy groups present as functional groups. On the other hand, the extraction efficiency of solutes toward the functional group depended on their molar refractions, i.e., induced dipole moments. The retention of the solutes to the stationary phase ultimately depended on not only strong intermolecular interactions, but also the effects of weak interactions such as the dispersion force.

  17. Retention of Halogens in Waste Glass

    Energy Technology Data Exchange (ETDEWEB)

    Hrma, Pavel R.

    2010-05-01

    In spite of their potential roles as melting rate accelerators and foam breakers, halogens are generally viewed as troublesome components for glass processing. Of five halogens, F, Cl, Br, I, and At, all but At may occur in nuclear waste. A nuclear waste feed may contain up to 10 g of F, 4 g of Cl, and ≤100 mg of Br and I per kg of glass. The main concern is halogen volatility, producing hazardous fumes and particulates, and the radioactive iodine 129 isotope of 1.7x10^7-year half life. Because F and Cl are soluble in oxide glasses and tend to precipitate on cooling, they can be retained in the waste glass in the form of dissolved constituents or as dispersed crystalline inclusions. This report compiles known halogen-retention data in both high-level waste (HLW) and low-activity waste (LAW) glasses. Because of its radioactivity, the main focus is on I. Available data on F and Cl were compiled for comparison. Though Br is present in nuclear wastes, it is usually ignored; no data on Br retention were found.

  18. Study on the dynamics of halogen elements in the agro-environment and these element`s deficiency, toxicity and environmental hazards by the application of the neutron activation analysis method

    Energy Technology Data Exchange (ETDEWEB)

    Yuita, Kouichi [National Inst. of Agro-Environmental Sciences, Tsukuba, Ibaraki (Japan)

    1998-03-01

    A neutron activation analysis method is an accurate and highly sensitive method for analyzing halogen elements (iodine, bromine and chlorine) except fluorine. It is unsubstitutable and valuable method especially for iodine (including radioactive {sup 129}I) and bromine which are present at lower levels. Halogen elements have high chemical and physiological activities and move widely in the environment. As a result, deficiency and an excess of halogen elements in plants and animals have occurred and artificial halogen compounds have caused environmental pollution in wide areas. We efficiently utilized the neutron activation analysis method and an activable tracer method to obtain valuable findings which contribute to the clarification of and measures against these actual problems and which are also concerned with the occurrence, distribution and migration of halogen elements in the environment, especially agricultural and forestry ecosystems in space and in time. (author)

  19. Measurement and prediction of aromatic solute distribution coefficients for aqueous-organic solvent systems. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Campbell, J.R.; Luthy, R.G.

    1984-06-01

    Experimental and modeling activities were performed to assess techniques for measurement and prediction of distribution coefficients for aromatic solutes between water and immiscible organic solvents. Experiments were performed to measure distribution coefficients in both clean water and wastewater systems, and to assess treatment of a wastewater by solvent extraction. The theoretical portions of this investigation were directed towards development of techniques for prediction of solute-solvent/water distribution coefficients. Experiments were performed to assess treatment of a phenolic-laden coal conversion wastewater by solvent extraction. The results showed that solvent extraction for recovery of phenolic material offered several wastewater processing advantages. Distribution coefficients were measured in clean water and wastewater systems for aromatic solutes of varying functionality with different solvent types. It was found that distribution coefficients for these compounds in clean water systems were not statistically different from distribution coefficients determined in a complex coal conversion process wastewater. These and other aromatic solute distribution coefficient data were employed for evaluation of modeling techniques for prediction of solute-solvent/water distribution coefficients. Eight solvents were selected in order to represent various chemical classes: toluene and benzene (aromatics), hexane and heptane (alkanes), n-octanol (alcohols), n-butyl acetate (esters), diisopropyl ether (ethers), and methylisobutyl ketone (ketones). The aromatic solutes included: nonpolar compounds such as benzene, toluene and naphthalene, phenolic compounds such as phenol, cresol and catechol, nitrogenous aromatics such as aniline, pyridine and aminonaphthalene, and other aromatic solutes such as naphthol, quinolinol and halogenated compounds. 100 references, 20 figures, 34 tables.

  20. Halogen-Mediated Conversion of Hydrocarbons to Commodities.

    Science.gov (United States)

    Lin, Ronghe; Amrute, Amol P; Pérez-Ramírez, Javier

    2017-03-08

    Halogen chemistry plays a central role in the industrial manufacture of various important chemicals, pharmaceuticals, and polymers. It involves the reaction of halogens or halides with hydrocarbons, leading to intermediate compounds which are readily converted to valuable commodities. These transformations, predominantly mediated by heterogeneous catalysts, have long been successfully applied in the production of polymers. Recent discoveries of abundant conventional and unconventional natural gas reserves have revitalized strong interest in these processes as the most cost-effective gas-to-liquid technologies. This review provides an in-depth analysis of the fundamental understanding and applied relevance of halogen chemistry in polymer industries (polyvinyl chloride, polyurethanes, and polycarbonates) and in the activation of light hydrocarbons. The reactions of particular interest include halogenation and oxyhalogenation of alkanes and alkenes, dehydrogenation of alkanes, conversion of alkyl halides, and oxidation of hydrogen halides, with emphasis on the catalyst, reactor, and process design. Perspectives on the challenges and directions for future development in this exciting field are provided.

  1. Repellency and toxicity of aromatic plant extracts against the mosquito Culex pipiens molestus (Diptera: Culicidae).

    Science.gov (United States)

    Traboulsi, Abdallah F; El-Haj, Samih; Tueni, Marie; Taoubi, Khalil; Nader, Natalie Abi; Mrad, Abir

    2005-06-01

    The insecticidal activities of essential oil extracts from leaves, flowers and roots of aromatic plants against fourth-instar larvae of the mosquito Culex pipiens molestus Forskal were determined. Extracts of Foeniculum vulgare Mill were the most toxic, followed by those of Ferula hermonis Boiss, Citrus sinensis Osbeck, Pinus pinea L, Laurus nobilis L and Eucalyptus spp with LC50 values of 24.5, 44.0, 60.0, 75.0, 117.0 and 120.0 mg litre(-1), respectively. Combination tests between the LC50 and the maximum sub-lethal concentration (MSLC) were determined. Over 20 major components were identified in extracts from each plant species tested. Five essential oils and nine pure components were studied for their repellency against mosquito bites. Terpineol and 1,8-cineole were the most effective against Culex pipiens molestus bites offering complete protection for 1.6 and 2 h, respectively.

  2. E. S. R. studies of halogenated pyrimidines in. gamma. -irradiated alkaline glasses. [Halogenated uracil bases; bromouridine; bromodeoxyuridine

    Energy Technology Data Exchange (ETDEWEB)

    Simpson, L D; Zimbrick, J D [Kansas Univ., Lawrence (USA)

    1975-11-01

    The reactions of mobile electrons (e/sup -//sub m/) and oxygen radical anions (O./sup -/) with halogenated bases and nucleosides have been studied in ..gamma..-irradiated alkaline glasses by e.s.r. and specific halogen-ion electrode techniques. It was shown that electrons react with halogenated uracil bases (XUr where X = Cl, Br, I but not F) by dissociative electron attachment to form uracil-5-yl radicals (U.) and halogen anions. The relative rates of reaction of e/sup -//sub m/ with XUr decreased in the sequence BrUr > ClUr > FUr > IUr. Thermal annealing studies carried out on U. in H/sub 2/O and D/sub 2/O matrices supported the hypothesis that U. in H/sub 2/O hydrates across the 5-6 double bond in the temperature region 135/sup 0/ to 155/sup 0/ K, and deuterates to a much smaller extent in D/sub 2/O at temperatures above 155/sup 0/ K. Studies on bromouridine and bromodeoxyuridine suggested that e/sup -/sub(m) reacts with the base moieties to form U. type radicals which abstract H. from the sugar moieties of adjacent nucleosides.

  3. 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.

  4. Increased polycyclic aromatic hydrocarbon toxicity following their photomodification in natural sunlight: impacts on the duckweed Lemna gibba L. G-3

    International Nuclear Information System (INIS)

    Huang, X.D.; Dixon, D.G.; Greenberg, B.M.

    1995-01-01

    The authors previously demonstrated that simulated solar radiation (SSR), with a fluence rate of only 40 mumol m -2 sec -1 , increased polycyclic aromatic hydrocarbon (PAH) toxicity to the duckweed Lemna gibba and that PAHs photomodified in SSR (generally oxygenation of the ring system) are more toxic than the parent compounds (Huang et al., Environ. Toxicol. Chem., 1993, 12, 1067-1077). It is not known, however, to what extent toxicity of PAHs can increase due to photomodification. Thus, natural sunlight, which has a high fluence rate (approximately 2000 mumol m -2 sec -1 ), was used to photomodify anthracene, benzo[a]pyrene, fluoranthene, phenanthrene, and pyrene. Toxicity was based on growth inhibition of L. gibba, measured as the rate of production of new leaves over an 8-day period. Initially, the toxicity of the PAHs applied in intact form was probed, with the compounds demonstrating greater toxicity in sunlight than in SSR. Next the PAHs were photomodified in sunlight prior to incubation with the plants. The half-lives of the PAHs in sunlight ranged from 12 min to 30 hr. Although most of the products of PAH photomodification are not yet identified, the degree that PAH toxicity increased following photomodification in sunlight could still be probed. The mixtures of photomodified chemicals that were derived from each PAH in sunlight were applied of L. gibba and growth inhibition under 100 mumol m -2 sec -1 of SSR was determined. The LC50s for the PAH photoproducts generated in sunlight were an order of magnitude lower than the LC50s for the PAHs applied in intact form. (author)

  5. Supercritical carbon dioxide extraction as a predictor of polycyclic aromatic hydrocarbon bioaccumulation and toxicity by earthworms in manufactured-gas plant site soils.

    Science.gov (United States)

    Kreitinger, Joseph P; Quiñones-Rivera, Antonio; Neuhauser, Edward F; Alexander, Martin; Hawthorne, Steven B

    2007-09-01

    The toxicity and uptake of polycyclic aromatic hydrocarbons (PAHs) by earthworms were measured in soil samples collected from manufactured-gas plant sites having a wide range in PAH concentrations (170-42,000 mg/kg) and soil characteristics. Samples varied from vegetated soils to pure lampblack soot and had total organic carbon contents ranging from 3 to 87%. The biota-soil accumulation factors (BSAFs) observed for individual PAHs in field-collected earthworms (Aporrectodea caliginosa) were up to 50-fold lower than the BSAFs predicted using equilibrium-partitioning theory. Acute toxicity to the earthworm Eisenia fetida was unrelated to total PAH concentration: Mortality was not observed in some soils having high concentrations of total PAHs (>42,000 mg/kg), whereas 100% mortality was observed in other soils having much lower concentrations of total PAHs (1,520 mg/kg). Instead, toxicity appeared to be related to the rapidly released fraction of PAHs determined by mild supercritical CO2 extraction (SFE). The results demonstrate that soils having approximately 16,000 mg rapidly released total PAH/kg organic carbon can be acutely toxic to earthworms and that the concentration of PAHs in soil that is rapidly released by SFE can estimate toxicity to soil invertebrates.

  6. Polynuclear aromatic hydrocarbons (PAHs) mediate cadmium toxicity to an emergent wetland species

    International Nuclear Information System (INIS)

    Zhang, Zhenhua; Rengel, Zed; Meney, Kathy; Pantelic, Ljiljana; Tomanovic, Radmila

    2011-01-01

    Growth and pollutant removal by emergent wetland plants may be influenced by interactions among mixed pollutants in constructed wetlands. A glasshouse experiment was conducted to investigate interactive effects of cadmium (Cd) x polynuclear aromatic hydrocarbons (PAHs) x plant treatments on growth of Juncus subsecundus, Cd and PAH removal from soil and the total number of microorganisms in soil. Growth and biomass of J. subsecundus were significantly influenced by interaction of Cd and PAHs, significantly decreasing with either Cd or PAH additions, but with the effect of Cd on plant growth being stronger than that of PAHs. The mixture of low Cd and low PAH lessened Cd toxicity to plants, resulting in improved plant growth and increased Cd accumulation in plant tissues, thus enhancing Cd removal by plants. The dissipation of PAHs in soils was significantly influenced by interactions of Cd, PAH and plant presence or absence. The total number of microorganisms in soils was significantly increased by the PAH additions. The interactive effect of Cd and PAHs on plant growth may be linked to the changes in the abundance of microorganisms in the rhizosphere, probably via a positive effect of PAH metabolites and/or phytohormones produced by microorganisms on plant growth.

  7. Determination of inorganic arsenic in algae using bromine halogenation and on-line nonpolar solid phase extraction followed by hydride generation atomic flourescence spectrometry

    Science.gov (United States)

    Accurate, stable and fast analysis of toxic inorganic arsenic (iAs) in complicated and arsenosugar-rich algae matrix is always a challenge. Herein, a novel analytical method for iAs in algae was reported, using bromine halogenation and on-line nonpolar solid phase extraction (SPE) followed by hydrid...

  8. Synthesis and antifungal activity of halogenated aromatic bis-γ-lactones analogous to avenaciolide

    Directory of Open Access Journals (Sweden)

    Pedro A. Castelo-Branco

    2012-01-01

    Full Text Available Here we describe the total syntheses and characterization by elemental analyses, infrared and NMR spectroscopy of three new compounds analogous to avenaciolide, a bis-γ-lactone isolated from Aspergillus avenaceus that possesses antifungal activity, where the octyl group of the natural product was replaced by aromatic groups containing chlorine and fluorine atoms. The effects of the avenaciolide, the novel compounds and their synthetic precursors on mycelia development and conidia germination of Colletotrichum gloeosporioides and Fusarium solani were evaluated in vitro. The title compounds were almost as active as avenaciolide. The absolute structures of the chlorinated analogs were determined by X-ray diffraction analysis.

  9. Scientific conferences: A big hello to halogen bonding

    Science.gov (United States)

    Erdelyi, Mate

    2014-09-01

    Halogen bonding connects a wide range of subjects -- from materials science to structural biology, from computation to crystal engineering, and from synthesis to spectroscopy. The 1st International Symposium on Halogen Bonding explored the state of the art in this fast-growing field of research.

  10. Characterization of organic aromatic compounds in soils affected by an uncontrolled tire landfill fire through the use of comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry.

    Science.gov (United States)

    Escobar-Arnanz, J; Mekni, S; Blanco, G; Eljarrat, E; Barceló, D; Ramos, L

    2018-02-09

    Discarded vehicle tires have become an increasing concern worldwide due to the enormous amount of wastes generated and the increasing evidence of health problems associated to their disposal and accidental combustion. Previous studies conducted involving either simulated or open uncontrolled tire fires have identified aromatics belonging to two main classes, volatile organic compounds and polycyclic aromatic compounds (PAHs), as the most relevant chemicals generated in these burning processes. As a consequence, and due to their recognized toxicity, most studies reported up to now have mainly focused on these two categories of compounds being information concerning the possible occurrence of other aromatic classes rather limited. In this study, the enhanced separation power and structural confirmation capabilities provided by comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-ToF MS) has been used, for the first time, for the non-targeted analysis of soils impacted by a tire fire and an ash collected at the scene of the fire. In total, 118 volatile and semi-volatile aromatic compounds have been differentiated. Among them, 104 compounds have been either positively or tentatively identified. PAHs with 3-5 rings and their alkyl-derivatives were the most numerous and relevant classes in the investigated samples. A significant number of sulfur, oxygen- and nitrogen-containing PAHs were also detected in the samples. The application of a script function to the raw GC×GC-ToF MS data allowed the fast filtering and automatic recognition of compounds containing halogens in their structure. This part of the study evidenced that only a limited number of regulated persistent organic pollutants were present in the investigated samples. However, it also revealed the presence of emerging organophosphorous flame retardants, whose levels in tire fire impacted soils are reported for the first time. Copyright © 2017 Elsevier B.V. All rights

  11. Selective C-H Halogenation with a Highly Fluorinated Manganese Porphyrin.

    Science.gov (United States)

    Li, Gang; Dilger, Andrew K; Cheng, Peter T; Ewing, William R; Groves, John T

    2018-01-26

    The selective C-H functionalization of aliphatic molecules remains a challenge in organic synthesis. While radical chain halogenation reactions provide efficient access to many halogenated molecules, the use of typical protocols for the selective halogenation of electron-deficient and strained aliphatic molecules is rare. Herein, we report selective C-H chlorination and fluorination reactions promoted by an electron-deficient manganese pentafluorophenyl porphyrin catalyst, Mn(TPFPP)Cl. This catalyst displays superior properties for the aliphatic halogenation of recalcitrant, electron-deficient, and strained substrates with unique regio- and stereoselectivity. UV/Vis analysis during the course of the reaction indicated that an oxo-Mn V species is responsible for hydrogen-atom abstraction. The observed stereoselectivity results from steric interactions between the bulky porphyrin ligand and the intermediate substrate radical in the halogen rebound step. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Influence of Halogen Substituents on the Catalytic Oxidation of 2,4,6-Halogenated Phenols by Fe(III-Tetrakis(p-hydroxyphenyl porphyrins and Potassium Monopersulfate

    Directory of Open Access Journals (Sweden)

    Seiya Nagao

    2011-12-01

    Full Text Available The influence of halogen substituents on the catalytic oxidation of 2,4,6-trihalogenated phenols (TrXPs by iron(III-porphyrin/KHSO5 catalytic systems was investigated. Iron(III-5,10,15,20-tetrakis(p-hydroxyphenylporphyrin (FeTHP and its supported variants were employed, where the supported catalysts were synthesized by introducing FeTHP into hydroquinone-derived humic acids via formaldehyde poly-condensation. F (TrFP, Cl (TrCP, Br (TrBP and I (TrIP were examined as halogen substituents for TrXPs. Although the supported catalysts significantly enhanced the degradation and dehalogenation of TrFP and TrCP, the oxidation of TrBP and TrIP was not enhanced, compared to the FeTHP catalytic system. These results indicate that the degree of oxidation of TrXPs is strongly dependent on the types of halogen substituent. The order of dehalogenation levels for halogen substituents in TrXPs was F > Cl > Br > I, consistent with their order of electronegativity. The electronegativity of a halogen substituent affects the nucleophilicity of the carbon to which it is attached. The levels of oxidation products in the reaction mixtures were analyzed by GC/MS after extraction with n-hexane. The most abundant dimer product from TrFP via 2,6-difluoroquinone is consistent with a scenario where TrXP, with a more electronegative halogen substituent, is readily oxidized, while less electronegative halogen substituents are oxidized less readily by iron(III-porphyrin/KHSO5 catalytic systems.

  13. Photoenhanced Toxicity of Petroleum to Aquatic Invertebrates and Fish

    Science.gov (United States)

    Photoenhanced toxicity is a distinct mechanism of petroleum toxicity that is mediated by the interaction of solar radiation with specific polycyclic aromatic compounds in oil. Phototoxicity is observed as a twofold to greater than 1000-fold increase in chemical toxicity to aquati...

  14. Synthesis and Pharmacology of Halogenated δ-Opioid-Selective [D-Ala2]Deltorphin II Peptide Analogues

    Science.gov (United States)

    Pescatore, Robyn; Marrone, Gina F.; Sedberry, Seth; Vinton, Daniel; Finkelstein, Netanel; Katlowitz, Yitzchak E.; Pasternak, Gavril W.; Wilson, Krista R.; Majumdar, Susruta

    2015-01-01

    Deltorphins are naturally occurring peptides produced by the skin of the giant monkey frog (Phyllomedusa bicolor). They are δ-opioid receptor-selective agonists. Herein, we report the design and synthesis of a peptide, Tyr-D-Ala-(pI)Phe-Glu-Ile-Ile-Gly-NH2 3 (GATE3-8), based on the [D-Ala2]deltorphin II template, which is δ-selective in in vitro radioligand binding assays over the μ- and κ-opioid receptors. It is a full agonist in [35S]GTPγS functional assays and analgesic when administered supraspinally to mice. Analgesia of 3 (GATE3-8) is blocked by the selective δ receptor antagonist naltrindole, indicating that the analgesic action of 3 is mediated by the δ-opioid receptor. We have established a radioligand in which 125I isincorporated into 3 (GATE3-8). The radioligand has a KD of 0.1 nM in Chinese hamster ovary (CHO) cells expressing the δ receptor. Additionally, a series of peptides based on 3 (GATE3-8) was synthesized by incorporating various halogens in the para position on the aromatic ring of Phe3. The peptides were characterized for binding affinity at the μ-, δ-, and κ-opioid receptors, which showed a linear correlation between binding affinity and the size of the halogen substituent. These peptides may be interesting tools for probing δ-opioid receptor pharmacology. PMID:25844930

  15. Synthesis and pharmacology of halogenated δ-opioid-selective [d-Ala(2)]deltorphin II peptide analogues.

    Science.gov (United States)

    Pescatore, Robyn; Marrone, Gina F; Sedberry, Seth; Vinton, Daniel; Finkelstein, Netanel; Katlowitz, Yitzchak E; Pasternak, Gavril W; Wilson, Krista R; Majumdar, Susruta

    2015-06-17

    Deltorphins are naturally occurring peptides produced by the skin of the giant monkey frog (Phyllomedusa bicolor). They are δ-opioid receptor-selective agonists. Herein, we report the design and synthesis of a peptide, Tyr-d-Ala-(pI)Phe-Glu-Ile-Ile-Gly-NH2 3 (GATE3-8), based on the [d-Ala(2)]deltorphin II template, which is δ-selective in in vitro radioligand binding assays over the μ- and κ-opioid receptors. It is a full agonist in [(35)S]GTPγS functional assays and analgesic when administered supraspinally to mice. Analgesia of 3 (GATE3-8) is blocked by the selective δ receptor antagonist naltrindole, indicating that the analgesic action of 3 is mediated by the δ-opioid receptor. We have established a radioligand in which (125)I is incorporated into 3 (GATE3-8). The radioligand has a KD of 0.1 nM in Chinese hamster ovary (CHO) cells expressing the δ receptor. Additionally, a series of peptides based on 3 (GATE3-8) was synthesized by incorporating various halogens in the para position on the aromatic ring of Phe(3). The peptides were characterized for binding affinity at the μ-, δ-, and κ-opioid receptors, which showed a linear correlation between binding affinity and the size of the halogen substituent. These peptides may be interesting tools for probing δ-opioid receptor pharmacology.

  16. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting under...

  17. Alkyne Benzannulation Reactions for the Synthesis of Novel Aromatic Architectures.

    Science.gov (United States)

    Hein, Samuel J; Lehnherr, Dan; Arslan, Hasan; J Uribe-Romo, Fernando; Dichtel, William R

    2017-11-21

    - and halogen-substituted alkynes. Through a combined experimental and computational approach, we have elucidated mechanistic insight and key principles that govern the regioselectivity outcome of the benzannulation of structurally diverse alkynes. We have applied these methods to prepare sterically hindered, shape-persistent aromatic systems, heterocyclic aromatic compounds, functionalized 2-aryne precursors, polyheterohalogenated naphthalenes, ortho-arylene foldamers, and graphene nanoribbons. As a result of these new synthetic avenues, aromatic structures with interesting properties were uncovered such as ambipolar charge transport in field effect transistors based on our graphene nanoribbons, conformational aspects of ortho-arylene architectures resulting from intramolecular π-stacking, and modulation of frontier molecular orbitals via protonation of heteroatom containing aromatic systems. Given the availability of many substituted 2-(phenylethynyl)benzaldehydes and the regioselectivity of the benzannulation reaction, naphthalenes can be prepared with control of the substitution pattern at seven of the eight substitutable positions. Researchers in a range of fields are likely to benefit directly from newly accessible molecular and polymeric systems derived from polyfunctionalized naphthalenes.

  18. Effect of pyrolysis temperature on polycyclic aromatic hydrocarbons toxicity and sorption behaviour of biochars prepared by pyrolysis of paper mill effluent treatment plant sludge.

    Science.gov (United States)

    Devi, Parmila; Saroha, Anil K

    2015-09-01

    The polycyclic aromatic hydrocarbons (PAHs) toxicity and sorption behaviour of biochars prepared from pyrolysis of paper mill effluent treatment plant (ETP) sludge in temperature range 200-700 °C was studied. The sorption behaviour was found to depend on the degree of carbonization where the fractions of carbonized and uncarbonized organic content in the biochar act as an adsorption media and partition media, respectively. The sorption and partition fractions were quantified by isotherm separation method and isotherm parameters were correlated with biochar properties (aromaticity, polarity, surface area, pore volume and ash content). The risk assessment for the 16 priority EPA PAHs present in the biochar matrix was performed and it was found that the concentrations of the PAHs in the biochar were within the permissible limits prescribed by US EPA (except BC400 and BC500 for high molecular weight PAHs). Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Incidence of real-world automotive parent and halogenated PAH in urban atmosphere.

    Science.gov (United States)

    Gao, Pan-Pan; Zhao, Yi-Bo; Ni, Hong-Gang

    2018-06-01

    This study reports results from a tunnel experiment impact of real-world traffic-related particle and gas parent and halogenated polycyclic aromatic hydrocarbons (PAHs and HPAHs) on urban air. The traffic related emission characteristics and subsequent environmental behavior of these compounds were investigated. To understand the significance of real-world transport emissions to the urban air, traffic-related mass emissions of PAHs and HPAHs were estimated based on measured emission factors. According to our results, PAHs and HPAHs emissions via particulate phase were greater than those via gaseous phase; particles in 2.1-3.3 μm size fraction, have the major contribution to particulate PAHs and HPAHs emissions. Over all, contribution of traffic-related emission of PAHs (only ∼3% of the total PAHs emission in China) is an overstated source of PAHs pollution in China. Actually, exhaust pipe emission contributed much less than the total traffic-related emission of pollutants. Copyright © 2018 Elsevier Ltd. All rights reserved.

  20. Photolysis of polycyclic aromatic hydrocarbons (PAHs) on Fe3+-montmorillonite surface under visible light: Degradation kinetics, mechanism, and toxicity assessments.

    Science.gov (United States)

    Zhao, Song; Jia, Hanzhong; Nulaji, Gulimire; Gao, Hongwei; Wang, Fu; Wang, Chuanyi

    2017-10-01

    Photochemical behavior of various polycyclic aromatic hydrocarbons (PAHs) on Fe 3+ -modified montmorillonite was explored to determine their potential kinetics, pathways, and mechanism under visible light. Depending on the type of PAH molecules, the transformation rate follows the order of benzo[a]pyrene ≈ anthracene > benzo[a]anthracene > phenanthrene. Quantum simulation results confirm the crucial role of "cation-π" interaction between Fe 3+ and PAHs on their transformation kinetics. Primary intermediates, including quinones, ring-opening products and benzene derivatives, were identified by gas chromatography-mass spectrometer (GC-MS), and the possible photodegradation pathway of benzo[a]pyrene was proposed. Meanwhile, radical intermediates, such as reactive oxygen species (ROS) and free organic radicals, were detected by electron paramagnetic resonance (EPR) technique. The photolysis of selected PAHs, such as anthracene and benzo[a]pyrene, on clay surface firstly occurs by electron transfer from PAHs to Fe 3+ -montmorillonite, followed by degradation involving photo-induced ROS such as ·OH and ·O 2 - . To investigate the acute toxicity of photolysis products, the Microtox ® toxicity test was performed during the photodegradation processes of various PAHs. As a result, the photo-irradiation initially induces increased toxicity by generating reactive intermediates, such as free organic radicals, and then the toxicity gradually decreases with increasing of reaction time. Overall, the present study provides useful information to understand the fate and photo-transformation of PAHs in contaminated soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Microbial reductive dehalogenation.

    OpenAIRE

    Mohn, W W; Tiedje, J M

    1992-01-01

    A wide variety of compounds can be biodegraded via reductive removal of halogen substituents. This process can degrade toxic pollutants, some of which are not known to be biodegraded by any other means. Reductive dehalogenation of aromatic compounds has been found primarily in undefined, syntrophic anaerobic communities. We discuss ecological and physiological principles which appear to be important in these communities and evaluate how widely applicable these principles are. Anaerobic commun...

  2. Estimation of Toxicity Equivalent Concentration (TEQ) of ...

    African Journals Online (AJOL)

    Estimation of Toxicity Equivalent Concentration (TEQ) of carcinogenic polycyclic aromatic hydrocarbons in soils from Idu Ekpeye playground and University of Port ... Effective soil remediation and detoxification method like Dispersion by chemical reaction technology should be deployed to clean-up sites to avoid soil toxicity ...

  3. Construction of Tungsten Halogen, Pulsed LED, and Combined Tungsten Halogen-LED Solar Simulators for Solar Cell I-V Characterization and Electrical Parameters Determination

    Directory of Open Access Journals (Sweden)

    Anon Namin

    2012-01-01

    Full Text Available I-V characterization of solar cells is generally done under natural sunlight or solar simulators operating in either a continuous mode or a pulse mode. Simulators are classified on three features of irradiance, namely, spectral match with respect to air mass 1.5, spatial uniformity, and temporal stability. Commercial solar simulators use Xenon lamps and halogen lamps, whereas LED-based solar simulators are being developed. In this work, we build and test seven simulators for solar cell characterization, namely, one tungsten halogen simulator, four monochromatic (red, green, blue, and white LED simulators, one multicolor LED simulator, and one tungsten halogen-blue LED simulator. The seven simulators provide testing at nonstandard test condition. High irradiance from simulators is obtained by employing elevated supply voltage to tungsten halogen lamps and high pulsing voltages to LEDs. This new approach leads to higher irradiance not previously obtained from tungsten halogen lamps and LEDs. From I-V curves, electrical parameters of solar cell are made and corrected based on methods recommended in the IEC 60891 Standards. Corrected values obtained from non-STC measurements are in good agreement with those obtained from Class AAA solar simulator.

  4. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Science.gov (United States)

    2010-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject to...

  5. Determination of chlorinated polycyclic aromatic hydrocarbons in water by solid-phase extraction coupled with gas chromatography and mass spectrometry.

    Science.gov (United States)

    Wang, Xianli; Kang, Haiyan; Wu, Junfeng

    2016-05-01

    Given the potential risks of chlorinated polycyclic aromatic hydrocarbons, the analysis of their presence in water is very urgent. We have developed a novel procedure for determining chlorinated polycyclic aromatic hydrocarbons in water based on solid-phase extraction coupled with gas chromatography and mass spectrometry. The extraction parameters of solid-phase extraction were optimized in detail. Under the optimal conditions, the proposed method showed wide linear ranges (1.0-1000 ng/L) with correlation coefficients ranging from 0.9952 to 0.9998. The limits of detection and the limits of quantification were in the range of 0.015-0.591 and 0.045-1.502 ng/L, respectively. Recoveries ranged from 82.5 to 102.6% with relative standard deviations below 9.2%. The obtained method was applied successfully to the determination of chlorinated polycyclic aromatic hydrocarbons in real water samples. Most of the chlorinated polycyclic aromatic hydrocarbons were detected and 1-monochloropyrene was predominant in the studied water samples. This is the first report of chlorinated polycyclic aromatic hydrocarbons in water samples in China. The toxic equivalency quotients of chlorinated polycyclic aromatic hydrocarbons in the studied tap water were 9.95 ng the toxic equivalency quotient m(-3) . 9,10-Dichloroanthracene and 1-monochloropyrene accounted for the majority of the total toxic equivalency quotients of chlorinated polycyclic aromatic hydrocarbons in tap water. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. The unique role of halogen substituents in the design of modern agrochemicals.

    Science.gov (United States)

    Jeschke, Peter

    2010-01-01

    The past 30 years have witnessed a period of significant expansion in the use of halogenated compounds in the field of agrochemical research and development. The introduction of halogens into active ingredients has become an important concept in the quest for a modern agrochemical with optimal efficacy, environmental safety, user friendliness and economic viability. Outstanding progress has been made, especially in synthetic methods for particular halogen-substituted key intermediates that were previously prohibitively expensive. Interestingly, there has been a rise in the number of commercial products containing 'mixed' halogens, e.g. one or more fluorine, chlorine, bromine or iodine atoms in addition to one or more further halogen atoms. Extrapolation of the current trend indicates that a definite growth is to be expected in fluorine-substituted agrochemicals throughout the twenty-first century. A number of these recently developed agrochemical candidates containing halogen substituents represent novel classes of chemical compounds with new modes of action. However, the complex structure-activity relationships associated with biologically active molecules mean that the introduction of halogens can lead to either an increase or a decrease in the efficacy of a compound, depending on its changed mode of action, physicochemical properties, target interaction or metabolic susceptibility and transformation. In spite of modern design concepts, it is still difficult to predict the sites in a molecule at which halogen substitution will result in optimal desired effects. This review describes comprehensively the successful utilisation of halogens and their unique role in the design of modern agrochemicals, exemplified by various commercial products from Bayer CropScience coming from different agrochemical areas.

  7. Special features of self-compensation of halogen donor action in lead telluride

    International Nuclear Information System (INIS)

    Kajdanov, V.I.; Nemov, S.A.; Ravich, Yu.I.; Dereza, A.Yu.

    1985-01-01

    Specific features of self-compensation of halogen donor action in lead telluride are investigasted. Lead telluride samples with chlorine additions (with tellurium excess) and, besides, with bromine- and iodine additions were studied in order to reveal general regularities in alloyind with all halogen donor impurities. Experimental dependences of the difference between the electron and hole concentrations (n-p) in PbTe as a function of an amount of introduced halogen impurities (Ni) are presented for samples with a maximum compensation at 295 K. General features of the n-p=f(Ni) dependence are presented for all halogens. The hypothesis on the kinetic mechanism of increasing the efficiency of self-compensation of halogen donor action in lead telluride is suggested

  8. Toxicity of oils and petroleum hydrocarbons to estuarine crustaceans

    Energy Technology Data Exchange (ETDEWEB)

    Tatem, H.E. (Army Engineer Waterways Experiment Station, Vicksburg, MS); Cox, B.A.; Anderson, J.W.

    1978-04-01

    Bioassay experiments with various life stages of three estuarine shrimp and soluble petroleum hydrocarbons (PH) revealed residual Bunker C oil and refined No. 2 fuel oil to be more toxic than two crude oils tested. Larvae of Palaemonetes pugio were slightly more sensitive to the PH than adults, while young penaeid shrimp were shown to be more resistant than older, larger individuals. Shrimp exposed to PH in conjunction with temperature and salinity changes were more susceptible to the PH. Some common aromatic and diaromatic PH, including three naphthalene compounds, were utilized in bioassays. Naphthalenes were highly toxic. The toxicity of petroleum products is closely related to aromatic hydrocarbon content, especially the naphthalenes and related hydrocarbons.

  9. Spectrographic determination of traces of halogens; Dosage de traces d'halogenes par la methode spectrographique

    Energy Technology Data Exchange (ETDEWEB)

    Melamed, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1961-07-01

    Hollow cathode source is employed for determining traces of halogens (fluorine - chlorine) in the uranium oxide U{sub 3}O{sub 8} qualitatively, detection of at least 40 ppm of fluorine, as alkali fluoride and 125 ppm of chlorine, is possible. (author) [French] Un tube a decharge a cathode creuse a ete utilise pour la determination spectrographique des halogenes (fluor - chlore) presentes a l'etat de traces dans un oxyde d'uranium U{sub 3}O{sub 8}. On a pu deceler qualitativement des teneurs de 40 ppm de fluor sous forme de fluorures alcalins. En ce qui concerne le chlore, la plus faible teneur decelee a ete de 125 ppm. (auteur)

  10. Polycyclic aromatic hydrocarbons and nitropolycyclic aromatic hydrocarbons in particulates emitted by motorcycles

    International Nuclear Information System (INIS)

    Pham, Chau Thuy; Kameda, Takayuki; Toriba, Akira; Hayakawa, Kazuichi

    2013-01-01

    We determined eleven PAHs and four NPAHs in particulates and regulated pollutants (CO, CO 2 , HC, NO x , PM) exhausted from motorcycles to figure out the characteristics of motorcycle exhausts. Fluoranthene and pyrene accounted for more than 50% of the total detected PAHs. Among four detected NPAHs, 6-nitrochrysene and 7-nitrobenz[a]anthracene were the predominant NPAHs and were highly correlated relationship with their parent PAHs (R = 0.93 and 0.97, respectively). The PM and HC emissions tended to be close to the PAH emissions. NO x and NPAHs were negatively correlated. Despite their small engine size, motorcycles emitted much more PM and PAHs, showed stronger PAH-related carcinogenicity and indirect-acting mutagenicity, but weaker NPAH-related direct-acting mutagenic potency than automobiles. This is the first study to analyze both PAHs and NPAHs emitted by motorcycles, which could provide useful information to design the emission regulations and standards for motorcycles such as PM. -- Highlights: ► We characterized PAHs and NPAHs distribution in motorcycle exhausts. ► NPAHs concentrations were about three orders of magnitude lower than those of PAHs. ► We found larger amounts of PM and PAHs in exhaust of motorcycles than of automobiles. ► Motorcycles showed stronger PAH-related toxicity than automobiles. ► Motorcycles showed weaker NPAH-related direct-acting mutagenicity than automobiles. -- Control polycyclic aromatic hydrocarbons and nitropolycyclic aromatic hydrocarbon in particulates emitted by motorcycles due to their toxic potency

  11. Halogenated organic compounds in archived whale oil: A pre-industrial record

    International Nuclear Information System (INIS)

    Teuten, Emma L.; Reddy, Christopher M.

    2007-01-01

    To provide additional evidence that several halogenated organic compounds (HOCs) found in environmental samples are natural and not industrially produced, we analyzed an archived whale oil sample collected in 1921 from the last voyage of the whaling ship Charles W. Morgan. This sample, which pre-dates large-scale industrial manufacture of HOCs, contained two methoxylated polybrominated diphenyl ethers (MeO-PBDEs), five halogenated methyl bipyrroles (MBPs), one halogenated dimethyl bipyrrole (DMBP), and tentatively one dimethoxylated polybrominated biphenyl (diMeO-PBB). This result indicates, at least in part, a natural source of the latter compounds. - Nine halogenated organic compounds have been detected in archived whale oil from the early 1920s

  12. Halogenated organic compounds in archived whale oil: A pre-industrial record

    Energy Technology Data Exchange (ETDEWEB)

    Teuten, Emma L. [Department of Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution, 360 Woods Hole Road, Woods Hole, MA 02543 (United States)]. E-mail: emma.teuten@plymouth.ac.uk; Reddy, Christopher M. [Department of Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution, 360 Woods Hole Road, Woods Hole, MA 02543 (United States)]. E-mail: creddy@whoi.edu

    2007-02-15

    To provide additional evidence that several halogenated organic compounds (HOCs) found in environmental samples are natural and not industrially produced, we analyzed an archived whale oil sample collected in 1921 from the last voyage of the whaling ship Charles W. Morgan. This sample, which pre-dates large-scale industrial manufacture of HOCs, contained two methoxylated polybrominated diphenyl ethers (MeO-PBDEs), five halogenated methyl bipyrroles (MBPs), one halogenated dimethyl bipyrrole (DMBP), and tentatively one dimethoxylated polybrominated biphenyl (diMeO-PBB). This result indicates, at least in part, a natural source of the latter compounds. - Nine halogenated organic compounds have been detected in archived whale oil from the early 1920s.

  13. Halogens are key cofactors in building of collagen IV scaffolds outside the cell.

    Science.gov (United States)

    Brown, Kyle L; Hudson, Billy G; Voziyan, Paul A

    2018-05-01

    The purpose of this review is to highlight recent advances in understanding the molecular assembly of basement membranes, as exemplified by the glomerular basement membrane (GBM) of the kidney filtration apparatus. In particular, an essential role of halogens in the basement membrane formation has been discovered. Extracellular chloride triggers a molecular switch within non collagenous domains of collagen IV that induces protomer oligomerization and scaffold assembly outside the cell. Moreover, bromide is an essential cofactor in enzymatic cross-linking that reinforces the stability of scaffolds. Halogenation and halogen-induced oxidation of the collagen IV scaffold in disease states damage scaffold function. Halogens play an essential role in the formation of collagen IV scaffolds of basement membranes. Pathogenic damage of these scaffolds by halogenation and halogen-induced oxidation is a potential target for therapeutic interventions.

  14. Halonium Ions as Halogen Bond Donors in the Solid State [XL2]Y Complexes.

    Science.gov (United States)

    Rissanen, Kari; Haukka, Matti

    2015-01-01

    The utilization of halogen bonding interactions is one of the most rapidly developing areas of supramolecular chemistry. While the other weak non-covalent interactions and their influence on the structure and chemistry of various molecules, complexes, and materials have been investigated extensively, the understanding, utilizations, and true nature of halogen bonding are still relatively unexplored. Thus its final impact in chemistry in general and in materials science has not yet been fully established. Because of the polarized nature of a Z-X bond (Z=electron-withdrawing atom or moiety and X=halogen atom), such a moiety can act as halogen bond donor when the halogen is polarized enough by the atom/moiety Z. The most studied and utilized halogen bond donor molecules are the perfluorohalocarbons, where Z is a perfluorinated aryl or alkyl moiety and X is either iodine or bromine. Complementing the contemporary halogen bonding research, this chapter reviews the solid state structural chemistry of the most extremely polarized halogen atoms, viz. halonium ions, X+, and discussed them as halogen bond donors in the solid state [XL2]Y complexes (X=halonium ion, Y=any anion).

  15. Ex-situ bioremediation of polycyclic aromatic hydrocarbons in sewage sludge

    DEFF Research Database (Denmark)

    Schmidt, Jens Ejbye; Larsen, S.B.; Karakashev, Dimitar Borisov

    2008-01-01

    Polycyclic aromatic hydrocarbons (PAH) are naturally occurring organic compounds. As a result of anthropogenic activities, PAH concentration has increased in the environment considerably. PAH are regarded as environmental pollutants because they have toxic, mutagenic and carcinogenic effects on l...

  16. Metal-Mediated Halogen Exchange in Aryl and Vinyl Halides: a Review

    Science.gov (United States)

    Evano, Gwilherm; Nitelet, Antoine; Thilmany, Pierre; Dewez, Damien F.

    2018-04-01

    Halogenated arenes and alkenes are of prime importance in many areas of science, especially in the pharmaceutical, agrochemical and chemical industries. While the simplest ones are commercially available, some of them are still hardly accessible depending on their substitution patterns and the nature of the halogen atom. Reactions enabling the selective and efficient replacement of the halogen atom of an aryl or alkenyl halide by another one, lighter or heavier, are therefore of major importance since they can be used for example to turn a less reactive aryl/alkenyl chloride into the more reactive iodinated derivatives or, in a reversed sense, to block an undesired reactivity, for late-stage modifications or for the introduction of a radionuclide. If some halogen exchange reactions are possible with activated substrates, they usually require catalysis with metal complexes. Remarkably efficient processes have been developed for metal-mediated halogen exchange in aryl and vinyl halides: they are overviewed, in a comprehensive manner, in this review article.

  17. Metabolism and Biomarkers of Heterocyclic Aromatic Amines in Molecular Epidemiology Studies: Lessons Learned from Aromatic Amines

    Science.gov (United States)

    2011-01-01

    Aromatic amines and heterocyclic aromatic amines (HAAs) are structurally related classes of carcinogens that are formed during the combustion of tobacco or during the high-temperature cooking of meats. Both classes of procarcinogens undergo metabolic activation by N-hydroxylation of the exocyclic amine group, to produce a common proposed intermediate, the arylnitrenium ion, which is the critical metabolite implicated in toxicity and DNA damage. However, the biochemistry and chemical properties of these compounds are distinct and different biomarkers of aromatic amines and HAAs have been developed for human biomonitoring studies. Hemoglobin adducts have been extensively used as biomarkers to monitor occupational and environmental exposures to a number of aromatic amines; however, HAAs do not form hemoglobin adducts at appreciable levels and other biomarkers have been sought. A number of epidemiologic studies that have investigated dietary consumption of well-done meat in relation to various tumor sites reported a positive association between cancer risk and well-done meat consumption, although some studies have shown no associations between well-done meat and cancer risk. A major limiting factor in most epidemiological studies is the uncertainty in quantitative estimates of chronic exposure to HAAs and, thus, the association of HAAs formed in cooked meat and cancer risk has been difficult to establish. There is a critical need to establish long-term biomarkers of HAAs that can be implemented in molecular epidemioIogy studies. In this review article, we highlight and contrast the biochemistry of several prototypical carcinogenic aromatic amines and HAAs to which humans are chronically exposed. The biochemical properties and the impact of polymorphisms of the major xenobiotic-metabolizing enzymes on the biological effects of these chemicals are examined. Lastly, the analytical approaches that have been successfully employed to biomonitor aromatic amines and HAAs, and

  18. DEGRADATION OF POLYNUCLEAR AROMATIC HYDROCARBONS UNDER BENCH-SCALE COMPOST CONDITIONS

    Science.gov (United States)

    The relationship between biomass growth and degradation of polynuclear aromatic hydrocarbons (PAHs) in soil, and subsequent toxicity reduction, was evaluated in 10 in-vessel, bench-scale compost units. Field soil was aquired from the Reilly Tar and Chemical Company Superfund site...

  19. Halogenated furanones inhibit quorum sensing through accelerated LuxR turnover

    DEFF Research Database (Denmark)

    Manefield, M.; Rasmussen, Thomas Bovbjerg; Henzter, M.

    2002-01-01

    fischeri overproduced in Escherichia coli. Whilst a stable interaction between the algal metabolite and the bacterial protein was not found, it was noted by Western analysis that the half-life of the protein is reduced up to 100-fold in the presence of halogenated furanones. This suggests that halogenated...... that the reduction in LuxR concentration is the mechanism by which furanones control expression of AHL-dependent phenotypes. The mode of action by which halogenated furanones reduce cellular concentrations of the LuxR protein remains to be characterized....

  20. Thermal behavior of halogenated imidebismaleimide resins

    International Nuclear Information System (INIS)

    Mohammad, A.; Al-Halim, N.Z.

    1995-01-01

    Several new poly-halogenated malecimides, bismaleimides and therir copoly resins were synthessised thermally from their corresponding amic acids. The synthesis was accomplished by two way method (amic acid-polimide) instead of the well-known three way method (amic acid-imide-polyimide). Thermal characterization of monomers and their cured resins was achieved using differential thermal analysis (DTA), dynamic thermogravimetric analysis (TGA) and isothermal gravimetric analysis (IGA). The effect of halogen substituent, especially in the ortho postion, is clear in the imidization proces, while polymerization proceeds almost equally in all systems. Thermal properties of homo and copolymers were correlated with their chemical structures. (author). 15 refs., 4

  1. Process for reducing halogen impurities in oil products

    Energy Technology Data Exchange (ETDEWEB)

    Basler, F.

    1990-08-14

    Oil products, in particular waste oils, may be efficiently reprocessed according to an economic and technically simple method for removing impurities, notably halogens. In this method, the oil product is treated at temperatures up to about 150{degree}C with an effective amount of an aqueous solution of at least one compound selected from the group consisting of a strong acid, a salt of a weak base and a strong acid and precursors thereof. The oil product obtained in this step is treated at increased temperatures with at least one halogen binding agent. The water and/or solids from the product so treated are separated out. The process of the invention can be carried out in a conventional stripping apparatus. The strong acid used in the first step is preferably selected from sulfurous acid, phosphoric acid, phosphorous acid, and phosphonic acid. The salt of the weak base and strong acid is preferably ammonium sulfate, ammonium bisulfate, ammonium sulfite, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphite, and ammonium phosphonic acid. The second step of the method is preferably a coagulation step in which organic halogen compounds break down into hydrogen halides which are neutralized by the added halogen binding agents. The preferred halogen binding agents are ammonia and/or an organic base. The coagulation is preferably carried out in heat exchangers so that the oil is heated in 3 stages and the oil from each stage is passed through a cascade tower. In the third step, additives may be used to enhance separation of the oil. Experiments are described to illustrate the method of the invention. 1 tab.

  2. Participation of the Halogens in Photochemical Reactions in Natural and Treated Waters

    Directory of Open Access Journals (Sweden)

    Yi Yang

    2017-10-01

    Full Text Available Halide ions are ubiquitous in natural waters and wastewaters. Halogens play an important and complex role in environmental photochemical processes and in reactions taking place during photochemical water treatment. While inert to solar wavelengths, halides can be converted into radical and non-radical reactive halogen species (RHS by sensitized photolysis and by reactions with secondary reactive oxygen species (ROS produced through sunlight-initiated reactions in water and atmospheric aerosols, such as hydroxyl radical, ozone, and nitrate radical. In photochemical advanced oxidation processes for water treatment, RHS can be generated by UV photolysis and by reactions of halides with hydroxyl radicals, sulfate radicals, ozone, and other ROS. RHS are reactive toward organic compounds, and some reactions lead to incorporation of halogen into byproducts. Recent studies indicate that halides, or the RHS derived from them, affect the concentrations of photogenerated reactive oxygen species (ROS and other reactive species; influence the photobleaching of dissolved natural organic matter (DOM; alter the rates and products of pollutant transformations; lead to covalent incorporation of halogen into small natural molecules, DOM, and pollutants; and give rise to certain halogen oxides of concern as water contaminants. The complex and colorful chemistry of halogen in waters will be summarized in detail and the implications of this chemistry for global biogeochemical cycling of halogen, contaminant fate in natural waters, and water purification technologies will be discussed.

  3. Photoinduced oxidation of sea salt halides by aromatic ketones: a source of halogenated radicals

    Directory of Open Access Journals (Sweden)

    A. Jammoul

    2009-07-01

    Full Text Available The interactions between triplet state benzophenone and halide anion species (Cl, Br and I have been studied by laser flash photolysis (at 355 nm in aqueous solutions at room temperature. The decay of the triplet state of benzophenone was followed at 525 nm. Triplet lifetime measurements gave rate constants, kq (M−1 s, close to diffusion controlled limit for iodide (~8×109 M−1 s, somewhat less for bromide (~3×108 M−1 s and much lower for chloride (<106 M−1 s. The halide (X quenches the triplet state; the resulting product has a transient absorption at 355 nm and a lifetime much longer than that of the benzophenone triplet state, is formed. This transient absorption feature matches those of the corresponding radical anion (X2. We therefore suggest that such reactive quenching is a photosensitized source of halogen in the atmosphere or the driving force for the chemical oxidation of the oceanic surface micro layer.

  4. First-principles studies on the effects of halogen adsorption on monolayer antimony.

    Science.gov (United States)

    Yeoh, Keat Hoe; Yoon, Tiem Leong; Ong, Duu Sheng; Lim, Thong Leng; Zuntu Abdullahi, Yusuf

    2017-09-27

    Using first-principles calculations, we carry out systematic studies on the electronic, magnetic and structural properties of halogenated β-phase antimonene. We consider two different levels of halogen adatom coverage i.e. Θ = 1/8 and Θ = 1/18. It is found that F, Cl and Br adatoms act as acceptors whereas the I adatom acts as a donor. For a high coverage of Θ = 1/8, halogenated β-phase antimonene exhibits metallic characteristics. With a lower coverage of Θ = 1/18, through the adsorption of F, Cl and Br the semiconducting unstrained antimonene becomes metallic. In contrast, I-adsorbed antimonene remains semiconducting but exhibits magnetic behavior. We further investigate the effects of bi-axial strain on the halogenated β-phase antimonene. It is found that bi-axial strain can only induce ferromagnetism on the halogenated antimonene at Θ = 1/18. However, the ferromagnetism is suppressed when the applied strain is high. We uncover that the emergence of strain-dependent magnetism is attributed to the presence of localized states in the bandgap resulting from collective effects of bi-axial strain and the adsorption of halogen atoms.

  5. Halogenated 1-Hydroxynaphthalene-2-Carboxanilides Affecting Photosynthetic Electron Transport in Photosystem II

    Directory of Open Access Journals (Sweden)

    Tomas Gonec

    2017-10-01

    Full Text Available Series of seventeen new multihalogenated 1-hydroxynaphthalene-2-carboxanilides was prepared and characterized. All the compounds were tested for their activity related to the inhibition of photosynthetic electron transport (PET in spinach (Spinacia oleracea L. chloroplasts. 1-Hydroxy-N-phenylnaphthalene-2-carboxamides substituted in the anilide part by 3,5-dichloro-, 4-bromo-3-chloro-, 2,5-dibromo- and 3,4,5-trichloro atoms were the most potent PET inhibitors (IC50 = 5.2, 6.7, 7.6 and 8.0 µM, respectively. The inhibitory activity of these compounds depends on the position and the type of halogen substituents, i.e., on lipophilicity and electronic properties of individual substituents of the anilide part of the molecule. Interactions of the studied compounds with chlorophyll a and aromatic amino acids present in pigment-protein complexes mainly in PS II were documented by fluorescence spectroscopy. The section between P680 and plastoquinone QB in the PET chain occurring on the acceptor side of PS II can be suggested as the site of action of the compounds. The structure-activity relationships are discussed.

  6. Halogenation dictates the architecture of amyloid peptide nanostructures.

    Science.gov (United States)

    Pizzi, Andrea; Pigliacelli, Claudia; Gori, Alessandro; Nonappa; Ikkala, Olli; Demitri, Nicola; Terraneo, Giancarlo; Castelletto, Valeria; Hamley, Ian W; Baldelli Bombelli, Francesca; Metrangolo, Pierangelo

    2017-07-20

    Amyloid peptides yield a plethora of interesting nanostructures though difficult to control. Here we report that depending on the number, position, and nature of the halogen atoms introduced into either one or both phenylalanine benzene rings of the amyloid β peptide-derived core-sequence KLVFF, four different architectures were obtained in a controlled manner. Our findings demonstrate that halogenation may develop as a general strategy to engineer amyloidal peptide self-assembly and obtain new amyloidal nanostructures.

  7. Birds and polycyclic aromatic hydrocarbons

    Science.gov (United States)

    Albers, P.H.

    2006-01-01

    Polycyclic aromatic hydrocarbons (PAH) are present throughout the global environment and are produced naturally and by activities of humans. Effects of PAH on birds have been determined by studies employing egg injection, egg immersion, egg shell application, single and multiple oral doses, subcutaneous injection, and chemical analysis of field-collected eggs and tissue. The four-to six-ring aromatic compounds are the most toxic to embryos, young birds, and adult birds. For embryos, effects include death, developmental abnormalities, and a variety of cellular and biochemical responses. For adult and young birds, effects include reduced egg production and hatching, increased clutch or brood abandonment, reduced growth, increased organweights, and a variety of biochemical responses. Trophic level accumulation is unlikely. Environmental exposure to PAH in areas of high human population or habitats affected by recent petroleum spills might be sufficient to adversely affect reproduction. Evidence of long-term effects of elevated concentrations of environmental PAH on bird populations is very limited and the mechanisms of effect are unclear.

  8. Theoretical and Experimental Study of the Friction Behavior of Halogen-Free Ionic Liquids in Elastohydrodynamic Regime

    Directory of Open Access Journals (Sweden)

    Karthik Janardhanan

    2016-05-01

    Full Text Available Ionic Liquids have emerged as effective lubricants and additives to lubricants, in the last decade. Halogen-free ionic liquids have recently been considered as more environmentally stable than their halogenated counterparts, which tend to form highly toxic and corrosive acids when exposed to moisture. Most of the studies using ionic liquids as lubricants or additives of lubricants have been done experimentally. Due to the complex nature of the lubrication mechanism of these ordered fluids, the development of a theoretical model that predicts the ionic liquid lubrication ability is currently one of the biggest challenges in tribology. In this study, a suitable and existing friction model to describe lubricating ability of ionic liquids in the elastohydrodynamic lubrication regime is identified and compared to experimental results. Two phosphonium-based, halogen-free ionic liquids are studied as additives to a Polyalphaolefin base oil in steel–steel contacts using a ball-on-flat reciprocating tribometer. Experimental conditions (speed, load and roughness are selected to ensure that operations are carried out in the elastohydrodynamic regime. Wear volume was also calculated for tests at high speed. A good agreement was found between the model and the experimental results when [THTDP][Phos] was used as an additive to the base oil, but some divergence was noticed when [THTDP][DCN] was added, particularly at the highest speed studied. A significant decrease in the steel disks wear volume is observed when 2.5 wt. % of the two ionic liquids were added to the base lubricant.

  9. Induction of bacterial antibiotic resistance by mutagenic halogenated nitrogenous disinfection byproducts

    International Nuclear Information System (INIS)

    Lv, Lu; Yu, Xin; Xu, Qian; Ye, Chengsong

    2015-01-01

    Halogenated nitrogenous disinfection byproducts (N-DBPs) raise concerns regarding their mutagenicity and carcinogenicity threatening public health. However, environmental consequence of their mutagenicity has received less attention. In this study, the effect of halogenated N-DBPs on bacterial antibiotic resistance (BAR) was investigated. After exposure to bromoacetamide (BAcAm), trichloroacetonitrile (TCAN) or tribromonitromethane (TBNM), the resistance of Pseudomonas aeruginosa PAO1 to both individual and multiple antibiotics (ciprofloxacin, gentamicin, polymyxin B, rifampin, tetracycline, ciprofloxacin + gentamicin and ciprofloxacin + tetracycline) was increased, which was predominantly ascribed to the overexpression of efflux pumps. The mechanism of this effect was demonstrated to be mutagenesis through sequencing and analyzing antibiotic resistance genes. The same induction phenomena also appeared in Escherichia coli, suggesting this effect may be universal to waterborne pathogens. Therefore, more attention should be given to halogenated N-DBPs, as they could increase not only genotoxicological risks but also epidemiological risks of drinking water. - Highlights: • The halogenated N-DBPs could induce bacterial antibiotic resistance. • Both individual and multiple resistances could be induced. • Efflux mechanism played an important role in the induced antibiotic resistance. • The halogenated N-DBPs induced bacterial antibiotic resistance via mutagenesis. • Effects of N-DBPs on antibiotic resistance may be universal to waterborne pathogens. - Halogenated N-DBPs could increase antibiotic resistance, even multidrug resistance via mutagenesis, contributing to the enrichment of antibiotic resistant bacteria in drinking water

  10. Concentration-dependent multiple chirality transition in halogen-bond-driven 2D self-assembly process

    Science.gov (United States)

    Miao, Xinrui; Li, Jinxing; Zha, Bao; Miao, Kai; Dong, Meiqiu; Wu, Juntian; Deng, Wenli

    2018-03-01

    The concentration-dependent self-assembly of iodine substituted thienophenanthrene derivative (5,10-DITD) is investigated at the 1-octanic acid/graphite interface using scanning tunneling microscopy. Three kinds of chiral arrangement and transition of 2D molecular assembly mainly driven by halogen bonding is clearly revealed. At high concentration the molecules self-assembled into a honeycomb-like chiral network. Except for the interchain van der Waals forces, this pattern is stabilized by intermolecular continuous Cdbnd O⋯I⋯S halogen bonds in each zigzag line. At moderate concentration, a chiral kite-like nanoarchitecture are observed, in which the Cdbnd O⋯I⋯S and I⋯Odbnd C halogen bonds, along with the molecule-solvent Cdbnd O⋯I⋯H halogen bonds are the dominated forces to determine the structural formation. At low concentration, the molecules form a chiral cyclic network resulting from the solvent coadsorption mainly by molecule-molecule Cdbnd O⋯I⋯S halogen bonds and molecule-solvent Cdbnd O⋯I⋯H halogen bonds. The density of molecular packing becomes lower with the decreasing of the solution concentration. The solution-concentration dependent self-assembly of thienophenanthrene derivative with iodine and ester chain moieties reveals that the type of intermolecular halogen bond and the number of the co-adsorbing 1-octanic acids by molecule-solvent Cdbnd O⋯I⋯H halogen bonds determine the formation and transformation of chirality. This research emphasizes the role of different types of halogen (I) bonds in the controllable supramolecular structures and provides an approach for the fabrication of chirality.

  11. Toxic Potential of Carcinogenic Polycyclic Aromatic Hydrocarbons ...

    African Journals Online (AJOL)

    DR. GODSON

    the levels of PAHs and cPAHs in crude oil samples from Gokana area and using the data to determine the ... Exploration and production activities of petroleum in ... discharges of crude oil to the environment which ... equivalent concentration of cPAHs in the soil around ... in the crude oil and establish its potential toxicity risk.

  12. Interactions between zooplankton and crude oil: toxic effects and bioaccumulation of polycyclic aromatic hydrocarbons.

    Directory of Open Access Journals (Sweden)

    Rodrigo Almeda

    Full Text Available We conducted ship-, shore- and laboratory-based crude oil exposure experiments to investigate (1 the effects of crude oil (Louisiana light sweet oil on survival and bioaccumulation of polycyclic aromatic hydrocarbons (PAHs in mesozooplankton communities, (2 the lethal effects of dispersant (Corexit 9500A and dispersant-treated oil on mesozooplankton, (3 the influence of UVB radiation/sunlight exposure on the toxicity of dispersed crude oil to mesozooplankton, and (4 the role of marine protozoans on the sublethal effects of crude oil and in the bioaccumulation of PAHs in the copepod Acartia tonsa. Mortality of mesozooplankton increased with increasing oil concentration following a sigmoid model with a median lethal concentration of 32.4 µl L(-1 in 16 h. At the ratio of dispersant to oil commonly used in the treatment of oil spills (i.e. 1∶20, dispersant (0.25 µl L(-1 and dispersant-treated oil were 2.3 and 3.4 times more toxic, respectively, than crude oil alone (5 µl L(-1 to mesozooplankton. UVB radiation increased the lethal effects of dispersed crude oil in mesozooplankton communities by 35%. We observed selective bioaccumulation of five PAHs, fluoranthene, phenanthrene, pyrene, chrysene and benzo[b]fluoranthene in both mesozooplankton communities and in the copepod A. tonsa. The presence of the protozoan Oxyrrhis marina reduced sublethal effects of oil on A. tonsa and was related to lower accumulations of PAHs in tissues and fecal pellets, suggesting that protozoa may be important in mitigating the harmful effects of crude oil exposure in copepods and the transfer of PAHs to higher trophic levels. Overall, our results indicate that the negative impact of oil spills on mesozooplankton may be increased by the use of chemical dispersant and UV radiation, but attenuated by crude oil-microbial food webs interactions, and that both mesozooplankton and protozoans may play an important role in fate of PAHs in marine environments.

  13. Interactions between Zooplankton and Crude Oil: Toxic Effects and Bioaccumulation of Polycyclic Aromatic Hydrocarbons

    Science.gov (United States)

    Almeda, Rodrigo; Wambaugh, Zoe; Wang, Zucheng; Hyatt, Cammie; Liu, Zhanfei; Buskey, Edward J.

    2013-01-01

    We conducted ship-, shore- and laboratory-based crude oil exposure experiments to investigate (1) the effects of crude oil (Louisiana light sweet oil) on survival and bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) in mesozooplankton communities, (2) the lethal effects of dispersant (Corexit 9500A) and dispersant-treated oil on mesozooplankton, (3) the influence of UVB radiation/sunlight exposure on the toxicity of dispersed crude oil to mesozooplankton, and (4) the role of marine protozoans on the sublethal effects of crude oil and in the bioaccumulation of PAHs in the copepod Acartia tonsa. Mortality of mesozooplankton increased with increasing oil concentration following a sigmoid model with a median lethal concentration of 32.4 µl L−1 in 16 h. At the ratio of dispersant to oil commonly used in the treatment of oil spills (i.e. 1∶20), dispersant (0.25 µl L−1) and dispersant- treated oil were 2.3 and 3.4 times more toxic, respectively, than crude oil alone (5 µl L−1) to mesozooplankton. UVB radiation increased the lethal effects of dispersed crude oil in mesozooplankton communities by 35%. We observed selective bioaccumulation of five PAHs, fluoranthene, phenanthrene, pyrene, chrysene and benzo[b]fluoranthene in both mesozooplankton communities and in the copepod A. tonsa. The presence of the protozoan Oxyrrhis marina reduced sublethal effects of oil on A. tonsa and was related to lower accumulations of PAHs in tissues and fecal pellets, suggesting that protozoa may be important in mitigating the harmful effects of crude oil exposure in copepods and the transfer of PAHs to higher trophic levels. Overall, our results indicate that the negative impact of oil spills on mesozooplankton may be increased by the use of chemical dispersant and UV radiation, but attenuated by crude oil-microbial food webs interactions, and that both mesozooplankton and protozoans may play an important role in fate of PAHs in marine environments. PMID:23840628

  14. Solar driven production of toxic halogenated and nitroaromatic compounds in natural seawater

    Energy Technology Data Exchange (ETDEWEB)

    Calza, Paola [Dipartimento di Chimica Analitica, Universita di Torino, via P. Giuria 5, 10125 Torino (Italy)], E-mail: paola.calza@unito.it; Massolino, Cristina; Pelizzetti, Ezio; Minero, Claudio [Dipartimento di Chimica Analitica, Universita di Torino, via P. Giuria 5, 10125 Torino (Italy)

    2008-07-15

    Natural seawater (NSW) sampled in March and June 2007 in the Gulf of Trieste, Italy, has been spiked with phenol and irradiated in a device simulating solar light spectrum and intensity. Opposite to the case of artificial seawater, for which phenol is slightly degraded by direct photolysis, in NSW the phenol degradation mediated by natural photosensitizers occurs, forming several secondary pollutants, including hydroxyderivatives (1,4-benzoquinone, resorcinol), three chlorophenol isomers, 2,3-dichlorophenol, 2- and 4-bromophenol, 2- and 4-nitrophenol, and several condensed products (2 and 4-phenoxyphenol, 2,2'-, 4,4'- and 2,4-bisphenol). These compounds are toxic to bacteria and other living organisms. Ecotoxicologic effect has been evaluated by using the Vibrio Fischeri luminescent bacteria assay. This technique uses marine organisms, and it is therefore well suited for the study on marine samples. A correlation exists between the intermediates evolution and the toxicity profile, as the largest toxicity is observed when compounds with the lower EC50 (halophenols, phenoxyphenols) are formed at higher concentration.

  15. Solar driven production of toxic halogenated and nitroaromatic compounds in natural seawater

    International Nuclear Information System (INIS)

    Calza, Paola; Massolino, Cristina; Pelizzetti, Ezio; Minero, Claudio

    2008-01-01

    Natural seawater (NSW) sampled in March and June 2007 in the Gulf of Trieste, Italy, has been spiked with phenol and irradiated in a device simulating solar light spectrum and intensity. Opposite to the case of artificial seawater, for which phenol is slightly degraded by direct photolysis, in NSW the phenol degradation mediated by natural photosensitizers occurs, forming several secondary pollutants, including hydroxyderivatives (1,4-benzoquinone, resorcinol), three chlorophenol isomers, 2,3-dichlorophenol, 2- and 4-bromophenol, 2- and 4-nitrophenol, and several condensed products (2 and 4-phenoxyphenol, 2,2'-, 4,4'- and 2,4-bisphenol). These compounds are toxic to bacteria and other living organisms. Ecotoxicologic effect has been evaluated by using the Vibrio Fischeri luminescent bacteria assay. This technique uses marine organisms, and it is therefore well suited for the study on marine samples. A correlation exists between the intermediates evolution and the toxicity profile, as the largest toxicity is observed when compounds with the lower EC50 (halophenols, phenoxyphenols) are formed at higher concentration

  16. Environmental contextualisation of potential toxic elements and polycyclic aromatic hydrocarbons in biochar

    International Nuclear Information System (INIS)

    Freddo, Alessia; Cai Chao; Reid, Brian J.

    2012-01-01

    Nine dissimilar biochars, produced from varying feedstock at different pyrolysis temperatures, are appraised with respect to concentrations of potentially toxic elements, specifically, metals, metalloids and polycyclic aromatic hydrocarbons (PAHs). Concentrations of the metals and metalloids varied with the following ranges (mg kg −1 ): 0.02–0.94, Cd; 0.12–6.48, Cr; 0.04–13.2, Cu; 0.1–1.37, Ni; 0.06–3.87, Pb; 0.94–207, Zn and 0.03–0.27, As. Σ 16 PAH concentrations (16 Environmental Protection Agency (EPA) PAHs) range between 0.08 mg kg −1 to 8.7 mg kg −1 . Subsequent comparison with background soil concentrations, concentration applied to the regulation of composted materials (Publicly Available Specification (PAS 100)) and European Union (EU) regulations relating to the application of sewage sludge to agricultural land suggest low risk associated with the concentrations of PTEs observed in biochar. Collectively, results suggest that environmental impacts attributable to metals, metalloids and PAHs associated with biochar following its application to soil are likely to be minimal. - Highlights: ► Concentrations of PTEs varied with feedstock and temperature of production. ► Of the PTEs Zn (0.94–207 mg kg −1 ) was of most priority. ► PTE levels did not infringe guidance values for compost or sewage sludge. ► Biochar ( −1 ) is unlikely to make any real difference to PTE concentrations in soil. - Environmental impacts attributable to metals, metalloids and PAHs associated with biochar following its application to soil are likely to be minimal.

  17. Synthesis of Isotactic-block-Syndiotactic Poly(methyl Methacrylate via Stereospecific Living Anionic Polymerizations in Combination with Metal-Halogen Exchange, Halogenation, and Click Reactions

    Directory of Open Access Journals (Sweden)

    Naoya Usuki

    2017-12-01

    Full Text Available Isotactic (it- and syndiotactic (st- poly(methyl methacrylates (PMMAs form unique crystalline stereocomplexes, which are attractive from both fundamental and application viewpoints. This study is directed at the efficient synthesis of it- and st-stereoblock (it-b-st- PMMAs via stereospecific living anionic polymerizations in combination with metal-halogen exchange, halogenation, and click reactions. The azide-capped it-PMMA was prepared by living anionic polymerization of MMA, which was initiated with t-BuMgBr in toluene at –78 °C, and was followed by termination using CCl4 as the halogenating agent in the presence of a strong Lewis base and subsequent azidation with NaN3. The alkyne-capped st-PMMA was obtained by living anionic polymerization of MMA, which was initiated via an in situ metal-halogen exchange reaction between 1,1-diphenylhexyl lithium and an α-bromoester bearing a pendent silyl-protected alkyne group. Finally, copper-catalyzed alkyne-azide cycloaddition (CuAAC between these complimentary pairs of polymers resulted in a high yield of it-b-st-PMMAs, with controlled molecular weights and narrow molecular weight distributions. The stereocomplexation was evaluated in CH3CN and was affected by the block lengths and ratios.

  18. Halogen bonding: A new retention mechanism for the solid phase extraction of perfluorinated iodoalkanes

    International Nuclear Information System (INIS)

    Yan Xiaoqing; Shen Qianjin; Zhao Xiaoran; Gao Haiyue; Pang Xue; Jin Weijun

    2012-01-01

    Highlights: ► Halogen bonding (XB) is firstly utilised in solid phase extraction. ► The perfluorinated iodine alkanes can be extracted by C-I⋯Cl − halogen bonding. ► The C-I⋯Cl − halogen bond is well characterised by spectroscopy methods. ► The analytes with strong halogen-bonding abilities can be selectively extracted. - Abstract: For the first time, halogen-bonding interaction is utilised in the solid phase extraction of perfluorinated iodoalkane (PFI). Nine PFIs, as model analytes, were tested, and analyses by UV, 19 F NMR and Raman spectroscopies demonstrate that the PFIs are extracted by a strong anion exchange (SAX) sorbent from n-hexane due to the C-I⋯Cl − halogen-bonding interactions. The results also show that the adsorptivities of SAX for the diiodoperfluoro-alkanes (diiodo-PFIs) were much stronger than those for the perfluoroalkyl iodides (monoiodo-PFIs). Specifically, the recoveries for 1,6-diiodoperfluorohexane and 1,8-diiodoperfluorooctane were higher than 80% when 100 mL of sample spiked with a 5 ng mL −1 analyte mixture was extracted. Interestingly, SAX had no adsorption for hexafluorobenzene at all, which is known to be unable to form a halogen bond with Cl − . The analytical performance of the halogen bond-based SPE-GC–MS method for the diiodo-PFIs was also examined in soil samples. The sorbent SAX enabled the selective extraction of four diiodo-PFIs successfully from soil samples. The recoveries of the diiodo-PFIs extracted from 5 g soil sample at the 100 ng g −1 spike level were in the range of 73.2–93.8% except 26.8% for 1,2-diiodoperfluoroethane. The limit of detection varied from 0.02 to 0.04 ng g −1 in soil samples. Overall, this work reveals the great application potential of halogen bonding in the field of solid phase extraction to selectively extract compounds with strong halogen-bonding abilities.

  19. Ultraviolet radiation and blue-light emissions from spotlights incorporating tungsten halogen lamps

    CERN Document Server

    MacKinlay, Alistair F; Whillock, M J

    1989-01-01

    This report summarises measurements of the ultraviolet radiation and blue-light emissions from eleven 'desk-top' tungsten halogen (quartz) lamps and one 'floor-standing' tungsten halogen (quartz) lamp available in the UK. Values of occupational hazard weighted and erythemally weighted ultraviolet radiation irradiance and measurements and relevant calculations of blue-light hazards are presented. It is concluded that the safety design of some desk-top tungsten halogen lamps is inadequate to prevent unnecessary exposure of the skin to potentially harmful ultraviolet radiation. It is recommended that all tungsten halogen lamps should have sufficient filtration to reduce their ultraviolet emissions to an acceptably low level. As long as the comfort aversion responses of the eye are respected, direct viewing of the lamps examined should not constitute a retinal hazard.

  20. Ultraviolet radiation and blue-light emissions from spotlights incorporating tungsten halogen lamps

    International Nuclear Information System (INIS)

    McKinlay, A.F.; Whillock, M.J.; Meulemans, C.C.E.

    1989-07-01

    This report summarises measurements of the ultraviolet radiation and blue-light emissions from eleven 'desk-top' tungsten halogen (quartz) lamps and one 'floor-standing' tungsten halogen (quartz) lamp available in the UK. Values of occupational hazard weighted and erythemally weighted ultraviolet radiation irradiance and measurements and relevant calculations of blue-light hazards are presented. It is concluded that the safety design of some desk-top tungsten halogen lamps is inadequate to prevent unnecessary exposure of the skin to potentially harmful ultraviolet radiation. It is recommended that all tungsten halogen lamps should have sufficient filtration to reduce their ultraviolet emissions to an acceptably low level. As long as the comfort aversion responses of the eye are respected, direct viewing of the lamps examined should not constitute a retinal hazard. (author)

  1. A metabolomics strategy to assess the combined toxicity of polycyclic aromatic hydrocarbons (PAHs) and short-chain chlorinated paraffins (SCCPs).

    Science.gov (United States)

    Wang, Feidi; Zhang, Haijun; Geng, Ningbo; Ren, Xiaoqian; Zhang, Baoqin; Gong, Yufeng; Chen, Jiping

    2018-03-01

    The combined toxicity of mixed chemicals is usually evaluated according to several specific endpoints, and other potentially toxic effects are disregarded. In this study, we provided a metabolomics strategy to achieve a comprehensive understanding of toxicological interactions between mixed chemicals on metabolism. The metabolic changes were quantified by a pseudotargeted analysis, and the types of combined effects were quantitatively discriminated according to the calculation of metabolic effect level index (MELI). The metabolomics strategy was used to assess the combined effects of polycyclic aromatic hydrocarbons (PAHs) and short-chain chlorinated paraffins (SCCPs) on the metabolism of human hepatoma HepG2 cells. Our data suggested that exposure to a combination of PAHs and SCCPs at human internal exposure levels could result in an additive effect on the overall metabolism, whereas diverse joint effects were observed on various metabolic pathways. The combined exposure could induce a synergistic up-regulation of phospholipid metabolism, an additive up-regulation of fatty acid metabolism, an additive down-regulation of tricarboxylic acid cycle and glycolysis, and an antagonistic effect on purine metabolism. SCCPs in the mixture acted as the primary driver for the acceleration of phospholipid and fatty acid metabolism. Lipid metabolism disorder caused by exposure to a combination of PAHs and SCCPs should be an important concern for human health. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. phytochemical composition and acute toxicity evaluation of aqueous

    African Journals Online (AJOL)

    DR. AMINU

    2012-12-02

    Dec 2, 2012 ... based upon single chemicals, many medicinal and aromatic plants exert their ... metaphorically used to describe toxic effects on larger and more complex ..... Chemical Industries. Branch, Division of Industrial Operations,.

  3. Determination of halogens by flame emission of metal halogenides

    International Nuclear Information System (INIS)

    Henrion, G.; Marquardt, D.; Stoecker, B.

    1979-01-01

    The A-B systems InF, InCl, InBr, and InI have been excited by laminar H 2 -N 2 flames in order to dermine individual halogens or their mixtures qualitatively or quantitatively. In optimizing the fuel gas composition two different behavior patterns have been found for band intensities, which are correlated with binding energies of InX (X = halogen). The low temperature of the flame leads to complicated matrix effects which first of all result from effects on excitation and from competitive reactions. In general, cations cause a decreased intensity. Therefore, salts have to be converted into hydrohalide acids by ion exchange. Qualitative determinations of individual halogens are possible at a 500 to 50,000fold excess of the others, whereas quantitative determinations can be performed at a 100 to 5,000fold excess in 10 -4 molar solutions with errors of 2 to 10 per cent. (author)

  4. High-temperature peaks of thermostimulated luminescence in the ammonium halogens

    International Nuclear Information System (INIS)

    Kim, L.M.; Musenova, Eh.K.; Mukhamedrakhimov, K.U.

    2003-01-01

    The ammonium halogen crystals (AHC) are the close analogs of the alkali halogen crystals by the type of chemical bonds and crystal lattice structure. The ammonium halogen after irradiation by X-rays within 80-300 K range have two peaks of thermo-stimulation luminescence. Its maximums in dependence of anions type are in the 110-120 K and 170-180 K ranges. The first range is related with activation of auto-localized holes migration, and the second one - with the NH 3 + defects decay. Experimentally is established, that the pure ammonium halogens have memory about the previous irradiation at heating up to 300 K. After repeat irradiation the recombination luminescence high-temperature peak's shoulder is appearing. The second luminescence peak's shoulder revealing does not depend on the impurity center nature. It is known, that in the AHC there is the next thermo-stimulation luminescence peak within 340-360 K. The thermal annealing of this peak leads to the memory effect disappearance. So, the observing phenomenon is related with own defect of the matrix in the cation sublattice. Experimentally is established, that at a room temperature the AHC memorizing about previous irradiation during 20 h

  5. Retention efficiencies of halogenated and non-halogenated hydrocarbons in selected wetland ecosystem in Lake Victoria Basin

    Directory of Open Access Journals (Sweden)

    Shadrack Mule

    2015-06-01

    Full Text Available The determination of retention efficiencies of halogenated and non-halogenated hydrocarbon in selected wetland ecosystems in Lake Victoria basin was carried out. Qualitative and quantitative determination of the presence of residual hydrocarbons in Kigwal/Kimondi, Nyando and Nzoia wetland ecosystems using Gas Chromatography - Mass Spectrometer (GC-MS instrument indicated the presence of residual organochlorines, organophosphorus, carbamates and synthetic pyrethroid hydrocarbons in water, sediment and plant materials. In order to compare the retention efficiencies of the wetlands, the wetland ecosystems were divided into three different sections, namely: inlet, mid and outlet. Calculations of mass balances of residual halogenated and non-halogenated hydrocarbons at the respective sections was done taking into account the partition of the studied compounds in samples of water, sediments and papyrus reed plant materials and analyzed using validated Gas Chromatography - Mass Spectrometer (GC-MS method. From the analysis, several residual hydrocarbons namely: bendiocarb, benzene hexachloride (BHC, carbaryl, cypermethrin, decis, deltamethrin, diazinon, dieldrin, DDT, DDD, DDE, malathion, propoxur, sumithion, 5-phenylrhodanine, 1,3,5-trichlorobenzene, 1-(2-phenoxybenzylhydrazine were detected and quantified. The levels of the selected residual hydrocarbons in water samples were used to calculate the retention efficiencies of a specific hydrocarbon and the values recorded. Generally, River Nyando wetland recorded mean percentage retention efficiencies of 76 and 94% for dry and rainy seasons respectively; Kigwal/Kimondi wetland had seasonal mean percentage retention efficiencies of 63 to 78%. River Nzoia also had calculated seasonal mean percentage retention efficiencies of between 56 to 88%. Dry season had lower mean percentages retention efficiencies as compared to rainy season in the three wetlands of interest during the period of study. The study

  6. The effects of polycyclic aromatic hydrocarbons on the immune system of fish: A review

    International Nuclear Information System (INIS)

    Reynaud, S.; Deschaux, P.

    2006-01-01

    Polycyclic aromatic hydrocarbons are an important class of environmental pollutants that are known to be carcinogenic and immunotoxic. This review summarizes the diverse literature on the effects of these pollutants on innate and acquired immunity in fish and the mechanism of PAH-induced immunotoxicity. Among innate immune parameters, many authors have focused on macrophage activities in fish exposed to polycyclic aromatic hydrocarbons. Macrophage respiratory burst appears especially sensitive to polycyclic aromatic hydrocarbons. Among acquired immune parameters, lymphocyte proliferation appears highly sensitive to polycyclic aromatic hydrocarbon exposure. However, the effects of polycyclic aromatic hydrocarbons on both specific and non-specific immunity are contradictory and depend on the mode of exposure, the dose used or the species studied. In contrast to mammals, fewer studies have been done in fish to determine the mechanism of polycyclic aromatic hydrocarbon-induced toxicity. This phenomenon seems to implicate different intracellular mechanisms such as metabolism by cytochrome P4501A, binding to the Ah-receptor, or increased intracellular calcium. Advances in basic knowledge of fish immunity should lead to improvements in monitoring fish health and predicting the impact of polycyclic aromatic hydrocarbons on fish populations, which is a fundamental ecotoxicological goal

  7. The effects of polycyclic aromatic hydrocarbons on the immune system of fish: A review

    Energy Technology Data Exchange (ETDEWEB)

    Reynaud, S. [Laboratoire d' Ecologie Alpine. UMR CNRS 5553. Universite Joseph Fourier. BP 53. 38041 Grenoble cedex 9 (France) and Laboratory of General and Comparative Immunophysiology, Science Teaching and Research Unit, 123, av. Albert Thomas, 87060 Limoges (France)]. E-mail: stephane.reynaud@ujf-grenoble.fr; Deschaux, P. [Laboratory of General and Comparative Immunophysiology, Science Teaching and Research Unit, 123, av. Albert Thomas, 87060 Limoges (France)

    2006-05-01

    Polycyclic aromatic hydrocarbons are an important class of environmental pollutants that are known to be carcinogenic and immunotoxic. This review summarizes the diverse literature on the effects of these pollutants on innate and acquired immunity in fish and the mechanism of PAH-induced immunotoxicity. Among innate immune parameters, many authors have focused on macrophage activities in fish exposed to polycyclic aromatic hydrocarbons. Macrophage respiratory burst appears especially sensitive to polycyclic aromatic hydrocarbons. Among acquired immune parameters, lymphocyte proliferation appears highly sensitive to polycyclic aromatic hydrocarbon exposure. However, the effects of polycyclic aromatic hydrocarbons on both specific and non-specific immunity are contradictory and depend on the mode of exposure, the dose used or the species studied. In contrast to mammals, fewer studies have been done in fish to determine the mechanism of polycyclic aromatic hydrocarbon-induced toxicity. This phenomenon seems to implicate different intracellular mechanisms such as metabolism by cytochrome P4501A, binding to the Ah-receptor, or increased intracellular calcium. Advances in basic knowledge of fish immunity should lead to improvements in monitoring fish health and predicting the impact of polycyclic aromatic hydrocarbons on fish populations, which is a fundamental ecotoxicological goal.

  8. Halogens determination in vegetable NBS standard reference materials

    International Nuclear Information System (INIS)

    Stella, R.; Genova, N.; Di Casa, M.

    1977-01-01

    Levels of all four halogens in Orchard Leaves, Pine Needles and Tomato Leaves NBS reference standards were determined. For fluorine a spiking isotope dilution method was used followed by HF absorption on glass beads. Instrumental nuclear activation analysis was adopted for chlorine and bromine determination. Radiochemical separation by a distillation procedure was necessary for iodine nuclear activation analysis after irradiation. Activation parameters of Cl, Br and I are reported. Results of five determinations for each halogen in Orchard Leaves, Pine Needles and Tomato Leaves NBS Standard Materials and Standard deviations of the mean are reported. (T.I.)

  9. Halogen Bonding Involving CO and CS with Carbon as the Electron Donor

    Directory of Open Access Journals (Sweden)

    Janet E. Del Bene

    2017-11-01

    Full Text Available MP2/aug’-cc-pVTZ calculations have been carried out to investigate the halogen-bonded complexes formed when CO and CS act as electron-pair donors through C to ClF, ClNC, ClCl, ClOH, ClCN, ClCCH, and ClNH2. CO forms only complexes stabilized by traditional halogen bonds, and all ClY molecules form traditional halogen-bonded complexes with SC, except ClF which forms only an ion-pair complex. Ion-pair complexes are also found on the SC:ClNC and SC:ClCl surfaces. SC:ClY complexes stabilized by traditional halogen bonds have greater binding energies than the corresponding OC:ClY complexes. The largest binding energies are found for the ion-pair SC–Cl+:−Y complexes. The transition structures which connect the complex and the ion pair on SC:ClNC and SC:ClCl potential surfaces provide the barriers for inter-converting these structures. Charge-transfer from the lone pair on C to the σ-hole on Cl is the primary charge-transfer interaction stabilizing OC:ClY and SC:ClY complexes with traditional halogen bonds. A secondary charge-transfer occurs from the lone pairs on Cl to the in-plane and out-of-plane π antibonding orbitals of ClY. This secondary interaction assumes increased importance in the SC:ClNH2 complex, and is a factor leading to its unusual structure. C–O and C–S stretching frequencies and 13C chemical shieldings increase upon complex formation with ClY molecules. These two spectroscopic properties clearly differentiate between SC:ClY complexes and SC–Cl+:−Y ion pairs. Spin–spin coupling constants 1xJ(C–Cl for OC:ClY complexes increase with decreasing distance. As a function of the C–Cl distance, 1xJ(C–Cl and 1J(C–Cl provide a fingerprint of the evolution of the halogen bond from a traditional halogen bond in the complexes, to a chlorine-shared halogen bond in the transition structures, to a covalent bond in the ion pairs.

  10. A Survey of Electron Impact Cross-Sections for Halogens and Halogen Compounds of Interest to Plasma Processing

    Science.gov (United States)

    Sharma, S. P.; Rao, M. V. V. S.; Arnold, James O. (Technical Monitor)

    1998-01-01

    Published electron impact cross section data on halogens Cl2, F2, and halogen containing compounds such as Cx Fy, HCl, Cx Cly Fz are reviewed and critically evaluated based on the information provided by various researchers. The present work reports data on electron impact excitation, ionization, dissociation, electron attachment, electron detachment, and photo detachment. Elastic scattering cross sections and data on bulk properties such as diffusion coefficients in various background gases are also evaluated. Since some of the cross sectional data is derived from indirect measurements such as drift velocity, care has been taken to reconcile the differences among the reported data with due attention to the measurement technique. In conclusion, the processes with no or very limited amount of data and questionable set of data are identified and recommendation for further research direction is made.

  11. Photoenhanced Toxicity of Petroleum to Aquatic Invertebrates and Fish: Review of State of the Science

    Science.gov (United States)

    Photoenhanced toxicity is a distinct mechanism of petroleum toxicity that is mediated by the interaction of solar radiation with specific polycyclic aromatic compounds (PACs) in oil. Phototoxicity is observed as a 2 to greater than 1000 fold increase in chemical toxicity to aqua...

  12. Halogen degassing during ascent and eruption of water-poor basaltic magma

    Science.gov (United States)

    Edmonds, M.; Gerlach, T.M.; Herd, Richard A.

    2009-01-01

    A study of volcanic gas composition and matrix glass volatile concentrations has allowed a model for halogen degassing to be formulated for K??lauea Volcano, Hawai'i. Volcanic gases emitted during 2004-2005 were characterised by a molar SO2/HCl of 10-64, with a mean of 33; and a molar HF/HCl of 0-5, with a mean of 1.0 (from approximately 2500 measurements). The HF/HCl ratio was more variable than the SO2/HCl ratio, and the two correlate weakly. Variations in ratio took place over rapid timescales (seconds). Matrix glasses of Pele's tears erupted in 2006 have a mean S, Cl and F content of 67, 85 and 173??ppm respectively, but are associated with a large range in S/F. A model is developed that describes the open system degassing of halogens from parental magmas, using the glass data from this study, previously published results and parameterisation of sulphur degassing from previous work. The results illustrate that halogen degassing takes place at pressures of < 1??MPa, equivalent to < ~ 35??m in the conduit. Fluid-melt partition coefficients for Cl and F are low (< 1.5); F only degasses appreciably at < 0.1??MPa above atmospheric pressure, virtually at the top of the magma column. This model reproduces the volcanic gas data and other observations of volcanic activity well and is consistent with other studies of halogen degassing from basaltic magmas. The model suggests that variation in volcanic gas halogen ratios is caused by exsolution and gas-melt separation at low pressures in the conduit. There is no evidence that either diffusive fractionation or near-vent chemical reactions involving halogens is important in the system, although these processes cannot be ruled out. The fluxes of HCl and HF from K??lauea during 2004-5 were ~ 25 and 12??t/d respectively. ?? 2008 Elsevier B.V.

  13. Syntheses of cytotoxic novel arctigenin derivatives bearing halogen and alkyl groups on aromatic rings.

    Science.gov (United States)

    Yamauchi, Satoshi; Wukirsari, Tuti; Ochi, Yoshiaki; Nishiwaki, Hisashi; Nishi, Kosuke; Sugahara, Takuya; Akiyama, Koichi; Kishida, Taro

    2017-09-01

    The new lignano-9,9'-lactones (α,β-dibenzyl-γ-butyrolactone lignans), which showed the higher cytotoxicity than arctigenin, were synthesized. The well-known cytotoxic arctigenin showed activity against HL-60 cells (EC 50 =12μM), however, it was inactive against HeLa cells (EC 50 >100μM). The synthesized (3,4-dichloro, 2'-butoxy)-derivative 55 and (3,4-dichloro, 4'-butyl)-derivative 66 bearing the lignano-9,9'-lactone structures showed the EC 50 values of 10μM and 9.4μM against HL-60 cells, respectively. Against HeLa cells, the EC 50 value of the derivative 66 was 27μM. By comparing the activities with the corresponding 9,9'-epoxy structure (tetrahydrofuran compounds), the importance of the lactone structure of 55 and 66 for the higher activities was shown. The substituents on the aromatic ring of the lignano-9,9'-lactones affected the cytotoxicity level, observing more than 10-fold difference. Copyright © 2017. Published by Elsevier Ltd.

  14. Cardiac toxicity of 5-ring polycyclic aromatic hydrocarbons is differentially dependent on the aryl hydrocarbon receptor 2 isoform during zebrafish development

    International Nuclear Information System (INIS)

    Incardona, John P.; Linbo, Tiffany L.; Scholz, Nathaniel L.

    2011-01-01

    Petroleum-derived compounds, including polycyclic aromatic hydrocarbons (PAHs), commonly occur as complex mixtures in the environment. Recent studies using the zebrafish experimental model have shown that PAHs are toxic to the embryonic cardiovascular system, and that the severity and nature of this developmental cardiotoxicity varies by individual PAH. In the present study we characterize the toxicity of the relatively higher molecular weight 5-ring PAHs benzo[a]pyrene (BaP), benzo[e]pyrene (BeP), and benzo[k]fluoranthene (BkF). While all three compounds target the cardiovascular system, the underlying role of the ligand-activated aryl hydrocarbon receptor (AHR2) and the tissue-specific induction of the cytochrome p450 metabolic pathway (CYP1A) were distinct for each. BaP exposure (40 μM) produced AHR2-dependent bradycardia, pericardial edema, and myocardial CYP1A immunofluorescence. By contrast, BkF exposure (4–40 μM) caused more severe pericardial edema, looping defects, and erythrocyte regurgitation through the atrioventricular valve that were AHR2-independent (i.e., absent myocardial or endocardial CYP1A induction). Lastly, exposure to BeP (40 μM) yielded a low level of CYP1A+ signal in the vascular endothelium of the head and trunk, without evident toxic effects on cardiac function or morphogenesis. Combined with earlier work on 3- and 4-ring PAHs, our findings provide a more complete picture of how individual PAHs may drive the cardiotoxicity of mixtures in which they predominate. This will improve toxic injury assessments and risk assessments for wild fish populations that spawn in habitats altered by overlapping petroleum-related human impacts such as oil spills, urban stormwater runoff, or sediments contaminated by legacy industrial activities. -- Highlights: ► PAH compounds with 5 rings in different arrangements caused differential tissue-specific patterns of CYP1A induction in zebrafish embryos. ► These compounds produced differential cardiac

  15. Toxicity alarm: Case history

    International Nuclear Information System (INIS)

    Hogan, D.; Retallack, J.

    1993-01-01

    In late fall 1991, the Novacor petrochemical plant near Joffre, Alberta experienced a toxicity alarm, the first since its startup 14 years ago. Fish exposed to a normal toxicity test were stressed within 2 h and showed 100% mortality after 24 h. A history of the events leading up to, during, and after the toxicity alarm is presented. The major effluent sources were three cooling water systems. Although these sources are well characterized, the event causes were not immediately clear. Initial toxic screening indicated that one was very toxic, another moderately toxic, and the third not toxic at all. All three systems utilized the same chemical treatment program to avoid fouling: stabilized phosphates with minor variants. The most toxic of the cooling systems operated at 10-12 cycles, had three chemicals for biocide control, and had three makeup streams. Toxic and nontoxic system characteristics were compared. An in-depth modified toxicity identification and evaluation program was then performed to identify and evaluate the cause of the toxicity alarm for future prevention. The most probable causes of toxicity were identified by elimination. The combination of high numbers of cycles, hydrocarbons in the makeup water, and bromine added as an antifoulant resulted in formation of aromatic bromamines which are capable of causing the toxic condition experienced. 2 tabs

  16. Flow cytometry detection of planktonic cells with polycyclic aromatic hydrocarbons sorbed to cell surfaces

    KAUST Repository

    Cerezo, Maria I.; Linden, Matthew; Agusti, Susana

    2017-01-01

    Polycyclic aromatic hydrocarbons are very important components of oil pollution. These pollutants tend to sorb to cell surfaces, exerting toxic effects on organisms. Our study developed a flow cytometric method for the detection of PAHs sorbed

  17. Anthropogenic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Hutzinger, O

    1982-01-01

    The chapters about lead and arsenic, beryllium, selenium and vanadium describe production, use and natural occurrence, chemistry, analytical methods, transport behavior in the environment, physical, chemical and photochemical reactions, metabolism, exposure and accumulation and toxicity. The chapter of C/sub 1/ and C/sub 2/ halocarbons deals with use patterns and losses to the environment, occurrence in the environment, distribution and degradation and effects on living organisms. The chapter of halogenated aromatics treats production and properties, uses and losses to and occurrence in the environment, distribution and degradation in the environment, effects on biological systems. The chapter of volatile aromatics involves production and emissions, concentration in the environment, metabolism and biological effects in mammals. The chapter on surfactants is divided in two parts: chemistry and environment.

  18. Risk assessment for halogenated solvents

    International Nuclear Information System (INIS)

    Travis, C.C.

    1988-01-01

    A recent development in the cancer risk area is the advent of biologically based pharmacokinetic and pharmacodynamic models. These models allow for the incorporation of biological and mechanistic data into the risk assessment process. These advances will not only improve the risk assessment process for halogenated solvents but will stimulate and guide basic research in the biological area

  19. Literature Survey and Further Studies on the 3-Alkylation of N-Unprotected 3-Monosubstituted Oxindoles. Practical Synthesis of N-Unprotected 3,3-Disubstituted Oxindoles and Subsequent Transformations on the Aromatic Ring.

    Science.gov (United States)

    Kókai, Eszter; Simig, Gyula; Volk, Balázs

    2016-12-26

    The paper provides a comprehensive review of the base-catalysed C3-alkylation of N-unprotected-3-monosubstituted oxindoles. Based on a few, non-systematic studies described in the literature using butyllithium as the deprotonating agent, an optimized method has now been elaborated, via the corresponding lithium salt, for the selective C3-alkylation of this family of compounds. The optimal excess of butyllithium and alkylating agent, and the role of the halogen atom in the latter (alkyl bromides vs. iodides) were also studied. The alkylation protocol has also been extended to some derivatives substituted at the aromatic ring. Finally, various substituents were introduced into the aromatic ring of the N-unprotected 3,3-dialkyloxindoles obtained by this optimized method.

  20. Literature Survey and Further Studies on the 3-Alkylation of N-Unprotected 3-Monosubstituted Oxindoles. Practical Synthesis of N-Unprotected 3,3-Disubstituted Oxindoles and Subsequent Transformations on the Aromatic Ring

    Directory of Open Access Journals (Sweden)

    Eszter Kókai

    2016-12-01

    Full Text Available The paper provides a comprehensive review of the base-catalysed C3-alkylation of N-unprotected-3-monosubstituted oxindoles. Based on a few, non-systematic studies described in the literature using butyllithium as the deprotonating agent, an optimized method has now been elaborated, via the corresponding lithium salt, for the selective C3-alkylation of this family of compounds. The optimal excess of butyllithium and alkylating agent, and the role of the halogen atom in the latter (alkyl bromides vs. iodides were also studied. The alkylation protocol has also been extended to some derivatives substituted at the aromatic ring. Finally, various substituents were introduced into the aromatic ring of the N-unprotected 3,3-dialkyloxindoles obtained by this optimized method.

  1. Examination of the structure-toxicity relationships of L-cysteine-S-conjugates of halogenated alkenes and their corresponding mercapturic acids in rat renal tissue slices.

    NARCIS (Netherlands)

    Stijntjes, G.J.; Commandeur, J.N.M.; te Koppele, J.M.; McGuinness, S; Gandolfi, A.J.; Vermeulen, N.P.E.

    1993-01-01

    Rat kidney slices were produced using a modified version of a mechanical tissue slicer. The slices were incubated with various concentrations of l-cysteine conjugates and mercapturic acids of halogenated alkenes in a submersion incubation system. The slices showed a time- and concentration-dependent

  2. Polycyclic aromatic hydrocarbons in some grounded coffee brands.

    Science.gov (United States)

    Grover, Inderpreet Singh; Sharma, Rashmi; Singh, Satnam; Pal, Bonamali

    2013-08-01

    Potentially toxic 16 priority polycyclic aromatic hydrocarbons (PAHs) were determined in four brands of grounded coffee. Four to 13 PAHs were detected. Concentrations of total PAHs in different brands of coffee samples were in the range of 831.7-1,589.7 μg/kg. Benzo[a]pyrene (2A: probable human carcinogen) was found in Nescafe Premium whereas naphthalene (2B: possible human carcinogen) was found in all the samples of coffee.

  3. The X40×10 Halogen Bonding Benchmark Revisited: Surprising Importance of (n-1)d Subvalence Correlation.

    Science.gov (United States)

    Kesharwani, Manoj K; Manna, Debashree; Sylvetsky, Nitai; Martin, Jan M L

    2018-03-01

    We have re-evaluated the X40×10 benchmark for halogen bonding using conventional and explicitly correlated coupled cluster methods. For the aromatic dimers at small separation, improved CCSD(T)-MP2 "high-level corrections" (HLCs) cause substantial reductions in the dissociation energy. For the bromine and iodine species, (n-1)d subvalence correlation increases dissociation energies and turns out to be more important for noncovalent interactions than is generally realized; (n-1)sp subvalence correlation is much less important. The (n-1)d subvalence term is dominated by core-valence correlation; with the smaller cc-pVDZ-F12-PP and cc-pVTZ-F12-PP basis sets, basis set convergence for the core-core contribution becomes sufficiently erratic that it may compromise results overall. The two factors conspire to generate discrepancies of up to 0.9 kcal/mol (0.16 kcal/mol RMS) between the original X40×10 data and the present revision.

  4. On the Toxicity of the Aromatic Diamines and their Tetramethylcarboxylic Acid Derivatives

    OpenAIRE

    Gili, Pedro; Mederos, Alfredo

    2000-01-01

    The use of the theoretical PALLAS 3.0 program, to study the toxic behaviour of tetramethylcarboxylic acids, potential pharmaceuticals derived from o-phenylenediamines, indicates that o-phenylenediamines are highly toxic (level 1), while the tetramethycarboxylic acid derivatives (o-PhDTA and 3,4-TDTA) are slightly toxic, similar to EDTA (level 3). Therefore these ligands o-PhDTA and 3,4-TDTA, similar to EDTA, can be used as sequestering agents of toxic metals and overload of essential metals i...

  5. FIELD SCREENING FOR HALOGENATED VOLATILE ORGANIC COMPOUNDS

    Energy Technology Data Exchange (ETDEWEB)

    John F. Schabron; Joseph F. Rovani, Jr.; Theresa M. Bomstad

    2003-07-01

    Western Research Institute (WRI) is continuing work toward the development of new screening methodology and a test kit to measure halogenated volatile organic compounds (VOCs) in the field. Heated diode and corona discharge sensors are commonly used to detect leaks of refrigerants from air conditioners, freezers, and refrigerators. They are both selective to the presence of halogens. In prior work, the devices were tested for response to carbon tetrachloride, heptane, toluene, and water vapors. In the current work, sensor response was evaluated with sixteen halogenated VOCs relative to carbon tetrachloride. The results show that the response of the various chlorinated VOCs is within an order of magnitude of the response to carbon tetrachloride for each of the sensors. Thus, for field screening a single response factor can be used. Both types of leak detectors are being further modified to provide an on-board LCD signal readout, which is related to VOC concentration. The units will be fully portable and will operate with 115-V line or battery power. Signal background, noise level, and response data on the Bacharach heated diode detector and the TIF corona discharge detector show that when the response curves are plotted against the log of concentration, the plot is linear to the upper limit for the particular unit, with some curvature at lower levels. When response is plotted directly against concentration, the response is linear at the low end and is curved at the high end. The dynamic ranges for carbon tetrachloride of the two devices from the lower detection limit (S/N=2) to signal saturation are 4-850 vapor parts per million (vppm) for the corona discharge unit and 0.01-70 vppm for the heated diode unit. Additional circuit modifications are being made to lower the detection limit and increase the dynamic response range of the corona discharge unit. The results indicate that both devices show potential utility for future analytical method development work toward

  6. Influence of activated carbon surface acidity on adsorption of heavy metal ions and aromatics from aqueous solution

    International Nuclear Information System (INIS)

    Sato, Sanae; Yoshihara, Kazuya; Moriyama, Koji; Machida, Motoi; Tatsumoto, Hideki

    2007-01-01

    Adsorption of toxic heavy metal ions and aromatic compounds onto activated carbons of various amount of surface C-O complexes were examined to study the optimum surface conditions for adsorption in aqueous phase. Cadmium(II) and zinc(II) were used as heavy metal ions, and phenol and nitrobenzene as aromatic compounds, respectively. Activated carbon was de-ashed followed by oxidation with nitric acid, and then it was stepwise out-gassed in helium flow up to 1273 K to gradually remove C-O complexes introduced by the oxidation. The oxidized activated carbon exhibited superior adsorption for heavy metal ions but poor performance for aromatic compounds. Both heavy metal ions and aromatics can be removed to much extent by the out-gassed activated carbon at 1273 K. Removing C-O complexes, the adsorption mechanisms would be switched from ion exchange to Cπ-cation interaction for the heavy metals adsorption, and from some kind of oxygen-aromatics interaction to π-π dispersion for the aromatics

  7. Halogenation of Hydraulic Fracturing Additives in the Shale Well Parameter Space

    Science.gov (United States)

    Sumner, A. J.; Plata, D.

    2017-12-01

    Horizontal Drilling and Hydraulic fracturing (HDHF) involves the deep-well injection of a `fracking fluid' composed of diverse and numerous chemical additives designed to facilitate the release and collection of natural gas from shale plays. The potential impacts of HDHF operations on water resources and ecosystems are numerous, and analyses of flowback samples revealed organic compounds from both geogenic and anthropogenic sources. Furthermore, halogenated chemicals were also detected, and these compounds are rarely disclosed, suggesting the in situ halogenation of reactive additives. To test this transformation hypothesis, we designed and operated a novel high pressure and temperature reactor system to simulate the shale well parameter space and investigate the chemical reactivity of twelve commonly disclosed and functionally diverse HDHF additives. Early results revealed an unanticipated halogenation pathway of α-β unsaturated aldehyde, Cinnamaldehyde, in the presence of oxidant and concentrated brine. Ongoing experiments over a range of parameters informed a proposed mechanism, demonstrating the role of various shale-well specific parameters in enabling the demonstrated halogenation pathway. Ultimately, these results will inform a host of potentially unintended interactions of HDHF additives during the extreme conditions down-bore of a shale well during HDHF activities.

  8. Global simulation of aromatic volatile organic compounds in the atmosphere

    Science.gov (United States)

    Cabrera Perez, David; Taraborrelli, Domenico; Pozzer, Andrea

    2015-04-01

    Among the large number of chemical compounds in the atmosphere, the organic group plays a key role in the tropospheric chemistry. Specifically the subgroup called aromatics is of great interest. Aromatics are the predominant trace gases in urban areas due to high emissions, primarily by vehicle exhausts and fuel evaporation. They are also present in areas where biofuel is used (i.e residential wood burning). Emissions of aromatic compounds are a substantial fraction of the total emissions of the volatile organic compounds (VOC). Impact of aromatics on human health is very important, as they do not only contribute to the ozone formation in the urban environment, but they are also highly toxic themselves, especially in the case of benzene which is able to trigger a range of illness under long exposure, and of nitro-phenols which cause detrimental for humans and vegetation even at very low concentrations. The aim of this work is to assess the atmospheric impacts of aromatic compounds on the global scale. The main goals are: lifetime and budget estimation, mixing ratios distribution, net effect on ozone production and OH loss for the most emitted aromatic compounds (benzene, toluene, xylenes, ethylbenzene, styrene and trimethylbenzenes). For this purpose, we use the numerical chemistry and climate simulation ECHAM/MESSy Atmospheric Chemistry (EMAC) model to build the global atmospheric budget for the most emitted and predominant aromatic compounds in the atmosphere. A set of emissions was prepared in order to include biomass burning, vegetation and anthropogenic sources of aromatics into the model. A chemical mechanism based on the Master Chemical Mechanism (MCM) was developed to describe the chemical oxidation in the gas phase of these aromatic compounds. MCM have been reduced in terms of number of chemical equation and species in order to make it affordable in a 3D model. Additionally other features have been added, for instance the production of HONO via ortho

  9. The Use of Modified Bentonite for Removal of Aromatic Organics from Contaminated Soil.

    Science.gov (United States)

    Gitipour; Bowers; Bodocsi

    1997-12-15

    This study investigates the clay-aromatic interactions with a view to the use of bentonite clay for binding benzene, toluene, ethylbenzene, and o-xylene (BTEX compounds) in contaminated soils. BTEX compounds are the most toxic aromatic constituents of gasoline present in many underground storage tanks. Modified (organophilic) and ordinary bentonites are used to remove these organics. The organophilic bentonites are prepared by replacing the exchangeable inorganic cations present in bentonite particles with a quaternary ammonium salt. Various clay-to-soil ratios were applied to determine the efficiency of the modified bentonite in enhancing the cement-based solidification/stabilization (S/S) of BTEX contaminated soils. Toxicity characteristics leaching procedure (TCLP) tests were performed on soil samples to evaluate the leaching of the organics. In addition, X-ray diffraction analyses were conducted to assess the changes in the basal spacing of the clays as a result of their interaction with BTEX compounds. The findings of this study reveal that organophilic bentonite can act as a successful adsorbent for removing the aromatic organics from contaminated soil. Thus, this material is viable for enhancing the performance of cement-based S/S processes, as an adsorbent for petroleum spills, and for landfill liners and slurry walls. Copyright 1997 Academic Press.

  10. The use of modified bentonite for removal of aromatic organics from contaminated soil

    International Nuclear Information System (INIS)

    Gitipour, S.; Bowers, M.T.; Bodocsi, A.

    1997-01-01

    This study investigates the clay-aromatic interactions with a view to the use of bentonite clay for binding benzene, toluene, ethylbenzene, and o-xylene (BTEX compounds) in contaminated soils. BTEX compounds are the most toxic aromatic constituents of gasoline present in many underground storage tanks. Modified (organophilic) and ordinary bentonites are used to remove these organics. The organophilic bentonites are prepared by replacing the exchangeable inorganic cations present in bentonite particles with a quaternary ammonium salt. Various clay-to-soil ratios were applied to determine the efficiency of the modified bentonite in enhancing the cement-based solidification/stabilization (S/S) of BTEX contaminated soils. Toxicity characteristics leaching procedure (TCLP) tests were performed on soil samples to evaluate the leaching of the organics. In addition, X-ray diffraction analyses were conducted to assess the changes in the basal spacing of the clays as a result of their interaction with BTEX compounds. The findings of this study reveal that organophilic bentonite can act as a successful adsorbent for removing the aromatic organics from contaminated soil. Thus, this material is viable for enhancing the performance of cement-based S/S processes, as an adsorbent for petroleum spills, and for landfill liners and slurry walls

  11. Design and screening of ASIC inhibitors based on aromatic diamidines for combating neurological disorders.

    Science.gov (United States)

    Chen, Xuanmao; Orser, Beverley A; MacDonald, John F

    2010-12-01

    Acid sensing ion channels (ASICs) are implicated in various brain functions including learning and memory and are involved in a number of neurological disorders such as pain, ischemic stroke, depression, and multiple sclerosis. We have recently defined ASICs as one of receptor targets of aromatic diamidines in neurons. Aromatic diamidines are DNA-binding agents and have long been used in the treatment of leishmaniasis, trypanosomiasis, pneumocystis pneumonia and babesiosis. Moreover, some aromatic diamidines are used as skin-care and baby products and others have potential to suppress tumor growth or to combat malaria. A large number of aromatic diamidines or analogs have been synthesized. Many efforts are being made to optimize the therapeutic spectrum of aromatic diamidines, i.e. to reduce toxicity, increase oral bioavailability and enhance their penetration of the blood-brain barrier. Aromatic diamidines therefore provide a shortcut of screening for selective ASIC inhibitors with therapeutic potential. Intriguingly nafamostat, a protease inhibitor for treating acute pancreatitis, also inhibits ASIC activities. Aromatic diamidines and nafamostat have many similarities although they belong to distinct classes of medicinal agents for curing different diseases. Here we delineate background, clinical application and drug development of aromatic diamidines that could facilitate the screening for selective ASIC inhibitors for research purposes. Further studies may lead to a drug with therapeutic value and extend the therapeutic scope of aromatic diamidines to combat neurological diseases. Copyright © 2010 Elsevier B.V. All rights reserved.

  12. Evaluation of remaining behavior of halogen on the fabrication of MOX pellet containing Am

    International Nuclear Information System (INIS)

    Ozaki, Yoko; Osaka, Masahiko; Obayashi, Hiroshi; Tanaka, Kenya

    2004-11-01

    It is important to limit the content of halogen elements, namely fluorine and chlorine that are sources of making cladding material corrode, in nuclear fuel from the viewpoint of quality assurance. The halogen content should be more carefully limited in the MOX fuel containing Americium (Am-MOX), which is fabricated in the Alpha-Gamma Facility (AGF) for irradiation testing to be conducted in the experimental fast reactor JOYO, because fluorine may remain in the sintered pellets owing to a formation of AmF 3 known to have a low vapor pressure and may exceeds the limit of 25 ppm. In this study, a series of experimental determination of halogen element in Am-MOX were performed by a combination method of pyrolysis and ion-chromatography for the purpose of an evaluation of behavior of remaining halogen through the sintering process. Oxygen potential, temperature and time were changed as experimental parameters and their effects on the remaining behavior of halogen were examined. It was confirmed that good pellets, which contained small amount of halogen, could be obtained by the sintering for 3 hour at 1700degC in the oxygen potential range from -520 to -390 kJ/mol. In order to analysis of fluorine chemical form in green pellet, thermal analysis was performed. AmF 3 and PuF 3 have been confirmed to remain in the green pellet. (author)

  13. Halogen Bonding from Dispersion-Corrected Density-Functional Theory: The Role of Delocalization Error.

    Science.gov (United States)

    Otero-de-la-Roza, A; Johnson, Erin R; DiLabio, Gino A

    2014-12-09

    Halogen bonds are formed when a Lewis base interacts with a halogen atom in a different molecule, which acts as an electron acceptor. Due to its charge transfer component, halogen bonding is difficult to model using many common density-functional approximations because they spuriously overstabilize halogen-bonded dimers. It has been suggested that dispersion-corrected density functionals are inadequate to describe halogen bonding. In this work, we show that the exchange-hole dipole moment (XDM) dispersion correction coupled with functionals that minimize delocalization error (for instance, BH&HLYP, but also other half-and-half functionals) accurately model halogen-bonded interactions, with average errors similar to other noncovalent dimers with less charge-transfer effects. The performance of XDM is evaluated for three previously proposed benchmarks (XB18 and XB51 by Kozuch and Martin, and the set proposed by Bauzá et al.) spanning a range of binding energies up to ∼50 kcal/mol. The good performance of BH&HLYP-XDM is comparable to M06-2X, and extends to the "extreme" cases in the Bauzá set. This set contains anionic electron donors where charge transfer occurs even at infinite separation, as well as other charge transfer dimers belonging to the pnictogen and chalcogen bonding classes. We also show that functional delocalization error results in an overly delocalized electron density and exact-exchange hole. We propose intermolecular Bader delocalization indices as an indicator of both the donor-acceptor character of an intermolecular interaction and the delocalization error coming from the underlying functional.

  14. Toxicity evaluation and prediction of toxic chemicals on activated sludge system.

    Science.gov (United States)

    Cai, Bijing; Xie, Li; Yang, Dianhai; Arcangeli, Jean-Pierre

    2010-05-15

    The gaps of data for evaluating toxicity of new or overloaded organic chemicals on activated sludge system resulted in the requirements for methodology of toxicity estimation. In this study, 24 aromatic chemicals typically existed in the industrial wastewater were selected and classified into three groups of benzenes, phenols and anilines. Their toxicity on activated sludge was then investigated. Two indexes of IC(50-M) and IC(50-S) were determined respectively from the respiration rates of activated sludge with different toxicant concentration at mid-term (24h) and short-term (30min) time intervals. Experimental results showed that the group of benzenes was the most toxic, followed by the groups of phenols and anilines. The values of IC(50-M) of the tested chemicals were higher than those of IC(50-S). In addition, quantitative structure-activity relationships (QSARs) models developed from IC(50-M) were more stable and accurate than those of IC(50-S). The multiple linear models based on molecular descriptors and K(ow) presented better reliability than single linear models based on K(ow). Among these molecular descriptors, E(lumo) was the most important impact factor for evaluation of mid-term toxicity. Copyright (c) 2009 Elsevier B.V. All rights reserved.

  15. Rational design of organic semiconductors for texture control and self-patterning on halogenated surfaces

    KAUST Repository

    Ward, Jeremy W.; Li, Ruipeng; Obaid, Abdulmalik; Payne, Marcia M.; Smilgies, Detlef Matthias; Anthony, John Edward; Amassian, Aram; Jurchescu, Oana D.

    2014-01-01

    new materials. Here, the influence of the interactions at the interface between a halogenated organic semiconductor (OSC) thin film and a halogenated self-assembled monolayer on the formation of the crystalline texture directly affecting

  16. Activation of the aryl hydrocarbon receptor is the major toxic mode of action of an organic extract of a reference urban dust particulate matter mixture: The role of polycyclic aromatic hydrocarbons

    International Nuclear Information System (INIS)

    Andrysik, Zdenek; Vondracek, Jan; Marvanova, Sona; Ciganek, Miroslav; Neca, Jiri; Pencikova, Katerina; Mahadevan, Brinda; Topinka, Jan; Baird, William M.; Kozubik, Alois; Machala, Miroslav

    2011-01-01

    Highlights: → SRM1649a extract and its fractions are potent activators of AhR in a model of epithelial cells. → AhR-dependent effects include both induction of CYP1 enzymes and disruption of cell proliferation control. → Polycyclic aromatic hydrocarbons present in the neutral SRM1649a fraction are major contributors to the AhR-mediated toxic effects. → Activation of AhR and related nongenotoxic effects occur at significantly lower doses than the formation of DNA adducts and activation of DNA damage response. → More attention should be paid to the AhR-dependent nongenotoxic events elicited by urban particulate matter constituents. - Abstract: Many of the toxic and carcinogenic effects of urban air pollution have been linked to polycyclic aromatic hydrocarbons (PAHs) adsorbed to airborne particulate matter (PM). The carcinogenic properties of PAHs in complex organic mixtures derived from PM have been chiefly attributed to their mutagenicity. Nevertheless, PAHs are also potent activators of the aryl hydrocarbon receptor (AhR), which may contribute to their nongenotoxic effects, including tumor promotion. As the genotoxicity of carcinogenic PAHs in complex mixtures derived from urban PM is often inhibited by other mixture constituents, the AhR-mediated activity of urban PM extracts might significantly contribute to the carcinogenic activity of such mixtures. In the present study, we used an organic extract of the urban dust standard reference material, SRM1649a, as a model mixture to study a range of toxic effects related to DNA damage and AhR activation. Both the organic extract and its neutral aromatic fraction formed a low number of DNA adducts per nucleotide in the liver epithelial WB-F344 cells model, without inducing DNA damage response, such as tumor suppressor p53 activation and apoptosis. In contrast, we found that this extract, as well as its neutral and polar fractions, were potent inducers of a range of AhR-mediated responses, including induction

  17. Selective Nitrate Recognition by a Halogen-Bonding Four-Station [3]Rotaxane Molecular Shuttle.

    Science.gov (United States)

    Barendt, Timothy A; Docker, Andrew; Marques, Igor; Félix, Vítor; Beer, Paul D

    2016-09-05

    The synthesis of the first halogen bonding [3]rotaxane host system containing a bis-iodo triazolium-bis-naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions and chloride, and exhibits enhanced recognition of anions relative to a hydrogen bonding analogue. This elaborate interlocked anion receptor functions via a novel dynamic pincer mechanism where upon nitrate anion binding, both macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodo-triazolium station anion recognition sites to form a unique 1:1 stoichiometric nitrate anion-rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the (1) H NMR anion binding results. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  18. Extraction and spectrophotometric determination of molybdenum with omicron-hydroxythiophenols and aromatic amines

    International Nuclear Information System (INIS)

    Zalov, A.Z.; Verdizade, N.A.

    2015-01-01

    The interaction of molybdenum (VI) with o-hydroxythiophenol derivatives (HTPDs) and aromatic amines (AAs) was studied. The following three HTPDs, which contain different halogen atoms at position 5, were used: 2-hydroxy-5-chlorothiophenol(HCTP), 2-hydroxy-5-bromothiophenol (HBTP), 2-hydroxy-5-iodothiophenol (HITP)). The examined AAs were aniline (An), Nmethylaniline (mAn) and N,N-dimethylaniline (dAn). The obtained ternary complexes have a composition of 1:2:2 (Mo(V):HBTP:AA). Optimal conditions for their liquid-liquid extraction (LLE) were found: organic solvent (chloroform), pH (4-6), concentration of the reagents 10-3moldm-3 (AA)) and 10-3moldm-3 (HTPD) and (1.2-1.5) ((1.3-1.5) extraction time(colour develops almost immediately after the reagents addition). The absorbance of the extracts is stable for at least 48 hours. The optimum shaking time is 10 min.). Under the optimal max) at 515-538 conditions, the complexes have absorption maxima ( 104dm3mol-1 cm-1. The max) between 3.1 nm and molar absorptivities ( 98.4%. The results suggested that linear degrees of extraction were max or relationships exist between the spectral characteristics ( max) and some fundamental properties of the halogen substituent in the HTPD (atomic mass and electronegativity). The effect of foreign ions on the LLE-spectrophotometric determination of molybdenum was examined and two sensitive, selective and precise procedures for molybdenum determination were proposed. The relative standard deviations for Mo 10-4 % were 4% (HCTP-An procedure) and 3% (HBTP-An content of (3-5) procedure). (author)

  19. On the ultrafast charge migration and subsequent charge directed reactivity in Cl⋯N halogen-bonded clusters following vertical ionization

    International Nuclear Information System (INIS)

    Chandra, Sankhabrata; Bhattacharya, Atanu; Periyasamy, Ganga

    2015-01-01

    In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation- and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH 2 , CF 3 , and COOH substituents) molecules paired with NH 3 (referred as ACl:NH 3 complex): these complexes exhibit halogen bonds. To the best of our knowledge, this is the first report on purely electron correlation- and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31 + G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl⋯NH 3 complex, the hole is predicted to migrate from the NH 3 -end to the ClCN-end of the NCCl⋯NH 3 complex in approximately 0.5 fs on the D 0 cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H 2 NCl:NH 3 , F 3 CCl:NH 3 , and HOOCCl:NH 3 , exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH 3 and HOCl:NH 3 complexes do not exhibit any charge migration following vertical ionization to the D 0 cation state, pointing to interesting halogen bond strength-dependent charge migration

  20. Effects-driven chemical fractionation of heavy fuel oil to isolate compounds toxic to trout embryos.

    Science.gov (United States)

    Bornstein, Jason M; Adams, Julie; Hollebone, Bruce; King, Thomas; Hodson, Peter V; Brown, R Stephen

    2014-04-01

    Heavy fuel oil (HFO) spills account for approximately 60% of ship-source oil spills and are up to 50 times more toxic than medium and light crude oils. Heavy fuel oils contain elevated concentrations of polycyclic aromatic hydrocarbons (PAHs) and alkyl-PAHs, known to be toxic to fish; however, little direct characterization of HFO toxicity has been reported. An effects-driven chemical fractionation was conducted on HFO 7102 to separate compounds with similar chemical and physical properties, including toxicity, to isolate the groups of compounds most toxic to trout embryos. After each separation, toxicity tests directed the next phase of fractionation, and gas chromatography-mass spectrometry analysis correlated composition with toxicity, with a focus on PAHs. Low-temperature vacuum distillation permitted the separation of HFO into 3 fractions based on boiling point ranges. The most toxic of these fractions underwent wax precipitation to remove long-chain n-alkanes. The remaining PAH-rich extract was further separated using open column chromatography, which provided distinct fractions that were grouped according to increasing aromatic ring count. The most toxic of these fractions was richest in PAHs and alkyl-PAHs. The results of the present study were consistent with previous crude oil studies that identified PAH-rich fractions as the most toxic. © 2013 SETAC.

  1. Degradation of polynuclear aromatic hydrocarbons under bench-scale compost conditions

    Energy Technology Data Exchange (ETDEWEB)

    Potter, C.L.; Glaser, J.A.; Chang, L.W.; Meier, J.R.; Dosani, M.A.; Herrmann, R.F. [US Environmental Protection Agency, Cincinnati, OH (United States). National Risk Management Research Lab.

    1999-05-15

    Polycyclic aromatic hydrocarbons are a concern at many sites, including wood-treating facilities and manufactured gas plants. This research sought to evaluate the relationship between aerobic biomass development and removal of 19 individual PAHs and toxicity from field soil during the composting process in in-vessel reactors located at the US Environmental Protection Agency (EPA) Test & Evaluation (T & E) Facility in Cincinnati, OH. Five compost amendment conditions were formulated from different nutrients or amendments to the reactor mixtures. Operating parameters of interest included aeration, moisture dynamics, and heat production. Toxicity tests were conducted to evaluate the effect of composting on soil toxicity. Seed germination and root elongation tests were evaluated in lettuce and oats, and genotoxicity (mitotic abberations) testing was performed on Allium cepa (onion). Composting of PAH contaminated soil decreased toxicity to earthworms and oat roots but had no significant effect on lettuce root toxicity. Untreated soil evoked genotoxicity in the Allium assay. After composting, no significant genotoxicity was observed in Reilly soil. 35 refs., 5 figs., 7 tabs.

  2. First principles study of halogens adsorption on intermetallic surfaces

    International Nuclear Information System (INIS)

    Zhu, Quanxi; Wang, Shao-qing

    2016-01-01

    Graphical abstract: - Highlights: • The linear relation between adsorbates induced work function change and dipole moment change also exists for intermetallic surfaces. • It is just a common linear relationship rather than a directly proportion. • A new weight parameter β is proposed to describe different factors effect on work function shift. - Abstract: Halides are often present at electrochemical environment, they can directly influence the electrode potential or zero charge potential through the induced work-function change. In this work, we focused in particular on the halogen-induced work function change as a function of the coverage of fluorine, chlorine, bromine and iodine on Al_2Au and Al_2Pt (110) surfaces. Results show that the real relation between work function change and dipole moment change for halogens adsorption on intermetallic surfaces is just a common linear relationship rather than a directly proportion. Besides, the different slopes between fitted lines and the theoretical slope employed in pure metal surfaces demonstrating that the halogens adsorption on intermetallic surfaces are more complicated. We also present a weight parameter β to describe different factors effect on work function shift and finally qualify which factor dominates the shift direction.

  3. Isostructurality and non-isostructurality in the series of halogenated organic crystal substances. The structure of Hal-aggregates

    International Nuclear Information System (INIS)

    Grineva, O.V.; Zorkij, P.M.

    2001-01-01

    Local characteristics and the type of intermolecular Hal-aggregates (ensembles of contacting halogen atoms of adjacent molecules) present in chemically similar halogenated crystal substances, differing only in the nature of Hal atoms, are compared. 23 series of halogenated hydrocarbons, including 57 crystal structures were considered. A clearly pronounced specificity of Hal-aggregates for compounds with a low and intermediate content of halogen was revealed. It was found that, as a rule, coordination number of Hal atom by Hal adjacent atoms increases in the series F-Cl-Br-I [ru

  4. Aromatic hydrocarbons

    International Nuclear Information System (INIS)

    Roder, M.

    1985-01-01

    Papers dealing with radiolysis of aromatic hydrocarbons of different composition (from benzene to terphenyls and hydrocarbons with condensed rings) as well as their mixtures (with alkanes, alkenes, other aromatic hydrocarbons) are reviewed. High radiation stability of aromatic hydrocarbons in condensed phases associated with peculiarities of molecular structure of compounds is underlined. Mechanisms of radiolytic processes, vaues of product yields are considered

  5. Halogens in pore water of peat bogs – the role of peat decomposition and dissolved organic matter

    Directory of Open Access Journals (Sweden)

    H. Biester

    2006-01-01

    Full Text Available Halogens are strongly enriched in peat and peatlands and such they are one of their largest active terrestrial reservoir. The enrichment of halogens in peat is mainly attributed to the formation of organohalogens and climatically controlled humification processes. However, little is known about release of halogens from the peat substrate and the distribution of halogens in the peat pore water. In this study we have investigated the distribution of chlorine, bromine and iodine in pore water of three pristine peat bogs located in the Magellanic Moorlands, southern Chile. Peat pore waters were collected using a sipping technique, which allows in situ sampling down to a depth greater than 6m. Halogens and halogen species in pore water were determined by ion-chromatography (IC (chlorine and IC-ICP-MS (bromine and iodine. Results show that halogen concentrations in pore water are 15–30 times higher than in rainwater. Mean concentrations of chlorine, bromine and iodine in pore water were 7–15 mg l−1, 56–123 μg l−1, and 10–20 μg l−1, which correspond to mean proportions of 10–15%, 1–2.3% and 0.5–2.2% of total concentrations in peat, respectively. Organobromine and organoiodine were the predominant species in pore waters, whereas chlorine in pore water was mostly chloride. Advection and diffusion of halogens were found to be generally low and halogen concentrations appear to reflect release from the peat substrate. Release of bromine and iodine from peat depend on the degree of peat degradation, whereas this relationship is weak for chlorine. Relatively higher release of bromine and iodine was observed in less degraded peat sections, where the release of dissolved organic carbon (DOC was also the most intensive. It has been concluded that the release of halogenated dissolved organic matter (DOM is the predominant mechanism of iodine and bromine release from peat.

  6. Halogen poisoning effect of Pt-TiO{sub 2} for formaldehyde catalytic oxidation performance at room temperature

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Xiaofeng; Cheng, Bei [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Luoshi Road 122#, Wuhan 430070 (China); Yu, Jiaguo, E-mail: jiaguoyu@yahoo.com [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Luoshi Road 122#, Wuhan 430070 (China); Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah 21589 (Saudi Arabia); Ho, Wingkei, E-mail: keithho@ied.edu.hk [Department of Science and Environmental Studies and Centre for Education in Environmental Sustainability, The Hong Kong Institute of Education, Tai Po, N.T. Hong Kong (China)

    2016-02-28

    Graphical abstract: - Highlights: • The Pt-TiO{sub 2} catalyst is deactivated by adsorption of halogen ions. • The halogen poison is mainly attributed to the active site blocking of the Pt surface. • Halogen ions and Pt form Pt−X coordination bonds. • Large halogen diameter exhibits severe poisoning effect. - Abstract: Catalytic decomposition of formaldehyde (HCHO) at room temperature is an important method for HCHO removal. Pt-based catalysts are the optimal catalyst for HCHO decomposition at room temperature. However, the stability of this catalyst remains unexplored. In this study, Pt-TiO{sub 2} (Pt-P25) catalysts with and without adsorbed halogen ions (including F{sup −}, Cl{sup −}, Br{sup −}, and I{sup −}) were prepared through impregnation and ion modification. Pt-TiO{sub 2} samples with adsorbed halogen ions exhibited reduced catalytic activity for formaldehyde decomposition at room temperature compared with the Pt-TiO{sub 2} sample; the catalytic activity followed the order of F-Pt-P25, Cl-Pt-P25, Br-Pt-P25, and I-Pt-P25. Characterization results (including XRD, TEM, HRTEM, BET, XPS, and metal dispersion) showed that the adsorbed halogen ions can poison Pt nanoparticles (NPs), thereby reducing the HCHO oxidation activity of Pt-TiO{sub 2}. The poison mechanism is due to the strong adsorption of halogen ions on the surface of Pt NPs. The adsorbed ions form coordination bonds with surface Pt atoms by transferring surplus electrons into the unoccupied 5d orbit of the Pt atom, thereby inhibiting oxygen adsorption and activation of the Pt NP surface. Moreover, deactivation rate increases with increasing diameter of halogen ions. This study provides new insights into the fabrication of high-performance Pt-based catalysts for indoor air purification.

  7. On the ultrafast charge migration and subsequent charge directed reactivity in Cl⋯N halogen-bonded clusters following vertical ionization

    Energy Technology Data Exchange (ETDEWEB)

    Chandra, Sankhabrata; Bhattacharya, Atanu, E-mail: atanub@ipc.iisc.ernet.in [Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore (India); Periyasamy, Ganga [Department of Chemistry, Central College Campus, Bangalore University, Bangalore (India)

    2015-06-28

    In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation- and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH{sub 2}, CF{sub 3}, and COOH substituents) molecules paired with NH{sub 3} (referred as ACl:NH{sub 3} complex): these complexes exhibit halogen bonds. To the best of our knowledge, this is the first report on purely electron correlation- and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31 + G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl⋯NH{sub 3} complex, the hole is predicted to migrate from the NH{sub 3}-end to the ClCN-end of the NCCl⋯NH{sub 3} complex in approximately 0.5 fs on the D{sub 0} cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H{sub 2}NCl:NH{sub 3}, F{sub 3}CCl:NH{sub 3}, and HOOCCl:NH{sub 3}, exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH{sub 3} and HOCl:NH{sub 3} complexes do not exhibit any charge migration following vertical ionization to the D{sub 0} cation state, pointing to interesting halogen bond strength-dependent charge migration.

  8. Reconciliation of Halogen-Induced Ozone Loss with the Total-Column Ozone Record

    Science.gov (United States)

    Shepherd, T. G.; Plummer, D. A.; Scinocca, J. F.; Hegglin, M. I.; Fioletov, V. E.; Reader, M. C.; Remsberg, E.; von Clarmann, T.; Wang, H. J.

    2014-01-01

    The observed depletion of the ozone layer from the 1980s onwards is attributed to halogen source gases emitted by human activities. However, the precision of this attribution is complicated by year-to-year variations in meteorology, that is, dynamical variability, and by changes in tropospheric ozone concentrations. As such, key aspects of the total-column ozone record, which combines changes in both tropospheric and stratospheric ozone, remain unexplained, such as the apparent absence of a decline in total-column ozone levels before 1980, and of any long-term decline in total-column ozone levels in the tropics. Here we use a chemistry-climate model to estimate changes in halogen-induced ozone loss between 1960 and 2010; the model is constrained by observed meteorology to remove the eects of dynamical variability, and driven by emissions of tropospheric ozone precursors to separate out changes in tropospheric ozone. We show that halogen-induced ozone loss closely followed stratospheric halogen loading over the studied period. Pronounced enhancements in ozone loss were apparent in both hemispheres following the volcanic eruptions of El Chichon and, in particular, Mount Pinatubo, which significantly enhanced stratospheric aerosol loads. We further show that approximately 40% of the long-term non-volcanic ozone loss occurred before 1980, and that long-term ozone loss also occurred in the tropical stratosphere. Finally, we show that halogeninduced ozone loss has declined by over 10% since stratospheric halogen loading peaked in the late 1990s, indicating that the recovery of the ozone layer is well underway.

  9. Effects of vehicle type and fuel quality on real world toxic emissions from diesel vehicles

    Science.gov (United States)

    Nelson, Peter F.; Tibbett, Anne R.; Day, Stuart J.

    Diesel vehicles are an important source of emissions of air pollutants, particularly oxides of nitrogen (NO x), particulate matter (PM), and toxic compounds with potential health impacts including volatile organic compounds (VOCs) such as benzene and aldehydes, and polycyclic aromatic hydrocarbons (PAHs). Current developments in engine design and fuel quality are expected to reduce these emissions in the future, but many vehicles exceed 10 years of age and may make a major contribution to urban pollutant concentrations and related health impacts for many years. In this study, emissions of a range of toxic compounds are reported using in-service vehicles which were tested using urban driving cycles developed for Australian conditions. Twelve vehicles were chosen from six vehicle weight classes and, in addition, two of these vehicles were driven through the urban drive cycle using a range of diesel fuel formulations. The fuels ranged in sulphur content from 24 to 1700 ppm, and in total aromatics from 7.7 to 33 mass%. Effects of vehicle type and fuel composition on emissions are reported. The results show that emissions of these toxic species were broadly comparable to those observed in previous dynamometer and tunnel studies. Emissions of VOCs and smaller PAHs such as naphthalene, which are derived largely from the combustion process, appear to be related, and show relatively little variability when compared with the variability in emissions of aldehydes and larger PAHs. In particular, aldehyde emissions are highly variable and may be related to engine operating conditions. Fuels of lower sulphur and aromatic content did not have a significant influence on emissions of VOCs and aldehydes, but tended to result in lower emissions of PAHs. The toxicity of vehicle exhaust, as determined by inhalation risk and toxic equivalency factor (TEF)-weighted PAH emissions, was reduced with fuels of lower aromatic content.

  10. Coal-tar-based pavement sealcoat, polycyclic aromatic Hydrocarbons (PAHs), and environmental health

    Science.gov (United States)

    Mahler, B.J.; Van Metre, P.C.

    2011-01-01

    Studies by the U.S. Geological Survey (USGS) have identified coal-tar-based sealcoat-the black, viscous liquid sprayed or painted on asphalt pavement such as parking lots-as a major source of polycyclic aromatic hydrocarbon (PAH) contamination in urban areas for large parts of the Nation. Several PAHs are suspected human carcinogens and are toxic to aquatic life.

  11. Iron Mineral Catalyzed C-H Activation As a Potential Pathway for Halogenation Processes

    Science.gov (United States)

    Tubbesing, C.; Schoeler, H. F.; Benzing, K.; Krause, T.; Lippe, S.; Rudloff, M.

    2014-12-01

    Due to increasing drinking water demand of mankind and an expected climate change the impact of salt lakes and salt deserts will increase within the next decades. Furthermore, a rising sea level influences coastal areas like salt marshes and abets processes which will lead to elevated organohalogen formation. An additional increase of the global warming potential, of particle formation and stratospheric ozone depletion is expected. Understanding these multifaceted processes is essential for mankind to be prepared for these alterations of the atmosphere. For example, Keppler et al. (2000) described the production of volatile halogenated organic compounds via oxidation of organic matter driven by ferric iron. However, the formation of long-chained alkyl halides in salt lakes is yet undisclosed. Despite the relative "inertness" of alkanes a direct halogenation of these compounds might be envisaged. In 2005 Vaillancourt et al. discovered a nonheme iron enzyme which is able to halogenate organic compounds via generating the high valent ferryl cation as reaction center. Based on various publications about C-H activation (Bergman, 2007) we postulate a halogenation process in which an iron containing minerals catalyse the C-H bond cleavage of organic compounds in soils. The generated organic radicals are highly reactive towards halides connected to the iron complex. We suggest that next to diagenetically altered iron containing enzymes, minerals such as oxides, hydroxides and sulfides are involved in abiotic halogenation processes. We applied the amino acid methionine as organic model compound and soluble iron species as reactants. All samples were incubated in aqueous phases containing various NaCl concentrations. As a result various halogenated ethanes and ethenes were identified as reaction products. References Bergman, R. G. (2007) Nature, 446(7134) 391-393 Keppler, F., et al. (2000) Nature, 403(6767) 298-301 Vaillancourt, F. H., et al. (2005) Nature, 436(7054) 1191-1194

  12. Development of halogen-free, heat-resistant, low-voltage wire for automotive use

    International Nuclear Information System (INIS)

    Ueno, Keiji; Suzuki, Sizuo; Takahagi, Masatoshi; Uda, Ikujiro

    1995-01-01

    The environmental load of our motorized society is of major concern, and includes considerations of recycling of automotive parts as the industrial wastes. The total average length of AV, AVX (electrical wire insulated with PVC, cross-linked PVC), and AEX (electrical wire insulated with cross-linked polyolefin) wires required for the harnesses in modern automobiles is approximately 2,000-3,000 meters per unit. However these electrical wires contain a large amount of halogen, which can generate the smoke and corrosive gas. In response to this problem the authors have developed the electron beam irradiated halogen-free, heat-resistant, low-voltage electrical wire which does not contain any halogen based polymer or flame retardants. The developed wire features the reliability equivalent to AEX wire with minimum environmental load. (Author)

  13. Comparison of passive and standard dosing of polycyclic aromatic hydrocarbons to the marine algae Phaeodactylum tricornutum

    DEFF Research Database (Denmark)

    Witt, G.; Niehus, N. C.; Konopka, K.

    2015-01-01

    Testing hydrophobic organic compounds (HOCs), like polycyclic aromatic hydrocarbons (PAHs), in aquatic toxicity tests is difficult due to compound losses through volatilization, sorption to the test vessel and culture medium constituents. This results in poorly defined exposure, the bioavailable...

  14. Recoil halogen reactions in liquid and frozen aqueous solutions of biomolecules

    International Nuclear Information System (INIS)

    Arsenault, L.J.; Blotcky, A.J.; Firouzbakht, M.L.; Rack, E.P.; Nebraska Univ., Omaha

    1982-01-01

    Reactions of recoil 38 Cl, 80 Br and 128 I have been studied in crystalline systems of 5-halouracil, 5-halo-2'-deoxyuridine and 5-halouridine as well as liquid and frozen aqueous solutions of these halogenated biomolecules. In all systems expect crystalline 5-iuodouracil the major product was the radio-labelled halide ion. There was no evidence for other halogen inorganic species. The major labelled organic product was the parent molecule. A recoil atom tracer technique was developed to acquire site information of the biomolecule solutes in the liquid and frozen aqueous systems. For all liquid and frozen aqueous systems, the halogenated biomolecules tended to aggregate. For liquid systems, the tendency for aggregation diminished as the solute concentration approached zero, where the probable state of the solute approached a monomolecular dispersion. Unlike the liquid state, the frozen ice lattice demonstated a ''caging effect'' for the solute aggregates which resulted in constant product yields over the whole concentration range. (orig.)

  15. Combined effects of prenatal polycyclic aromatic hydrocarbons and material hardship on child IQ.

    Science.gov (United States)

    Vishnevetsky, Julia; Tang, Deliang; Chang, Hsin-Wen; Roen, Emily L; Wang, Ya; Rauh, Virginia; Wang, Shuang; Miller, Rachel L; Herbstman, Julie; Perera, Frederica P

    2015-01-01

    Polycyclic aromatic hydrocarbons are common carcinogenic and neurotoxic urban air pollutants. Toxic exposures, including air pollution, are disproportionately high in communities of color and frequently co-occur with chronic economic deprivation. We examined whether the association between child IQ and prenatal exposure to polycyclic aromatic hydrocarbons differed between groups of children whose mothers reported high vs. low material hardship during their pregnancy and through child age 5. We tested statistical interactions between hardships and polycyclic aromatic hydrocarbons, as measured by DNA adducts in cord blood, to determine whether material hardship exacerbated the association between adducts and IQ scores. Prospective cohort. Participants were recruited from 1998 to 2006 and followed from gestation through age 7 years. Urban community (New York City) A community-based sample of 276 minority urban youth EXPOSURE MEASURE: Polycyclic aromatic hydrocarbon-DNA adducts in cord blood as an individual biomarker of prenatal polycyclic aromatic hydrocarbon exposure. Maternal material hardship self-reported prenatally and at multiple timepoints through early childhood. Child IQ at 7 years assessed using the Wechsler Intelligence Scale for Children. Significant inverse effects of high cord PAH-DNA adducts on full scale IQ, perceptual reasoning and working memory scores were observed in the groups whose mothers reported a high level of material hardship during pregnancy or recurring high hardship into the child's early years, and not in those without reported high hardship. Significant interactions were observed between high cord adducts and prenatal hardship on working memory scores (β = -8.07, 95% CI (-14.48, -1.66)) and between high cord adducts and recurrent material hardship (β = -9.82, 95% CI (-16.22, -3.42)). The findings add to other evidence that socioeconomic disadvantage can increase the adverse effects of toxic physical "stressors" like air pollutants

  16. Spectroscopic Diagnosis of Excited-State Aromaticity: Capturing Electronic Structures and Conformations upon Aromaticity Reversal.

    Science.gov (United States)

    Oh, Juwon; Sung, Young Mo; Hong, Yongseok; Kim, Dongho

    2018-03-06

    Aromaticity, the special energetic stability derived from cyclic [4 n + 2]π-conjugated electronic structures, has been the topic of intense interest in chemistry because it plays a critical role in rationalizing molecular stability, reactivity, and physical/chemical properties. Recently, the pioneering work by Colin Baird on aromaticity reversal, postulating that aromatic (antiaromatic) character in the ground state reverses to antiaromatic (aromatic) character in the lowest excited triplet state, has attracted much scientific attention. The completely reversed aromaticity in the excited state provides direct insight into understanding the photophysical/chemical properties of photoactive materials. In turn, the application of aromatic molecules to photoactive materials has led to numerous studies revealing this aromaticity reversal. However, most studies of excited-state aromaticity have been based on the theoretical point of view. The experimental evaluation of aromaticity in the excited state is still challenging and strenuous because the assessment of (anti)aromaticity with conventional magnetic, energetic, and geometric indices is difficult in the excited state, which practically restricts the extension and application of the concept of excited-state aromaticity. Time-resolved optical spectroscopies can provide a new and alternative avenue to evaluate excited-state aromaticity experimentally while observing changes in the molecular features in the excited states. Time-resolved optical spectroscopies take advantage of ultrafast laser pulses to achieve high time resolution, making them suitable for monitoring ultrafast changes in the excited states of molecular systems. This can provide valuable information for understanding the aromaticity reversal. This Account presents recent breakthroughs in the experimental assessment of excited-state aromaticity and the verification of aromaticity reversal with time-resolved optical spectroscopic measurements. To

  17. Development of no halogen incombustible cables for atomic energy

    International Nuclear Information System (INIS)

    Ishii, Nobumasa; Kimura, Hitoshi; Fujimura, Shun-ichi

    1990-01-01

    In upgrading light water reactor technology, it is important to improve the reliability of machinery and equipment, to make regular inspection efficient, to extend the period of continuous operation, to optimize operation cycle and to improve the maintainability of plant facilities. For the cables for nuclear power stations, high incombustibility is required, and at present halogen system incombustible materials are used. Recently the development of no halogen incombustible cables has been advanced, with which the generation of corrosive gas and smoke at the time of fires is slight. In this study, the application of such no halogen incombustible cables to nuclear power stations and the improvement of reliability of the cables were investigated. The cables to be developed are those for electric power, control and instrumentation in BWR plants and insulated electric wires. The required characteristics are incombustibility, no generation of smoke and corrosive gas at the time of fires, radiation resistance and steam resistance in LOCA. The selection of base polymers, metal hydrates and radiation protectors, the evaluation of radiation resistance and steam resistance, the examination of the corrosive and poisonous properties of generated gas and smoke generation and so on are reported. The development was successful. (K.I.)

  18. Chlorine dioxide as phenol and H2S scavenger - formation of halogenated phenols and subsequent environmental risk

    Energy Technology Data Exchange (ETDEWEB)

    Melbye, Alf G.; Faksness, Liv-Guri; Knudsen, Boerre Leif

    2006-03-15

    Formation of halogenated phenols as side products from treatment of produced water with aqueous chlorine dioxide has been investigated. The literature describes formation of halogenated hydrocarbons in effluent treatment using chlorine, hypochlorite and chlorine dioxide. A new chlorine dioxide product, originally intended as a H2S scavenger in the oil and gas industry, has been tested both as a phenol scavenger and H2S-scavenger for produced water applications. The concern about the possible formation of halogenated by-products initiated laboratory testing of chlorine dioxide as phenol and H2S scavenger for produced water applications. The tests also included synthetic matrixes containing phenols, and the tests show that halogenated phenols, mainly brominated species, are found in produced water after treatment with chlorine dioxide. Due to potential environmental risk from halogenated organic contaminants, the use of chlorine dioxide as phenol and H2S scavenger is not recommended. (Author)

  19. Determination of N-containing halogenated natural products using gas chromatography in combination of a nitrogen-phosphorus-detector

    Energy Technology Data Exchange (ETDEWEB)

    Melcher, J.; Vetter, W. [Hohenheim Univ., Stuttgart (Germany). Inst. fuer Lebensmittelchemie

    2004-09-15

    In the last few years several nonpolar halogenated natural products (HNPs) such as Q1, MHC-1, BC-2, BC-3, BC-10 were detected at elevated concentrations in marine biota samples. In addition, there are still some abundant peaks of halogenated compounds frequently found in the gas chromatograms of many marine samples which have not yet been identified. Some of the known halogenated natural products (Q1, HDBPs including BC-10, bromoindoles) contain N-heterocyclic backbones. Since nitrogen is scarcely found in anthropogenic halogenated compounds, the detection of N-containing halogenated substances may be used as a first indicator for the presence of HNPs in a sample extract. In the presented method we studied the suitability of a nitrogen phosphorous detector (NPD) for quantification of Q1 and the detection of Ncontaining compounds in marine biota. Analyses were accompanied with GC/ECD analyses.

  20. A 19F NMR study of C-I....pi- halogen bonding

    DEFF Research Database (Denmark)

    Hauchecorne, Dieter; vand er Veken, Benjamin J.; Herrebout, Wouter A.

    2011-01-01

    The formation of halogen bonded complexes between toluene-d8 and the perfluoroiodopropanes 1-C3F7I and 2-C3F7I has been investigated using 19F NMR spectroscopy. For both Lewis acids, evidence was found for the formation of a C–I⋯π halogen bonded complex. The complex formed is a 1:1 type. Using sp...... results are supported by ab initio calculations at the B3LYP-PCM/6-311++G(d,p) + LanL2DZ∗ level....

  1. Photometabolism of Heterocyclic Aromatic Compounds by Rhodopseudomonas palustris OU 11

    Science.gov (United States)

    Sasikala, C.; Ramana, C. V.; Rao, P. Raghuveer

    1994-01-01

    Rhodopseudomonas palustris OU 11 (ATCC 51186; DSM 7375) isolated from a pond of chemical industry effluent could anaerobically photometabolize heterocyclic aromatic compounds belonging to the pyridine and pyrazine groups only after a period of adaptation on pyrazinoic acid of 5 to 6 weeks. Growth on heterocyclic compounds was light dependent. The effects of various concentrations of heterocyclic compounds on growth suggest that higher concentrations of these compounds inhibit growth and are toxic. PMID:16349307

  2. Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

    Science.gov (United States)

    Li, Jin-Feng; Sun, Yin-Yin; Bai, Hongcun; Li, Miao-Miao; Li, Jian-Li; Yin, Bing

    2015-06-01

    The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M2(CN)5]-1 (M = Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca2(CN)5]-1 which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green's function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.

  3. Contamination levels, toxicity profiles, and emission sources of polycyclic aromatic hydrocarbons (PAHs) in the soils of an emerging industrial town and its environs in the Southeastern Nigeria.

    Science.gov (United States)

    Ofomatah, Anthony C; Okoye, Chukwuma O B

    2017-11-09

    Polycyclic aromatic hydrocarbon (PAH) concentrations in Nnewi and its environs were determined. Soil samples were extracted by sonication using hexane:dichloromethane (3:1) mixture and determined by gas chromatography-flame ionization detection. The total PAHs concentrations (μg/kg) were 16.681 to 46.815, being three orders of magnitude lower than the maximum permissible level recommended by the Agency for Toxic Substances and Disease Registry (ATSDR). These concentrations followed this order: industrial ˃ farmlands ˃ commercial ˃ residential. Industrialized areas showed higher concentrations (p ˂ 0.05) than the other areas. Diagnostic ratios show that the major source of PAHs was the open burning of industrial and agricultural wastes, as shown by the occurrence of highest concentrations in the industrial areas, followed by agricultural areas. Benzo[a]pyrene equivalent values showed non-pollution and very low toxicity. Nevertheless, it was clear that industrialization has had some impact on the PAHs levels in soils and the total environment in this area and could be problematic with time, except with proper environmental management.

  4. Halogen bond tunability II: the varying roles of electrostatic and dispersion contributions to attraction in halogen bonds

    Czech Academy of Sciences Publication Activity Database

    Riley, Kevin Eugene; Murray, J. S.; Fanfrlík, Jindřich; Řezáč, Jan; Solá, R. J.; Concha, M. C.; Ramos, F. M.; Politzer, P.

    2013-01-01

    Roč. 19, č. 11 (2013), s. 4651-4659 ISSN 1610-2940 R&D Projects: GA ČR GBP208/12/G016 Grant - others:Operational Program Research and Development for Innovations(XE) CZ.1.05/2.1.00/03.0058 Institutional support: RVO:61388963 Keywords : dispersion * electrostatics * halogen bonding * noncovalent interactions Subject RIV: CE - Biochemistry Impact factor: 1.867, year: 2013

  5. Effect of three polycyclic aromatic hydrocarbons on nodulation of Rhizobium tropici CIAT 899 on Phaseolus vulgaris

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Paredes, Y.; Ferrera-Cerrato, R.; Alarcon, A.

    2009-07-01

    Polycyclic aromatic hydrocarbons (PAH) are ubiquitous organic pollutants that are considered toxic and carcinogenic compounds to living organisms. There us scarce information about the effect of PAH on symbiotic systems such as Azolla-Anabaena, arbuscular mycorrhizal fungi-plants, or legume-rhizobia. (Author)

  6. Polycyclic aromatic hydrocarbons in the samples of environment

    International Nuclear Information System (INIS)

    Velkova, V.; Vybohova, E.; Bubenikova, T.

    2006-01-01

    Polycyclic aromatic hydrocarbons (pAHs) represent one group of toxic organic substances in the environment. We determined PAHs in the samples of water and river sediments from river Zolna, in the samples of soils and plants from surrounding of Zolna. The river Zolna flows directly through word-processing factory area. The impregnation division together with associated impregnated materials store is considered the most important source of PAH contamination in the surrounding area. We analysed the 16 compounds (PAHs) by List of the priority pollutants by EPA by the HPLC method. (authors)

  7. Comparison of UV irradiation and p-fluorphenylaline as selective agents for production of aromatic compounds in plant cell culture

    International Nuclear Information System (INIS)

    Quesnel, A.A.; Ellis, B.E.

    1989-01-01

    Resistance to UV irradiation, and to the toxicity of p-fluorophenylalanine, can both be mediateted in plants by enhanced synthesis of aromatic compounds. These selective agents were applied to cell cultures of Nicotiana tabacum, Anchusa officinalis and Catharanthus roseur, and the production of aromatic metabolites in the resulting resistant lines of each species was compared. While Nicotiana and Anchusa cultures responded to each selective agent ith an enhanced accumulation of aromatic compounds, the Catharanthus cultures acquired resistance through other, unknown, mechanisms. Some degree of cross-resistance was observed between cultures selected individually for resistance to each agent (author). 26 refs.; 2 figs.; 1 tab

  8. Hemoglobin binding of aromatic amines: molecular dosimetry and quantitative structure-activity relationships for N-oxidation.

    Science.gov (United States)

    Sabbioni, G

    1993-01-01

    Aromatic amines are important intermediates in industrial manufacturing. N-Oxidation to N-hydroxyarylamines is a key step in determining the genotoxic properties of aromatic amines. N-Hydroxyarylamines can form adducts with DNA, with tissue proteins, and with the blood proteins albumin and hemoglobin in a dose-dependent manner. The determination of hemoglobin adducts is a useful tool for biomonitoring exposed populations. We have established the hemoglobin binding index (HBI) [(mmole compound/mole hemoglobin)/(mmole compound/kg body weight)] of several aromatic amines in female Wistar rats. Including the values from other researchers obtained in the same rat strain, the logarithm of hemoglobin binding (logHBI) was plotted against the following parameters: the sum of the Hammett constants(sigma sigma = sigma p + sigma m), pKa, logP (octanol/water), the half-wave oxidation potential (E1/2), and the electronic descriptors of the amines and their corresponding nitrenium ions obtained by semi-empirical calculations (MNDO, AMI, and PM3), such as atomic charge densities, energies of the highest occupied molecular orbit and lowest occupied molecular orbit and their coefficients, the bond order of C-N, the dipole moments, and the reaction enthalpy [MNDOHF, AM1HF or PM3HF = Hf(nitrenium) - Hf(amine)]. The correlation coefficients were determined from the plots of all parameters against log HBI for all amines by means of linear regression analysis. The amines were classified in three groups: group 1, all parasubstituted amines (maximum, n = 9); group 2, all amines with halogens (maximun, n = 11); and group 3, all amines with alkyl groups (maximum, n = 13).(ABSTRACT TRUNCATED AT 250 WORDS) PMID:8319626

  9. Tuning the viscosity of halogen free bulk heterojunction inks for inkjet printed organic solar cells

    NARCIS (Netherlands)

    Lamont, C.A.; Eggenhuisen, T.M.; Coenen, M.J.J.; Slaats, T.W.L.; Andriessen, R.; Groen, P.

    2015-01-01

    For the solution processing of organic photovoltaics on an industrial scale, the exclusion of halogenated solvents is a necessity. However, the limited solubility of most semiconducting polymer/fullerene blends in non-halogenated solvents results in ink formulations with low viscosities which poses

  10. Impact of enhanced ozone deposition and halogen chemistry on tropospheric ozone over the Northern Hemisphere

    Science.gov (United States)

    Fate of ozone in marine environments has been receiving increased attention due to the tightening of ambient air quality standards. The role of deposition and halogen chemistry is examined through incorporation of an enhanced ozone deposition algorithm and inclusion of halogen ch...

  11. WILDLIFE TOXICITY REFERENCE VALUES FOR POLYNUCLEAR AROMATIC HYDROCARBONS AND DDT

    Science.gov (United States)

    The presentation will provide an overview of the procedures used in deriving mammalian and avian wildlife toxicity reference values to be used in development of ecological soil screening levels (Eco-SSLs).

  12. Decontamination of soil containing POPs by the combined action of solid Fenton-like reagents and microwaves.

    Science.gov (United States)

    Cravotto, Giancarlo; Di Carlo, Stefano; Ondruschka, Bernd; Tumiatti, Vander; Roggero, Carlo Maria

    2007-10-01

    The effect on halogenated aromatics of solid, non-toxic oxidants such as sodium percarbonate and the urea/hydrogen peroxide complex (Fenton-like reagents) was investigated. A microwaves-assisted, solvent-free method for soil decontamination is presented. It marks a considerable advance in the search of more efficient, environment-friendly procedures for the degradative oxidation of persistent organic pollutants. Residual pollutants in treated soil samples were determined by GC/MS analysis after solvent extraction or direct thermal desorption. Results showed that 4-chloronaphthol, 2,4-dichlorophenoxyacetic acid and p-nonylphenol had been degraded completely, 2,4-dibromophenol to a large extent.

  13. Development and characteristics of halogen-free flame-retardant cables for nuclear power plants

    Energy Technology Data Exchange (ETDEWEB)

    Kanemitsuya, K.; Furukawa, K.; Tachibana, T.; Ohara, H.; Ebiike, Y.; Hamachi, K.; Makino, M. (Mitsubishi Cable Industries Ltd., Tokyo (Japan))

    1992-10-01

    Halogen-free flame-retardant (HF-FR) cables for use in nuclear power plants, especially in pressurized water type (PWR) plants, have been developed to advancing the safety and reliability of nuclear power plants. HF-FR cables generate no corrosive gases and minimal amount of toxic gases and smoke during fires, and are accordingly quite safe in comparison with the conventional cables which can cause the secondary calamity by eliminating a large amount of hydrogen halide gas and smoke. HF-FR ethylene-propylene rubber (EPR) and crosslinked polyolefin (XLPO) are used as insulating materials, and HF-FR ethylene-vinyl acetate (EVA) elastomer and polyolefin (PO) are used as jacketing materials. The results of a series of experiments on several types of HF-FR cables have revealed that these cables fully satisfy every requirement, including reliability under LOCA (Loss of Coolant Accidents) simulated conditions, long-term (40y) reliability under thermal and [gamma]-ray exposure, and flame resistivity under vertical tray test (IEEE Std. 383). (author).

  14. Ambient aromatic hydrocarbon measurements at Welgegund, South Africa

    Science.gov (United States)

    Jaars, K.; Beukes, J. P.; van Zyl, P. G.; Venter, A. D.; Josipovic, M.; Pienaar, J. J.; Vakkari, V.; Aaltonen, H.; Laakso, H.; Kulmala, M.; Tiitta, P.; Guenther, A.; Hellén, H.; Laakso, L.; Hakola, H.

    2014-07-01

    Aromatic hydrocarbons are associated with direct adverse human health effects and can have negative impacts on ecosystems due to their toxicity, as well as indirect negative effects through the formation of tropospheric ozone and secondary organic aerosol, which affect human health, crop production and regional climate. Measurements of aromatic hydrocarbons were conducted at the Welgegund measurement station (South Africa), which is considered to be a regionally representative background site. However, the site is occasionally impacted by plumes from major anthropogenic source regions in the interior of South Africa, which include the western Bushveld Igneous Complex (e.g. platinum, base metal and ferrochrome smelters), the eastern Bushveld Igneous Complex (platinum and ferrochrome smelters), the Johannesburg-Pretoria metropolitan conurbation (> 10 million people), the Vaal Triangle (e.g. petrochemical and pyrometallurgical industries), the Mpumalanga Highveld (e.g. coal-fired power plants and petrochemical industry) and also a region of anticyclonic recirculation of air mass over the interior of South Africa. The aromatic hydrocarbon measurements were conducted with an automated sampler on Tenax-TA and Carbopack-B adsorbent tubes with heated inlet for 1 year. Samples were collected twice a week for 2 h during daytime and 2 h during night-time. A thermal desorption unit, connected to a gas chromatograph and a mass selective detector was used for sample preparation and analysis. Results indicated that the monthly median (mean) total aromatic hydrocarbon concentrations ranged between 0.01 (0.011) and 3.1 (3.2) ppb. Benzene levels did not exceed the local air quality standard limit, i.e. annual mean of 1.6 ppb. Toluene was the most abundant compound, with an annual median (mean) concentration of 0.63 (0.89) ppb. No statistically significant differences in the concentrations measured during daytime and night-time were found, and no distinct seasonal patterns were

  15. Model study of multiphase DMS oxidation with a focus on halogens

    Directory of Open Access Journals (Sweden)

    R. von Glasow

    2004-01-01

    Full Text Available We studied the oxidation of dimethylsulfide (DMS in the marine boundary layer (MBL with a one-dimensional numerical model and focused on the influence of halogens. Our model runs show that there is still significant uncertainty about the end products of the DMS addition pathway, which is especially caused by uncertainty in the product yield of the reaction of the intermediate product methyl sulfinic acid (MSIA with OH. BrO strongly increases the importance of the addition branch in the oxidation of DMS even when present at mixing ratios smaller than 0.5pmol mol-1. The inclusion of halogen chemistry leads to higher DMS oxidation rates and smaller DMS to SO2 conversion efficiencies. The DMS to SO2 conversion efficiency is also drastically reduced under cloudy conditions. In cloud-free model runs between 5 and 15% of the oxidized DMS reacts further to particulate sulfur, in cloudy runs this fraction is almost 100%. Sulfate production by HOClaq and HOBraq is important in cloud droplets even for small Br- deficits and related small gas phase halogen concentrations. In general, more particulate sulfur is formed when halogen chemistry is included. A possible enrichment of HCO3- in fresh sea salt aerosol would increase pH values enough to make the reaction of S(IV* (=SO2,aq+HSO3-+SO32- with O3 dominant for sulfate production. It leads to a shift from methyl sulfonic acid (MSA to non-sea salt sulfate (nss-SO42- production but increases the total nss-SO42- only somewhat because almost all available sulfur is already oxidized to particulate sulfur in the base scenario. We discuss how realistic this is for the MBL. We found the reaction MSAaq+OH to contribute about 10% to the production of nss-SO42- in clouds. It is unimportant for cloud-free model runs. Overall we find that the presence of halogens leads to processes that decrease the albedo of stratiform clouds in the MBL.

  16. Chalcogen- and halogen-bonds involving SX2 (X = F, Cl, and Br) with formaldehyde.

    Science.gov (United States)

    Mo, Lixin; Zeng, Yanli; Li, Xiaoyan; Zhang, Xueying; Meng, Lingpeng

    2016-07-01

    The capacity of SX2 (X = F, Cl, and Br) to engage in different kinds of noncovalent bonds was investigated by ab initio calculations. SCl2 (SBr2) has two σ-holes upon extension of Cl (Br)-S bonds, and two σ-holes upon extension of S-Cl (Br) bonds. SF2 contains only two σ-holes upon extension of the F-S bond. Consequently, SCl2 and SBr2 form chalcogen and halogen bonds with the electron donor H2CO while SF2 forms only a chalcogen bond, i.e., no F···O halogen bond was found in the SF2:H2CO complex. The S···O chalcogen bond between SF2 and H2CO is the strongest, while the strongest halogen bond is Br···O between SBr2 and H2CO. The nature of these two types of noncovalent interaction was probed by a variety of methods, including molecular electrostatic potentials, QTAIM, energy decomposition, and electron density shift maps. Termolecular complexes X2S···H2CO···SX'2 (X = F, Cl, Br, and X' = Cl, Br) were constructed to study the interplay between chalcogen bonds and halogen bonds. All these complexes contained S···O and Cl (Br)···O bonds, with longer intermolecular distances, smaller values of electron density, and more positive three-body interaction energies, indicating negative cooperativity between the chalcogen bond and the halogen bond. In addition, for all complexes studied, interactions involving chalcogen bonds were more favorable than those involving halogen bonds. Graphical Abstract Molecular electrostatic potential and contour map of the Laplacian of the electron density in Cl2S···H2CO···SCl2 complex.

  17. Rational design of organic semiconductors for texture control and self-patterning on halogenated surfaces

    KAUST Repository

    Ward, Jeremy W.

    2014-05-15

    Understanding the interactions at interfaces between the materials constituting consecutive layers within organic thin-film transistors (OTFTs) is vital for optimizing charge injection and transport, tuning thin-film microstructure, and designing new materials. Here, the influence of the interactions at the interface between a halogenated organic semiconductor (OSC) thin film and a halogenated self-assembled monolayer on the formation of the crystalline texture directly affecting the performance of OTFTs is explored. By correlating the results from microbeam grazing incidence wide angle X-ray scattering (μGIWAXS) measurements of structure and texture with OTFT characteristics, two or more interaction paths between the terminating atoms of the semiconductor and the halogenated surface are found to be vital to templating a highly ordered morphology in the first layer. These interactions are effective when the separating distance is lower than 2.5 dw, where dw represents the van der Waals distance. The ability to modulate charge carrier transport by several orders of magnitude by promoting "edge-on" versus "face-on" molecular orientation and crystallographic textures in OSCs is demonstrated. It is found that the "edge-on" self-assembly of molecules forms uniform, (001) lamellar-textured crystallites which promote high charge carrier mobility, and that charge transport suffers as the fraction of the "face-on" oriented crystallites increases. The role of interfacial halogenation in mediating texture formation and the self-patterning of organic semiconductor films, as well as the resulting effects on charge transport in organic thin-film transistors, are explored. The presence of two or more anchoring sites between a halogenated semiconductor and a halogenated self-assembled monolayer, closer than about twice the corresponding van der Waals distance, alter the microstructure and improve electrical properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Ambient aromatic hydrocarbon measurements at Welgegund, South Africa

    Energy Technology Data Exchange (ETDEWEB)

    Jaars, K.; Beukes, J. P.; van Zyl, P. G.; Venter, A. D.; Josipovic, M.; Pienaar, J. J.; Vakkari, Ville; Aaltonen, H.; Laakso, H.; Kulmala, M.; Tiitta, P.; Guenther, Alex B.; Hellen, H.; Laakso, L.; Hakola, H.

    2014-07-11

    Aromatic hydrocarbons are associated with direct adverse human health effects and can have negative impacts on ecosystems due to their toxicity, as well as indirect negative effects through the formation of tropospheric ozone and secondary organic aerosol that affect human health, crop production and regional climate. Measurements were conducted at the Welgegund measurement station (South Africa) that is considered to be a regionally representative background site. However, the site is occasionally impacted by plumes from major anthropogenic source regions in the interior of South Africa, which include the western Bushveld Igneous Complex (e.g. platinum, base metal and ferrochrome smelters), the eastern Bushveld Igneous Complex (platinum and ferrochrome smelters), the Johannesburg-Pretoria metropolitan conurbation (>10 million people), the Vaal Triangle (e.g. petrochemical and industries), the Mpumalanga Highveld (e.g. coal-fired power plants and petrochemical industry) and also a region of anti-cyclonic recirculation of air mass over the interior of South Africa. The aromatic hydrocarbon measurements were conducted with an automated sampler on Tenax-TA and Carbopack-B adsorbent tubes with heated inlet for one year. Samples were collected twice a week for two hours during daytime and two hours 1 during night-time. A thermal desorption unit, connected to a gas chromatograph and a mass 2 selective detector was used for sample preparation and analysis. Results indicated that the 3 monthly median total aromatic hydrocarbon concentrations ranged between 0.01 to 3.1 ppb. 4 Benzene levels did not exceed local air quality standards. Toluene was the most abundant 5 species, with an annual median concentration of 0.63 ppb. No statistically significant 6 differences in the concentrations measured during daytime and night-time were found and no distinct seasonal patterns were observed. Air mass back trajectory analysis proved that the lack of seasonal cycles could be

  19. Flame retardant synergism between molybdenum and halogen-containing compounds in unsaturated polyesters. [Smoke suppression

    Energy Technology Data Exchange (ETDEWEB)

    Skinner, G.A.; Parker, L.E.; Marshall, P.J.

    1978-01-01

    Oxygen index results for a series of unsaturated polyesters, containing molybdenum oxide and various halogenated compounds, have provided definite evidence for some form of flame retardant synergistic effect between molybdenum and halogen. With the halogenated compounds used, the magnitude of the effect was greater in the presence of bromine but was dependent on the type of compound. When dibromoneopentyl glycol was used as the bromine source, the synergistic effect exhibited by molybdenum oxide was comparable to that shown by antimony oxide. Since molybdenum oxide also acts as a smoke suppressant, it could offer a useful alternative to antimony oxide particularly in the light of probable changes in standards and regulatory control regarding smoke emission. 4 figures, 2 tables.

  20. Study of the halogenation of EuBa[sub 2]Cu[sub 3]O[sub 6]. Etude de l'halogenation de EuBa[sub 2]Cu[sub 3]O[sub 6

    Energy Technology Data Exchange (ETDEWEB)

    Kabeya, D.T. (Rennes-1 Univ., 35 (France). Lab. de Chimie du Solide et Inorganique Moleculaire); Mokhtari, M. (Rennes-1 Univ., 35 (France). Lab. de Chimie du Solide et Inorganique Moleculaire); Perrin, C. (Rennes-1 Univ., 35 (France). Lab. de Chimie du Solide et Inorganique Moleculaire); Sergent, M. (Rennes-1 Univ., 35 (France). Lab. de Chimie du Solide et Inorganique Moleculaire); Grushko, Yu. (Russian Academy of Sciences, Gatchina (Russian Federation). Nuclear Physics Inst.); Kokovina, L. (Russian Academy of Sciences, Gatchina (Russian Federation). Nuclear Physics Inst.); Rozhniakova, N. (Russian Academy of Sciences, Gatchina (Russian Federation). Nuclear Physics Inst.)

    1994-11-01

    Sintered samples of EuBa[sub 2]Cu[sub 3]O[sub 6] have been halogenated at low temperature (t<300 C) by treatments under NF[sub 3] or CCl[sub 4] flow diluted in nitrogen, or by reaction with iodine in sealed tubes. Such mild conditions of synthesis allowed to avoid the decomposition of the material during the reactions. The incorporation of the halogen in the sample has been evidenced by the weight gain, by the evolution of the unit-cell parameters and by SEM and EDS analyses. After fluorination and chlorination, the samples become superconducting, but no superconducting behaviour is observed after iodination. These results are compared to the ones previously obtained during the halogenation of YBa[sub 2]Cu[sub 3]O[sub 6]. (orig.).

  1. UARS Halogen Occultation Experiment (HALOE) Level 2 V001

    Data.gov (United States)

    National Aeronautics and Space Administration — The HALOE home page on the WWW is http://haloe.gats-inc.com/home/index.php The Halogen Occultation Experiment (HALOE) on NASA's Upper Atmosphere Research Satellite...

  2. Biogas from MSW landfill: Composition and determination of chlorine content with the AOX (adsorbable organically bound halogens) technique

    International Nuclear Information System (INIS)

    Rey, M.D.; Font, R.; Aracil, I.

    2013-01-01

    An exhaustive characterization of the biogas from some waste disposal facilities has been carried out. The analysis includes the main components (methane, carbon dioxide, nitrogen and oxygen) as well as trace components such as hydrogen sulphide, ammonia and VOCs (volatile organic compounds) including siloxanes and halogenated compounds. VOCs were measured by GC/MS (Gas Chromatography/Mass Spectrometry) using two different procedures: thermal desorption of the Tenax TA and Carbotrap 349 tubes and SPME (Solid Phase Micro-Extraction). A method has been established to measure the total halogen content of the biogas with the AOX (adsorbable organically bound halogens) technique. The equipment used to analyze the samples was a Total Organic Halogen Analyzer (TOX-100). Similar results were obtained when comparing the TOX (Total Organic Halogen) values with those obtained by GC/MS. The halogen content in all the samples was under 22 mg Cl/Nm 3 which is below the limit of 150 mg/Nm 3 proposed in the Spanish Regulations for any use of the biogas. The low chlorine content in the biogas studied, as well as the low content of other trace compounds, makes it suitable for use as a fuel for electricity generating engines

  3. Modulation of prion polymerization and toxicity by rationally designed peptidomimetics.

    Science.gov (United States)

    Srivastava, Ankit; Sharma, Sakshi; Sadanandan, Sandhya; Gupta, Sakshi; Singh, Jasdeep; Gupta, Sarika; Haridas, V; Kundu, Bishwajit

    2017-01-01

    Misfolding and aggregation of cellular prion protein is associated with a large array of neurological disorders commonly called the transmissible spongiform encephalopathies. Designing inhibitors against prions has remained a daunting task owing to limited information about mechanism(s) of their pathogenic self-assembly. Here, we explore the anti-prion properties of a combinatorial library of bispidine-based peptidomimetics (BPMs) that conjugate amino acids with hydrophobic and aromatic side chains. Keeping the bispidine unit unaltered, a series of structurally diverse BPMs were synthesized and tested for their prion-modulating properties. Administration of Leu- and Trp-BPMs delayed and completely inhibited the amyloidogenic conversion of human prion protein (HuPrP), respectively. We found that each BPM induced the HuPrP to form unique oligomeric nanostructures differing in their biophysical properties, cellular toxicities and response to conformation-specific antibodies. While Leu-BPMs were found to stabilize the oligomers, Trp-BPMs effected transient oligomerization, resulting in the formation of non-toxic, non-fibrillar aggregates. Yet another aromatic residue, Phe, however, accelerated the aggregation process in HuPrP. Molecular insights obtained through MD (molecular dynamics) simulations suggested that each BPM differently engages a conserved Tyr 169 residue at the α2-β2 loop of HuPrP and affects the stability of α2 and α3 helices. Our results demonstrate that this new class of molecules having chemical scaffolds conjugating hydrophobic/aromatic residues could effectively modulate prion aggregation and toxicity. © 2017 The Author(s); published by Portland Press Limited on behalf of the Biochemical Society.

  4. Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

    International Nuclear Information System (INIS)

    Li, Jin-Feng; Sun, Yin-Yin; Li, Miao-Miao; Li, Jian-Li; Yin, Bing; Bai, Hongcun

    2015-01-01

    The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M 2 (CN) 5 ] −1 (M =  Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca 2 (CN) 5 ] −1 which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green’s function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties

  5. Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jin-Feng; Sun, Yin-Yin; Li, Miao-Miao; Li, Jian-Li; Yin, Bing, E-mail: rayinyin@nwu.edu.cn [MOE Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Bai, Hongcun [Key Laboratory of Energy Source and Chemical Engineering, Ningxia University, Yinchuan, Ningxia 750021 (China)

    2015-06-15

    The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M{sub 2}(CN){sub 5}]{sup −1} (M =  Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca{sub 2}(CN){sub 5}]{sup −1} which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green’s function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.

  6. Self-assembly of iodine in superfluid helium droplets. Halogen bonds and nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    He, Yunteng; Zhang, Jie; Lei, Lei; Kong, Wei [Department of Chemistry, Oregon State University, Corvallis, OR (United States)

    2017-03-20

    We present evidence of halogen bond in iodine clusters formed in superfluid helium droplets based on results from electron diffraction. Iodine crystals are known to form layered structures with intralayer halogen bonds, with interatomic distances shorter than the sum of the van der Waals radii of the two neighboring atoms. The diffraction profile of dimer dominated clusters embedded in helium droplets reveals an interatomic distance of 3.65 Aa, much closer to the value of 3.5 Aa in iodine crystals than to the van der Waals distance of 4.3 Aa. The profile from larger iodine clusters deviates from a single layer structure; instead, a bi-layer structure qualitatively fits the experimental data. This work highlights the possibility of small halogen bonded iodine clusters, albeit in a perhaps limited environment of superfluid helium droplets. The role of superfluid helium in guiding the trapped molecules into local potential minima awaits further investigation. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. Competition of hydrogen bonds and halogen bonds in complexes of hypohalous acids with nitrogenated bases.

    Science.gov (United States)

    Alkorta, Ibon; Blanco, Fernando; Solimannejad, Mohammad; Elguero, Jose

    2008-10-30

    A theoretical study of the complexes formed by hypohalous acids (HOX, X = F, Cl, Br, I, and At) with three nitrogenated bases (NH 3, N 2, and NCH) has been carried out by means of ab initio methods, up to MP2/aug-cc-pVTZ computational method. In general, two minima complexes are found, one with an OH...N hydrogen bond and the other one with a X...N halogen bond. While the first one is more stable for the smallest halogen derivatives, the two complexes present similar stabilities for the iodine case and the halogen-bonded structure is the most stable one for the hypoastatous acid complexes.

  8. Ab Initio Calculations on Halogen Bond Between N-Br and Electron-donating Groups

    Institute of Scientific and Technical Information of China (English)

    WANG Yan-hua; CHEN Xue-song; ZOU Jian-wei; YU Qing-sen

    2007-01-01

    Ab initio calculations of complexes formed between N-bromosuccinimide and a series of electron-donating groups were performed at the level of MP2/Lanl2DZ* to gain a deeper insight into the nature of the N-Br halogen stronger halogen-bonding complex than the C-Br. A comparison of neutral hydrogen bond complex series reveals that the electron-donating capacities of the atoms decrease in the order, N>O>S; O(sp3)>O(sp2), which is adequate for the C-Br halogen bonding. Interaction energies, in conjunction with the geometrical parameters show that the affinitive capacity of trihalide anions X-3 with N-bromosuccinimide are markedly lower than that of the corresponding X- with N-bromosuccinimide, even lower than those of neutral molecules with N-bromosuccinimide. AIM analyses further confirmed the above results.

  9. Selenium-Mediated Dehalogenation of Halogenated Nucleosides and its Relevance to the DNA Repair Pathway.

    Science.gov (United States)

    Mondal, Santanu; Manna, Debasish; Mugesh, Govindasamy

    2015-08-03

    Halogenated nucleosides can be incorporated into the newly synthesized DNA of replicating cells and therefore are commonly used in the detection of proliferating cells in living tissues. Dehalogenation of these modified nucleosides is one of the key pathways involved in DNA repair mediated by the uracil-DNA glycosylase. Herein, we report the first example of a selenium-mediated dehalogenation of halogenated nucleosides. We also show that the mechanism for the debromination is remarkably different from that of deiodination and that the presence of a ribose or deoxyribose moiety in the nucleosides facilitates the deiodination. The results described herein should help in understanding the metabolism of halogenated nucleosides in DNA and RNA. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Aromatic chemical feedstocks from coal

    Energy Technology Data Exchange (ETDEWEB)

    Collin, G

    1982-06-01

    Liquid byproducts of coal carbonization meet some 25% of the world demand for aromatic chemicals, currently at approx. 30 million t/a, in particular 15% of the demand for benzene and over 95% of the demand for condensed aromatics and heteroaromatics. Industrial processing of the aromatic byproducts of coal pressure gasification is carried out to only a minor extent. Other methods that may be employed in future to obtain carbochemical aromatic compounds are solvolysis and supercritical gas extraction, the catalytic liquid-phase hydrogenation and hydropyrolysis of coal, which also permit recovery of benzene and homologues, phenols, and condensed and partially hydrogenated aromatics, and the synthesis of aromatics using methanol as the key compound. As with the present means of obtaining aromatic chemicals from coal, the processes that may in the future be applied on an industrial scale to obtain pure aromatics will only be economically feasible if linked with the manufacture of other mass products and combined with the present production of carbochemical aromatics.

  11. Aromatic raw materials from coal

    Energy Technology Data Exchange (ETDEWEB)

    Collin, G

    1982-06-01

    Liquid byproducts of coal carbonization meet some 25% of the world demand for aromatic chemicals, currently at approx. 30 million t/a, in particular 15% of the demand for benzene and over 95% of the demand for condensed aromatics and heteroaromatics. Industrial processing of the aromatic byproducts of coal pressure gasification is carried out to only a minor extent. Other methods that may be employed in future to obtain carbochemical aromatic compounds are solvolysis and supercritical gas extraction, the catalytic liquid-phase hydrogenation and hydropyrolysis of coal, which also permit recovery of benzene and homologues, phenols, and condensed and partially hydrogenated aromatics, and the synthesis of aromatics using methanol as the key compound. As with the present means of obtaining aromatic chemicals from coal, the processes that may in future be applied on an industrial scale to obtain pure aromatics will only be economically feasible if linked with the manufacture of other mass products and combined with the present production of carbochemical aromatics. (In German)

  12. Benchmark Calculations of Noncovalent Interactions of Halogenated Molecules

    Czech Academy of Sciences Publication Activity Database

    Řezáč, Jan; Riley, Kevin Eugene; Hobza, Pavel

    2012-01-01

    Roč. 8, č. 11 (2012), s. 4285-4292 ISSN 1549-9618 R&D Projects: GA ČR GBP208/12/G016 Institutional support: RVO:61388963 Keywords : halogenated molecules * noncovalent interactions * benchmark calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.389, year: 2012

  13. Polar Flattening and the Strength of Halogen Bonding

    Czech Academy of Sciences Publication Activity Database

    Sedlák, Robert; Kolář, Michal H.; Hobza, Pavel

    2015-01-01

    Roč. 11, č. 10 (2015), s. 4727-4732 ISSN 1549-9618 R&D Projects: GA ČR GBP208/12/G016 Institutional support: RVO:61388963 Keywords : density functional theory * interaction energies * halogen bonding Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.301, year: 2015

  14. Heavy metals, PAHs and toxicity in stormwater wet detention ponds

    DEFF Research Database (Denmark)

    Wium-Andersen, Tove; Nielsen, Asbjørn Haaning; Hvitved-Jacobsen, Thorkild

    2011-01-01

    Concentrations of 6 different heavy metals and total Polycyclic Aromatic Hydrocarbons (PAH) were determined in stormwater runoff and in the pond water of two Danish wet detention ponds. The pond water samples were analyzed for toxic effects, using the algae Selenastrum capricornutum as a test...... organism. Stormwater and pond water from a catchment with light industry showed high levels of heavy metals, especially zinc and copper. The pond water showed high toxic effects and copper were found to be the main toxicant. Additionally, a large part of the copper was suspected to be complex bound......, reducing the potential toxicity of the metal. Another catchment (residential) produced stormwater and pond water with moderate concentration of heavy metals. The pond water occasionally showed toxic effects but no correlation between heavy metals and toxicity was identified. PAHs concentrations were...

  15. The Effect of Intermolecular Halogen Bond on 19F DNP Enhancement in 1, 4-Diiodotetrafluorobenzene/4-OH-TEMPO Supramolecular Assembly

    Directory of Open Access Journals (Sweden)

    GAO Shan

    2017-12-01

    Full Text Available Halogen bond, as hydrogen bond, is a non-covalent bond. Dynamic nuclear polarization (DNP technique has been used previously to study hydrogen bonds-mediated intermolecular interactions. However, no study has been carried out so far to study the halogen bond-mediated intermolecular interactions with DNP. In this work, 19F DNP polarization efficiency of the halogen bonds existing in supramolecular assembling by 4-OH-TEMPO and 1,4-diiodotetrafluorobenzene (DITFB was studied on a home-made DNP system. The formation of intermolecular halogen bonds appeared to increase 19F DNP polarization efficiency, suggesting that the spin-spin interactions among electrons were weakened by the halogen bonds, resulting in an increased T2e and a larger saturation factor.

  16. Isomorphism of 2-methylnaphthalene and 2-halonaphthalenes as a revealer of a special interaction between methyl and halogen

    Science.gov (United States)

    Calvet, T.; Cuevas-Diarte, M. A.; Haget, Y.; Mondieig, D.; Kok, I. C.; Verdonk, M. L.; Van Miltenburg, J. C.; Oonk, H. A. J.

    1999-03-01

    The systems 2-methylnaphthalene+2-chloronaphthalene and 2-methylnaphthalene+2-bromonaphthalene belong to the exceptional group of binary systems where the formation of mixed crystals goes together with a solid-liquid phase diagram with a maximum. For these systems a thermodynamic analysis is presented which is based on new phase diagram and thermochemical data. The excess Gibbs energies, excess enthalpies, and excess entropies of the mixed crystalline state all are negative. These properties correspond to a net attraction between methyl and substituted halogen. Additional evidence of such an attraction is given by the outcome of a statistical search on intermolecular contacts, in the crystalline state of pure substances, among methyl+halogen, halogen+halogen, and methyl+methyl.

  17. Process for crosslinking methylene-containing aromatic polymers with ionizing radiation

    Science.gov (United States)

    Bell, Vernon L. (Inventor); Havens, Stephen J. (Inventor)

    1990-01-01

    A process for crosslinking aromatic polymers containing radiation-sensitive methylene groups (-CH2-) by exposing the polymers to ionizing radiation thereby causing crosslinking of the polymers through the methylene groups is described. Crosslinked polymers are resistant to most organic solvents such as acetone, alcohols, hydrocarbons, methylene, chloride, chloroform, and other halogenated hydrocarbons, to common fuels and to hydraulic fluids in contrast to readily soluble uncrosslinked polymers. In addition, the degree of crosslinking of the polymers depends upon the percentage of the connecting groups which are methylene which ranges from 5 to 50 pct and preferably from 25 to 50 pct of the connecting groups, and is also controlled by the level of irradiation which ranges from 25 to 1000 Mrads and preferably from 25 to 250 Mrads. The temperature of the reaction conditions ranges from 25 to 200 C and preferably at or slightly above the glass transition temperature of the polymer. The crosslinked polymers are generally more resistant to degradation at elevated temperatures such as greater than 150 C, have a reduced tendency to creep under load, and show no significant embrittlement of parts fabricated from the polymers.

  18. Prenatal exposure to polycyclic aromatic hydrocarbons/aromatics, BDNF and child development

    International Nuclear Information System (INIS)

    Perera, Frederica; Phillips, David H.; Wang, Ya; Roen, Emily; Herbstman, Julie; Rauh, Virginia; Wang, Shuang; Tang, Deliang

    2015-01-01

    Objectives: Within a New York City (NYC) birth cohort, we assessed the associations between polycyclic aromatic hydrocarbon (PAH) and other aromatic DNA adducts and brain derived neurotrophic factor (BDNF) concentrations in umbilical cord blood, and neurodevelopment at age 2 years and whether BDNF is a mediator of the associations between PAH/aromatic-DNA adducts and neurodevelopment. Methods: PAH/aromatic-DNA adduct concentrations in cord blood were measured in 505 children born to nonsmoking African-American and Dominican women residing in NYC, and a subset was assessed for neurodevelopment at 2 years using the Bayley Scales of Infant Development Mental Development Index (MDI). A spectrum of PAH/aromatic-DNA adducts was measured using the 32 P-postlabeling assay; DNA adducts formed by benzo[a]pyrene (B[a]P), a representative PAH, were measured by High Performance Liquid Chromatography (HPLC)/fluorescence. BDNF mature protein in cord blood plasma was quantified by an ELISA. Multivariate regression analysis, adjusting for potential confounders, was conducted. Results: PAH/aromatic-DNA adduct concentration measured by postlabeling was inversely associated with BDNF concentration (p=0.02) and with MDI scores at 2 years (p=0.04). BDNF level was positively associated with MDI scores (p=0.003). Restricting to subjects having all three measures (PAH/aromatic-DNA adducts by postlabeling, MDI, and BDNF), results were similar but attenuated (p=0.13, p=0.05, p=0.01, respectively). Associations between B[a]P-DNA adducts and BDNF and B[a]P-DNA adducts and MDI at age 2 years were not significant. At age 3 years, the positive association of BDNF with MDI was not observed. Conclusions: The results at age 2 suggest that prenatal exposure to a spectrum of PAH/aromatic pollutants may adversely affect early neurodevelopment, in part by reducing BDNF levels during the fetal period. However, the same relationship was not seen at age 3. - Highlights: • Cord blood Polycyclic Aromatic

  19. Prenatal exposure to polycyclic aromatic hydrocarbons/aromatics, BDNF and child development

    Energy Technology Data Exchange (ETDEWEB)

    Perera, Frederica, E-mail: fpp1@columbia.edu [Department of Environmental Health Sciences, Mailman School of Public Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Phillips, David H. [Analytical and Environmental Sciences Division, MRC-PHE Centre for Environment and Health, King' s College London, Franklin-Wilkins Building, London SE1 9NH (United Kingdom); Wang, Ya [Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Department of Biostatistics, Mailman School of Public Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Roen, Emily; Herbstman, Julie [Department of Environmental Health Sciences, Mailman School of Public Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Rauh, Virginia [Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); The Heilbrunn Department of Population and Family Health, Columbia University, 60 Haven Avenue, New York, NY 10032 (United States); Wang, Shuang [Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Department of Biostatistics, Mailman School of Public Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Tang, Deliang [Department of Environmental Health Sciences, Mailman School of Public Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States)

    2015-10-15

    Objectives: Within a New York City (NYC) birth cohort, we assessed the associations between polycyclic aromatic hydrocarbon (PAH) and other aromatic DNA adducts and brain derived neurotrophic factor (BDNF) concentrations in umbilical cord blood, and neurodevelopment at age 2 years and whether BDNF is a mediator of the associations between PAH/aromatic-DNA adducts and neurodevelopment. Methods: PAH/aromatic-DNA adduct concentrations in cord blood were measured in 505 children born to nonsmoking African-American and Dominican women residing in NYC, and a subset was assessed for neurodevelopment at 2 years using the Bayley Scales of Infant Development Mental Development Index (MDI). A spectrum of PAH/aromatic-DNA adducts was measured using the {sup 32}P-postlabeling assay; DNA adducts formed by benzo[a]pyrene (B[a]P), a representative PAH, were measured by High Performance Liquid Chromatography (HPLC)/fluorescence. BDNF mature protein in cord blood plasma was quantified by an ELISA. Multivariate regression analysis, adjusting for potential confounders, was conducted. Results: PAH/aromatic-DNA adduct concentration measured by postlabeling was inversely associated with BDNF concentration (p=0.02) and with MDI scores at 2 years (p=0.04). BDNF level was positively associated with MDI scores (p=0.003). Restricting to subjects having all three measures (PAH/aromatic-DNA adducts by postlabeling, MDI, and BDNF), results were similar but attenuated (p=0.13, p=0.05, p=0.01, respectively). Associations between B[a]P-DNA adducts and BDNF and B[a]P-DNA adducts and MDI at age 2 years were not significant. At age 3 years, the positive association of BDNF with MDI was not observed. Conclusions: The results at age 2 suggest that prenatal exposure to a spectrum of PAH/aromatic pollutants may adversely affect early neurodevelopment, in part by reducing BDNF levels during the fetal period. However, the same relationship was not seen at age 3. - Highlights: • Cord blood Polycyclic

  20. A systematic structural study of halogen bonding versus hydrogen bonding within competitive supramolecular systems

    Directory of Open Access Journals (Sweden)

    Christer B. Aakeröy

    2015-09-01

    Full Text Available As halogen bonds gain prevalence in supramolecular synthesis and materials chemistry, it has become necessary to examine more closely how such interactions compete with or complement hydrogen bonds whenever both are present within the same system. As hydrogen and halogen bonds have several fundamental features in common, it is often difficult to predict which will be the primary interaction in a supramolecular system, especially as they have comparable strength and geometric requirements. To address this challenge, a series of molecules containing both hydrogen- and halogen-bond donors were co-crystallized with various monotopic, ditopic symmetric and ditopic asymmetric acceptor molecules. The outcome of each reaction was examined using IR spectroscopy and, whenever possible, single-crystal X-ray diffraction. 24 crystal structures were obtained and subsequently analyzed, and the synthon preferences of the competing hydrogen- and halogen-bond donors were rationalized against a background of calculated molecular electrostatic potential values. It has been shown that readily accessible electrostatic potentials can offer useful practical guidelines for predicting the most likely primary synthons in these co-crystals as long as the potential differences are weighted appropriately.

  1. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15-December 31, 1984

    International Nuclear Information System (INIS)

    1985-01-01

    Energetic halogen atoms or ions, activated by various nuclear transformations are studied in gas, high pressure and condensed phase saturated and unsaturated hydrocarbons, halomethanes, and liquid and solid aqueous solutions of biomolecular and organic solutes in order to understand better the mechanisms and dynamics of high energy monovalent species. The experimental program and its goals remain the same, consisting of four interrelated areas: (1) The stereochemistry of energetic 18 F, /sup 34m/Cl, and 38 Cl substitution reactions with chiral molecules in the gas and condensed phase is studied. (2) The gas to condensed state transition in halogen high energy chemistry, involving energetic chlorine, bromine, and iodine reactions in halomethanes, saturated and unsaturated hydrocarbons and aqueous solutions of biomolecules and alkyl halides is being investigated in more detail. Current attention is given to defining the nature of the enhancement yields in the condensed phase. Specifically, energetic halogen reactions in liquid and frozen aqueous solutions or organic and biomolecular solutes are studied. (3) Reactions of bromine and iodine activated by isomeric transition with halogenated biomolecular and organic solutes in liquid and frozen aqueous solutions are being studied in an attempt to learn more about the activation events in the condensed phase. (4) The applications of hot chemistry techniques and theory to neutron activation analysis of biological systems are being continued. Current attention is given to developing procedures for trace molecular determinations in biological systems. The applications of hot halogen atoms as site indicators in liquid and frozen aqueous solutions of halogenated bases and nucleosides are currently being developed. 14 references

  2. Toxicity of jet fuel aliphatic and aromatic hydrocarbon mixtures on human epidermal Keratinocytes: evaluation based on in vitro cytotoxicity and interleukin-8 release

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Jen-Hung (Chung-Shan Medical University Hospital, Department of Dermatology, Taichung, Taiwan, R.O.C); Lee, Chia-Hue; Tsang, Chau-Loong [National Chung-Hsing University, College of Veterinary Medicine, Taichung (Taiwan); Monteiro-Riviere, Nancy A.; Riviere, Jim E. [North Carolina State University, Center for Chemical Toxicology Research and Pharmacokinetics (CCTRP), Raleigh, NC (United States); Chou, Chi-Chung [National Chung-Hsing University, College of Veterinary Medicine, Taichung (Taiwan); National Chung-Hsing University, College of Veterinary Medicine, Taichung (Taiwan)

    2006-08-15

    Jet fuels are complex mixtures of aliphatic (ALI) and aromatic (ARO) hydrocarbons that vary significantly in individual cytotoxicity and proinflammatory activity in human epidermal keratinocytes (HEK). In order to delineate the toxicological interactions among individual hydrocarbons in a mixture and their contributions to cutaneous toxicity, nine ALI and five ARO hydrocarbons were each divided into five (high/medium/low cytotoxic and strong/weak IL-8 induction) groups and intra/inter-mixed to assess for their mixture effects on HEK mortality and IL-8 release. Addition of single hydrocarbon to JP-8 fuel was also evaluated for their changes in fuel dermatotoxicity. The results indicated that when hydrocarbons were mixed, HEK mortality and IL-8 release were not all predictable by their individual ability affecting these two parameters. The lowest HEK mortality (7%) and the highest IL-8 production were induced with mixtures including high cytotoxic and weak IL-8 inductive ARO hydrocarbons. Antagonistic reactions not consistently correlated with ALI carbon chain length and ARO structure were evident and carried different weight in the overall mixture toxicities. Single addition of benzene, toluene, xylene or ethylbenzene for up to tenfold in JP-8 did not increase HEK mortality while single addition of ALI hydrocarbons exhibited dose-related differential response in IL-8. In an all ALI environment, no single hydrocarbon is the dominating factor in the determination of HEK cytotoxicity while deletion of hexadecane resulted in a 2.5-fold increase in IL-8 production. Overall, decane, undecane and dodecane were the major hydrocarbons associated with high cytotoxicity while tetradecane, pentadecane and hexadecane were those which had the greatest buffering effect attenuating dermatotoxicity. The mixture effects must be considered when evaluating jet fuel toxicity to HEK. (orig.)

  3. Substrate specific hydrolysis of aromatic and aromatic-aliphatic esters in orchid tissue cultures

    Directory of Open Access Journals (Sweden)

    Agnieszka Mironowicz

    2014-01-01

    Full Text Available We found that tissue cultures of higher plants were able, similarly as microorganisms, to transform low-molecular-weight chemical compounds. In tissue cultures of orchids (Cymbidium 'Saint Pierre' and Dendrobium phalaenopsis acetates of phenols and aromatic-aliphatic alcohols were hydrolyzed, whereas methyl esters of aromatic and aromatic-aliphatic acids did not undergo this reaction. Acetates of racemic aromatic-aliphatic alcohols were hydrolyzed with distinct enantiospecificity.

  4. Global impacts of tropospheric halogens (Cl, Br, I on oxidants and composition in GEOS-Chem

    Directory of Open Access Journals (Sweden)

    T. Sherwen

    2016-09-01

    Full Text Available We present a simulation of the global present-day composition of the troposphere which includes the chemistry of halogens (Cl, Br, I. Building on previous work within the GEOS-Chem model we include emissions of inorganic iodine from the oceans, anthropogenic and biogenic sources of halogenated gases, gas phase chemistry, and a parameterised approach to heterogeneous halogen chemistry. Consistent with Schmidt et al. (2016 we do not include sea-salt debromination. Observations of halogen radicals (BrO, IO are sparse but the model has some skill in reproducing these. Modelled IO shows both high and low biases when compared to different datasets, but BrO concentrations appear to be modelled low. Comparisons to the very sparse observations dataset of reactive Cl species suggest the model represents a lower limit of the impacts of these species, likely due to underestimates in emissions and therefore burdens. Inclusion of Cl, Br, and I results in a general improvement in simulation of ozone (O3 concentrations, except in polar regions where the model now underestimates O3 concentrations. Halogen chemistry reduces the global tropospheric O3 burden by 18.6 %, with the O3 lifetime reducing from 26 to 22 days. Global mean OH concentrations of 1.28  ×  106 molecules cm−3 are 8.2 % lower than in a simulation without halogens, leading to an increase in the CH4 lifetime (10.8 % due to OH oxidation from 7.47 to 8.28 years. Oxidation of CH4 by Cl is small (∼  2 % but Cl oxidation of other VOCs (ethane, acetone, and propane can be significant (∼  15–27 %. Oxidation of VOCs by Br is smaller, representing 3.9 % of the loss of acetaldehyde and 0.9 % of the loss of formaldehyde.

  5. Thermodynamics parameters for binding of halogenated benzotriazole inhibitors of human protein kinase CK2α.

    Science.gov (United States)

    Winiewska, Maria; Kucińska, Katarzyna; Makowska, Małgorzata; Poznański, Jarosław; Shugar, David

    2015-10-01

    The interaction of human CK2α (hCK2α) with nine halogenated benzotriazoles, TBBt and its analogues representing all possible patterns of halogenation on the benzene ring of benzotriazole, was studied by biophysical methods. Thermal stability of protein-ligand complexes, monitored by calorimetric (DSC) and optical (DSF) methods, showed that the increase in the mid-point temperature for unfolding of protein-ligand complexes (i.e. potency of ligand binding to hCK2α) follow the inhibitory activities determined by biochemical assays. The dissociation constant for the ATP-hCK2α complex was estimated with the aid of microscale thermophoresis (MST) as 4.3±1.8 μM, and MST-derived dissociation constants determined for halogenated benzotriazoles, when converted according to known ATP concentrations, perfectly reconstruct IC50 values determined by the biochemical assays. Ligand-dependent quenching of tyrosine fluorescence, together with molecular modeling and DSC-derived heats of unfolding, support the hypothesis that halogenated benzotriazoles bind in at least two alternative orientations, and those that are efficient hCK2α inhibitors bind in the orientation which TBBt adopts in its complex with maize CK2α. DSC-derived apparent heat for ligand binding (ΔΔHbind) is driven by intermolecular electrostatic interactions between Lys68 and the triazole ring of the ligand, as indicated by a good correlation between ΔΔHbind and ligand pKa. Overall results, additionally supported by molecular modeling, confirm that a balance of hydrophobic and electrostatic interactions contribute predominantly (~40 kJ/mol), relative to possible intermolecular halogen/hydrogen bonding (less than 10 kJ/mol), in binding of halogenated benzotriazoles to the ATP-binding site of hCK2α. This article is part of a Special Issue entitled: Inhibitors of Protein Kinases. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety

    Energy Technology Data Exchange (ETDEWEB)

    Hissung, A; Isildar, M; von Sonntag, C [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany, F.R.). Inst. fuer Strahlenforschung; Witzel, H [Biochemisches Institut der Westfaelischen Wilhelms-Universitaet, Muenster, West Germany

    1981-02-01

    The pulse radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety (2'-bromo-2'-deoxyuridine 4, 3'-deoxy-3'-iodothymidine 5, 5'-deoxy-5'-iodouridine 6) has been studied. G(Hal) were determined by conductometry varying the experimental conditions (pH, saturation with Ar, N/sub 2/O or air, addition of t-butanol). The results indicate that solvated electrons both add to the nucleobases and eliminate halogen ions from the halogenated sugar moiety. In the case of 4(and possibly of 5) the radical anion of the base transfers (k approximately 10/sup 5/s/sup -1/) an electron to the sugar-bound halogen atom thus cleaving the C-Hal bond. In competition with this reaction there is a protonation of the radical anion of the base by protons and by water. For the latter reaction constant of k = 5 x 10/sup 3/ M/sup -1/s/sup -1/ was estimated. Compound 4 has also been investigated by product analysis after 60-Co-..gamma..-irradiation. In aerated solutions erythrose is formed with a G-value of 0.12. Its precursor radical is the 2'-radical generated from 4 by dissociative electron capture which reacts with O/sub 2/ to the corresponding peroxyl radical. Erythrose is formed after a sequence of reactions, one of which involves the scission of the C-1'-C-2'bond. Under this condition G(HBr) as measured by pulse radiolysis is 0.8. Thus erythrose is formed in 15 per cent yield with respect to its precursor radical. This result is of importance in assessing the precursor radical of a similar product observed in irradiated DNA.

  7. Radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety

    International Nuclear Information System (INIS)

    Hissung, A.; Isildar, M.; Sonntag, C. von; Witzel, H.

    1981-01-01

    The pulse radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety (2'-bromo-2'-deoxyuridine 4, 3'-deoxy-3'-iodothymidine 5, 5'-deoxy-5'-iodouridine 6) has been studied. G(Hal) were determined by conductometry varying the experimental conditions (pH, saturation with Ar, N 2 O or air, addition of t-butanol). The results indicate that solvated electrons both add to the nucleobases and eliminate halogen ions from the halogenated sugar moiety. In the case of 4(and possibly of 5) the radical anion of the base transfers (k approximately 10 5 s -1 ) an electron to the sugar-bound halogen atom thus cleaving the C-Hal bond. In competition with this reaction there is a protonation of the radical anion of the base by protons and by water. For the latter reaction constant of k = 5 x 10 3 M -1 s -1 was estimated. Compound 4 has also been investigated by product analysis after 60-Co-γ-irradiation. In aerated solutions erythrose is formed with a G-value of 0.12. Its precursor radical is the 2'-radical generated from 4 by dissociative electron capture which reacts with O 2 to the corresponding peroxyl radical. Erythrose is formed after a sequence of reactions, one of which involves the scission of the C-1'-C-2'bond. Under this condition G(HBr) as measured by pulse radiolysis is 0.8. Thus erythrose is formed in 15 per cent yield with respect to its precursor radical. This result is of importance in assessing the precursor radical of a similar product observed in irradiated DNA. (author)

  8. Halogen bond preferences of thiocyanate ligand coordinated to Ru(II) via sulphur atom

    Science.gov (United States)

    Ding, Xin; Tuikka, Matti; Hirva, Pipsa; Haukka, Matti

    2017-09-01

    Halogen bonding between [Ru(bpy)(CO)2(S-SCN)2] (bpy = 2,2'-bipyridine), I2 was studied by co-crystallising the metal compound and diiodine from dichloromethane. The only observed crystalline product was found to be [Ru(bpy)(CO)2(S-SCN)2]ṡI2 with only one NCSṡṡṡI2 halogen bond between I2 and the metal coordinated S atom of one of the thiocyanate ligand. The dangling nitrogen atoms were not involved in halogen bonding. However, computational analysis suggests that there are no major energetic differences between the NCSṡṡṡI2 and SCNṡṡṡI2 bonding modes. The reason for the observed NCSṡṡṡI2 mode lies most probably in the more favourable packing effects rather than energetic preferences between NCSṡṡṡI2 and SCNṡṡṡI2 contacts.

  9. Organohalide respiration in pristine environments: implications for the natural halogen cycle.

    Science.gov (United States)

    Atashgahi, Siavash; Häggblom, Max M; Smidt, Hauke

    2018-03-01

    Halogenated organic compounds, also termed organohalogens, were initially considered to be of almost exclusively anthropogenic origin. However, over 5000 naturally synthesized organohalogens are known today. This has also fuelled the hypothesis that the natural and ancient origin of organohalogens could have primed development of metabolic machineries for their degradation, especially in microorganisms. Among these, a special group of anaerobic microorganisms was discovered that could conserve energy by reducing organohalogens as terminal electron acceptor in a process termed organohalide respiration. Originally discovered in a quest for biodegradation of anthropogenic organohalogens, these organohalide-respiring bacteria (OHRB) were soon found to reside in pristine environments, such as the deep subseafloor and Arctic tundra soil with limited/no connections to anthropogenic activities. As such, accumulating evidence suggests an important role of OHRB in local natural halogen cycles, presumably taking advantage of natural organohalogens. In this minireview, we integrate current knowledge regarding the natural origin and occurrence of industrially important organohalogens and the evolution and spread of OHRB, and describe potential implications for natural halogen and carbon cycles. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

  10. Photofragmentation spectra of halogenated methanes in the VUV photon energy range

    Energy Technology Data Exchange (ETDEWEB)

    Cartoni, Antonella, E-mail: antonella.cartoni@uniroma1.it [Dipartimento di Chimica e Tecnologie del Farmaco, Sapienza Università di Roma, P.le Aldo Moro 5, Roma 00185 (Italy); Bolognesi, Paola; Fainelli, Ettore; Avaldi, Lorenzo [CNR-IMIP, Area della Ricerca di Roma 1, Monterotondo Scalo (Rm) 00015 (Italy)

    2014-05-14

    In this paper an investigation of the photofragmentation of dihalomethanes CH{sub 2}X{sub 2} (X = F, Cl, Br, I) and chlorinated methanes (CH{sub n}Cl{sub 4−n} with n = 0–3) with VUV helium, neon, and argon discharge lamps is reported and the role played by the different halogen atoms is discussed. Halogenated methanes are a class of molecules used in several fields of chemistry and the study of their physical and chemical proprieties is of fundamental interest. In particular their photodissociation and photoionization are of great importance since the decomposition of these compounds in the atmosphere strongly affects the environment. The results of the present work show that the halogen-loss is the predominant fragmentation channel for these molecules in the VUV photon energy range and confirm their role as reservoir of chlorine, bromine, and iodine atoms in the atmosphere. Moreover, the results highlight the peculiar feature of CH{sub 2}F{sub 2} as a source of both fluorine and hydrogen atoms and the characteristic formation of I{sub 2}{sup +} and CH{sub 2}{sup +} ions from the photofragmentation of the CH{sub 2}I{sub 2} molecule.

  11. Mutagenic activity of halogenated propanes and propenes: effect of bromine and chlorine positioning.

    Science.gov (United States)

    Låg, M; Omichinski, J G; Dybing, E; Nelson, S D; Søderlund, E J

    1994-10-01

    A series of halogenated propanes and propenes were studied for mutagenic effects in Salmonella typhimurium TA100 in the absence or presence of NADPH plus liver microsomes from phenobarbital-induced rats as an exogenous metabolism system. The cytotoxic and mutagenic effects of the halogenated propane 1,2-dibromo-3-chloropropane (DBCP) has previously been studied in our laboratories. These studies showed that metabolic activation of DBCP was required to exert its detrimental effects. All of the trihalogenated propane analogues were mutagenic when the microsomal activation system was included. The highest mutagenic activity was obtained with 1,2,3-tribromopropane, with approximately 50-fold higher activity than the least mutagenic trihalogenated propane, 1,2,3-trichloropropane. The order of mutagenicity was as follows: 1,2,3-tribromopropane > or = 1,2-dibromo- 3-chloropropane > 1,3-dibromo-2-chloropropane > or = 1,3-dichloro-2-bromopropane > 1-bromo-2,3-dichloropropane > 1,2,3-trichloropropane. Compared to DBCP, the dihalogenated propanes were substantially less mutagenic. Only 1,2-dibromopropane was mutagenic and its mutagenic potential was approximately 1/30 of that of DBCP. In contrast to DBCP, 1,2-dibromopropane showed similar mutagenic activity with and without the addition of an activation system. The halogenated propenes 2,3-dibromopropene and 2-bromo-3-chloropropene were mutagenic to the bacteria both in the absence and presence of the activation system, whereas 2,3-dichloropropene did not show any mutagenic effect. The large differences in mutagenic potential between the various halogenated propanes and propenes are proposed to be due to the formation of different possible proximate and ultimate mutagenic metabolites resulting from the microsomal metabolism of the various halogenated propanes and propenes, and to differences in the rate of formation of the metabolites. Pathways are proposed for the formation of genotoxic metabolites of di- and trihalogenated

  12. Chiral halogenated Schiff base compounds: green synthesis, anticancer activity and DNA-binding study

    Science.gov (United States)

    Ariyaeifar, Mahnaz; Amiri Rudbari, Hadi; Sahihi, Mehdi; Kazemi, Zahra; Kajani, Abolghasem Abbasi; Zali-Boeini, Hassan; Kordestani, Nazanin; Bruno, Giuseppe; Gharaghani, Sajjad

    2018-06-01

    Eight enantiomerically pure halogenated Schiff base compounds were synthesized by reaction of halogenated salicylaldehydes with 3-Amino-1,2-propanediol (R or S) in water as green solvent at ambient temperature. All compounds were characterized by elemental analyses, NMR (1H and 13C), circular dichroism (CD) and FT-IR spectroscopy. FS-DNA binding studies of these compounds carried out by fluorescence quenching and UV-vis spectroscopy. The obtained results revealed that the ligands bind to DNA as: (Rsbnd ClBr) > (Rsbnd Cl2) > (Rsbnd Br2) > (Rsbnd I2) and (Ssbnd ClBr) > (Ssbnd Cl2) > (Ssbnd Br2) > (Ssbnd I2), indicating the effect of halogen on binding constant. In addition, DNA-binding constant of the Ssbnd and R-enantiomers are different from each other. The ligands can form halogen bonds with DNA that were confirmed by molecular docking. This method was also measured the bond distances and bond angles. The study of obtained data can have concluded that binding affinity of the ligands to DNA depends on strength of halogen bonds. The potential anticancer activity of ligands were also evaluated on MCF-7 and HeLa cancer cell lines by using MTT assay. The results showed that the anticancer activity and FS-DNA interaction is significantly dependent on the stereoisomers of Schiff base compounds as R-enantiomers displayed significantly higher activity than S-enantiomers. The molecular docking was also used to illustrate the specific DNA-binding of synthesized compounds and groove binding mode of DNA interaction was proposed for them. In addition, molecular docking results indicated that there are three types of bonds (Hsbnd and X-bond and hX-bond) between synthesized compounds and base pairs of DNA.

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

    International Nuclear Information System (INIS)

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

    2015-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Maley, Adam M.; Falk, Kyle A.; Hoover, Luke; Earlywine, Elly B.; Seymour, Michael D. [Department of Chemistry, Hope College, 35 E. 12th Street, Holland, MI 49423 (United States); DeYoung, Paul A. [Department of Physics, Hope College, 27 Graves Place, Holland, MI 49423 (United States); Blum, Arlene [Green Science Policy Institute, Box 5455, Berkeley, CA 94705 (United States); Stapleton, Heather M. [Nicholas School of the Environment, Duke University, LSRC Box 90328, Durham, NC 27708 (United States); Peaslee, Graham F., E-mail: peaslee@hope.edu [Department of Chemistry, Hope College, 35 E. 12th Street, Holland, MI 49423 (United States)

    2015-09-01

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

  15. The influence of microplastics and halogenated contaminants in feed on toxicokinetics and gene expression in European seabass (Dicentrarchus labrax)

    DEFF Research Database (Denmark)

    Granby, Kit; Rainieri, Sandra; Rasmussen, Rie Romme

    2018-01-01

    When microplastics pollute fish habitats, it may be ingested by fish, thereby contaminating fish with sorbed contaminants. The present study investigates how combinations of halogenated contaminants and microplastics associated with feed are able to alter toxicokinetics in European seabass...... and affect the fish. Microplastic particles (2%) were added to the feed either with sorbed contaminants or as a mixture of clean microplastics and chemical contaminants, and compared to feed containing contaminants without microplastics. For the contaminated microplastic diet, the accumulation...... days of exposure indicate that microplastics might indeed exacerbate the toxic effects (liver metabolism, immune system, oxidative stress) of some chemical contaminants sorbed to microplastics. Seabass quickly metabolised BDE99 to BDE47 by debromination, probably mediated by deiodinase enzymes...

  16. Can Halogen Enrichment in Reduced Enstatite Chondrites Provide Clues to Volatile Accretion in the Early Earth?

    Science.gov (United States)

    Clay, P. L.; Burgess, R.; Busemann, H.; Ruzié, L.; Joachim, B.; Ballentine, C.

    2013-12-01

    Understanding how the Earth obtained and ultimately retained its volatiles is important for our overall understanding of large scale planetary evolution. Numerous models exist for the heterogeneous accretion of volatiles to early Earth, but accounting for all elements through accretion of typical planetary building blocks (e.g., CI chondrites) is difficult. Proto-planetary collisions resulting in the accretion of volatile-poor material under reducing conditions followed by accretion of volatile-rich material under oxidizing conditions has been suggested in such models [e.g., 1]. The heavy halogens (Cl, Br and I), a group of moderately volatile elements, are excellent tracers of planetary processing due to their low abundance and incompatible nature. Therefore characterizing halogen abundance and distribution in materials that accreted to form the planets, e.g., primitive meteorites, is crucial. One group of primitive meteorites, the enstatite chondrites (EC's), are amongst the most reduced materials in the solar system as evidenced by their unique mineral assemblage. Yet despite forming under ultra-reducing conditions, they are enriched in the moderately volatile elements, such as the halogens. The ECs are of particular interest owing to their oxygen isotopic composition which plots along the terrestrial fractionation line, linking them isotopically to the Earth-Moon system. These samples can thus potentially provide clues on the accretion of moderately volatile element rich material under reducing conditions, such as it may have existed during the early stages of Earth's accretion. Chlorine, Br and I concentrations in ECs were determined through step-heating small neutron-irradiated samples (0.3 to 3.3 mg) and measured by mass spectrometry using the noble gas proxy isotopes 38ArCl/Cl, 80KrBr/Br and 128XeI/I. The EH chondrites are consistently enriched in the heavy halogens (up to 330 ppm Cl, 2290 ppb Br and 180 ppb I), compared to other ordinary and carbonaceous

  17. Parsing of the free energy of aromatic-aromatic stacking interactions in solution

    Energy Technology Data Exchange (ETDEWEB)

    Kostjukov, Viktor V.; Khomytova, Nina M. [Department of Physics, Sevastopol National Technical University, Sevastopol 99053, Crimea (Ukraine); Hernandez Santiago, Adrian A.; Tavera, Anna-Maria Cervantes; Alvarado, Julieta Salas [Faculty of Chemical Sciences, Autonomous University of Puebla, Puebla (Mexico); Evstigneev, Maxim P., E-mail: max_evstigneev@mail.ru [Department of Physics, Sevastopol National Technical University, Sevastopol 99053, Crimea (Ukraine)

    2011-10-15

    Graphical abstract: Highlights: > A protocol for decomposition of the free energy of aromatic stacking is developed. > The factors stabilizing/destabilizing stacking of aromatic molecules are defined. > Hydrophobic contribution is found to be dominant. - Abstract: We report an analysis of the energetics of aromatic-aromatic stacking interactions for 39 non-covalent reactions of self- and hetero-association of 12 aromatic molecules with different structures and charge states. A protocol for computation of the contributions to the total energy from various energetic terms has been developed and the results are consistent with experiment in 92% of all the systems studied. It is found that the contributions from hydrogen bonds and entropic factors are always unfavorable, whereas contributions from van-der-Waals, electrostatic and/or hydrophobic effects may lead to stabilizing or destabilizing factors depending on the system studied. The analysis carried out in this work provides an answer to the questions 'What forces stabilize/destabilize the stacking of aromatic molecules in aqueous-salt solution and what are their relative importance?'

  18. Parsing of the free energy of aromatic-aromatic stacking interactions in solution

    International Nuclear Information System (INIS)

    Kostjukov, Viktor V.; Khomytova, Nina M.; Hernandez Santiago, Adrian A.; Tavera, Anna-Maria Cervantes; Alvarado, Julieta Salas; Evstigneev, Maxim P.

    2011-01-01

    Graphical abstract: Highlights: → A protocol for decomposition of the free energy of aromatic stacking is developed. → The factors stabilizing/destabilizing stacking of aromatic molecules are defined. → Hydrophobic contribution is found to be dominant. - Abstract: We report an analysis of the energetics of aromatic-aromatic stacking interactions for 39 non-covalent reactions of self- and hetero-association of 12 aromatic molecules with different structures and charge states. A protocol for computation of the contributions to the total energy from various energetic terms has been developed and the results are consistent with experiment in 92% of all the systems studied. It is found that the contributions from hydrogen bonds and entropic factors are always unfavorable, whereas contributions from van-der-Waals, electrostatic and/or hydrophobic effects may lead to stabilizing or destabilizing factors depending on the system studied. The analysis carried out in this work provides an answer to the questions 'What forces stabilize/destabilize the stacking of aromatic molecules in aqueous-salt solution and what are their relative importance?'

  19. Evaluation of 10 aliphatic halogenated hydrocarbons in the mouse bone marrow micronucleus test.

    Science.gov (United States)

    Crebelli, R; Carere, A; Leopardi, P; Conti, L; Fassio, F; Raiteri, F; Barone, D; Ciliutti, P; Cinelli, S; Vericat, J A

    1999-03-01

    Ten halogenated aliphatic hydrocarbons (carbon tetrachloride, 1-chlorohexane, 2,3-dichlorobutane, 1,2-dichloroethane, 1,2-dichloroethylene, 1,3-dichloropropane, hexachloroethane, 1,1,2-trichloroethane, 1,2,3-trichloropropane and 1,1,3-trichloropropene), previously assayed in genetic assays in fungi, were evaluated in the mouse bone marrow micronucleus test in order to assess their genotoxicity in vivo. All chemicals were administered once i.p. at 40 and 70-80% of their respective LD50 to male and female CD-1 mice, 24 and 48 h before killing. All treatments produced evident clinical symptoms, but no marked depression of bone marrow proliferation. No statistically significant increases in the incidence of micronucleated polychromatic erythrocytes over the control values were observed at any sampling time with any of the 10 halogenated hydrocarbons assayed. The comparison of the results obtained in this study with the findings provided by in vitro micronucleus assays on the same chemicals, reported by other authors, indicate that mouse bone marrow is weakly sensitive to the genotoxic effects induced by halogenated hydrocarbons in other test systems. This suggests that the role of such an assay in carcinogen screening may be questionable for this chemical class. An examination of mouse bone marrow micronucleus test results with the halogenated aliphatic hydrocarbons classified as carcinogens by IARC supports this conclusion.

  20. Copper-catalyzed recycling of halogen activating groups via 1,3-halogen migration.

    Science.gov (United States)

    Grigg, R David; Van Hoveln, Ryan; Schomaker, Jennifer M

    2012-10-03

    A Cu(I)-catalyzed 1,3-halogen migration reaction effectively recycles an activating group by transferring bromine or iodine from a sp(2) to a benzylic carbon with concomitant borylation of the Ar-X bond. The resulting benzyl halide can be reacted in the same vessel under a variety of conditions to form an additional carbon-heteroatom bond. Cross-over experiments using an isotopically enriched bromide source support intramolecular transfer of Br. The reaction is postulated to proceed via a Markovnikov hydrocupration of the o-halostyrene, oxidative addition of the resulting Cu(I) complex into the Ar-X bond, reductive elimination of the new sp(3) C-X bond, and final borylation of an Ar-Cu(I) species to turn over the catalytic cycle.

  1. [Near infrared light irradiator using halogen lamp].

    Science.gov (United States)

    Ide, Yasuo

    2012-07-01

    The practical electric light bulb was invented by Thomas Alva Edison in 1879. Halogen lamp is the toughest and brightest electric light bulb. With light filter, it is used as a source of near infrared light. Super Lizer and Alphabeam are made as near infrared light irradiator using halogen lamp. The light emmited by Super Lizer is linear polarized near infrared light. The wave length is from 600 to 1,600 nm and strongest at about 1,000 nm. Concerning Super Lizer, there is evidence of analgesic effects and normalization of the sympathetic nervous system. Super Lizer has four types of probes. SG type is used for stellate ganglion irradiation. B type is used for narrow area irradiation. C and D types are for broad area irradiation. The output of Alphabeam is not polarized. The wave length is from 700 to 1,600 nm and the strongest length is about 1,000nm. Standard attachment is used for spot irradiation. Small attachment is used for stellate ganglion irradiation. Wide attachment is used for broad area irradiation. The effects of Alphabeam are thought to be similar to that of Super Lizer.

  2. Exposure to polycyclic aromatic hydrocarbons with special focus on cancer

    Directory of Open Access Journals (Sweden)

    Thamaraiselvan Rengarajan

    2015-03-01

    Full Text Available Polycyclic aromatic hydrocarbons (PAHs are a group of compounds consisting of two or more fused aromatic rings. Most of them are formed during incomplete combustion of organic materials such as wood and fossil fuels, petroleum products, and coal. The composition of PAH mixtures varies with the source and is also affected by selective weathering effects in the environment. PAHs are ubiquitous pollutants frequently found in a variety of environments such as fresh water and marine sediments, the atmosphere, and ice. Due to their widespread distribution, the environmental pollution due to PAHs has aroused global concern. Many PAHs and their epoxides are highly toxic, mutagenic and/or carcinogenic to microorganisms as well as to higher forms of life including humans. The main aim of this review is to provide contemporary information on PAH sources, route of exposure, worldwide emission rate, and adverse effects on humans, especially with reference to cancer.

  3. Engineering Aromatic-Aromatic Interactions To Nucleate Folding in Intrinsically Disordered Regions of Proteins.

    Science.gov (United States)

    Balakrishnan, Swati; Sarma, Siddhartha P

    2017-08-22

    Aromatic interactions are an important force in protein folding as they combine the stability of a hydrophobic interaction with the selectivity of a hydrogen bond. Much of our understanding of aromatic interactions comes from "bioinformatics" based analyses of protein structures and from the contribution of these interactions to stabilizing secondary structure motifs in model peptides. In this study, the structural consequences of aromatic interactions on protein folding have been explored in engineered mutants of the molten globule protein apo-cytochrome b 5 . Structural changes from disorder to order due to aromatic interactions in two variants of the protein, viz., WF-cytb5 and FF-cytb5, result in significant long-range secondary and tertiary structure. The results show that 54 and 52% of the residues in WF-cytb5 and FF-cytb5, respectively, occupy ordered regions versus 26% in apo-cytochrome b 5 . The interactions between the aromatic groups are offset-stacked and edge-to-face for the Trp-Phe and Phe-Phe mutants, respectively. Urea denaturation studies indicate that both mutants have a C m higher than that of apo-cytochrome b 5 and are more stable to chaotropic agents than apo-cytochrome b 5 . The introduction of these aromatic residues also results in "trimer" interactions with existing aromatic groups, reaffirming the selectivity of the aromatic interactions. These studies provide insights into the aromatic interactions that drive disorder-to-order transitions in intrinsically disordered regions of proteins and will aid in de novo protein design beyond small peptide scaffolds.

  4. Tuning the electronic structure of graphene through alkali metal and halogen atom intercalation

    Science.gov (United States)

    Ahmad, Sohail; Miró, Pere; Audiffred, Martha; Heine, Thomas

    2018-04-01

    The deposition, intercalation and co-intercalation of heavy alkali metals and light halogens atoms in graphene mono- and bilayers have been studied using first principles density-functional calculations. Both the deposition and the intercalation of alkali metals gives rise to n-type doping due to the formation of M+-C- pairs. The co-intercalation of a 1:1 ratio of alkali metals and halogens derives into the formation of ionic pairs among the intercalated species, unaltering the electronic structure of the layered material.

  5. Evaluation of the phototoxicity of unsubstituted and alkylated polycyclic aromatic hydrocarbons to mysid shrimp (Americamysis bahia): Validation of predictive models.

    Science.gov (United States)

    Finch, Bryson E; Marzooghi, Solmaz; Di Toro, Dominic M; Stubblefield, William A

    2017-08-01

    Crude oils are composed of an assortment of hydrocarbons, some of which are polycyclic aromatic hydrocarbons (PAHs). Polycyclic aromatic hydrocarbons are of particular interest due to their narcotic and potential phototoxic effects. Several studies have examined the phototoxicity of individual PAHs and fresh and weathered crude oils, and several models have been developed to predict PAH toxicity. Fingerprint analyses of oils have shown that PAHs in crude oils are predominantly alkylated. However, current models for estimating PAH phototoxicity assume toxic equivalence between unsubstituted (i.e., parent) and alkyl-substituted compounds. This approach may be incorrect if substantial differences in toxic potency exist between unsubstituted and substituted PAHs. The objective of the present study was to examine the narcotic and photo-enhanced toxicity of commercially available unsubstituted and alkylated PAHs to mysid shrimp (Americamysis bahia). Data were used to validate predictive models of phototoxicity based on the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap approach and to develop relative effect potencies. Results demonstrated that photo-enhanced toxicity increased with increasing methylation and that phototoxic PAH potencies vary significantly among unsubstituted compounds. Overall, predictive models based on the HOMO-LUMO gap were relatively accurate in predicting phototoxicity for unsubstituted PAHs but are limited to qualitative assessments. Environ Toxicol Chem 2017;36:2043-2049. © 2017 SETAC. © 2017 SETAC.

  6. Differential toxicity of heterocyclic aromatic amines and their mixture in metabolically competent HepaRG cells

    International Nuclear Information System (INIS)

    Dumont, Julie; Josse, Rozenn; Lambert, Carine; Antherieu, Sebastien; Le Hegarat, Ludovic; Aninat, Caroline; Robin, Marie-Anne; Guguen-Guillouzo, Christiane

    2010-01-01

    Human exposure to heterocyclic aromatic amines (HAA) usually occurs through mixtures rather than individual compounds. However, the toxic effects and related mechanisms of co-exposure to HAA in humans remain unknown. We compared the effects of two of the most common HAA, 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) and 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), individually or in combination, in the metabolically competent human hepatoma HepaRG cells. Various endpoints were measured including cytotoxicity, apoptosis, oxidative stress and DNA damage by the comet assay. Moreover, the effects of PhIP and/or MeIQx on mRNA expression and activities of enzymes involved in their activation and detoxification pathways were evaluated. After a 24 h treatment, PhIP and MeIQx, individually and in combination, exerted differential effects on apoptosis, oxidative stress, DNA damage and cytochrome P450 (CYP) activities. Only PhIP induced DNA damage. It was also a stronger inducer of CYP1A1 and CYP1B1 expression and activity than MeIQx. In contrast, only MeIQx exposure resulted in a significant induction of CYP1A2 activity. The combination of PhIP with MeIQx induced an oxidative stress and showed synergistic effects on apoptosis. However, PhIP-induced genotoxicity was abolished by a co-exposure with MeIQx. Such an inhibitory effect could be explained by a significant decrease in CYP1A2 activity which is responsible for PhIP genotoxicity. Our findings highlight the need to investigate interactions between HAA when assessing risks for human health and provide new insights in the mechanisms of interaction between PhIP and MeIQx.

  7. Pro-aromatic and anti-aromatic π-conjugated molecules: an irresistible wish to be diradicals

    KAUST Repository

    Zeng, Zebing

    2015-01-01

    © 2015 The Royal Society of Chemistry. Aromaticity is an important concept to understand the stability and physical properties of π-conjugated molecules. Recent studies on pro-aromatic and anti-aromatic molecules revealed their irresistible tendency to become diradicals in the ground state. Diradical character thus becomes another very important concept and it is fundamentally correlated to the physical (optical, electronic and magnetic) properties and chemical reactivity of most of the organic optoelectronic materials. Molecules with distinctive diradical character show unique properties which are very different from those of traditional closed-shell π-conjugated systems, and thus they have many potential applications in organic electronics, spintronics, non-linear optics and energy storage. This critical review first introduces the fundamental electronic structure of Kekulé diradicals within the concepts of anti-aromaticity and pro-aromaticity in the context of Hückel aromaticity and diradical character. Then recent research studies on various stable/persistent diradicaloids based on pro-aromatic and anti-aromatic compounds are summarized and discussed with regard to their synthetic chemistry, physical properties, structure-property relationships and potential material applications. A summary and personal perspective is given at the end.

  8. Developmental toxicity of clarified slurry oil, syntower bottoms, and distillate aromatic extract administered as a single oral dose to pregnant rats

    Energy Technology Data Exchange (ETDEWEB)

    Feuston, M.H.; Mackerer, C.R. [Stonybrook Labs., Princeton, NJ (United States)

    1996-09-01

    Clarified slurry oil (CSO), syntower bottoms (STB), and distillate aromatic extract (DAE) are refinery streams produced by processing crude oil. Available data indicate that some refinery streams are developmentally toxic by the dermal route of exposure. However, there is no conclusive evidence for their being teratogenic. The present studies were designed to further explore the suspected teratogenic potency of refinery streams while at the same time limiting embryolethality. In general, evidence of maternal toxicity (i.e., decreased body weight gain, decreased thymus weight) was observed at doses greater than or equal to 500 mg/kg. For each refinery stream tested, the incidence of resorption was greatest on GD 11. A common pattern of fetal malformations was observed for all of the refinery streams tested and included cleft palate, diaphragmatic hernia, and paw and tail defects. The incidence and type of malformation observed were influenced by the gestation day of exposure. The incidence and type of malformation observed were influenced by the gestation day of exposure. The incidences of external and skeletal malformations were greatest on GD 11 and 12 for fetuses exposed to CSO; on GD 13 and 14, the incidence of malformation was comparable for CSO- and STB-exposed fetuses. The incidence of visceral anomalies was greatest on GD 11-13 for fetuses exposed to CSO and STB; on Gestation D 14, the incidence was comparable for each of the refinery streams tested. In general, the ability to produce adverse effects on development was greatest for CSO and least for DAE. Effects produced by STB were comparable to or less severe than those observed for CSO. 24 refs., 11 tabs.

  9. The anomalous halogen bonding interactions between chlorine and bromine with water in clathrate hydrates.

    Science.gov (United States)

    Dureckova, Hana; Woo, Tom K; Udachin, Konstantin A; Ripmeester, John A; Alavi, Saman

    2017-10-13

    Clathrate hydrate phases of Cl 2 and Br 2 guest molecules have been known for about 200 years. The crystal structure of these phases was recently re-determined with high accuracy by single crystal X-ray diffraction. In these structures, the water oxygen-halogen atom distances are determined to be shorter than the sum of the van der Waals radii, which indicates the action of some type of non-covalent interaction between the dihalogens and water molecules. Given that in the hydrate phases both lone pairs of each water oxygen atom are engaged in hydrogen bonding with other water molecules of the lattice, the nature of the oxygen-halogen interactions may not be the standard halogen bonds characterized recently in the solid state materials and enzyme-substrate compounds. The nature of the halogen-water interactions for the Cl 2 and Br 2 molecules in two isolated clathrate hydrate cages has recently been studied with ab initio calculations and Natural Bond Order analysis (Ochoa-Resendiz et al. J. Chem. Phys. 2016, 145, 161104). Here we present the results of ab initio calculations and natural localized molecular orbital analysis for Cl 2 and Br 2 guests in all cage types observed in the cubic structure I and tetragonal structure I clathrate hydrates to characterize the orbital interactions between the dihalogen guests and water. Calculations with isolated cages and cages with one shell of coordinating molecules are considered. The computational analysis is used to understand the nature of the halogen bonding in these materials and to interpret the guest positions in the hydrate cages obtained from the X-ray crystal structures.

  10. Molecular Engineering of Non-Halogenated Solution-Processable Bithiazole based Electron Transport Polymeric Semiconductors

    KAUST Repository

    Fu, Boyi

    2015-04-01

    The electron deficiency and trans planar conformation of bithiazole is potentially beneficial for the electron transport performance of organic semiconductors. However, the incorporation of bithiazole into polymers through a facile synthetic strategy remains a challenge. Herein, 2,2’-bithiazole was synthesized in one step and copolymerized with dithienyldiketopyrrolopyrrole to afford poly(dithienyldiketopyrrolopyrrole-bithiazole), PDBTz. PDBTz exhibited electron mobility reaching 0.3 cm2V-1s-1 in organic field-effect transistor (OFET) configuration; this contrasts with a recently discussed isoelectronic conjugated polymer comprising an electron rich bithiophene and dithienyldiketopyrrolopyrrole, which displays merely hole transport characteristics. This inversion of charge carrier transport characteristics confirms the significant potential for bithiazole in the development of electron transport semiconducting materials. Branched 5-decylheptacyl side chains were incorporated into PDBTz to enhance polymer solubility, particularly in non-halogenated, more environmentally compatible solvents. PDBTz cast from a range of non-halogenated solvents exhibited film morphologies and field-effect electron mobility similar to those cast from halogenated solvents.

  11. Molecular Engineering of Non-Halogenated Solution-Processable Bithiazole based Electron Transport Polymeric Semiconductors

    KAUST Repository

    Fu, Boyi; Wang, Cheng-Yin; Rose, Bradley Daniel; Jiang, Yundi; Chang, Mincheol; Chu, Ping-Hsun; Yuan, Zhibo; Fuentes-Hernandez, Canek; Bernard, Kippelen; Bredas, Jean-Luc; Collard, David M.; Reichmanis, Elsa

    2015-01-01

    The electron deficiency and trans planar conformation of bithiazole is potentially beneficial for the electron transport performance of organic semiconductors. However, the incorporation of bithiazole into polymers through a facile synthetic strategy remains a challenge. Herein, 2,2’-bithiazole was synthesized in one step and copolymerized with dithienyldiketopyrrolopyrrole to afford poly(dithienyldiketopyrrolopyrrole-bithiazole), PDBTz. PDBTz exhibited electron mobility reaching 0.3 cm2V-1s-1 in organic field-effect transistor (OFET) configuration; this contrasts with a recently discussed isoelectronic conjugated polymer comprising an electron rich bithiophene and dithienyldiketopyrrolopyrrole, which displays merely hole transport characteristics. This inversion of charge carrier transport characteristics confirms the significant potential for bithiazole in the development of electron transport semiconducting materials. Branched 5-decylheptacyl side chains were incorporated into PDBTz to enhance polymer solubility, particularly in non-halogenated, more environmentally compatible solvents. PDBTz cast from a range of non-halogenated solvents exhibited film morphologies and field-effect electron mobility similar to those cast from halogenated solvents.

  12. Mercury and halogens in coal: Chapter 2

    Science.gov (United States)

    Kolker, Allan; Quick, Jeffrey C.; Granite, Evan J.; Pennline, Henry W.; Senior, Constance L.

    2014-01-01

    Apart from mercury itself, coal rank and halogen content are among the most important factors inherent in coal that determine the proportion of mercury captured by conventional controls during coal combustion. This chapter reviews how mercury in coal occurs, gives available concentration data for mercury in U.S. and international commercial coals, and provides an overview of the natural variation in halogens that influence mercury capture. Three databases, the U.S. Geological Survey coal quality (USGS COALQUAL) database for in-ground coals, and the 1999 and 2010 U.S. Environmental Protection Agency (EPA) Information Collection Request (ICR) databases for coals delivered to power stations, provide extensive results for mercury and other parameters that are compared in this chapter. In addition to the United States, detailed characterization of mercury is available on a nationwide basis for China, whose mean values in recent compilations are very similar to the United States in-ground mean of 0.17 ppm mercury. Available data for the next five largest producers (India, Australia, South Africa, the Russian Federation, and Indonesia) are more limited and with the possible exceptions of Australia and the Russian Federation, do not allow nationwide means for mercury in coal to be calculated. Chlorine in coal varies as a function of rank and correspondingly, depth of burial. As discussed elsewhere in this volume, on a proportional basis, bromine is more effective than chlorine in promoting mercury oxidation in flue gas and capture by conventional controls. The ratio of bromine to chlorine in coal is indicative of the proportion of halogens present in formation waters within a coal basin. This ratio is relatively constant except in coals that have interacted with deep-basin brines that have reached halite saturation, enriching residual fluids in bromine. Results presented here help optimize mercury capture by conventional controls and provide a starting point for

  13. Halogenated hydrocarbons - an environmental problem

    Energy Technology Data Exchange (ETDEWEB)

    Schoeler, H F; Thofern, E

    1984-01-01

    The paper provides a survey of the incidence of highly volatile halogenated hydrocarbons in ground, surface and drinking water as well as in the snows of Western Germany. Almost the entire production of chlorinated solvents is released into the environment. The absorption media are mostly soil, water and atmosphere. Whereas in the atmosphere elimination reactions take place, solvents that have passed the soil get into the ground water owing to their persistence and can cause considerable pollutions of drinking water. Moreover haloforms may occur in drinking water, which are produced during chlorine disinfection of pre-treated water.

  14. [Impact of the decrease of nitrous oxide use on the consumption of halogenated agents].

    Science.gov (United States)

    Laverdure, F; Gaudin, A; Bourgain, J-L

    2013-11-01

    Nitrous oxide (N2O) toxicity and its impact on pollution lead to restrict its use. A decrease of N2O consumption should increase the hypnotic inhaled consumption. This monocentric study estimated consumptions and costs of halogenated agents (HA) and N2O over 5 years when the N2O consumption was reduced. Retrospective from a computerized database. Between 2006 and 2010, 34,097 procedures were studied after two meetings exposing the risks of the N2O. At the end of anesthesia, consumptions of hypnotic agents (millilitres transmitted by the injectors and the blender) were archived in the database. The annual consumption of agents was obtained by adding the individual consumptions, then divided by the annual number of cases. The costs were given by the hospital pharmacy from invoices. N2O consumption per anesthesia constantly decreased during the study, from 75.1L by act to 22.7L. The sum of the annual consumptions of N2O and air did not change suggesting that total fresh gas flow remained stable. Between 2006 and 2010, the sevoflurane consumption by act increased by 25%, from 16.5 to 20.6mL, and desflurane consumption by 37%, from 46.1 to 63.1mL by patient. The costs of the administration of hypnotic agents remained stable. N2O consumption decrease had an impact on the consumption of HA. The cost reduction of the N2O was counterbalanced by the increase of halogenated vapor cost. The profit of the ecological impact of the reduction in N2O use could be quantified. Copyright © 2013 Société française d’anesthésie et de réanimation (Sfar). Published by Elsevier SAS. All rights reserved.

  15. Chronic toxicity of polycyclic aromatic compounds to the springtail Folsomia candida and the enchytraeid Enchytraeus crypticus.

    NARCIS (Netherlands)

    Droge, S.T.J.; Leon Paumen, M; Bleeker, E.A.J.; Kraak, M.H.S.; van Gestel, C.A.M.

    2006-01-01

    An urgent need exists for incorporating heterocyclic compounds and (bio)transformation products in ecotoxicological test schemes and risk assessment of polycyclic aromatic compounds (PACs). The aim of the present study therefore was to determine the chronic effects of (heterocyclic) PACs on two

  16. Linking toxicity profiles to pollutants in sludge and sediments

    Czech Academy of Sciences Publication Activity Database

    Stiborová, H.; Kolář, Michal; Vrkoslavová, J.; Pulkrabová, J.; Hajslova, J.; Demnerová, K.; Uhlík, O.

    2017-01-01

    Roč. 321, zima (2017), s. 672-680 ISSN 0304-3894 R&D Projects: GA ČR(CZ) GA15-02328S Institutional support: RVO:68378050 Keywords : polycyclic aromatic-hydrocarbons * Toxicity * Contamination * Sludge * Sediments * Priority pollutants * Constrained correspondence analysis (CCS) Subject RIV: EB - Genetics ; Molecular Biology OBOR OECD: Other biological topics Impact factor: 6.065, year: 2016

  17. Monitoring of polycyclic aromatic hydrocarbons (PAH) in food supplements containing botanicals and other ingredients on the Dutch market

    NARCIS (Netherlands)

    Martena, M.J.; Grutters, M.; Groot, de H.N.; Konings, E.J.M.; Rietjens, I.

    2011-01-01

    Food supplements can contain polycyclic aromatic hydrocarbons (PAH). The European Food Safety Authority (EFSA) has defined 16 priority PAH that are both genotoxic and carcinogenic and identified eight priority PAH (PAH8) or four of these (PAH4) as good indicators of the toxicity and occurrence of

  18. Microbial Hydrocarbon and ToxicPollutant Degradation Method

    Energy Technology Data Exchange (ETDEWEB)

    Schlueter, Dietrich [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Janabi, Mustafa [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); O' Neil, James [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Budinger, Thomas [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2011-08-16

    The goal of this project is to determine optimum conditions for bacterial oxidation of hydrocarbons and long-chain alkanes that are representative of petroleum contamination of the environment. Polycyclic Aromatic Hydrocarbons (PAHs) are of concern because of their toxicity, low volatility, and resistance to microbial degradation, especially under anaerobic conditions. The uniqueness of our approach is to use carbon-11 in lieu of the traditional use of carbon-14.

  19. Bioremediation a potential approach for soil contaminated with polycyclic aromatic hydrocarbons: An Overview

    OpenAIRE

    Norzila Othman; Mohd Irwan Juki; Norhana Hussain; Suhaimi Abdul Talib

    2011-01-01

    Polycyclic aromatic hydrocarbons (PAHs) represent a group of priority pollutants which are present at high concentration in soils of many industrially contaminated sites. Standards and criteria for the remediation of soils contaminated with PAHs vary widely between countries. Bioremediation has gained preference as a technology for remediation contaminated sites as it is less expensive and more environmental friendly. Bioremediation utilizes microorganisms to degrade PAHs to less toxic compou...

  20. 40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

    Science.gov (United States)

    2010-07-01

    ... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... and halogen HAP or HAP metals? (a) You must meet each emission limit in Table 3 to this subpart that... section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you must...

  1. Polycyclic aromatic hydrocarbons (PAHs) in wetland soils under different land uses in a coastal estuary: toxic levels, sources and relationships with soil organic matter and water-stable aggregates.

    Science.gov (United States)

    Xiao, Rong; Bai, Junhong; Wang, Junjing; Lu, Qiongqiong; Zhao, Qingqing; Cui, Baoshan; Liu, Xinhui

    2014-09-01

    The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in the soils from industrial, wharf, cropland, milldam and natural wetland sites to characterize their distributions, toxic levels and possible sources in the Pearl River Estuary and identify their relationships with soil organic matter (SOM) and water-stable aggregates (WSAs). Our results indicate that the average concentration of total PAHs in this region reached a moderate pollution level, which was higher than that in other larger estuaries in Asia. The average level of total PAHs in industrial soils was 1.2, 1.5, 1.6 and 2.3 times higher than those in soils from wharf, cropland, milldam and natural wetland sites, respectively. Greater accumulation of PAHs occurred in the middle and/or bottom soil layers where 3-ring PAHs were dominant. Industrial soils also exhibited the highest toxic levels with the highest toxic equivalent concentrations of PAHs, followed by wharf and milldam soils, and the cropland and wetland soils had the lowest toxicity. The diagnostic ratios suggested that PAHs primarily originated from biomass and coal combustion at industrial and milldam sites, and petroleum combustion was determined to be the primary source of PAHs at the wharf, cropland and wetland sites. Both 3-ring and 4-ring PAHs in the milldam and wharf soils were significantly positively correlated with the SOM, whereas the 4,5,6-ring PAHs and total PAHs in industrial soils and the 2-ring PAHs in cropland soils were significantly negatively correlated with the SOM. In addition, large WSAs also exhibited a significant positive correlation with PAHs. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Potential for photoenhanced toxicity of spilled oil in Prince William Sound and Gulf of Alaska Waters

    International Nuclear Information System (INIS)

    Barron, M.G.; Ka'aihue, L.

    2001-01-01

    Photoenhanced toxicity is the increase in the toxicity of a chemical in the presence of ultraviolet light (UV) compared to a standard laboratory test conducted with fluorescent lighting (minimal UV). Oil products, weathered oil, and specific polycyclic aromatic compounds present in oil are 2 to greater than 1000 times more toxic in the presence of UV. The photoenhanced toxicity of oil to fish and aquatic invertebrates appears to occur through a process of photosensitization, rather than photomodification of the aqueous phase oil. In photosensitization, the bioaccumulated chemical transfers light energy to other molecules causing toxicity through tissue damage rather than a narcosis mechanism. The available evidence indicates that phototoxic components of oil are specific 3-5 ring polycyclic aromatic hydrocarbons (PAHs) and heterocycles. Determinants of photoenhanced toxicity include the extent of oil bioaccumulation in aquatic organisms and the spectra and intensity of UV exposure. No studies have specifically investigated the photoenhanced toxicity of spilled oil in Alaska waters. Although there are substantial uncertainties, the results of this evaluation indicate there is potential for photoenhanced toxicity of spilled oil in Prince William Sound and the Gulf of Alaska. The potential hazard of photoenhanced toxicity may be greatest for embryo and larval stages of aquatic organisms that are relatively translucent to UV and inhabit the photic zone of the water column and intertidal areas. Photoenhanced toxicity should be considered in oil spill response because the spatial and temporal extent of injury to aquatic organisms may be underestimated if based on standard laboratory bioassays and existing toxicity databases. Additionally, the choice of counter measures and oil removal operations may influence the degree of photoenhanced toxicity. (author)

  3. Use of REMPI-TOFMS for real-time measurement of trace aromatics during operation of aircraft ground equipment

    Science.gov (United States)

    Gullett, Brian; Touati, Abderrahmane; Oudejans, Lukas

    Emissions of aromatic air toxics from aircraft ground equipment (AGE) were measured with a resonance enhanced multiphoton ionization-time of flight mass spectrometry (REMPI-TOFMS) system consisting of a pulsed solid state laser for photoionization and a TOFMS for mass discrimination. This instrument was capable of characterizing turbine emissions and the effect of varying load operations on pollutant production. REMPI-TOFMS is capable of high selectivity and low detection limits (part per trillion to part per billion) in real time (1 s resolution). Hazardous air pollutants and criteria pollutants were measured during startups and idle and full load operations. Measurements of compounds such as benzene, toluene, ethylbenzene, xylenes, styrene, and polycyclic aromatic hydrocarbons compared well with standard methods. Startup emissions from the AGE data showed persistent concentrations of pollutants, unlike those from a diesel generator, where a sharp spike in emissions rapidly declined to steady state levels. The time-resolved responses of air toxics concentrations varied significantly by source, complicating efforts to minimize these emissions with common operating prescriptions. The time-resolved measurements showed that pollutant concentrations decline (up to 5×) in a species-specific manner over the course of multiple hours of operation, complicating determination of accurate and precise emission factors via standard extractive sampling. Correlations of air toxic concentrations with more commonly measured pollutants such as CO or PM were poor due to the relatively greater changes in the measured toxics' concentrations.

  4. The risk of contamination of food with toxic substances present in animal feed

    NARCIS (Netherlands)

    Kan, C.A.; Meijer, G.A.L.

    2007-01-01

    Toxic substances such as dioxins, mycotoxins, heavy metals, pesticides, veterinary drugs and polycyclic aromatic hydrocarbons are almost ubiquitous in the environment. Thus, they are also present in ingredients for animal feed. Adequate risk management depends on knowledge of absorption, metabolism,

  5. Compound deterioration properties of non-halogen flame-resisting cables

    International Nuclear Information System (INIS)

    Yamamoto, Yasuaki; Yagyu, Hideki; Onishi, Takao; Kamiharako, Shinji

    1984-01-01

    Conventional flame-resisting cables release harmful gas such as hydrogen chloride and smoke on burning. To improve this disadvantage, the cables for nuclear power plants using new non-halogen flame-resisting insulating material have been developed. In this experiment, the non-halogen flame-resisting cables were subjected to the environmental test with varying test conditions. The test conditions included the order of exposure (heat treatment, γ-ray irradiation and steam exposure) and dose rate. After the environmental test, the mechanical and electrical properties of the samples were measured. In all test conditions, the samples did not crack in bending, and withstood the bending and withstand-voltage in-water test. The tensile strength and a.c. breakdown voltage did not change, and were stable. The elongation decreased greatly, but maintained the value of about 100 %, and the volumetric resistivity decreased by only one figure. It was confirmed that these cables were able to withstand various environmental tests. (Yoshitake, I.)

  6. Determination of halogen content in glass for assessment of melter decontamination factors

    International Nuclear Information System (INIS)

    Goles, R.W.

    1996-03-01

    Melter decontamination factor (DF) values for the halogens (fluorine, chlorine, and iodine) are important to the Hanford Waste Vitrification Plant (HWVP) process because of the potential influence of DF on secondary-waste recycle strategies (fluorine and chlorine) as well as its impact on off-gas emissions (iodine). This study directly establishes the concentrations of halides-in HWVP simulated reference glasses rather than relying on indirect off-gas data. For fluorine and chlorine, pyrohydrolysis coupled with halide (ion chromatographic) detection has proven to be a useful analytical approach suitable for glass matrices, sensitive enough for the range of halogens encountered, and compatible with remote process support applications. Results obtained from pyrohydrolytic analysis of pilot-scale ceramic melter (PSCM) -22 and -23 glasses indicate that the processing behavior of fluorine and chlorine is quite variable even under similar processing conditions. Specifically, PSCM-23 glass exhibited a ∼90% halogen (F and Cl) retention efficiency, while only 20% was incorporated in PSCM-22 glass. These two sets of very dissimilar test results clearly do not form a sufficient basis for establishing design DF values for fluorine and chlorine. Because the present data do not provide any new halogen volatility information, but instead reconfirm the validity of previously obtained offgas derived values, melter DF values of 4, 2, and 1 for fluorine, chlorine, and iodine, respectively, are recommended for adoption; these values were conservatively established by a team of responsible engineers at Westinghouse Hanford Company (WHC) and Pacific Northwest Laboratory (PNL) on the basis of average behavior for many comparable melter tests. In the absence of further HWVP process data, these average melter DFs are the best values currently available

  7. Composes inter-halogenes sous pression: etude des transformations structurales dans le monobromure d'iode sous forme dense

    Science.gov (United States)

    Bouchard, Alexandre

    La famille des composes halogenes et inter-halogenes representent des solides moleculaires adoptant des phases denses communes avec des solides moleculaires diatomiques comme l'azote et l'hydrogene. Parmi les transformations structurales et electroniques induites sous haute pression et observees dans ces solides, on note, entre autres, la dissociation moleculaire et la metallisation. De plus, l'etude des phases denses de l'iode a permis recemment l'observation d'une structure cristalline possedant une modulation dite incommensurable, c'est-a-dire une modulation possedant une periodicite differente de celle de la structure cristalline, jetant ainsi une lumiere nouvelle sur le processus de dissociation moleculaire dans les solides halogenes. Dans ce memoire, on propose d'etudier les changements structuraux dans monobromure d'iode (IBr), un compose inter-halogene possedant des proprietes structurales semblables a celles de deux composes halogenes, soit l'iode (I 2) et le brome (Br2) sous leur forme solide. Des experiences de diffraction des rayons X de poudres en utilisant un rayonnement synchrotron ont ete realisees a temperature ambiante sur l'IBr en variant la pression jusqu'aux environs de 60 GPa. La nature chimique particuliere du compose IBr a necessite la mise au point de techniques de chargement d'echantillon destinees a preserver l'integrite chimique de la substance utilisee. On rapporte egalement l'observation d'une phase de l'IBr presentant une modulation incommensurable. Les phases observees dans l'IBr permettent d'etablir des paralleles avec les phases denses rapportees dans I2 et Br2 par le biais d'un modele phenomenologique decrivant la sequence structurale des solides halogenes sous forme condensee.

  8. Development of an enzymatic fiber-optic biosensor for detection of halogenated hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Bidmanova, Sarka; Chaloupkova, Radka; Damborsky, Jiri; Prokop, Zbynek [Masaryk University, Loschmidt Laboratories, Department of Experimental Biology and Research Centre for Toxic Compounds in the Environment, Faculty of Science, Brno (Czech Republic)

    2010-11-15

    An enzyme-based biosensor was developed by co-immobilization of purified enzyme haloalkane dehalogenase (EC 3.8.1.5) and a fluorescence pH indicator on the tip of an optical fiber. Haloalkane dehalogenase catalyzes hydrolytic dehalogenation of halogenated aliphatic hydrocarbons, which is accompanied by a pH change influencing the fluorescence of the indicator. The pH sensitivity of several fluorescent dyes was evaluated. The selected indicator 5(6)-carboxyfluorescein was conjugated with bovine serum albumin and its reaction was tested under different immobilization conditions. The biosensor was prepared by cross-linking of the conjugate in tandem with haloalkane dehalogenase using glutaraldehyde vapor. The biosensor, stored for 24 h in 50 mM phosphate buffer (pH 7.5) prior to measurement, was used after 15 min of equilibration, the halogenated compound was added, and the response was monitored for 30 min. Calibration of the biosensor with 1,2-dibromoethane and 3-chloro-2-(chloromethyl)-1-propene showed an excellent linear dependence, with detection limits of 0.133 and 0.014 mM, respectively. This biosensor provides a new tool for continuous in situ monitoring of halogenated environmental pollutants. (orig.)

  9. Polycyclic aromatic hydrocarbon metabolism in mullets, Chelon labrosus, treated by polychlorinated biphenyls

    International Nuclear Information System (INIS)

    Narbonne, J.F.; Suteau, P.; Daubeze, M.; Audy, C.

    1987-01-01

    Contamination of the ocean by hydrocarbons has become a major environmental problem. Consequently, it is not surprising that residues of potentially toxic xenobiotics, such as benzo(a)pyrene (B(a)P), are present in marine species used as human food. The oxidative metabolism of aromatic hydrocarbons proceeds via intermediate arene oxides. Some of these metabolites are very reactive electrophiles and may interact with cellular macromolecules such as proteins, DNA and RNA. Thus, the ability of an organism to further metabolize arene oxides can be an important protective mechanism against the possible toxic effect of these molecules. The existence of hepatic cytochrome P-450 dependent monooxygenase activities in fish is now well established. The exposure of fish to polychlorinated biphenyls (PCB) increases both the monooxygenase activities and the total amount of cytochrome P-450 in the microsomal fractions of fish liver. The purpose of this study was to compare the toxication-detoxication balance in both control and PCB induced estuarine fish (Grey mullets)

  10. Quantum Chemical Examination of the Sequential Halogen Incorporation Scheme for the Modeling of Speciation of I/Br/Cl-Containing Trihalomethanes.

    Science.gov (United States)

    Zhang, Chenyang; Li, Maodong; Han, Xuze; Yan, Mingquan

    2018-02-20

    The recently developed three-step ternary halogenation model interprets the incorporation of chlorine, bromine, and iodine ions into natural organic matter (NOM) and formation of iodine-, bromine-, and chlorine-containing trihalomethanes (THMs) based on the competition of iodine, bromine, and chlorine species at each node of the halogenation sequence. This competition is accounted for using the dimensionless ratios (denoted as γ) of kinetic rates of reactions of the initial attack sites or halogenated intermediates with chlorine, bromine, and iodine ions. However, correlations between the model predictions made and mechanistic aspects of the incorporation of halogen species need to be ascertained in more detail. In this study, quantum chemistry calculations were first used to probe the formation mechanism of 10 species of Cl-/Br-/I- THMs. The HOMO energy (E HOMO ) of each mono-, bi-, or trihalomethanes were calculated by B3LYP method in Gaussian 09 software. Linear correlations were found to exist between the logarithms of experimentally determined kinetic preference coefficients γ reported in prior research and, on the other hand, differences of E HOMO values between brominated/iodinated and chlorinated halomethanes. One notable exception from this trend was that observed for the incorporation of iodine into mono- and di-iodinated intermediates. These observations confirm the three-step halogen incorporation sequence and the factor γ in the statistical model. The combined use of quantum chemistry calculations and the ternary sequential halogenation model provides a new insight into the microscopic nature of NOM-halogen interactions and the trends seen in the behavior of γ factors incorporated in the THM speciation models.

  11. Performance analysis of photoresistor and phototransistor for automotive’s halogen and xenon bulbs light output

    Science.gov (United States)

    Rammohan, A.; Kumar, C. Ramesh

    2017-11-01

    Illumination of any light is measured using a different kind of calibrated equipment’s available in the market such as a goniometer, spectral radiometer, photometer, Lux meter and camera based systems which directly display the illumination of automotive headlights light distribution in the unit of lux, foot-candles, lumens/sq. ft. and Lambert etc., In this research, we dealt with evaluating the photo resistor or Light Dependent Resistor (LDR) and phototransistor whether it is useful for sensing light patterns of Automotive Halogen and Xenon bulbs. The experiments are conducted during night hours under complete dark space. We have used the headlamp setup available in TATA SUMO VICTA vehicle in the Indian market and conducted the experiments separately for Halogen and Xenon bulbs under low and high beam operations at various degrees and test points within ten meters of distance. Also, we have compared the light intensity of halogen and xenon bulbs to prove the highest light intensity between halogen and Xenon bulbs. After doing a rigorous test with these two sensors it is understood both are good to sensing beam pattern of automotive bulbs and even it is good if we use an array of sensors or a mixed combination of sensors for measuring illumination purposes under perfect calibrations.

  12. 40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

    Science.gov (United States)

    2010-07-01

    ... Halogen HAP Emissions or HAP Metals Emissions From Process Vents 3 Table 3 to Subpart FFFF of Part 63... to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP... following table that applies to your process vents that contain hydrogen halide and halogen HAP emissions or...

  13. Computer-assisted engineering of the synthetic pathway for biodegradation of a toxic persistent pollutant.

    Science.gov (United States)

    Kurumbang, Nagendra Prasad; Dvorak, Pavel; Bendl, Jaroslav; Brezovsky, Jan; Prokop, Zbynek; Damborsky, Jiri

    2014-03-21

    Anthropogenic halogenated compounds were unknown to nature until the industrial revolution, and microorganisms have not had sufficient time to evolve enzymes for their degradation. The lack of efficient enzymes and natural pathways can be addressed through a combination of protein and metabolic engineering. We have assembled a synthetic route for conversion of the highly toxic and recalcitrant 1,2,3-trichloropropane to glycerol in Escherichia coli, and used it for a systematic study of pathway bottlenecks. Optimal ratios of enzymes for the maximal production of glycerol, and minimal toxicity of metabolites were predicted using a mathematical model. The strains containing the expected optimal ratios of enzymes were constructed and characterized for their viability and degradation efficiency. Excellent agreement between predicted and experimental data was observed. The validated model was used to quantitatively describe the kinetic limitations of currently available enzyme variants and predict improvements required for further pathway optimization. This highlights the potential of forward engineering of microorganisms for the degradation of toxic anthropogenic compounds.

  14. Factors affecting elimination of polycyclic aromatic hydrocarbons from traditional smoked common carp meat

    Science.gov (United States)

    Babić, J.; Vidaković, S.; Škaljac, S.; Kartalović, B.; Ljubojević, D.; Ćirković, M.; Teodorović, V.

    2017-09-01

    Smoking techniques have been progressively improved and different procedures have been developed in different regions for treating fish. In these times, the technology is mainly used for enrichment of fish with specific taste and odour, to extend the shelf-life of these perishable products and appearance required widely on the market. A lot of chemical contaminants such as polycyclic aromatic hydrocarbons (PAHs) are formed during the combustion of fuel in the smoking process. PAHs are a group of compounds that have been the subject of great concern in the recent years due to their toxic, mutagenic and/or carcinogenic potentials to humans. These fact can have a significant impact on the acceptance of these products by consumers. In this review article, the objective is to describe factors affecting elimination of polycyclic aromatic hydrocarbons from traditional smoked common carp meat.

  15. Correlates of Cytochrome P450 1A1 Expression in Bottlenose Dolphin (Tursiops truncatus) Integument Biopsies

    NARCIS (Netherlands)

    Wilson, J.Y.; Wells, R.; Anguilar, A.; Borrell, A.; Tornero, V.; Reijnders, P.J.H.; Moore, M.

    2007-01-01

    Integument biopsy is a nondestructive method for sampling free-ranging cetaceans, which allows for the determination of both contaminant concentrations and biomarker responses. Cytochrome P450 1A1 (CYP1A1) expression is induced by polycyclic aromatic hydrocarbons and planar halogenated aromatic

  16. Theoretical studies of the structures and local aromaticity of conjugated polycyclic hydrocarbons using three aromatic indices

    Science.gov (United States)

    Sakai, Shogo; Kita, Yuki

    2013-07-01

    The structures and local aromaticity of some conjugated polycyclic hydrocarbons (from the butadienoid, acene, and phenylene series) are studied using ab initio MO and density functional methods. The aromaticities of the molecules are estimated using three indices: the nucleus-independent chemical shift (NICS), the harmonic oscillator model of aromaticity (HOMA), and the index of deviation from aromaticity (IDA). Assessment of the relationships between the structures and the aromatic indices shows that the IDA values correspond best to the characteristics of the conjugated polycyclic hydrocarbon structures.

  17. Protection of halogenated DNA from strand breakage and sister-chromatid exchange induced by the topoisomerase I inhibitor camptothecin

    International Nuclear Information System (INIS)

    Orta, Manuel Luis; Mateos, Santiago; Cantero, Gloria; Wolff, Lisa J.; Cortes, Felipe

    2008-01-01

    The fundamental nuclear enzyme DNA topoisomerase I (topo I), cleaves the double-stranded DNA molecule at preferred sequences within its recognition/binding sites. We have recently reported that when cells incorporate halogenated nucleosides analogues of thymidine into DNA, it interferes with normal chromosome segregation, as shown by an extraordinarily high yield of endoreduplication, and results in a protection against DNA breakage induced by the topo II poison m-AMSA [F. Cortes, N. Pastor, S. Mateos, I. Dominguez, The nature of DNA plays a role in chromosome segregation: endoreduplication in halogen-substituted chromosomes, DNA Repair 2 (2003) 719-726; G. Cantero, S. Mateos, N. Pastor; F. Cortes, Halogen substitution of DNA protects from poisoning of topoisomerase II that results in DNA double-strand breaks (DSBs), DNA Repair 5 (2006) 667-674]. In the present investigation, we have assessed whether the presence of halogenated nucleosides in DNA diminishes the frequency of interaction of topo I with DNA and thus the frequency with which the stabilisation of cleavage complexes by the topo I poison camptothecin (CPT) takes place, in such a way that it protects from chromosome breakage and sister-chromatid exchange. This protective effect is shown to parallel a loss in halogen-substituted cells of the otherwise CPT-increased catalytic activity bound to DNA

  18. Pharmacological evaluation of halogenated and non-halogenated arylpiperazin-1-yl-ethyl-benzimidazoles as D(2) and 5-HT(2A) receptor ligands.

    Science.gov (United States)

    Tomić, Mirko; Vasković, Djurdjica; Tovilović, Gordana; Andrić, Deana; Penjišević, Jelena; Kostić-Rajačić, Sladjana

    2011-05-01

    Five groups of previously synthesized and initially screened non-substituted and 4-halogenated arylpiperazin-1-yl-ethyl-benzimidazoles were estimated for their in-vitro binding affinities at the rat D(2) , 5-HT(2A) , and α(1) -adrenergic receptors. Among all these compounds, 2-methoxyphenyl and 2-chlorophenyl piperazines demonstrate the highest affinities for the tested receptors. The effects of 4-halogenation of benzimidazoles reveal that substitution with bromine may greatly increase the affinity of the compounds for the studied receptors, while the effect of substitution with chlorine is less remarkable. Most of the tested components show 5-HT(2A)/D(2) pK(i) binding ratios slightly above or less than 1, while only 4-chloro-6-(2-{4-[3-(trifluoromethyl)phenyl]piperazin-1-yl}ethyl)-1H-benzimidazole expresses an appropriate higher binding ratio (1.14), which was indicated for atypical neuroleptics. This compound exhibits a non-cataleptic action in rats and prevents d-amphetamine-induced hyperlocomotion in mice, which suggest its atypical antipsychotic potency. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Microbial production of the aromatic building-blocks (S)-styrene oxide and (R)-1,2-phenylethanediol from renewable resources.

    Science.gov (United States)

    McKenna, Rebekah; Pugh, Shawn; Thompson, Brian; Nielsen, David R

    2013-12-01

    (S)-Styrene oxide and (R)-1,2-phenylethanediol are chiral aromatic molecular building blocks used commonly as precursors to pharmaceuticals and other specialty chemicals. Two pathways have been engineered in Escherichia coli for their individual biosynthesis directly from glucose. The novel pathways each constitute extensions of the previously engineered styrene pathway, developed by co-expressing either styrene monooxygenase (SMO) or styrene dioxygenase (SDO) to convert styrene to (S)-styrene oxide and (R)-1,2-phenylethanediol, respectively. StyAB from Pseudomonas putida S12 was determined to be the most effective SMO. SDO activity was achieved using NahAaAbAcAd of Pseudomonas sp. NCIB 9816-4, a naphthalene dioxygenase with known broad substrate specificity. Production of phenylalanine, the precursor to both pathways, was systematically enhanced through a number of mutations, most notably via deletion of tyrA and over-expression of tktA. As a result, (R)-1,2-phenylethanediol reached titers as high as 1.23 g/L, and at 1.32 g/L (S)-styrene oxide titers already approach their toxicity limit. As with other aromatics, product toxicity was strongly correlated with a model of membrane accumulation and disruption. This study additionally demonstrates that greater flux through the styrene pathway can be achieved if its toxicity is addressed, as achieved in this case by reacting styrene to less toxic products. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Cyano-containing ionic liquids for the extraction of aromatic hydrocarbons from an aromatic/aliphatic mixture

    NARCIS (Netherlands)

    Meindersma, G.W.; Haan, de A.B.

    2012-01-01

    Ionic liquids can replace conventional solvents in aromatic/aliphatic extractions, if they have higher aromatic distribution coefficients and higher or similar aromatic/aliphatic selectivities. Also physical properties, such as density and viscosity, must be taken into account if a solvent is

  1. Chromatographic resolution of closely related species in pharmaceutical chemistry: dehalogenation impurities and mixtures of halogen isomers.

    Science.gov (United States)

    Regalado, Erik L; Zhuang, Ping; Chen, Yadan; Makarov, Alexey A; Schafer, Wes A; McGachy, Neil; Welch, Christopher J

    2014-01-07

    In recent years, the use of halogen-containing molecules has proliferated in the pharmaceutical industry, where the incorporation of halogens, especially fluorine, has become vitally important for blocking metabolism and enhancing the biological activity of pharmaceuticals. The chromatographic separation of halogen-containing pharmaceuticals from associated isomers or dehalogenation impurities can sometimes be quite difficult. In an attempt to identify the best current tools available for addressing this important problem, a survey of the suitability of four chromatographic method development platforms (ultra high-performance liquid chromatography (UHPLC), core shell HPLC, achiral supercritical fluid chromatography (SFC) and chiral SFC) for separating closely related mixtures of halogen-containing pharmaceuticals and their dehalogenated isosteres is described. Of the 132 column and mobile phase combinations examined for each mixture, a small subset of conditions were found to afford the best overall performance, with a single UHPLC method (2.1 × 50 mm, 1.9 μm Hypersil Gold PFP, acetonitrile/methanol based aqueous eluents containing either phosphoric or perchloric acid with 150 mM sodium perchlorate) affording excellent separation for all samples. Similarly, a survey of several families of closely related halogen-containing small molecules representing the diversity of impurities that can sometimes be found in purchased starting materials for synthesis revealed chiral SFC (Chiralcel OJ-3 and Chiralpak IB, isopropanol or ethanol with 25 mM isobutylamine/carbon dioxide) as well as the UHPLC (2.1 × 50 mm, 1.8 μm ZORBAX RRHD Eclipse Plus C18 and the Gold PFP, acetonitrile/methanol based aqueous eluents containing phosphoric acid) as preferred methods.

  2. A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer

    Directory of Open Access Journals (Sweden)

    K. Toyota

    2004-01-01

    Full Text Available A new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry to investigate photochemical interactions between volatile organic compounds (VOCs and reactive halogen species in the marine boundary layer (MBL. Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit description of oxidative degradation of up to C3-hydrocarbons (CH4, C2H6, C3H8, C2H4, C3H6, and C2H2 initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in forming halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO and alkenes (especially C3H6 are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from a reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. The reaction between Br atoms and C2H2 is shown to be unimportant for determining the degree of bromine activation in the remote MBL. These results imply that reactive halogen chemistry can mediate a link between the oceanic emissions of VOCs and the behaviors of compounds that are sensitive to halogen chemistry such as dimethyl

  3. Structure and biocatalytic scope of thermophilic flavin-dependent halogenase and flavin reductase enzymes.

    Science.gov (United States)

    Menon, Binuraj R K; Latham, Jonathan; Dunstan, Mark S; Brandenburger, Eileen; Klemstein, Ulrike; Leys, David; Karthikeyan, Chinnan; Greaney, Michael F; Shepherd, Sarah A; Micklefield, Jason

    2016-10-04

    Flavin-dependent halogenase (Fl-Hal) enzymes have been shown to halogenate a range of synthetic as well as natural aromatic compounds. The exquisite regioselectively of Fl-Hal enzymes can provide halogenated building blocks which are inaccessible using standard halogenation chemistries. Consequently, Fl-Hal are potentially useful biocatalysts for the chemoenzymatic synthesis of pharmaceuticals and other valuable products, which are derived from haloaromatic precursors. However, the application of Fl-Hal enzymes, in vitro, has been hampered by their poor catalytic activity and lack of stability. To overcome these issues, we identified a thermophilic tryptophan halogenase (Th-Hal), which has significantly improved catalytic activity and stability, compared with other Fl-Hal characterised to date. When used in combination with a thermostable flavin reductase, Th-Hal can efficiently halogenate a number of aromatic substrates. X-ray crystal structures of Th-Hal, and the reductase partner (Th-Fre), provide insights into the factors that contribute to enzyme stability, which could guide the discovery and engineering of more robust and productive halogenase biocatalysts.

  4. A Protein Data Bank survey reveals shortening of intermolecular hydrogen bonds in ligand-protein complexes when a halogenated ligand is an H-bond donor.

    Science.gov (United States)

    Poznański, Jarosław; Poznańska, Anna; Shugar, David

    2014-01-01

    Halogen bonding in ligand-protein complexes is currently widely exploited, e.g. in drug design or supramolecular chemistry. But little attention has been directed to other effects that may result from replacement of a hydrogen by a strongly electronegative halogen. Analysis of almost 30000 hydrogen bonds between protein and ligand demonstrates that the length of a hydrogen bond depends on the type of donor-acceptor pair. Interestingly, lengths of hydrogen bonds between a protein and a halogenated ligand are visibly shorter than those estimated for the same family of proteins in complexes with non-halogenated ligands. Taking into account the effect of halogenation on hydrogen bonding is thus important when evaluating structural and/or energetic parameters of ligand-protein complexes. All these observations are consistent with the concept that halogenation increases the acidity of the proximal amino/imino/hydroxyl groups and thus makes them better, i.e. stronger, H-bond donors.

  5. UV-visible and resonance Raman spectroscopy of halogen molecules in clathrate hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Janda, K.C.; Kerenskaya, G.; Goldsheleger, I.U.; Apkarian, V.A.; Fleischer, E.B. [California Univ., Irvine, CA (United States). Dept. of Chemistry

    2008-07-01

    Resonance Raman spectroscopy was used to study halogen clathrate hydrate solids. In particular, this paper presented an ultraviolet-visible spectra for a polycrystalline sample of chlorine clathrate hydrate and two single crystal samples of bromine clathrate hydrate. UV-visible spectroscopy was used to study the interactions between the halogen guest molecule and the host water lattice. The spectrum for chlorine hydrate had a strong temperature dependence, while the spectra for bromine clathrate hydrate single crystals had a stable cubic type 2 structure as well as a tetragonal structure. A metastable cubic type 1 structure was also observed. Resonance Raman spectroscopy showed how the molecules fit into the host cages. 25 refs., 2 tabs., 7 figs.

  6. Processing of atmospheric polycyclic aromatic hydrocarbons by fog in an urban environment.

    Science.gov (United States)

    Ehrenhauser, Franz S; Khadapkar, Kalindi; Wang, Youliang; Hutchings, James W; Delhomme, Olivier; Kommalapati, Raghava R; Herckes, Pierre; Wornat, Mary J; Valsaraj, Kalliat T

    2012-10-26

    Polycyclic aromatic hydrocarbons (PAH) are ubiquitous pollutants in the atmosphere, predominantly known for their toxicity. Although there has been substantial work on the atmospheric degradation of PAH, little is known about how the presence of atmospheric droplets (e.g., a fog cloud) affects the fate of PAH. In order to assess the processing of PAH and their corresponding oxidation products during a fog event, two field-sampling campaigns in Fresno, CA and Davis, CA were conducted. The simultaneous evaluation of concentrations of the PAH and oxygenated polycyclic aromatic compounds (OPAC) in the gas phase, particulate matter and fog water droplets before, during and after fog allows for the characterization of transformative and transport processes in a fog cloud. By tracking the ratio of OPAC to PAH in the individual atmospheric phases, two major polycyclic aromatic compounds-processing pathways can be identified: (i) the dissolution of OPAC from particulate matter and (ii) the uptake and oxidation of PAH in the fog water droplets. Wet deposition steadily decreases the pollutant concentration in the fog cloud droplets during a fog event; however, uptake and concentration via evaporative water loss upon the dissipation of a fog cloud cause an increase in the atmospheric pollutant concentration.

  7. Attosecond Time Delay in Photoionization of Noble-Gas and Halogen Atoms

    Directory of Open Access Journals (Sweden)

    Liang-Wen Pi

    2018-02-01

    Full Text Available Ultrafast processes are now accessible on the attosecond time scale due to the availability of ultrashort XUV laser pulses. Noble-gas and halogen atoms remain important targets due to their giant dipole resonance and Cooper minimum. Here, we calculate photoionization cross section, asymmetry parameter and Wigner time delay using the time-dependent local-density approximation (TDLDA, which includes the electron correlation effects. Our results are consistent with experimental data and other theoretical calculations. The asymmetry parameter provides an extra layer of access to the phase information of the photoionization processes. We find that halogen atoms bear a strong resemblance on cross section, asymmetry parameter and time delay to their noble-gas neighbors. Our predicted time delay should provide a guidance for future experiments on those atoms and related molecules.

  8. SYNTHESIS AND STUDY OF HALOGENATED BENZYLAMIDES OF SOME ISOCYCLIC AND HETEROCYCLIC ACIDS AS POTENTIAL ANTICONVULSANTS.

    Science.gov (United States)

    Strupińska, Marzanna; Rostafińska-Suchar, Grażyna; Pirianowicz-Chaber, Elżbieta; Grabczuk, Mateusz; Józwenko, Magdalena; Kowalczyk, Hubert; Szuba, Joanna; Wójcicka, Monika; Chen, Tracy; Mazurek, Aleksander P

    2015-01-01

    A series of potential anticonvulsants have been synthesized. There are eight fluorobenzylamides and three chlorobenzylamides of isocyclic or heterocyclic acids. Two not halogenated benzylamides were also synthesized to compare the effect of halogenation. The aim of the research performed was to evaluate whether halogenation of the mother structure is able to improve its anticonvulsant activity. The compounds were tested in Anticonvulsant Screening Project (ASP) of Antiepileptic Drug Development Program (ADDP) of NIH. Compound 1 showed MES ED50 = 80.32 mg/kg, PI = 3.16. Compound 7 showed CKM ED50 = 56.72 mg/kg. Compound 8 showed MES ED50 = 34.23 mg/kg and scPTZ ED50 > 300 mg/kg, PI = 8.53.Compound 13 showed 6Hz ED50 = 78.96, PI = 3.37. The results indicate that fluorination does not improve activity, whereas chlorination in our experiment even reduces it.

  9. Aromater i drikkevand

    DEFF Research Database (Denmark)

    Nyeland, B. A.; Hansen, A. B.

    DMU har den 10. Juni 1997 afholdt en præstationsprøvning: Aromater i drikkevand. Der deltog 21 laboratorier i præstationsprøvningen. Prøvningen omfattede 6 vandige prøver og 6 ampuller indeholdende 6 aromater. Laboratorierne spikede de tilsendte vandprøver med indholdet fra ampullerne...

  10. Computational insights into the photocyclization of diclofenac in solution: effects of halogen and hydrogen bonding.

    Science.gov (United States)

    Bani-Yaseen, Abdulilah Dawoud

    2016-08-21

    The effects of noncovalent interactions, namely halogen and hydrogen bonding, on the photochemical conversion of the photosensitizing drug diclofenac (DCF) in solution were investigated computationally. Both explicit and implicit solvent effects were qualitatively and quantitatively assessed employing the DFT/6-31+G(d) and SQM(PM7) levels of theory. Full geometry optimizations were performed in solution for the reactant DCF, hypothesized radical-based intermediates, and the main product at both levels of theories. Notably, in good agreement with previous experimental results concerning the intermolecular halogen bonding of DCF, the SQM(PM7) method revealed different values for d(ClO, Å) and ∠(C-ClO, °) for the two chlorine-substituents of DCF, with values of 2.63 Å/162° and 3.13 Å/142° for the trans and cis orientations, respectively. Employing the DFT/6-31+G(d) method with implicit solvent effects was not conclusive; however, explicit solvent effects confirmed the key contribution of hydrogen and halogen bonding in stabilizing/destabilizing the reactant and hypothesized intermediates. Interestingly, the obtained results revealed that a protic solvent such as water can increase the rate of photocyclization of DCF not only through hydrogen bonding effects, but also through halogen bonding. Furthermore, the atomic charges of atoms majorly involved in the photocyclization of DCF were calculated using different methods, namely Mulliken, Hirshfeld, and natural bond orbital (NBO). The obtained results revealed that in all cases there is a notable nonequivalency in the noncovalent intermolecular interactions of the two chlorine substituents of DCF and the radical intermediates with the solvent, which in turn may account for the discrepancy of their reactivity in different media. These computational results provide insight into the importance of halogen and hydrogen bonding throughout the progression of the photochemical conversion of DCF in solution.

  11. Fluorescence method for enzyme analysis which couples aromatic amines with aromatic aldehydes

    Science.gov (United States)

    Smith, R.E.; Dolbeare, F.A.

    1980-10-21

    Analysis of proteinases is accomplished using conventional amino acid containing aromatic amine substrates. Aromatic amines such as 4-methoxy-2-naphthylamine (4M2NA), 2-naphthylamine, aminoisophthalic acid dimethyl ester, p-nitroaniline, 4-methoxy-1-aminofluorene and coumarin derivatives resulting from enzymatic hydrolysis of the substrate couples with aromatic aldehydes such as 5-nitrosalicylaldehyde (5-NSA), benzaldehyde and p-nitrobenzaldehyde to produce Schiff-base complexes which are water insoluble. Certain Schiff-base complexes produce a shift from blue to orange-red (visible) fluorescence. Such complexes are useful in the assay of enzymes. No Drawings

  12. Is there theoretical evidence for mutual influence between halogen

    Indian Academy of Sciences (India)

    Based on many-body analysis, two and three-body terms of interaction energies have a positive contribution to the total interaction energy. It was found that the amount of charge transfer in the triads is higher than that in the corresponding dyads. AIM analyses showed that the halogen and pnicogen-hydride bonds in the ...

  13. A Protein Data Bank survey reveals shortening of intermolecular hydrogen bonds in ligand-protein complexes when a halogenated ligand is an H-bond donor.

    Directory of Open Access Journals (Sweden)

    Jarosław Poznański

    Full Text Available Halogen bonding in ligand-protein complexes is currently widely exploited, e.g. in drug design or supramolecular chemistry. But little attention has been directed to other effects that may result from replacement of a hydrogen by a strongly electronegative halogen. Analysis of almost 30000 hydrogen bonds between protein and ligand demonstrates that the length of a hydrogen bond depends on the type of donor-acceptor pair. Interestingly, lengths of hydrogen bonds between a protein and a halogenated ligand are visibly shorter than those estimated for the same family of proteins in complexes with non-halogenated ligands. Taking into account the effect of halogenation on hydrogen bonding is thus important when evaluating structural and/or energetic parameters of ligand-protein complexes. All these observations are consistent with the concept that halogenation increases the acidity of the proximal amino/imino/hydroxyl groups and thus makes them better, i.e. stronger, H-bond donors.

  14. Formation of Sulfonyl Aromatic Alcohols by Electrolysis of a Bisazo Reactive Dye

    Directory of Open Access Journals (Sweden)

    María P. Elizalde-González

    2012-12-01

    Full Text Available Five sulfonyl aromatic alcohols, namely 4-((2-hydroxyethylsulfonylphenol, 4-((2-(2-((4-hydroxyphenylsulfonylethoxyvinylsulfonylphenol, 4-(ethylsulfonylphenol, 4-(vinylsulfonylphenol and 5-((4-aminophenylsulfonyl-2-penten-1-ol were identified by LC-ESI-Qq-TOF-MS as products formed by electrolysis of the bisazo reactive dye Reactive Black 5 (RB5. Since electrolyses were performed in an undivided cell equipped with Ni electrodes in alkaline medium, amines like 4-(2-methoxyethylsulfonylbenzene-amine (MEBA with m/z 216 were also suspected to be formed due to the plausible chemical reaction in the bulk or the cathodic reduction of RB5 and its oxidation by-products. Aiming to check this hypothesis, a method was used for the preparation of MEBA with 98% purity, via chemical reduction also of the dye RB5. The logP of the synthesized sulfonyl aromatic compounds was calculated and their logkw values were determined chromatographically. These data were discussed in regard to the relationship between hydrophobicity/lipophilicity and toxicity.

  15. Laboratory Investigations of Stratospheric Halogen Chemistry

    Science.gov (United States)

    Wine, Paul H.; Nicovich, J. Michael; Stickel, Robert E.; Hynes, Anthony J.

    1997-01-01

    A final report for the NASA-supported project on laboratory investigations of stratospheric halogen chemistry is presented. In recent years, this project has focused on three areas of research: (1) kinetic, mechanistic, and thermochemical studies of reactions which produce weakly bound chemical species of atmospheric interest; (2) development of flash photolysis schemes for studying radical-radical reactions of stratospheric interest; and (3) photochemistry studies of interest for understanding stratospheric chemistry. The first section of this paper contains a discussion of work which has not yet been published. All subsequent chapters contain reprints of published papers that acknowledge support from this grant.

  16. From small aromatic molecules to functional nanostructured carbon by pulsed laser-induced photochemical stitching

    Directory of Open Access Journals (Sweden)

    R. R. Gokhale

    2012-06-01

    Full Text Available A novel route employing UV laser pulses (KrF Excimer, 248 nm to cleave small aromatic molecules and stitch the generated free radicals into functional nanostructured forms of carbon is introduced. The process differs distinctly from any strategies wherein the aromatic rings are broken in the primary process. It is demonstrated that this pulsed laser-induced photochemical stitching (PLPS process when applied to routine laboratory solvents (or toxic chemical wastes when discarded Chlorobenzene and o-Dichlorobenzene yields Carbon Nanospheres (CNSs comprising of graphene-like sheets assembled in onion-like configurations. This room temperature process implemented under normal laboratory conditions is versatile and clearly applicable to the whole family of haloaromatic compounds without and with additions of precursors or other nanomaterials. We further bring out its applicability for synthesis of metal-oxide based carbon nanocomposites.

  17. The Halogenated Metabolism of Brown Algae (Phaeophyta, Its Biological Importance and Its Environmental Significance

    Directory of Open Access Journals (Sweden)

    Stéphane La Barre

    2010-03-01

    Full Text Available Brown algae represent a major component of littoral and sublittoral zones in temperate and subtropical ecosystems. An essential adaptive feature of this independent eukaryotic lineage is the ability to couple oxidative reactions resulting from exposure to sunlight and air with the halogenations of various substrates, thereby addressing various biotic and abiotic stresses i.e., defense against predators, tissue repair, holdfast adhesion, and protection against reactive species generated by oxidative processes. Whereas marine organisms mainly make use of bromine to increase the biological activity of secondary metabolites, some orders of brown algae such as Laminariales have also developed a striking capability to accumulate and to use iodine in physiological adaptations to stress. We review selected aspects of the halogenated metabolism of macrophytic brown algae in the light of the most recent results, which point toward novel functions for iodide accumulation in kelps and the importance of bromination in cell wall modifications and adhesion properties of brown algal propagules. The importance of halogen speciation processes ranges from microbiology to biogeochemistry, through enzymology, cellular biology and ecotoxicology.

  18. Noncomparative scaling of aromaticity through electron itinerancy

    International Nuclear Information System (INIS)

    Paul, Satadal; Goswami, Tamal; Misra, Anirban

    2015-01-01

    Aromaticity is a multidimensional concept and not a directly observable. These facts have always stood in the way of developing an appropriate theoretical framework for scaling of aromaticity. In the present work, a quantitative account of aromaticity is developed on the basis of cyclic delocalization of π-electrons, which is the phenomenon leading to unique features of aromatic molecules. The stabilization in molecular energy, caused by delocalization of π-electrons is obtained as a second order perturbation energy for archetypal aromatic systems. The final expression parameterizes the aromatic stabilization energy in terms of atom to atom charge transfer integral, onsite repulsion energy and the population of spin orbitals at each site in the delocalized π-electrons. An appropriate computational platform is framed to compute each and individual parameter in the derived equation. The numerical values of aromatic stabilization energies obtained for various aromatic molecules are found to be in close agreement with available theoretical and experimental reports. Thus the reliable estimate of aromaticity through the proposed formalism renders it as a useful tool for the direct assessment of aromaticity, which has been a long standing problem in chemistry

  19. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1980-February 14, 1981

    International Nuclear Information System (INIS)

    1981-02-01

    The stereochemistry of high energy 18 F, /sup 34m/Cl, and 76 Br substitution reactions involving enantiomeric molecules in the gas and condensed phase is studied. The gas to condensed state transition in halogen high energy chemistry, involving chlorine, bromine, and iodine activated by the (n,γ) and (I.T.) processes in halomethanes, saturated and unsaturated hydrocarbons is being investigated in more detail. Special attention is given to defining the nature of the enhancement yields in the condensed phase. High energy halogen reactions in liquid and frozen aqueous solutions of organic and biomolecular solutes are studied in an attempt to learn more about these reactions. The applications of high energy chemistry techniques and theory to neutron activation analysis of biological systems are being continued. Special attention is given to developing procedures for trace molecular determinations in biological systems. The applications of hot halogen atoms as indicators of solute-solute interactions in liquid and frozen aqueous solutions of halogenated bases and nucleosides are being developed. Experiments are designed to explain the mechanisms of the radioprotection offered biomolecular solutes trapped within the frozen ice lattice. Reactions of bromine and iodine activated by isomeric transition with halogenated biomolecular solutes in liquid and frozen aqueous solutions are studied. The high energy reactions of iodine with the isomers of pentene have been studied in low pressure gaseous systems employing additives and rare gas moderators and liquid systems. Reactivity of excited complex formation and structural effects of electrophilic iodine attack on the pi-bond systems are studied

  20. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1980-February 14, 1981

    Energy Technology Data Exchange (ETDEWEB)

    1981-02-01

    The stereochemistry of high energy /sup 18/F, /sup 34m/Cl, and /sup 76/Br substitution reactions involving enantiomeric molecules in the gas and condensed phase is studied. The gas to condensed state transition in halogen high energy chemistry, involving chlorine, bromine, and iodine activated by the (n,..gamma..) and (I.T.) processes in halomethanes, saturated and unsaturated hydrocarbons is being investigated in more detail. Special attention is given to defining the nature of the enhancement yields in the condensed phase. High energy halogen reactions in liquid and frozen aqueous solutions of organic and biomolecular solutes are studied in an attempt to learn more about these reactions. The applications of high energy chemistry techniques and theory to neutron activation analysis of biological systems are being continued. Special attention is given to developing procedures for trace molecular determinations in biological systems. The applications of hot halogen atoms as indicators of solute-solute interactions in liquid and frozen aqueous solutions of halogenated bases and nucleosides are being developed. Experiments are designed to explain the mechanisms of the radioprotection offered biomolecular solutes trapped within the frozen ice lattice. Reactions of bromine and iodine activated by isomeric transition with halogenated biomolecular solutes in liquid and frozen aqueous solutions are studied. The high energy reactions of iodine with the isomers of pentene have been studied in low pressure gaseous systems employing additives and rare gas moderators and liquid systems. Reactivity of excited complex formation and structural effects of electrophilic iodine attack on the pi-bond systems are studied.

  1. Three-dimensional aromatic networks.

    Science.gov (United States)

    Toyota, Shinji; Iwanaga, Tetsuo

    2014-01-01

    Three-dimensional (3D) networks consisting of aromatic units and linkers are reviewed from various aspects. To understand principles for the construction of such compounds, we generalize the roles of building units, the synthetic approaches, and the classification of networks. As fundamental compounds, cyclophanes with large aromatic units and aromatic macrocycles with linear acetylene linkers are highlighted in terms of transannular interactions between aromatic units, conformational preference, and resolution of chiral derivatives. Polycyclic cage compounds are constructed from building units by linkages via covalent bonds, metal-coordination bonds, or hydrogen bonds. Large cage networks often include a wide range of guest species in their cavity to afford novel inclusion compounds. Topological isomers consisting of two or more macrocycles are formed by cyclization of preorganized species. Some complicated topological networks are constructed by self-assembly of simple building units.

  2. Hazardous materials in aquatic environments of the Mississippi River Basin Project management. Technical quarterly progress report, April 1, 1996--June 30, 1996

    Energy Technology Data Exchange (ETDEWEB)

    McLachlan, J.; Ide, C.F.; O`Connor, S.

    1996-08-01

    This quarterly report summarizes accomplishments for the Project examining hazardous materials in aquatic environments of the Mississippi River Basin. Among the many research areas summarized are the following: assessment of mechanisms of metal-induced reproductive toxicity in aquatic species as a biomarker of exposure; hazardous wastes in aquatic environment;ecological sentinels of aquatic contamination in the lower Mississippi River System; remediation of selected contaminants; rapid on-site immunassay for heavy metal contamination; molecular mechanisms of developmental toxicity induced by retinoids and retinoid-like molecules; resuseable synthetic membranes for the removal of aromatic and halogenated organic pollutants from waste water; Effects of steroid receptor activation in neurendocrine cell of the mammalian hypothalamus; modeling and assessment of environmental quality of louisiana bayous and swamps; enhancement of environmental education. The report also contains a summary of publications resulting from this project and an appendix with analytical core protocals and target compounds and metals.

  3. Neutron activation analysis for study of distribution patterns of organo-halogen pollutants in apple

    International Nuclear Information System (INIS)

    Zhang Hong; Luo Jialing; Sun Huibin; Chai Zhifang; Chinese Academy of Sciences, Beijing

    2007-01-01

    The distribution characteristics of organo-halogens in apple and their sources were studied by neutron activation analysis combined with statistical analysis. The results indicated that concentrations of organo-halogens in apple were in the order of organo-chlorine >> organo-bromine > organo-iodine, and concentrations of the organo-chlorine in four parts of apple were in the order of seed >> peel >> endocarp ≥ pulp. Also, the organo-chlorine, -bromine and-iodine in apple were found to have different sources. The latter two were mainly from naturally synthetic products by plant itself, while the former was mainly from anthropogenic pollutants. (authors)

  4. Halogen effect for improving high temperature oxidation resistance of Ti-50Al by anodization

    Science.gov (United States)

    Mo, Min-Hua; Wu, Lian-Kui; Cao, Hua-Zhen; Lin, Jun-Pin; Zheng, Guo-Qu

    2017-06-01

    The high temperature oxidation resistance of Ti-50Al was significantly improved via halogen effect which was achieved by anodizing in an ethylene glycol solution containing with fluorine ion. The anodized Ti-50Al with holes and micro-cracks could be self-repaired during oxidation at 1000 °C. The thickness of the oxide scale increases with the prolonging of oxidation time. On the basis of halogen effect for improving the high temperature oxidation resistance of Ti-50Al by anodization, only fluorine addition into the electrolyte can effectively improve the high temperature oxidation resistance of Ti-50Al.

  5. Identification of prenatal toxic components of complex PAH mixtures derived from fossil fuel combustion employing rodent embryo culture systems

    International Nuclear Information System (INIS)

    Irvin, T.R.; Akgerman, A.

    1991-01-01

    Many adverse health effects caused by combustion-generated toxins have been recognized for some time. Acute pulmonary toxicity among urban populations has been repeatedly recorded during periods of high smoke, soot, and organo-particulate pollution. The combustion of coals and petroleum-derived fuels results in emission of particulate and organic vapor-phase components to the atmosphere. Isolation of these particle-absorbed compounds and subsequent toxicological testing has further indicated the importance of chronic, low-level exposure to airborne combustion-generated toxins in the etiology of many forms of human cancer; particulate phases of these emissions have been found to contain polycyclic aromatic hydrocarbons and heterocyclic organic compounds, absorbed onto the particle matrix, which possess potent carcinogenic and mutagenic properties. In this paper, the authors define a postimplantation rat embryo culture system constructed to identify prenatal toxic components of complex polycyclic aromatic hydrocarbon soots. Employing this culture system, we also describe its application to identify prenatal toxic components of diesel soot particulates

  6. Boiling Heat Transfer to Halogenated Hydrocarbon Refrigerants

    Science.gov (United States)

    Yoshida, Suguru; Fujita, Yasunobu

    The current state of knowledge on heat transfer to boiling refrigerants (halogenated hydrocarbons) in a pool and flowing inside a horizontal tube is reviewed with an emphasis on information relevant to the design of refrigerant evaporators, and some recommendations are made for future research. The review covers two-phase flow pattern, heat transfer characteristics, correlation of heat transfer coefficient, influence of oil, heat transfer augmentation, boiling from tube-bundle, influence of return bend, burnout heat flux, film boiling, dryout and post-dryout heat transfer.

  7. Toxic effects on and structure-toxicity relationships of phenylpropanoids, terpenes, and related compounds in Aedes aegypti larvae.

    Science.gov (United States)

    Santos, Sandra R L; Silva, Viviane B; Melo, Manuela A; Barbosa, Juliana D F; Santos, Roseli L C; de Sousa, Damião P; Cavalcanti, Sócrates C H

    2010-12-01

    In the search for toxic compounds against Aedes aegypti L. (Diptera: Culicidae) larvae, a collection of commercially available aromatic and aliphatic diversely substituted compounds were selected and evaluated. p-Cymene exhibited the highest larvicidal potency LC₅₀ = 51 ppm, whereas 1,8-cineole exhibited the lowest activity value LC₅₀ = 1419 ppm. To aid future work on the search for larvicidal compounds, the structure-toxicity relationships of this collection have been evaluated. The presence of lipophilic groups results in an overall increase in potency. In general, the presence of hydroxyl groups resulted in less potent compounds. However, methylation of such hydroxyls led to an overall increase in potency. The most potent compounds showed comparably good larvicidal activity in A. aegypti larvae as other terpenes, which we assume to be the result of the increased lipophilicity.

  8. Gas-liquid partitioning of halogenated volatile organic compounds in aqueous cyclodextrin solutions

    Energy Technology Data Exchange (ETDEWEB)

    Ondo, Daniel; Barankova, Eva [Department of Physical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic); Dohnal, Vladimir, E-mail: dohnalv@vscht.cz [Department of Physical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic)

    2011-08-15

    Highlights: > Binding of halogenated VOCs with cyclodextrins examined through g-l partitioning. > Complex stabilities reflect host-guest size matching and hydrophobic interaction. > Presence of halogens in the guest molecule stabilizes the binding. > Thermodynamic origin of the binding varies greatly among the systems studied. > Results obey the guest-CD global enthalpy-entropy compensation relationship. - Abstract: Gas-liquid partitioning coefficients (K{sub GL}) were measured for halogenated volatile organic compounds (VOCs), namely 1-chlorobutane, methoxyflurane, pentafluoropropan-1-ol, heptafluorobutan-1-ol, {alpha},{alpha},{alpha}-trifluorotoluene, and toluene in aqueous solutions of natural {alpha}-, {beta}-, and {gamma}-cyclodextrins (CDs) at temperatures from (273.35 to 326.35) K employing the techniques of headspace gas chromatography and inert gas stripping. The binding constants of the 1:1 inclusion complex formation between the VOCs and CDs were evaluated from the depression of the VOCs volatility as a function of CD concentration. The host-guest size matching and the hydrophobic interaction concept were used to rationalize the observed widely different affinity of the VOC-CD pairs to form the inclusion complex. The enthalpic and entropic component of the standard Gibbs free energy of complex formation as derived from the temperature dependence of the binding constant indicate the thermodynamic origin of the binding to vary greatly among the systems studied, but follow the global enthalpy-entropy compensation relationships reported previously in the literature.

  9. Hydration of the Atlantis Massif: Halogen, Noble Gas and In-Situ δ18O Constraints

    Science.gov (United States)

    Williams, M. J.; Kendrick, M. A.; Rubatto, D.

    2017-12-01

    A combination of halogen (Cl, Br, I), noble gases (He, Ne, Ar, Kr and Xe) and in situ oxygen isotope analysis have been utilized to investigate the fluid-mobile element record of hydration and alteration processes at the Atlantis Massif (30°N on the Mid-Atlantic Ridge). The sample suite investigated includes serpentinite, talc-amphibole ± chlorite schist and hydrated gabbro recovered by seafloor drilling undertaken at sites on a transect across the Atlantis Massif during IODP Expedition 357. Serpentine mesh and veins analysed in-situ by SHRIMP SI exhibit δ18O from 6‰ down to ≈0‰, suggesting serpentinization temperatures of 150 to >280°C and water/rock ratios >5. Differences of 1.5-2.5‰ are observed between adjacent generations of serpentine, but the δ18O range is similar at each investigated drilling site. Halogen and noble gas abundances in serpentinites, talc-amphibole schist and hydrated gabbro have been measured by noble gas mass spectrometry of both irradiated and non-irradiated samples. Serpentinites contain low abundances of halogens and noble gases (e.g. 70-430 ppm Cl, 4.7-12.2 x 10-14 mol/g 36Ar) relative to other seafloor serpentinites. The samples have systematically different Br/Cl and I/Cl ratios related to their mineralogy. Serpentinites retain mantle-like Br/Cl with a wide variation in I/Cl that stretches toward seawater values. Talc-amphibole schists exhibit depletion of Br and I relative to Cl with increasing Cl abundances, suggesting tremolite exerts strong control on halogen abundance ratios. Serpentinites show no evidence of interaction with halogen-rich sedimentary pore fluids. Iodine abundances are variable across serpentinites, and are decoupled from Br and Cl; iodine enrichment (up to 530 ppb) is observed within relatively oxidised and clay-bearing samples. Serpentinized harzburgites exhibit distinct depletion of Kr and Xe relative to atmospheric 36Ar in seawater. Oxygen isotope compositions and low abundances of both halogens

  10. Mid-latitude Ozone Depletion Events Caused by Halogens from the Great Salt Lake in Utah

    Science.gov (United States)

    Fibiger, D. L.; Goldberger, L.; Womack, C.; McDuffie, E. E.; Dube, W. P.; Franchin, A.; Middlebrook, A. M.; Thornton, J. A.; Brown, S. S.

    2017-12-01

    Halogens are highly reactive chemicals and play an important role in atmospheric chemistry. They can be involved in many cycles which influence the oxidizing capacity of the atmosphere, including through destruction of ozone (O3). While the influence of halogens on O3 is well documented in the arctic, there are very few observations of O3 depletion driven by halogens in the mid-latitudes. To date, the most comprehensive study observed co-occurring plumes of BrO and depleted O3 near the Dead Sea in 1997. During the Utah Wintertime Fine Particulate Study (UWFPS) in winter 2017, simultaneous measurements of a comprehensive suite of halogen measurements by I- chemical ionization mass spectrometry and O3 from cavity ring-down spectroscopy, both at 1-second time resolution, were taken on a NOAA Twin Otter Aircraft over the Great Salt Lake and in the surrounding valleys. Many O3 depletion events were observed over the lake with O3 values sometimes below the instrument detection limit of 0.5 ppbv. Corresponding increases in BrO and/or ClO were observed. Many of these events were caused by extremely high levels of halogens (up to 1 ppmv Cl2) emitted from the U.S. Magnesium plant on the edge of the lake. The O3 depletion caused by U.S. Magnesium was usually isolated to a distinct vertical layer, but in other cases O3 depletion was vertically mixed and the origin of halogen activation was not immediately clear. The most complete O3 depletion was observed over the lake, but there were smaller events of a few ppbv observed in the adjacent valleys, including the highly populated Salt Lake Valley, with corresponding plumes of BrO and ClO, due to transport from the lake. Additionally, meteorology played a role in the observed O3 depletion. The strongest O3 depletion was observed during inversion events, when there is a low boundary layer and little mixing out of the air above the lake. During non-inversion conditions, only small depletions were observed, covering a much smaller

  11. Efficient and Selective Reduction of Aromatic Nitro Compounds to Aromatic Amines by NbCl{sub 5}/Indium System

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Byung Woo; Kim, Duckil; Kim, Hyung Min; Kang, Sung Ho [Korea Univ., Seoul (Korea, Republic of)

    2012-09-15

    Aromatic amines find applicability in diverse fields including dyes, pharmaceuticals, agrochemicals, and photographic materials. To date, there are a variety of methods, which can be used to convert aromatic nitro compounds to their corresponding amines. Some of them include Cp{sub 2}TiCl{sub 2}/In, Al/NH{sub 4}Cl, (NH{sub 4}){sub 2}SO{sub 4}/NaBH{sub 4}, NiCl{sub 2}6H{sub 2}O/In, HI, Sm/I{sub 2}, In/NH{sub 4}Cl, B{sub 4}H{sub 10}/Pd/C, Co{sub 2}(CO){sub 8}/H{sub 2}O and In/HCl. However, most methods still lack the desired chemo-selectivity when other reducible functional groups are present in the nitroarene and often require long reaction times, or harsh reaction conditions. Consequently, efficient and selective methods for the reduction of aromatic nitro compounds continue to be developed. It has been reported that NbCl{sub 5}/Zn system is used as a reagent for reducing sulfoxides, epoxides, and amine N-oxides.12 Because of the close resemblance of indium to zinc in several respects, including first ionization potential, we considered that NbCl{sub 5}/In system can be an efficient reducing agent for the conversion of aromatic nitro compounds to the corresponding amines. Recently, indium metal has attracted much attention for its unique properties such as low toxicity and high stability in water and air compared with other metals. In continuation of our interest in exploring the utility of metal-metal salt system in organic synthesis, we would like to report an efficient and chemo-selective method for the reduction of various aromatic nitro compounds to the corresponding amines by treatment with NbCl{sub 5}/In system (eq. 1). The new reduction system was generated by the addition of indium powder to a stirred solution of niobium(V) chloride in THF under sonication. The generation of low-valent niobium species was examined at room temperature with an excess of indium metal. The observations suggest that this procedure can be applied for the chemo

  12. Chemical cleaning-associated generation of dissolved organic matter and halogenated byproducts in ceramic MBR: Ozone versus hypochlorite.

    Science.gov (United States)

    Sun, Huifang; Liu, Hang; Han, Jiarui; Zhang, Xiangru; Cheng, Fangqin; Liu, Yu

    2018-04-24

    This study characterized the dissolved organic matter (DOM) and byproducts generated after the exposure of activated sludge to ozone and NaClO in ceramic MBR. It was found that NaClO triggered more significant release of DOM than ozone. Proteins with the molecular weight greater than 20 kDa and humic acid like-substances were the principal components of DOM generated by NaClO, while ozone was found to effectively degrade larger biopolymers to low molecular weight substances. The results showed that more than 80% of DOM generated by NaClO and ozone could pass through the 0.2-μm ceramic membrane. Furthermore, total organic chlorine (TOCl) was determined to be the principal species of halogenated byproducts in both cases, while the generation of TOCl by NaClO was much more significant than that by ozone. Only a small fraction of TOCl was removed by the 0.2-μm ceramic membrane. More importantly, the toxic bioassays further revealed that the supernatant of sludge suspension and permeate in the MBR with NaClO cleaning exhibited higher developmental toxicity to the polychaete embryos than those by ozone. The results clearly showed that on-line chemical cleaning with ozone should be a more eco-friendly and safer approach for sustaining long-term membrane permeability in ceramic MBR. Copyright © 2018 Elsevier Ltd. All rights reserved.

  13. Origin of the X-Hal (Hal = Cl, Br) bond-length change in the halogen-bonded complexes.

    Science.gov (United States)

    Wang, Weizhou; Hobza, Pavel

    2008-05-01

    The origin of the X-Hal bond-length change in the halogen bond of the X-Hal...Y type has been investigated at the MP2(full)/6-311++G(d,p) level of theory using a natural bond orbital analysis, atoms in molecules procedure, and electrostatic potential fitting methods. Our results have clearly shown that various theories explaining the nature of the hydrogen bond cannot be applied to explain the origin of the X-Hal bond-length change in the halogen bond. We provide a new explanation for this change. The elongation of the X-Hal bond length is caused by the electron-density transfer to the X-Hal sigma* antibonding orbital. For the blue-shifting halogen bond, the electron-density transfer to the X-Hal sigma* antibonding orbital is only of minor importance; it is the electrostatic attractive interaction that causes the X-Hal bond contraction.

  14. A facile approach towards increasing the nitrogen-content in nitrogen-doped carbon nanotubes via halogenated catalysts

    International Nuclear Information System (INIS)

    Ombaka, L.M.; Ndungu, P.G.; Omondi, B.; McGettrick, J.D.; Davies, M.L.; Nyamori, V.O.

    2016-01-01

    Nitrogen-doped carbon nanotubes (N-CNTs) have been synthesized at 850 °C via a CVD deposition technique by use of three ferrocenyl derivative catalysts, i.e. para-CN, -CF_3 and -Cl substituted-phenyl rings. The synthesized catalysts have been characterized by NMR, IR, HR-MS and XRD. The XRD analysis of the para-CF_3 catalyst indicates that steric factors influence the X-ray structure of 1,1′-ferrocenylphenyldiacrylonitriles. Acetonitrile or pyridine was used as carbon and nitrogen sources to yield mixtures of N-CNTs and carbon spheres (CS). The N-CNTs obtained from the para-CF_3 catalysts, in pyridine, have the highest nitrogen-doping level, show a helical morphology and are less thermally stable compared with those synthesized by use of the para-CN and -Cl as catalyst. This suggests that fluorine heteroatoms enhance nitrogen-doping in N-CNTs and formation of helical-N-CNTs (H-N-CNTs). The para-CF_3 and para-Cl catalysts in acetonitrile yielded iron-filled N-CNTs, indicating that halogens promote encapsulation of iron into the cavity of N-CNT. The use of acetonitrile, as carbon and nitrogen source, with the para-CN and -Cl as catalysts also yielded a mixture of N-CNTs and carbon nanofibres (CNFs), with less abundance of CNFs in the products obtained using para-Cl catalysts. However, para-CF_3 catalyst in acetonitrile gave N-CNTs as the only shaped carbon nanomaterials. - Graphical abstract: Graphical abstract showing the synthesis of N-CNTs using halogenated-ferrocenyl derivatives as catalyst with pyridine or acetonitrile as nitrogen and carbon sources via the chemical vapour deposition technique. - Highlights: • N-CNTs were synthesized from halogenated ferrocenyl catalysts. • Halogenated catalysts promote nitrogen-doping and pyridinic nitrogen in N-CNTs. • Halogenated catalysts facilitate iron filling of N-CNTs.

  15. Oxidative stress in chemical toxicity

    Energy Technology Data Exchange (ETDEWEB)

    Kappus, H.

    1986-05-01

    The toxic effect of compounds which undergo redox cycling enzymatic one-electron reduction are reviewed. First of all, the enzymatic reduction of these compounds leads to reactive intermediates, mainly radicals which react with oxygen, whereby superoxide anion radicals are formed. Further oxygen metabolites are hydrogen peroxide, singlet oxygen and hydroxyl radicals. The role of these oxygen metabolites in toxicity is discussed. The occurrence of lipid peroxidation during redox cycling of quinonoide compounds, e.g., adriamycin, and the possible relationship to their toxicity is critically evaluated. It is shown that iron ions play a crucial role in lipid peroxidation induced by redox cycling compounds. DNA damage by metal chelates, e.g., bleomycin, is discussed on the basis of findings that enzymatic redox cycling of a bleomycin-iron complex has been observed. The involvement of hydroxyl radicals in bleomycin-induced DNA damage occurring during redox cycling in cell nuclei is claimed. Redox cycling of other substances, e.g., aromatic amines, is discussed in relation to carcinogenesis. Other chemical groups, e.g., nitroaromatic compounds, hydroxylamines and azo compounds are included. Other targets for oxygen radical attack, e.g., proteins, are also dealt with. It is concluded that oxygen radical formation by redox cycling may be a critical event in toxic effects of several compounds if the protective mechanisms of cells are overwhelmed.

  16. Long-term Studies of Marine Halogen Release

    Science.gov (United States)

    Tschritter, J.; Holla, R.; Frieß, U.; Platt, U.

    2009-04-01

    Institute of Enviromental Physics, Heidelberg, Germany. Long term measurements of atmospheric trace gases using multi-axis DOAS instruments are pursued at the new SOLAS observatory on the island of Sao Vicente, (Cape Verde). This research is part of the SOPRAN (Surface Ocean Processes in the ANthropocene) project (Fördernummer:03F0462F). Reactive halogen species (RHS) such as bromine- and iodine- containing species play major roles in the chemistry of ozone in both the troposphere and lower stratosphere and thus possibly influence the ozone budget on a global scale. In addition iodine-species emitted from the ocean surface have been shown to be responsible for the production of new atmospheric particles in the marine boundary layer. This may have an effect on cloud formation and radiation transfer on local and global scales. Long term measurements of RHS abundances will help to identify their key regions and processes for formation. A new long term Multi-MAX-DOAS instrument has been installed at the SOLAS observatory on the island of Sao Vicente, (Cape Verde). The main focus of these unique measurements is the investigation of reactive halogen chemistry in the subtropical marine boundary layer based on measurements of BrO, IO, and possibly OIO. Because of its wide spectral range also the use for O4-retrievals to gain aerosol profiles is possible. IO has been detected with mixing ratios up to 1.3 ppt. For BrO an upper limit of 2 ppt could be determined.

  17. Toxicity of eight polycyclic aromatic compounds to red clover (Trifolium pratense), ryegrass (Lolium perenne), and mustard (Sinapsis alba)

    DEFF Research Database (Denmark)

    Sverdrup, L.E.; Krogh, P.H.; Nielsen, T.

    2003-01-01

    three weeks of exposure, seed emergence and seedling weight (fresh weight and dry weight) were determined. Exposure concentrations were verified with chemical analysis. The substances tested were four polycyclic aromatic hydrocarbons (fluoranthene, pyrene, phenanthrene and fluorene), the N-, S-, and O...

  18. Formation of halogenated C-, N-DBPs from chlor(am)ination and UV irradiation of tyrosine in drinking water

    International Nuclear Information System (INIS)

    Chu Wenhai; Gao Naiyun; Krasner, Stuart W.; Templeton, Michael R.; Yin Daqiang

    2012-01-01

    The formation of regulated and emerging halogenated carbonaceous (C-) and nitrogenous disinfection by-products (N-DBPs) from the chlor(am)ination and UV irradiation of tyrosine (Tyr) was investigated. Increased chlorine contact time and/or Cl 2 /Tyr ratio increased the formation of most C-DBPs, with the exception of 4-chlorophenol, dichloroacetonitrile, and dichloroacetamideChloroform and dichloroacetic acid increased with increasing pH, dichloroacetonitrile first increased and then decreased, and other DBPs had maximum yields at pH 7 or 8. The addition of ammonia significantly reduced the formation of most C-DBPs but increased 4-chlorophenol, dichloroacetonitrile, dichloroacetamide, and trichloroacetonitrile yields for short prechlorination contact times before dosing ammonia. When UV irradiation and chlorination were performed simultaneously, the concentrations of the relatively stable C-DBPs increased, and the concentrations of dichloroacetonitrile, dichloroacetamide, and 4-chlorophenol decreased with increasing UV dose. This information was used to develop a mechanistic model for the formation of intermediate DBPs and end products from the interaction of disinfectants with tyrosine. Highlights: ► Increased contact time and/or Cl 2 /Tyr decreased the formation of some N-DBPs. ► Changing the pH of disinfection decreases the formation of some N-DBPs. ► N-DBP yields increased for short prechlorination contact time before dosing ammonia. ► Low pressure UV before chlorination did not impact the formation of DBPs from Tyr. ► A novel integrated formation pathway of halogenated C-, N-DBPs is proposed. - Exploring the integrated formation mechanism of regulated and emerging highly toxic DBPs, which is expected to preferably reduce their occurrence in drinking water.

  19. Impact of enhanced ozone deposition and halogen chemistry on model performance

    Science.gov (United States)

    In this study, an enhanced ozone deposition scheme due to the interaction of iodide in sea-water and atmospheric ozone and the detailed chemical reactions of organic and inorganic halogen species are incorporated into the hemispheric Community Multiscale Air Quality model. Prelim...

  20. Tumour radiosensitization with the halogenated pyrimidines 5'-bromo-and 5'-iododeoxyuridine

    International Nuclear Information System (INIS)

    Epstein, A.H.; Cook, J.A.; Goffman, T.; Glatstein, E.

    1993-01-01

    The authors review studies of the use of iododeoxyuridine (IdUrd) and bromodeoxyuridine as radiosensitizers and attempt to correlate the clinical outcome for patients treated with radiation and IdUrd with the extent of halogenated pyrimidine cellular uptake and incorporation. (U.K.)

  1. Airborne persistent toxic substances (PTSs) in China: occurrence and its implication associated with air pollution.

    Science.gov (United States)

    Wang, Pu; Zhang, Qinghua; Li, Yingming; Matsiko, Julius; Zhang, Ya; Jiang, Guibin

    2017-08-16

    In recent years, China suffered from extensive air pollution due to the rapidly expanding economic and industrial developments. Its severe impact on human health has raised great concern currently. Persistent toxic substances (PTSs), a large group of environmental pollutants, have also received much attention due to their adverse effects on both the ecosystem and public health. However, limited studies have been conducted to reveal the airborne PTSs associated with air pollution at the national scale in China. In this review, we summarized the occurrence and variation of airborne PTSs in China, especially in megacities. These PTSs included polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), halogenated flame retardants (HFRs), perfluorinated compounds (PFCs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs) and heavy metals. The implication of their occurrence associated with air pollution was discussed, and the emission source of these chemicals was concluded. Most reviewed studies have been conducted in east and south China with more developed economy and industry. Severe contamination of airborne PTSs generally occurred in megacities with large populations, such as Guangzhou, Shanghai and Beijing. However, the summarized results suggested that industrial production and product consumption are the major sources of most PTSs in the urban environment, while unintentional emission during anthropogenic activities is an important contributor to airborne PTSs. It is important that fine particles serve as a major carrier of most airborne PTSs, which facilitates the long-range atmospheric transport (LRAT) of PTSs, and therefore, increases the exposure risk of the human body to these pollutants. This implied that not only the concentration and chemical composition of fine particles but also the absorbed PTSs are of particular concern when air pollution occurs.

  2. Rigid aromatic linking moiety in cationic lipids for enhanced gene transfection efficiency.

    Science.gov (United States)

    Wang, Bing; Zhao, Rui-Mo; Zhang, Ji; Liu, Yan-Hong; Huang, Zheng; Yu, Qing-Ying; Yu, Xiao-Qi

    2017-08-18

    Although numerous cationic lipids have been developed as non-viral gene vectors, the structure-activity relationship (SAR) of these materials remains unclear and needs further investigation. In this work, a series of lysine-derived cationic lipids containing linkages with different rigidity were designed and synthesized. SAR studies showed that lipids with rigid aromatic linkage could promote the formation of tight liposomes and enhance DNA condensation, which is essential for the gene delivery process. These lipids could give much higher transfection efficiency than those containing more flexible aliphatic linkage in various cell lines. Moreover, the rigid aromatic linkage also affords the material higher serum tolerance ability. Flow cytometry assay revealed that the target lipids have good cellular uptake, while confocal microscopy observation showed weaker endosome escape than Lipofectamine 2000. To solve such problem and further increase the transfection efficiency, some lysosomotropic reagents were used to improve the endosome escape of lipoplex. As expected, higher transfection efficiency than Lipofectamine 2000 could be obtained via this strategy. Cytotoxicity assay showed that these lipids have lower toxicity in various cell lines than Lipofectamine 2000, suggesting their potential for further application. This work demonstrates that a rigid aromatic linkage might distinctly improve the gene transfection abilities of cationic lipids and affords information to construct safe and efficient gene vector towards practical application. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  3. Effect of Ozonation and Biological Activated Carbon Treatment of Wastewater Effluents on Formation of N-nitrosamines and Halogenated Disinfection Byproducts.

    Science.gov (United States)

    Chuang, Yi-Hsueh; Mitch, William A

    2017-02-21

    Ozonation followed by biological activated carbon (O 3 /BAC) is being considered as a key component of reverse osmosis-free advanced treatment trains for potable wastewater reuse. Using a laboratory-scale O 3 /BAC system treating two nitrified wastewater effluents, this study characterized the effect of different ozone dosages (0-1.0 mg O 3 /mg dissolved organic carbon) and BAC empty bed contact times (EBCT; 15-60 min) on the formation after chlorination or chloramination of 35 regulated and unregulated halogenated disinfection byproducts (DBPs), 8 N-nitrosamines, and bromate. DBP concentrations were remarkably similar between the two wastewaters across O 3 /BAC conditions. Ozonation increased bromate, TCNM, and N-nitrosodimethylamine, but ozonation was less significant for other DBPs. DBP formation generally decreased significantly with BAC treatment at 15 min EBCT, but little further reduction was observed at higher EBCT where low dissolved oxygen concentrations may have limited biological activity. The O 3 /BAC-treated wastewaters met regulatory levels for trihalomethanes (THMs), haloacetic acids (HAAs), and bromate, although N-nitrosodimethylamine exceeded the California Notification Level in one case. Regulated THMs and HAAs dominated by mass. When DBP concentrations were weighted by measures of their toxic potencies, unregulated haloacetonitriles, haloacetaldehydes, and haloacetamides dominated. Assuming toxicity is additive, the calculated DBP-associated toxicity of the O 3 /BAC-treated chloraminated effluents were comparable or slightly higher than those calculated in a recent evaluation of Full Advanced Treatment trains incorporating reverse osmosis.

  4. Noncovalent Halogen Bonding as a Mechanism for Gas-Phase Clustering

    DEFF Research Database (Denmark)

    Wegeberg, Christina; Donald, William A.; McKenzie, Christine

    2017-01-01

    in the crystalline phases of PhIO2 and its derivatives serve as models for the structures of larger gas-phase clusters, and calculations on simple model gas-phase dimer and trimer clusters result in similar motifs. This is the first account of halogen bonding playing an extensive role in gas-phase associations....

  5. Transformation among Aromatic Iodinated Disinfection Byproducts in the Presence of Monochloramine: From Monoiodophenol to Triiodophenol and Diiodonitrophenol.

    Science.gov (United States)

    Gong, Tingting; Tao, Yuxian; Zhang, Xiangru; Hu, Shaoyang; Yin, Jinbao; Xian, Qiming; Ma, Jian; Xu, Bin

    2017-09-19

    Aromatic iodinated disinfection byproducts (DBPs) are a newly identified category of highly toxic DBPs. Among the identified aromatic iodinated DBPs, 2,4,6-triiodophenol and 2,6-diiodo-4-nitrophenol have shown relatively widespread occurrence and high toxicity. In this study, we found that 4-iodophenol underwent transformation to form 2,4,6-triiodophenol and 2,6-diiodo-4-nitrophenol in the presence of monochloramine. The transformation pathways were investigated, the decomposition kinetics of 4-iodophenol and the formation of 2,4,6-triiodophenol and 2,6-diiodo-4-nitrophenol were studied, the factors affecting the transformation were examined, the toxicity change during the transformation was evaluated, and the occurrence of the proposed transformation pathways during chloramination of source water was verified. The results revealed that 2,4,6-triiodophenol and 2,6-diiodo-4-nitrophenol, which could account for 71.0% of iodine in the transformed 4-iodophenol, were important iodinated transformation products of 4-iodophenol in the presence of monochloramine. The transformation pathways of 4-iodophenol in the presence of monochloramine were proposed and verified. The decomposition of 4-iodophenol in the presence of monochloramine followed a pseudo-second-order decay. Various factors including monochloramine dose, pH, temperature, nitrite concentration, and free chlorine contact time (before chloramination) affected the transformation. The cytotoxicity of the chloraminated 4-iodophenol samples increased continuously with contact time. The proposed transformation pathways occurred during chloramination of source water.

  6. Unexpected gender difference in sensitivity to the acute toxicity of dioxin in mice

    Energy Technology Data Exchange (ETDEWEB)

    Pohjanvirta, Raimo, E-mail: raimo.pohjanvirta@helsinki.fi [Department of Food Hygiene and Environmental Health, Faculty of Veterinary Medicine, University of Helsinki, P.O. Box 66, FI-00014 University of Helsinki (Finland); Miettinen, Hanna, E-mail: hanna.miettinen@crl.com [Department of Environmental Health, National Institute for Health and Welfare, P.O. Box 95, FI-70701 Kuopio (Finland); Sankari, Satu, E-mail: satu.sankari@helsinki.fi [Central Laboratory of the Department of Equine and Small Animal Medicine, Faculty of Veterinary Medicine, University of Helsinki, P.O. Box 57, FI-00014 University of Helsinki (Finland); Hegde, Nagabhooshan [Department of Food Hygiene and Environmental Health, Faculty of Veterinary Medicine, University of Helsinki, P.O. Box 66, FI-00014 University of Helsinki (Finland); Lindén, Jere, E-mail: jere.linden@helsinki.fi [Department of Food Hygiene and Environmental Health, Faculty of Veterinary Medicine, University of Helsinki, P.O. Box 66, FI-00014 University of Helsinki (Finland); Department of Veterinary Biosciences, Faculty of Veterinary Medicine, University of Helsinki, P.O. Box 66, FI-00014 University of Helsinki (Finland)

    2012-07-15

    The acute toxicity of the ubiquitous environmental contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) varies widely among species and strains. Previous studies in rats have established that females are approximately 2-fold more sensitive to TCDD lethality than males. However, there is a surprising gap in the literature regarding possible gender-related sensitivity differences in mice. In the present study, by using three substrains of TCDD-sensitive C57BL/6 mice and transgenic mice on this background, we demonstrated that: 1) in contrast to the situation in rats, female mice are the more resistant gender; 2) the magnitude of the divergence between male and female mice depends on the substrain, but can amount to over 10-fold; 3) AH receptor protein expression levels or mutations in the primary structure of this receptor are not involved in the resistance of female mice of a C57BL/6 substrain, despite their acute LD{sub 50} for TCDD being over 5000 μg/kg; 4) transgenic mice that globally express the rat wildtype AH receptor follow the mouse type of gender difference; 5) in gonadectomized mice, ovarian estrogens appear to enhance TCDD resistance, whereas testicular androgens seem to augment TCDD susceptibility; and 6) the gender difference correlates best with the severity of liver damage, which is also reflected in hepatic histopathology and the expression of pro-inflammatory cytokines, especially IL-6. Hence, the two closely related rodent species most often employed in toxicological risk characterization studies, rat and mouse, represent opposite examples of the influence of gender on dioxin sensitivity, further complicating the risk assessment of halogenated aromatic hydrocarbons. -- Highlights: ► In contrast to rats, male mice are more sensitive to TCDD toxicity than female mice. ► The resistance of female C57BL/6Kuo mice matches or exceeds that of male DBA/2 mice. ► The resistance of female C57BL/6Kuo mice is not based on AHR structure or abundance.

  7. Unexpected gender difference in sensitivity to the acute toxicity of dioxin in mice

    International Nuclear Information System (INIS)

    Pohjanvirta, Raimo; Miettinen, Hanna; Sankari, Satu; Hegde, Nagabhooshan; Lindén, Jere

    2012-01-01

    The acute toxicity of the ubiquitous environmental contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) varies widely among species and strains. Previous studies in rats have established that females are approximately 2-fold more sensitive to TCDD lethality than males. However, there is a surprising gap in the literature regarding possible gender-related sensitivity differences in mice. In the present study, by using three substrains of TCDD-sensitive C57BL/6 mice and transgenic mice on this background, we demonstrated that: 1) in contrast to the situation in rats, female mice are the more resistant gender; 2) the magnitude of the divergence between male and female mice depends on the substrain, but can amount to over 10-fold; 3) AH receptor protein expression levels or mutations in the primary structure of this receptor are not involved in the resistance of female mice of a C57BL/6 substrain, despite their acute LD 50 for TCDD being over 5000 μg/kg; 4) transgenic mice that globally express the rat wildtype AH receptor follow the mouse type of gender difference; 5) in gonadectomized mice, ovarian estrogens appear to enhance TCDD resistance, whereas testicular androgens seem to augment TCDD susceptibility; and 6) the gender difference correlates best with the severity of liver damage, which is also reflected in hepatic histopathology and the expression of pro-inflammatory cytokines, especially IL-6. Hence, the two closely related rodent species most often employed in toxicological risk characterization studies, rat and mouse, represent opposite examples of the influence of gender on dioxin sensitivity, further complicating the risk assessment of halogenated aromatic hydrocarbons. -- Highlights: ► In contrast to rats, male mice are more sensitive to TCDD toxicity than female mice. ► The resistance of female C57BL/6Kuo mice matches or exceeds that of male DBA/2 mice. ► The resistance of female C57BL/6Kuo mice is not based on AHR structure or abundance.

  8. Phototoxicity of individual polycyclic aromatic hydrocarbons and petroleum to marine invertebrate larvae and juveniles

    International Nuclear Information System (INIS)

    Pelletier, M.C.; Burgess, R.M.; Ho, K.T.; Kuhn, A.; McKinney, R.A.; Ryba, S.A.

    1997-01-01

    Phototoxicity resulting from photoactivated polycyclic aromatic hydrocarbons (PAHs) has been reported in the literature for a variety of freshwater organisms. The magnitude of increase in PAH toxicity often exceeds a factor of 100. In the marine environment phototoxicity to marine organisms has not been reported for individual or complex mixtures of PAHs. In this study, larvae and juveniles of the bivalve, Mulinia lateralis, and juveniles of the mysid shrimp, Mysidopsis bahia, were exposed to individual known phototoxic PAHs (anthracene, fluoranthene, pyrene), as well as the water-accommodated fractions of several petroleum products (Fuel Oil number-sign 2, Arabian Light Crude, Prudhoe Bay Crude, Fuel Oil number-sign 6) containing PAHs. Phototoxicity of individual PAHs was 12 to >50,000 times that of conventional toxicity. Three of the petroleum products demonstrated phototoxicity while the lightest product, Fuel Oil number-sign 2, was not phototoxic at the concentrations tested. The phototoxicity of petroleum products appears to be dependent on the composition and concentrations of phototoxic PAHs present: lighter oils have fewer multiple aromatic ring, phototoxic compounds while heavier oils have higher levels of these types of molecules. This study shows that phototoxicity can occur in marine waters to marine species. Further, the occurrence of oil in marine waters presents the additional risk of phototoxicity not routinely assessed for during oil spills

  9. Radiation-induced DNA damage in halogenated pyrimidine incorporated cells and its correlation with radiosensitivity

    International Nuclear Information System (INIS)

    Watanabe, R.; Nikjoo, H.

    2003-01-01

    Cells with DNA containing 5-halogenated pyrimidines in place of thymidine show significant reductions of slope (Do) and shoulder (Dq) of their radiation survival curves. Similar radiosensitization has also been observed in the yield of DNA strand breaks. The purpose of this study is to obtain an insight into the mechanism of cell lethality by examining the relationship between the spectrum of DNA damage and the cell survival. In this study we estimated the enhancement of strand breaks due to incorporation of halogenated pyrimidine, the complexity of DNA damage and the probability of the initial DNA damage leading to cell inactivation. Monte Carlo track structure methods were used to model and simulate the induction of strand breakage by X-rays. The increase of DNA strand break was estimated by assuming the excess strand break was caused by the highly reactive uracil radicals at the halouracil substituted sites. The assumption of the enhancement mechanism of strand breaks was examined and verified by comparison with experimental data for induction of SSB and DSB. The calculated DNA damage spectrum shows the increase in complexity of strand breaks is due to incorporation of halogenated pyrimidines. The increase in the yield of DSB and cell lethality show similar trend at various degrees of halogenated pyrimidine substitution. We asked the question whether this agreement supports the hypothesis that DSB is responsible for cell lethality? The estimated number of lethal damage from the cell survival using a linear-quadratic model is much less than the initial yield of DSB. This work examines the correlation of cell lethality as a function of frequencies of complex form of double strand breaks

  10. to view fulltext PDF

    Indian Academy of Sciences (India)

    The nucleophilic displacement of a halogen atom attached to an aromatic ~ng is not a very favourable process.l. Polyfluorinated aromatics are interesting in this regard, since the fluorine atom can act as a leaving group, as well as an activating group. Hexafluorobenzene, therefore, has been a popular molecule to exam- ine ...

  11. Strong CH/O interactions between polycyclic aromatic hydrocarbons and water: Influence of aromatic system size.

    Science.gov (United States)

    Veljković, Dušan Ž

    2018-03-01

    Energies of CH/O interactions between water molecule and polycyclic aromatic hydrocarbons with a different number of aromatic rings were calculated using ab initio calculations at MP2/cc-PVTZ level. Results show that an additional aromatic ring in structure of polycyclic aromatic hydrocarbons significantly strengthens CH/O interactions. Calculated interaction energies in optimized structures of the most stable tetracene/water complex is -2.27 kcal/mol, anthracene/water is -2.13 kcal/mol and naphthalene/water is -1.97 kcal/mol. These interactions are stronger than CH/O contacts in benzene/water complex (-1.44 kcal/mol) while CH/O contacts in tetracene/water complex are even stronger than CH/O contacts in pyridine/water complexes (-2.21 kcal/mol). Electrostatic potential maps for different polycyclic aromatic hydrocarbons were calculated and used to explain trends in the energies of interactions. Copyright © 2017 Elsevier Inc. All rights reserved.

  12. Multicomponent mixed dopant optimization for rapid screening of polycyclic aromatic hydrocarbons using ultra high performance liquid chromatography coupled to atmospheric pressure photoionization high-resolution mass spectrometry

    KAUST Repository

    Sioud, Salim; Amad, Maan H.; Al-Talla, Zeyad

    2012-01-01

    with water-soluble organic solvents. In order to achieve a more efficient and less toxic dopant, a multicomponent mixed dopant was explored. METHODS A multicomponent mixed dopant for non-targeted rapid screening of polycyclic aromatic hydrocarbons (PAHs

  13. Occurrence and Concentrations of Toxic VOCs in the Ambient Air of Gumi, an Electronics-Industrial City in Korea

    Directory of Open Access Journals (Sweden)

    Sung-Ok Baek

    2015-08-01

    Full Text Available This study was carried out to characterize the occurrence and concentrations of a variety of volatile organic compounds (VOCs including aliphatic, aromatic, halogenated, nitrogenous, and carbonyl compounds, in the ambient air of Gumi City, where a large number of electronics industries are found. Two field monitoring campaigns were conducted for a one year period in 2003/2004 and 2010/2011 at several sampling sites in the city, representing industrial, residential and commercial areas. More than 80 individual compounds were determined in this study, and important compounds were then identified according to their abundance, ubiquity and toxicity. The monitoring data revealed toluene, trichloroethylene and acetaldehyde to be the most significant air toxics in the city, and their major sources were mainly industrial activities. On the other hand, there was no clear evidence of an industrial impact on the concentrations of benzene and formaldehyde in the ambient air of the city. Overall, seasonal variations were not as distinct as locational variations in the VOCs concentrations, whereas the within-day variations showed a typical pattern of urban air pollution, i.e., increase in the morning, decrease in the afternoon, and an increase again in the evening. Considerable decreases in the concentrations of VOCs from 2003 to 2011 were observed. The reductions in the ambient concentrations were confirmed further by the Korean PRTR data in industrial emissions within the city. Significant decreases in the concentrations of benzene and acetaldehyde were also noted, whereas formaldehyde appeared to be almost constant between the both campaigns. The decreased trends in the ambient levels were attributed not only to the stricter regulations for VOCs in Korea, but also to the voluntary agreement of major companies to reduce the use of organic solvents. In addition, a site planning project for an eco-friendly industrial complex is believed to play a contributory

  14. Effects of biochar and the earthworm Eisenia fetida on the bioavailability of polycyclic aromatic hydrocarbons and potentially toxic elements

    International Nuclear Information System (INIS)

    Gomez-Eyles, Jose L.; Sizmur, Tom; Collins, Chris D.; Hodson, Mark E.

    2011-01-01

    Polycyclic aromatic hydrocarbons (PAHs) and potentially toxic elements (PTEs) were monitored over 56 days in calcareous contaminated-soil amended with either or both biochar and Eisenia fetida. Biochar reduced total (449 to 306 mg kg -1 ) and bioavailable (cyclodextrin extractable) (276 to 182 mg kg -1 ) PAHs, PAH concentrations in E. fetida (up to 45%) but also earthworm weight. Earthworms increased PAH bioavailability by >40%. Combined treatment results were similar to the biochar-only treatment. Earthworms increased water soluble Co (3.4 to 29.2 mg kg -1 ), Cu (60.0 to 120.1 mg kg -1 ) and Ni (31.7 to 83.0 mg kg -1 ) but not As, Cd, Pb or Zn; biochar reduced water soluble Cu (60 to 37 mg kg -1 ). Combined treatment results were similar to the biochar-only treatment but gave a greater reduction in As and Cd mobility. Biochar has contaminated land remediation potential, but its long-term impact on contaminants and soil biota needs to be assessed. - Research highlights: → Biochar reduced total and bioavailable PAH concentrations. → Biochar was less effective at immobilising PTEs, due to its low cation exchange capacity. → E. fetida increased PAH bioavailability and PTE mobility. → When used in combination biochar reduced the concentration of PTEs mobilised by E. fetida. → Biochar had a negative effect on E. fetida in terms of weight loss. - Biochar decreased PAH biovailability but was less effective at reducing PTE mobility, whilst E. fetida increased both PAH and PTE bioavailability.

  15. Effects of biochar and the earthworm Eisenia fetida on the bioavailability of polycyclic aromatic hydrocarbons and potentially toxic elements

    Energy Technology Data Exchange (ETDEWEB)

    Gomez-Eyles, Jose L., E-mail: j.l.gomezeyles@reading.ac.u [University of Reading, School of Human and Environmental Sciences, Soil Research Centre, Reading, RG6 6DW Berkshire (United Kingdom); Sizmur, Tom; Collins, Chris D.; Hodson, Mark E. [University of Reading, School of Human and Environmental Sciences, Soil Research Centre, Reading, RG6 6DW Berkshire (United Kingdom)

    2011-02-15

    Polycyclic aromatic hydrocarbons (PAHs) and potentially toxic elements (PTEs) were monitored over 56 days in calcareous contaminated-soil amended with either or both biochar and Eisenia fetida. Biochar reduced total (449 to 306 mg kg{sup -1}) and bioavailable (cyclodextrin extractable) (276 to 182 mg kg{sup -1}) PAHs, PAH concentrations in E. fetida (up to 45%) but also earthworm weight. Earthworms increased PAH bioavailability by >40%. Combined treatment results were similar to the biochar-only treatment. Earthworms increased water soluble Co (3.4 to 29.2 mg kg{sup -1}), Cu (60.0 to 120.1 mg kg{sup -1}) and Ni (31.7 to 83.0 mg kg{sup -1}) but not As, Cd, Pb or Zn; biochar reduced water soluble Cu (60 to 37 mg kg{sup -1}). Combined treatment results were similar to the biochar-only treatment but gave a greater reduction in As and Cd mobility. Biochar has contaminated land remediation potential, but its long-term impact on contaminants and soil biota needs to be assessed. - Research highlights: Biochar reduced total and bioavailable PAH concentrations. Biochar was less effective at immobilising PTEs, due to its low cation exchange capacity. E. fetida increased PAH bioavailability and PTE mobility. When used in combination biochar reduced the concentration of PTEs mobilised by E. fetida. Biochar had a negative effect on E. fetida in terms of weight loss. - Biochar decreased PAH biovailability but was less effective at reducing PTE mobility, whilst E. fetida increased both PAH and PTE bioavailability.

  16. Melanosomal formation of PMEL core amyloid is driven by aromatic residues.

    Science.gov (United States)

    Hee, Jia Shee; Mitchell, Susan M; Liu, Xinran; Leonhardt, Ralf M

    2017-03-08

    PMEL is a pigment cell protein that forms physiological amyloid in melanosomes. Many amyloids and/or their oligomeric precursors are toxic, causing or contributing to severe, incurable diseases including Alzheimer's and prion diseases. Striking similarities in intracellular formation pathways between PMEL and various pathological amyloids including Aβ and PrP Sc suggest PMEL is an excellent model system to study endocytic amyloid. Learning how PMEL fibrils assemble without apparent toxicity may help developing novel therapies for amyloid diseases. Here we identify the critical PMEL domain that forms the melanosomal amyloid core (CAF). An unbiased alanine-scanning screen covering the entire region combined with quantitative electron microscopy analysis of the full set of mutants uncovers numerous essential residues. Many of these rely on aromaticity for function suggesting a role for π-stacking in melanosomal amyloid assembly. Various mutants are defective in amyloid nucleation. This extensive data set informs the first structural model of the CAF and provides insights into how the melanosomal amyloid core forms.

  17. Atmospheric chlorinated polycyclic aromatic hydrocarbons in East Asia.

    Science.gov (United States)

    Kakimoto, Kensaku; Nagayoshi, Haruna; Konishi, Yoshimasa; Kajimura, Keiji; Ohura, Takeshi; Hayakawa, Kazuichi; Toriba, Akira

    2014-09-01

    This study estimates atmospheric concentrations of chlorinated polycyclic aromatic hydrocarbons (ClPAHs) and polycyclic aromatic hydrocarbons (PAHs) in East Asia using a Gas Chromatograph with High Resolution Mass Spectrometer (GC-HRMS). ClPAHs are ubiquitously generated from PAHs through substitution, and some ClPAHs show higher aryl hydrocarbon receptor (AhR)-mediated activities than their parent PAHs. Atmospheric particles were collected using a high-volume air sampler equipped with a quartz-fiber filter. We determined the ClPAH concentrations of atmospheric particles collected in Japan (Sapporo, Sagamihara, Kanazawa, and Kitakyushu), Korea (Busan), and China (Beijing). The concentrations of ClPAHs were highest in the winter Beijing sample, where the total mean concentration was approximately 15-70 times higher than in the winter samples from Japan and Korea. The concentrations of Σ19ClPAHs and Σ9PAHs were significantly correlated in the Kanazawa and the Busan samples. This indicates that within those cities ClPAHs and PAHs share the same origin, implying direct chlorination of parent PAHs. Toxic equivalent concentrations (TEQs) of the total ClPAHs and PAHs were lowest in Kanazawa in the summer, reaching 1.18 and 2610fg-TEQm(-3) respectively, and highest in Beijing in the winter, reaching 627 and 4240000fg-TEQm(-3) respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. Cooperativity of halogen, chalcogen, and pnictogen bonds in infinite molecular chains by electronic structure theory.

    Science.gov (United States)

    George, Janine; Deringer, Volker L; Dronskowski, Richard

    2014-05-01

    Halogen bonds (XBs) are intriguing noncovalent interactions that are frequently being exploited for crystal engineering. Recently, similar bonding mechanisms have been proposed for adjacent main-group elements, and noncovalent "chalcogen bonds" and "pnictogen bonds" have been identified in crystal structures. A fundamental question, largely unresolved thus far, is how XBs and related contacts interact with each other in crystals; similar to hydrogen bonding, one might expect "cooperativity" (bonds amplifying each other), but evidence has been sparse. Here, we explore the crucial step from gas-phase oligomers to truly infinite chains by means of quantum chemical computations. A periodic density functional theory (DFT) framework allows us to address polymeric chains of molecules avoiding the dreaded "cluster effects" as well as the arbitrariness of defining a "large enough" cluster. We focus on three types of molecular chains that we cut from crystal structures; furthermore, we explore reasonable substitutional variants in silico. We find evidence of cooperativity in chains of halogen cyanides and also in similar chalcogen- and pnictogen-bonded systems; the bonds, in the most extreme cases, are amplified through cooperative effects by 79% (I···N), 90% (Te···N), and 103% (Sb···N). Two experimentally known organic crystals, albeit with similar atomic connectivity and XB characteristics, show signs of cooperativity in one case but not in another. Finally, no cooperativity is observed in alternating halogen/acetone and halogen/1,4-dioxane chains; in fact, these XBs weaken each other by up to 26% compared to the respective gas-phase dimers.

  19. Development of a chronic sediment toxicity test for marine benthic amphipods

    International Nuclear Information System (INIS)

    DeWitt, T.H.; Redmond, M.S.; Sewall, J.E.; Swartz, R.C.

    1992-12-01

    The results of the research effort culminated in the development of a research method for assessing the chronic toxicity of contaminated marine and estuarine sediments using the benthic amphipod, Leptocheirus plumulosus. The first chapter describes the efforts at collecting, handling, and culturing four estuarine amphipods from Chesapeake Bay, including L. plumulosus. This chapter includes maps of the distribution and abundance of these amphipods within Chesapeake Bay and methodologies for establishing cultures of amphipods which could be readily adopted by other laboratories. The second chapter reports the development of acute and chronic sediment toxicity test methods for L. plumulosus, its sensitivity to non-contaminant environmental variables, cadmium, two polynuclear aromatic hydrocarbons, and contaminated sediment from Baltimore Harbor, MD. The third chapter reports the authors attempts to develop a chronic sediment toxicity test with Ampelisca abdita

  20. High-energy-density hydrogen-halogen fuel cells for advanced military applications

    International Nuclear Information System (INIS)

    Balko, E.N.; McElroy, J.F.

    1981-01-01

    It is pointed out that hydrogen-halogen fuel cell systems are particularly suited for an employment as ground power sources for military applications. The large cell potential and reversible characteristics of the H 2 Cl 2 and H 2 Br 2 couples permit high energy storage density and efficient energy conversion. When used as flow batteries, the fluid nature of the reactants in the hydrogen-halogen systems has several advantages over power sources which involve solid phases. Very deep discharge is possible without degradation of subsequent performance, and energy storage capacity is limited only by the external reactant storage volume. Very rapid chemical recharging is possible through replenishment of the reactant supply. A number of H 2 Cl 2 and H 2 Br 2 fuel cell systems have been studied. These systems use the same solid polymer electrolyte (SPE) cell technology originally developed for H2/O2 fuel cells. The results of the investigation are illustrated with the aid of a number of graphs

  1. Pulse shape discrimination in non-aromatic plastics

    Energy Technology Data Exchange (ETDEWEB)

    Paul Martinez, H.; Pawelczak, Iwona; Glenn, Andrew M.; Leslie Carman, M.; Zaitseva, Natalia; Payne, Stephen

    2015-01-21

    Recently it has been demonstrated that plastic scintillators have the ability to distinguish neutrons from gamma rays by way of pulse shape discrimination (PSD). This discovery has lead to new materials and new capabilities. Here we report our work with the effects of aromatic, non-aromatic, and mixed aromatic/non-aromatic matrices have on the performance of PSD plastic scintillators.

  2. Selective hydrogenation of halogenated arenes using porous manganese oxide (OMS-2) and platinum supported OMS-2 catalysts.

    Science.gov (United States)

    McManus, Iain J; Daly, Helen; Manyar, Haresh G; Taylor, S F Rebecca; Thompson, Jillian M; Hardacre, Christopher

    2016-07-04

    Porous manganese oxide (OMS-2) and platinum supported on OMS-2 catalysts have been shown to facilitate the hydrogenation of the nitro group in chloronitrobenzene to give chloroaniline with no dehalogenation. Complete conversion was obtained within 2 h at 25 °C and, although the rate of reaction increased with increasing temperature up to 100 °C, the selectivity to chloroaniline remained at 99.0%. Use of Pd/OMS-2 or Pt/Al2O3 resulted in significant dechlorination even at 25 °C and 2 bar hydrogen pressure giving a selectivity to chloroaniline of 34.5% and 77.8%, respectively, at complete conversion. This demonstrates the potential of using platinum group metal free catalysts for the selective hydrogenation of halogenated aromatics. Two pathways were observed for the analogous nitrobenzene hydrogenation depending on the catalyst used. The hydrogenation of nitrobenzene was found to follow a direct pathway to aniline and nitrosobenzene over Pd/OMS-2 in contrast to the OMS and Pt/OMS-2 catalysts which resulted in formation of nitrosobenzene, azoxybenzene and azobenzene/hydrazobenzene intermediates before complete conversion to aniline. These results indicate that for Pt/OMS-2 the hydrogenation proceeds predominantly over the support with the metal acting to dissociate hydrogen. In the case of Pd/OMS-2 both the hydrogenation and hydrogen adsorption occur on the metal sites.

  3. Impact of bromide on halogen incorporation into organic moieties in chlorinated drinking water treatment and distribution systems.

    Science.gov (United States)

    Tan, J; Allard, S; Gruchlik, Y; McDonald, S; Joll, C A; Heitz, A

    2016-01-15

    The impact of elevated bromide concentrations (399 to 750 μg/L) on the formation of halogenated disinfection by-products (DBPs), namely trihalomethanes, haloacetic acids, haloacetonitriles, and adsorbable organic halogen (AOX), in two drinking water systems was investigated. Bromine was the main halogen incorporated into all of the DBP classes and into organic carbon, even though chlorine was present in large excess to maintain a disinfectant residual. Due to the higher reactivity of bromine compared to chlorine, brominated DBPs were rapidly formed, followed by a slower increase in chlorinated DBPs. Higher bromine substitution and incorporation factors for individual DBP classes were observed for the chlorinated water from the groundwater source (lower concentration of dissolved organic carbon (DOC)), which contained a higher concentration of bromide, than for the surface water source (higher DOC). The molar distribution of adsorbable organic bromine to chlorine (AOBr/AOCl) for AOX in the groundwater distribution system was 1.5:1 and almost 1:1 for the surface water system. The measured (regulated) DBPs only accounted for 16 to 33% of the total organic halogen, demonstrating that AOX measurements are essential to provide a full understanding of the formation of halogenated DBPs in drinking waters. In addition, the study demonstrated that a significant proportion (up to 94%) of the bromide in source waters can be converted AOBr. An evaluation of AOBr and AOCl through a second groundwater treatment plant that uses conventional treatment processes for DOC removal produced 70% of AOX as AOBr, with 69% of the initial source water bromide converted to AOBr. Exposure to organobromine compounds is suspected to result in greater adverse health consequences than their chlorinated analogues. Therefore, this study highlights the need for improved methods to selectively reduce the bromide content in source waters. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1979-February 14, 1980

    Energy Technology Data Exchange (ETDEWEB)

    Rack, E.P.

    1980-02-01

    The program consists of six interrelated areas: (1) Reactions of iodine with alkenes and alkynes activated by radiative neutron capture and isomeric transition in low pressure gaseous systems employing additives and rare gas moderators, high pressure, and liquid systems. Special attention was given to the reactivity of excited complex formation and structural effects of electrophilic iodine attack on various pi-bond systems. (2) The gas-to-condensed phase transition in halogen high energy chemistry. Current interest involves the study of caging effects of an ice lattice on recombination reactions involving neutron-irradiated frozen aqueous solutions of halogenated organic and biochemical solutes in order to learn more about kinetic energy effects, halogen size, solute molecule size, steric effects and hydrogen bonding within an ice lattice cage. (3) Systematics of halogen hot atom reactions. The reactions of /sup 80m/Br, /sup 80/Br, /sup 82m/Br + /sup 82/Br, /sup 82/Br, /sup 82/Br, /sup 128/I, /sup 130/I, and /sup 130m/I + /sup 130/I activated by radiative neutron capture or isomeric transition in hydrocarbons and halo-substituted alkanes in low pressure and high pressure gaseous systems employing additives and rare gas moderators are currently being studied. (4) Mathematical and computer simulation studies of caging events within an ice lattice are being investigated. (5) At Brookhaven National Laboratory, cyclotron-produced chlorine and fluorine hot atoms substitution reactions with molecules possessing a single chiral center are under investigation to determine the role of hot atom kinetic energy, halogen atom, enantioner structure, steric effects and phase on the extent of substitution by retention of configuration or by Walden inversion. (6) The applications of high energy techniques and concepts to neutron activation analysis for trace element determinations in biological systems was continued.

  5. Cellular effects of halogen blue light from dental curing unit

    International Nuclear Information System (INIS)

    Trosic, I.; Pavicic, I.; Jukic, S.

    2008-01-01

    Full text: Halogen curing lights are the most frequently used polymerization source in dental offices. Light-cured bonding systems have become increasingly popular among clinicians because they offer a number of advantages over self-cured adhesives. The effort to increase polymerization quality releases the commercially available high power light density dental curing units. Emitted visible blue light belongs to the range of nonionizing radiation. Common concern in both, patients and dentist grows with regard to the unfavorable effects on the pulp tissue. The aim of study was to evaluate the time and dose dependence effect of halogen light curing unit (Elipar TriLight, ESPE Dental AG, Germany) at the disposed condition modes in vitro. A quartz-tungsten-halogen light source emits radiation of the wavelengths between 400 and 515 nm. This halogen blue light source operates in the three illumination modes, medium (M), exponential (E) and standard (S), and five illumination times. The total irradiance or the light intensity was measured by the light intensity control area on the control panel of device and mean light intensity given by manufacturer was 800 m W/cm 2 . Continuous culture of V79 cells was illuminated in triplicate. The influence of medium mode (M), exponential (E) and standard (S) illumination during 20, 40 and 80 sec on the cell viability, colony forming ability and proliferation of V79 cell culture was investigated. Trypan blue exclusion test was used to determine cell viability, both, in the treated and control cell samples. Colony forming ability was assessed for each exposure time and mode by colony count on post-exposure day 7. Cell proliferation was determined by cell counts for each time and mode of exposure during five post-exposure days. Statistical difference were determined at p<0.05 (Statistica 7.0, StatSoft Inc., USA). Viability of cells was not affected by blue light in view of exposure time and modes. Regardless to exposure or illumination

  6. Structural study of some halogen oxyfluorides

    International Nuclear Information System (INIS)

    Tantot, Georges.

    1976-12-01

    Some halogen oxyfluorides are studied from a structural point of view by vibrational spectroscopy and nuclear magnetic resonance. Force constant and molecular orbital calculations are added to the experimental data. The pyramidal shape of ClO 2 F under its three physical states is confirmed. In the gas and liquid phases an intermolecular association is observed. A similar interaction takes place in ClOF 3 . ClO 3 F has only a solid state transition above 10K. The structures of ClO 2 F and KBrO 2 F 2 are partly determined. The theoretical calculations are well correlated with the experimental data. They suggest a major influence of the ligands [fr

  7. Microbial reductive dehalogenation.

    Science.gov (United States)

    Mohn, W W; Tiedje, J M

    1992-01-01

    A wide variety of compounds can be biodegraded via reductive removal of halogen substituents. This process can degrade toxic pollutants, some of which are not known to be biodegraded by any other means. Reductive dehalogenation of aromatic compounds has been found primarily in undefined, syntrophic anaerobic communities. We discuss ecological and physiological principles which appear to be important in these communities and evaluate how widely applicable these principles are. Anaerobic communities that catalyze reductive dehalogenation appear to differ in many respects. A large number of pure cultures which catalyze reductive dehalogenation of aliphatic compounds are known, in contrast to only a few organisms which catalyze reductive dehalogenation of aromatic compounds. Desulfomonile tiedjei DCB-1 is an anaerobe which dehalogenates aromatic compounds and is physiologically and morphologically unusual in a number of respects, including the ability to exploit reductive dehalogenation for energy metabolism. When possible, we use D. tiedjei as a model to understand dehalogenating organisms in the above-mentioned undefined systems. Aerobes use reductive dehalogenation for substrates which are resistant to known mechanisms of oxidative attack. Reductive dehalogenation, especially of aliphatic compounds, has recently been found in cell-free systems. These systems give us an insight into how and why microorganisms catalyze this activity. In some cases transition metal complexes serve as catalysts, whereas in other cases, particularly with aromatic substrates, the catalysts appear to be enzymes. Images PMID:1406492

  8. Graphene and graphene nanocomposites for the removal of aromatic organic compounds from the water: systematic review

    Science.gov (United States)

    Monsores Paixão, Monique; Tadeu Gomes Vianna, Marco; Marques, Marcia

    2018-01-01

    Aromatic organic pollutants are highly toxic to the human and environmental health and are considered as priority pollutants by regulatory agencies. Managing contaminated sites with organic pollutants is one of the major environmental challenges today. Of all technologies that have been proposed to remove contaminants, adsorption is recognized worldwide as an attractive option due to its versatility, wide applicability and economic viability. Recent studies report the use of graphene (GN), a recently carbon nanomaterial, and its derivatives in sorption processes for the removal of aromatic organic compounds. The present review has shown that GN structures are a promising alternative to traditional adsorbent materials, with excellent results in the removal of organic compounds from water, due to their unique structural characteristics and great adsorption capacity for organic compounds. Although, there is still a long way to go until that practical applications can be implemented.

  9. Aromatic-Aromatic Interactions in Biological System: Structure Activity Relationships

    International Nuclear Information System (INIS)

    Rajagopal, Appavu; Deepa, Mohan; Govindaraju, Munisamy

    2016-01-01

    While, intramolecular hydrogen bonds have attracted the greatest attention in studies of peptide conformations, the recognition that several other weakly polar interactions may be important determinants of folded structure has been growing. Burley and Petsko provided a comprehensive overview of the importance of weakly polar interactions, in shaping protein structures. The interactions between aromatic rings, which are spatially approximate, have attracted special attention. A survey of the proximal aromatic residue pairs in proteins, allowed Burley and Petsko to suggest that, “phenyl ring centroids are separated by a preferential distance of between 4.5 and 7 Å, and dihedral angles approximately 90° are most common”

  10. Aromatic-Aromatic Interactions in Biological System: Structure Activity Relationships

    Energy Technology Data Exchange (ETDEWEB)

    Rajagopal, Appavu; Deepa, Mohan [Molecular Biophysics Unit, Indian Institute of Sciences-Bangalore, Karnataka (India); Govindaraju, Munisamy [Bio-Spatial Technology Research Unit, Department of Environmental Biotechnology, School of Environmental Sciences, Bharathidasan University, Tiruchirappalli, Tamil Nadu (India)

    2016-02-26

    While, intramolecular hydrogen bonds have attracted the greatest attention in studies of peptide conformations, the recognition that several other weakly polar interactions may be important determinants of folded structure has been growing. Burley and Petsko provided a comprehensive overview of the importance of weakly polar interactions, in shaping protein structures. The interactions between aromatic rings, which are spatially approximate, have attracted special attention. A survey of the proximal aromatic residue pairs in proteins, allowed Burley and Petsko to suggest that, “phenyl ring centroids are separated by a preferential distance of between 4.5 and 7 Å, and dihedral angles approximately 90° are most common”.

  11. Organic Pollutants in Shale Gas Flowback and Produced Waters: Identification, Potential Ecological Impact, and Implications for Treatment Strategies

    Science.gov (United States)

    2017-01-01

    Organic contaminants in shale gas flowback and produced water (FPW) are traditionally expressed as total organic carbon (TOC) or chemical oxygen demand (COD), though these parameters do not provide information on the toxicity and environmental fate of individual components. This review addresses identification of individual organic contaminants in FPW, and stresses the gaps in the knowledge on FPW composition that exist so far. Furthermore, the risk quotient approach was applied to predict the toxicity of the quantified organic compounds for fresh water organisms in recipient surface waters. This resulted in an identification of a number of FPW related organic compounds that are potentially harmful namely those compounds originating from shale formations (e.g., polycyclic aromatic hydrocarbons, phthalates), fracturing fluids (e.g., quaternary ammonium biocides, 2-butoxyethanol) and downhole transformations of organic compounds (e.g., carbon disulfide, halogenated organic compounds). Removal of these compounds by FPW treatment processes is reviewed and potential and efficient abatement strategies are defined. PMID:28376616

  12. Induction and prevention of micronuclei and chromosomal aberrations in cultured human lymphocytes exposed to the light of halogen tungsten lamps.

    Science.gov (United States)

    D'Agostini, F; Caimo, A; De Filippi, S; De Flora, S

    1999-07-01

    Previous studies have shown that the light emitted by halogen tungsten lamps contains UV radiation in the UV-A, UV-B and UV-C regions, induces mutations and irreparable DNA damage in bacteria, enhances the frequency of micronuclei in cultured human lymphocytes and is potently carcinogenic to the skin of hairless mice. The present study showed that the light emitted by an uncovered, traditional halogen lamp induces a significant, dose-related and time-related increase not only in micronuclei but also in chromosome-type aberrations, such as breaks, and even more in chromatid-type aberrations, such as isochromatid breaks, exchanges and isochromatid/chromatid interchanges, all including gaps or not, in cultured human lymphocytes. All these genotoxic effects were completely prevented by shielding the same lamp with a silica glass cover, blocking UV radiation. A new model of halogen lamp, having the quartz bulb treated in order to reduce the output of UV radiation, was considerably less genotoxic than the uncovered halogen lamp, yet induction of chromosomal alterations was observed at high illuminance levels.

  13. Biotoxicity assessment and toxicity mechanism on coal gasification wastewater (CGW): A comparative analysis of effluent from different treatment processes.

    Science.gov (United States)

    Ma, Weiwei; Han, Yuxing; Xu, Chunyan; Han, Hongjun; Zhu, Hao; Li, Kun; Zheng, Mengqi

    2018-05-04

    Even though coal gasification wastewater (CGW) treated by various biochemical treatment processes generally met the national discharge standard, its potential biotoxicity was still unknown. Therefore, in this study, bioassay with Tetrahymena thermophila (T. thermophila) was conducted to comprehensively evaluate the variation of biotoxicity in raw CGW and the treated effluent from lab-scale micro-electrolysis integrated with biological reactor (MEBR), single iron-carbon micro-electrolysis (ICME) and conventional activated sludge (CAS) processes. The results illustrated that raw CGW presented intensive acute toxicity with 24 h EC 50 value of 8.401% and toxic unit (TU) value of 11.90. Moreover, it performed significant cell membrane destruction and DNA damage even at 10% dilution concentration. The toxicant identification results revealed that multiple toxic polar compounds such as phenolic, heterocyclic and polycyclic aromatic compounds were the main contributors for biotoxicity. Furthermore, these compounds could accelerate oxidative stress, thereby inducing oxidative damage of cell membrane and DNA. As for treated effluent, TU value was decreased by 90.58% in MEBR process. An effective biotoxicity reduction was achieved in MEBR process owing to high removal efficiency in polar organic toxicants. In contrast, effluent from ICME and CAS processes presented relatively high acute toxicity and genotoxicity, because various heterocyclic and polycyclic aromatic compounds were difficult to be degraded in these processes. Therefore, it was suggested that MEBR was a potential and feasible process for improving CGW treatment and minimizing ecological risk. Copyright © 2018. Published by Elsevier B.V.

  14. SYNTHESIZING DERIVATIVES FROM CYCLOPENTANONE ANALOGUE CURCUMIN AND THEIR TOXIC, ANTIOXIDANT AND ANTI-INFLAMMATORY ACTIVITIES

    Directory of Open Access Journals (Sweden)

    Adel Zamri1

    2011-11-01

    Full Text Available Three types of cyclopentanone derivatives have been synthesized from aromatic aldehyde and ketone derivatives undera base condition through aldol condensation. These cyclopentanone products were 2,5-dibenzylidene-cyclopentanone(a, 2,5-bis-(4-hydroxy-benzylidene-cyclopentanone (b, and 2,5-bis-(4-hydroxy-benzylidene-cyclopentanone (cwhich has a yield of 63-99%. The chemical structure of these compounds were determined using UV, IR and NMRspectroscopy. In order to clarify the role of hydroxyl and amine moieties, toxic, antioxidant and anti-inflammatoryactivities were carried out. The toxic test indicated that the compounds showed strong toxicity. In addition, the presenceof hydroxyl and amine groups on both rings of curcumin increased the antioxidant and anti-inflammatory activities

  15. Persistence and dioxin-like toxicity of carbazole and chlorocarbazoles in soil.

    Science.gov (United States)

    Mumbo, John; Henkelmann, Bernhard; Abdelaziz, Ahmed; Pfister, Gerd; Nguyen, Nghia; Schroll, Reiner; Munch, Jean Charles; Schramm, Karl-Werner

    2015-01-01

    Halogenated carbazoles have recently been detected in soil and water samples, but their environmental effects and fate are unknown. Eighty-four soil samples obtained from a site with no recorded history of pollution were used to assess the persistence and dioxin-like toxicity of carbazole and chlorocarbazoles in soil under controlled conditions for 15 months. Soil samples were divided into two temperature conditions, 15 and 20 °C, both under fluctuating soil moisture conditions comprising 19 and 44 drying-rewetting cycles, respectively. This was characterized by natural water loss by evaporation and rewetting to -15 kPa. Accelerated solvent extraction (ASE) and cleanup were performed after incubation. Identification and quantification were done using high-resolution gas chromatogram/mass spectrometer (HRGC/MS), while dioxin-like toxicity was determined by ethoxyresorufin-O-deethylase (EROD) induction in H4IIA rat hepatoma cells assay and multidimensional quantitative structure-activity relationships (mQSAR) modelling. Carbazole, 3-chlorocarbazole and 3,6-dichlorocarbazole were detected including trichlorocarbazole not previously reported in soils. Carbazole and 3-chlorocarbazole showed significant dissipation at 15 °C but not at 20 °C incubating conditions indicating that low temperature could be suitable for dissipation of carbazole and chlorocarbazoles. 3,6-Dichlorocarbazole was resistant at both conditions. Trichlorocarbazole however exhibited a tendency to increase in concentration with time. 3-Chlorocarbazole, 3,6-dibromocarbazole and selected soil extracts exhibited EROD activity. Dioxin-like toxicity did not decrease significantly with time, whereas the sum chlorocarbazole toxic equivalence concentrations (∑TEQ) did not contribute significantly to the soil assay dioxin-like toxicity equivalent concentrations (TCDD-EQ). Carbazole and chlorocarbazoles are persistent with the latter also toxic in natural conditions.

  16. Advances towards aromatic oligoamide foldamers

    DEFF Research Database (Denmark)

    Hjelmgaard, Thomas; Plesner, Malene; Dissing, Mette Marie

    2014-01-01

    We have efficiently synthesized 36 arylopeptoid dimers with ortho-, meta-, and para-substituted aromatic backbones and tert-butyl or phenyl side chains. The dimers were synthesized by using a "submonomer method" on solid phase, by applying a simplified common set of reaction conditions. X......-ray crystallographic analysis of two of these dimers disclosed that the tert-butyl side chain invokes a cis amide conformation with a comparatively more closely packed structure of the surrounding aromatic backbone while the phenyl side chain results in a trans amide conformation with a more open, extended structure...... of the surrounding aromatic backbone. Investigation of the X-ray structures of two arylopeptoid dimers disclosed that the tert-butyl side chain invokes a cis amide conformation with a closely packed structure of the surrounding aromatic backbone while the phenyl side chain results in a trans amide conformation...

  17. High power light emitting diode (LED) arrays versus halogen light polymerization of oral biomaterials: Barcol hardness, compressive strength and radiometric properties.

    Science.gov (United States)

    Mills, Robin W; Uhl, Alexander; Blackwell, Gordon B; Jandt, Klaus D

    2002-07-01

    The clinical performance of light polymerized dental composites is greatly influenced by the quality of the light curing unit (LCU) used. Commonly used halogen LCUs have some specific drawbacks such as decreasing light output with time. This may result in a low degree of monomer conversion of the composites with negative clinical implications. Previous studies have shown that blue light emitting diode (LED) LCUs have the potential to polymerize dental composites without having the drawbacks of halogen LCUs. Since these studies were carried out LED technology has advanced significantly and commercial LED LCUs are now becoming available. This study investigates the Barcol hardness as a function of depth, and the compressive strength of dental composites that had been polymerized for 40 or 20s with two high power LED LCU prototypes, a commercial LED LCU, and a commercial halogen LCU. In addition the radiometric properties of the LCUs were characterized. The two high power prototype LED LCUs and the halogen LCU showed a satisfactory and similar hardness-depth performance whereas the hardness of the materials polymerized with the commercial LED LCU rapidly decreased with sample depth and reduced polymerization time (20 s). There were statistically significant differences in the overall compressive strengths of composites polymerized with different LCUs at the 95% significance level (p = 0.0016) with the two high power LED LCU prototypes and the halogen LCU forming a statistically homogenous group. In conclusion, LED LCU polymerization technology can reach the performance level of halogen LCUs. One of the first commercial LED LCUs however lacked the power reserves of the high power LED LCU prototypes.

  18. Characterization of selected volatile organic compounds, polycyclic aromatic hydrocarbons and carbonyl compounds at a roadside monitoring station

    Science.gov (United States)

    Ho, K. F.; Lee, S. C.; Chiu, Gloria M. Y.

    Volatile organic compounds (VOCs), PAHs and carbonyl compounds are the major toxic components in Hong Kong. Emissions from motor vehicles have been one of the primary pollution sources in the metropolitan areas throughout Hong Kong for a long time. A 1-yr monitoring program for VOCs, PAHs and carbonyl compounds had been performed at a roadside urban station at Hong Kong Polytechnic University in order to determine the variations and correlations of each selected species (VOCs, PAHs and carbonyl compounds). This study is aimed to analyze toxic volatile organic compounds (benzene, toluene, ethylbenzene and xylene), two carbonyl compounds (formaldehyde, acetaldehyde), and selective polycyclic aromatic hydrocarbons. The monitoring program started from 16 April 1999 to 30 March 2000. Ambient VOC concentrations, many of which originate from the same sources as particulate PAHs and carbonyls compounds, show significant quantities of benzene, toluene and xylenes. Correlations and multivariate analysis of selected gaseous and particulate phase organic pollutants were performed. Source identification by principle component analysis and hierarchical cluster analysis allowed the identification of four sources (factors) for the roadside monitoring station. Factor 1 represents the effect of diesel vehicle exhaust. Factor 2 shows the contribution of aromatic compounds. Factor 3 explains photochemical products—formaldehyde and acetaldehyde. Factor 4 explains the effect of gasoline vehicle exhaust.

  19. Quadrupole coupling constants and isomeric Moessbauer shifts for halogen-containing gold, platinum, niobium, tantalum and antimony compounds

    International Nuclear Information System (INIS)

    Poleshchuk, O. K.; Branchadell, V.; Ritter, R. A.; Fateev, A. V.

    2008-01-01

    We have analyzed by means of Density functional theory calculations the nuclear quadrupole coupling constants of a range of gold, antimony, platinum, niobium and tantalum compounds. The geometrical parameters and halogen nuclear quadrupole coupling constants obtained by these calculations substantially corresponded to the data of microwave and nuclear quadrupole resonance spectroscopy. An analysis of the quality of the calculations that employ pseudo-potentials and all-electron basis sets for the halogen compounds was carried out. The zero order regular approximation (ZORA) method is shown to be a viable alternative for the calculation of halogen coupling constants in molecules. In addition, the ZORA model, in contrast to the pseudo-potential model, leads to realistic values of all metal nuclear quadrupole coupling constants. From Klopman's approach, it follows that the relationship between the electrostatic bonding and covalent depends on the nature of the central atom. The results on Moessbauer chemical shifts are also in a good agreement with the coordination number of the central atom.

  20. Quadrupole coupling constants and isomeric Moessbauer shifts for halogen-containing gold, platinum, niobium, tantalum and antimony compounds

    Energy Technology Data Exchange (ETDEWEB)

    Poleshchuk, O. K., E-mail: poleshch@tspu.edu.ru [Tomsk State Pedagogical University (Russian Federation); Branchadell, V. [Universitat Autonoma de Barcelona, Departament de Quimica (Spain); Ritter, R. A.; Fateev, A. V. [Tomsk State Pedagogical University (Russian Federation)

    2008-01-15

    We have analyzed by means of Density functional theory calculations the nuclear quadrupole coupling constants of a range of gold, antimony, platinum, niobium and tantalum compounds. The geometrical parameters and halogen nuclear quadrupole coupling constants obtained by these calculations substantially corresponded to the data of microwave and nuclear quadrupole resonance spectroscopy. An analysis of the quality of the calculations that employ pseudo-potentials and all-electron basis sets for the halogen compounds was carried out. The zero order regular approximation (ZORA) method is shown to be a viable alternative for the calculation of halogen coupling constants in molecules. In addition, the ZORA model, in contrast to the pseudo-potential model, leads to realistic values of all metal nuclear quadrupole coupling constants. From Klopman's approach, it follows that the relationship between the electrostatic bonding and covalent depends on the nature of the central atom. The results on Moessbauer chemical shifts are also in a good agreement with the coordination number of the central atom.

  1. Biosurfactant-enhanced bioremediation of polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Cameotra, S.S.; Bollag, J.M. [Penn State University, University Park, PA (USA). Soil Biochemical Lab.

    2003-07-01

    Biosurfactants are surface-active compounds synthesized by it wide variety of micro-organisms. They are molecules that have both hydrophobic and hydrophilic domains and are capable of lowering the surface tension and the interfacial tension of the growth medium. Biosurfactants possess different chemical structures - lipopeptides, glycolipids, neutral lipids, and fatty acids. They are nontoxic biomolecules that are biodegradable. Biosurfactants also exhibit strong emulsification of hydrophobic compounds and form stable emulsions. Polycyclic aromatic hydrocarbons (PAHs) can be toxic, mutagenic, and carcinogenic compounds that pollute the environment. They are released to the environment its a result of spillage of oil and byproducts of coal treatment processes. The low water solubility of PAHs limits their availability to microorganisms, which is a potential problem for bioremediation of PAH-contaminated sites. Microbially produced surfactants enhance the bioavailability of these hydrophobic compounds for bioremediation. Therefore, biosurfactant-enhanced solubility of PAHs has potential applications in bioremediation.

  2. Allergic contact dermatitis due to highly reactive halogenated compounds

    Energy Technology Data Exchange (ETDEWEB)

    Pickering, F C; Ive, F A

    1983-11-01

    Ten cases of dermatitis in a fine organic chemicals plant are reported. These cases were all due to exposure to chemical compounds with reactive bromine or chlorine atoms. This type of chemical is always extremely irritant, but evidence is put forward to suggest that these cases were the result of allergic sensitization. Chemicals with reactive halogen atoms should always be handled with extreme care and patch testing should be approached with caution.

  3. Biotransformation and induction: implications for toxicity, bioaccumulation and monitoring of environmental xenobiotics in fish

    International Nuclear Information System (INIS)

    Kleinow, K.M.; Melancon, M.J.; Lech, J.J.

    1987-01-01

    Biotransformation of xenobiotics in fish occurs by many of the same reactions as in mammals. These reactions have been shown to affect the bioaccumulation, persistence, residue dynamics, and toxicity of select chemicals in fish. P-450-dependent monooxygenase activity of fish can be induced by polycyclic aromatic hydrocarbons, but phenobarbital-type agents induce poorly, if at all. Fish monooxygenase activity exhibits ideal temperature compensation and sex-related variation. Induction of monooxygenase activity by polycyclic aromatic hydrocarbons can result in qualitative as well as quantitative changes in the metabolic profile of a chemical. Induction can also alter toxicity. In addition, multiple P-450 isozymes have been described for several fish species. The biotransformation productions of certain chemicals have been related to specific P-450 isozymes, and the formation of these products can be influenced by induction. Exposure of fish to low levels of certain environmental contaminants has resulted in induction of specific monooxygenase activities and monitoring of such activities has been suggested as a means of identifying areas of pollutant exposure in the wild

  4. Polycyclic Aromatic Hydrocarbons in Surface Sediments from the Southern Shores of the Caspian Sea, Anzali City: Toxicity Assessment and Source Identification

    Directory of Open Access Journals (Sweden)

    Rokhsareh Azimi

    2015-10-01

    Full Text Available The Caspian Sea has recently experienced great damages due to intense pressure from human activities, petroleum contaminant discharges from oil extraction and refining activities, and domestic and industrial wastewaters discharged into the environment. The aim of this study was to determine the sources and levels of one of the most dangerous oil pollutants ‒ polycyclic aromatic hydrocarbons ‒ in the southern shores of the Caspian Sea (Anzali City. The data would be compared with standard PAHs concentrations in order to derive the information required for designing appropriate management measures. For the purposes of this study, nine surface sediment samples were collected from the experimental field and gas chromatography with mass spectrometry (GC-MS was used to analyze the samples for their contaminants. The total PAHs concentrations ranged from 736 to 9009 ng g-1d.w with an increasing trend along the east-west direction. Also, multiple indexes were used to detect the petrogenic origin of these compounds. Compared with sediment quality guidelines (SQGs of Florida (TELs/PELs, the levels for half the PAH compounds exceeded TELs. Moreover, naphthalene, fluorine, and phenanthrene concentrations exceeded the PELs in some stations, indicating likely acute toxic effects. However, comparison with sediment quality guidelines (SQGs of the United States (TELs/PELs revealed that most of the compounds at the stations investigated were lower than ERLs. It was concluded that the quality guidelines of the Florida State are more conservative for protecting the biotic organisms in the region.

  5. Development of a flameproof elastic elastomeric fiber

    Science.gov (United States)

    Howarth, J. T.; Nilgrom, J.; Massucco, A.; Sheth, S. G.; Dawn, F. S.

    1971-01-01

    Various flexible polyurethane structures containing halogen were synthesized from polyesters derived from aliphatic or aromatic polyols and dibasic acids. Aliphatic halide structures could not be used because they are unstable at the required reaction temperatures, giving of hydrogen halide which hydrolyzes the ester linkages. In contract, halogen-containing aromatic polyols were stable and satisfactory products were made. The most promising composition, a brominated neopentyl glycol capped with toluene disocyanate, was used as a conventional diisocyanate, in conjunction with hydroxy-terminated polyethers or polyesters to form elastomeric urethanes containing about 10% bromine with weight. Products made in this manner will not burn in air, have an oxygen index value of about 25, and have tensile strength values of about 5,000 psi at 450% elongation. The most efficient additives for imparting flame retardancy to Spandex urethanes are aromatic halides and the most effective of these are the bromide compounds. Various levels of flame retardancy have been achieved depending on the levels of additives used.

  6. 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

  7. Strength and Character of Halogen Bonds in Protein-Ligand Complexes

    Czech Academy of Sciences Publication Activity Database

    Riley, Kevin Eugene; Hobza, Pavel

    2011-01-01

    Roč. 11, č. 10 (2011), s. 4272-4278 ISSN 1528-7483 R&D Projects: GA MŠk LC512 Grant - others:Research and Development for Innovations of European Social Fund(XE) CZ.1.05/2.1.00/03.0058 Institutional research plan: CEZ:AV0Z40550506 Keywords : halogen bond * protein-ligand complexes * calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.720, year: 2011

  8. A halogen-free synthesis of gold nanoparticles using gold(III) oxide

    International Nuclear Information System (INIS)

    Sashuk, Volodymyr; Rogaczewski, Konrad

    2016-01-01

    Gold nanoparticles are one of the most used nanomaterials. They are usually synthesized by the reduction of gold(III) chloride. However, the presence of halide ions in the reaction mixture is not always welcome. In some cases, these ions have detrimental influence on the morphology and structure of resulting nanoparticles. Here, we present a simple and halogen-free procedure to prepare gold nanoparticles by reduction of gold(III) oxide in neat oleylamine. The method provides the particles with an average size below 10 nm and dispersity of tens of percent. The process of nanoparticle formation was monitored using UV–Vis spectroscopy. The structure and chemical composition of the nanoparticles was determined by SEM, XPS and EDX. We also proposed the mechanism of reduction of gold(III) oxide based on MS, IR and NMR data. Importantly, the synthetic protocol is general and applicable for the preparation of other coinage metal nanoparticles from the corresponding metal oxides. For instance, we demonstrated that the absence of halogen enables efficient alloying of metals when preparing gold–silver bimetallic nanoparticles.

  9. Halogen doping of II-VI semiconductors during molecular beam epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Waag, A.; Litz, Th.; Fischer, F.; Heinke, H.; Scholl, S.; Hommel, D.; Landwehr, G. (Physikalisches Inst. der Univ. Wuerzburg (Germany)); Bilger, G. (Zentrum fuer Sonnenenergie und Wasserstoff-Forschung, Stuttgart (Germany))

    1994-04-14

    Results on the halogen doping of CdTe, (CdMn)Te as well as (CdMg)Te thin films and quantum well structures are reported. The structures were grown by molecular beam epitaxy. The samples have been investigated by Van der Pauw, photoconductivity, X-ray diffraction, XPS and SIMS measurements. ZnCl[sub 2] and ZnBr[sub 2] have been used as dopant sources. Free carrier concentrations at room temperature above 10[sup 18] cm[sup -3] can easily be achieved for CdTe for a wide range of Cd/Te flux ratios and substrate temperatures. In the ternary alloys, the free carrier concentration decreases drastically with increasing x-values, despite a constant incorporation of the dopant species. In addition, persistent photoconductivity has been observed in n-type doped ternary thin films at low temperatures. The decrease of the free carrier concentration with x-value is common to other wide-gap ternary alloys, and the reason for it is discussed in the frame of DX-like deep donor impurities in ternary II-VI compounds. In first experiments on planar halogen doping of CdTe, a doping level of 5x10[sup 18] cm[sup -3] could be reached in the doped regions, the highest value ever reported for CdTe. A clear influence of dopant incorporation on the structural quality of CdTe thin films has been seen even for dopant concentrations of as low as 10[sup 18] cm[sup -3]. The FWHM of the rocking curves decreased by a factor of 2 with increasing dopant incorporation. SIMS as well as XPS measurements demonstrate that the Cl/Zn and Br/Zn ratio in the doped films is 2/1, but no chemical shift corresponding to Zn-Cl or Zn-Br bonds could be detected. A model for the incorporation of the halogens is proposed on the basis of these results

  10. Converting lignin to aromatics: step by step

    NARCIS (Netherlands)

    Strassberger, Z.I.

    2014-01-01

    Lignin, the glue that holds trees together, is the most abundant natural resource of aromatics. In that respect, it is a far more advanced resource than crude oil. This is because lignin already contains the aromatic functional groups. Thus, catalytic conversion of lignin to high-value aromatics is

  11. Flue gas corrosion through halogen compounds in fuel gas

    Energy Technology Data Exchange (ETDEWEB)

    Eisenmann, R

    1987-04-01

    The halogens of chlorine and fluorine greatly influence the corrosion speed of metal materials. If small quantities of chlorinated and/or fluorinated hydrocarbons are present in fuel gas like in landfill gas, they must not result in enhanced corrosion of gas appliances. Data from literature and the initial results of tests run by the author indicate that quantities at about 10 mg/cbm (in terms of chlorine) can be assumed not to cause any noticeable acceleration of corrosion speed.

  12. Environmental and economic implications of a shift to halogen-free printed wiring boards

    Energy Technology Data Exchange (ETDEWEB)

    Bergendahl, C.G.; Johansson, G.; Zackrisson, M. [IVF Industrial Research and Development Corp., Moelndal (Sweden); Lichtenvort, K. [Technical Univ. of Berlin (Germany); Nyyssoenen, J. [Aspocomp Oy, Salo (Finland)

    2004-07-01

    The 'Restriction of Hazardous Substances Directive' (RoHS) and the 'Waste from Electrical and Electronic Equipment Directive' (WEEE) enforced by the European Commission require new materials and processes to be implemented in the production of electrical and electronic equipment (EEE). In response to this, the project grEEEn (Cost Management System for greening Electrical and Electronic Equipment) was defined and carried out within the 5th framework programme of the EU. This paper presents the grEEEn method and the outcome of applying the method on a case study. The study addressed the material shift in printed wiring boards (PWBs), from the traditional FR4 material containing halogenated flame retardants to halogen-free FR4 materials. The paper presents the product, process and scenario modelling and the results from analysing costs, environmental profile and legal compliance. (orig.)

  13. Optical modulation in nematic phase of halogen substituted hydrogen bonded liquid crystals

    Science.gov (United States)

    Vijayakumar, V. N.; Madhu Mohan, M. L. N.

    2012-01-01

    A series of halogen-substituted hydrogen-bonded liquid crystalline complexes have been designed and synthesised. A successful attempt has been made to form complementary hydrogen bonding between the dodecyloxy benzoic acid (12BAO) and halogen-substituted benzoic acids and the physical properties exhibited by the individual complexes are studied. The complexes obtained are analysed by polarising optical microscope (POM), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and dielectric studies. The formation of complementary hydrogen bond is confirmed through FTIR spectra. An interesting feature of this series is the observation of a field-induced transition (FiT) in nematic phase. Another interesting phenomenon is the observation of a new smectic X phase (worm-like texture) in all the synthesised complexes. Dielectric relaxation studies in the smectic C phase of these hydrogen bonded complexes along with the Arrhenius and the Cole-Cole plots are discussed. Optical tilt angle in smectic C phase and the corresponding fitted data analysis concur with the Mean field theory prediction.

  14. Hydrogenated and halogenated blue phosphorene as Dirac materials: A first principles study

    International Nuclear Information System (INIS)

    Sun, Minglei; Wang, Sake; Yu, Jin; Tang, Wencheng

    2017-01-01

    Highlights: • The fully hydrogenated and halogenated blue phosphorenes are 2D Dirac materials. • The Dirac cone in fluorinated and iodinated blue phosphorenes lies exactly at the Fermi level. • The mass density of hydrogenated and fluorinated blue phosphorenes is rather small. - Abstract: Using first-principles calculations, we systematically investigate the structures and electronic properties of fully hydrogenated and halogenated blue phosphorene (P_2X_2). All these systems possess Dirac cone at high-symmetry K point, which are mainly contributed by P s p_x p_y orbitals. The Dirac cone in P_2F_2 and P_2I_2 systems lies exactly at the Fermi level. Formation energy analysis denotes that all the systems are energetically stable except P_2I_2. The mass density for P_2H_2 and P_2F_2 systems is rather small. Our calculations proposed that these systems, especially P_2F_2 system, have great potential applications in future nanoelectronics.

  15. Negative atomic halogens incident on argon and molecular nitrogen: electron detachment studies

    International Nuclear Information System (INIS)

    Jalbert, G; Medina, A; Magalhaes, S D; Wolff, W; Barros, A L F de; Carrilho, P; Rocha, A B; Faria, N V de Castro

    2007-01-01

    During the last years we have measured total detachment cross sections of atomic and cluster anions colliding with gases in the velocity range of 0.2 to 1.8 a.u. In particular, we measured negative atomic halogens incident on argon and molecular nitrogen. These last data are for the first time analyzed using the simple semi-classical model that we have developed. For that purpose, the values of elastic plus inelastic cross sections for impact of free electrons on Ar and N 2 , the latter showing a shape resonance, convoluted with the anion's outermost electron momentum distribution yielded the overall shape of the anion cross sections. Inclusion of a velocity independent additive term, interpreted as an effective area of the collision region, led to accurate absolute cross section values. The high affinity of the halogens and the existence of a not well described resonance in the e-N 2 collision, are characteristics that may be used to delimit the scope and validity of the model

  16. A simple and automated sample preparation system for subsequent halogens determination: Combustion followed by pyrohydrolysis.

    Science.gov (United States)

    Pereira, L S F; Pedrotti, M F; Vecchia, P Dalla; Pereira, J S F; Flores, E M M

    2018-06-20

    A simple and automated system based on combustion followed by a pyrohydrolysis reaction was proposed for further halogens determination. This system was applied for digestion of soils containing high (90%) and also low (10%) organic matter content for further halogens determination. The following parameters were evaluated: sample mass, use of microcrystalline cellulose and heating time. For analytes absorption, a diluted alkaline solution (6 mL of 25 mmol L -1  NH 4 OH) was used in all experiments. Up to 400 mg of soil with high organic matter content and 100 mg of soil with low organic matter content (mixed with 400 mg of cellulose) could be completely digested using the proposed system. Quantitative results for all halogens were obtained using less than 12 min of sample preparation step (about 1.8 min for sample combustion and 10 min for pyrohydrolysis). The accuracy was evaluated using a certified reference material of coal and spiked samples. No statistical difference was observed between the certified values and results obtained by the proposed method. Additionally, the recoveries obtained using spiked samples were in the range of 98-103% with relative standard deviation values lower than 5%. The limits of quantification obtained for F, Cl, Br and I for soil with high (400 mg of soil) and low (100 mg of soil) organic matter were in the range of 0.01-2 μg g -1 and 0.07-59 μg g -1 , respectively. The proposed system was considered as a simple and suitable alternative for soils digestion for further halogens determination by ion chromatography and inductively coupled plasma mass spectrometry techniques. Copyright © 2018 Elsevier B.V. All rights reserved.

  17. Time-resolved studies define the nature of toxic IAPP intermediates, providing insight for anti-amyloidosis therapeutics

    Science.gov (United States)

    Abedini, Andisheh; Plesner, Annette; Cao, Ping; Ridgway, Zachary; Zhang, Jinghua; Tu, Ling-Hsien; Middleton, Chris T; Chao, Brian; Sartori, Daniel J; Meng, Fanling; Wang, Hui; Wong, Amy G; Zanni, Martin T; Verchere, C Bruce; Raleigh, Daniel P; Schmidt, Ann Marie

    2016-01-01

    Islet amyloidosis by IAPP contributes to pancreatic β-cell death in diabetes, but the nature of toxic IAPP species remains elusive. Using concurrent time-resolved biophysical and biological measurements, we define the toxic species produced during IAPP amyloid formation and link their properties to induction of rat INS-1 β-cell and murine islet toxicity. These globally flexible, low order oligomers upregulate pro-inflammatory markers and induce reactive oxygen species. They do not bind 1-anilnonaphthalene-8-sulphonic acid and lack extensive β-sheet structure. Aromatic interactions modulate, but are not required for toxicity. Not all IAPP oligomers are toxic; toxicity depends on their partially structured conformational states. Some anti-amyloid agents paradoxically prolong cytotoxicity by prolonging the lifetime of the toxic species. The data highlight the distinguishing properties of toxic IAPP oligomers and the common features that they share with toxic species reported for other amyloidogenic polypeptides, providing information for rational drug design to treat IAPP induced β-cell death. DOI: http://dx.doi.org/10.7554/eLife.12977.001 PMID:27213520

  18. Heavy metal-immobilizing organoclay facilitates polycyclic aromatic hydrocarbon biodegradation in mixed-contaminated soil

    International Nuclear Information System (INIS)

    Biswas, Bhabananda; Sarkar, Binoy; Mandal, Asit; Naidu, Ravi

    2015-01-01

    Highlights: • A novel metal-immobilizing organoclay (MIOC) synthesized and characterized. • MIOC immobilizes toxic metals and reduces metal bioavailability. • It enhances PAH-bioavailability to soil bacteria. • It improves microbial growth and activities in mixed-contaminated soils. • MIOC facilitates PAH-biodegradation in metal co-contaminated soils. - Abstract: Soils contaminated with a mixture of heavy metals and polycyclic aromatic hydrocarbons (PAHs) pose toxic metal stress to native PAH-degrading microorganisms. Adsorbents such as clay and modified clay minerals can bind the metal and reduce its toxicity to microorganisms. However, in a mixed-contaminated soil, an adsorption process more specific to the metals without affecting the bioavailability of PAHs is desired for effective degradation. Furthermore, the adsorbent should enhance the viability of PAH-degrading microorganisms. A metal-immobilizing organoclay (Arquad ® 2HT-75-bentonite treated with palmitic acid) (MIOC) able to reduce metal (cadmium (Cd)) toxicity and enhance PAH (phenanthrene) biodegradation was developed and characterized in this study. The MIOC differed considerably from the parent clay in terms of its ability to reduce metal toxicity (MIOC > unmodified bentonite > Arquad–bentonite). The MIOC variably increased the microbial count (10–43%) as well as activities (respiration 3–44%; enzymatic activities up to 68%), and simultaneously maintained phenanthrene in bioavailable form in a Cd-phenanthrene mixed-contaminated soil over a 21-day incubation period. This study may lead to a new MIOC-assisted bioremediation technique for PAHs in mixed-contaminated soils

  19. Heavy metal-immobilizing organoclay facilitates polycyclic aromatic hydrocarbon biodegradation in mixed-contaminated soil

    Energy Technology Data Exchange (ETDEWEB)

    Biswas, Bhabananda; Sarkar, Binoy [Centre for Environmental Risk Assessment and Remediation, University of South Australia, Mawson Lakes Campus, SA 5095 (Australia); Cooperative Research Centre for Contamination Assessment and Remediation of the Environment, P.O. Box 486, Salisbury, SA 5106 (Australia); Mandal, Asit [Centre for Environmental Risk Assessment and Remediation, University of South Australia, Mawson Lakes Campus, SA 5095 (Australia); Division of Soil Biology, Indian Institute of Soil Science, Bhopal, Madhya Pradesh (India); Naidu, Ravi [Centre for Environmental Risk Assessment and Remediation, University of South Australia, Mawson Lakes Campus, SA 5095 (Australia); Cooperative Research Centre for Contamination Assessment and Remediation of the Environment, P.O. Box 486, Salisbury, SA 5106 (Australia)

    2015-11-15

    Highlights: • A novel metal-immobilizing organoclay (MIOC) synthesized and characterized. • MIOC immobilizes toxic metals and reduces metal bioavailability. • It enhances PAH-bioavailability to soil bacteria. • It improves microbial growth and activities in mixed-contaminated soils. • MIOC facilitates PAH-biodegradation in metal co-contaminated soils. - Abstract: Soils contaminated with a mixture of heavy metals and polycyclic aromatic hydrocarbons (PAHs) pose toxic metal stress to native PAH-degrading microorganisms. Adsorbents such as clay and modified clay minerals can bind the metal and reduce its toxicity to microorganisms. However, in a mixed-contaminated soil, an adsorption process more specific to the metals without affecting the bioavailability of PAHs is desired for effective degradation. Furthermore, the adsorbent should enhance the viability of PAH-degrading microorganisms. A metal-immobilizing organoclay (Arquad{sup ®} 2HT-75-bentonite treated with palmitic acid) (MIOC) able to reduce metal (cadmium (Cd)) toxicity and enhance PAH (phenanthrene) biodegradation was developed and characterized in this study. The MIOC differed considerably from the parent clay in terms of its ability to reduce metal toxicity (MIOC > unmodified bentonite > Arquad–bentonite). The MIOC variably increased the microbial count (10–43%) as well as activities (respiration 3–44%; enzymatic activities up to 68%), and simultaneously maintained phenanthrene in bioavailable form in a Cd-phenanthrene mixed-contaminated soil over a 21-day incubation period. This study may lead to a new MIOC-assisted bioremediation technique for PAHs in mixed-contaminated soils.

  20. Toxicity of benz(a)anthracene and fluoranthene to marine phytoplankton in culture: Does cell size really matter?

    International Nuclear Information System (INIS)

    Othman, Hiba Ben; Leboulanger, Christophe; Le Floc’h, Emilie; Hadj Mabrouk, Hassine; Sakka Hlaili, Asma

    2012-01-01

    Highlights: ► Polycyclic aromatic hydrocarbons (PAHs) in the marine environment are a hazardous chemical legacy. ► Benz(a)anthracene and fluoranthene are toxic to phytoplankton photosynthesis and growth in culture. ► Acute (photosynthesis) and chronic (population growth) effects have different thresholds. ► Toxicity depends on both the species selected as a model and the compound considered. ► Further study of the size/sensitivity relationship is required to draw more general conclusions. - Abstract: The toxicity of benz(a)anthracene and fluoranthene (polycyclic aromatic hydrocarbons, PAHs) was evaluated on seven species of marine algae in culture belonging to pico-, nano-, and microphytoplankton, exposed to increasing concentrations of up to 2 mg L −1 . The short-term (24 h) toxicity was assessed using chlorophyll a fluorescence transients, linked to photosynthetic parameters. The maximum quantum yield Fv/Fm was lower at the highest concentrations tested and the toxicity thresholds were species-dependent. For acute effects, fluoranthene was more toxic than benz(a)anthracene, with LOECs of 50.6 and 186 μg L −1 , respectively. After 72 h exposure, there was a dose-dependent decrease in cell density, fluoranthene being more toxic than benz(a)anthracene. The population endpoint at 72 h was affected to a greater extent than the photosynthetic endpoint at 24 h. EC50 was evaluated using the Hill model, and species sensitivity was negatively correlated to cell biovolume. The largest species tested, the dinoflagellate Alexandrium catenella, was almost insensitive to either PAH. The population endpoint EC50s for fluoranthene varied from 54 μg L −1 for the picophytoplankton Picochlorum sp. to 418 μg L −1 for the larger diatom Chaetoceros muelleri. The size/sensitivity relationship is proposed as a useful model when there is a lack of ecotoxicological data on hazardous chemicals, especially in marine microorganisms.

  1. Investigating the application of a nitroreductase-expressing transgenic zebrafish line for high-throughput toxicity testing

    Directory of Open Access Journals (Sweden)

    Anna C. Chlebowski

    Full Text Available Nitroreductase enzymes are responsible for the reduction of nitro functional groups to amino functional groups, and are found in a range of animal models, zebrafish (Danio rerio excluded. Transgenic zebrafish models have been developed for tissue-specific cell ablation, which use nitroreductase to ablate specific tissues or cell types following exposure to the non-toxic pro-drug metronidazole (MTZ. When metabolized by nitroreductase, MTZ produces a potent cytotoxin, which specifically ablates the tissue in which metabolism occurs. Uses, beyond tissue-specific cell ablation, are possible for the hepatocyte-specific Tg(l-fabp:CFP-NTRs891 zebrafish line, including investigations of the role of nitroreductase in the toxicity of nitrated compounds. The hepatic ablation characteristics of this transgenic line were explored, in order to expand its potential uses. Embryos were exposed at 48, 72, or 96 h post fertilization (hpf to a range of MTZ concentrations, and the ablation profiles were compared. Ablation occurred at a 10-fold lower concentration than previously reported. Embryos were exposed to a selection of other compounds, with and without MTZ, in order to investigate alternative uses for this transgenic line. Test compounds were selected based on: their ability to undergo nitroreduction, known importance of hepatic metabolism to toxicity, and known pharmaceutical hepatotoxins. Selected compounds included nitrated polycyclic aromatic hydrocarbons (nitro-PAHs, the PAHs retene and benzo[a]pyrene, and the pharmaceuticals acetaminophen and flutamide. The results suggest a range of potential roles of the liver in the toxicity of these compounds, and highlight the additional uses of this transgenic model in toxicity testing. Keywords: Zebrafish, Transgenic, Nitroreductase, Nitrated polycyclic aromatic hydrocarbon, Tissue ablation, Pharmaceuticals

  2. Sydney Tar Ponds: Some problems in quantifying toxic waste

    Energy Technology Data Exchange (ETDEWEB)

    Furimsky, E. [IMAF Group, Ottawa, ON (Canada)

    2002-07-01

    Information on the type and amount of hazardous and toxic waste is required to develop a meaningful strategy and estimate a realistic cost for clean up of the Sydney Tar Pond site which is located on Cape Breton, in the province of Nova Scotia, Canada. The site covers the area of the decommissioned Sysco (Sydney Steel Corporation) plant. The materials of concern include BTEX (benzene, toluene, ethylbenzene, and xylenes), PAH (polycyclic aromatic hydrocarbons), PCB (polychlorinated biphenyl), and particulates laden with toxic metals, such as arsenic, lead, and others. The originally nontoxic materials such as soil, blast furnace slag, and vegetation, as well as surface and ground waters, which were subsequently contaminated, must also be included if they fail tests prescribed by environmental regulations. An extensive sampling program must be undertaken to obtain data for an accurate estimate of the waste to be cleaned and disposed of. Apparently, 700,000 tons of toxic waste which is believed to be present on the site, may represent only a fraction of the actual amount. The clean-up of the site is only part of the solution. Toxic waste has to be disposed of in accordance with environmental regulations.

  3. Sydney tar ponds: some problems in quantifying toxic waste.

    Science.gov (United States)

    Furimsky, Edward

    2002-12-01

    Information on the type and amount of hazardous and toxic waste is required to develop a meaningful strategy and estimate a realistic cost for clean up of the Sydney Tar Pond site which is located on Cape Breton, in the province of Nova Scotia, Canada. The site covers the area of the decommissioned Sysco (Sydney Steel Corporation) plant. The materials of concern include BTEX (benzene, toluene, ethylbenzene, and xylenes), PAH (polycyclic aromatic hydrocarbons), PCB (polychlorinated biphenyl), and particulates laden with toxic metals, such as arsenic, lead, and others. The originally nontoxic materials such as soil, blast furnace slag, and vegetation, as well as surface and ground waters, which were subsequently contaminated, must also be included if they fail tests prescribed by environmental regulations. An extensive sampling program must be undertaken to obtain data for an accurate estimate of the waste to be cleaned and disposed of. Apparently, 700,000 tons of toxic waste, which is believed to be present on the site, may represent only a fraction of the actual amount. The clean-up of the site is only part of the solution. Toxic waste has to be disposed of in accordance with environmental regulations.

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

    Science.gov (United States)

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

    2016-01-01

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

  5. High atmosphere–ocean exchange of semivolatile aromatic hydrocarbons

    KAUST Repository

    González-Gaya, Belén

    2016-05-16

    Polycyclic aromatic hydrocarbons, and other semivolatile aromatic-like compounds, are an important and ubiquitous fraction of organic matter in the environment. The occurrence of semivolatile aromatic hydrocarbons is due to anthropogenic sources such as incomplete combustion of fossil fuels or oil spills, and other biogenic sources. However, their global transport, fate and relevance for the carbon cycle have been poorly assessed, especially in terms of fluxes. Here we report a global assessment of the occurrence and atmosphere-ocean fluxes of 64 polycyclic aromatic hydrocarbons analysed in paired atmospheric and seawater samples from the tropical and subtropical Atlantic, Pacific and Indian oceans. The global atmospheric input of polycyclic aromatic hydrocarbons to the global ocean is estimated at 0.09 Tg per month, four times greater than the input from the Deepwater Horizon spill. Moreover, the environmental concentrations of total semivolatile aromatic-like compounds were 10 2 -10 3 times higher than those of the targeted polycyclic aromatic hydrocarbons, with a relevant contribution of an aromatic unresolved complex mixture. These concentrations drive a large global deposition of carbon, estimated at 400 Tg C yr -1, around 15% of the oceanic CO2 uptake. © 2016 Macmillan Publishers Limited.

  6. Prediction of enthalpy and standard Gibbs energy of vaporization of haloaromatics from atomic properties.

    Science.gov (United States)

    Monte, M J S; Almeida, A R R P; Liebman, J F

    2015-11-01

    Halogenated benzenes form a class of pollutants with a huge number of members - 1504 distinct benzene compounds, where one or more hydrogen atoms are replaced by halogens, may exist theoretically. This study presents a user friendly method for accurate prediction of vapor pressures and enthalpies of vaporization, at 298.15 K, of any mono or poly halobenzene compound. The derived equations for the prediction of those vaporization properties depend just on the number of each constituent halogen atom. This is a consequence of the absence of intramolecular interactions between the halogen atoms, revealed after examining vaporization results of ca. 40 halogenated benzenes. In order to rationalize the estimation equations, the contribution of the halogen atoms for the referred to above properties of vaporization was decomposed into two atomic properties - the volume and electron affinity. Extension of the applicability of the estimation method to substituted benzenes containing other substituent groups beyond halogen atoms as well as to some polycyclic aromatic species was tested with success. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Renal cysteine conjugate C-S lyase mediated toxicity of halogenated alkenes in primary cultures of human and rat proximal tubular cells.

    Science.gov (United States)

    McGoldrick, Trevor A; Lock, Edward A; Rodilla, Vicente; Hawksworth, Gabrielle M

    2003-07-01

    Proximal tubular cells from human (HPT) and rat (RPT) kidneys were isolated, grown to confluence and incubated with S-(1,2-dichlorovinyl)- l-cysteine (DCVC), S-(1,2,2-trichlorovinyl)- l-cysteine (TCVC), S-(1,1,2,2-tetrafluoroethyl)- l-cysteine (TFEC) and S-(2-chloro-1,1-difluorethyl)- l-cysteine (CDFEC), the cysteine conjugates of nephrotoxicants. The cultures were exposed to the conjugates for 12, 24 and 48 h and the toxicity determined using the MTT assay. All four conjugates caused dose-dependent toxicity to RPT cells over the range 50-1,000 microM, the order of toxicity being DCVC>TCVC>TFEC=CDFEC. The inclusion of aminooxyacetic acid (AOAA; 250 microM), an inhibitor of pyridoxal phosphate-dependent enzymes such as C-S lyase, afforded protection, indicating that C-S lyase has a role in the bioactivation of these conjugates. In HPT cultures only DCVC caused significant time- and dose-dependent toxicity. Exposure to DCVC (500 microM) for 48 h decreased cell viability to 7% of control cell values, whereas co-incubation of DCVC (500 microM) with AOAA (250 microM) resulted in cell viability of 71%. Human cultures were also exposed to S-(1,2-dichlorovinyl)-glutathione (DCVG). DCVG was toxic to HPT cells, but the onset of toxicity was delayed compared with the corresponding cysteine conjugate. AOAA afforded almost complete protection from DCVG toxicity. Acivicin (250 microM), an inhibitor of gamma-glutamyl transferase (gamma-GT), partially protected against DCVG (500 microM)-induced toxicity at 48 h (5% viability and 53% viability in the absence and presence of acivicin, respectively). These results suggest that DCVG requires processing by gamma-GT prior to bioactivation by C-S lyase in HPT cells. The activity of C-S lyase, using TFEC as a substrate, and glutamine transaminase K (GTK) was measured in rat and human cells with time in culture. C-S lyase activity in RPT and HPT cells decreased to approximately 30% of fresh cell values by the time the cells reached

  8. Arginine-aromatic interactions and their effects on arginine-induced solubilization of aromatic solutes and suppression of protein aggregation

    KAUST Repository

    Shah, Dhawal

    2011-09-21

    We examine the interaction of aromatic residues of proteins with arginine, an additive commonly used to suppress protein aggregation, using experiments and molecular dynamics simulations. An aromatic-rich peptide, FFYTP (a segment of insulin), and lysozyme and insulin are used as model systems. Mass spectrometry shows that arginine increases the solubility of FFYTP by binding to the peptide, with the simulations revealing the predominant association of arginine to be with the aromatic residues. The calculations further show a positive preferential interaction coefficient, Γ XP, contrary to conventional thinking that positive Γ XP\\'s indicate aggregation rather than suppression of aggregation. Simulations with lysozyme and insulin also show arginine\\'s preference for aromatic residues, in addition to acidic residues. We use these observations and earlier results reported by us and others to discuss the possible implications of arginine\\'s interactions with aromatic residues on the solubilization of aromatic moieties and proteins. Our results also highlight the fact that explanations based purely on Γ XP, which measures average affinity of an additive to a protein, could obscure or misinterpret the underlying molecular mechanisms behind additive-induced suppression of protein aggregation. © 2011 American Institute of Chemical Engineers (AIChE).

  9. Arginine-aromatic interactions and their effects on arginine-induced solubilization of aromatic solutes and suppression of protein aggregation

    KAUST Repository

    Shah, Dhawal; Li, Jianguo; Shaikh, Abdul Rajjak; Rajagopalan, Raj

    2011-01-01

    We examine the interaction of aromatic residues of proteins with arginine, an additive commonly used to suppress protein aggregation, using experiments and molecular dynamics simulations. An aromatic-rich peptide, FFYTP (a segment of insulin), and lysozyme and insulin are used as model systems. Mass spectrometry shows that arginine increases the solubility of FFYTP by binding to the peptide, with the simulations revealing the predominant association of arginine to be with the aromatic residues. The calculations further show a positive preferential interaction coefficient, Γ XP, contrary to conventional thinking that positive Γ XP's indicate aggregation rather than suppression of aggregation. Simulations with lysozyme and insulin also show arginine's preference for aromatic residues, in addition to acidic residues. We use these observations and earlier results reported by us and others to discuss the possible implications of arginine's interactions with aromatic residues on the solubilization of aromatic moieties and proteins. Our results also highlight the fact that explanations based purely on Γ XP, which measures average affinity of an additive to a protein, could obscure or misinterpret the underlying molecular mechanisms behind additive-induced suppression of protein aggregation. © 2011 American Institute of Chemical Engineers (AIChE).

  10. Computational Study of Chemical Reactivity Using Information-Theoretic Quantities from Density Functional Reactivity Theory for Electrophilic Aromatic Substitution Reactions.

    Science.gov (United States)

    Wu, Wenjie; Wu, Zemin; Rong, Chunying; Lu, Tian; Huang, Ying; Liu, Shubin

    2015-07-23

    The electrophilic aromatic substitution for nitration, halogenation, sulfonation, and acylation is a vastly important category of chemical transformation. Its reactivity and regioselectivity is predominantly determined by nucleophilicity of carbon atoms on the aromatic ring, which in return is immensely influenced by the group that is attached to the aromatic ring a priori. In this work, taking advantage of recent developments in quantifying nucleophilicity (electrophilicity) with descriptors from the information-theoretic approach in density functional reactivity theory, we examine the reactivity properties of this reaction system from three perspectives. These include scaling patterns of information-theoretic quantities such as Shannon entropy, Fisher information, Ghosh-Berkowitz-Parr entropy and information gain at both molecular and atomic levels, quantitative predictions of the barrier height with both Hirshfeld charge and information gain, and energetic decomposition analyses of the barrier height for the reactions. To that end, we focused in this work on the identity reaction of the monosubstituted-benzene molecule reacting with hydrogen fluoride using boron trifluoride as the catalyst in the gas phase. We also considered 19 substituting groups, 9 of which are ortho/para directing and the other 9 meta directing, besides the case of R = -H. Similar scaling patterns for these information-theoretic quantities found for stable species elsewhere were disclosed for these reactions systems. We also unveiled novel scaling patterns for information gain at the atomic level. The barrier height of the reactions can reliably be predicted by using both the Hirshfeld charge and information gain at the regioselective carbon atom. The energy decomposition analysis ensued yields an unambiguous picture about the origin of the barrier height, where we showed that it is the electrostatic interaction that plays the dominant role, while the roles played by exchange-correlation and

  11. Diversity of band gap and photoluminescence properties of lead halide perovskite: A halogen-dependent spectroscopic study

    Science.gov (United States)

    Yu, Wenlei; Jiang, Yunfeng; Zhu, Xiuwei; Luo, Chunhua; Jiang, Kai; Chen, Liangliang; Zhang, Juan

    2018-05-01

    The effects of halogen substitution on microstructure, optical absorption, and phonon modes for perovskite CH3NH3PbX3 (MAPbX3, X = I/Br/Cl) films grown on FTO substrates have been investigated. The X-ray diffraction analysis exhibited good crystallization, and the strong diffraction peak assigned to (1 0 0) c for X = Br/Cl shifted toward a higher angle compared to (1 1 0) t of MAPbI3. Band-gap tuning from 1.63 to 2.37 to 3.11 eV in the I-Br-Cl series can be found due to the halogen effects. These energy values closely match the positions of peak determined from photoluminescence experiments. The remarkable absorption dip and emission peak appear for the MAPbBr3, suggesting higher crystallinity under the same preparation conditions. The wavenumbers of main IR-vibrations slightly decrease with ionic radius of the halogen increasing (in the order of Cl-Br-I), which related to the increasing polarizability. These results provide important progress towards the understanding of the halide role in the realization of high performance MAPbX3-based solar cells.

  12. Natural elimination of volatile halogenated hydrocarbons from the environment

    Energy Technology Data Exchange (ETDEWEB)

    Harress, H.M.; Grathwohl, P.; Torunski, H.

    1987-01-01

    Recently carried out field investigations of groundwater contaminations with volatile halogenated hydrocarbons have shown evidence of natural elimination of these hazardous substances. This elimination effects is rare and observed in connection with special geological conditions. With regard to some contaminated sites, the following mechanisms for this behaviour are discussed: 1. Stripping by naturally ascending gases. 2. Sorption on soil organic matter. 3. Biodegradation. The so far compiled knowledge allowed to develop further research programmes, which are pursued in various projects.

  13. Linking precious metal enrichment and halogen cycling in mafic magmatic systems: insights from the Rum layered intrusion, NW Scotland

    Science.gov (United States)

    Kelly, A. P.; O'Driscoll, B.; Clay, P. L.; Burgess, R.

    2017-12-01

    Layered intrusions host the world's largest known concentrations of the platinum-group elements (PGE). Emphasis has been attached to the role of halogen-bearing fluids in concentrating the precious metals, but whether this occurs at the magmatic stage, or via subsequent metasomatism, is actively debated. One obstacle to progress has been the analytical difficulty of measuring low abundances of the halogens in the cumulate products of layered intrusions. To elucidate the importance of the halogens in facilitating PGE-mineralisation, as well as fingerprint halogen provenance and assess the importance of halogen cycling in mafic magma systems more generally, a suite of samples encompassing different stages of activity of the Palaeogene Rum layered intrusion was investigated. Halogen abundances were measured by neutron irradiation noble gas mass spectrometric analysis, permitting the detection of relatively low (ppm-ppb) abundances of Cl, Br and I in mg-sized samples. The samples include PGE-enriched chromite seams, various cumulates (e.g., peridotites), picrites (approximating the Rum parental magma), and pegmatites representing volatile-rich melts that circulated the intrusion at a late-stage in its solidification history. The new data reveal that PGE-bearing chromite seams contain relatively low Cl concentrations (2-3 ppm), with high molar ratios of Br/Cl and I/Cl (0.005 and 0.009, respectively). The picrites and cumulates have Br/Cl and I/Cl ratios close to sub-continental lithospheric mantle values of approximately 0.0013 and 0.00002, respectively, and thus likely reflect the Rum magma source region. A positive correlation between Cl and Br signifies comparable partitioning behaviour in all samples. However, I is more variable, displaying a positive correlation with Cl for more primitive samples (e.g. picrite and peridotite), and seemingly decoupling from Br and Cl in chromite seams and pegmatites. The relative enrichment of I over Cl in the chromite seams points

  14. Benzo-thia-fused [n]Thienoacenequinodimethanes with Small to Moderate Diradical Characters: The Role of Pro-aromaticity versus Anti-aromaticity

    KAUST Repository

    Shi, Xueliang

    2016-01-19

    Open-shell singlet diradicaloids recently have received much attention due to their unique optical, electronic and magnetic properties and promising applications in materials science. Among various diradicaloids, quinoidal π-conjugated molecules have become the prevailing designs. However, there still lacks fundamental understanding on how the fusion mode and pro-aromaticity/anti-aromaticity affect their diradical character and physical properties. In this work, a series of pro-aromatic benzo-thia-fused [n]thienoacenequinodimethanes (Thn-TIPS (n=1-3) and BDTh-TIPS) were synthesized and compared with the previously reported anti-aromatic bisindeno-[n]thienoacenes (Sn-TIPS, n=1-4). The ground-state geometric and electronic structures of these new quinoidal molecules were systematically investigated by X-ray crystallographic analysis, variable temperature NMR, ESR, SQUID, Raman, and electronic absorption spectroscopy, assisted by DFT calculations. It was found that the diradical character index (y0) increased from nearly zero for Th1-TIPS to 2.4% for Th2-TIPS, 18.2% for Th3-TIPS, and 38.2% for BDTh-TIPS, due to the enhanced aromatic stabilization. Consequently, with the extension of molecular size, the one-photon absorption spectra are gradually red-shifted, the two-photon absorption (TPA) cross section values increase, and the singlet excited state lifetimes decrease. By comparison with the corresponding anti-aromatic analogues Sn-TIPS (n=1-3), the pro-aromatic Thn-TIPS (n=1-3) exhibit larger diradical character, longer singlet excited state lifetime and larger TPA cross section value. At the same time, they display distinctively different electronic absorption spectra and improved electrochemical amphotericity. Spectroelectrochemical studies revealed a good linear relationship between the optical energy gaps and the molecular length in the neutral, radical cationic and dicationic forms. Our research work disclosed the significant difference between the pro-aromatic

  15. Benzo-thia-fused [n]Thienoacenequinodimethanes with Small to Moderate Diradical Characters: The Role of Pro-aromaticity versus Anti-aromaticity

    KAUST Repository

    Shi, Xueliang; Quintero, EstefanÍ a; Lee, Sangsu; Jing, Linzhi; Herng, Tun Seng; Zheng, Bin; Huang, Kuo-Wei; Ló pez Navarrete, Juan T.; Ding, Jun; Kim, Dongho; Casado, Juan; Chi, Chunyan

    2016-01-01

    Open-shell singlet diradicaloids recently have received much attention due to their unique optical, electronic and magnetic properties and promising applications in materials science. Among various diradicaloids, quinoidal π-conjugated molecules have become the prevailing designs. However, there still lacks fundamental understanding on how the fusion mode and pro-aromaticity/anti-aromaticity affect their diradical character and physical properties. In this work, a series of pro-aromatic benzo-thia-fused [n]thienoacenequinodimethanes (Thn-TIPS (n=1-3) and BDTh-TIPS) were synthesized and compared with the previously reported anti-aromatic bisindeno-[n]thienoacenes (Sn-TIPS, n=1-4). The ground-state geometric and electronic structures of these new quinoidal molecules were systematically investigated by X-ray crystallographic analysis, variable temperature NMR, ESR, SQUID, Raman, and electronic absorption spectroscopy, assisted by DFT calculations. It was found that the diradical character index (y0) increased from nearly zero for Th1-TIPS to 2.4% for Th2-TIPS, 18.2% for Th3-TIPS, and 38.2% for BDTh-TIPS, due to the enhanced aromatic stabilization. Consequently, with the extension of molecular size, the one-photon absorption spectra are gradually red-shifted, the two-photon absorption (TPA) cross section values increase, and the singlet excited state lifetimes decrease. By comparison with the corresponding anti-aromatic analogues Sn-TIPS (n=1-3), the pro-aromatic Thn-TIPS (n=1-3) exhibit larger diradical character, longer singlet excited state lifetime and larger TPA cross section value. At the same time, they display distinctively different electronic absorption spectra and improved electrochemical amphotericity. Spectroelectrochemical studies revealed a good linear relationship between the optical energy gaps and the molecular length in the neutral, radical cationic and dicationic forms. Our research work disclosed the significant difference between the pro-aromatic

  16. Tumour radiosensitization with the halogenated pyrimidines 5'-bromo-and 5'-iododeoxyuridine

    Energy Technology Data Exchange (ETDEWEB)

    Epstein, A.H.; Cook, J.A.; Goffman, T. (National Cancer Inst., Bethesda, MD (United States)); Glatstein, E. (Texas Univ., Dallas, TX (United States). Southwestern Medical Center)

    1993-02-01

    The authors review studies of the use of iododeoxyuridine (IdUrd) and bromodeoxyuridine as radiosensitizers and attempt to correlate the clinical outcome for patients treated with radiation and IdUrd with the extent of halogenated pyrimidine cellular uptake and incorporation. (U.K.).

  17. Determination of inorganic arsenic in algae using bromine halogenation and on-line nonpolar solid phase extraction followed by hydride generation atomic fluorescence spectrometry.

    Science.gov (United States)

    Zhang, Weihong; Qi, Yuehan; Qin, Deyuan; Liu, Jixin; Mao, Xuefei; Chen, Guoying; Wei, Chao; Qian, Yongzhong

    2017-08-01

    Accurate, stable and fast analysis of toxic inorganic arsenic (iAs) in complicated and arsenosugar-rich algae matrix is always a challenge. Herein, a novel analytical method for iAs in algae was reported, using bromine halogenation and on-line nonpolar solid phase extraction (SPE) followed by hydride generation atomic fluorescence spectrometry (HG-AFS). The separation of iAs from algae was first performed by nonpolar SPE sorbent using Br - for arsenic halogenation. Algae samples were extracted with 1% perchloric acid. Then, 1.5mL extract was reduced by 1% thiourea, and simultaneously reacted (for 30min) with 50μL of 10% KBr for converting iAs to AsBr 3 after adding 3.5mL of 70% HCl to 5mL. A polystyrene (PS) resin cartridge was employed to retain arsenicals, which were hydrolyzed, eluted from the PS resin with H 2 O, and categorized as iAs. The total iAs was quantified by HG-AFS. Under optimum conditions, the spiked recoveries of iAs in real algae samples were in the 82-96% range, and the method achieved a desirable limit of detection of 3μgkg -1 . The inter-day relative standard deviations were 4.5% and 4.1% for spiked 100 and 500μgkg -1 respectively, which proved acceptable for this method. For real algae samples analysis, the highest presence of iAs was found in sargassum fusiforme, followed by kelp, seaweed and laver. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1979-February 14, 1980

    International Nuclear Information System (INIS)

    Rack, E.P.

    1980-02-01

    The program consists of six interrelated areas: (1) Reactions of iodine with alkenes and alkynes activated by radiative neutron capture and isomeric transition in low pressure gaseous systems employing additives and rare gas moderators, high pressure, and liquid systems. Special attention was given to the reactivity of excited complex formation and structural effects of electrophilic iodine attack on various pi-bond systems. (2) The gas-to-condensed phase transition in halogen high energy chemistry. Current interest involves the study of caging effects of an ice lattice on recombination reactions involving neutron-irradiated frozen aqueous solutions of halogenated organic and biochemical solutes in order to learn more about kinetic energy effects, halogen size, solute molecule size, steric effects and hydrogen bonding within an ice lattice cage. (3) Systematics of halogen hot atom reactions. The reactions of /sup 80m/Br, 80 Br, /sup 82m/Br + 82 Br, 82 Br, 82 Br, 128 I, 130 I, and /sup 130m/I + 130 I activated by radiative neutron capture or isomeric transition in hydrocarbons and halo-substituted alkanes in low pressure and high pressure gaseous systems employing additives and rare gas moderators are currently being studied. (4) Mathematical and computer simulation studies of caging events within an ice lattice are being investigated. (5) At Brookhaven National Laboratory, cyclotron-produced chlorine and fluorine hot atoms substitution reactions with molecules possessing a single chiral center are under investigation. (6) The applications of high energy techniques and concepts to neutron activation analysis for trace elements and trace molecule determinations in biological systems was continued

  19. Toxics release inventory: List of toxic chemicals within the polychlorinated alkanes category and guidance for reporting

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-02-01

    Section 313 of the Emergency Planning and Community Right-to-Know Act of 1986 (EPCRA) requires certain facilities manufacturing, processing, or otherwise using listed toxic chemicals to report their environmental releases of such chemicals annually. On November 30, 1994 EPA added 286 chemicals and chemical categories. Six chemical categories (nicotine and salts, strychnine and salts, polycyclic aromatic compounds, water dissociable nitrate compounds, diisocyanates, and polychlorinated alkanes) are included in these additions. At the time of the addition, EPA indicated that the Agency would develop, as appropriate, interpretations and guidance that the Agency determines are necessary to facilitate accurate reporting for these categories. This document constitutes such guidance for the polychlorinated alkanes category.

  20. Modeling time-dependent toxicity to aquatic organisms from pulsed exposure of PAHs in urban road runoff

    International Nuclear Information System (INIS)

    Zhang Wei; Ye Youbin; Tong Yindong; Ou Langbo; Hu Dan; Wang Xuejun

    2011-01-01

    Understanding of the magnitude of urban runoff toxicity to aquatic organisms is important for effective management of runoff quality. In this paper, the aquatic toxicity of polycyclic aromatic hydrocarbons (PAHs) in urban road runoff was evaluated through a damage assessment model. Mortality probability of the organisms representative in aquatic environment was calculated using the monitored PAHs concentration in road runoff. The result showed that the toxicity of runoff in spring was higher than those in summer. Analysis of the time-dependent toxicity of series of runoff water samples illustrated that the toxicity of runoff water in the final phase of a runoff event may be as high as those in the initial phase. Therefore, the storm runoff treatment systems or strategies designed for capture and treatment of the initial portion of runoff may be inappropriate for control of runoff toxicity. - Research highlights: → Toxicity resulting from realistic exposure patterns of urban runoff is evaluated. → Toxicity of runoff water in the final phase is as high as the initial phase. → Treatment of the initial runoff portion is inappropriate to abate runoff toxicity. - Toxicity to aquatic organisms after sequential pulsed exposure to PAHs in urban road runoff is evaluated.

  1. Solution and solid-phase halogen and C-H hydrogen bonding to perrhenate.

    Science.gov (United States)

    Massena, Casey J; Riel, Asia Marie S; Neuhaus, George F; Decato, Daniel A; Berryman, Orion B

    2015-01-28

    (1)H NMR spectroscopic and X-ray crystallographic investigations of a 1,3-bis(4-ethynyl-3-iodopyridinium)benzene scaffold with perrhenate reveal strong halogen bonding in solution, and bidentate association in the solid state. A nearly isostructural host molecule demonstrates significant C-H hydrogen bonding to perrhenate in the same phases.

  2. Degradation of halogenated aliphatic compounds by the ammonia- oxidizing bacterium Nitrosomonas europaea.

    OpenAIRE

    Vannelli, T; Logan, M; Arciero, D M; Hooper, A B

    1990-01-01

    Suspensions of Nitrosomonas europaea catalyzed the ammonia-stimulated aerobic transformation of the halogenated aliphatic compounds dichloromethane, dibromomethane, trichloromethane (chloroform), bromoethane, 1,2-dibromoethane (ethylene dibromide), 1,1,2-trichloroethane, 1,1,1-trichloroethane, monochloroethylene (vinyl chloride), gem-dichloroethylene, cis- and trans-dichloroethylene, cis-dibromoethylene, trichloroethylene, and 1,2,3-trichloropropane, Tetrachloromethane (carbon tetrachloride),...

  3. Polycyclic aromatic hydrocarbons affect survival and development of common snapping turtle (Chelydra serpentina) embryos and hatchlings

    Energy Technology Data Exchange (ETDEWEB)

    Van Meter, Robin J [School of Environmental Science, Engineering, and Policy and Department of Bioscience and Biotechnology, Drexel University, 3141 Chestnut Street, Philadelphia, PA 19104 (United States); Spotila, James R [School of Environmental Science, Engineering, and Policy and Department of Bioscience and Biotechnology, Drexel University, 3141 Chestnut Street, Philadelphia, PA 19104 (United States); Avery, Harold W [School of Environmental Science, Engineering, and Policy and Department of Bioscience and Biotechnology, Drexel University, 3141 Chestnut Street, Philadelphia, PA 19104 (United States)

    2006-08-15

    Polycyclic aromatic hydrocarbons (PAHs) are toxic compounds found in the John Heinz National Wildlife Refuge in Philadelphia, Pennsylvania. We assessed the impact of PAHs and crude oil on snapping turtle development and behavior by exposing snapping turtle eggs from the Refuge and from three clean reference sites to individual PAHs or a crude oil mixture at stage 9 of embryonic development. Exposure to PAHs had a significant effect on survival rates in embryos from one clean reference site, but not in embryos from the other sites. There was a positive linear relationship between level of exposure to PAHs and severity of deformities in embryos collected from two of the clean reference sites. Neither righting response nor upper temperature tolerance (critical thermal maximum, CTM) of snapping turtle hatchlings with no or minor deformities was significantly affected by exposure to PAHs. - Exposure to polycyclic aromatic hydrocarbons on the egg reduces survival of snapping turtle embryos and causes developmental abnormalities.

  4. Polycyclic aromatic hydrocarbons affect survival and development of common snapping turtle (Chelydra serpentina) embryos and hatchlings

    International Nuclear Information System (INIS)

    Van Meter, Robin J.; Spotila, James R.; Avery, Harold W.

    2006-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are toxic compounds found in the John Heinz National Wildlife Refuge in Philadelphia, Pennsylvania. We assessed the impact of PAHs and crude oil on snapping turtle development and behavior by exposing snapping turtle eggs from the Refuge and from three clean reference sites to individual PAHs or a crude oil mixture at stage 9 of embryonic development. Exposure to PAHs had a significant effect on survival rates in embryos from one clean reference site, but not in embryos from the other sites. There was a positive linear relationship between level of exposure to PAHs and severity of deformities in embryos collected from two of the clean reference sites. Neither righting response nor upper temperature tolerance (critical thermal maximum, CTM) of snapping turtle hatchlings with no or minor deformities was significantly affected by exposure to PAHs. - Exposure to polycyclic aromatic hydrocarbons on the egg reduces survival of snapping turtle embryos and causes developmental abnormalities

  5. Perspectives on halogen bonding and other sigma-hole interactions: Lex parsimoniae (Occam's Razor)

    Czech Academy of Sciences Publication Activity Database

    Politzer, P.; Riley, Kevin Eugene; Bulat, F. A.; Murray, J. S.

    2012-01-01

    Roč. 998, SI (2012), s. 2-8 ISSN 2210-271X Institutional research plan: CEZ:AV0Z40550506 Keywords : halogen bonding * alpha-Hole bonding * hydrogen bonding * electrostatics /polarization * dispersion * electrostatic potentials Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.139, year: 2012

  6. PATTERN RECOGNITION STUDIES OF HALOGENATED ORGANIC COMPOUNDS USING CONDUCTING POLYMER SENSOR ARRAYS. (R825323)

    Science.gov (United States)

    Direct measurement of volatile and semivolatile halogenated organic compounds of environmental interest was carried out using arrays of conducting polymer sensors. Mathematical expressions of the sensor arrays using microscopic polymer network model is described. A classical, non...

  7. Rapid determination of 9 aromatic amines in mainstream cigarette smoke by modified dispersive liquid liquid microextraction and ultraperformance convergence chromatography tandem mass spectrometry.

    Science.gov (United States)

    Deng, Huimin; Yang, Fei; Li, Zhonghao; Bian, Zhaoyang; Fan, Ziyan; Wang, Ying; Liu, Shanshan; Tang, Gangling

    2017-07-21

    Aromatic amines in mainstream cigarette smoke have long been monitored due to their carcinogenic toxicity. In this work, a reliable and rapid method was developed for the simultaneous determination of 9 aromatic amines in mainstream cigarette smoke by modified dispersive liquid liquid microextraction (DLLME) and ultraperformance convergence chromatography tandem mass spectrometry (UPC 2 -MS/MS). Briefly, the particulate phase of the cigarette smoke was captured by a Cambridge filter pad, and diluted hydrogen chloride aqueous solution is employed to extract the aromatic amines under mechanical shaking. After alkalization with sodium hydroxide solution, small amount of toluene was introduced to further extract and enrich aromatic amines by modified DLLME under vortexing. After centrifugation, toluene phase was purified by a universal QuEChERS cleanup kit and was finally analyzed by UPC 2 -MS/MS. Attributing to the superior performance of UPC 2 -MS/MS, this novel approach allowed the separation and determination of 9 aromatic amines within 5.0min with satisfactory resolution and sensitivity. The proposed method was finally validated using Kentucky reference cigarette 3R4F, and emission levels of targeted aromatic amines determined were comparable to previously reported methods At three different spiked levels, the recoveries of most analytes were ranged from 74.01% to 120.50% with relative standard deviation (RSD) less than 12%, except that the recovery of p-toluidine at low spiked level and 3-aminobiphenyl at medium spiked level was 62.77% and 69.37% respectively. Thus, this work provides a novel alternative method for the simultaneous analysis of 9 aromatic amines in mainstream cigarette smoke. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Low molecular weight halogenated hydrocarbons (LMHHs) in Mediterranean sea water: Preliminary observations

    International Nuclear Information System (INIS)

    Elder, D.L.; Villeneuve, J.P.; Harvey, G.R.

    1976-01-01

    Halogenated organic compounds containing 1-3 carbon atoms are among the most extensively produced synthetic chemicals. Within this group of compounds are solvents such as chloroform, carbon tetrachloride, trichloroethane and the chlorofluoro carbons or freons which are used as refrigerants and aerosol sprays. Once produced many of these compounds are eventually released to the environment

  9. Rearrangements in the halogenation of tetraalkylethylenes with N-halosuccinimides and tert-butyl hypochlorite

    NARCIS (Netherlands)

    Meijer, E.W.; Kellogg, R.M.; Wynberg, H.

    1982-01-01

    The reaction of N-halosuccinimides and Me3COCl with tetraalkylethylenes involves halo-cation addn. to the double bond in a fast reaction, followed by abstraction of an allylic proton, resulting in a double bond shift. Homoallylic halogenation occurs in tetraalkylethylenes which can not undergo a

  10. Bicyclic Baird-type aromaticity

    Science.gov (United States)

    Cha, Won-Young; Kim, Taeyeon; Ghosh, Arindam; Zhang, Zhan; Ke, Xian-Sheng; Ali, Rashid; Lynch, Vincent M.; Jung, Jieun; Kim, Woojae; Lee, Sangsu; Fukuzumi, Shunichi; Park, Jung Su; Sessler, Jonathan L.; Chandrashekar, Tavarekere K.; Kim, Dongho

    2017-12-01

    Classic formulations of aromaticity have long been associated with topologically planar conjugated macrocyclic systems. The theoretical possibility of so-called bicycloaromaticity was noted early on. However, it has yet to be demonstrated by experiment in a simple synthetic organic molecule. Conjugated organic systems are attractive for studying the effect of structure on electronic features. This is because, in principle, they can be modified readily through dedicated synthesis. As such, they can provide useful frameworks for testing by experiment with fundamental insights provided by theory. Here we detail the synthesis and characterization of two purely organic non-planar dithienothiophene-bridged [34]octaphyrins that permit access to two different aromatic forms as a function of the oxidation state. In their neutral forms, these congeneric systems contain competing 26 and 34 π-electronic circuits. When subject to two-electron oxidation, electronically mixed [4n+1]/[4n+1] triplet biradical species in the ground state are obtained that display global aromaticity in accord with Baird's rule.

  11. Hydrogenated and halogenated blue phosphorene as Dirac materials: A first principles study

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Minglei [School of Mechanical Engineering, Southeast University, Nanjing, Jiangsu 211189 (China); Wang, Sake [Department of Physics, Southeast University, Nanjing, Jiangsu 210096 (China); Yu, Jin [School of Materials Science and Engineering, Southeast University, Nanjing, Jiangsu 211189 (China); Tang, Wencheng, E-mail: 101000185@seu.edu.cn [School of Mechanical Engineering, Southeast University, Nanjing, Jiangsu 211189 (China)

    2017-01-15

    Highlights: • The fully hydrogenated and halogenated blue phosphorenes are 2D Dirac materials. • The Dirac cone in fluorinated and iodinated blue phosphorenes lies exactly at the Fermi level. • The mass density of hydrogenated and fluorinated blue phosphorenes is rather small. - Abstract: Using first-principles calculations, we systematically investigate the structures and electronic properties of fully hydrogenated and halogenated blue phosphorene (P{sub 2}X{sub 2}). All these systems possess Dirac cone at high-symmetry K point, which are mainly contributed by P s p{sub x} p{sub y} orbitals. The Dirac cone in P{sub 2}F{sub 2} and P{sub 2}I{sub 2} systems lies exactly at the Fermi level. Formation energy analysis denotes that all the systems are energetically stable except P{sub 2}I{sub 2}. The mass density for P{sub 2}H{sub 2} and P{sub 2}F{sub 2} systems is rather small. Our calculations proposed that these systems, especially P{sub 2}F{sub 2} system, have great potential applications in future nanoelectronics.

  12. Analysis of fire deaths in Poland and influence of smoke toxicity.

    Science.gov (United States)

    Giebułtowicz, Joanna; Rużycka, Monika; Wroczyński, Piotr; Purser, David A; Stec, Anna A

    2017-08-01

    Dwelling fires have changed over the years because building contents and the materials used in then have changed. They all contribute to an ever-growing diversity of chemical species found in fires, many of them highly toxic. These arise largely from the changing nature of materials in interior finishes and furniture, with an increasing content of synthetic materials containing higher levels of nitrogen, halogen and phosphorus additives. While there is still a belief that carbon monoxide is the major lethal toxic agent in fires, the hydrogen cyanide and acid gases released from these additives are now well-recognised as major contributory causes of incapacitation, morbidity and mortality in domestic fires. Data for the total number of 263 fire death cases in the Mazowieckie region (mainly Warsaw area) of Poland between 2003-2011 for dwellings fires were obtained from pathologists, forensic toxicologists, fire fighters and analysed. Factors contributing to the death such as the findings of the full post mortem examination (age, sex, health status, burns), the toxicological analysis (carbon monoxide, alcohol etc.), and a thorough investigation of the scene (fire conditions, fuel, etc.) were taken into account and are summarised. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Evaluation of wear rate of dental composites polymerized by halogen or LED light curing units

    Directory of Open Access Journals (Sweden)

    Alaghehmand H.

    2006-08-01

    Full Text Available Background and Aim: Sufficient polymerization is a critical factor to obtain optimum physical properties and clinical efficacy of resin restorations. The aim of this study was to evaluate wear rates of composite resins polymerized by two different systems Light Emitting Diodes (LED to and Halogen lamps. Materials and Methods: In this laboratory study, 20 specimens of A3 Tetric Ceram composite were placed in brass molds of 2*10*10 mm dimensions and cured for 40 seconds with 1 mm distance from surface. 10 specimens were cured with LED and the other 10 were cured with Halogen unit. A device with the ability to apply force was developed in order to test the wear of composites. After storage in distilled water for 10 days, the specimens were placed in the wear testing machine. A chrome cobalt stylus with 1.12 mm diameter was applied against the specimens surfaces with a load of 2 kg. The weight of each samples before and after 5000, 10000, 20000, 40000, 80000 and 120000 cycles was measured using an electronic balance with precision of 10-4 grams. Data were analyzed using t test and paired t test. P0.05. Conclusion: Based on the results of this study, LED and halogen light curing units resulted in a similar wear rate in composite resin restorations.

  14. Volatilisation of aromatic hydrocarbons from soil

    DEFF Research Database (Denmark)

    Lindhardt, B.; Christensen, T.H.

    1996-01-01

    The non-steady-state fluxes of aromatic hydrocarbons were measured in the laboratory from the surface of soils contaminated with coal tar Four soil samples from a former gasworks site were used for the experiments. The fluxes were quantified for 11 selected compounds, 4 mono- and 7 polycyclic...... aromatic hydrocarbons, for a period of up to 8 or 16 days. The concentrations of the selected compounds in the soils were between 0.2 and 3,100 mu g/g. The study included the experimental determination of the distribution coefficient of the aromatic hydrocarbons between the sorbed phase and the water under...... saturated conditions. The determined distribution coefficients showed that the aromatic hydrocarbons were more strongly sorbed to the total organic carbon including the coal tar pitch - by a factor of 8 to 25 - than expected for natural organic matter. The fluxes were also estimated using an analytical...

  15. Emission factors of polycyclic and nitro-polycyclic aromatic hydrocarbons from residential combustion of coal and crop residue pellets.

    Science.gov (United States)

    Yang, Xiaoyang; Liu, Shijie; Xu, Yisheng; Liu, Yu; Chen, Lijiang; Tang, Ning; Hayakawa, Kazuichi

    2017-12-01

    Polycyclic aromatic hydrocarbons (PAHs) and nitro-polycyclic aromatic hydrocarbons (NPAHs) are toxic pollutants mainly produced during fossil fuel combustion. Domestic coal stoves, which emit large amounts of PAHs and NPAHs, are widely used in the Chinese countryside. In this study, emission factors (Efs) for 13 PAH species and 21 NPAH species for four raw coal (three bituminous and one anthracite), one honeycomb briquette, and one crop residue pellet (peanut hulls) samples burned in a typical Chinese rural cooking stove were determined experimentally. The PAH and NPAH Efs for the six fuels were 3.15-49 mg/kg and 0.32-100 μg/kg, respectively. Peanut hulls had very high Efs for both PAHs and NPAHs, and honeycomb briquettes had the lowest Efs. 2-Nitropyrene and 2-nitrofluoranthene, which are NPAHs typically found in secondary organic aerosol, were detected in the emissions from some fuels, suggesting that chemical reactions may have occurred in the dilution tunnel between the flue gas leaving the stove and entering the sampler. The 1-nitropyrene to pyrene diagnostic ratios for coal and peanut hulls were 0.0001 ± 0.0001 and 0.0005, respectively. These were in the same order of magnitude as reference ratios for emissions during coal combustion. The 6-nitrobenzo[a]pyrene to benzo[a]pyrene ratios for the fuels were determined, and the ratios for coal and peanut hulls were 0.0010 ± 0.0001 and 0.0014, respectively. The calculated potential toxic risks indicated that peanut hull emissions were very toxic, especially in terms of NPAHs, compared with emissions from the other fuels. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Quantitative structure-activity relationships for chronic toxicity of alkyl-chrysenes and alkyl-benz[a]anthracenes to Japanese medaka embryos (Oryzias latipes).

    Science.gov (United States)

    Lin, Hongkang; Morandi, Garrett D; Brown, R Stephen; Snieckus, Victor; Rantanen, Toni; Jørgensen, Kåre B; Hodson, Peter V

    2015-02-01

    Alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) are a class of compounds found at significant concentrations in crude oils, and likely the main constituents responsible for the chronic toxicity of oil to fish. Alkyl substituents at different locations on the aromatic rings change the size and shape of PAH molecules, which results in different interactions with tissue receptors and different severities of toxicity. The present study is the first to report the toxicity of several alkylated derivatives of chrysene and benz[a]anthracene to the embryos of Japanese medaka (Oryzias latipes) using the partition controlled delivery (PCD) method of exposure. The PCD method maintained the desired exposure concentrations by equilibrium partitioning of hydrophobic test compounds from polydimethylsiloxane (PDMS) films. Test concentrations declined by only 13% over a period of 17 days. Based on the prevalence of signs of blue sac disease (BSD), as expressed by median effective concentrations (EC50s), benz[a]anthracene (B[a]A) was more toxic than chrysene. Alkylation generally increased toxicity, except at position 2 of B[a]A. Alkyl-PAHs substituted in the middle region had a lower EC50 than those substituted at the distal region. Except for B[a]A and 7-methylbenz[a]anthracene (7-MB), estimated EC50 values were higher than their solubility limits, which resulted in limited toxicity within the range of test concentrations. The regression between log EC50s and logKow values provided a rough estimation of structure-activity relationships for alkyl-PAHs, but Kow alone did not provide a complete explanation of the chronic toxicity of alkyl PAHs. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Crystallochemical analysis of rare-earth halogen-containing π-complexes

    International Nuclear Information System (INIS)

    Blatova, O.A.; Blatov, V.A.; Serezhkin, V.N.

    2001-01-01

    Dependence of the size of Ln atom action in coordination polyhedrons LnC n X m (X = F, Cl, Br) on its nature, coordination number, oxidation state and number of Ln-X bonds, was studied using 96 halogen-containing π-complexes of rare earth and yttrium (Ln) by way of example. A method of estimating ligand sizes in coordination sphere using the Voronoi-Dirichlet molecular polyhedrons was suggested. Influence of the ligands sizes on stability of π-complexes and presence of specific interactions in their structure was analyzed [ru

  18. Impacts of halogen additions on mercury oxidation, in a slipstream selective catalyst reduction (SCR), reactor when burning sub-bituminous coal.

    Science.gov (United States)

    Cao, Yan; Gao, Zhengyang; Zhu, Jiashun; Wang, Quanhai; Huang, Yaji; Chiu, Chengchung; Parker, Bruce; Chu, Paul; Pant, Wei-Ping

    2008-01-01

    This paper presents a comparison of impacts of halogen species on the elemental mercury (Hg(0)) oxidation in a real coal-derived flue gas atmosphere. It is reported there is a higher percentage of Hg(0) in the flue gas when burning sub-bituminous coal (herein Powder River Basin (PRB) coal) and lignite, even with the use of selective catalytic reduction (SCR). The higher Hg(0)concentration in the flue gas makes it difficult to use the wet-FGD process for the mercury emission control in coal-fired utility boilers. Investigation of enhanced Hg(0) oxidation by addition of hydrogen halogens (HF, HCl, HBr, and HI) was conducted in a slipstream reactor with and without SCR catalysts when burning PRB coal. Two commercial SCR catalysts were evaluated. SCR catalyst no. 1 showed higher efficiencies of both NO reduction and Hg(0) oxidation than those of SCR catalyst no. 2. NH3 addition seemed to inhibit the Hg(0) oxidation, which indicated competitive processes between NH3 reduction and Hg(0) oxidation on the surface of SCR catalysts. The hydrogen halogens, in the order of impact on Hg(0) oxidation, were HBr, HI, and HCl or HF. Addition of HBr at approximately 3 ppm could achieve 80% Hg(0) oxidation. Addition of HI at approximately 5 ppm could achieve 40% Hg(0) oxidation. In comparison to the empty reactor, 40% Hg(0) oxidation could be achieved when HCl addition was up to 300 ppm. The enhanced Hg(0) oxidation by addition of HBr and HI seemed not to be correlated to the catalytic effects by both evaluated SCR catalysts. The effectiveness of conversion of hydrogen halogens to halogen molecules or interhalogens seemed to be attributed to their impacts on Hg(0) oxidation.

  19. Assessing the ecological risk of polycyclic aromatic hydrocarbons in sediments at Langkawi Island, Malaysia.

    Science.gov (United States)

    Nasher, Essam; Heng, Lee Yook; Zakaria, Zuriati; Surif, Salmijah

    2013-01-01

    Tourism-related activities such as the heavy use of boats for transportation are a significant source of petroleum hydrocarbons that may harm the ecosystem of Langkawi Island. The contamination and toxicity levels of polycyclic aromatic hydrocarbon (PAH) in the sediments of Langkawi were evaluated using sediment quality guidelines (SQGs) and toxic equivalent factors. Ten samples were collected from jetties and fish farms around the island in December 2010. A gas chromatography/flame ionization detector (GC/FID) was used to analyse the 18 PAHs. The concentration of total PAHs was found to range from 869 ± 00 to 1637 ± 20 ng g⁻¹ with a mean concentration of 1167.00 ± 24 ng g⁻¹, lower than the SQG effects range-low (3442 ng g⁻¹). The results indicated that PAHs may not cause acute biological damage. Diagnostic ratios and principal component analysis suggested that the PAHs were likely to originate from pyrogenic and petrogenic sources. The toxic equivalent concentrations of the PAHs ranged from 76.3 to 177 ng TEQ/g d.w., which is lower compared to similar studies. The results of mean effects range-median quotient of the PAHs were lower than 0.1, which indicate an 11% probability of toxicity effect. Hence, the sampling sites were determined to be the low-priority sites.

  20. Bioassay of polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Van Kirk, E.A.

    1980-08-01

    A positive relationship was found between the photodynamic activity of 24 polycyclic aromatic hydrocarbons versus published results on the mutagenicity, carcinogenicity, and initiation of unscheduled DNA synthesis. Metabolic activation of benzo(a)pyrene resulted in detection of increased mutagenesis in Paramecium tetraurelia as found also in the Ames Salmonella assay. The utility of P. tetraurelia as a biological detector of hazardous polycyclic aromatic hydrocarbons is discussed.

  1. Quantitative structure–activity relationships for toxicity and genotoxicity of halogenated aliphatic compounds: Wing spot test of Drosophila melanogaster

    Czech Academy of Sciences Publication Activity Database

    Chroust, K.; Pavlová, M.; Prokop, Z.; Mendel, Jan; Božková, K.; Kubát, Z.; Zajíčková, V.; Damborský, J.

    2007-01-01

    Roč. 67, č. 1 (2007), s. 152-159 ISSN 0045-6535 Institutional research plan: CEZ:AV0Z60930519 Keywords : toxicity * wing spot test * QSAR Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 2.739, year: 2007

  2. RELATING DAILY SOLAR ULTRAVIOLET RADIATION DOSE IN SALT MARSH-ASSOCIATED ESTUARINE SYSTEMS TO LABORATORY ASSESSMENTS OF PHOTOACTIVATED POLYCYCLIC AROMATIC HYDROCARBON TOXICITY

    Science.gov (United States)

    Estuaries of the southeastern United States not only serve an important nursery function but also are common repositories of polycyclic aromatic hydrocarbons (PAHs) derived from upland activities. Thus, these habitats may be at risk for PAHphototoxicity. To better characterize ...

  3. How non-conventional feedstocks will affect aromatics technologies

    Energy Technology Data Exchange (ETDEWEB)

    Koehler, E. [Clariant Produkte (Deutschland) GmbH, Muenchen (Germany)

    2013-11-01

    The abundance of non-conventional feedstocks such as coal and shale gas has begun to affect the availability of traditional base chemicals such as propylene and BTX aromatics. Although this trend is primarily fueled by the fast growing shale gas economy in the US and the abundance of coal in China, it will cause the global supply and demand situation to equilibrate across the regions. Lower demand for gasoline and consequently less aromatics rich reformate from refineries will further tighten the aromatics markets that are expected to grow at healthy rates, however. Refiners can benefit from this trend by abandoning their traditional fuel-oriented business model and becoming producers of petrochemical intermediates, with special focus on paraxylene (PX). Cheap gas from coal (via gasification) or shale reserves is an advantaged feedstock that offers a great platform to make aromatics in a cost-competitive manner, especially in regions where naphtha is in short supply. Gas condensates (LPG and naphtha) are good feedstocks for paraffin aromatization, and methanol from coal or (shale) gas can be directly converted to BTX aromatics (MTA) or alkylated with benzene or toluene to make paraxylene. Most of today's technologies for the production and upgrading of BTX aromatics and their derivatives make use of the unique properties of zeolites. (orig.)

  4. Halogen bonding from a hard and soft acids and bases perspective: investigation by using density functional theory reactivity indices.

    Science.gov (United States)

    Pinter, Balazs; Nagels, Nick; Herrebout, Wouter A; De Proft, Frank

    2013-01-07

    Halogen bonds between the trifluoromethyl halides CF(3)Cl, CF(3)Br and CF(3)I, and dimethyl ether, dimethyl sulfide, trimethylamine and trimethyl phosphine were investigated using Pearson's hard and soft acids and bases (HSAB) concept with conceptual DFT reactivity indices, the Ziegler-Rauk-type energy-decomposition analysis, the natural orbital for chemical valence (NOCV) framework and the non-covalent interaction (NCI) index. It is found that the relative importance of electrostatic and orbital (charge transfer) interactions varies as a function of both the donor and acceptor molecules. Hard and soft interactions were distinguished and characterised by atomic charges, electrophilicity and local softness indices. Dual-descriptor plots indicate an orbital σ hole on the halogen similar to the electrostatic σ hole manifested in the molecular electrostatic potential. The predicted high halogen-bond-acceptor affinity of N-heterocyclic carbenes was evidenced in the highest complexation energy for the hitherto unknown CF(3) I·NHC complex. The dominant NOCV orbital represents an electron-density deformation according to a n→σ*-type interaction. The characteristic signal found in the reduced density gradient versus electron-density diagram corresponds to the non-covalent interaction between contact atoms in the NCI plots, which is the manifestation of halogen bonding within the NCI theory. The unexpected C-X bond strengthening observed in several cases was rationalised within the molecular orbital framework. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Mineralization of polycyclic and n-heterocyclic aromatic compounds in hydrocarbon-contaminated soils

    International Nuclear Information System (INIS)

    Grosser, R.J.; Warshawsky, D.; Vestal, J.R.

    1995-01-01

    The comparative mineralization of eight polycyclic aromatic compounds in five soils collected from an abandoned coal tar refinery in eastern Ohio was determined. The soils showed differences only in total extractable hydrocarbon content of the soil chemical characteristics measured. The compounds studied included five polycyclic aromatic hydrocarbons (phenanthrene, anthracene, pyrene, and carcinogenic benz[a]anthracene and benzo[a]pyrene) and three N-heterocyclic aromatics (9H-carbazole, and carcinogenic 7H-dibenzo[c,g]carbazole and dibenz[a,j]acridine). Mineralization was measured by serum bottle radiorespirometry. Only phenanthrene, anthracene, pyrene, benz[a]anthracene, and carbazole were mineralized in the soils after 64 d. Two of the soils with eight to 15 times the hexane -extractable hydrocarbon content consistently showed more rapid initial rates and higher overall extents of mineralization compared to the other three soils. Overall extents of mineralization ranged from 38 to 55% for phenanthrene, 10 to 60% for anthracene, 25 to 70% for pyrene, background to 40% for benz[a]anthracene, and 25 to 50% for carbazole after 64 d. Extents of mineralization by indigenous soil microbiota appear to be more dependent on the chemical characteristics of the soil and not soil total biomass and activity. Cultures capable of degrading phenanthrene, anthracene, and pyrene were obtained following enrichment techniques. A Mycobacterium sp. capable of degrading these three compounds was isolated and reintroduced into two of the soils, resulting in mineralization enhanced above that of the indigenous soil microbial population. These data indicate that the future success of bioremediation methods relies on the characterization of environmental parameters affecting microbial degradation as well as the isolation of microbial populations that can reduce toxicity in the environment

  6. Pyrimidine and halogenated pyrimidines near edge x-ray absorption fine structure spectra at C and N K-edges: experiment and theory

    International Nuclear Information System (INIS)

    Bolognesi, P.; O'Keeffe, P.; Ovcharenko, Y.; Coreno, M.; Avaldi, L.; Feyer, V.; Plekan, O.; Prince, K. C.; Zhang, W.; Carravetta, V.

    2010-01-01

    The inner shell excitation of pyrimidine and some halogenated pyrimidines near the C and N K-edges has been investigated experimentally by near edge x-ray absorption fine structure spectroscopy and theoretically by density functional theory calculations. The selected targets, 5-Br-pyrimidine, 2-Br-pyrimidine, 2-Cl-pyrimidine, and 5-Br-2-Cl-pyrimidine, allow the effects of the functionalization of the pyrimidine ring to be studied either as a function of different halogen atoms bound to the same molecular site or as a function of the same halogen atom bound to different molecular sites. The results show that the individual characteristics of the different spectra of the substituted pyrimidines can be rationalized in terms of variations in electronic and geometrical structures of the molecule depending on the localization and the electronegativity of the substituent.

  7. Exploring the C-X…π Halogen Bonding Motif: An Infrared and Raman Study of the Complexes of CF3X (X = Cl, Br and I with the Aromatic Model Compounds Benzene and Toluene

    Directory of Open Access Journals (Sweden)

    Wouter A. Herrebout

    2013-06-01

    Full Text Available The formation of halogen bonded complexes formed between the trifluorohalomethanes CF3Cl, CF3Br and CF3I and the Lewis bases benzene and toluene at temperatures below 150K was investigated using FTIR and Raman spectroscopy. Experiments using liquid krypton as solvent show that for both CF3Br and CF3I substantial fractions of the monomers can be involved in 1:1 complexes. In addition, weak absorptions illustrating the formation of 2:1 complexes between CF3I and benzene are observed. Using spectra recorded at temperatures between 120 and 140 K, observed information on the relative stability was obtained for all complexes by determining the complexation enthalpies in solution. The resulting values for CF3Br.benzene, CF3I.benzene and (CF3I2.benzene are −6.5(3, −7.6(2 and −14.5(9 kJ mol−1. The values for CF3Br.toluene and CF3I.toluene are −6.2(5 and −7.4(5 kJ mol−1. The experimental complexation enthalpies are compared with theoretical data obtained by combining results from MP2/aug-cc-pVDZ(-PP and MP2/aug-cc-pVTZ(-PP ab initio calculations, from statistical thermodynamical calculations and from Monte Carlo Free Energy Perturbation simulations. The data are also compared with results derived for other C-X···π halogen bonded complexes involving unsaturated Lewis bases such as ethene and ethyne.

  8. Aromatization of n-octane over Pd/C catalysts

    KAUST Repository

    Yin, Mengchen; Natelson, Robert H.; Campos, Andrew A.; Kolar, Praveen; Roberts, William L.

    2013-01-01

    Gas-phase aromatization of n-octane was investigated using Pd/C catalyst. The objectives were to: (1) determine the effects of temperature (400-600 °C), weight hourly space velocity (WHSV) (0.8-∞), and hydrogen to hydrocarbon molar ratio (MR) (0-6) on conversion, selectivity, and yield (2) compare the activity of Pd/C with Pt/C and Pt/KL catalysts and (3) test the suitability of Pd/C for aromatization of different alkanes including n-hexane, n-heptane, and n-octane. Pd/C exhibited the best aromatization performance, including 54.4% conversion and 31.5% aromatics yield at 500 °C, WHSV = 2 h-1, and a MR of 2. The Pd/C catalyst had higher selectivity towards the preferred aromatics including ethylbenzene and xylenes, whereas Pt/KL had higher selectivity towards benzene and toluene. The results were somewhat consistent with adsorbed n-octane cyclization proceeding mainly through the six-membered ring closure mechanism. In addition, Pd/C was also capable of catalyzing aromatization of n-hexane and n-heptane. © 2012 Elsevier Ltd. All rights reserved.

  9. Proximate Composition, Mineral Content and Fatty Acids Analyses of Aromatic and Non-Aromatic Indian Rice

    Directory of Open Access Journals (Sweden)

    Deepak Kumar Verma

    2017-01-01

    Full Text Available Awareness on nutritive value and health benefits of rice is of vital importance in order to increase the consumption of rice in daily diet of the human beings. In this study, a total of six aromatic and two non-aromatic rice accessions grown in India were analysed for their nutritional quality attributes including proximate composition, mineral contents and fatty acids. Data with three replications were used to measure Pearson's simple correlation co-efficient in order to establish the relationship among various nutritional quality attributes. The result on proximate composition showed that Govind Bhog had the highest moisture (13.57% and fat (0.92% content, which signifies its tasty attribute. Badshah Bhog exhibited the highest fibre content (0.85%, carbohydrate content (82.70% and food energy (365.23 kCal per 100 g. Among the minerals, the higher Ca (98.75 mg/kg, Zn (17.00 mg/kg and Fe (31.50 mg/kg were in Gopal Bhog, whereas the highest Na (68.85 mg/kg was in Badshah Bhog, the highest K (500.00 mg/kg was in Swetganga, Khushboo and Sarbati. The highest contents of unsaturated fatty acids viz. oleic acid (49.14%, linoleic acid (46.99% and linolenic acid (1.27% were found in Sarbati, whereas the highest content of saturated fatty acids viz. myristic acid (4.60% and palmitic acid (31.91% were found in Govind Bhog and stearic acid (6.47% in Todal. The identified aromatic rice accessions Gopal Bhog, Govind Bhog and Badshah Bhog and non-aromatic rice accession Sarbati were found nutritionally superior among all eight tested accessions. The nutritional quality oriented attributes in this study were competent with recognized prominent aromatic and non-aromatic rice accessions as an index of their nutritional worth and recommend to farmers and consumers which may be graded as export quality rice with good unique nutritional values in international market.

  10. Quantitative Analysis of Mixed Halogen Dioxins and Furans in Fire Debris Utilizing Atmospheric Pressure Ionization Gas Chromatography-Triple Quadrupole Mass Spectrometry.

    Science.gov (United States)

    Organtini, Kari L; Myers, Anne L; Jobst, Karl J; Reiner, Eric J; Ross, Brian; Ladak, Adam; Mullin, Lauren; Stevens, Douglas; Dorman, Frank L

    2015-10-20

    Residential and commercial fires generate a complex mixture of volatile, semivolatile, and nonvolatile compounds. This study focused on the semi/nonvolatile components of fire debris to better understand firefighter exposure risks. Using the enhanced sensitivity of gas chromatography coupled to atmospheric pressure ionization-tandem mass spectrometry (APGC-MS/MS), complex fire debris samples collected from simulation fires were analyzed for the presence of potentially toxic polyhalogenated dibenzo-p-dioxins and dibenzofurans (PXDD/Fs and PBDD/Fs). Extensive method development was performed to create multiple reaction monitoring (MRM) methods for a wide range of PXDD/Fs from dihalogenated through hexa-halogenated homologue groups. Higher halogenated compounds were not observed due to difficulty eluting them off the long column used for analysis. This methodology was able to identify both polyhalogenated (mixed bromo-/chloro- and polybromo-) dibenzo-p-dioxins and dibenzofurans in the simulated burn study samples collected, with the dibenzofuran species being the dominant compounds in the samples. Levels of these compounds were quantified as total homologue groups due to the limitations of commercial congener availability. Concentration ranges in household simulation debris were observed at 0.01-5.32 ppb (PXDFs) and 0.18-82.11 ppb (PBDFs). Concentration ranges in electronics simulation debris were observed at 0.10-175.26 ppb (PXDFs) and 0.33-9254.41 ppb (PBDFs). Samples taken from the particulate matter coating the firefighters' helmets contained some of the highest levels of dibenzofurans, ranging from 4.10 ppb to 2.35 ppm. The data suggest that firefighters and first responders at fire scenes are exposed to a complex mixture of potentially hundreds to thousands of different polyhalogenated dibenzo-p-dioxins and dibenzofurans that could negatively impact their health.

  11. Biodegradation Of Polycyclic Aromatic Hydrocarbons In Petroleum Oil Contaminating The Environment

    International Nuclear Information System (INIS)

    Partila, A.M.

    2013-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants in urban atmospheres (Chen et al., 2013). PAHs enter the environment via incomplete combustion of fossil fuels and accidental leakage of petroleum products, and as components of products such as creosote (Muckian et al., 2009). Due to PAHs carcinogenic activity, they have been included in the European Union (EU) and the Environmental Protection Agency (EPA) priority pollutant lists. Human exposure to PAHs occurs in three ways, inhalation, dermal contact and consumption of contaminated foods, which account for 88-98% of such contamination; in other words, diet is the major source of human exposure to these contaminants (Rey-Salgueiro et al., 2008). Both the World Health Organization and the UK Expert Panel on Air Quality Standards (EPAQS) have considered benzo(a)pyrene (BaP) as a marker of the carcinogenic potency of the polycyclic aromatic hydrocarbons (PAH) mixture (Delgado-Saborit et al., 2011). Polycyclic aromatic and heavier aliphatic hydrocarbons, which have a stable recalcitrant molecular structure, exhibit high hydrophobicity and low aqueous solubility, are not readily removed from soil through leaching and volatilization (Brassington et al., 2007). The hydrophobicity of PAHs limits desorption to the aqueous phase (Donlon et al., 2002). Six main ways of dissipation, i.e. disappearance, are recognized in the environment: volatilization, photooxidation, Aim of the Work chemical oxidation, sorption, leaching and biodegradation. Microbial degradation is considered to be the main process involved in the dissipation of PAH (Yuan et al., 2002). Thus, more and more research interests are turning to the biodegradation of PAHs. Some microorganisms can utilize PAHs as a source of carbon and energy so that PAHs can be degraded to carbon dioxide and water, or transformed to other nontoxic or low-toxic substances (Perelo, 2010). Compared with other physical and chemical methods such as combustion

  12. Discriminative stimulus effects of inhaled 1,1,1-trichloroethane in mice: comparison to other hydrocarbon vapors and volatile anesthetics.

    Science.gov (United States)

    Shelton, Keith L

    2009-04-01

    Because the toxicity of many inhalants precludes evaluation in humans, drug discrimination, an animal model of subjective effects, can be used to gain insights on their poorly understood abuse-related effects. The purpose of the present study was to train a prototypic inhalant that has known abuse liability, 1,1,1-trichloroethane (TCE), as a discriminative stimulus in mice, and compare it to other classes of inhalants. Eight B6SJLF1/J mice were trained to discriminate 10 min of exposure to 12,000 ppm inhaled TCE vapor from air and seven mice were trained to discriminate 4,000 ppm TCE from air. Tests were then conducted to characterize the discriminative stimulus of TCE and to compare it to representative aromatic and chlorinated hydrocarbon vapors, volatile halogenated anesthetics as well as an odorant compound. Only the 12,000 ppm TCE versus the air discrimination group exhibited sufficient discrimination accuracy for substitution testing. TCE vapor concentration- and exposure time-dependently substituted for the 12,000 ppm TCE vapor training stimulus. Full substitution was produced by trichloroethylene, toluene, enflurane, and sevoflurane. Varying degrees of partial substitution were produced by the other volatile test compounds. The odorant, 2-butanol, did not produce any substitution for TCE. The discriminative stimulus effects of TCE are shared fully or partially by chlorinated and aromatic hydrocarbons as well as by halogenated volatile anesthetics. However, these compounds can be differentiated from TCE both quantitatively and qualitatively. It appears that the degree of similarity is not solely a function of chemical classification but may also be dependent upon the neurochemical effects of the individual compounds.

  13. Toxicity of benz(a)anthracene and fluoranthene to marine phytoplankton in culture: Does cell size really matter?

    Energy Technology Data Exchange (ETDEWEB)

    Othman, Hiba Ben [UMR 5119 ECOSYM, CNRS-IRD-Universite Montpellier II-Ifremer-Universite Montpellier I, SMEL 2 rue des Chantiers, F-34200 Sete (France); Laboratoire de Cytologie Vegetale et Phytoplanctonologie, Faculte des Sciences de Bizerte, Universite de Carthage, Zarzouna 7021, Bizerte (Tunisia); Leboulanger, Christophe, E-mail: christophe.leboulanger@ird.fr [UMR 5119 ECOSYM, CNRS-IRD-Universite Montpellier II-Ifremer-Universite Montpellier I, SMEL 2 rue des Chantiers, F-34200 Sete (France); Le Floc' h, Emilie [UMS MEDIMEER, CNRS-Universite Montpellier II, SMEL 2 rue des Chantiers F-34200 Sete (France); Hadj Mabrouk, Hassine; Sakka Hlaili, Asma [Laboratoire de Cytologie Vegetale et Phytoplanctonologie, Faculte des Sciences de Bizerte, Universite de Carthage, Zarzouna 7021, Bizerte (Tunisia)

    2012-12-15

    Highlights: Black-Right-Pointing-Pointer Polycyclic aromatic hydrocarbons (PAHs) in the marine environment are a hazardous chemical legacy. Black-Right-Pointing-Pointer Benz(a)anthracene and fluoranthene are toxic to phytoplankton photosynthesis and growth in culture. Black-Right-Pointing-Pointer Acute (photosynthesis) and chronic (population growth) effects have different thresholds. Black-Right-Pointing-Pointer Toxicity depends on both the species selected as a model and the compound considered. Black-Right-Pointing-Pointer Further study of the size/sensitivity relationship is required to draw more general conclusions. - Abstract: The toxicity of benz(a)anthracene and fluoranthene (polycyclic aromatic hydrocarbons, PAHs) was evaluated on seven species of marine algae in culture belonging to pico-, nano-, and microphytoplankton, exposed to increasing concentrations of up to 2 mg L{sup -1}. The short-term (24 h) toxicity was assessed using chlorophyll a fluorescence transients, linked to photosynthetic parameters. The maximum quantum yield Fv/Fm was lower at the highest concentrations tested and the toxicity thresholds were species-dependent. For acute effects, fluoranthene was more toxic than benz(a)anthracene, with LOECs of 50.6 and 186 {mu}g L{sup -1}, respectively. After 72 h exposure, there was a dose-dependent decrease in cell density, fluoranthene being more toxic than benz(a)anthracene. The population endpoint at 72 h was affected to a greater extent than the photosynthetic endpoint at 24 h. EC50 was evaluated using the Hill model, and species sensitivity was negatively correlated to cell biovolume. The largest species tested, the dinoflagellate Alexandrium catenella, was almost insensitive to either PAH. The population endpoint EC50s for fluoranthene varied from 54 {mu}g L{sup -1} for the picophytoplankton Picochlorum sp. to 418 {mu}g L{sup -1} for the larger diatom Chaetoceros muelleri. The size/sensitivity relationship is proposed as a useful model when

  14. Kinetic mechanism and enantioselectivity of halohydrin dehalogenase from Agrobacterium radiobacter

    NARCIS (Netherlands)

    Tang, Lixia; Lutje Spelberg, Jeffrey H.; Fraaije, Marco W.; Janssen, DB

    2003-01-01

    Halohydrin dehalogenase (HheC) from Agrobacterium radiobacter AD1 catalyzes the reversible intramolecular nucleophilic displacement of a halogen by a hydroxyl group in vicinal haloalcohols, producing the corresponding epoxides. The enzyme displays high enantioselectivity toward some aromatic

  15. Degradation of halogenated aliphatic compounds by the ammonia- oxidizing bacterium Nitrosomonas europaea.

    Science.gov (United States)

    Vannelli, T; Logan, M; Arciero, D M; Hooper, A B

    1990-01-01

    Suspensions of Nitrosomonas europaea catalyzed the ammonia-stimulated aerobic transformation of the halogenated aliphatic compounds dichloromethane, dibromomethane, trichloromethane (chloroform), bromoethane, 1,2-dibromoethane (ethylene dibromide), 1,1,2-trichloroethane, 1,1,1-trichloroethane, monochloroethylene (vinyl chloride), gem-dichloroethylene, cis- and trans-dichloroethylene, cis-dibromoethylene, trichloroethylene, and 1,2,3-trichloropropane, Tetrachloromethane (carbon tetrachloride), tet