Sample records for weight halogenated hydrocarbons

  1. Informative document halogenated hydrocarbon-containing waste

    NARCIS (Netherlands)

    Verhagen H


    This "Informative document halogenated hydrocarbon-containing waste" forms part of a series of "Informative documents waste materials". These documents are conducted by RIVM on the instructions of the Directorate General for the Environment, Waste Materials Directorate, in

  2. Boiling Heat Transfer to Halogenated Hydrocarbon Refrigerants (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.


    Model halogenated aromatic and aliphatic hydrocarbons and halogenated phenols were dehalogenated in seconds by solvated electrons generated from sodium in both anhydrous liquid ammonia and ammonia/water solutions. The minimum sodium required to completely dehalogenate these mo...

  4. Separation of toxic metal ions, hydrophilic hydrocarbons, hydrophobic fuel and halogenated hydrocarbons and recovery of ethanol from a process stream (United States)

    Kansa, Edward J.; Anderson, Brian L.; Wijesinghe, Ananda M.; Viani, Brian E.


    This invention provides a process to tremendously reduce the bulk volume of contaminants obtained from an effluent stream produced subsurface remediation. The chemicals used for the subsurface remediation are reclaimed for recycling to the remediation process. Additional reductions in contaminant bulk volume are achieved by the ultra-violet light destruction of halogenated hydrocarbons, and the complete oxidation of hydrophobic fuel hydrocarbons and hydrophilic hydrocarbons. The contaminated bulk volume will arise primarily from the disposal of the toxic metal ions. The entire process is modular, so if there are any technological breakthroughs in one or more of the component process modules, such modules can be readily replaced.

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

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    Carvan, M.J. III.


    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.

  6. Self-cleaning liner for halogenated hydrocarbon control in landfill leachate. (United States)

    He, Shichong; Zhu, Lizhong


    Sorptive landfill liners can prevent the migration of the leachate pollutants. However, their sorption ability will decrease over time. A method should be developed to maintain the sorption ability of landfill liners. In this study, we combined cetyltrimethylammonium bromide-bentonite (CTMAB-bentonite) and zero-valent iron (ZVI) to develop a self-cleaning liner that can retain its sorption ability for a long period. Batch experiments and calculation simulations were employed to analyse the sorption ability of this liner material and the ecological risk of halogenated hydrocarbons. The results showed that CTMAB-bentonite could sorb halogenated hydrocarbons well, with saturated sorption capacities (Q m) of 10.2, 14.5, 6.69, 18.5, 29.4, and 49.7 mg·g(-1) for dichloroethane (DCA), trichloroethane (TCA), dichloroethene (DCE), trichloroethylene (TCE), tetrachloroethylene (PCE), and 1,3- dichloropropene (1,3-DCP), respectively. Using the mixture of 0.5 g iron and 0.5 g CTMAB-bentonite could dramatically increase the removal efficiency of DCE, TCE, and PCE. The reaction with ZVI did not change the structure of CTMAB-bentonite and its sorption ability remained consistent. Calculation results suggested that the self-cleaning landfill liner would dramatically decrease the hazard index (HI) of the eluate. However, the humic acid and salt in leachate would cause a reduction in the removal of halogenated hydrocarbons.

  7. Remote carboxylation of halogenated aliphatic hydrocarbons with carbon dioxide (United States)

    Juliá-Hernández, Francisco; Moragas, Toni; Cornella, Josep; Martin, Ruben


    Catalytic carbon-carbon bond formation has enabled the streamlining of synthetic routes when assembling complex molecules. It is particularly important when incorporating saturated hydrocarbons, which are common motifs in petrochemicals and biologically relevant molecules. However, cross-coupling methods that involve alkyl electrophiles result in catalytic bond formation only at specific and previously functionalized sites. Here we describe a catalytic method that is capable of promoting carboxylation reactions at remote and unfunctionalized aliphatic sites with carbon dioxide at atmospheric pressure. The reaction occurs via selective migration of the catalyst along the hydrocarbon side-chain with excellent regio- and chemoselectivity, representing a remarkable reactivity relay when compared with classical cross-coupling reactions. Our results demonstrate that site-selectivity can be switched and controlled, enabling the functionalization of less-reactive positions in the presence of a priori more reactive ones. Furthermore, we show that raw materials obtained in bulk from petroleum processing, such as alkanes and unrefined mixtures of olefins, can be used as substrates. This offers an opportunity to integrate a catalytic platform en route to valuable fatty acids by transforming petroleum-derived feedstocks directly.

  8. Process for simultaneously processing of used metal and/or metal scrap and scrap containing halogenated hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Dapper, G.; Kirchner, W.; Sloterdijk, W.; Verbraak, C.A.


    A process is presened for reducing environmental pollution resulting from disposal of waste containing halogenated hydrocarbons by simultaneous treatment with used metal and/or metal scrap at elevated temperatures. The halogenated hydrocarbons are pyrolyzed and the resulting hydrogen halide containing gas is brought into contact with the used metal and/or metal scrap at elevated temperatures so as to form metal halogenides that are volatile under the conditions applied. The volatile metal halogenides are largely separated from the gaseous mixture formed, and at least part of the remaining gaseous mixture and/or hydrocarbon residue is used as fuel to maintain the required temperature. The waste feed compositions and process conditions can be chosen to effect separation between various metals by selective halogenation and condensation, and substantially all of the hydrogen halide can be tied up and recovered as metal halogenides.

  9. High Molecular Weight Petrogenic and Pyrogenic Hydrocarbons in Aquatic Environments (United States)

    Abrajano, T. A., Jr.; Yan, B.; O'Malley, V.


    the extensive geochemical and analytical framework that was meticulously built by petroleum geochemists over the years (e.g., Tissot and Welte, 1984; Peters et al., 1992; Peters and Moldowan, 1993; Engel and Macko, 1993; Moldowan et al., 1995; Wang et al., 1999; Faksness et al., 2002).Hydrocarbon compounds present in petroleum or pyrolysis by-products can be classified based on their composition, molecular weight, organic structure, or some combination of these criteria. For example, a report of the Committee on Intrinsic Remediation of the US NRC classified organic contaminants into HMW hydrocarbons, low molecular weight (LMW) hydrocarbons, oxygenated hydrocarbons, halogenated aliphatics, halogenated aromatics, and nitroaromatics (NRC, 2000). Hydrocarbons are compounds comprised exclusively of carbon and hydrogen and they are by far the dominant components of crude oil, processed petroleum hydrocarbons (gasoline, diesel, kerosene, fuel oil, and lubricating oil), coal tar, creosote, dyestuff, and pyrolysis waste products. These hydrocarbons often occur as mixtures of a diverse group of compounds whose behavior in near-surface environments is governed by their chemical structure and composition, the geochemical conditions and media of their release, and biological factors, primarily microbial metabolism, controlling their transformation and degradation.Hydrocarbons comprise from 50% to 99% of compounds present in refined and unrefined oil, and compounds containing other elements such as oxygen, nitrogen, and sulfur are present in relatively smaller proportions. Hydrocarbon compounds have carbons joined together as single C - C bonds (i.e., alkanes), double or triple C=C bonds (i.e., alkenes or olefins), or via an aromatic ring system with resonating electronic structure (i.e., aromatics). Alkanes, also called paraffins, are the dominant component of crude oil, with the carbon chain forming either straight (n-alkanes), branched (iso-alkanes), or cyclic (naphthenes

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

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


    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.

  11. [Pollution of Halogenated Polycyclic Aromatic Hydrocarbons in Atmospheric Particulate Matters of Shenzhen]. (United States)

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


    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.

  12. Polydiphenylamine/Zeolite Y composites and electrical conductivity responses toward halogenated hydrocarbons

    Directory of Open Access Journals (Sweden)

    Tharaporn Permpool


    Full Text Available Composites of polydiphenylamine (D-PDPA and zeolite Y with H+ as the cation (Y_H+ have been fabricated to be used as a sensing material towards non-halogenated and halogenated solvents (hexane, dichloromethane, 1, 2-dichloroethane, chloroform. These composites are toxic towards human and environment and are widely used as solvents in various industries. Polydiphenylamine, zeolite Y, and their composites are characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, particle size analysis, surface area, and pore size analysis. The effects of the Si/Al ratio, zeolite content, and vapor concentrations are investigated. The electrical conductivity sensitivity of the composites towards the solvents is higher than the pristine D-PDPA by ~1 order of magnitude. The composites can discriminate a non-halogenated solvent from halogenated solvents. They possess maximum electrical conductivity sensitivity values towards dichloromethane, but the composites do not respond to hexane. Generally, the sensitivity of the composites increases with increasing zeolite content and vapor concentration. The interactions between the composites and the vapors are investigated by FT-IR spectroscopy and UV-Vis spectroscopy. A mechanism for the interaction between the composites and the solvents is proposed.

  13. The development of a structure-activity relationship for the reduction of halogenated aromatic hydrocarbons in anaerobic water-sediment systems

    NARCIS (Netherlands)

    Peijnenburg WJGM; ' t Hart MJ; den Hollander HA; van de Meent D; Verboom JH; Wolfe NL


    This report deals with the results of a study on the degradation of halogenated aromatic hydrocarbons in anoxic sediment-water systems. First of all several transformation processes are shown to take place, leading to formation of a variety of products. In this a clear distinction could be made


    The prokarotic, endogenous storage polymer poly--hydroxybutyrate (PHB) accumulated in soil from a methane-enriched, halogenated hydrocarbon-degrading soil column. Based on phospholipid ester-linked fatty acid (PLFA) profiles, this mocrocosm has been previously reported to be sign...

  15. UVA Photoirradiation of Halogenated-Polycyclic Aromatic Hydrocarbons Leading to Induction of Lipid Peroxidation

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    Peter P. Fu


    Full Text Available Since the finding in the 1930s, a large number of polycyclic aromatic hydrocarbons (PAHs of different structures have been tested for potential tumorigenicity. Structure-activity relationships of halo-PAHs have been investigated to determine the regions of a PAH that may be involved in cancer initiation. From these studies, a number of halo-PAHs were found to be tumorigenic in experimental animals. It was not until the 1980s that halo-PAHs were found to be present in the environment, including municipal incinerator fly ash, urban air, coal combustion, soil, snow, automobile exhausts, and tap water. Due to their widespread presence in the environment and their genotoxic activities, including carcinogenicity, many of these compounds may pose a health risk to humans. Although the biological activities, including metabolism, mutagenicity, and carcinogenicity, of halo-PAHs have been studied their phototoxicity and photo-induced biological activity have not been well examined. In this study, we study the photoirradiation of a series of structure-related halo-PAHs by UVA light in the presence of a lipid, methyl linoleate, and determine as to whether or not these compounds can induce lipid peroxidation. The halo-PAHs chosen for study include 2-bromonaphthalene, 1-chloroanthracene, 9,10-dibromoanthracene, 9-chlorophenanthrene, 9-bromophenanthrene, 7-chlorobenz[a]anthracene, 7-bromobenz[a]anthracene, 7-bromo-5-methylbenz[a]anthracene, 6-chlorobenzo[a]pyrene, and 6-bromobenzo[a]pyrene. The results indicate that upon photoirradiation by UVA all these compounds induced lipid peroxidation at different levels. These results suggest that halo-PAHs may be harmful to human health.

  16. Cooperation and competition between halogen bonding and van der Waals forces in supramolecular engineering at the aliphatic hydrocarbon/graphite interface: position and number of bromine group effects. (United States)

    Zha, Bao; Dong, Meiqiu; Miao, Xinrui; Peng, Shan; Wu, Yican; Miao, Kai; Hu, Yi; Deng, Wenli


    Herein, the photophysical properties of two π-conjugated thienophenanthrene derivatives (6,9- and 5,10-DBTD) are reported. Their self-assembled monolayers in aliphatic hydrocarbon solvents under different concentrations were investigated by scanning tunneling microscopy on a graphite surface. The STM results revealed that the self-assembled structures of the two geometrical isomers exhibited absolutely different behaviors. At the aliphatic solvent/graphite interface, 6,9-DBTD produced almost a single stable coassembled linear structure, except for that with n-tridecane as the solvent. However, the self-assembly of 5,10-DBTD showed structural diversity, and it presented a gradient variety through increasing the chain length of the aliphatic solvents as well as the solution concentration. All ordered self-assembled adlayers critically depend on not only the interchain van der Waals (vdW) interactions, but also on multiple intermolecular interactions, including BrO[double bond, length as m-dash]C and BrS hetero-halogen bonds, homo-BrBr interactions, and HBr and HO hydrogen bonds. We proposed that the cooperation and competition of the intermolecular interactions involving a Br atom and interchain vdW forces induce this structural variety. Density functional theory calculations support to unravel the different elementary structural units based on halogen bonds and hydrogen bonds and were useful tools to dissect and explain the formation mechanism.

  17. A composite catalyst containing an halogen, a noble metal and at least an additional metal, and its utilization for aromatization of C2-C12 hydrocarbons

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    Alario, F.; Benazzi, E.; Deves, J.M.


    A composite catalyst is proposed for aromatization reactions of hydrocarbons containing from 2 to 12 carbon atoms per molecule, and more especially from 3 to 10 C atoms per molecule; the catalyst contains: a MFI structure zeolite which skeleton is composed of silicon, aluminium and/or gallium and which crystallites external faces have been modified after synthesis; a matrix; at least a noble metal from the platinum family and at least an additional metal chosen among tin, germanium, indium, copper, iron, molybdenum, gallium, thallium, gold, silver, ruthenium, chromium, tungsten and lead; at least an halogen (chlorine); eventually gallium and/or zinc; and eventually, at least one element chosen among alkaline and alkaline-earth metals. 2 tabs.

  18. Accumulation of poly-beta-hydroxybutyrate in a methane-enriched, halogenated hydrocarbon-degrading soil column: Implications for microbial community structure and nutritional status

    Energy Technology Data Exchange (ETDEWEB)

    Nichols, P.D.; White, D.C.


    The prokarotic, endogenous storage polymer poly-B-hydroxybutyrate (PHB) accumulated in soil from a methane-enriched, halogenated hydrocarbon-degrading soil column. Two strains analyzed of the type II methanotroph Methylobacterium organophilum were found to contain PHB, with PHB/PLFA ratios similar to those determined for the methane-enriched soil column, suggesting that methanotrophic bacteria enriched in the methane-amended column produced PHB. Control soil and sodium azide-inhibited material, in which methanotroph markers were below detection, did not contain PHB. Biochemical assays, based on the differences observed, can be used to monitor shifts in microbial biomass, community structure and nutritional status of systems used to model microbial biotransformation processes. The study illustrates that biochemical procedures have the potential to monitor the stimulated populations of a native soil microbial community capable of degrading pollutants.

  19. Reactions of halobenzenes with methanol on the microporous solid acids hbeta, HZSM-5, and HSAPO-5: halogenation does not improve the hydrocarbon pool. (United States)

    Marcus, David M; Song, Weiguo; Abubakar, Saifudin M; Jani, Emma; Sassi, Alain; Haw, James F


    The reactions of fluorobenzene, 3-fluorotoluene, and three isomers of difluorotoluene, chlorobenzene, and bromobenzene with excesses of methanol were investigated on the large-pore catalysts HBeta (*BEA) and HSAPO-5 (AFI), and on the medium-pore HZSM-5 (MFI). Flow reactor studies in pulse mode with GC-MS detection revealed that the fluorobenzene derivatives were readily methylated at, for example, 375 degrees C, but not even pentamethylfluorobenzene was obviously active as a reaction center for methanol-to-olefin (MTO) catalysis. Carbon-labeling studies revealed that small amounts of methylbenzenes were formed by defluorination, and these aromatic hydrocarbons seemed to account for the small yields of olefins (and their secondary reaction products) observed. Loss of one fluorine was also evident in the products for one of the difluorotoluene isomers. On HSAPO-5 the activity order for ring-methylation of halobenzenes was F > Cl > Br. On HZSM-5, chlorobenzene and especially bromobenzene lost halogen through a route forming halomethane. These largely negative results will nevertheless be useful in testing theoretical models of the detailed reaction steps in the hydrocarbon pool mechanism for MTO catalysis.

  20. Bioremediation of Mixtures of High Molecular Weight Polycyclic Aromatic Hydrocarbons (United States)

    Xu, H.; Wu, J.; Shi, X.; Sun, Y.


    Although bioremediation has been considered as one of the most promising means to remove polycyclic aromatic hydrocarbons (PAHs) from polluted environments, the efficacy of PAHs bioremediation still remains challenged, especially for high molecular weight PAHs (HMW PAHs) and their mixtures. This study was focused on (a) isolation and characterization of pure strain and mixed microbial communities able to degrade HMW PAHs and (b) further evaluation of the ability of the isolated microbes to degrade HMW PAHs mixtures in the absence and presence of indigenous flora. Fluoranthene, benzo[b]fluoranthene and pyrene were selected as the representative HMW PAHs in this study. A pure bacterial strain, identified as Herbaspirillum chlorophenolicum FA1, was isolated from activated sludge. A mixed bacterial community designated as consortium-4 was isolated from petroleum contaminated soils, containing Pseudomonas sp. FbP1、Enterobacter sp. FbP2、Hydrogenophaga sp. FbP3 and Luteolibacter pohnpeiensis. FbP4. To our knowledge, this is the first study to demonstrate that bacterial strains of Herbaspirillum chlorophenolicum FA1 and Luteolibacter pohnpeiensis. FbP4 can also degrade fluoranthene, benzo[b]fluoranthene and pyrene. Experiment results showed that both strain FA1 and consortium-4 could degrade fluoranthene, benzo[b]fluoranthene and pyrene within a wide range of temperature, pH and initial PAHs concentration. Degradation of HMW PAHs mixtures (binary and ternary) demonstrated the interactive effects that can alter the rate and extent of biodegradation within a mixture. The presence of indigenous flora was found to either increase or decrease the degradation of HMW PAHs, suggesting possible synergistic or competition effects. Biodegradation kinetics of HMW PAHs for sole substrates, binary and ternary systems was evaluated, with the purpose to better characterize and compare the biodegradation process of individual HMW PAH and mixtures of HMW PAHs. Results of this study

  1. Polycyclic aromatic hydrocarbons and halogenated persistent organic pollutants in canned fish and seafood products: smoked versus non-smoked products. (United States)

    Drabova, Lucie; Pulkrabova, Jana; Kalachova, Kamila; Tomaniova, Monika; Kocourek, Vladimir; Hajslova, Jana


    In this study, levels of several groups of environmental contaminants represented by PAHs, PCBs, organochlorine pesticides and polybrominated diphenyl ethers were determined in various types of canned smoked and non-smoked fish and seafood products (54 samples) obtained from the Czech market. PAHs were detected in all of the studied samples, and at least one of the target halogenated persistent organic pollutants was present above the LOQ in 85% of the samples. The levels of PAHs, PCBs, organochlorine pesticides (mainly DDTs) and polybrominated diphenyl ethers found in the canned products varied in the range of 1.4-116 µg kg(-1), 0.6-59.6 µg kg(-1), 0.6-82.7 µg kg(-1) and 0.1-2.1 µg kg(-1) can content, respectively. Smoked sprats were the most contaminated fish product (n = 12) in which the highest levels of both PAHs and persistent organic pollutants were found. In 67% of the samples of smoked sprats in oil, the level of benzo[a]pyrene exceeded the maximum level of 5 µg kg(-1) established for smoked fish by European Union legislation. The distribution of target analytes between oil and fish fractions was also assessed. Significantly higher levels of PAHs were measured in the oil fraction.

  2. Aqueous geochemistry of low molecular weight hydrocarbons at elevated temperatures and pressures: constraints from mineral buffered laboratory experiments (United States)

    Seewald, Jeffrey S.


    Organic matter, water, and minerals coexist at elevated temperatures and pressures in sedimentary basins and participate in a wide range of geochemical processes that includes the generation of oil and natural gas. A series of laboratory experiments were conducted at 300 to 350°C and 350 bars to examine chemical interactions involving low molecular weight aqueous hydrocarbons with water and Fe-bearing minerals under hydrothermal conditions. Mineral buffers composed of hematite-magnetite-pyrite, hematite-magnetite, and pyrite-pyrrhotite-magnetite were added to each experiment to fix the redox state of the fluid and the activity of reduced sulfur species. During each experiment the chemical system was externally modified by addition of ethene, ethane, propene, 1-butene, or n-heptane, and variations in the abundance of aqueous organic species were monitored as a function of time and temperature. Results of the experiments indicate that decomposition of aqueous n-alkanes proceeds through a series of oxidation and hydration reactions that sequentially produce alkenes, alcohols, ketones, and organic acids as reaction intermediaries. Organic acids subsequently undergo decarboxylation and/or oxidation reactions to form carbon dioxide and shorter chain saturated hydrocarbons. This alteration assemblage is compositionally distinct from that produced by thermal cracking under anhydrous conditions, indicating that the presence of water and minerals provide alternative reaction pathways for the decomposition of hydrocarbons. The rate of hydrocarbon oxidation decreases substantially under reducing conditions and in the absence of catalytically active aqueous sulfur species. These results represent compelling evidence that the stability of aqueous hydrocarbons at elevated temperatures in natural environments is not a simple function of time and temperature alone. Under the appropriate geochemical conditions, stepwise oxidation represents a mechanism for the decomposition of low

  3. Chronic Toxicity Of High Molecular Weight Polynuclear Aromatic Hydrocarbon- Pyrene On Freshwater Cyanobacterium Anabaena Fertlissima Rao

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    Jignasha G Patel


    Full Text Available The aim of this work was to determine the consequences of Polynuclear aromatic hydrocarbon – Pyrene in response to growth, pigments and metabolic study on Anabaena fertilissima Rao. Test organisms were treated at different doses and encountered LC50 (Lethal concentration at which 50% growth reduction occur concentration separately at 1.5 mg/l, 3.0 mg/l and 6.0 mg/l respectively for Anabaena fertilissima Rao. The influence of Pyrene on growth, pigments, release of metabolites such as carbohydrates, protein, amino acid, phenols was carried out. The test doses caused a concentration dependent decrease in pigments like carotenoids and phycobilliproteins and showed more sensitivity to pyrene. Depletion of carbohydrate by 13% to 81% and proteins by 47% to 93% was encountered with rise in pyrene concentrations after 16th day of exposure. However, phenols were found to rise by 27% to 50% with increased pyrene concentrations on the contrary, amino acids were reported to decline by 79% to 92%. This study therefore suggests high molecular weight pyrene that decreases in metabolite content and enzyme activity can be used as a signal of PAHs toxicity in cyanobacteria. International Journal of Environment, Volume-2, Issue-1, Sep-Nov 2013, Pages 175-183 DOI:

  4. Tropospheric Halogen Chemistry (United States)

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


    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

  5. Production Of Low Molecular Weight Hydrocarbons By Volcanic Eruptions On Early Mars (United States)

    Segura, Antígona; Navarro-González, Rafael


    Methane and other larger hydrocarbons have been proposed as possible greenhouse gases on early Mars. In this work we explore if volcanic processes may have been a source for such molecules based on theoretical and experimental considerations. Geologic evidence and numerical simulations indicate that explosive volcanism was widely distributed throughout Mars. Volcanic lightning is typically produced in such explosive volcanism. Therefore this geologic setting was studied to determine if lightning could be a source for hydrocarbons in volcanic plumes. Volcanic lightning was simulated by focusing a high-energy infrared laser beam inside of a Pyrex reactor that contained the proposed volcanic gas mixture composed of 64% CH4, 24% H2, 10% H2O and 2% N2, according to an accretion model and the nitrogen content measured in Martian meteorites. The analysis of products was performed by gas chromatography coupled to infrared and mass spectroscopy. Eleven hydrocarbons were identified among the products, of which acetylene (C2H2) was the most abundant. A thermochemical model was used to determine which hydrocarbons could arise only from volcanic heat. In this case, acetylene and ethylene are formed at magmatic temperatures. Our results indicate that explosive volcanism may have injected into the atmosphere of early Mars ˜6×1012 g yr-1 of acetylene, and ˜2×1012 g yr-1 of 1,3-butadiyne, both produced by volcanic lightning, ˜5×1011 g yr-1 of ethylene produced by volcanic heat, and 1013 g yr-1 of methane.

  6. Analytical system for stable carbon isotope measurements of low molecular weight (C2-C6) hydrocarbons

    NARCIS (Netherlands)

    Zuiderweg, A.T.; Holzinger, R.; Roeckmann, T.


    We present setup, testing and initial results from a new automated system for stable carbon isotope ratio measurements on C2 to C6 atmospheric hydrocarbons. The inlet system allows analysis of trace gases from air samples ranging from a few liters for urban samples and samples with high mixing

  7. Bench-scale optimization of bioaugmentation strategies for treatment of soils contaminated with high molecular weight polyaromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Straube, W.l.; Jones-Meehan, J.; Pritchard, P.H.; Jones, W.R. [University of Maryland Biotechnology Institute, Baltimore, MD (United States). Center of Marine Biotechnology


    The chemical composition of crude oil, creosote, and refined petroleum includes hundreds of different alkanes and aromatic hydrocarbons, among which are the carcinogenic polycyclic aromatic hydrocarbons (PAHs). Some compounds in hydrocarbon-contaminated soils are rapidly removed by the activities of autochthonous bacterial populations while other PAHs, especially those with four or more fused aromatic rings, are refractory to biodegradation. The persistence of high molecular weight of polyaromatic hydrocarbons (hPAHs) in soils implies either that their low solubility renders them poorly available to bacteria, or that autochthonous bacteria do not contain the metabolic or co-metabolic pathways required for their degradation or both. The rate and extent of PAH degradation in contaminated soil is not always predictable for standard biological treatment strategies. This study examines a matrix of treatments suitable for land farming in order to identify those that maximize the removal of hPAHs. The treatments include those intended to increase the bioavailability of hPAH, such as additions of biosurfactant-producing bacteria (i.e. Pseudomonas aeruginosa No. 64) and addition of light oils, as well as treatments intended to increase the metabolic potential of the bacterial community. The latter includes the addition of inorganic nutrients and bacterial strains capable of degrading hPAHs co-metabolically (i.e. Sphingomonas paucimobilis EPA 505). The efficacy of immobilizing PAH-degrading bacteria on vermiculite is also considered, as will be the monitoring of leachate for biodegradation of PAHs in a simulated land farming operation. 17 refs., 4 figs.

  8. Production of low molecular weight hydrocarbons by volcanic eruptions on early Mars. (United States)

    Segura, Antígona; Navarro-González, Rafael


    Methane and other larger hydrocarbons have been proposed as possible greenhouse gases on early Mars. In this work we explore if volcanic processes may have been a source for such molecules based on theoretical and experimental considerations. Geologic evidence and numerical simulations indicate that explosive volcanism was widely distributed throughout Mars. Volcanic lightning is typically produced in such explosive volcanism. Therefore this geologic setting was studied to determine if lightning could be a source for hydrocarbons in volcanic plumes. Volcanic lightning was simulated by focusing a high-energy infrared laser beam inside of a Pyrex reactor that contained the proposed volcanic gas mixture composed of 64% CH(4), 24% H(2), 10% H(2)O and 2% N(2), according to an accretion model and the nitrogen content measured in Martian meteorites. The analysis of products was performed by gas chromatography coupled to infrared and mass spectroscopy. Eleven hydrocarbons were identified among the products, of which acetylene (C(2)H(2)) was the most abundant. A thermochemical model was used to determine which hydrocarbons could arise only from volcanic heat. In this case, acetylene and ethylene are formed at magmatic temperatures. Our results indicate that explosive volcanism may have injected into the atmosphere of early Mars approximately 6 x 10(12) g yr(-1) of acetylene, and approximately 2 x 10(12) g yr(-1) of 1,3-butadiyne, both produced by volcanic lightning, approximately 5 x 10(11) g yr(-1) of ethylene produced by volcanic heat, and 10(13) g yr(-1) of methane.

  9. High molecular weight non-polar hydrocarbons as pure model substances and in motor oil samples can be ionized without fragmentation by atmospheric pressure chemical ionization mass spectrometry. (United States)

    Hourani, Nadim; Kuhnert, Nikolai


    High molecular weight non-polar hydrocarbons are still difficult to detect by mass spectrometry. Although several studies have targeted this problem, lack of good self-ionization has limited the ability of mass spectrometry to examine these hydrocarbons. Failure to control ion generation in the atmospheric pressure chemical ionization (APCI) source hampers the detection of intact stable gas-phase ions of non-polar hydrocarbon in mass spectrometry. Seventeen non-volatile non-polar hydrocarbons, reported to be difficult to ionize, were examined by an optimized APCI methodology using nitrogen as the reagent gas. All these analytes were successfully ionized as abundant and intact stable [M-H](+) ions without the use of any derivatization or adduct chemistry and without significant fragmentation. Application of the method to real-life hydrocarbon mixtures like light shredder waste and car motor oil was demonstrated. Despite numerous reports to the contrary, it is possible to ionize high molecular weight non-polar hydrocarbons by APCI, omitting the use of additives. This finding represents a significant step towards extending the applicability of mass spectrometry to non-polar hydrocarbon analyses in crude oil, petrochemical products, waste or food. Copyright © 2012 John Wiley & Sons, Ltd.

  10. Analytical system for stable carbon isotope measurements of low molecular weight (C2-C6 hydrocarbons

    Directory of Open Access Journals (Sweden)

    T. Röckmann


    Full Text Available We present setup, testing and initial results from a new automated system for stable carbon isotope ratio measurements on C2 to C6 atmospheric hydrocarbons. The inlet system allows analysis of trace gases from air samples ranging from a few liters for urban samples and samples with high mixing ratios, to many tens of liters for samples from remote unpolluted regions with very low mixing ratios. The centerpiece of the sample preparation is the separation trap, which is used to separate CO2 and methane from the compounds of interest. The main features of the system are (i the capability to sample up to 300 l of air, (ii long term (since May 2009 operational δ13C accuracy levels in the range 0.3–0.8 ‰ (1-σ, and (iii detection limits of order 1.5–2.5 ngC (collected amount of substance for all reported compounds. The first application of this system was the analysis of 21 ambient air samples taken during 48 h in August 2009 in Utrecht, the Netherlands. Results obtained are generally in good agreement with those from similar urban ambient air studies. Short sample intervals allowed by the design of the instrument help to illustrate the complex diurnal behavior of hydrocarbons in an urban environment, where diverse sources, dynamical processes, and chemical reactions are present.

  11. Halogenated fatty acids

    DEFF Research Database (Denmark)

    Mu, Huiling; Sundin, Peter; Wesén, Clas


    and separation method. This review covers separation by solid phase chromatography, gel permeation chromatography, and liquid-liquid extraction, followed by halogen determination. All studies performed according to this outline have indicated that the major organohalogen compounds are chlorinated fatty acids...... bound in different lipids. For the detection and identification of individual, halogenated fatty acid methyl esters (FAMEs) liberated from the lipids, gas chromatography (GC) has been employed together with detection methods such as electron capture detection, electrolytic conductivity detection (ELCD......), 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...

  12. The role of vanadium bromoperoxidase in the biosynthesis of halogenated marine natural products. (United States)

    Butler, Alison; Carter-Franklin, Jayme N


    Halogenated natural products are frequently reported metabolites in marine seaweeds. These compounds span a range from halogenated indoles, terpenes, acetogenins, phenols, etc., to volatile halogenated hydrocarbons that are produced on a very large scale. In many cases these halogenated marine metabolites possess biological activities of pharmacological interest. Given the abundance of halogenated marine natural products found in marine organisms and their potentially important biological activities, the biogenesis of these compounds has intrigued marine natural product chemists for decades. Over a quarter of a century ago, a possible role for haloperoxidase enzymes was first suggested in the biogenesis of certain halogenated marine natural products, although this was long before haloperoxidases were discovered in marine organisms. Since that time, FeHeme- and Vanadium-haloperoxidases (V-HPO) have been discovered in many marine organisms. The structure and catalytic activity of vanadium haloperoxidases is reviewed herein, including the importance of V-HPO-catalyzed bromination and cyclization of terpene substrates.

  13. Drinking water interlaboratory ring test. Part 6., Results of some halogenated hydrocarbons. CHCl{sub 3}, CHCl{sub 2}Br, CHClBr{sub 2}, CHBr{sub 3}, CH{sub 3}CCl{sub 3}, trichloroethylene, tetrachloroethylene and CCl{sub 4}; Circuito interlaboratorio Unichim sulle acque potabili. Parte 6., Elaborazione dati e risultati di alcuni idrocarburi alogenati

    Energy Technology Data Exchange (ETDEWEB)

    Cavaterra, E.; Divo, C.; Bottazzini, N. [Unichim Milan (Italy); Alava, F. [Bergamo Ambiente e Servizi, Bergamo (Italy); Bettinelli, M. [Electric Power Production Company, Piacenza (Italy); Bonfiglioli, F. [Azienda Mediterranea Gas e Acqua, Genoa (Italy)


    In this paper results of statistical treatment of experimental data obtained in some cycles of an interlaboratory ring test relating to determination of content of some halogenated hydrocarbons in drinking water are reported. Means, variances and parameters of precision and accuracy of some analytical techniques and methods employed by laboratories participating to the ring test will be reported and discussed. [Italian] Nel presente lavoro vengono riportati i risultati dell'elaborazione statistica dei dati sperimentali ottenuti in alcuni cicli del circuito interlaboratorio e relativi ai seguenti idrocarburi alogenati: CHCl{sub 3}, CHCl{sub 2}Br, CHClBr{sub 2}, CHBr{sub 3}, CH{sub 3}CCl{sub 3}, trielina, percloroetilene, CCL{sub 4} e totali. Vengono riportati e discussi i valori medi e la varianza ed infine i dati di accuratezza e precisione delle tecniche o metodi d'analisi impiegati dai laboratori partecipanti al circuito.

  14. Predicting accurate fluorescent spectra for high molecular weight polycyclic aromatic hydrocarbons using density functional theory (United States)

    Powell, Jacob; Heider, Emily C.; Campiglia, Andres; Harper, James K.


    The ability of density functional theory (DFT) methods to predict accurate fluorescence spectra for polycyclic aromatic hydrocarbons (PAHs) is explored. Two methods, PBE0 and CAM-B3LYP, are evaluated both in the gas phase and in solution. Spectra for several of the most toxic PAHs are predicted and compared to experiment, including three isomers of C24H14 and a PAH containing heteroatoms. Unusually high-resolution experimental spectra are obtained for comparison by analyzing each PAH at 4.2 K in an n-alkane matrix. All theoretical spectra visually conform to the profiles of the experimental data but are systematically offset by a small amount. Specifically, when solvent is included the PBE0 functional overestimates peaks by 16.1 ± 6.6 nm while CAM-B3LYP underestimates the same transitions by 14.5 ± 7.6 nm. These calculated spectra can be empirically corrected to decrease the uncertainties to 6.5 ± 5.1 and 5.7 ± 5.1 nm for the PBE0 and CAM-B3LYP methods, respectively. A comparison of computed spectra in the gas phase indicates that the inclusion of n-octane shifts peaks by +11 nm on average and this change is roughly equivalent for PBE0 and CAM-B3LYP. An automated approach for comparing spectra is also described that minimizes residuals between a given theoretical spectrum and all available experimental spectra. This approach identifies the correct spectrum in all cases and excludes approximately 80% of the incorrect spectra, demonstrating that an automated search of theoretical libraries of spectra may eventually become feasible.

  15. Biodegradation of low and high molecular weight hydrocarbons in petroleum refinery wastewater by a thermophilic bacterial consortium. (United States)

    Pugazhendi, Arulazhagan; Abbad Wazin, Hadeel; Qari, Huda; Basahi, Jalal Mohammad Al-Badry; Godon, Jean Jacques; Dhavamani, Jeyakumar


    Clean-up of contaminated wastewater remains to be a major challenge in petroleum refinery. Here, we describe the capacity of a bacterial consortium enriched from crude oil drilling site in Al-Khobar, Saudi Arabia, to utilize polycyclic aromatic hydrocarbons (PAHs) as sole carbon source at 60°C. The consortium reduced low molecular weight (LMW; naphthalene, phenanthrene, fluorene and anthracene) and high molecular weight (HMW; pyrene, benzo(e)pyrene and benzo(k)fluoranthene) PAH loads of up to 1.5 g/L with removal efficiencies of 90% and 80% within 10 days. PAH biodegradation was verified by the presence of PAH metabolites and evolution of carbon dioxide (90 ± 3%). Biodegradation led to a reduction of the surface tension to 34 ± 1 mN/m thus suggesting biosurfactant production by the consortium. Phylogenetic analysis of the consortium revealed the presence of the thermophilic PAH degrader Pseudomonas aeruginosa strain CEES1 (KU664514) and Bacillus thermosaudia (KU664515) strain CEES2. The consortium was further found to treat petroleum wastewater in continuous stirred tank reactor with 96 ± 2% chemical oxygen demand removal and complete PAH degradation in 24 days.

  16. Halogenated solvent remediation (United States)

    Sorenson, Jr., Kent S.


    Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. An illustrative method includes adding an electron donor for microbe-mediated anaerobic reductive dehalogenation of the halogenated solvents, which electron donor enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative electron donors include C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, salts thereof, esters of C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, and mixtures thereof, of which lactic acid, salts of lactic acid--such as sodium lactate, lactate esters, and mixtures thereof are particularly illustrative. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the electron donor.

  17. Halogenated fatty acids

    DEFF Research Database (Denmark)

    Mu, Huiling; Wesén, Clas; Sundin, Peter


    , chlorinated lipids have been found in meat exposed to hypochlorite disinfected water, and in chlorine-treated flour and in products made from such flour. Following exposure to chlorine bleached pulp mill effluents, aquatic organisms may have elevated concentrations of chlorinated fatty acids in their lipids....... However, a natural production of halogenated fatty acids is also possible. In this paper we summarize the present knowledge of the occurrence of halogenated fatty acids in lipids and suggested ways of their formation. In Part II (Trends Anal. Chem. 16 (1997) 274) we deal with methods...

  18. Asymmetric bifurcated halogen bonds. (United States)

    Novák, Martin; Foroutan-Nejad, Cina; Marek, Radek


    Halogen bonding (XB) is being extensively explored for its potential use in advanced materials and drug design. Despite significant progress in describing this interaction by theoretical and experimental methods, the chemical nature remains somewhat elusive, and it seems to vary with the selected system. In this work we present a detailed DFT analysis of three-center asymmetric halogen bond (XB) formed between dihalogen molecules and variously 4-substituted 1,2-dimethoxybenzene. The energy decomposition, orbital, and electron density analyses suggest that the contribution of electrostatic stabilization is comparable with that of non-electrostatic factors. Both terms increase parallel with increasing negative charge of the electron donor molecule in our model systems. Depending on the orientation of the dihalogen molecules, this bifurcated interaction may be classified as 'σ-hole - lone pair' or 'σ-hole - π' halogen bonds. Arrangement of the XB investigated here deviates significantly from a recent IUPAC definition of XB and, in analogy to the hydrogen bonding, the term bifurcated halogen bond (BXB) seems to be appropriate for this type of interaction.

  19. 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...

  20. On the Development of a Very Rapid Gas Chromatographic Method for the Analysis of High Molecular Weight Hydrocarbons in Cigarette Smoke

    Directory of Open Access Journals (Sweden)

    Coleman III WM


    Full Text Available A very rapid, flash-gas chromatographic (GC, quantitative method for the analysis of high molecular weight saturated hydrocarbons in cigarette smoke has been developed. The method was fast, accurate and precise. Sample turn around times were approximately six minutes, with an accompanying average percent relative standard deviation (%RSD of less than 10%. Four linear saturated hydrocarbons with 27, 29, 31 and 33 carbon atoms were quantitated in an array of reference cigarettes ranging in “tar” deliveries from approximately 2 to approximately 20 mg. By use of a cyclohexane extraction of cigarette smoke captured on Cambridge filter pads, the extraction efficiency was determined to be greater than 95% for each hydrocarbon. The approach represents a significant advance over current analytical procedures that require, on average, greater than 30-min sample turn around times.

  1. Spatial association analysis between hydrocarbon fields and sedimentary residual magnetic anomalies using Weights of Evidence: An example from the Triassic Province of Algeria (United States)

    Allek, Karim; Boubaya, Djamel; Bouguern, Abderrahmane; Hamoudi, Mohamed


    The presence of near-surface magnetic anomalies over oil and gas accumulations and their contribution to exploration remain somewhat controversial despite encouraging results and an improved understanding of genetic links between hydrocarbon seepage-induced alterations and near-surface magnetic minerals. This controversy is likely to remain since the cause of shallow-sourced sedimentary magnetic anomalies may well be microseepage related, but could also result from other sources such as cultural features and detrital magnetite. The definite way of discriminating between them remains a challenge. In this paper we examine means to deal with this particular purpose using a Bayesian technique known as 'Weights-of-Evidence'. The technique is implemented in GIS to explore spatial associations between known hydrocarbon fields within the central Triassic province of Algeria and sedimentary residual magnetic anomalies. We use the results to show possible application of the method to the recognition of some characteristics (amplitude and width) of anomalies assumed to be induced by hydrocarbon microseepages. Our results reveal strong spatial association with certain typical class of anomalies, confirming therefore hypothesis that hydrocarbon microseepages may result in detectable magnetic anomalies. It is possible to use the anomalies occurring outside the known gas and oil fields to make informed decisions in the selection of new targets for more detailed hydrocarbon exploration.

  2. Identification of polar transformation products and high molecular weight polycyclic aromatic hydrocarbons (PAHs) in contaminated soil following bioremediation. (United States)

    Chibwe, Leah; Davie-Martin, Cleo L; Aitken, Michael D; Hoh, Eunha; Massey Simonich, Staci L


    Bioremediation is a technique commonly used to reduce the toxicity associated with polycyclic aromatic hydrocarbons (PAHs) in contaminated soils. However, the efficacy of bioremedial applications is evaluated based on the removal of a subset of parent (or unsubstituted) PAHs and does not incorporate toxic polar transformation products or the more mutagenic high molecular weight PAHs (MW≥302amu or MW302-PAHs). Previously, an effects-directed analysis approach was used to assess the effect of bioremediation on the toxicity of a coal tar-contaminated soil. Increased genotoxicity and developmental toxicity was measured postbioremedation in the more polar soil extract fractions, as compared to the less polar fractions where the targeted PAHs eluted, and could not be attributed to the 88 target PAHs analyzed for (including selected oxygen-containing PAHs). In this study, comprehensive two-dimensional gas chromatography time-of-flight and liquid chromatography quadrupole time-of-flight mass spectrometry were used to characterize transformation products in the soil extract fractions identified as toxic, previously. Additionally, the degradation of 12MW302-PAHs, picene (MW=278) and coronene (MW=300) were evaluated following bioremediation. Non-targeted analysis resulted in the tentative identification of 10 peaks with increased intensity postbioremediation (based on mass spectral library matching and fragmentation patterns from >5000 candidate peaks in the soil extracts). Several of these compounds contained oxygen, suggesting they would be relatively polar. MW302-PAHs were not significantly degraded during bioremediation, suggesting that the carcinogenic potential associated with these PAHs might remain unchanged. The results of this study suggest that polar transformation products, and MW302-PAHs, should be considered for realistic risk assessment of bioremediated soils. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Halogenated benzenes, effect on xenobiotic metabolism and the toxicity of other chemicals. [Insecticides, rats

    Energy Technology Data Exchange (ETDEWEB)

    Carlson, G.P.


    The insecticide EPN and six halogenated benzenes were administered orally to rats over a period of 14 days. The animals were killed 24 h after the last dose. Graphs are presented to show effects of halogenated benzene on EPN detoxification; liver to body weight ratio; and activities of benzpyrene hydroxylase, azoreductase, UDP glucuronyltransferase, and microsomal cytochrome c reductase. A significant enlargement of the liver was found. The results showed that the halogenated benzenes were capable of altering xenobiotic metabolism. (HLW)

  4. Halogen Chemistry in the CMAQ Model (United States)

    Halogens (iodine and bromine) emitted from oceans alter atmospheric chemistry and influence atmospheric ozone mixing ratio. We previously incorporated a representation of detailed halogen chemistry and emissions of organic and inorganic halogen species into the hemispheric Commun...

  5. Geochemistry of low-molecular-weight hydrocarbons in core samples of lower foarcian age (posidonia shale) in the Hils syncline area. Hydrocarbon formation and maturity. Zur Geochemie niedrigmolekularer Kohlenwasserstoffe im Posidonienschiefer der Hilsmulde. Kohlenwasserstoffbildung und Reifeaspekte

    Energy Technology Data Exchange (ETDEWEB)

    Schaefer, R.G. (Forschungszentrum Juelich GmbH (Germany). Inst. fuer Erdoel und Organische Geochemie)


    Compositional changes in the light hydrocarbon fraction of sedimentary rocks and petroleum are known to reflect their maturation history. The present contribution comprises the analysis of low-molecular-weight hydrocarbons in core samples of Lower Toarcian age ('Posidonia Shale', Lias {epsilon}). The sample series, obtained by shallow-borehole drilling in the Hils syncline area, Lower Saxony Basin, northern Germany, represents an exceptionally organic matter rich petroleum source rock (type-II kerogen) of a wide maturity range (mean vitrinite reflectance, R{sub r} between 0.5 and 1.5%). About 30 compounds in the C{sub 2}-C{sub 7} molecular range, including benzene and toluene, were determined by means of a combined thermovapourization/capillary GC method. Both, quantity and composition are discussed in relation to maturity at seven locations. Correlations between R{sub r} and 'chemical' maturity parameters based on compositional changes of acyclic and alicyclic C{sub 7}-hydrocarbons as well as indications of migration processes are presented. (orig.).

  6. Hydrocarbon toxicity: A review. (United States)

    Tormoehlen, L M; Tekulve, K J; Nañagas, K A


    Clinical effects of hydrocarbon exposure have been reported since 1897. These substances are ubiquitous, and their exposures are common. The specific hydrocarbon and route of exposure will determine the clinical effect, and an understanding of this is helpful in the care of the hydrocarbon-exposed patient. To complete a comprehensive review of the literature on hydrocarbon toxicity and summarize the findings. Relevant literature was identified through searches of Medline (PubMed/OVID) and Cochrane Library databases (inclusive of years 1975-2013), as well as from multiple toxicology textbooks. Bibliographies of the identified articles were also reviewed. Search terms included combinations of the following: hydrocarbons, inhalants, encephalopathy, coma, cognitive deficits, inhalant abuse, huffing, sudden sniffing death, toluene, renal tubular acidosis, metabolic acidosis, arrhythmia, dermatitis, and aspiration pneumonitis. All pertinent clinical trials, observational studies, and case reports relevant to hydrocarbon exposure and published in English were reviewed. Chronic, occupational hydrocarbon toxicity was not included. Exposure to hydrocarbons occurs through one of the following routes: inhalation, ingestion with or without aspiration, or dermal exposure. Inhalational abuse is associated with central nervous system depression, metabolic acidosis, and arrhythmia. The exact mechanism of the CNS depression is unknown, but experimental evidence suggests effects on NMDA, dopamine, and GABA receptors. Chronic toluene inhalation causes a non-anion gap metabolic acidosis associated with hypokalemia. Halogenated hydrocarbon abuse can cause a fatal malignant arrhythmia, termed "sudden sniffing death". Individuals who regularly abuse hydrocarbons are more likely to be polysubstance users, exhibit criminal or violent behavior, and develop memory and other cognitive deficits. Heavy, long-term use results in cerebellar dysfunction, encephalopathy, weakness, and dementia

  7. CYP63A2, a Catalytically Versatile Fungal P450 Monooxygenase Capable of Oxidizing Higher-Molecular-Weight Polycyclic Aromatic Hydrocarbons, Alkylphenols, and Alkanes (United States)

    Syed, Khajamohiddin; Porollo, Aleksey; Lam, Ying Wai; Grimmett, Paul E.


    Cytochrome P450 monooxygenases (P450s) are known to oxidize hydrocarbons, albeit with limited substrate specificity across classes of these compounds. Here we report a P450 monooxygenase (CYP63A2) from the model ligninolytic white rot fungus Phanerochaete chrysosporium that was found to possess a broad oxidizing capability toward structurally diverse hydrocarbons belonging to mutagenic/carcinogenic fused-ring higher-molecular-weight polycyclic aromatic hydrocarbons (HMW-PAHs), endocrine-disrupting long-chain alkylphenols (APs), and crude oil aliphatic hydrocarbon n-alkanes. A homology-based three-dimensional (3D) model revealed the presence of an extraordinarily large active-site cavity in CYP63A2 compared to the mammalian PAH-oxidizing (CYP3A4, CYP1A2, and CYP1B1) and bacterial aliphatic-hydrocarbon-oxidizing (CYP101D and CYP102A1) P450s. This structural feature in conjunction with ligand docking simulations suggested potential versatility of the enzyme. Experimental characterization using recombinantly expressed CYP63A2 revealed its ability to oxidize HMW-PAHs of various ring sizes, including 4 rings (pyrene and fluoranthene), 5 rings [benzo(a)pyrene], and 6 rings [benzo(ghi)perylene], with the highest enzymatic activity being toward the 5-ring PAH followed by the 4-ring and 6-ring PAHs, in that order. Recombinant CYP63A2 activity yielded monohydroxylated PAH metabolites. The enzyme was found to also act as an alkane ω-hydroxylase that oxidized n-alkanes with various chain lengths (C9 to C12 and C15 to C19), as well as alkyl side chains (C3 to C9) in alkylphenols (APs). CYP63A2 showed preferential oxidation of long-chain APs and alkanes. To our knowledge, this is the first P450 identified from any of the biological kingdoms that possesses such broad substrate specificity toward structurally diverse xenobiotics (PAHs, APs, and alkanes), making it a potent enzyme biocatalyst candidate to handle mixed pollution (e.g., crude oil spills). PMID:23416995

  8. 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


    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)

  9. Offspring DNA methylation of the aryl-hydrocarbon receptor repressor gene is associated with maternal BMI, gestational age, and birth weight. (United States)

    Burris, Heather H; Baccarelli, Andrea A; Byun, Hyang-Min; Cantoral, Alejandra; Just, Allan C; Pantic, Ivan; Solano-Gonzalez, Maritsa; Svensson, Katherine; Tamayo y Ortiz, Marcela; Zhao, Yan; Wright, Robert O; Téllez-Rojo, Martha M


    Prenatal smoke exposure, maternal obesity, aberrant fetal growth, and preterm birth are all risk factors for offspring metabolic syndrome. Cord blood aryl-hydrocarbon receptor repressor (AHRR) DNA methylation is responsive to maternal smoking during pregnancy. AHRR serves not only to inhibit aryl-hydrocarbon receptor (AHR) transcription, which is involved in mediating xenobiotic metabolism, but it is also involved in cell growth and differentiation. Other than maternal smoking, other predictors of offspring AHRR DNA methylation status remain unknown; we sought to identify them among newborns. We enrolled pregnant women in the PROGRESS birth cohort in Mexico City. Using pyrosequencing, we analyzed DNA methylation of 3 CpG sites within the AHRR gene promoter from the umbilical cord blood of 531 infants. We used generalized estimating equations to account for the correlation of DNA methylation between CpG sites. Multivariable models were used to adjust for maternal age, BMI, education, parity, smoke-exposure, infant sex, gestational age, and birth weight-for-gestational age. AHRR DNA methylation was positively associated with maternal BMI (P = 0.0009) and negatively associated with the length of gestation (P offspring of obese vs. normal weight mothers and 3.1% higher in preterm vs. term infants, representing a third and a half standard deviation differences in methylation, respectively. In conclusion, offspring AHRR DNA methylation was associated with maternal obesity during pregnancy as well as infant gestational age and birth weight-for-gestational age. Further work to discover the health impacts of altered AHRR DNA methylation is warranted.

  10. The Halogen Occultation Experiment (United States)

    Russell, James M., III; Gordley, Larry L.; Park, Jae H.; Drayson, S. R.; Hesketh, W. D.; Cicerone, Ralph J.; Tuck, Adrian F.; Frederick, John E.; Harries, John E.; Crutzen, Paul J.


    The Halogen Occultation Experiment (HALOE) uses solar occultation to measure vertical profiles of O3, HCl, HF, CH4, H2O, NO, NO2, aerosol extinction, and temperature versus pressure with an instantaneous vertical field of view of 1.6 km at the earth limb. Latitudinal coverage is from 80 deg S to 80 deg N over the course of 1 year and includes extensive observations of the Antarctic region during spring. The altitude range of the measurements extends from about 15 km to about 60-130 km, depending on channel. Experiment operations have been essentially flawless, and all performance criteria either meet or exceed specifications. Internal data consistency checks, comparisons with correlative measurements, and qualitative comparisons with 1985 atmospheric trace molecule spectroscopy (ATMOS) results are in good agreement. Examples of pressure versus latitude cross sections and a global orthographic projection for the September 21 to October 15, 1992, period show the utility of CH4, HF, and H2O as tracers, the occurrence of dehydration in the Antarctic lower stratosphere, the presence of the water vapor hygropause in the tropics, evidence of Antarctic air in the tropics, the influence of Hadley tropical upwelling, and the first global distribution of HCl, HF, and NO throughout the stratosphere. Nitric oxide measurements extend through the lower thermosphere.

  11. Salting-out assisted liquid-liquid extraction and partial least squares regression to assay low molecular weight polycyclic aromatic hydrocarbons leached from soils and sediments (United States)

    Bressan, Lucas P.; do Nascimento, Paulo Cícero; Schmidt, Marcella E. P.; Faccin, Henrique; de Machado, Leandro Carvalho; Bohrer, Denise


    A novel method was developed to determine low molecular weight polycyclic aromatic hydrocarbons in aqueous leachates from soils and sediments using a salting-out assisted liquid-liquid extraction, synchronous fluorescence spectrometry and a multivariate calibration technique. Several experimental parameters were controlled and the optimum conditions were: sodium carbonate as the salting-out agent at concentration of 2 mol L- 1, 3 mL of acetonitrile as extraction solvent, 6 mL of aqueous leachate, vortexing for 5 min and centrifuging at 4000 rpm for 5 min. The partial least squares calibration was optimized to the lowest values of root mean squared error and five latent variables were chosen for each of the targeted compounds. The regression coefficients for the true versus predicted concentrations were higher than 0.99. Figures of merit for the multivariate method were calculated, namely sensitivity, multivariate detection limit and multivariate quantification limit. The selectivity was also evaluated and other polycyclic aromatic hydrocarbons did not interfere in the analysis. Likewise, high performance liquid chromatography was used as a comparative methodology, and the regression analysis between the methods showed no statistical difference (t-test). The proposed methodology was applied to soils and sediments of a Brazilian river and the recoveries ranged from 74.3% to 105.8%. Overall, the proposed methodology was suitable for the targeted compounds, showing that the extraction method can be applied to spectrofluorometric analysis and that the multivariate calibration is also suitable for these compounds in leachates from real samples.

  12. Synthesis of pyrrolnitrin and related halogenated phenylpyrroles. (United States)

    Morrison, Matthew D; Hanthorn, Jason J; Pratt, Derek A


    A general approach to halogenated arylpyrroles, including the antifungal natural product pyrrolnitrin, is described using newly synthesized halogenated pyrroles and 2,6-disubstituted nitrobenzenes or 2,6-disubstituted anilines.

  13. Occurrence and concentrations of selected trace elements, halogenated organic compounds, and polycyclic aromatic hydrocarbons in streambed sediments and results of water-toxicity testing in Westside Creeks and the San Antonio River, San Antonio, Texas, 2014 (United States)

    Crow, Cassi L.; Wilson, Jennifer T.; Kunz, James L.


    Sediment samples and samples for water-toxicity testing were collected during 2014 from several streams in San Antonio, Texas, known locally as the Westside Creeks (Alazán, Apache, Martínez, and San Pedro Creeks) and from the San Antonio River. Samples were collected during base flow and after periods of stormwater runoff (poststorm conditions) to determine baseline sediment- and water-quality conditions. Streambed-sediment samples were analyzed for selected constituents, including trace elements and organic contaminants such as pesticides, polychlorinated biphenyls (PCBs), brominated flame retardants, and polycyclic aromatic hydrocarbons (PAHs). Potential risks of contaminants in sediment were evaluated by comparing concentrations of contaminants in sediment to two effects-based sediment-quality guidelines: (1) a lower level, called the threshold effect concentration, below which, harmful effects to benthic biota are not expected, and (2) a higher level, the probable effect concentration (PEC), above which harmful effects are expected to occur frequently. Samples for water-toxicity testing were collected from each stream to provide information about fish toxicity in the study area. The trace metal lead was detected at potentially toxic concentrations greater than the PEC in both the base-flow and poststorm samples collected at two sites sampled on San Pedro Creek. The PECs for the pesticides dichlorodiphenyldichloroethane, dichlorodiphenyldichloroethylene, dichlorodiphenyltrichloroethane, and chlordane were exceeded in some of the samples at the same two sites on San Pedro Creek. Brominated flame retardants and polybrominated diphenyl ether (PBDE) 85, 153, and 154 were found in all streambed-sediment samples. Federal Environmental Quality Guidelines established by Environment Canada for PBDE 99 and PBDE 100 were exceeded in all samples in which PBDE 99 was detected and in a majority of the samples in which PBDE 100 was detected; the greatest concentrations

  14. 40 CFR 721.505 - Halogenated acrylonitrile. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated acrylonitrile. 721.505... Substances § 721.505 Halogenated acrylonitrile. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated acrylonitrile, (PMN P-90-299) is...

  15. Halogen and Cl isotopic systematics in Martian phosphates: Implications for the Cl cycle and surface halogen reservoirs on Mars (United States)

    Bellucci, J. J.; Whitehouse, M. J.; John, T.; Nemchin, A. A.; Snape, J. F.; Bland, P. A.; Benedix, G. K.


    The Cl isotopic compositions and halogen (Cl, F, Br, and I) abundances in phosphates from eight Martian meteorites, spanning most rock types and ages currently available, have been measured in situ by Secondary Ion Mass Spectrometry (SIMS). Likewise, the distribution of halogens has been documented by x-ray mapping. Halogen concentrations range over several orders of magnitude up to some of the largest concentrations yet measured in Martian samples or on the Martian surface, and the inter-element ratios are highly variable. Similarly, Cl isotope compositions exhibit a larger range than all pristine terrestrial igneous rocks. Phosphates in ancient (>4 Ga) meteorites (orthopyroxenite ALH 84001 and breccia NWA 7533) have positive δ37Cl anomalies (+1.1 to + 2.5 ‰). These samples also exhibit explicit whole rock and grain scale evidence for hydrothermal or aqueous activity. In contrast, the phosphates in the younger basaltic Shergottite meteorites (Phosphates with the largest negative δ37Cl anomalies display zonation in which the rims of the grains are enriched in all halogens and have significantly more negative δ37Cl anomalies suggestive of interaction with the surface of Mars during the latest stages of basalt crystallization. The phosphates with no textural, major element, or halogen enrichment evidence for mixing with this surface reservoir have an average δ37Cl of - 0.6 ‰, supporting a similar initial Cl isotope composition for Mars, the Earth, and the Moon. Oxidation and reduction of chlorine are the only processes known to strongly fractionate Cl isotopes, both positively and negatively, and perchlorate has been detected in weight percent concentrations on the Martian surface. The age range and obvious mixing history of the phosphates studied here suggest perchlorate formation and halogen cycling via brines, which have been documented on the Martian surface, has been active throughout Martian history.

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

    CERN Document Server

    MacKinlay, Alistair F; Whillock, M J


    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.

  17. Organic halogens in landfill leachates

    DEFF Research Database (Denmark)

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


    compounds behind the high TOX could not be found. Conversely, part of the TOX could be attributed to halogenated humic substances that can not be analysed with conventional organic contaminant analyses. Even though TOX can still be considered an indicator of leachate contamination in the aquifers, attempts...

  18. Halogen Bonding in Nucleic Acid Complexes. (United States)

    Kolář, Michal H; Tabarrini, Oriana


    Halogen bonding (X-bonding) has attracted notable attention among noncovalent interactions. This highly directional attraction between a halogen atom and an electron donor has been exploited in knowledge-based drug design. A great deal of information has been gathered about X-bonds in protein-ligand complexes, as opposed to nucleic acid complexes. Here we provide a thorough analysis of nucleic acid complexes containing either halogenated building blocks or halogenated ligands. We analyzed close contacts between halogens and electron-rich moieties. The phosphate backbone oxygen is clearly the most common halogen acceptor. We identified 21 X-bonds within known structures of nucleic acid complexes. A vast majority of the X-bonds is formed by halogenated nucleobases, such as bromouridine, and feature excellent geometries. Noncovalent ligands have been found to form only interactions with suboptimal interaction geometries. Hence, the first X-bonded nucleic acid binder remains to be discovered.

  19. Reduction of Aromatic Hydrocarbons by Zero-Valent Iron and Palladium Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young-Hun; Shin, Won Sik; Ko, Seok-Oh; Kim, Myung-Chul


    Permeable reactive barrier (PRB) is an alternative technology for soil and groundwater remediation. Zero valent iron, which is the most popular PRB material, is only applicable to halogenated aliphatic organics and some heavy metals. The objective of this study was to investigate reductive dechlorination of halogenated compounds and reduction of non-halogenated aromatic hydrocarbons using zero valent metals (ZVMs) and catalysts as reactive materials for PRBs. A group of small aromatic hydrocarbons such as monochlorophenols, phenol and benzene were readily reduced with palladium catalyst and zero valent iron. Poly-aromatic hydrocarbons (PAHs) were also tested with the catalysts and zero valent metal combinations. The aromatic rings were reduced and partly reduced PAHs were found as the daughter compounds. The current study demonstrates reduction of aromatic compounds by ZVMs and modified catalysts and implicates that PRB is applicable not only for halogenated organic compounds but nonhalogenated aromatic compounds such as PAHs.

  20. Diversified essential properties in halogenated graphenes


    Tran, Ngoc Thanh Thuy; Nguyen, Duy Khanh; E., Glukhova O.; Lin, Ming-Fa


    The significant halogenation effects on the essential properties of graphene are investigated by the first-principles method. The geometric structures, electronic properties, and magnetic configurations are greatly diversified under the various halogen adsorptions. Fluorination, with the strong multi-orbital chemical bondings, can create the buckled graphene structure, while the other halogenations do not change the planar {\\sigma} bonding in the presence of single-orbital hybridization. Elec...

  1. Mycoremediation of hydrocarbons with basidiomycetes-a review. (United States)

    Treu, Roland; Falandysz, Jerzy


    The literature on hydrocarbon remediation with basidiomycetes was reviewed. Two ecological groups are considered for bioremediation, the saprotrophic basidiomycetes (white-rot and brown-rot fungi) and the ectomycorrhizal basidiomycetes. A remarkable capacity of basidiomycetes for in vitro degradation of simple and recalcitrant hydrocarbons, such as PAH, persistent organic pollutants (POPs), halogenated HC, aromatic HC and phenols, explosives and dyes was reported for many species. However, there is a need for more studies on the practical feasibility of field applications with basidiomycetes.

  2. Biodegradation of polycyclic aromatic hydrocarbons (PAHs) in spent ...

    African Journals Online (AJOL)



    Feb 16, 2015 ... hydrocarbons (PAHs) by gas chromatography after extracting with hexane and dichloromethane (3:1). The initial PAHs ... ostreatus is found more effective as a biodegradation agent for PAHs in contaminated soils when compared with P. ... compounds, polychlorinated biphenyls phenols and halogenated ...

  3. Enhanced reactive metal wall for dehalogenation of hydrocarbons (United States)

    Howson, P.E.; Mackenzie, P.D.; Horney, D.P.


    A method is provided for remediation of contaminated solutions using a tiered metal wall or column. The tiered metal wall or column has at least three zones with graduated sizes of reducing metal particles. Contaminated solutions pass through the tiered wall or column to dehalogenate contaminant halogenated hydrocarbons. 3 figs.

  4. Enhanced reactive metal wall for dehalogenation of hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Howson, Paul E. (Latham, NY); Mackenzie, Patricia D. (Clifton Park, NY); Horney, David P. (Mayfield, NY)


    A method is provided for remediation of contaminated solutions using a tiered metal wall or column. The tiered metal wall or column has at least three zones with graduated sizes of reducing metal particles. Contaminated solutions pass through the tiered wall or column to dehalogenate contaminant halogenated hydrocarbons.

  5. Offspring DNA methylation of the aryl-hydrocarbon receptor repressor gene is associated with maternal BMI, gestational age, and birth weight


    Burris, Heather H.; Baccarelli, Andrea A; Byun, Hyang-Min; Cantoral, Alejandra; Just, Allan C.; Pantic, Ivan; Solano-Gonzalez, Maritsa; Svensson, Katherine; Tamayo y Ortiz, Marcela; ZHAO, YAN; Robert O Wright; Téllez-Rojo, Martha M.


    Prenatal smoke exposure, maternal obesity, aberrant fetal growth, and preterm birth are all risk factors for offspring metabolic syndrome. Cord blood aryl-hydrocarbon receptor repressor (AHRR) DNA methylation is responsive to maternal smoking during pregnancy. AHRR serves not only to inhibit aryl-hydrocarbon receptor (AHR) transcription, which is involved in mediating xenobiotic metabolism, but it is also involved in cell growth and differentiation. Other than maternal smoking, other predicto...

  6. Organic halogens in spruce forest throughfall

    DEFF Research Database (Denmark)

    Öberg, G.; Johansen, C.; Grøn, C.


    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....... 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....

  7. Halogen-specific total organic halogen analysis: Assessment by recovery of total bromine. (United States)

    Langsa, Markus; Allard, Sebastien; Kristiana, Ina; Heitz, Anna; Joll, Cynthia A


    Determination of halogen-specific total organic halogen (TOX) is vital for studies of disinfection of waters containing bromide, since total organic bromine (TOBr) is likely to be more problematic than total organic chlorine. Here, we present further halogen-specific TOX method optimisation and validation, focusing on measurement of TOBr. The optimised halogen-specific TOX method was validated based on the recovery of model compounds covering different classes of disinfection by-products (haloacetic acids, haloacetonitriles, halophenols and halogenated benzenes) and the recovery of total bromine (mass balance of TOBr and bromide concentrations) during disinfection of waters containing dissolved organic matter and bromide. The validation of a halogen-specific TOX method based on the mass balance of total bromine has not previously been reported. Very good recoveries of organic halogen from all model compounds were obtained, indicating high or complete conversion of all organic halogen in the model compound solution through to halide in the absorber solution for ion chromatography analysis. The method was also successfully applied to monitor conversion of bromide to TOBr in a groundwater treatment plant. An excellent recovery (101%) of total bromine was observed from the raw water to the post-chlorination stage. Excellent recoveries of total bromine (92%-95%) were also obtained from chlorination of a synthetic water containing dissolved organic matter and bromide, demonstrating the validity of the halogen-specific TOX method for TOBr measurement. The halogen-specific TOX method is an important tool to monitor and better understand the formation of halogenated organic compounds, in particular brominated organic compounds, in drinking water systems. Copyright © 2017. Published by Elsevier B.V.

  8. Anaerobic Microbial Transformation of Aromatic Hydrocarbons and Mixtures of Aromatic Hydrocarbons and Halogenated Solvents. (United States)


    scintillation cocktail, but one was pretreated with 1 mL of 1 N HCI, the other with 1 mL of 1 N NaOH , whereas the third received no pretreatment. (sheet silicates such as biotite and vermiculite ) in the presence of sulfide, and with iron sulfide minerals (pyrite, marcasite). The...Kriegman, M.R., and M. Reinhard. 1990. Reduction of hexachloroethane and carbon tetrachloride at surfaces of biotite, vermiculite , pyrite, and

  9. Treatment System for Removing Halogenated Compounds from Contaminated Sources (United States)

    Quinn, Jacqueline W. (Inventor); Clausen, Christian A. (Inventor); Yestrebsky, Cherie L. (Inventor)


    A treatment system and a method for removal of at least one halogenated compound, such as PCBs, found in contaminated systems are provided. The treatment system includes a polymer blanket for receiving at least one non-polar solvent. The halogenated compound permeates into or through a wall of the polymer blanket where it is solubilized with at least one non-polar solvent received by said polymer blanket forming a halogenated solvent mixture. This treatment system and method provides for the in situ removal of halogenated compounds from the contaminated system. In one embodiment, the halogenated solvent mixture is subjected to subsequent processes which destroy and/or degrade the halogenated compound.

  10. Halogen-bonding-triggered supramolecular gel formation (United States)

    Meazza, Lorenzo; Foster, Jonathan A.; Fucke, Katharina; Metrangolo, Pierangelo; Resnati, Giuseppe; Steed, Jonathan W.


    Supramolecular gels are topical soft materials involving the reversible formation of fibrous aggregates using non-covalent interactions. There is significant interest in controlling the properties of such materials by the formation of multicomponent systems, which exhibit non-additive properties emerging from interaction of the components. The use of hydrogen bonding to assemble supramolecular gels in organic solvents is well established. In contrast, the use of halogen bonding to trigger supramolecular gel formation in a two-component gel (‘co-gel’) is essentially unexplored, and forms the basis for this study. Here, we show that halogen bonding between a pyridyl substituent in a bis(pyridyl urea) and 1,4-diiodotetrafluorobenzene brings about gelation, even in polar media such as aqueous methanol and aqueous dimethylsulfoxide. This demonstrates that halogen bonding is sufficiently strong to interfere with competing gel-inhibitory interactions and create a ‘tipping point’ in gel assembly. Using this concept, we have prepared a halogen bond donor bis(urea) gelator that forms co-gels with halogen bond acceptors.

  11. Electroreductive Remediation of Halogenated Environmental Pollutants. (United States)

    Martin, Erin T; McGuire, Caitlyn M; Mubarak, Mohammad S; Peters, Dennis G


    Electrochemical reduction of halogenated organic compounds is gaining increasing attention as a strategy for the remediation of environmental pollutants. We begin this review by discussing key components (cells, electrodes, solvents, and electrolytes) in the design of a procedure for degrading a targeted pollutant, and we describe and contrast some experimental techniques used to explore and characterize the electrochemical behavior of that pollutant. Then, we describe how to probe various mechanistic features of the pertinent electrochemistry (including stepwise versus concerted carbon-halogen bond cleavage, identification of reaction intermediates, and elucidation of mechanisms). Knowing this information is vital to the successful development of a remediation procedure. Next, we outline techniques, instrumentation, and cell designs involved in scaling up a benchtop experiment to an industrial-scale system. Finally, the last and major part of this review is directed toward surveying electrochemical studies of various categories of halogenated pollutants (chlorofluorocarbons; disinfection byproducts; pesticides, fungicides, and bactericides; and flame retardants) and looking forward to future developments.

  12. Evaluation of Halogenated Coumarins for Antimosquito Properties

    Directory of Open Access Journals (Sweden)

    Venugopala K. Narayanaswamy


    Full Text Available Mosquitoes are the major vectors of parasites and pathogens affecting humans and domestic animals. The widespread development of insecticide resistance and negative environmental effects of most synthetic compounds support an interest in finding and developing alternative products against mosquitoes. Natural coumarins and synthetic coumarin analogues are known for their several pharmacological properties, including being insecticidal. In the present study halogenated coumarins (3-mono/dibromo acetyl, 6-halogenated coumarin analogues were screened for larvicidal, adulticidal, and repellent properties against Anopheles arabiensis, a zoophilic mosquito that is one of the dominant vectors of malaria in Africa. Five compounds exerted 100% larval mortality within 24 h of exposure. All coumarins and halogenated coumarins reversibly knocked down adult mosquitoes but did not kill them after 24 h of exposure. Repellent properties could not be evidenced. Five compounds were considered potential larvicidal agents for further research and development, while adulticidal activity was considered only mild to moderate.

  13. Strength, character, and directionality of halogen bonds involving cationic halogen bond donors. (United States)

    Riley, Kevin E; Tran, Khanh-An


    Halogen bonds involving cationic halogen bond donors and anionic halogen bond acceptors have recently been recognized as being important in stabilizing the crystal structures of many salts. Theoretical characterization of these types of interactions, most importantly in terms of their directionality, has been limited. Here we generate high-quality symmetry adapted perturbation theory potential energy curves of a H3N-C[triple bond, length as m-dash]C-Br+Cl- model system in order to characterize halogen bonds involving charged species, in terms of contributions from electrostatics, exchange, induction, and dispersion, with special emphasis on analyzing contributions that are most responsible for the directionality of these interactions. It is found that, as in the case of neutral halogen bonds, exchange forces are important contributors to the directionality of charged halogen bonds, however, it is also found that induction effects, which contribute little to the stability and directionality of neutral halogen bonds, play a large role in the directionality of halogen bonds involving charged species. Potential energy curves based on the ωB97X-D/def2-TZVP/C-PCM method, which includes an implicit solvation model in order to mimic the effects of the crystal medium, are produced for both the H3N-C[triple bond, length as m-dash]C-Br+Cl- model system and for the 4-bromoaniliniumCl- dimer, which is based on the real 4-bromoanilinium chloride salt, whose crystal structure has been determined experimentally. It is found that, within a crystal-like medium, charged halogen bond are significantly weaker than in the gas phase, having optimum interaction energies up to approximately -20 kcal mol-1.

  14. Solubilisation des hydrocarbures dans les solutions micellaires Influence de la structure et de la masse moléculaire Solubilization of Hydrocarbons in Micellar Solutions Influence of Structure and Molecular Weight

    Directory of Open Access Journals (Sweden)

    Baviere M.


    oil. Such research must result in the adapting of procedures, in searching for solutions and in setting limits to the process from this standpoint. This article describes the methodology and preliminary results leading to the comparing of the phase behavior of mixtures containing model hydrocarbons having different structures, normal alkanes and alkylbenzenes or stock-tank crudes. The methodology is based on the correlations worked out by Reed and Healy [1] between the, existence of low interfacial tensions and the obtaining of a phase diagram having a specific configuration said to be of the Winsor Type III [7]. In this configuration, the multiphase zone contains, in particular, a three-phase domain in which an intermediate micellar phase is in equilibrium with an aqueous phase and a hydrocarbon phase. When the affinity of the surfactant for the water and the hydrocarbon is the same, the micellar phase contains equal amounts of water and hydrocarbon. The system is then considered, by convention to be an optimal one. In mixtures of water, amphiphilic compounds (surfactant and alcohol and hydrocarbons having different molecular weights and structures, the solubilizing power is measured at the reference point obtained by adjusting the molecular weight of the surfactant. However, all optimal systems are not equivalent. Solubilization is all the greater and hence the lowering of the interfacial tension is all the more marked as the energies of cohesion between the surfactant and the water and hydrocarbon are strong. This approach is fruitful for interpreting performance variations when some parameters of the system are modified, such as the molecular weight and structure of the hydrocarbon or the salinity of the water. During this study, we show that the optimal molecular weight of the surfactant varies linearly with that of the pure hydrocarbon (alkane or alkylbenzene, at least within the range of molecular weights examined here. Solubilization also varies linearly. This

  15. Halogen Bonds in Novel Polyhalogen Monoanions. (United States)

    Wang, Changwei; Danovich, David; Shaik, Sason; Mo, Yirong


    Polyhalogen monoanions [X 2n+1 ] - (X=Cl and Br; n=1, 2, 3, 4, and 5) have been systematically studied using the block-localized wave function (BLW) method, which offers a valence bond (VB) analysis. For each species, the most stable isomer can be described as a central halide anion X - non-classically bonded to a number of dihalogen molecules X 2 via "halogen bonds". VB analyses confirm the dominant role of the charge-transfer interaction between the lone pair on X - and the σ-anti-bonding orbital of X 2 molecule (n→σ*) in X 3 - and higher analogues. Thus, our study demonstrates that these halogen bonds are essentially dative covalent interactions. Importantly, the charge-transfer interaction between [X 2n-1 ] - and X 2 decreases with the increasing n, in accord with the weakening of the Lewis basicity as characterized by the corresponding HOMO energy. The reduction of the charge transfer interaction underscores the reduction of covalence in halogen bonds in [X 2n+1 ] - . This tendency highlights the anti-cooperative effect in polyhalogen monoanions. All in all, the halogen bond between X - and nX 2 molecules exhibits the same trends as in X - with a single X 2 molecule. In other words, halogen bonding in the larger clusters derives from the same bonding mechanism as the [X 3 ] - anion. As such, the X - ⋅⋅⋅X 2 halogen bond at different bond lengths forms a gauge of covalence for the entire [X 2n+1 ] - family. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Dual (C, H) isotope fractionation in anaerobic low molecular weight (poly)aromatic hydrocarbon (PAH) degradation: potential for field studies and mechanistic implications. (United States)

    Bergmann, Franz D; Abu Laban, Nidal M F H; Meyer, Armin H; Elsner, Martin; Meckenstock, Rainer U


    Anaerobic polycyclic aromatic hydrocarbon (PAH) degradation is a key process for natural attenuation of oil spills and contaminated aquifers. Assessments by stable isotope fractionation, however, have largely been limited to monoaromatic hydrocarbons. Here, we report on measured hydrogen isotope fractionation during strictly anaerobic degradation of the PAH naphthalene. Remarkable large hydrogen isotopic enrichment factors contrasted with much smaller values for carbon: ε(H) = -100‰ ± 15‰, ε(C) = -5.0‰ ± 1.0‰ (enrichment culture N47); ε(H) = -73‰ ± 11‰, ε(C) = -0.7‰ ± 0.3‰ (pure culture NaphS2). This reveals a considerable potential of hydrogen isotope analysis to assess anaerobic degradation of PAHs. Furthermore, we investigated the conclusiveness of dual isotope fractionation to characterize anaerobic aromatics degradation. C and H isotope fractionation during benzene degradation (ε(C) = -2.5‰ ± 0.2‰; ε(H) = -55‰ ± 4‰ (sulfate-reducing strain BPL); ε(C) = -3.0‰ ± 0.5‰; ε(H) = -56‰ ± 8‰ (iron-reducing strain BF)) resulted in dual isotope slopes (Λ = 20 ± 2; 17 ± 1) similar to those reported for nitrate-reducers. This breaks apart the current picture that anaerobic benzene degradation by facultative anaerobes (denitrifiers) can be distinguished from that of strict anaerobes (sulfate-reducers, fermenters) based on the stable isotope enrichment factors.

  17. Halogens in chondritic meteorites and terrestrial accretion (United States)

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


    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

  18. Halogen Chemistry in Volcanic Plumes (Invited) (United States)

    Roberts, Tjarda


    Volcanoes release vast amounts of gases and particles in the atmosphere. Volcanic halogens (HF, HCl, HBr, HI) are co-emitted alongside SO2, and observations show rapid formation of BrO and OClO in the plume as it disperses into the troposphere. The development of 1D and Box models (e.g. PlumeChem) that simulate volcanic plume halogen chemistry aims to characterise how volcanic reactive halogens form and quantify their atmospheric impacts. Following recent advances, these models can broadly reproduce the observed downwind BrO/SO2 ratios using "bromine-explosion" chemistry schemes, provided they use a "high-temperature initialisation" to inject radicals (OH, Cl, Br and possibly NOx) which "kick-start" the low-temperature chemistry cycles that convert HBr into reactive bromine (initially as Br2). The modelled rise in BrO/SO2 and subsequent plateau/decline as the plume disperses downwind reflects cycling between reactive bromine, particularly Br-BrO, and BrO-HOBr-BrONO2. BrCl is produced when aerosol becomes HBr-depleted. Recent model simulations suggest this mechanism for reactive chlorine formation can broadly account for OClO/SO2 reported at Mt Etna. Predicted impacts of volcanic reactive halogen chemistry include the formation of HNO3 from NOx and depletion of ozone. This concurs with HNO3 widely reported in volcanic plumes (although the source of NOx remains under question), as well as observations of ozone depletion reported in plumes from several volcanoes (Mt Redoubt, Mt Etna, Eyjafjallajokull). The plume chemistry can transform mercury into more easily deposited and potentially toxic forms, for which observations are limited. Recent incorporation of volcanic halogen chemistry in a 3D regional model of degassing from Ambrym (Vanuatu) also predicts how halogen chemistry causes depletion of OH to lengthen the SO2 lifetime, and highlights the potential for halogen transport from the troposphere to the stratosphere. However, the model parameter-space is vast and

  19. 40 CFR 721.329 - Halogenated benzyl ester acrylate (generic). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated benzyl ester acrylate... Specific Chemical Substances § 721.329 Halogenated benzyl ester acrylate (generic). (a) Chemical substance... halogenated benzyl ester acrylate (PMN P-90-1527) is subject to reporting under this section for the...

  20. Apparatus for hydrocarbon extraction (United States)

    Bohnert, George W.; Verhulst, Galen G.


    Systems and methods for hydrocarbon extraction from hydrocarbon-containing material. Such systems and methods relate to extracting hydrocarbon from hydrocarbon-containing material employing a non-aqueous extractant. Additionally, such systems and methods relate to recovering and reusing non-aqueous extractant employed for extracting hydrocarbon from hydrocarbon-containing material.

  1. Aqueous secondary formation of brominated, chlorinated, and mixed halogenated pyrene in presence of halide ions. (United States)

    Sankoda, Kenshi; Toda, Izumi; Sekiguchi, Kazuhiko; Nomiyama, Kei; Shinohara, Ryota


    We examined the secondary production of halogenated derivatives of polycyclic aromatic hydrocarbons (PAHs) in surface seawater. Pyrene was selected as the model compound and exposed to UV irradiation in synthetic seawater for various irradiation times. Pyrene underwent rapid photochemical reactions that produced various halogenated derivatives including 1-chloropyrene, 1-bromopyrene, three unidentified dichloropyrenes, and three unidentified bromochloropyrenes. The production of 1-chloropyrene (220-360 nM) was higher than that of 1-bromopyrene (7.3-12 nM), reflecting the high chlorine content of seawater. A pilot field survey was conducted to test the environmental implications of these results, and fresh, brackish, and seawater samples were collected in southwestern Japan. The variation in the concentration ratios between 1-chloropyrene and pyrene implied the presence of a specific source of 1-chloropyrene in coastal water, which can be partly explained by the secondary production observed in our photolysis experiments. In sum, the photochemical reactions of PAHs are a potential secondary source of halogenated PAHs, especially in marine environments heavily contaminated with PAHs. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Halogenated Organic Compounds Identified in Hydraulic Fracturing Wastewaters Using Ultrahigh Resolution Mass Spectrometry. (United States)

    Luek, Jenna L; Schmitt-Kopplin, Philippe; Mouser, Paula J; Petty, William Tyler; Richardson, Susan D; Gonsior, Michael


    Large volumes of water return to the surface following hydraulic fracturing of deep shale formations to retrieve oil and natural gas. Current understanding of the specific organic constituents in these hydraulic fracturing wastewaters is limited to hydrocarbons and a fraction of known chemical additives. In this study, we analyzed hydraulic fracturing wastewater samples using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) as a nontargeted technique to assign unambiguous molecular formulas to singly charged molecular ions. Halogenated molecular formulas were identified and confirmed using isotopic simulation and MS-MS fragmentation spectra. The abundance of halogenated organic compounds in flowback fluids rather than older wastewaters suggested that the observed molecular ions might have been related to hydraulic fracturing additives and related subsurface reactions, such as through the reaction of shale-extracted chloride, bromide, and iodide with strong oxidant additives (e.g., hypochlorite, persulfate, hydrogen peroxide) and subsequently with diverse dissolved organic matter. Some molecular ions matched the exact masses of known disinfection byproducts including diiodoacetic acid, dibromobenzoic acid, and diiodobenzoic acid. The identified halogenated organic compounds, particularly iodinated organic molecules, are absent from inland natural systems and these compounds could therefore play an important role as environmental tracers.

  3. Halogenated indole alkaloids from marine invertebrates. (United States)

    Pauletti, Patrícia Mendonça; Cintra, Lucas Silva; Braguine, Caio Guedes; da Silva Filho, Ademar Alves; Silva, Márcio Luís Andrade E; Cunha, Wilson Roberto; Januário, Ana Helena


    This review discusses the isolation, structural elucidation, and biological activities of halogenated indole alkaloids obtained from marine invertebrates. Meridianins and related compounds (variolins, psammopemmins, and aplicyanins), as well as aplysinopsins and leptoclinidamines, are focused on. A compilation of the (13)C-NMR spectral data of these selected natural indole alkaloids is also provided.

  4. Tolerance of Antarctic soil fungi to hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Hughes, Kevin A.; Bridge, Paul; Clark, Melody S. [British Antarctic Survey, Natural Environment Research Council, High Cross, Madingley Road, Cambridge CB3 0ET (United Kingdom)


    Little is known about the effects of hydrocarbons and fuel oil on Antarctic filamentous fungi in the terrestrial Antarctic environment. Growth of fungi and bacteria from soils around Rothera Research Station (Adelaide Island, Antarctic Peninsula) was assessed in the presence of ten separate aromatic and aliphatic hydrocarbons [marine gas oil (MGO), dodecane, hexadecane, benzoic acid, p-hydroxybenzoic acid, toluene, phenol, biphenyl, naphthalene and m- and p-xylenes with ethylbenzene]. Aromatic hydrocarbons inhibited soil microbial growth more than aliphatic hydrocarbons. Soil microorganisms from a moss patch, where little previous impact or hydrocarbon contamination had occurred, were less tolerant of hydrocarbons than those from high impact sites. Fungal growth rates of Mollisia sp., Penicillium commune, Mortierella sp., Trichoderma koningii, Trichoderma sp. and Phoma herbarum were assessed in the presence of hydrocarbons. Generally, aromatic hydrocarbons inhibited or stopped hyphal extension, though growth rates increased with some aliphatic hydrocarbons. Hyphal dry weight measurements suggested that Mortierella sp. may be able to use dodecane as sole carbon and energy source. Hydrocarbon-degrading Antarctic fungi may have use in future hydrocarbon spill bioremediation. (author)

  5. Bioremediation of high molecular weight polyaromatic hydrocarbons co-contaminated with metals in liquid and soil slurries by metal tolerant PAHs degrading bacterial consortium. (United States)

    Thavamani, Palanisami; Megharaj, Mallavarapu; Naidu, Ravi


    Bioremediation of polyaromatic hydrocarbons (PAH) contaminated soils in the presence of heavy metals have proved to be difficult and often challenging due to the ability of toxic metals to inhibit PAH degradation by bacteria. In this study, a mixed bacterial culture designated as consortium-5 was isolated from a former manufactured gas plant (MGP) site. The ability of this consortium to utilise HMW PAHs such as pyrene and BaP as a sole carbon source in the presence of toxic metal Cd was demonstrated. Furthermore, this consortium has proven to be effective in degradation of HMW PAHs even from the real long term contaminated MGP soil. Thus, the results of this study demonstrate the great potential of this consortium for field scale bioremediation of PAHs in long term mix contaminated soils such as MGP sites. To our knowledge this is the first study to isolate and characterize metal tolerant HMW PAH degrading bacterial consortium which shows great potential in bioremediation of mixed contaminated soils such as MGP.

  6. Nephrotoxicity of halogenated alkenyl cysteine-S-conjugates

    Energy Technology Data Exchange (ETDEWEB)

    Nagelkerke, J.F.; Boogaard, P.J. (Univ. of Leiden (Netherlands))


    In 1916 a relationship was postulated between the occurrence of aplastic anemia in cattle and the soy bean meal that they had been fed, which had been extracted with trichloroethylene. The toxic compound was later identified as S-(1,2-dichlorovinyl)-L-cysteine (DCV-Cys). In addition to effects on the hemopoietic system it also produced nephrotoxicity in calves. In rats only renal tubular necrosis was found. Further research demonstrated that other halogenated hydrocarbons produced similar nephrotoxicity. The haloalkenyl cysteine-S-conjugates (Cys-D-conjugates) have extensively been studied; this has provided new insight into the biochemical processes that lead to nephrotoxicity. It has been shown that a combination of transport processes and specific metabolic pathways, resulting in reactive intermediates that bind to cellular macromolecules, makes the kidney vulnerable to the noxious effects of the haloakenyl Cys-S-conjugates. The first part of this review gives a brief overview of the bioactivation of the haloalkenes; in the second part the present knowledge of the underlying mechanisms of cytotoxicity is outlined.

  7. Halogen bonding origin properties and applications (United States)

    Hobza, Pavel


    σ-hole bonding represents an unusual and novel type of noncovalent interactions in which atom with σ- hole interacts with Lewis base such as an electronegative atom (oxygen, nitrogen, …) or aromatic systems. This bonding is of electrostatic nature since the σ-hole bears a positive charge. Dispersion energy forms equally important energy term what is due to the fact that two heavy atoms (e.g. halogen and oxygen) having high polarizability lie close together (the respective distance is typically shorter than the sum of van der Waals radii). Among different types of σ-hole bondings the halogen bonding is by far the most known but chalcogen and pnictogen bondings are important as well.

  8. Halogen bonding origin properties and applications

    Energy Technology Data Exchange (ETDEWEB)

    Hobza, Pavel [Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, 166 10 Prague (Czech Republic); Regional Center of Advanced Technologies and Materials, Department of Physical Chemistry, Palacky University, 77146 Olomouc (Czech Republic)


    σ-hole bonding represents an unusual and novel type of noncovalent interactions in which atom with σ- hole interacts with Lewis base such as an electronegative atom (oxygen, nitrogen, …) or aromatic systems. This bonding is of electrostatic nature since the σ-hole bears a positive charge. Dispersion energy forms equally important energy term what is due to the fact that two heavy atoms (e.g. halogen and oxygen) having high polarizability lie close together (the respective distance is typically shorter than the sum of van der Waals radii). Among different types of σ-hole bondings the halogen bonding is by far the most known but chalcogen and pnictogen bondings are important as well.

  9. Halogen-induced organic aerosol (XOA) formation and decarboxylation of carboxylic acids by reactive halogen species - a time-resolved aerosol flow-reactor study (United States)

    Ofner, Johannes; Zetzsch, Cornelius


    from aliphatic or aromatic precursors is coupled to the formation of carboxylic acids by saturation of reactive radical sites with oxygen, but carboxylic acids themselves can be destroyed by RHS, leading to further fragmentation of the carbon structure. References Cai, X., and Griffin, R. J.: Secondary aerosol formation from the oxidation of biogenic hydrocarbons by chlorine atoms, J. Geophys. Res., 111, D14206/14201-D14206/14214, 2006. Cai, X., Ziemba, L. D., and Griffin, R. J.: Secondary aerosol formation from the oxidation of toluene by chlorine atoms, Atmos. Environ., 42, 7348-7359, 2008. Ofner, J., Krüger, H.-U., and Zetzsch, C.: Circular multireflection cell for optical spectroscopy, Appl. Opt., 49, 5001-5004, 2010. Ofner, J., Balzer, N., Buxmann, J., Grothe, H., Schmitt-Kopplin, Ph., Platt, U., and Zetzsch, C.: Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms, Atmos. Chem. Phys., 12, 5787-5806, 2012.

  10. Enzymatic halogenation and dehalogenation reactions: pervasive and mechanistically diverse


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


    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 substr...

  11. PAH (Polycyclic Aromatic Hydrocarbon) bioaccumulation and PAHs/shell weight index in Ruditapes philippinarum (Adams & Reeve, 1850) from the Vallona lagoon (northern Adriatic Sea, NE Italy). (United States)

    Cacciatore, Federica; Bernarello, Valentina; Boscolo Brusà, Rossella; Sesta, Giulio; Franceschini, Gianluca; Maggi, Chiara; Gabellini, Massimo; Lamberti, Clauda Virno


    The Vallona lagoon is a transitional area located in the Po River delta (NE, ITALY) traditionally exploited for Manila clam (Ruditapes philippinarum) farming. During 2007-2008, a pipeline was buried in the middle of the lagoon to connect an off-shore structure to facilities on land. PAH levels were monitored in Manila clams and sediments before, during and after the pipeline construction to assess the impact of the activities through the pattern of distribution of the PAH compounds. PAH bioaccumulation in clams displayed seasonal fluctuations with higher levels in autumnal and wintry surveys than in spring-summer. Principal component analysis applied to PAHs in clams highlighted a petrogenic input during ante operam period and a pyrolytic origin during the burying activities. On the contrary, sediment PAH concentrations resulted quite similar both among sites and periods. Biota-Sediment-Accumulation-Factor values also confirmed that sediments were not the major source of PAH pollution for clams in this study. The welfare of clams was examined through two physiological indices (condition index and survival in air) to check the effects of the activities on a commercial resource. Both physiological indices exhibited seasonal variations connected to natural endogenous and exogenous factors; however survival in air was the most sensitive index in highlighting the effects of the pipeline burying activities. Finally, to ensure that PAH bioavailability assessment was not affected by seasonal variation of soft tissues of molluscs, PAHs/shell weight index was applied. Higher levels of this index were observed before and during the burying activities, whilst, after that, values significantly lowered. Moreover, the normalization enabled us to highlight the PAH uptake from clams in some particular periods and to compare different populations in a long-term biomonitoring program with data obtained from different periods of the year. Copyright © 2017 Elsevier Inc. All rights

  12. 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


    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

  13. Dehalogenation of halogenated fumigants by polysulfide salts. (United States)

    Bondarenko, S; Zheng, W; Yates, S R; Gan, J


    Halogenated fumigants are among the most heavily used pesticides in agriculture. Because of their high mobility and toxicological characteristics, the contamination of air or groundwater by these compounds has been a great environmental concern. In this study, we investigated dehalogenation of several halogenated fumigants by polysulfides. The reaction of polysulfides and methyl iodide (MeI), 1,3-dichloropropene (1,3-D), and chloropicrin (CP) was very rapid. When the initial fumigant and polysulfide concentrations were both 0.2 mM, the observed 50% disappearance time values (DT50) of MeI, cis-1,3-D, and trans-1,3-D were 27.2, 29.6, and 102 h, respectively. When the initial polysulfide concentration was 1.0 mM, the corresponding DT50 values were only 2.2, 1.6, and 3.8 h. Under similar conditions, the reaction with CP was even more rapid than with the other fumigants. In 0.2 mM polysulfide solution, more than 90% of the spiked CP disappeared in 1 h after the initiation of the reaction. The reaction between fumigants and polysulfides also progressed at enhanced rates when the polysulfide solution was initially purged with nitrogen. Analysis of reaction kinetics and initial products suggests that the reaction is SN2 nucleophilic substitution for MeI and 1,3-D but likely reductive dehalogenation for CP. Given the high reactivity of polysulfide salts toward halogenated fumigants, this reaction may be used as a pollution mitigation strategy, such as for disposal of fumigant wastes, treatment of fumigant-containing wastewater, and cleanup of fumigant residues in environmental media.

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

    Directory of Open Access Journals (Sweden)

    J. Ofner


    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.

  15. Halogenation of aromatic compounds: thermodynamic, mechanistic and ecological aspects

    NARCIS (Netherlands)

    Dolfing, J.


    Biological halogenation of aromatic compounds implies the generation of reducing equivalents in the form of e.g. NADH. Thermodynamic calculations show that coupling the halogenation step to a step in which the reducing equivalents are oxidized with a potent oxidant such as O2 or N2O makes the

  16. Scientific conferences: A big hello to halogen bonding (United States)

    Erdelyi, Mate


    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.

  17. Benchmark Calculations of Noncovalent Interactions of Halogenated Molecules. (United States)

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


    We present a set of 40 noncovalent complexes of organic halides, halohydrides, and halogen molecules where the halogens participate in a variety of interaction types. The set, named X40, covers electrostatic interactions, London dispersion, hydrogen bonds, halogen bonding, halogen-π interactions, and stacking of halogenated aromatic molecules. Interaction energies at equilibrium geometries were calculated using a composite CCSD(T)/CBS scheme where the CCSD(T) contribution is calculated using triple-ζ basis sets with diffuse functions on all atoms but hydrogen. For each complex, we also provide 10 points along the dissociation curve calculated at the CCSD(T)/CBS level. We use this accurate reference to assess the accuracy of selected post-HF methods.

  18. Organic amendment optimization for treatment of hydrocarbon ...

    African Journals Online (AJOL)

    Sugar cane cachasse was tested as an organic soil amendment at 0, 2, 4 and 9% (dry weight), for the remediation of hydrocarbon contaminated soil (with an average initial concentration of 14,356 mg/Kg), which had been pre-treated by the incorporation of 4% (dry weight) calcium hydroxide according to the ...

  19. [Near infrared light irradiator using halogen lamp]. (United States)

    Ide, Yasuo


    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.

  20. [Dermatologic risks of quartz-halogen lamps]. (United States)

    Cesarini, J P; Muel, B


    Halogene sources are used increasingly in general illumination. Their quartz envelop is technically necessary, but presents the disadvantage of to letting the emitted UVA, UVB and UVC go through. Originally used as in indirect lighting, they have been introduced as desk-top lamps, without filter. We have proceeded to the verification of their output with a spectrophotometer calibrated by actinometry and we have calculated their relative erythemal efficacy according to the Parrish's action spectrum for human erythema. We found that, at 10 cm from the human skin, the irradiance was able to induce a minimal erythema in about 10 minutes on clear back skin. At working distance (50 cm), a barely perceptible erythema could be observed on the back of the hands after 8 consecutive hours working. We also found that sunburn cells were present in the skin sensitized with a potent phototoxic agent (8-methoxypsoralen) applied 15 minutes before a 4-6 minutes irradiation with the halogen source (at 20 cm), thus, indicating a potential risk for local phototoxicity and photoallergy. The cumulative doses per year, for 4 hours exposure per day, five days a week, reaches 125 minimal erythemal doses, equivalent to the average yearly exposure of individuals for work and leisure. If one assumes that this regimen is maintained for 30 years, the risk for induction of skin cancers on the dorsal aspect of the hands and the forearms, may be increased by a 3.4 factor, according to the widely accepted previsional models.(ABSTRACT TRUNCATED AT 250 WORDS)

  1. On The Nature of the Halogen Bond. (United States)

    Wang, Changwei; Danovich, David; Mo, Yirong; Shaik, Sason


    The wide-ranging applications of the halogen bond (X-bond), notably in self-assembling materials and medicinal chemistry, have placed this weak intermolecular interaction in a center of great deal of attention. There is a need to elucidate the physical nature of the halogen bond for better understanding of its similarity and differences vis-à-vis other weak intermolecular interactions, for example, hydrogen bond, as well as for developing improved force-fields to simulate nano- and biomaterials involving X-bonds. This understanding is the focus of the present study that combines the insights of a bottom-up approach based on ab initio valence bond (VB) theory and the block-localized wave function (BLW) theory that uses monomers to reconstruct the wave function of a complex. To this end and with an aim of unification, we studied the nature of X-bonds in 55 complexes using the combination of VB and BLW theories. Our conclusion is clear-cut; most of the X-bonds are held by charge transfer interactions (i.e., intermolecular hyperconjugation) as envisioned more than 60 years ago by Mulliken. This is consistent with the experimental and computational findings that X-bonds are more directional than H-bonds. Furthermore, the good linear correlation between charge transfer energies and total interaction energies partially accounts for the success of simple force fields in the simulation of large systems involving X-bonds.

  2. Evaluation of wear rate of dental composites polymerized by halogen or LED light curing units

    Directory of Open Access Journals (Sweden)

    Alaghehmand H.


    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.

  3. Description of Immundisolibacter cernigliae gen. nov., sp. nov., a high-molecular-weight polycyclic aromatic hydrocarbon-degrading bacterium within the class Gammaproteobacteria, and proposal of Immundisolibacterales ord. nov. and Immundisolibacteraceae fam. nov. (United States)

    Corteselli, Elizabeth M; Aitken, Michael D; Singleton, David R


    The bacterial strain TR3.2T was isolated from aerobic bioreactor-treated soil from a polycyclic aromatic hydrocarbon (PAH)-contaminated site in Salisbury, NC, USA. Strain TR3.2T was identified as a member of 'Pyrene Group 2' or 'PG2', a previously uncultivated cluster of organisms associated with the degradation of high-molecular-weight PAHs by stable-isotope probing. Based on its 16S rRNA gene sequence, the strain was classified as a member of the class Gammaproteobacteria but possessed only 90.5 % gene identity to its closest described relative, Methylococcus capsulatus strain Bath. Strain TR3.2T grew on the PAHs pyrene, phenanthrene, anthracene, benz[a]anthracene and fluorene, as well as the azaarene carbazole, and could additionally metabolize a limited number of organic acids. Optimal growth occurred aerobically under mesophilic temperature, neutral pH and low salinity conditions. Strain TR3.2T was catalase and oxidase positive. Predominant fatty acids were C17 : 0 cyclo and C16 : 0. Genomic G+C content of the single chromosome was 67.79 mol% as determined by complete genome sequencing. Due to the high sequence divergence from any cultivated species and its unique physiological properties compared to its closest relatives, strain TR3.2T is proposed as a representative of a novel order, family, genus and species within the class Gammaproteobacteria, for which the name Immundisolibacter cernigliae gen. nov., sp. nov. is proposed. The associated order and family are therefore proposed as Immundisolibacteralesord. nov. and Immundisolibacteraceaefam. nov. The type strain of the species is TR3.2T (=ATCC TSD-58T=DSM 103040T).

  4. Determination of high-molecular weight polycyclic aromatic hydrocarbons in high performance liquid chromatography fractions of coal tar standard reference material 1597a via solid-phase nanoextraction and laser-excited time-resolved Shpol'skii spectroscopy. (United States)

    Wilson, Walter B; Alfarhani, Bassam; Moore, Anthony F T; Bisson, Cristina; Wise, Stephen A; Campiglia, Andres D


    This article presents an alternative approach for the analysis of high molecular weight - polycyclic aromatic hydrocarbons (HMW-PAHs) with molecular mass 302 Da in complex environmental samples. This is not a trivial task due to the large number of molecular mass 302 Da isomers with very similar chromatographic elution times and similar, possibly even virtually identical, mass fragmentation patterns. The method presented here is based on 4.2K laser-excited time-resolved Shpol'skii spectroscopy, a high resolution spectroscopic technique with the appropriate selectivity for the unambiguous determination of PAHs with the same molecular mass. The potential of this approach is demonstrated here with the analysis of a coal tar standard reference material (SRM) 1597a. Liquid chromatography fractions were submitted to the spectroscopic analysis of five targeted isomers, namely dibenzo[a,l]pyrene, dibenzo[a,e]pyrene, dibenzo[a,i]pyrene, naphtho[2,3-a]pyrene and dibenzo[a,h]pyrene. Prior to analyte determination, the liquid chromatographic fractions were pre-concentrated with gold nanoparticles. Complete analysis was possible with microliters of chromatographic fractions and organic solvents. The limits of detection varied from 0.05 (dibenzo[a,l]pyrene) to 0.24 µg L(-1) (dibenzo[a,e]pyrene). The excellent analytical figures of merit associated to its non-destructive nature, which provides ample opportunity for further analysis with other instrumental methods, makes this approach an attractive alternative for the determination of PAH isomers in complex environmental samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Independent Evolution of Six Families of Halogenating Enzymes.

    Directory of Open Access Journals (Sweden)

    Gangming Xu

    Full Text Available 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.

  6. Enzymatic Halogenation and Dehalogenation Reactions: Pervasive and Mechanistically Diverse. (United States)

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


    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.

  7. Palladium-Catalyzed Directed Halogenation of Bipyridine N-Oxides. (United States)

    Zucker, Sina P; Wossidlo, Friedrich; Weber, Manuela; Lentz, Dieter; Tzschucke, C Christoph


    The palladium-catalyzed directed C-H halogenation of bipyridine N-oxides was investigated. Using NCS or NBS (N-chloro- or N-bromosuccinimide) and 5 mol % Pd(OAc)2 in chlorobenzene (0.10 molar) at 110 °C, pyridine-directed functionalization took place and 3-chloro- or 3-bromobipyridine N-oxides were obtained in high yields. The reaction is sensitive to steric hindrance by 4- and 6'-substituents. Only in the latter case, where coordination of palladium by the pyridine is hindered, 3'-halogenation directed by the N-oxide function was observed. The halogenated products were deoxygenated by PCl3 or PBr3.

  8. Insights into enzymatic halogenation from computational studies

    Directory of Open Access Journals (Sweden)

    Hans Martin Senn


    Full Text Available The halogenases are a group of enzymes that have only come to the fore over the last ten years thanks to the discovery and characterization of several of novel representatives. They have re-vealed the fascinating variety of distinct chemical mechanisms that nature utilizes to activate and introduce halogens into organic substrates. Computational studies using a range of approaches have already elucidated many details of the mechanisms of these enzymes, often in synergistic combination with experiment. This Review summarizes the main insights gained from these stud-ies. It also seeks to identify open questions that are amenable to computational investigations. The studies discussed herein also serve to illustrate some of the limitations of the current computa-tional approaches and the challenges encountered in computational mechanistic enzymology.

  9. Halogenated coumarin derivatives as novel seed protectants. (United States)

    Brooker, N; Windorski, J; Bluml, E


    Development of new and improved antifungal compounds that are target-specific is backed by a strong Federal, public and commercial mandate. Many plant-derived chemicals have proven fungicidal properties, including the coumarins (1,2-Benzopyrone) found in a variety of plants such as clover, sweet woodruff and grasses. Preliminary research has shown the coumarins to be a highly active group of molecules with a wide range of antimicrobial activity against both fungi and bacteria. It is believed that these cyclic compounds behave as natural pesticidal defence molecules for plants and they represent a starting point for the exploration of new derivative compounds possessing a range of improved antifungal activity. Within this study, derivatives of coumarin that were modified with halogenated side groups were screened for their antifungal activity against a range of soil-borne plant pathogenic fungi. Fungi included in this in vitro screen included Macrophomina phaseolina (charcoal rot), Phytophthora spp. (damping off and seedling rot), Rhizoctonia spp. (damping off and root rot) and Pythium spp. (seedling blight), four phylogenetically diverse and economically important plant pathogens. Studies indicate that these halogenated coumarin derivatives work very effectively in vitro to inhibit fungal growth and some coumarin derivatives have higher antifungal activity and stability as compared to the original coumarin compound alone. The highly active coumarin derivatives are brominated, iodinated and chlorinated compounds and results suggest that besides being highly active, very small amounts can be used to achieve LD100 rates. In addition to the in vitro fungal inhibition assays, results of polymer seed coating compatibility and phytotoxicity testing using these compounds as seed treatments will also be reported. These results support additional research in this area of natural pesticide development.

  10. Ring halogenation of 1,8- and 4,5- dialkylisoquinolines. 1,8- oyobi 4,5- dialkylisoquinolines rui no kaku halogen ka hanno

    Energy Technology Data Exchange (ETDEWEB)

    Niimi, A.; Saito, T.; Tanaka, F.; Nagao, Y.; Abe, Y.; Misono, T. (Science Univ. of Tokyo, Tokyo (Japan). Faculty of Science and Technology)


    In this paper, synthesis of halogenoisoquinoline by nucleus substituting halogenation was investigated. Since syntesis of isoquinoline with an alkyl group at its peri-position is difficult, it has not been done often, but here, among these syntheses, halogenation of 1,8-dimethylisoquinoline 1 and 5,6-dihydro-4H-benzo bdec isoquinoline 2 was made. For halogenation, two kinds of methods were studied, namely the method with free bromine and iodine in sulfuric acid in the presence of silver sulfate and the method with N-bromo and N-chlorosuccinimide in sulfuric acid. As a result, in either case, concerning 1 above, the 5-position was halogenated, and concerning 2 above, the 9-position was halogenated, hence it was elucidated that the positions were halogenated which were similar to the case of the halogenation of alkylquinolines such as 8-methylquinolines with the 5- and 7-positions to be halogenated. 11 refs., 2 figs., 3 tabs.

  11. Halogen chemistry reduces tropospheric O3 radiative forcing

    DEFF Research Database (Denmark)

    Sherwen, Tomás; Evans, Mat J.; Carpenter, Lucy J.


    to be represented in chemistry-transport models for an accurate simulation of present-day O3. Using the GEOS-Chem model we show that tropospheric halogen chemistry is likely more active in the present day than in the preindustrial. This is due to increased oceanic iodine emissions driven by increased surface O3......  ∼ 50 % of this reduction to increased bromine flux from the stratosphere,  ∼ 35 % to the ocean–atmosphere iodine feedback, and  ∼ 15 % to increased tropospheric sources of anthropogenic halogens. This reduction of tropospheric O3 radiative forcing due to halogens (0.087 Wm−2) is greater than that from...... the radiative forcing of stratospheric O3 (∼ 0.05 Wm−2). Estimates of RFTO3 that fail to consider halogen chemistry are likely overestimates (∼ 25 %)...

  12. Cardioprotective Effects Induced by Preconditioning with Halogenated Anesthetics

    Directory of Open Access Journals (Sweden)

    Papurica Marius


    Full Text Available Background: Numerous studies discuss the protective effects of halogenated anesthetics on myocyte injury induced by the ischemia-reperfusion syndrome of the heart. This mechanism is known as pharmacological preconditioning.

  13. UARS Halogen Occultation Experiment (HALOE) Level 3AT V001 (United States)

    National Aeronautics and Space Administration — The Halogen Occultation Experiment (HALOE) Level 3AT data product consists of daily vertical profiles of temperature, aerosol extinction and concentrations of HCl,...

  14. UARS Halogen Occultation Experiment (HALOE) Level 2 V001 (United States)

    National Aeronautics and Space Administration — The HALOE home page on the WWW is The Halogen Occultation Experiment (HALOE) on NASA's Upper Atmosphere Research Satellite...

  15. Halogenation dictates the architecture of amyloid peptide nanostructures. (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


    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.

  16. Data for fire hazard assessment of selected non-halogenated and halogenated fire retardants: Report of Test FR 3983 (United States)

    Harris, R. H.; Babrauskas, V.; Levin, B. C.; Paabo, M.


    Five plastic materials, with and without fire retardants, were studied to compare the fire hazards of non-halogenated fire retardant additives with halogenated flame retardents. The plastic materials were identified by the sponsors as unsaturated polyesters, thermoplastic high density, low density and cross-linked low density polyethylenes, polypropylene, flexible and rigid poly(vinyl chlorides), and cross-linked and thermoplastic ethylene-vinyl acetate copolymers. The non-halogenated fire retardants tested were aluminum hydroxide, also known as alumina trihydrate, sodium alumino-carbonate, and magnesium hydroxide. The halogenated flame retardants were chlorine or bromine/antimony oxides. The plastics were studied using the Cone Calorimeter and the cup furnace smoke toxicity method (high density polyethylene only). The Cone Calorimeter provided data on mass consumed; time to ignition; peak rate and peak time of heat release; total heat release; effective heat of combustion; average yields of CO, CO2, HCl, and HBr; and average smoke obscuration. The concentrations of toxic gases generated in the cup furnace smoke toxicity method were used to predict the toxic potency of the mixed thermal decomposition products. The data from the Cone Calorimeter indicate that the non-halogenated fire retardants were, in most of the tested plastic formulations, more effective than the halogenated flame retardants in increasing the time to ignition. The non-halogenated fire retardants were also more effective in reducing the mass consumed, peak rate of heat release, total heat released, and effective smoke produced. The use of halogenated flame retardants increased smoke production and CO yields and, additionally, produced the known acid gases and toxic irritants, HCl and HBr, in measureable quantities.

  17. The relative roles of electrostatics and dispersion in the stabilization of halogen bonds. (United States)

    Riley, Kevin E; Hobza, Pavel


    In this work we highlight recent work aimed at the characterization of halogen bonds. Here we discuss the origins of the σ-hole, the modulation of halogen bond strength by changing of neighboring chemical groups (i.e. halogen bond tuning), the performance of various computational methods in treating halogen bonds, and the strength and character of the halogen bond, the dihalogen bond, and two hydrogen bonds in bromomethanol dimers (which serve as model complexes) are compared. Symmetry adapted perturbation theory analysis of halogen bonding complexes indicates that halogen bonds strongly depend on both dispersion and electrostatics. The electrostatic interaction that occurs between the halogen σ-hole and the electronegative halogen bond donor is responsible for the high degree of directionality exhibited by halogen bonds. Because these noncovalent interactions have a strong dispersion component, it is important that the computational method used to treat a halogen bonding system be chosen very carefully, with correlated methods (such as CCSD(T)) being optimal. It is also noted here that most forcefield-based molecular mechanics methods do not describe the halogen σ-hole, and thus are not suitable for treating systems with halogen bonds. Recent attempts to improve the molecular mechanics description of halogen bonds are also discussed.

  18. Negative Halogen Ions for Fusion Applications

    Energy Technology Data Exchange (ETDEWEB)

    Grisham, L.R.; Kwan, J.W.; Hahto, S.K.; Hahto, S.T.; Leung, K.N.; Westenskow, G.


    Over the past quarter century, advances in hydrogen negative ion sources have extended the usable range of hydrogen isotope neutral beams to energies suitable for large magnetically confined fusion devices. Recently, drawing upon this experience, negative halogen ions have been proposed as an alternative to positive ions for heavy ion fusion drivers in inertial confinement fusion, because electron accumulation would be prevented in negative ion beams, and if desired, the beams could be photo-detached to neutrals. This paper reports the results of an experiment comparing the current density and beam emittance of Cl+ and Cl- extracted from substantially ion-ion plasmas with that of Ar+ extracted from an ordinary electron-ion plasma, all using the same source, extractor, and emittance scanner. At similar discharge conditions, the Cl- current was typically 85 – 90% of the positive chlorine current, with an e-/ Cl- ratio as low as seven without grid magnets. The Cl- was as much as 76% of the Ar+ current from a discharge with the same RF drive. The minimum normalized beam emittance and inferred ion temperatures of Cl+, Cl-, and Ar+ were all similar, so the current density and optical quality of Cl- appear as suitable for heavy ion fusion driver applications as a positive noble gas ion of similar mass. Since F, I, and Br should all behave similarly in an ion source, they should also be suitable as driver beams.

  19. Thraustochytrid protists degrade hydrocarbons

    Digital Repository Service at National Institute of Oceanography (India)

    Raikar, M.T.; Raghukumar, S.; Vani, V.; David, J.J.; Chandramohan, D.

    that thraustochytrids have the capability to utilize a wide range of organic nitrogen and carbon compounds for their nutrition. However, the capability of these protists to degrade hydrocarbons has not been examined so far. Hydrocarbons occur in seawater either... chromatography. (1) Gravimetry: Tarballs were extracted from experimental flasks with 10 ml of carbon tetrachloride, the extract transferred to pre- weighed Petri dish and the solvent allowed to RAIKAR et al.: THRAUSTOCHYTRID PROTISTS DEGRADE HYDROCARBONS...

  20. Halogenated Natural Products in Dolphins: Brain-Blubber Distribution and Comparison with Halogenated Flame Retardants. (United States)

    Barón, E; Hauler, C; Gallistl, C; Giménez, J; Gauffier, P; Castillo, J J; Fernández-Maldonado, C; de Stephanis, R; Vetter, W; Eljarrat, E; Barceló, D


    Halogenated natural products (MHC-1, TriBHD, TetraBHD, MeO-PBDEs, Q1, and related PMBPs) and halogenated flame retardants (PBDEs, HBB, Dec 602, Dec 603, and DP) in blubber and brain are reported from five Alboran Sea delphinids (Spain). Both HNPs and HFRs were detected in brain, implying that they are able to surpass the blood-brain barrier and reach the brain, which represents a new finding for some compounds, such as Q1 and PMBPs, MHC-1, TriBHD, TetraBHD, or Dec 603. Moreover, some compounds (TetraBHD, BDE-153, or HBB) presented higher levels in brain than in blubber. This study evidence the high concentrations of HNPs in the marine environment, especially in top predators. It shows the importance of further monitoring these natural compounds and evaluating their potential toxicity, when most studies focus on anthropogenic compounds only. While no bioaccumulation was found for ∑HNPs, ∑HFRs increased significantly with body size for both common and striped dolphins. Studies evaluating BBB permeation mechanisms of these compounds together with their potential neurotoxic effects in dolphins are recommended.

  1. Prevalence of polycyclic aromatic hydrocarbons (PAHs) degrading ...

    African Journals Online (AJOL)

    Recalcitrant pollutants such as polycyclic aromatic hydrocarbons (PAHs) are difficult to degrade and have been the focus for biodegradation. They form a class of pollutant on a global scale. In an attempt to contribute to the search for suitable microbial culture with potential to biodegrade low and high molecular weight PAHs ...

  2. Halogenated flame retardants in bobcats from the midwestern United States. (United States)

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


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

  3. Halogenated hydrocarbon pesticides and other volatile organic contaminants provide analytical challenges in global trading. (United States)

    Budnik, Lygia T; Fahrenholtz, Svea; Kloth, Stefan; Baur, Xaver


    Protection against infestation of a container cargo by alien species is achieved by mandatory fumigation with pesticides. Most of the effective fumigants are methyl and ethyl halide gases that are highly toxic and are a risk to both human health and the environment. There is a worldwide need for a reliable and robust analytical screening procedure for these volatile chemicals in a multitude of health and environmental scenarios. We have established a highly sensitive broad spectrum mass spectrometry method combined with thermal desorption gas chromatography to detect, identify and quantify volatile pesticide residues. Using this method, 1201 random ambient air samples taken from freight containers arriving at the biggest European ports of Hamburg and Rotterdam were analyzed over a period of two and a half years. This analytical procedure is a valuable strategy to measure air pollution from these hazardous chemicals, to help in the identification of pesticides in the new mixtures/formulations that are being adopted globally and to analyze expired breath samples after suspected intoxication in biomonitoring.

  4. Stable carbon isotope monitoring of in situ bioaugmentation for enhanced reductive dechlorination of halogenated hydrocarbons (United States)

    Bill, M.; Conrad, M. E.; Sorenson, K.; Wymore, R.; Lamar, M.; Chamberlain, S.; Trotsky, J.


    Injection of electron donor to stimulate reductive dechlorination of trichloroethene (TCE) has been demonstrated to be an effective strategy for remediation of contaminated groundwater. At a number of sites, however, complete reductive dechlorination of TCE to ethene is not attained because the appropriate microbial community is not present. Addition of Dehalococcoides spp. to groundwater to achieve complete reductive dechlorination of TCE is being tested at Naval Weapons Station Seal Beach, CA. To help assess the effectiveness of this process, the stable carbon isotope compositions of TCE and its byproducts, cis-dichloroethene (cDCE), vinyl chloride (VC) and ethene are being measured during the experiment. Two different methods of bioremediation are being tested. In the “active” cell groundwater is continuously pumped from downgradient wells and re-injected into two upgradient wells. Electron donor (1-3% Na-lactate) has been added to the injection line either weekly or monthly. In the “passive” cell, no circulation of groundwater is done, but electron donor is added to three injection wells monthly. When reducing conditions were reached in the groundwater (late 2008), the bioaugmentation culture was added to both experimental cells with the electron donor. In the active cell, addition of electron donor prior to introduction of the bioaugmentation culture stimulated significant increases in the concentrations of cDCE, but only trace VC and ethene. In the passive cell, production of cDCE was observed, but at lower levels. The δ13C values of TCE ranged from -20‰ to 28‰ (averaging -24‰). The δ13C values of cDCE were generally 1-2‰ per mil lower than those of the TCE, representing fractionation during the biological conversion from TCE to cDCE. Following bioaugmentation, significant production of VC has been observed in the active cell, with corresponding increases in δ13C values of TCE and cDCE. In several wells, the δ13C values of the cDCE have become higher than that of the TCE, indicating efficient conversion of cDCE to VC. To date, only low levels of ethene have been observed in the active cell and this is reflected by the δ13C values of the VC, which are approaching the initial δ13C values of TCE. In the passive cell, dechlorination to VC is observed but less widespread than in the active cell. Where VC is observed, however, there is also significant production of ethene. The δ13C values of both cDCE and VC in these wells have been shifted to very high values (to as high as 1‰ for cDCE and -4‰ for VC) indicating significant levels of complete reductive dechlorination are occurring in this cell. The variations in the carbon isotope compositions of TCE and byproducts clearly indicate that bioaugmentation has led to significantly enhanced levels of reductive dechlorination at this site.

  5. The Relationship Between Stratum Corneum Diffusion Coeficients and Temperature for Halogenated Hydrocarbons

    National Research Council Canada - National Science Library

    Caracci, M


    ...: chemical partition coefficient and the pathlength of diffusion. In the idealized expression of diffusion given in the Stokes-Einstein equation, diffusion is described in terms of kinetic energy and the viscous resistance of diffusion...


    Energy Technology Data Exchange (ETDEWEB)

    John F. Schabron; Susan S. Sorini; Joseph F. Rovani Jr


    Western Research Institute (WRI) has developed new methodology and a test kit to screen soil or water samples for halogenated volatile organic compounds (HVOCs) in the field. The technology has been designated the X-Wand{trademark} screening tool. The new device uses a heated diode sensor that is commonly used to detect leaks of refrigerants from air conditioners, freezers, and refrigerators. This sensor is selective to halogens. It does not respond to volatile aromatic hydrocarbons, such as those in gasoline, and it is not affected by high humidity. In the current work, the heated diode leak detectors were modified further to provide units with rapid response and enhanced sensitivity. The limit of detection for trichloroethylene TCE in air is 0.1 mg/m{sup 3} (S/N = 2). The response to other HVOCS relative to TCE is similar. Variability between sensors and changes in a particular sensor over time can be compensated for by normalizing sensor readings to a maximum sensor reading at 1,000 mg/m{sup 3} TCE. The soil TCE screening method was expanded to include application to water samples. Assuming complete vaporization, the detection limit for TCE in soil is about 1 ug/kg (ppb) for a 25-g sample in an 8-oz jar. The detection limit for TCE in water is about 1 ug/L (ppb) for a 25-mL sample in an 8-oz jar. This is comparable to quantitation limits of EPA GC/MS laboratory methods. A draft ASTM method for screening TCE contaminated soils using a heated diode sensor was successfully submitted for concurrent main committee and subcommittee balloting in ASTM Committee D 34 on Waste Management. The method was approved as ASTM D 7203-05, Standard Test Method for Screening Trichloroethylene (TCE)-Contaminated Soil Using a Heated Diode Sensor.

  7. Regulated and unregulated halogenated disinfection byproduct formation from chlorination of saline groundwater. (United States)

    Szczuka, Aleksandra; Parker, Kimberly M; Harvey, Cassandra; Hayes, Erin; Vengosh, Avner; Mitch, William A


    Coastal utilities exploiting mildly saline groundwater (Groundwater from North Carolina coastal aquifers is characterized by large variations in concentrations of halides (bromide up to 10,600 μg/L) and dissolved organic carbon (up to 5.7 mg-C/L). Formation of 33 regulated and unregulated halogenated DBPs, including trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles, haloacetamides, and haloacetaldehydes, was measured after simulated chlorination of 24 coastal North Carolina groundwater samples under typical chlorination conditions. Results of chlorination simulation show that THM levels exceeded the Primary Maximum Contaminant Levels in half of the chlorinated samples. Addition of halides to a low salinity groundwater (110 mg/L chloride) indicated that elevated bromide triggered DBP formation, but chloride was not a critical factor for their formation. DBP speciation, but not overall molar formation, was strongly correlated with bromide variations in the groundwater. THMs and HAAs dominated the measured halogenated DBPs on a mass concentration basis. When measured concentrations were weighted by metrics of toxic potency, haloacetonitriles, and to a lesser degree, haloacetaldehydes and HAAs, were the predominant contributors to calculated DBP-associated toxicity. For some samples exhibiting elevated ammonia concentrations, the addition of chlorine to form chloramines in situ significantly reduced halogenated DBP concentrations and calculated toxicity. HAAs dominated the calculated toxicity of chloraminated waters. Reverse osmosis treatment of saline groundwater (chloride >250 mg/L) can reduce DBP formation by removing halides and organic precursors. However, we show that in a case where reverse osmosis permeate is blended with a separate raw groundwater, the residual bromide level in the permeate could still exceed that in the raw groundwater, and thereby induce DBP formation in the blend. DBP-associated calculated toxicity increased for

  8. Hydrocarbon Spectral Database (United States)

    SRD 115 Hydrocarbon Spectral Database (Web, free access)   All of the rotational spectral lines observed and reported in the open literature for 91 hydrocarbon molecules have been tabulated. The isotopic molecular species, assigned quantum numbers, observed frequency, estimated measurement uncertainty and reference are given for each transition reported.

  9. Plant hydrocarbon recovery process

    Energy Technology Data Exchange (ETDEWEB)

    Dzadzic, P.M.; Price, M.C.; Shih, C.J.; Weil, T.A.


    A process for production and recovery of hydrocarbons from hydrocarbon-containing whole plants in a form suitable for use as chemical feedstocks or as hydrocarbon energy sources which process comprises: (A) pulverizing by grinding or chopping hydrocarbon-containing whole plants selected from the group consisting of euphorbiaceae, apocynaceae, asclepiadaceae, compositae, cactaceae and pinaceae families to a suitable particle size, (B) drying and preheating said particles in a reducing atmosphere under positive pressure (C) passing said particles through a thermal conversion zone containing a reducing atmosphere and with a residence time of 1 second to about 30 minutes at a temperature within the range of from about 200* C. To about 1000* C., (D) separately recovering the condensable vapors as liquids and the noncondensable gases in a condition suitable for use as chemical feedstocks or as hydrocarbon fuels.

  10. Ozone-Activated Halogenation of Mono- and Dimethylbipyrrole in Seawater. (United States)

    Kumar, Abdhesh; Borgen, Miles; Aluwihare, Lihini I; Fenical, William


    Polyhalogenated N-methylbipyrroles of two different structure classes have been detected worldwide in over 100 environmental samples including seawater, bird eggs, fish, dolphin blubber, and in the breast milk of humans that consume seafood. These molecules are concentrated in the fatty tissues in comparable abundance to some of the most important anthropogenic contaminants, such as the halogenated flame-retardants and pesticides. Although the origin of these compounds is still unknown, we present evidence that the production of these materials can involve the direct ozone activated seawater halogenation of N-methylbipyrrole precursors. This observation shows that environmental polyhalogenated bipyrroles can be produced via an abiotic process, and implies that the ozone activated halogenation of a variety of natural and anthropogenic seawater organics may be a significant process occurring in surface ocean waters.

  11. Biodegradation of Trihalomethanes and Other Halogenated Aliphatic Compounds (United States)

    Smith, G. B.


    The biological dehalogenation of common water pollutants such as trichloromethane (chloroform) and other halogenated aliphatic compounds was the subject of this project. Samples from diverse water environments such as from groundwater contaminated with halogenated compounds and wastewaters from regional treatment plants were studied to identify conditions that favor certain dehalogenation reactions over others. Gene probe analyses of DNA extracted from the dichlormethane-degrading wastewater indicated the presence of the gene coding for dichloromethane dehalogenase, indicating the genetic basis for the dechlorination activity observed. These studies indicate that methanogenic bacteria are the organisms responsible for the chloroform dechlorination. Dechlorination of a common chlorofluorocarbon (CFC-11) was identified in samples taken from a regional aquifer contaminated with halogenated aliphatic compounds.

  12. Distribution of halogens during fluid-mediated apatite replacement (United States)

    Kusebauch, Christof; John, Timm; Whitehouse, Martin J.


    Apatite (Ca5(PO4)3(F,Cl,OH)) is one the most abundant halogen containing minerals in the crust. It is present in many different rock types and stable up to P-T conditions of the mantle. Although probably not relevant for the halogen budget of the mantle, apatite is potentially a carrier phase of halogens into the mantle via subduction processes and therefore important for the global halogen cycle. Different partitioning behavior of the halogens between apatite and melt/fluids causes fractionation of these elements. In hydrothermal environments apatite reacts via a coupled dissolution-reprecipitation process that leads to apatite halogen compositions which are in (local) equilibrium with the hydrothermal fluid. This behavior enables apatite to be used as fluid probe and as a tool for tracking fluid evolution during fluid-rock interaction. Here, we present a combined experimental and field related study focused on replacement of apatite under hydrothermal conditions, to investigate the partitioning of halogens between apatite and fluids. Experiments were conducted in a cold seal pressure apparatus at 0.2 GPa and temperatures ranging from 400-700°C using halogen bearing solutions of different composition (KOH, NaF, NaCl, NaBr, NaI) to promote the replacement of Cl-apatite. The halogen composition of reacted apatite was analyzed by electron microprobe (EMPA) and secondary ion mass spectrometry (SIMS). The data was used to calculate partition coefficients of halogens between fluid and apatite. Our new partitioning data show that fluorine is the most compatible halogen followed by chlorine, bromine and iodine. Comparison between partition coefficients of the apatite-fluid system and coefficients derived in the apatite-melt system reveals values for F that are one to two orders of magnitude higher. In contrast, Cl and Br show a similar partition behavior in fluid and melt systems. Consequently, apatite that formed by fluid-rock interaction will fractionate F from Cl more

  13. Plasma devices for hydrocarbon reformation

    KAUST Repository

    Cha, Min Suk


    Plasma devices for hydrocarbon reformation are provided. Methods of using the devices for hydrocarbon reformation are also provided. The devices can include a liquid container to receive a hydrocarbon source, and a plasma torch configured to be submerged in the liquid. The plasma plume from the plasma torch can cause reformation of the hydrocarbon. The device can use a variety of plasma torches that can be arranged in a variety of positions in the liquid container. The devices can be used for the reformation of gaseous hydrocarbons and/or liquid hydrocarbons. The reformation can produce methane, lower hydrocarbons, higher hydrocarbons, hydrogen gas, water, carbon dioxide, carbon monoxide, or a combination thereof.

  14. The role of halogen species in the troposphere. (United States)

    Platt, U; Hönninger, G


    While the role of reactive halogen species (e.g. Cl, Br) in the destruction of the stratospheric ozone layer is well known, their role in the troposphere was investigated only since their destructive effect on boundary layer ozone after polar sunrise became obvious. During these 'Polar Tropospheric Ozone Hole' events O(3) is completely destroyed in the lowest approximately 1000 m of the atmosphere on areas of several million square kilometres. Up to now it was assumed that these events were confined to the polar regions during springtime. However, during the last few years significant amounts of BrO and Cl-atoms were also found outside the Arctic and Antarctic boundary layer. Recently even higher BrO mixing ratios (up to 176 ppt) were detected by optical absorption spectroscopy (DOAS) in the Dead Sea basin during summer. In addition, evidence is accumulating that BrO (at levels around 1-2 ppt) is also occurring in the free troposphere at all latitudes. In contrast to the stratosphere, where halogens are released from species, which are very long lived in the troposphere, likely sources of boundary layer Br and Cl are autocatalytic oxidation of sea salt halides (the 'Bromine Explosion'), while precursors of free tropospheric BrO and coastal IO probably are short-lived organo-halogen species. At the levels suggested by the available measurements reactive halogen species have a profound effect on tropospheric chemistry: In the polar boundary layer during 'halogen events' ozone is usually completely lost within hours or days. In the free troposphere the effective O(3)-losses due to halogens could be comparable to the known photochemical O(3) destruction. Further interesting consequences include the increase of OH levels and (at low NO(X)) the decrease of the HO(2)/OH ratio in the free troposphere.

  15. Reactive halogen species above salt lakes and salt pans


    Holla, Robert


    Salt lakes can be found on all continents and saline soils cover 2.5% of the land surface of the earth (FAO, 2012). This thesis investigates the presence of reactive halogen species (RHS) above salt lakes and saline soils to evaluate their relevance for tropospheric chemistry of the planetary boundary layer. Ground-based MAX-DOAS and LP-DOAS measurements were conducted at salt lakes and two other sites with high halogen content. Prior to this work, RHS were found at three salt ...

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

    Energy Technology Data Exchange (ETDEWEB)

    Miura, Michiko; Wu, Haitao


    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.

  17. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic). (United States)


    ... 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...

  18. Characterization of hydrocarbon utilizing fungi from hydrocarbon ...

    African Journals Online (AJOL)

    Prof. Ogunji

    Microorganisms play diverse roles in biotechnology; one of such roles is ... hydrocarbon polluted sites using vapour phase transfer technique with ... The purified fungal isolates were identified based on .... Cytochrome P450 monooxygenase systems which incorporate molecular .... substrate specificity on marine bacteria.

  19. A multidisciplinary weight of evidence approach for environmental risk assessment at the Costa Concordia wreck: Integrative indices from Mussel Watch. (United States)

    Regoli, Francesco; Pellegrini, David; Cicero, Anna Maria; Nigro, Marco; Benedetti, Maura; Gorbi, Stefania; Fattorini, Daniele; D'Errico, Giuseppe; Di Carlo, Marta; Nardi, Alessandro; Gaion, Andrea; Scuderi, Alice; Giuliani, Silvia; Romanelli, Giulia; Berto, Daniela; Trabucco, Benedetta; Guidi, Patrizia; Bernardeschi, Margherita; Scarcelli, Vittoria; Frenzilli, Giada


    A complex framework of chemical, biological and oceanographic activities was immediately activated after the Costa Concordia shipwreck, to assess possible contamination events and the environmental impact during both emergency and wreck removal operations. In the present paper, we describe the results obtained with caged mussels, Mytilus galloprovincialis, chosen as bioindicator organisms to detect variations of bioavailability and the early onset of molecular and cellular effects (biomarkers). Seven translocation experiments were carried out during the first year from the incident, with organisms deployed at 2 depths in 3 different sites. After 4-6 weeks, tissue concentrations were measured for the main classes of potentially released chemicals (trace metals, polycyclic aromatic hydrocarbons, volatile and aliphatic hydrocarbons, polychlorinated biphenyls, halogenated pesticides, organotin compounds, brominated flame retardants, anionic surfactants); a wide battery of biomarkers covered responses indicative of exposure, detoxification, oxidative stress, cell damage and genotoxic effects. Results excluded serious contamination events or a consistent increase of environmental pollution although some episodic spills with reversible effects were detected. Data were elaborated within a quantitative weight of evidence (WOE) model which provided synthetic hazard indices for each typology of data, before their overall integration in an environmental risk index, which generally ranged from slight to moderate. The proposed WOE model was confirmed a useful tool to summarize large datasets of complex data in integrative indices, and to simplify the interpretation for stakeholders and decision makers, thus supporting a more comprehensive process of "site-oriented" management decisions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  20. Thermophilic slurry-phase treatment of petroleum hydrocarbon waste sludges

    Energy Technology Data Exchange (ETDEWEB)

    Castaldi, F.J.; Bombaugh, K.J. [Radian Corp., Austin, TX (United States); McFarland, B. [Chevron Research and Technology Co., Richmond, CA (United States)


    Chemoheterotrophic thermophilic bacteria were used to achieve enhanced hydrocarbon degradation during slurry-phase treatment of oily waste sludges from petroleum refinery operations. Aerobic and anaerobic bacterial cultures were examined under thermophilic conditions to assess the effects of mode of metabolism on the potential for petroleum hydrocarbon degradation. The study determined that both aerobic and anaerobic thermophilic bacteria are capable of growth on petroleum hydrocarbons. Thermophilic methanogenesis is feasible during the degradation of hydrocarbons when a strict anaerobic condition is achieved in a slurry bioreactor. Aerobic thermophilic bacteria achieved the largest apparent reduction in chemical oxygen demand, freon extractable oil, total and volatile solid,s and polycyclic aromatic hydrocarbons (PAHs) when treating oily waste sludges. The observed shift with time in the molecular weight distribution of hydrocarbon material was more pronounced under aerobic metabolic conditions than under strict anaerobic conditions. The changes in the hydrocarbon molecular weight distribution, infrared spectra, and PAH concentrations during slurry-phase treatment indicate that the aerobic thermophilic bioslurry achieved a higher degree of hydrocarbon degradation than the anaerobic thermophilic bioslurry during the same time period.

  1. Using supercritical fluids to refine hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Yarbro, Stephen Lee


    This is a method to reactively refine hydrocarbons, such as heavy oils with API gravities of less than and bitumen-like hydrocarbons with viscosities greater than 1000 cp at standard temperature and pressure using a selected fluid at supercritical conditions. The reaction portion of the method delivers lighter weight, more volatile hydrocarbons to an attached contacting device that operates in mixed subcritical or supercritical modes. This separates the reaction products into portions that are viable for use or sale without further conventional refining and hydro-processing techniques. This method produces valuable products with fewer processing steps, lower costs, increased worker safety due to less processing and handling, allow greater opportunity for new oil field development and subsequent positive economic impact, reduce related carbon dioxide, and wastes typical with conventional refineries.

  2. Formation of halogenated organic byproducts during medium-pressure UV and chlorine coexposure of model compounds, NOM and bromide. (United States)

    Zhao, Quan; Shang, Chii; Zhang, Xiangru; Ding, Guoyu; Yang, Xin


    When chlorine is applied before or during UV disinfection of bromide-containing water, interactions between chlorine, bromide and UV light are inevitable. Formation of halogenated organic byproducts was studied during medium-pressure UV (MPUV) and chlorine coexposure of phenol, nitrobenzene and benzoic acid and maleic acid, chosen to represent electron-donating aromatics, electron-withdrawing aromatics, and aliphatic structures in natural organic matter (NOM), respectively. All were evaluated in the presence and absence of bromide. MPUV and chlorine coexposure of phenol produced less total organic halogen (TOX, a collective parameter for halogenated organic byproducts) than chlorination in the dark, and more haloacetic acids instead of halophenols. Increases in TOX were found in the coexposure of nitrobenzene and benzoic acid, but maleic acid was rather inert during coexposure. The presence of bromide increased the formation of brominated TOX but did not significantly affect total TOX formation, in spite of the fact that it reduced hydroxyl radical levels. MPUV and chlorine coexposure of NOM gave a higher differential UV absorbance of NOM and a larger shift to lower molecular weight compounds than chlorination in the dark. However, TOX formation with NOM remained similar to that observed from dark chlorination. Copyright © 2011 Elsevier Ltd. All rights reserved.

  3. Measurements of hydrocarbon emissions from a boreal fen using the REA technique

    Directory of Open Access Journals (Sweden)

    S. Haapanala


    Full Text Available Fluxes of biogenic volatile organic compounds (VOC and methane were measured above a boreal fen. Vegetation on the fen is dominated by Sphagnum mosses and sedges. A relaxed eddy accumulation (REA system with dynamic deadband was designed and constructed for the measurements. Methane, C2-C6 hydrocarbons and some halogenated hydrocarbons were analysed from the samples by gas chromatographs equipped with FID and ECD. A significant flux of isoprene and methane was detected during the growing seasons. Isoprene emission was found to follow the common isoprene emission algorithm. Average standard emission potential of isoprene was 680 µg m-2 h-1. Fluxes of other non-methane hydrocarbons were below detection limit.

  4. Aromatization process of hydrocarbons containing 2 to 4 carbon atoms in the presence of MFI structure zeolite

    Energy Technology Data Exchange (ETDEWEB)

    Alario, F.; Deves, J.M.


    The invention describes an aromatization process of hydrocarbons comprising 2 to 4 carbon atoms per molecule in the presence of a composite catalyst which contains: a MFI structure zeolite containing an element chosen among alkaline or alkaline-earth metals, with a structure made of Silicon, Aluminium and / or Gallium; a matrix; platinum metals and additive metal chosen among Stain, Germanium, Indium, Copper, Iron, Molybdenum, Gallium, Thallium, Gold, Silver, Ruthenium, Chrome, Tungsten and Lead at least; an halogen chosen among Fluorine, Chlorine, Bromine and Iodine at least; Gallium and Zinc possibly; alkaline or alkaline-earth metal in the matrix preferentially. The invention describes also catalyst preparation and use for hydrocarbons aromatization reactions.

  5. Is there theoretical evidence for mutual influence between halogen ...

    Indian Academy of Sciences (India)

    Ab initio MP2/6-311++G(d,p) level calculations have been carried out to investigate the interplay between the halogen and pnicogen-hydride bonds in NCX...OPH₃...HMgY complexes (X = F, Cl, Br; Y = F, Cl, Br, H). The results indicated that the cooperative effects are obvious in the target complexes. These effects were ...

  6. 40 CFR 721.535 - Halogenated alkane (generic). (United States)


    ... Section 721.535 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES... reporting. (1) The chemical substance identified generically as halogenated alkane (PMN P-01-433) is subject... part apply to this section except as modified by this paragraph. (1) Recordkeeping. Recordkeeping...

  7. Manganese Catalyzed C–H Halogenation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Wei; Groves, John T.


    The remarkable aliphatic C–H hydroxylations catalyzed by the heme-containing enzyme, cytochrome P450, have attracted sustained attention for more than four decades. The effectiveness of P450 enzymes as highly selective biocatalysts for a wide range of oxygenation reactions of complex substrates has driven chemists to develop synthetic metalloporphyrin model compounds that mimic P450 reactivity. Among various known metalloporphyrins, manganese derivatives have received considerable attention since they have been shown to be versatile and powerful mediators for alkane hydroxylation and olefin epoxidation. Mechanistic studies have shown that the key intermediates of the manganese porphyrin-catalyzed oxygenation reactions include oxo- and dioxomanganese(V) species that transfer an oxygen atom to the substrate through a hydrogen abstraction/oxygen recombination pathway known as the oxygen rebound mechanism. Application of manganese porphyrins has been largely restricted to catalysis of oxygenation reactions until recently, however, due to ultrafast oxygen transfer rates. In this Account, we discuss recently developed carbon–halogen bond formation, including fluorination reactions catalyzed by manganese porphyrins and related salen species. We found that biphasic sodium hypochlorite/manganese porphyrin systems can efficiently and selectively convert even unactivated aliphatic C–H bonds to C–Cl bonds. An understanding of this novel reactivity derived from results obtained for the oxidation of the mechanistically diagnostic substrate and radical clock, norcarane. Significantly, the oxygen rebound rate in Mn-mediated hydroxylation is highly correlated with the nature of the trans-axial ligands bound to the manganese center (L–MnV$=$O). Based on the ability of fluoride ion to decelerate the oxygen rebound step, we envisaged that a relatively long-lived substrate radical could be trapped by a Mn–F fluorine source, effecting carbon–fluorine bond

  8. Accuracy of LED and halogen radiometers using different light sources. (United States)

    Roberts, Howard W; Vandewalle, Kraig S; Berzins, David W; Charlton, David G


    To determine the accuracy of commercially available, handheld light-emitting diode (LED) and halogen-based radiometers using LED and quartz-tungsten-halogen (QTH) curing lights with light guides of various diameters. The irradiance of an LED curing light (L.E. Demetron 1, SDS/Kerr, Orange, CA, USA) and a QTH curing light (Optilux 501, SDS/Kerr) were measured using multiple units of an LED (Demetron L.E.D. Radiometer, SDS/Kerr) and a halogen radiometer (Demetron 100, SDS/Kerr) and compared with each other and to a laboratory-grade power meter (control). Measurements were made using five light guides with distal light guide diameters of 4, 7, 8, 10, and 12.5 mm. For each light guide, five readings were made with each of three radiometers of each radiometer type. Data were analyzed with two-way analysis of variance/Tukey; alpha = 0.05. In general, both handheld radiometer types exhibited significantly different irradiance readings compared with the control meter. Additionally, readings between radiometer types were found to differ slightly, but were correlated. In general, the LED radiometer provided slightly lower irradiance readings than the halogen radiometer, irrespective of light source. With both types of handheld radiometers, the use of the larger-diameter light guides tended to overestimate the irradiance values as seen in the control, while smaller-diameter light guides tended to underestimate. The evaluated LED or halogen handheld radiometers may be used interchangeably to determine the irradiance of both LED and QTH visible-light-curing units. Measured differences between the two radiometer types were small and probably not clinically significant. However, the diameter of light guides may affect the accuracy of the radiometers, with larger-diameter light guides overestimating and smaller-diameter guides underestimating the irradiance value measured by the control instrument.

  9. Brønsted acid-catalyzed α-halogenation of ynamides from halogenated solvents and pyridine-N-oxides. (United States)

    Kim, Seung Woo; Um, Tae-Woong; Shin, Seunghoon


    The keteniminium ions generated from the protonation of ynamides formed reversible adducts with counter anions and pyridine-N-oxides as well as halogenated solvents. Above 80 °C, the halonium ions selectively undergo a rate-limiting attack by pyridine-N-oxides, leading to (E)-haloenamides in good yields.

  10. Emission of Volatile OrganoHalogens by Southern African Solar Salt Works (United States)

    Kotte, Karsten; Weissflog, Ludwig; Lange, Christian Albert; Huber, Stefan; Pienaar, Jacobus J.


    hyper-saline environments, rich in chloride, bromide and partly iodide. They can be seen as semi natural reactors for hypersaline microorganisms like bacteria, algae and archaea as they can be found in natural hypersaline environments as well. To assess possible VOX emission of solar salt works the Walfishbay Salt Refiners (PTY) LTD (Namibia) were investigated and sediments of several crystallizer pans where collected. Only affected by natural temperature and radiation regime the VOX production inside the tightly closed incubation vials were determined regularly for several months by using headspace GC combined with an electron capture detector. Besides a number of non halogenated volatile hydrocarbons, detected by a self modified purge and trap GC/MS system the following VOX have been identified: CHCl3, CH3J, CH3Br, CCl4, C2HCl3, C2Cl4. According to earlier experiments on natural salt sediments of Southern Russia a biosynthesis process involving halophilic archaea is highly probable. Although the metabolic routes entailed are not yet identified. Obtained long term emission data are presented by focussing on possible meteorological propulsion as solar and UV radiation as well as temperature. Discussing the incubation experiments Southern African solar salt works reveal to represent interesting sources of chemically active VOX.

  11. Isolation of 3-methyl-1-butene from a hydrocarbon stream

    Energy Technology Data Exchange (ETDEWEB)

    Drake, C.A.


    A process is described for recovering 3-methyl-1-butene from a hydrocarbon stream containing 3-methyl-1-butene and compounds which form azeotropes with 3-methyl-1-butene comprising extractive distillation of the hydrocarbon stream with a solvent mixture comprising dimethylformamide and sulfolane solvent mixture present in an amount ranging from about 0.1 to about 20 times the weight of the hydrocarbon stream. The dimethylformamide in the dimethylformamide/Sulfolane solvent mixture is present in an amount ranging from about 30 weight percent to about 70 weight percent based on the weight of the mixture. This separates insolubles containing the 3-methyl-l-butene as the overhead product stream from the bottoms product containing soluble compounds, the compounds that form azeotropes with 3-methyl-l-butene and the solvent mixture and thereafter recovering the 3-methyl-1-butene from the insolubles.

  12. Effect of detergent and sawdust addition on hydrocarbon reduction ...

    African Journals Online (AJOL)

    Soil Total Hydrocarbon Content (THC) and okra growth performance (shoot length, leaf number, root length, total fresh weight, dry weight, leaf area and leaf area ratio) were analyzed. Results showed significant (p=0.05) reductions in THC of 44.23%, 26.5%, 70.80% and 10.79%, in detergent (20 g), sawdust (200 g), ...

  13. Comparative study of halogen- and hydrogen-bond interactions between benzene derivatives and dimethyl sulfoxide. (United States)

    Zheng, Yan-Zhen; Deng, Geng; Zhou, Yu; Sun, Hai-Yuan; Yu, Zhi-Wu


    The halogen bond, similar to the hydrogen bond, is an important noncovalent interaction and plays important roles in diverse chemistry-related fields. Herein, bromine- and iodine-based halogen-bonding interactions between two benzene derivatives (C6 F5 Br and C6 F5 I) and dimethyl sulfoxide (DMSO) are investigated by using IR and NMR spectroscopy and ab initio calculations. The results are compared with those of interactions between C6 F5 Cl/C6 F5 H and DMSO. First, the interaction energy of the hydrogen bond is stronger than those of bromine- and chlorine-based halogen bonds, but weaker than iodine-based halogen bond. Second, attractive energies depend on 1/r(n) , in which n is between three and four for both hydrogen and halogen bonds, whereas all repulsive energies are found to depend on 1/r(8.5) . Third, the directionality of halogen bonds is greater than that of the hydrogen bond. The bromine- and iodine-based halogen bonds are strict in this regard and the chlorine-based halogen bond only slightly deviates from 180°. The directional order is iodine-based halogen bond>bromine-based halogen bond>chlorine-based halogen bond>hydrogen bond. Fourth, upon the formation of hydrogen and halogen bonds, charge transfers from DMSO to the hydrogen- and halogen-bond donors. The CH3 group contributes positively to stabilization of the complexes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Halogens and the Chemistry of the Free Troposphere (United States)

    Lary, David John


    The role of halogens in both the marine boundary layer and the stratosphere has long been recognized, while their role in the free troposphere is often not considered in global chemical models. However, a careful examination of free-tropospheric chemistry constrained by observations using a full chemical data assimilation system shows that halogens do play a significant role in the free troposphere. In particular, the chlorine initiation of methane oxidation in the free troposphere can contribute more than 10%, and in some regions up to 50%, of the total rate of initiation. The initiation of methane oxidation by chlorine is particularly important below the polar vortex and in northern mid-latitudes. Likewise, the hydrolysis of BrONO2 alone can contribute more than 35% of the HNO3 production rate in the free-troposphere.

  15. Halogen light versus LED for bracket bonding: shear bond strength. (United States)

    Carvalho, Paulo Eduardo Guedes; dos Santos, Valdemir Muzulon; Isber, Hassan; Cotrim-Ferreira, Flávio Augusto


    LED light-curing devices seek to provide a cold light activator which allows protocols of material polymerization with shorter duration. The present study aimed to evaluate the shear bond strength of bracket bonding using three types of light-curing devices: One with halogen light (Optilight Plus - Gnatus) and two with LEDs (Optilight CL - Gnatus and Elipar Freelight - 3M/ESPE). Comparing the results by analysis of variance, the Gnatus LED device showed an inferior statistical behavior in relation to other light sources, when activated by a short time. But, when it was used for 40 seconds, the polymerization results were consistent with the other evaluated sources. The device with the best average performance was the halogen light, followed by the 3M/ESPE LED. It was concluded that the LEDs may be indicated in orthodontic practice, as long as a protocol is used for the application of light with the activation time of 40 seconds.

  16. Biocidal properties of metal oxide nanoparticles and their halogen adducts (United States)

    Haggstrom, Johanna A.; Klabunde, Kenneth J.; Marchin, George L.


    Nanosized metal oxide halogen adducts possess high surface reactivities due to their unique surface morphologies. These adducts have been used as reactive materials against vegetative cells, such as Escherichia coli as well as bacterial endospores, including Bacillus subtilis and Bacillus anthracis (Δ Sterne strain). Here we report high biocidal activities against gram-positive bacteria, gram-negative bacteria, and endospores. The procedure consists of a membrane method. Transmission electron micrographs are used to compare nanoparticle-treated and untreated cells and spores. It is proposed that the abrasive character of the particles, the oxidative power of the halogens/interhalogens, and the electrostatic attraction between the metal oxides and the biological material are responsible for high biocidal activities. While some activity was demonstrated, bacterial endospores were more resistant to nanoparticle treatment than the vegetative bacteria.

  17. Total organic halogen (TOX) in human urine: A halogen-specific method for human exposure studies. (United States)

    Y Kimura, Susana; Zheng, Weiwei; N Hipp, Taylor; M Allen, Joshua; D Richardson, Susan


    Disinfection by-products (DBPs) are a complex mixture of compounds unintentionally formed as a result of disinfection processes used to treat drinking water. Effects of long-term exposure to DBPs are mostly unknown and were the subject of recent epidemiological studies. However, most bioanalytical methods focus on a select few DBPs. In this study, a new comprehensive bioanalytical method has been developed that can quantify mixtures of organic halogenated compounds, including DBPs, in human urine as total organic chlorine (TOCl), total organic bromine (TOBr), and total organic iodine (TOI). The optimized method consists of urine dilution, adsorption to activated carbon, pyrolysis of activated carbon, absorption of gases in an aqueous solution, and halide analysis with ion chromatography and inductively coupled plasma-mass spectrometry. Spike recoveries for TOCl, TOBr, and TOI measurements ranged between 78% and 99%. Average TOCl, TOBr, and TOI concentrations in five urine samples from volunteers who consumed tap water were 1850, 82, and 21.0μg/L as X-, respectively. Volunteers who consumed spring water (control) had TOCl, TOBr, and TOI average concentrations in urine of 1090, 88, and 10.3μg/L as X-, respectively. TOCl and TOI in the urine samples from tap water consumers were higher than the control. However, TOBr was slightly lower in tap water urine samples compared to mineral water urine samples, indicating other sources of environmental exposure other than drinking water. A larger sample population that consumes tap water from different cities and mineral water is needed to determine TOCl, TOBr, and TOI exposure from drinking water. Copyright © 2017. Published by Elsevier B.V.

  18. Halogen acid electrolysis in solid polymer electrolyte cells

    Energy Technology Data Exchange (ETDEWEB)

    Balko, E.N.; McElroy, J.F.; LaConti, A.B.


    The use of solid polymer electrolyte systems has been extended to the electrolysis of aqueous HCl and HBr. The reduced internal losses in these cells permits the production of hydrogen and the halogen at an energy consumption considerably less than that reported previously. Data are presented for the operational characteristics of the solid polymer electrolyte acid electrolysers operating over a range of current densities, pressures, feedstock compositions, and temperatures.

  19. Quantum Mechanical Studies of Charge Assisted Hydrogen and Halogen Bonds


    Nepal, Binod


    This dissertation is mainly focused on charge assisted noncovalent interactions specially hydrogen and halogen bonds. Generally, noncovalent interactions are only weak forces of interaction but an introduction of suitable charge on binding units increases the strength of the noncovalent bonds by a several orders of magnitude. These charge assisted noncovalent interactions have wide ranges of applications from crystal engineering to drug design. Not only that, nature accomplishes a number of i...

  20. Force Field Model of Periodic Trends in Biomolecular Halogen Bonds. (United States)

    Scholfield, Matthew R; Ford, Melissa Coates; Vander Zanden, Crystal M; Billman, M Marie; Ho, P Shing; Rappé, Anthony K


    The study of the noncovalent interaction now defined as a halogen bond (X-bond) has become one of the fastest growing areas in experimental and theoretical chemistry--its applications as a design tool are highly extensive. The significance of the interaction in biology has only recently been recognized, but has now become important in medicinal chemistry. We had previously derived a set of empirical potential energy functions to model the structure-energy relationships for bromines in biomolecular X-bonds (BXBs). Here, we have extended this force field for BXBs (ffBXB) to the halogens (Cl, Br, and I) that are commonly seen to form stable X-bonds. The ffBXB calculated energies show a remarkable one-to-one linear relationship to explicit BXB energies determined from an experimental DNA junction system, thereby validating the approach and the model. The resulting parameters allow us to interpret the stabilizing effects of BXBs in terms of well-defined physical properties of the halogen atoms, including their size, shape, and charge, showing periodic trends that are predictable along the Group VII column of elements. Consequently, we have established the ffBXB as an accurate computational tool that can be applied, for example, for the design of new therapeutic compounds against clinically important targets and new biomolecular-based materials.

  1. Structure-Energy Relationships of Halogen Bonds in Proteins. (United States)

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


    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. The origin of Reactive Halogen Species in the Polar Troposphere (United States)

    Platt, U.


    Reactive halogen species (RHS) play an important role in various parts of the troposphere e.g. in coastal regions, over salt pans, in volcanic plumes and in polar regions. Despite much progress in recent years the origin and some of the chemical interactions of reactive halogen species (RHS) in the polar troposphere are still not quantitatively understood. Among the many unanswered questions are: Why is there an Antarctic - Arctic asymmetry of reactive iodine species? What drives the autocatalytic bromine release from sea salt (the bromine explosion)? Why does the bromine explosion almost exclusively occur during springtime? What is the effect of coupling cycles involving different halogens? What is the vertical extent of the layer containing RHS? The presentation gives an overview of new ground-based field observations illustrating the above questions and providing answers to some of them. Also, recent advances in satellite observations of tropospheric BrO are discussed. In particular new insight is being gained from the synergistic use of satellite observations and ground based measurements of BrO. Also the question of a NOx - driven (rather than HOx - driven) bromine explosion is discussed.

  3. Halogenated high {Tc} superconductors and method of preparation

    Energy Technology Data Exchange (ETDEWEB)

    Radousky, H.B.; Glass, R.S.; Fluss, M.J.


    Disclosed is a method for producing a superconductor of the R-Ba-Cu-O system which comprises of selecting an insulating material of the formula RBa{sub x}Cu{sub y}O{sub z} where R is selected from the group consisting of Y, La, Pr, Nd, Sm, Eu, Gd, Ho, Er, Tm, and Lu, and where x ranges from about 1.7 to about 2.3, y ranges from about 2.7 to about 3.3 and z ranges from about 5.0 to about 6.99, and halogenating said material with a halogen selected from the group consisting of chlorine, bromine, iodine, and mixtures thereof, while maintaining said material at a temperature ranging from about 160 to about 440{degrees}C, for a period of time sufficient to cause incorporation of said halogen into said material. Also, disclosed are the materials produced by the method and articles of manufacture incorporating said materials as electronic circuitry components.

  4. Pop-like halogenated natural products in antarctic sponges

    Energy Technology Data Exchange (ETDEWEB)

    Vetter, W. [Hohenheim Univ., Stuttgart (Germany); Janussen, D. [Senckenbergische Naturforschende Gesellschaft (Natur-Museum und Forschungs-Institut), Frankfurt am Main (Germany)


    Persistent organic pollutants (POPs) are major contaminants of our days. This group of chemicals comprises a number of halogenated compounds used as pesticides (DDT, lindane, chlordane, toxaphene and others) as well as industrial chemicals (PCBs, PCNs, CPs, and brominated flameretardants). Although the list of known POPs including isomers and metabolites is long, there are frequent reports on the detection of unknown organohalogen compounds in the literature. Recent work demonstrated that some of these unknown peaks in gas chromatograms originate from halogenated natural products (HNPs). Sometimes, HNPs have been found at remarkably high concentrations in marine birds, mammals and fish. Due to the structural similarities with anthropogenic POPs, these substances may possess a potential risk for wildlife and man. HNPs are known to be produced with an overwhelming variety by marine organisms such as algae, sponges, microorganisms and others. In this study we have screened different species of Antarctic sponges on the occurrence of halogenated compounds which may be of environmental concern. Thus, we were only interested in lipophilic and persistent HNPs. Following that, we applied our standard sample clean-up procedure for the analysis of nonpolar POPs. Two steps on deactivated and activated silica yielded compounds with similar polarity as PCBs, chloropesticides and brominated analogues in the sample extracts. Additionally, all samples were treated with concentrated sulphuric acid in order to eliminate labile (non-presistent) HNPs.

  5. Alumino-silicate catalyst and use for aromatization of hydrocarbons comprising 5 to 12 carbon atoms

    Energy Technology Data Exchange (ETDEWEB)

    Alario, F.; Deves, J.M.


    The invention describes a composite catalyst which contains: a MFI structure zeolite in the form hydrogen, containing in its structure Silicon, Aluminium and / or Gallium at least; a matrix; platinum metals at least and additive metal chosen among Stain, Germanium, Indium, Copper, Iron, Molybdenum, Gallium, Thallium, Gold, Silver, Ruthenium, Chrome, Tungsten and Lead at least; an halogen chosen among Fluorine, Chlorine, Bromine and Iodine at least; possibly, doping element chosen among Gallium and Zinc and possibly alkaline or alkaline-earth metal in the matrix preferentially. The invention describes also the use of this catalyst for aromatization reactions of hydrocarbons containing 5 to 12 carbon atoms per molecule.

  6. MFI structure catalyst and utilization for aromatization hydrocarbons comprising 5 to 12 carbon atoms

    Energy Technology Data Exchange (ETDEWEB)

    Alario, F.; Deves, J.M.


    The invention describes a composite catalyst which contains: a MFI structure zeolite containing, at least, an element chosen among alkaline or alkaline-earth metals, with a structure made of Silicon, Aluminium and / or Gallium; a matrix; platinum metals and additive metal chosen among Stain, Germanium, Indium, Copper, Iron, Molybdenum, Gallium, Thallium, Gold, Silver, Ruthenium, Chrome, Tungsten and Lead at least; an halogen chosen among Fluorine, Chlorine, Bromine and Iodine at least; Gallium and Zinc possibly; alkaline or alkaline-earth metal in the matrix preferentially. The invention describes also the use of this catalyst for aromatization reactions of hydrocarbons containing 5 to 12 carbon atoms per molecule.

  7. [The role of halogenation in the electro-oxidation of halogenated anilines in acetonitrile as the solvent]. (United States)

    Pusztai, S; Dankházi, T; Farsang, G


    The 4-halogeno-, 2,4-dihalogeno- and 2,4,6-trihalogenoanilines were the model substances of the research described. Acetonitrile being one of the most popular aprotic solvent was used. The halogeno monomers were chloro and bromoanilines. The electrodimerised substrate is stabilised by rejecting halogenide ion and protons. The rejected halogenide ions are oxidisable more easier compared to the substrate therefore the halogene formed substitutes both the substrate, and the dimer as well. The protons formed during the oxidation bind by the strong base monomer primary amine. Because of these not only a simple electrodimerisation will take place, but protonised monomers, higher halogenated monomers, and the corresponding dimer molecules are formed in the solution.

  8. Inhalation Cancer Risk Associated with Exposure to Complex Polycyclic Aromatic Hydrocarbon Mixtures in an Electronic Waste and Urban Area in South China (United States)

    Wang, Jing; Chen, Shejun; Tian, Mi; Zheng, Xiaobo; Gonzales, Leah; Ohura, Takeshi; Mai, Bixian; Simonich, Staci L. Massey


    Atmospheric particulate matter samples were collected from May 2010 to April 2011 in a rural e-waste area and in Guangzhou, South China, to estimate the lifetime inhalation cancer risk from exposure to parent polycyclic aromatic hydrocarbons (PAHs), high molecular weight PAHs (MW 302 PAHs), and halogenated PAHs (HPAHs). Seasonal variations in the PAH concentrations and profile within and between the e-waste and urban areas indicated different PAH sources in the two areas. Benzo[b]fluoranthene, BaP, dibenz[ah]anthracene, and dibenzo[al]pyrene made the most significant contribution to the inhalation cancer risk. MW 302 PAHs accounting for 18.0% of the total cancer risk in the e-waste area and 13.6% in the urban area, while HPAHs made a minor contribution (e-waste area and from 9.3 to 737 per million people in Guangzhou. PAH exposure accounted for 0.02 to 1.94% of the total lung cancer cases in Guangzhou. On average, the inhalation cancer risk in the e-waste area was 1.6 times higher than in the urban area. The e-waste dismantling activities in South China led to higher inhalation cancer risk due to PAH exposure than the urban area. PMID:22913732

  9. The Role of Vanadium Bromoperoxidase in the Biosynthesis of Halogenated Marine Natural Products


    Franklin, Jayme N.


    The widespread occurrence of bromine- and chlorine-containing marine natural products has prompted investigations into the biosynthesis of halogenated marine metabolites. Halogenating enzymes, such as haloperoxidases, have long been thought to be involved in the biogenesis of halogenated marine natural products. Vanadium bromoperoxidases (V-BrPO) have been identified and isolated from all major classes of marine algae, and catalyze the two-electron oxidation of bromide by hydrogen peroxide. ...

  10. Theoretical study on O $\\cdots $ Br and O $\\cdots $ Cl halogen ...

    Indian Academy of Sciences (India)

    In this work, theoretical calculations were carried out using B3LYP/6-31++G∗∗, MP2/6-31++G∗∗ and MP2/aug-cc-pVDZ methods on a series of O ⋯ X halogen bonds between CH2O andCH3CHO as halogen bond acceptor with X-Y (X = Cl, Br; Y = CF3, CF2 H, CFH2, CN, CCH, CCCN) as halogen bond donors.

  11. Br and O···Cl halogen bonds in some small model molecular systems

    Indian Academy of Sciences (India)

    Abstract. Halogen bonding interactions of type X···O=C are important in various fields including bio- logical systems. In this work, theoretical calculations were carried out using B3LYP/6-31++G**, MP2/6-. 31++G** and MP2/aug-cc-pVDZ methods on a series of O··· X halogen bonds between CH2O and CH3CHO as halogen ...

  12. Regiodivergent halogenation of vinylogous esters: one-pot, transition-metal-free access to differentiated haloresorcinols. (United States)

    Chen, Xiaohong; Martinez, Jenny S; Mohr, Justin T


    We report an efficient method for the regiodivergent synthesis of halogenated resorcinol derivatives using readily available vinylogous esters and sulfonyl halide halogen donors. Either the 4- or 6-haloresorcinol isomer is accessible from a common precursor. In contrast to conventional oxidants for arene halogenation, mild sulfonyl halides allow broad functional group compatibility. The strategy inherently differentiates the two resorcinol oxygen atoms and enhances the potential for complex molecule synthesis.


    African Journals Online (AJOL)


    e trapping configurations of the faults mbedding shale were presumed to be the creation of multiple reservoir of hydrocarbon bearing formations one horizon to the other and. (Figure 2). The vertical f the major and subsidiary growth t the amount of throw of both major s are small and varied from line to line survey but ...

  14. Halogens, Barium and Uranium in Mantle Fluid Inclusions (United States)

    Villa, I. M.; Peverelli, V.; Oglialoro, E.; Pettke, D. T.; Frezzotti, M. L.


    Halogens are an underexplored geochemical marker. A way to measure halogens at ng/g levels is measuring Ar, Kr and Xe in irradiated samples [1,2]. We derive absolute halogen amounts from rare gas amounts via scapolite monitor SY [2]. Kr-Xe systematics also yield Ba and U concentrations. We combined irradiation with stepheating on carbonate-sulfate-rich fluid inclusions (FI)-bearing xe­no­liths from El Hierro, Canarias: spinel harzburgite XML-7 and spinel dunite XML-1 [3]. Three components are recognized in the rare gas release. (1) Atmospheric surface contamination occurs up to 1000 °C. (2) FI decrepitation by laboratory heating occurs above 1200 °C [4], corresponding to the release of 80,82Kr and 128Xe in the 1200 and 1400 °C steps. Br whole-rock concentrations are 3-8 ng/g; the molar Br/Cl and I/Cl ratios in the harzburgite FI, 9 E-4 resp. 2 E-4, are identical to those in the dunite FI. This sets the halogens in our FI apart from MORB [2]. Halogen-derived rare gases are closely associated to artificial 131Xe from Ba; Ba has a high affinity of for CO2-rich fluids. Daughter minerals in multiphase FI were identified by Raman micro­spectroscopy [4]. The calculated Ba concentrations are 2-6 µg/g. (3) The third component is U-derived 134,136Xe and 86Kr released in a spike at 1000 °C, decoupled from FI. This requires a different carrier than FI, e.g. Ti oxides. As U concentrations are 10-20 pg/g, the U-bearing phase needs to be below a ppm, invisible by petro­graphy. The 136Xe/134Xe ratio > 1 suggests retention of radio­genic Xe. However, analysis of an unirradiated sample detected no radiogenic Xe. It is likely that Xe-U produced in the core of the McMaster reactor (thermal, epithermal and fast neutrons) has a different isotopic composition from that in textbooks, as proposed by [2].[1] Jeffery & Reynolds (1961) J.Geophys. Res. 66, 3582 [2] Kendrick (2012) Chem. Geol. 292, 116 [3] Oglialoro et al (2015) AGU Fall Meeting abstract V21C-3046 [4] Roedder (1965

  15. Vibration and thermal vacuum qualification test results for a low-voltage tungsten-halogen light (United States)

    Sexton, J. Andrew


    The results of a space flight qualification test program for a low-voltage, quartz tungsten-halogen light are presented. The test program was designed to qualify a halogen light for use in the Pool Boiling Experiment, a Get Away Special (GAS) payload that will be flown in the space shuttle payload bay. Vibration and thermal vacuum tests were performed. The test results indicated that the halogen light will survive the launch and ascent loads, and that the convection-free environment associated with the GAS payload system will not detrimentally affect the operation of the halogen light.

  16. Halogenated furanones inhibit quorum sensing through accelerated LuxR turnover

    DEFF Research Database (Denmark)

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


    and fortifying these proteins against proteolytic degradation (Zhu & Winans, 2001). Halogenated furanones produced by the macroallga Delisea pulchra inhibit AHL-dependent gene expression. This study assayed for an in vivo interaction between a tritiated halogenated furanone and the LuxR protein of Vibrio...... 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...

  17. Recovering hydrocarbons with surfactants from lignin

    Energy Technology Data Exchange (ETDEWEB)

    Naae, D.G.; Whittington, L.E.; Ledoux, W.A.; Debons, F.E.


    This patent describes a method of recovering hydrocarbons from an underground hydrocarbon formation penetrated by at least one injection well and at least one production well, which comprises: injecting into the formation through an injection well a surfactant slug comprising about 0.1% to about 10% by weight of surfactants produced from lignin, the surfactants produced by placing lignin in contact with water, converting the lignin into low molecular weight lignin phenols by reducing the lignin in the presence of a reducing agent of carbon monoxide or hydrogen creating a reduction reaction mixture comprising oil soluble lignin phenols, the reduction occurring at a temperature greater than about 200/sup 0/C and a pressure greater than about 100 psi, recovering the oil soluble lignin phenols from the reduction mixture, and converting the lignin phenols into lignin surfactants by a reaction selected from the group consisting of alkoxylation, sulfonation, sulfation, aklylation, sulfomethylation, and alkoxysulfation; injecting into the formation through the injection well a drive fluid to push the surfactant slug towards a production well; and recovering hydrocarbons at the production well.

  18. Microbial degradation of petroleum hydrocarbons. (United States)

    Varjani, Sunita J


    Petroleum hydrocarbon pollutants are recalcitrant compounds and are classified as priority pollutants. Cleaning up of these pollutants from environment is a real world problem. Bioremediation has become a major method employed in restoration of petroleum hydrocarbon polluted environments that makes use of natural microbial biodegradation activity. Petroleum hydrocarbons utilizing microorganisms are ubiquitously distributed in environment. They naturally biodegrade pollutants and thereby remove them from the environment. Removal of petroleum hydrocarbon pollutants from environment by applying oleophilic microorganisms (individual isolate/consortium of microorganisms) is ecofriendly and economic. Microbial biodegradation of petroleum hydrocarbon pollutants employs the enzyme catalytic activities of microorganisms to enhance the rate of pollutants degradation. This article provides an overview about bioremediation for petroleum hydrocarbon pollutants. It also includes explanation about hydrocarbon metabolism in microorganisms with a special focus on new insights obtained during past couple of years. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. How do halogen bonds (S-O⋯I, N-O⋯I and C-O⋯I) and halogen-halogen contacts (C-I⋯I-C, C-F⋯F-C) subsist in crystal structures? A quantum chemical insight. (United States)

    Pandiyan, B Vijaya; Deepa, P; Kolandaivel, P


    Thirteen X-ray crystal structures containing various non-covalent interactions such as halogen bonds, halogen-halogen contacts and hydrogen bonds (I⋯N, I⋯F, I⋯I, F⋯F, I⋯H and F⋯H) were considered and investigated using the DFT-D3 method (B97D/def2-QZVP). The interaction energies were calculated at MO62X/def2-QZVP and MP2/aug-cc-pvDZ level of theories. The higher interaction and dispersion energies (2nd crystal) of -9.58 kcal mol -1 and -7.10 kcal mol -1 observed for 1,4-di-iodotetrafluorobenzene bis [bis (2-phenylethyl) sulfoxide] structure indicates the most stable geometrical arrangement in the crystal packing. The electrostatic potential values calculated for all crystal structures have a positive σ-hole, which aids understanding of the nature of σ-hole bonds. The significance of the existence of halogen bonds in crystal packing environments was authenticated by replacing iodine atoms by bromine and chlorine atoms. Nucleus independent chemical shift analysis reported on the resonance contribution to the interaction energies of halogen bonds and halogen-halogen contacts. Hirshfeld surface analysis and topological analysis (atoms in molecules) were carried out to analyze the occurrence and strength of all non-covalent interactions. These analyses revealed that halogen bond interactions were more dominant than hydrogen bonding interactions in these crystal structures. Graphical Abstract Molecluar structure of 1,4-Di-iodotetrafluorobenzene bis(thianthrene 5-oxide) moelcule and its corresponding molecular electrostatic potential map for the view of σ-hole.

  20. Direct hydrocarbon fuel cells (United States)

    Barnett, Scott A.; Lai, Tammy; Liu, Jiang


    The direct electrochemical oxidation of hydrocarbons in solid oxide fuel cells, to generate greater power densities at lower temperatures without carbon deposition. The performance obtained is comparable to that of fuel cells used for hydrogen, and is achieved by using novel anode composites at low operating temperatures. Such solid oxide fuel cells, regardless of fuel source or operation, can be configured advantageously using the structural geometries of this invention.

  1. Measurements of halogen oxides in the Western Pacific (United States)

    Wittrock, Folkard; Walker, Hannah; Heard, Dwayne; Ingham, Trevor; Lampel, Johannes; Horbanski, Martin; Großmann, Katja; Bracher, Astrid; Sentian, Justin; Vrekoussis, Mihalis; Huang, Ru-Jin; Peters, Enno; Schönhardt, Anja; Richter, Andreas; Burrows, John P.


    Reactive halogens such as iodine, bromine and their oxides have received growing attention in the past years owing to their strong impact on tropospheric composition. In particular, reactive halogens deplete ozone and alter the HOx and NOx ratios, consequently changing the oxidizing capacity of the troposphere. The halogen oxides iodine monoxide (IO) and bromine monoxide (BrO), generated from the reaction of atomic I and Br with ozone, play a central role in these processes. Iodine atoms may be released by photolysis of precursor substances such as I2 or volatile iodocarbons emitted from the marine biosphere. Inorganic release processes are also being considered, but they are so far uncertain. Bromine precursors include organic as well as inorganic sources. Here we report on measurements of IO and BrO during and related to the SHIVA field campaign, which has been carried out in November 2011 in the Western Pacific around Borneo. Different techniques have been applied in order to detect the trace gases: cavity-enhanced differential optical absorption spectroscopy (CE-DOAS), multi axis (MAX)-DOAS, airborne multi axis (AMAX)-DOAS and laser induced fluorescence (LIF, discussed in detail in Heard et al.). While for BrO no clear signal above the detection limit was found, IO levels up to 2.5 ppt were found in the open Sulu Sea and similar levels up to 2 ppt close to seaweed farms around Semporna, Malaysia. In this area both MAX-DOAS and AMAX-DOAS observations gave indication for the presence of uplifted layers of IO. These results are discussed and interpreted by using complementary observations of the main precursor substances. In addition correlation studies taking into account meteorological and oceanic parameters have been carried out to identify possible source processes. Finally the ground-based IO observations have been compared to satellite observations and a reasonable agreement was found.

  2. Cardioprotection with halogenated gases: how does it occur? (United States)

    Guerrero-Orriach, Jose Luis; Escalona Belmonte, Juan Jose; Ramirez Fernandez, Alicia; Ramirez Aliaga, Marta; Rubio Navarro, Manuel; Cruz Mañas, Jose


    Numerous studies have studied the effect of halogenated agents on the myocardium, highlighting the beneficial cardiac effect of the pharmacological mechanism (preconditioning and postconditioning) when employed before and after ischemia in patients with ischemic heart disease. Anesthetic preconditioning is related to the dose-dependent signal, while the degree of protection is related to the concentration of the administered drug and the duration of the administration itself. Triggers for postconditioning and preconditioning might have numerous pathways in common; mitochondrial protection and a decrease in inflammatory mediators could be the major biochemical elements. Several pathways have been identified, including attenuation of NFκB activation and reduced expression of TNFα, IL-1, intracellular adhesion molecules, eNOS, the hypercontraction reduction that follows reperfusion, and antiapoptotic activating kinases (Akt, ERK1/2). It appears that the preconditioning and postconditioning triggers have numerous similar paths. The key biochemical elements are protection of the mitochondria and reduction in inflammatory mediators, both of which are developed in various ways. We have studied this issue, and have published several articles on cardioprotection with halogenated gases. Our results confirm greater cardioprotection through myocardial preconditioning in patients anesthetized with sevoflurane compared with propofol, with decreasing levels of troponin and N-terminal brain natriuretic peptide prohormone. The difference between our studies and previous studies lies in the use of sedation with sevoflurane in the postoperative period. The results could be related to a prolonged effect, in addition to preconditioning and postconditioning, which could enhance the cardioprotective effect of sevoflurane in the postoperative period. With this review, we aim to clarify the importance of various mechanisms involved in preconditioning and postconditioning with halogenated


    Energy Technology Data Exchange (ETDEWEB)

    Kent M. Ervin, Principal Investigator


    Gas phase negative ion chemistry methods are employed to determine enthalpies of formation of hydrocarbon radicals that are important in combustion processes and to investigate the dynamics of ion-molecule reactions. Using guided ion beam tandem mass spectrometry, we measure collisional threshold energies of endoergic proton transfer and hydrogen atom transfer reactions of hydrocarbon molecules with negative reagent ions. The measured reaction threshold energies for proton transfer yield the relative gas phase acidities. In an alternative methodology, competitive collision-induced dissociation of proton-bound ion-molecule complexes provides accurate gas phase acidities relative to a reference acid. Combined with the electron affinity of the R {center_dot} radical, the gas phase acidity yields the RH bond dissociation energy of the corresponding neutral molecule, or equivalently the enthalpy of formation of the R{center_dot} organic radical, using equation: D(R-H) = {Delta}{sub acid}H(RH) + EA(R) - IE(H). The threshold energy for hydrogen abstraction from a hydrocarbon molecule yields its hydrogen atom affinity relative to the reagent anion, providing the RH bond dissociation energy directly. Electronic structure calculations are used to evaluate the possibility of potential energy barriers or dynamical constrictions along the reaction path, and as input for RRKM and phase space theory calculations. In newer experiments, we have measured the product velocity distributions to obtain additional information on the energetics and dynamics of the reactions.

  4. Synthesis and pharmacological evaluation in mice of halogenated cannabidiol derivatives. (United States)

    Usami, N; Okuda, T; Yoshida, H; Kimura, T; Watanabe, K; Yoshimura, H; Yamamoto, I


    Six halogenated derivatives of cannabidiol (CBD, 1) substituted on the aromatic ring at the 3' and/or 5' position, 3'-chloro- (2), 3',5'-dichloro- (3), 3'-bromo- (4), 3',5'-dibromo- (5), 3'-iodo- (6) and 3',5'-diiodo-CBD (7) were synthesized and their pharmacological effects of barbiturate-induced sleep prolongation, anticonvulsant effects and locomotor activity were evaluated by intravenous (i.v.) injection in mice. 2 (10 mg/kg, i.v., 69 +/- 10 min) significantly prolonged pentobarbital-induced sleeping time by 3.1-fold, compared to control (22 +/- 2 min), although other 1 derivatives used did not significantly affect the sleeping time. 2, 4 and 6 (10 mg/kg, i.v.) significantly prolonged hexobarbital-induced sleeping time by 2.0-, 2.0- and 2.3-fold, respectively, compared with control (52 +/- 5 min). On the other hand, 1 and all halogenated derivatives did not significantly prolong barbital-induced sleeping time. The monohalogenated derivatives, 2, 4 and 6 were able to prolong pentobarbital and hexobarbital-induced sleeping time, although the dihalogenated derivatives, 3, 5 and 7 did not exhibit a prolongation of the sleeping time. All halogenated derivatives of 1 except for brominated derivatives (2, 3, 6, 7) tended to prolong tonic seizure latency induced by pentylenetetrazol. 1 and its halogenated derivatives did not exhibit any prolongation of seizure latency induced by picrotoxin or strychnine. Maximal electroshock test demonstrated that 1 and 4 exhibited almost the same potency in their anticonvulsant effects, although other 1 derivatives 2, 3, 5, 6 and 7 did not show significant effect up to a dose of 63 mg/kg, i.v. The ED50 values (mg/kg, i.v.) of 1 and 4 were 38 and 44, respectively. 1 and 4 also showed anticonvulsant effect in minimal and maximal electroshock-threshold tests. 2, 4 and 6 tended to decrease the total distance (horizontal activity) and number of rearings (vertical activity) of mice, whereas 3, 5 and 7 tended to increase the number of

  5. Comparison of shear bond strength of orthodontic brackets bonded with halogen and plasma arc light curing

    Directory of Open Access Journals (Sweden)

    Mohammad Hossein IndianJPsychiatry


    Conclusion: Using the plasma arc system is superior to other methods due to reduced curing time. Also, since in using the halogen light system, an increase in curing periods from different angles resulted in a significant increase in shear bond strength; it is advisable to apply the halogen light from different angles.

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

  7. Investigation of non-halogenated solvent mixtures for high throughput fabrication of polymerfullerene solar cells

    NARCIS (Netherlands)

    Schmidt-Hansberg, B.; Sanyal, M.; Grossiord, N.; Galagan, Y.O.; Baunach, M.; Klein, M.F.G.; Colsmann, A.; Scharfer, P.; Lemmer, U.; Dosch, H.; Michels, J.J; Barrena, E.; Schabel, W.


    The rapidly increasing power conversion efficiencies of organic solar cells are an important prerequisite towards low cost photovoltaic fabricated in high throughput. In this work we suggest indane as a non-halogenated replacement for the commonly used halogenated solvent o-dichlorobenzene. Indane

  8. Analysis of an unusual hetero-halogen bonded trimer using charge ...

    Indian Academy of Sciences (India)

    Halogen bond; electron density analysis; multipole refinement; intermolecular interaction. 1. Introduction. Hydrogen bonding is among the most widely studied noncovalent interactions in literature.1 3 Close on its heels comes the halogen bonding owing to its strength and directionality.4,5 In this context, the nature of halo-.

  9. Environmental and human exposure to persistent halogenated compounds derived from e-waste in China. (United States)

    Ni, Hong-Gang; Zeng, Hui; Tao, Shu; Zeng, Eddy Y


    Various classes of persistent halogenated compounds (PHCs) can be released into the environment due to improper handling and disposal of electronic waste (e-waste), which creates severe environmental problems and poses hazards to human health as well. In this review, polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), tetrabromobisphenol A (TBBPA), polybrominated phenols (PBPs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), and chlorinated polycyclic aromatic hydrocarbons (ClPAHs) are the main target contaminants for examination. As the world's largest importer and recycler of e-waste, China has been under tremendous pressure to deal with this huge e-waste situation. This review assesses the magnitude of the e-waste problems in China based on data obtained from the last several years, during which many significant investigations have been conducted. Comparative analyses of the concentrations of several classes of toxic compounds, in which e-waste recycling sites are compared with reference sites in China, have indicated that improper e-waste handling affects the environment of dismantling sites more than that of control sites. An assessment of the annual mass loadings of PBDEs, PBBs, TBBPA, PBPs, PCDD/Fs, and ClPAHs from e-waste in China has shown that PBDEs are the dominant components of PHCs in e-waste, followed by ClPAHs and PCDD/Fs. The annual loadings of PBDEs, ClPAHs, and PCDD/Fs emission were estimated to range from 76,200 to 182,000, 900 to 2,000 and 3 to 8 kg/year, respectively. However, PCDD/Fs and ClPAHs should not be neglected because they are also primarily released from e-waste recycling processes. Overall, the magnitude of human exposure to these toxics in e-waste sites in China is at the high end of the global range. Copyright 2010 SETAC.

  10. Hydrocarbon polymeric binder for advanced solid propellant (United States)

    Potts, J. E. (Editor)


    A series of DEAB initiated isoprene polymerizations were run in the 5-gallon stirred autoclave reactor. Polymerization run parameters such as initiator concentration and feed rate were correlated with the molecular weight to provide a basis for molecular weight control in future runs. Synthetic methods were developed for the preparation of n-1,3-alkadienes. By these methods, 1,3-nonadiene was polymerized using DEAB initiator to give an ester-telechelic polynonadiene. This was subsequently hydrogenated with copper chromite catalyst to give a hydroxyl terminated saturated liquid hydrocarbon prepolymer having greatly improved viscosity characteristics and a Tg 18 degrees lower than that of the hydrogenated polyisoprenes. The hydroxyl-telechelic saturated polymers prepared by the hydrogenolysis of ester-telechelic polyisoprene were reached with diisocyanates under conditions favoring linear chain extension gel permeation chromatography was used to monitor this condensation polymerization. Fractions having molecular weights above one million were produced.

  11. Novel Halogenated Pyrazine-Based Chalcones as Potential Antimicrobial Drugs. (United States)

    Kucerova-Chlupacova, Marta; Vyskovska-Tyllova, Veronika; Richterova-Finkova, Lenka; Kunes, Jiri; Buchta, Vladimir; Vejsova, Marcela; Paterova, Pavla; Semelkova, Lucia; Jandourek, Ondrej; Opletalova, Veronika


    Chalcones, i.e., compounds with the chemical pattern of 1,3-diphenylprop-2-en-1-ones, exert a wide range of bio-activities, e.g., antioxidant, anti-inflammatory, anticancer, anti-infective etc. Our research group has been focused on pyrazine analogues of chalcones; several series have been synthesized and tested in vitro on antifungal and antimycobacterial activity. The highest potency was exhibited by derivatives with electron withdrawing groups (EWG) in positions 2 and 4 of the ring B. As halogens also have electron withdrawing properties, novel halogenated derivatives were prepared by Claisen-Schmidt condensation. All compounds were submitted for evaluation of their antifungal and antibacterial activity, including their antimycobacterial effect. In the antifungal assay against eight strains of selected fungi, growth inhibition of Candida glabrata and Trichophyton interdigitale (formerly T. mentagrophytes) was shown by non-alkylated derivatives with 2-bromo or 2-chloro substitution. In the panel of selected bacteria, 2-chloro derivatives showed the highest inhibitory effect on Staphylococcus sp. In addition, all products were also screened for their antimycobacterial activity against Mycobacterium tuberculosis H37RV My 331/88, M. kansasii My 235/80, M. avium 152/80 and M. smegmatis CCM 4622. Some of the examined compounds, inhibited growth of M. kansasii and M. smegmatis with minimum inhibitory concentrations (MICs) comparable with those of isoniazid.

  12. Novel Halogenated Pyrazine-Based Chalcones as Potential Antimicrobial Drugs

    Directory of Open Access Journals (Sweden)

    Marta Kucerova-Chlupacova


    Full Text Available Chalcones, i.e., compounds with the chemical pattern of 1,3-diphenylprop-2-en-1-ones, exert a wide range of bio-activities, e.g., antioxidant, anti-inflammatory, anticancer, anti-infective etc. Our research group has been focused on pyrazine analogues of chalcones; several series have been synthesized and tested in vitro on antifungal and antimycobacterial activity. The highest potency was exhibited by derivatives with electron withdrawing groups (EWG in positions 2 and 4 of the ring B. As halogens also have electron withdrawing properties, novel halogenated derivatives were prepared by Claisen-Schmidt condensation. All compounds were submitted for evaluation of their antifungal and antibacterial activity, including their antimycobacterial effect. In the antifungal assay against eight strains of selected fungi, growth inhibition of Candida glabrata and Trichophyton interdigitale (formerly T. mentagrophytes was shown by non-alkylated derivatives with 2-bromo or 2-chloro substitution. In the panel of selected bacteria, 2-chloro derivatives showed the highest inhibitory effect on Staphylococcus sp. In addition, all products were also screened for their antimycobacterial activity against Mycobacterium tuberculosis H37RV My 331/88, M. kansasii My 235/80, M. avium 152/80 and M. smegmatis CCM 4622. Some of the examined compounds, inhibited growth of M. kansasii and M. smegmatis with minimum inhibitory concentrations (MICs comparable with those of isoniazid.

  13. Preparation and properties studies of halogen-free flame retardant form-stable phase change materials based on paraffin/high density polyethylene composites

    Energy Technology Data Exchange (ETDEWEB)

    Cai, Yibing; Wei, Qufu; Huang, Fenglin; Gao, Weidong [Key Laboratory of Eco-textiles, Ministry of Education, Jiangnan University, Wuxi, 214122, Jiangsu (China)


    The halogen-free flame retardant form-stable phase change materials (PCM) based on paraffin/high density polyethylene (HDPE) composites were prepared by using twin-screw extruder technique. The structures and properties of the form-stable PCM composites based on intumescent flame retardant system with expandable graphite (EG) and different synergistic additives, such as ammonium polyphosphate (APP) and zinc borate (ZB) were characterized by scanning electronic microscope (SEM), thermogravimetric analyses (TGA), dynamic Fourier-transform infrared (FTIR) spectra, differential scanning calorimeter (DSC) and Cone calorimeter test. The TGA results showed that the halogen-free flame retardant form-stable PCM composites produced a larger amount of charred residue at 700{sup o}C, although the onset of weight loss of the halogen-free flame retardant form-stable PCM composites occurred at a lower temperature due to the thermal decomposition of flame retardant. The DSC measurements indicated that the additives of flame retardant had little effect on the thermal energy storage property, and the temperatures of phase change peaks and the latent heat of the paraffin showed better occurrence during the freezing process. The dynamic FTIR monitoring results revealed that the breakdowns of main chains (HDPE and paraffin) and formations of various residues increased with increasing thermo-oxidation temperature. It was also found from the Cone calorimeter tests that the peak of heat release rate (PHRR) decreased significantly. Both the decrease of the PHRR and the structure of charred residue after combustion indicated that there was a synergistic effect between the EG and APP, contributing to the improved flammability of the halogen-free flame retardant form-stable PCM composites. (author)

  14. Preparation and properties studies of halogen-free flame retardant form-stable phase change materials based on paraffin/high density polyethylene composites

    Energy Technology Data Exchange (ETDEWEB)

    Cai Yibing [Key Laboratory of Eco-textiles, Ministry of Education, Jiangnan University, Wuxi, 214122, Jiangsu (China)], E-mail:; Wei Qufu; Huang Fenglin; Gao Weidong [Key Laboratory of Eco-textiles, Ministry of Education, Jiangnan University, Wuxi, 214122, Jiangsu (China)


    The halogen-free flame retardant form-stable phase change materials (PCM) based on paraffin/high density polyethylene (HDPE) composites were prepared by using twin-screw extruder technique. The structures and properties of the form-stable PCM composites based on intumescent flame retardant system with expandable graphite (EG) and different synergistic additives, such as ammonium polyphosphate (APP) and zinc borate (ZB) were characterized by scanning electronic microscope (SEM), thermogravimetric analyses (TGA), dynamic Fourier-transform infrared (FTIR) spectra, differential scanning calorimeter (DSC) and Cone calorimeter test. The TGA results showed that the halogen-free flame retardant form-stable PCM composites produced a larger amount of charred residue at 700 deg. C, although the onset of weight loss of the halogen-free flame retardant form-stable PCM composites occurred at a lower temperature due to the thermal decomposition of flame retardant. The DSC measurements indicated that the additives of flame retardant had little effect on the thermal energy storage property, and the temperatures of phase change peaks and the latent heat of the paraffin showed better occurrence during the freezing process. The dynamic FTIR monitoring results revealed that the breakdowns of main chains (HDPE and paraffin) and formations of various residues increased with increasing thermo-oxidation temperature. It was also found from the Cone calorimeter tests that the peak of heat release rate (PHRR) decreased significantly. Both the decrease of the PHRR and the structure of charred residue after combustion indicated that there was a synergistic effect between the EG and APP, contributing to the improved flammability of the halogen-free flame retardant form-stable PCM composites.

  15. The effect of mineral fillers on the rheological, mechanical and thermal properties of halogen-free flame-retardant polypropylene/expandable graphite compounds (United States)

    Mattausch, Hannelore; Laske, Stephan; Hohenwarter, Dieter; Holzer, Clemens


    In many polyolefin applications, such as electrical cables or automotive applications, the fire protection is a very important task. Unfortunately flame-retardant polymeric materials are often halogenated and form toxic substances in case of fire, which explains the general requirement to reduce the halogen content to zero. Non-halogenated, state-of-the-art flame retardants must be incorporated into the polymer in very high grades (> 40 wt%) leading to massive decrease in mechanical properties and/or processability. In this research work halogen-free flame-retardant polypropylene (PP) /expandable graphite (EG) were filled with minerals fillers such as layered silicates (MMT), magnesium hydroxide (MgOH), zeolite (Z) and expanded perlite (EP) in order to enhance the flame-retardant effect. The rheological, mechanical and thermal properties of these materials were investigated to gain more fundamental knowledge about synergistic combinations of flame-retardants and other additives. The rheological properties were characterized with a rotational rheometer with plate-plate setup. The EG/EP/PP compound exhibited the highest increase in viscosity (˜ 37 %). As representative value for the mechanical properties the Young's modulus was chosen. The final Young's modulus values of the twofold systems gained higher values than the single ones. Thermo gravimetric analysis (TGA) was utilized to investigate the material with respect to volatile substances and combustion behavior. All materials decomposed in one-step degradation. The EG filled compounds showed a significant increase in sample weight due to the expansion of EG. The combustion behavior of these materials was characterized by cone calorimeter tests. Especially combinations of expandable graphite with mineral fillers exhibit a reduction of the peak heat release rate during cone calorimeter measurements of up to 87% compared to pure PP.

  16. Gamma radiolysis of chlorinated hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Arbon, R.E.; Mincher, B.J.; Meikrantz, D.H.


    This program is the Idaho National Engineering Laboratory (INEL) component of a joint collarborative effort with Lawrence Livermore National Laboratory (LLNL). The purpose of this effort is to demonstrate a viable process for breaking down hazardous halogenated organic wastes to simpler, non-hazardous waste using high energy ionizing radiation. The INEL effort focuses on the use of spent reactor fuel gamma radiation sources to decompose complex wastes such as PCBs. At LLNL, halogenated solvents such as carbon tetrachloride and trichloroethylene are being studied using accelerator radiation sources. The INEL irradiation experiments concentrated on a single PCB congener so that a limited set of decomposition reactions could be studied. The congener 2,2{prime}, 3,3{prime},4,5{prime},6,6{prime} - octachlorobiphenyl was examined following exposure to various gamma doses at the Advanced Test Reactor (AIR) spent fuel pool. The decomposition rates and products in several solvents are discussed. 3 refs.

  17. Gamma radiolysis of chlorinated hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Arbon, R.E.; Mincher, B.J.; Meikrantz, D.H.


    This program is the Idaho National Engineering Laboratory (INEL) component of a joint collarborative effort with Lawrence Livermore National Laboratory (LLNL). The purpose of this effort is to demonstrate a viable process for breaking down hazardous halogenated organic wastes to simpler, non-hazardous waste using high energy ionizing radiation. The INEL effort focuses on the use of spent reactor fuel gamma radiation sources to decompose complex wastes such as PCBs. At LLNL, halogenated solvents such as carbon tetrachloride and trichloroethylene are being studied using accelerator radiation sources. The INEL irradiation experiments concentrated on a single PCB congener so that a limited set of decomposition reactions could be studied. The congener 2,2{prime}, 3,3{prime},4,5{prime},6,6{prime} - octachlorobiphenyl was examined following exposure to various gamma doses at the Advanced Test Reactor (AIR) spent fuel pool. The decomposition rates and products in several solvents are discussed. 3 refs.

  18. Final technical report for the Center for Catalytic Hydrocarbon Functionalization (an EFRC)

    Energy Technology Data Exchange (ETDEWEB)

    Gunnoe, Thomas Brent [Univ. of Virginia, Charlottesville, VA (United States)


    Greater than 95% of all materials produced by the chemical industry are derived from a small slate of simple hydrocarbons that are derived primarily from natural gas and petroleum, predominantly through oxygenation, C–C bond formation, halogenation or amination. Yet, current technologies for hydrocarbon conversion are typically high temperature, multi-step processes that are energy and capital intensive and result in excessive emissions (including carbon dioxide). The Center for Catalytic Hydrocarbon Functionalization (CCHF) brought together research teams with the broad coalition of skills and knowledge needed to make the fundamental advances in catalysis required for next-generation technologies to convert hydrocarbons (particularly light alkanes and methane) at high efficiency and low cost. Our new catalyst technologies offer many opportunities including enhanced utilization of natural gas in the transportation sector (via conversion to liquid fuels), more efficient generation of electricity from natural gas using direct methane fuel cells, reduced energy consumption and waste production for large petrochemical processes, and the preparation of high value molecules for use in biological/medical applications or the agricultural sector. The five year collaborative project accelerated fundamental understanding of catalyst design for the conversion of C–H bonds to functionalized products, essential to achieve the goals listed above, as evidenced by the publication of 134 manuscripts. Many of these fundamental advancements provide a foundation for potential commercialization, as evidenced by the submission of 11 patents from research support by the CCHF.

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

    Directory of Open Access Journals (Sweden)

    Yi Yang


    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.

  20. Halogens and their role in polar boundary-layer ozone depletion

    Directory of Open Access Journals (Sweden)

    W. R. Simpson


    Full Text Available During springtime in the polar regions, unique photochemistry converts inert halide salt ions (e.g. Br into reactive halogen species (e.g. Br atoms and BrO that deplete ozone in the boundary layer to near zero levels. Since their discovery in the late 1980s, research on ozone depletion events (ODEs has made great advances; however many key processes remain poorly understood. In this article we review the history, chemistry, dependence on environmental conditions, and impacts of ODEs. This research has shown the central role of bromine photochemistry, but how salts are transported from the ocean and are oxidized to become reactive halogen species in the air is still not fully understood. Halogens other than bromine (chlorine and iodine are also activated through incompletely understood mechanisms that are probably coupled to bromine chemistry. The main consequence of halogen activation is chemical destruction of ozone, which removes the primary precursor of atmospheric oxidation, and generation of reactive halogen atoms/oxides that become the primary oxidizing species. The different reactivity of halogens as compared to OH and ozone has broad impacts on atmospheric chemistry, including near complete removal and deposition of mercury, alteration of oxidation fates for organic gases, and export of bromine into the free troposphere. Recent changes in the climate of the Arctic and state of the Arctic sea ice cover are likely to have strong effects on halogen activation and ODEs; however, more research is needed to make meaningful predictions of these changes.

  1. The effects of halogen elements on the opening of an icosahedral B12 framework (United States)

    Gong, Liang-Fa; Li, Wei; Osorio, Edison; Wu, Xin-Min; Heine, Thomas; Liu, Lei


    The fully halogenated or hydrogenated B12X122- (X = H, F, Cl, Br and I) clusters are confirmed to be icosahedral. On the other hand, the bare B12 cluster is shown to have a planar structure. A previous study showed that a transformation from an icosahedron to a plane happens when 5 to 7 iodine atoms are remained [P. Farràs et al., Chem. - Eur. J. 18, 13208-13212 (2012)]. Later, the transition was confirmed to be seven iodine atoms based on an infrared spectroscopy study [M. R. Fagiania et al., Chem. Phys. Lett. 625, 48-52 (2015)]. In this study, we investigated the effects of different halogen atoms on the opening of the B12 icosahedral cage by means of density functional theory calculations. We found that the halogen elements do not have significant effects on the geometries of the clusters. The computed infrared (IR) spectra show similar representative peaks for all halogen doped clusters. Interestingly, we found a blue-shift in the IR spectra with the increase in the mass of the halogen atoms. Further, we compared the Gibbs free energies at different temperatures for different halogen atoms. The results show that the Gibbs free energy differences between open and close structures of B12X7- become larger when heavier halogen atoms are presented. This interesting finding was subsequently investigated by the energy decomposition analysis.

  2. Participation of the Halogens in Photochemical Reactions in Natural and Treated Waters. (United States)

    Yang, Yi; Pignatello, Joseph J


    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. Noncovalent interactions in halogenated ionic liquids: theoretical study and crystallographic implications. (United States)

    Li, Haiying; Lu, Yunxiang; Wu, Weihong; Liu, Yingtao; Peng, Changjun; Liu, Honglai; Zhu, Weiliang


    In recent years, several specific imidazolium-based ionic liquids with halogen substituents on the imidazole ring as well as on the alkyl chains have been reported. In this work, noncovalent interactions in four halogenated ionic liquids, i.e. 2-bromo-/iodo- and 4,5-dibromo-/diiodo-1,3-dimethylimidazolium trifluoromethanesulfonates, were systematically investigated using density functional theory calculations. The structural and energetic properties of the ion pairs for such ionic liquids have been fully examined and compared with the non-halogenated ones. It was found that C-X···O halogen bonds, C-H···O hydrogen bonds, and electrostatic interactions with the anion located over the imidazole ring in the ion pairs. In addition, the structures and energetics of two ion pairs for such ionic liquids were also explored to reproduce experimental observations. The halogen-bonded ring structures and the conformers with the concurrent C-H···O and C-X···O contacts were predicted, consistent with the X-ray crystal structures of corresponding organic salts. Finally, the implications of the observed structural and energetic features of ion pairs on the design of halogen-bonding ionic liquids were discussed. The results presented herein should provide useful information in the development of novel halogenated ionic liquids used for specific tasks ranging from organic synthesis to gas absorption.

  4. Cardioprotection with halogenated gases: how does it occur?

    Directory of Open Access Journals (Sweden)

    Guerrero-Orriach JL


    Full Text Available Jose Luis Guerrero-Orriach,1–3 Juan Jose Escalona Belmonte,1 Alicia Ramirez Fernandez,1 Marta Ramirez Aliaga,1 Manuel Rubio Navarro,1 Jose Cruz Mañas1 1Department of Cardioanesthesiology, Virgen de la Victoria University Hospital, 2Instituto de Investigación Biomédica de Málaga (IBIMA, 3Department of Pharmacology and Pediatrics, University of Malaga, Malaga, Spain Abstract: Numerous studies have studied the effect of halogenated agents on the myocardium, highlighting the beneficial cardiac effect of the pharmacological mechanism (preconditioning and postconditioning when employed before and after ischemia in patients with ischemic heart disease. Anesthetic preconditioning is related to the dose-dependent signal, while the degree of protection is related to the concentration of the administered drug and the duration of the administration itself. Triggers for postconditioning and preconditioning might have numerous pathways in common; mitochondrial protection and a decrease in inflammatory mediators could be the major biochemical elements. Several pathways have been identified, including attenuation of NFκB activation and reduced expression of TNFα, IL-1, intracellular adhesion molecules, eNOS, the hypercontraction reduction that follows reperfusion, and antiapoptotic activating kinases (Akt, ERK1/2. It appears that the preconditioning and postconditioning triggers have numerous similar paths. The key biochemical elements are protection of the mitochondria and reduction in inflammatory mediators, both of which are developed in various ways. We have studied this issue, and have published several articles on cardioprotection with halogenated gases. Our results confirm greater cardioprotection through myocardial preconditioning in patients anesthetized with sevoflurane compared with propofol, with decreasing levels of troponin and N-terminal brain natriuretic peptide prohormone. The difference between our studies and previous studies lies in

  5. 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


    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.

  6. Influence of halogen substituents on the catalytic oxidation of 2,4,6-halogenated phenols by Fe(III)-tetrakis(p-hydroxyphenyl) porphyrins and potassium monopersulfate. (United States)

    Fukushima, Masami; Mizutani, Yusuke; Maeno, Shouhei; Zhu, Qianqian; Kuramitz, Hideki; Nagao, Seiya


    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-hydroxyphenyl)porphyrin (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.

  7. Thermophysical Properties of Hydrocarbon Mixtures (United States)

    SRD 4 NIST Thermophysical Properties of Hydrocarbon Mixtures (PC database for purchase)   Interactive computer program for predicting thermodynamic and transport properties of pure fluids and fluid mixtures containing up to 20 components. The components are selected from a database of 196 components, mostly hydrocarbons.

  8. Halogenation generates effective modulators of amyloid-Beta aggregation and neurotoxicity.

    Directory of Open Access Journals (Sweden)

    H Edward Wong

    Full Text Available Halogenation of organic compounds plays diverse roles in biochemistry, including selective chemical modification of proteins and improved oral absorption/blood-brain barrier permeability of drug candidates. Moreover, halogenation of aromatic molecules greatly affects aromatic interaction-mediated self-assembly processes, including amyloid fibril formation. Perturbation of the aromatic interaction caused by halogenation of peptide building blocks is known to affect the morphology and other physical properties of the fibrillar structure. Consequently, in this article, we investigated the ability of halogenated ligands to modulate the self-assembly of amyloidogenic peptide/protein. As a model system, we chose amyloid-beta peptide (Aβ, which is implicated in Alzheimer's disease, and a novel modulator of Aβ aggregation, erythrosine B (ERB. Considering that four halogen atoms are attached to the xanthene benzoate group in ERB, we hypothesized that halogenation of the xanthene benzoate plays a critical role in modulating Aβ aggregation and cytotoxicity. Therefore, we evaluated the modulating capacities of four ERB analogs containing different types and numbers of halogen atoms as well as fluorescein as a negative control. We found that fluorescein is not an effective modulator of Aβ aggregation and cytotoxicity. However, halogenation of either the xanthenes or benzoate ring of fluorescein substantially enhanced the inhibitory capacity on Aβ aggregation. Such Aβ aggregation inhibition by ERB analogs except rose bengal correlated well to the inhibition of Aβ cytotoxicity. To our knowledge, this is the first report demonstrating that halogenation of aromatic rings substantially enhance inhibitory capacities of small molecules on Aβ-associated neurotoxicity via Aβ aggregation modulation.

  9. Aromatization process of hydrocarbons containing 2 to 4 carbon atoms in the presence of alumino-silicate catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Alario, F.; Deves, J.M.


    The invention describes an aromatization process of hydrocarbons comprising 2 to 4 carbon atoms per molecule in the presence of a composite catalyst which contains: a MFI structure zeolite in the form hydrogen, containing in its structure Silicon, Aluminium and / or Gallium at least; a matrix; platinum metals at least and additive metal chosen among Stain, Germanium, Indium, Copper, Iron, Molybdenum, Gallium, Thallium, Gold, Silver, Ruthenium, Chrome, Tungsten and Lead at least; an halogen chosen among Fluorine, Chlorine, Bromine and Iodine at least; doping element chosen among Gallium and Zinc possibly and possibly alkaline or alkaline-earth metal.

  10. Selective C(sp(2))-H Halogenation of "Click" 4-Aryl-1,2,3-triazoles. (United States)

    Goitia, Asier; Gómez-Bengoa, Enrique; Correa, Arkaitz


    Selective bromination reactions of "click compounds" are described. Electron-neutral and electron-deficient arenes selectively undergo unprecedented Pd-catalyzed C-H ortho-halogenations assisted by simple triazoles as modular directing groups, whereas electron-rich arenes are regioselectively halogenated following an electrophilic aromatic substitution reaction pathway. These C-H halogenation procedures exhibit a wide group tolerance, complement existing bromination procedures, and represent versatile synthetic tools of utmost importance for the late-stage diversification of "click compounds". The characterization of a triazole-containing palladacycle and density functional theory studies supported the mechanism proposal.

  11. Induction of Axial Chirality in 8-Arylquinolines through Halogenation Reactions Using Bifunctional Organocatalysts. (United States)

    Miyaji, Ryota; Asano, Keisuke; Matsubara, Seijiro


    The enantioselective syntheses of axially chiral heterobiaryls were accomplished through the aromatic electrophilic halogenation of 3-(quinolin-8-yl)phenols with bifunctional organocatalysts that control the molecular conformations during successive halogenations. Axially chiral quinoline derivatives, which have rarely been synthesized in an enantioselective catalytic manner, were afforded in moderate-to-good enantioselectivities through bromination, and an analogous protocol also enabled enantioselective iodination. In addition, this catalytic reaction, which allows enantioselective control through the use of mono-ortho-substituted substrates, allowed the asymmetric synthesis of 8-arylquinoline derivatives bearing two different halogen groups in high enantioselectivities. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Competition of hydrogen bonds and halogen bonds in complexes of hypohalous acids with nitrogenated bases. (United States)

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


    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.

  13. α-Halogenated oxaphosphinanes: Synthesis, unexpected reactions and evaluation as inhibitors of cancer cell proliferation. (United States)

    Babouri, Rachida; Rolland, Marc; Sainte-Catherine, Odile; Kabouche, Zahia; Lecouvey, Marc; Bakalara, Norbert; Volle, Jean-Noël; Virieux, David; Pirat, Jean-Luc


    This paper describes the preparation and the biological evaluation of α-halogenated oxaphosphinanes. These halogen derivatives were synthetized from a short and stereoselective synthetic sequence starting by previously described hydroxy-precursors 1 and 2 with respectively a glucose and mannose-like configuration. The in vitro biological tests of these unnatural halogenated phosphinosugars, on several cell lines, highlighted, for some of them, their antiproliferative and anti migration and invasion properties at nanomolar concentration. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  14. Fluorescence cell imaging and manipulation using conventional halogen lamp microscopy.

    Directory of Open Access Journals (Sweden)

    Kazuo Yamagata

    Full Text Available Technologies for vitally labeling cells with fluorescent dyes have advanced remarkably. However, to excite fluorescent dyes currently requires powerful illumination, which can cause phototoxic damage to the cells and increases the cost of microscopy. We have developed a filter system to excite fluorescent dyes using a conventional transmission microscope equipped with a halogen lamp. This method allows us to observe previously invisible cell organelles, such as the metaphase spindle of oocytes, without causing phototoxicity. Cells remain healthy even after intensive manipulation under fluorescence observation, such as during bovine, porcine and mouse somatic cell cloning using nuclear transfer. This method does not require expensive epifluorescence equipment and so could help to reduce the science gap between developed and developing countries.

  15. Iron Coordination and Halogen-Bonding Assisted Iodosylbenzene Activation

    DEFF Research Database (Denmark)

    Wegeberg, Christina; Poulsen de Sousa, David; McKenzie, Christine

    The iron complex of the hexadentate ligand N,N,N'-tris(2-pyridylmethyl)ethylendiamine-N'-acetate (tpena) efficiently catalyzes selective oxidations of electron-rich olefins and sulfides by insoluble iodosylbenzene (PhIO). Surprisingly, these reactions are faster and more selective than homogenous...... catalytic mixtures using soluble terminal oxygen transfer agents. Isolation of a reactive iron-terminal oxidant adduct, an unique Fe(III)-OIPh complex, is facilitated by strong stabilizing supramolecular halogen-bonding. L3-edge XANES suggests +1.6 for the average oxidation state for the iodine atom3...... in the iron(III)-coordinated PhIO. This represents a reduction of iodine relative to the original “hypervalent” (+3) PhIO. The equivalent of electron density must be removed from the {(tpena)Fe(III)O} moiety, however Mössbauer spectroscopy shows that the iron atom is not high valent....

  16. Microwave assisted pyrolysis of halogenated plastics recovered from waste computers. (United States)

    Rosi, Luca; Bartoli, Mattia; Frediani, Marco


    Microwave Assisted Pyrolysis (MAP) of the plastic fraction of Waste from Electric and Electronic Equipment (WEEE) from end-life computers was run with different absorbers and set-ups in a multimode batch reactor. A large amount of various different liquid fractions (up to 76.6wt%) were formed together with a remarkable reduction of the solid residue (up to 14.2wt%). The liquid fractions were characterized using the following different techniques: FT-IR ATR, 1H NMR and a quantitative GC-MS analysis. The liquid fractions showed low density and viscosity, together with a high concentration of useful chemicals such as styrene (up to 117.7mg/mL), xylenes (up to 25.6mg/mL for p-xylene) whereas halogenated compounds were absent or present in a very low amounts. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Vanadium bromoperoxidase-catalyzed biosynthesis of halogenated marine natural products. (United States)

    Carter-Franklin, Jayme N; Butler, Alison


    Marine red algae (Rhodophyta) are a rich source of bioactive halogenated natural products. The biogenesis of the cyclic halogenated terpene marine natural products, in particular, has attracted sustained interest in part because terpenes are the biogenic precursors of many bioactive metabolites. The first enzymatic asymmetric bromination and cyclization of a terpene, producing marine natural products isolated from red algae, is reported. Vanadium bromoperoxidase (V-BrPO) isolated from marine red algae (species of Laurencia, Plocamium, Corallina) catalyzes the bromination of the sesquiterpene (E)-(+)-nerolidol producing alpha-, beta-, and gamma-snyderol and (+)-3beta-bromo-8-epicaparrapi oxide. alpha-Snyderol, beta-snyderol, and (+)-3beta-bromo-8-epicaparrapi oxide have been isolated from Laurencia obtusa, and each have also been isolated from other species of marine red algae. gamma-Snyderol is a proposed intermediate in other bicyclo natural products. Single diastereomers of beta-snyderol, gamma-snyderol, and mixed diastereomers of (+)-3beta-bromo-8-epicaparrapi oxide (de = 20-25%) are produced in the enzyme reaction, whereas two diastereomers of these compounds are formed in the synthesis with 2,4,4,6-tetrabromocyclohexa-2,5-dienone (TBCO). V-BrPO likely functions by catalyzing the two-electron oxidation of bromide ion by hydrogen peroxide producing a bromonium ion or equivalent in the active site that brominates one face of the terminal olefin of nerolidol. These results establish V-BrPO's role in the biosynthesis of brominated cyclic sesquiterpene structures from marine red algae for the first time.

  18. The Brenner Moor - A saline bog as a source for halogenated and non-halogenated volatile compounds (United States)

    Krause, T.; Studenroth, S.; Furchner, M.; Hoffman, A.; Lippe, S.; Kotte, K.; Schöler, H. F.


    The Brenner Moor is a small bog in the catchment area of the river Trave located in Schleswig-Holstein, North Germany, between Baltic and North Sea. The bog is fed by several saline springs with chloride concentrations up to 15 g/L. The high chloride concentrations and the high organic content of the peat make the Brenner Moor an ideal source for the abiotic formation of volatile organic halogenated compounds (VOX). VOX play an important role in the photochemical processes of the lower atmosphere and information on the atmospheric input from saline soils like the Brenner Moor will help to understand the global fluxes of VOX. Soil samples were taken in spring 2011 from several locations and depths in the vicinity of the Brenner Moor. The samples were freeze-dried, ground and incubated in water emphasising an abiotic character for the formation of volatile organic compounds. 1,2-dichloroethane and trichloromethane are the main halogenated compounds emitted from soils of the Brenner Moor. The abiotic formation of trichloromethane as well as other trihalomethanes has been part of intensive studies. A well known source is the decarboxylation of trichloroacetic acid and trichloroacetyl-containing compounds to trichloromethane [1]. Huber et al. discovered another pathway in which catechol, as a model compound for organic substances, is oxidised under Fenton-like conditions with iron(III), hydrogen peroxide and halides to form trihalomethanes [2]. Besides the halogenated compounds, the formation of sulphur compounds such as dimethyl sulfide and dimethyl disulfide and several furan derivatives could be detected which also have an impact on atmospheric chemistry, especially particle formation of clouds. Furan, methylfuran and dimethylfuran are compounds that can be obtained under Fenton-like oxidation from catechol, methyl- and dimethylcatechol and are known to be produced in natural soils [3]. A novel class of furan derivatives that are formed under abiotic conditions from

  19. 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


    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.

  20. Enzymatic Halogenation: A Timely Strategy for Regioselective C-H Activation. (United States)

    Schnepel, Christian; Sewald, Norbert


    Halogenating enzymes are increasingly attracting attention for biocatalytic C-H functionalization. Despite its importance for synthetic chemistry, selective introduction of halogens using conventional approaches often remains challenging, whereas biocatalysis offers excellent catalyst-controlled selectivity without requiring protecting groups or hazardous reagents. Owing to the high prevalence of halogenated secondary metabolites, a still growing repertoire of halogenases has been identified. Recently, flavin-dependent tryptophan halogenases came into focus for synthetic use. Nevertheless, these enzymes still suffer from severe deficiencies. Herein, current attempts in optimizing tryptophan halogenases have been compiled. Enzyme discovery, structure elucidation and mechanisms are reviewed with focus on biosynthesis of halogenated arenes. Emphasis is also given to random and rational engineering, high-throughput screening and implementation of halogenases into one-pot processes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Changes in patterns of persistent halogenated compounds through a pelagic food web in the Baltic Sea

    DEFF Research Database (Denmark)

    Stephansen, Diana Agnete; Svendsen, Tore Christian; Vorkamp, Katrin


    The concentrations and patterns of persistent halogenated compounds (PHCs), including polychlorinated biphenyls (PCBs), DDT, hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB) and polybrominated diphenyl ethers (PBDEs) were examined in a pelagic food web from the southern Baltic Sea consisting...

  2. Correction: Benchmark thermochemistry of chloramines, bromamines, and bromochloramines: halogen oxidants stabilized by electron correlation. (United States)

    Trogolo, Daniela; Arey, J Samuel


    Correction for 'Benchmark thermochemistry of chloramines, bromamines, and bromochloramines: halogen oxidants stabilized by electron correlation' by Daniela Trogolo et al., Phys. Chem. Chem. Phys., 2015, 17, 3584-3598.


    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...

  4. UARS Halogen Occultation Experiment (HALOE) Level 2 V019 (UARHA2FN) at GES DISC (United States)

    National Aeronautics and Space Administration — The Halogen Occultation Experiment (HALOE) Level 2 data product consists of daily vertical profiles of temperature, aerosol extinciton and pressure, as well as...

  5. UARS Halogen Occultation Experiment (HALOE) Level 3AT V019 (UARHA3AT) at GES DISC (United States)

    National Aeronautics and Space Administration — The Halogen Occultation Experiment (HALOE) Level 3AT data product consists of daily vertical profiles of temperature, aerosol extinction and concentrations of HCl,...


    Directory of Open Access Journals (Sweden)

    S. A. Konovalova


    Full Text Available The hydrohalogenation of N-arylaminocarbonyl-1,4-benzoquinone monoimines is optimal method to obtain the halogenated derivatives. This method allows obtaining the pure products in high yield with a halogen atom in the aminophenol ring. The bromination of N-arylaminocarbonyl-1,4-benzoquinone monoimines and their reduced forms allows obtaining of individual products only in several cases. The bromination allows synthesizing of products with a halogen atom not only in the aminophenol ring, but in the aryl moiety too. As a result of the experiment we have found the optimal conditions to synthesis the N-arylaminocarbonyl-1,4-benzoquinone monoimine derivatives containing halogen atom. The bromination and hydrohalogenation products with one free ortho-position toward to the imine carbon atom of the quinoid ring can be used as synthons in the synthesis of heterocyclic compounds – 1,3-benzoxazole derivatives.

  7. Pd-Catalyzed regioselective C-H halogenation of quinazolinones and benzoxazinones. (United States)

    Dabiri, Minoo; Farajinia Lehi, Noushin; Kazemi Movahed, Siyavash; Khavasi, Hamid Reza


    A Pd-catalyzed ortho-selective halogenation of benzoxazinone and quinazolinone scaffolds has been described employing N-halosuccinimide as both a halogen source and an oxidant reagent via C-H bond activation. This transformation shows high chemo- and regioselectivities and demonstrates a broad range of benzoxazinone and quinazolinone substrates with different functional groups and has been scaled up to the gram level.

  8. Advances in Metal-Catalyzed Cross-Coupling Reactions of Halogenated Quinazolinones and Their Quinazoline Derivatives

    Directory of Open Access Journals (Sweden)

    Malose Jack Mphahlele


    Full Text Available Halogenated quinazolinones and quinazolines are versatile synthetic intermediates for the metal-catalyzed carbon–carbon bond formation reactions such as the Kumada, Stille, Negishi, Sonogashira, Suzuki-Miyaura and Heck cross-coupling reactions or carbon-heteroatom bond formation via the Buchwald-Hartwig cross-coupling to yield novel polysubstituted derivatives. This review presents an overview of the application of these methods on halogenated quinazolin-4-ones and their quinazolines to generate novel polysubstituted derivatives.

  9. Adsorption of halogenated hydrocarbons from aqueous solutions by wetted and non-wetted hydrophobic and hydrophilic sorbents: equilibria

    NARCIS (Netherlands)

    Rexwinkel, Glenn; Rexwinkel, G.; Heesink, Albertus B.M.; van Swaaij, Willibrordus Petrus Maria


    Single-solute adsorption equilibria of 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethene, trans-1,2-dichloroethene, chloroform, 2,4-dichorophenol, and dichloromethane dissolved in water have been measured, using both wetted and nonwetted hydrophobic Amberlite XAD-4 resin at 20 °C. The


    Concentration-dependent induction of cytochrome P4501A (CYP1A) and intracellular porphyrin accumulation were observed following treatment of chicken embryo hepatocyte (CEH) cultures with 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), 2,3,7,8-tetrachlorodibenzofuran (TCDF), 3,3',4,4'...

  11. Source apportionment of hydrocarbons measured in the Eagle Ford shale (United States)

    Roest, G. S.; Schade, G. W.


    The rapid development of unconventional oil and gas in the US has led to hydrocarbon emissions that are yet to be accurately quantified. Emissions from the Eagle Ford Shale in southern Texas, one of the most productive shale plays in the U.S., have received little attention due to a sparse air quality monitoring network, thereby limiting studies of air quality within the region. We use hourly atmospheric hydrocarbon and meteorological data from three locations in the Eagle Ford Shale to assess their sources. Data are available from the Texas commission of environmental quality (TCEQ) air quality monitors in Floresville, a small town southeast of San Antonio and just north of the shale area; and Karnes city, a midsize rural city in the center of the shale. Our own measurements were carried out at a private ranch in rural Dimmit County in southern Texas from April to November of 2015. Air quality monitor data from the TCEQ were selected for the same time period. Non-negative matrix factorization in R (package NMF) was used to determine likely sources and their contributions above background. While the TCEQ monitor data consisted mostly of hydrocarbons, our own data include both CO, CO2, O3, and NOx. We find that rural Dimmit County hydrocarbons are dominated by oil and gas development sources, while central shale hydrocarbons at the TCEQ monitoring sites have a mix of sources including car traffic. However, oil and gas sources also dominate hydrocarbons at Floresville and Karnes City. Toxic benzene is nearly exclusively due to oil and gas development sources, including flaring, which NMF identifies as a major hydrocarbon source in Karnes City. Other major sources include emissions of light weight alkanes (C2-C5) from raw natural gas emissions and a larger set of alkanes (C2-C10) from oil sources, including liquid storage tanks.

  12. Comparison of shear bond strength of orthodontic brackets bonded with halogen and plasma arc light curing. (United States)

    Toodehzaeim, Mohammad Hossein; Kazemi, Alireza Danesh; Aghili, Hossein Agha; Barzegar, Kazem; Fallahtafti, Taranom


    Reduced time and appropriate bond strength of brackets is one of the most important aspects of orthodontic treatments. Prolonged halogen light curing for bonding of brackets is undesirable, so the purpose of this study was to compare the shear bond strength of brackets bonded with halogen light and plasma arc system. MATERIALS AND MEHODS: This was an experimental in vitro study. A total of 60 intact premolar teeth were collected and divided into four groups. Stainless steel orthodontic brackets were bonded to them. In groups 1 and 2, curing was done using halogen light given for 20 seconds from two and four angles. In groups 3 and 4, curing was carried out using the plasma arc system for 6 seconds from two and four angles. The shear bond strength was recorded by Instron. The statistics of ANOVA, Tukey's test, and T-test were used in data analysis. There was a statistically significant difference in shear bond strength among the four groups (P = 0.043) and between group 1 with group 2 (P = 0.035). Yet, there was no statistically significant difference between brackets bonded with plasma arc and those bonded with halogen light or between the two groups of plasma arc. Using the plasma arc system is superior to other methods due to reduced curing time. Also, since in using the halogen light system, an increase in curing periods from different angles resulted in a significant increase in shear bond strength; it is advisable to apply the halogen light from different angles.

  13. Estimations of the thermodynamic properties of halogenated benzenes as they relate to their environment mobility. (United States)

    Monte, Manuel J S; Almeida, Ana R R P


    In this work, several simple new equations for predicting important environmental mobility properties, at T = 298.15 K, were derived for halogenated benzenes: standard Gibbs energy of hydration, aqueous solubility, octanol-water partition coefficients, and Henry's law constants. A discussion on our previous estimates of other related properties (standard Gibbs energy and vapor pressure of sublimation and of vaporization) and their relation with entropy of fusion is also presented. As we aimed to estimate these properties for any of the ca. 1500 halogenated benzenes that may exist theoretically, an equation for estimating the temperature of fusion was also derived, since some of the proposed predictive equations (solubility of solids and Gibbs energy of sublimation) require its knowledge. For the other estimated properties just the number of each halogen that replaces hydrogen atoms in the halogenated benzene is needed. It was found that the coefficients that multiply the number of halogen atoms in the predictive equations vary linearly with the volume of the halogen atom. Copyright © 2017 Elsevier Ltd. All rights reserved.

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


    Seiya Nagao; Hideki Kuramitz; Qianqian Zhu; Shouhei Maeno; Masami Fukushima; Yusuke Mizutani


    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-hydroxyphenyl)porphyrin (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 substituen...


    African Journals Online (AJOL)


    Scomber scombrus), suya beef and plantain (Musa paradiasca) sold and consumed in Amassoma town were screened for the presence of 15 polycyclic aromatic hydrocarbons (PAHs). Concentration of chromium, lead and cadmium were also ...

  16. Growth of hydrocarbon utilizing microorganisms

    Digital Repository Service at National Institute of Oceanography (India)

    Bhosle, N.B.; Mavinkurve, S.

    Two isolates from marine mud having broad spectrum hydrocarbon utilizing profile were identified as Arthrobacter simplex and Candida tropicalis.Both the organisms grew exponentially on crude oil. The cell yield of the organisms was influenced...

  17. Hydrocarbon Leak Detection Sensor Project (United States)

    National Aeronautics and Space Administration — FTT is proposing the development of a sensor to detect the presence of hydrocarbons in turbopump Inter-Propellant Seals (IPS). The purpose of the IPS is to prevent...

  18. Aliphatic hydrocarbons of the fungi. (United States)

    Weete, J. D.


    Review of studies of aliphatic hydrocarbons which have been recently detected in the spores of phytopathogenic fungi, and are found to be structurally very similar to the alkanes of higher plants. It appears that the hydrocarbon components of the few mycelial and yeast forms reported resemble the distribution found in bacteria. The occurence and distribution of these compounds in the fungi is discussed. Suggested functional roles of fungal spore alkanes are presented.

  19. Bioassay of polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Van Kirk, E.A.


    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.

  20. Separation of aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Grishchenko, N.F.; Yablochkina, M.N.; Shapiro, L.P.; Rogozkin, V.A.


    An optimal system of extraction has been developed making it possible to produce benzene, toluene and xylenes economically and with high efficiency.The raw material used for catalytic reforming consists of narrow-boiling-range gasoline fractiions at 62 to 85, 62 to 105 and 105 to 140/sup 0/C. Processing of the first fraction makes it possible to produce benzene; the second, benzene and toluene; and the third, toluene and xylenes. The addition of reforming extraction units has made it possible to produce aromatic hydrocarbons suitable for any specialized application. At the current time the output of benzene with extraction plants is about 60 percent of the total output, of toluene more than 80 percent and of xylene more than 50 percent. The key technological indicators are given for the processes of extraction with hydrous polyglycols. For new higher-capacity plants, in addition to extraction with tetraethylene glycol, the 'Ekstars' process has been developed for extraction with a hybrid solvent based on propylene carbonate. For eliminating the presence of unsaturated compounds, a process has been developed for the selective hydrogenation of reforming catalysis products. The process is carried out in an additional reactor included in the catalytic reforming system, at 160 to 250/sup 0/C with an aluminoplatinic catalyst in a combined steam and gas mixture flow at a pressure of 1.5 to 3.5 MPa. (JMT)


    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez Cruz, D.J.


    Venezuela is an important player in the energy world, because of its hydrocarbons reserves. The process for calculating oil and associated gas reserves is described bearing in mind that 90% of the gas reserves of Venezuela are associated to oil. Likewise, an analysis is made of the oil reserves figures from 1975 to 2003. Reference is also made to inconsistencies found by international experts and the explanations offered in this respect by the Ministry of Energy and Petroleum (MENPET) and Petroleos de Venezuela (PDVSA) regarding the changes that took place in the 1980s. In turn, Hubbert's Law is explained to determine peak production of conventional oil that a reservoir or field will reach, as well as its relationship with remaining reserves. Emphasis is placed on the interest of the United Nations on this topic. The reserves of associated gas are presented along with their relationship with the different crude oils that are produced and with injected gas, as well as with respect to the possible changes that would take place in the latter if oil reserves are revised. Some recommendations are submitted so that the MENPET starts preparing the pertinent policies ruling reserves. (auth)

  2. Evaluation of hydrocarbon potential

    Energy Technology Data Exchange (ETDEWEB)

    Cashman, P.H.; Trexler, J.H. Jr. [Univ. of Nevada, Reno, NV (United States)


    Task 8 is responsible for assessing the hydrocarbon potential of the Yucca Mountain vincinity. Our main focus is source rock stratigraphy in the NTS area in southern Nevada. (In addition, Trexler continues to work on a parallel study of source rock stratigraphy in the oil-producing region of east central Nevada, but this work is not funded by Task 8.) As a supplement to the stratigraphic studies, we are studying the geometry and kinematics of deformation at NTS, particularly as these pertain to reconstructing Paleozoic stratigraphy and to predicting the nature of the Late Paleozoic rocks under Yucca Mountain. Our stratigraphic studies continue to support the interpretation that rocks mapped as the {open_quotes}Eleana Formation{close_quotes} are in fact parts of two different Mississippian units. We have made significant progress in determining the basin histories of both units. These place important constraints on regional paleogeographic and tectonic reconstructions. In addition to continued work on the Eleana, we plan to look at the overlying Tippipah Limestone. Preliminary TOC and maturation data indicate that this may be another potential source rock.

  3. Halogen light versus LED for bracket bonding: shear bond strength

    Directory of Open Access Journals (Sweden)

    Paulo Eduardo Guedes Carvalho


    Full Text Available INTRODUCTION: LED light-curing devices seek to provide a cold light activator which allows protocols of material polymerization with shorter duration. OBJECTIVE: The present study aimed to evaluate the shear bond strength of bracket bonding using three types of light-curing devices: One with halogen light (Optilight Plus - Gnatus and two with LEDs (Optilight CL - Gnatus and Elipar Freelight - 3M/ESPE. RESULTS: Comparing the results by analysis of variance, the Gnatus LED device showed an inferior statistical behavior in relation to other light sources, when activated by a short time. But, when it was used for 40 seconds, the polymerization results were consistent with the other evaluated sources. The device with the best average performance was the halogen light, followed by the 3M/ESPE LED. CONCLUSION: It was concluded that the LEDs may be indicated in orthodontic practice, as long as a protocol is used for the application of light with the activation time of 40 seconds.INTRODUÇÃO: os aparelhos de fotopolimerização por LED buscam proporcionar uma luz ativadora fria, que possibilite protocolos de polimerização do material com menor tempo de duração. OBJETIVO: avaliar a resistência à tração da colagem de braquetes, utilizando três tipos de aparelhos fotoativadores: um de luz halógena (Optilight Plus - Gnatus e outros dois de LED (Optilight CL - Gnatus; e Elipar Freelight - 3M/Espe. RESULTADOS: comparando os resultados por meio da análise de variância, o aparelho de LED Gnatus apresentou comportamento estatístico inferior em relação às outras fontes de luz, quando ativado por tempo reduzido. Já quando foi utilizado o tempo de 40 segundos, os resultados de polimerização foram compatíveis com as demais fontes avaliadas. O aparelho que apresentou melhor desempenho médio foi o de luz halógena, seguido pelo LED 3M/Espe. CONCLUSÃO: concluiu-se que os LEDs podem ser indicados na prática ortodôntica, uma vez que seja utilizado

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

    Energy Technology Data Exchange (ETDEWEB)

    Yan Xiaoqing; Shen Qianjin; Zhao Xiaoran; Gao Haiyue; Pang Xue [College of Chemistry, Beijing Normal University, Beijing 100875 (China); Jin Weijun, E-mail: [College of Chemistry, Beijing Normal University, Beijing 100875 (China)


    Highlights: Black-Right-Pointing-Pointer Halogen bonding (XB) is firstly utilised in solid phase extraction. Black-Right-Pointing-Pointer The perfluorinated iodine alkanes can be extracted by C-I Midline-Horizontal-Ellipsis Cl{sup -} halogen bonding. Black-Right-Pointing-Pointer The C-I Midline-Horizontal-Ellipsis Cl{sup -} halogen bond is well characterised by spectroscopy methods. Black-Right-Pointing-Pointer 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, {sup 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 Midline-Horizontal-Ellipsis Cl{sup -} 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{sup -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{sup -}. 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{sup -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{sup -1} in soil samples. Overall, this work reveals the great application potential of halogen bonding in the field of solid


    Graham, E A


    The central lobular necrosis in the liver, which has been regarded by some writers as characteristic of late chloroform poisoning, has been produced experimentally with a number of other drugs. It is, therefore, in no sense peculiar to chloroform poisoning. Substances which have been shown to produce a morphological picture indistinguishable from that of late chloroform poisoning are: (a) dichlor- and tetrachlormethane, (b) tribrom- and triiodomethane, (c) monochlor-, monobrom-, and monoiodoethane, also the dibromethane; that is, in general, the halogen substituted aliphatic hydrocarbons containing one or two carbon atoms. Presumably similar results might be obtained with the higher members of the same series. The mechanism by which chloroform produces its characteristic tissue changes must accordingly be considered as a group reaction. Outside the body the similarities between the chemical behavior of different members of this group have been correlated by Nef on the basis of the type of dissociation which these substances undergo and the differences in their behavior on the basis of the differences of the degree to which such dissociations occur. According to the work of Nef, the group of substances under discussion has the property of dissociating to yield a halogen acid and an unsaturated alkylidene rest. Thus with chloroform the type of dissociation may be expressed thus: See PDF for Equation In this paper the view is developed that the changes characteristic of late poisonings with the above named group, namely edema, multiple hemorrhages, fat infiltration, and necrosis are ascribable (1) to acids and (2) to the fact that the amount of acid formed parallels the chemical dissociability of the drug outside of the body. Favoring the view that acid is responsible for the changes are the following observations. 1. All the characteristic features of late chloroform poisoning have been produced merely by the administration of hydrochloric acid, except, however, for

  6. Rotational Spectra of Halogenated Ethers Used as Volatile Anaesthetics (United States)

    Vega-Toribio, Alicia; Lesarri, Alberto; Suenram, Richard D.; Grabow, Jens-Uwe


    Following previous microwave investigations by Suenram et al., we will report on the rotational spectrum of several halogenated ethers used as volatile anaesthetics, including sevoflurane ((CF_3)_2CH-O-CH_2F), isoflurane (CF_3CHCl-O-CHF_2), enflurane (CHFClCF_2-O-CHF_2) and methoxyflurane (CHCl_2CF_2-O-CH_3). This study has been conducted in the 6-18 GHz centimetre-wave region using Balle-Flygare-type FT-microwave spectroscopy. The results will include the analysis of the rotational spectra of minor species in natural abundance (^{13}C and ^{18}O in some cases), structural calculations and auxiliary ab initio modelling. The conformational and structural conclusions will be compared with previous gas-phase electron diffraction and solid-state X-ray diffraction analysis. R. D. Suenram, D. J. Brugh, F. J. Lovas and C. Chu, 51st OSU Int. Symp. On Mol. Spectrosc., Columbus, OH, 1999, RB07

  7. Modification of halogen specificity of a vanadium-dependent bromoperoxidase. (United States)

    Ohshiro, Takashi; Littlechild, Jennifer; Garcia-Rodriguez, Esther; Isupov, Michail N; Iida, Yasuaki; Kobayashi, Takushi; Izumi, Yoshikazu


    The halide specificity of vanadium-dependent bromoperoxidase (BPO) from the marine algae, Corallina pilulifera, has been changed by a single amino acid substitution. The residue R397 has been substituted by the other 19 amino acids. The mutant enzymes R397W and R397F showed significant chloroperoxidase (CPO) activity as well as BPO activity. These mutant enzymes were purified and their properties were investigated. The maximal velocities of CPO activities of the R397W and R397F enzymes were 31.2 and 39.2 units/mg, and the K(m) values for Cl(-) were 780 mM and 670 mM, respectively. Unlike the native enzyme, both mutant enzymes were inhibited by NaN(3). In the case of the R397W enzyme, the incorporation rate of vanadate into the active site was low, compared with the R397F and the wild-type enzyme. These results supported the existence of a specific halogen binding site within the catalytic cleft of vanadium haloperoxidases.

  8. Modeling cooperative effects in halogen-bonded infinite linear chains. (United States)

    Adasme-Carreño, Francisco; Alzate-Morales, Jans; Ireta, Joel


    Non-additivity in noncovalent interactions is an important aspect of complex systems that can lead to stronger (cooperative) interactions when three or more molecular units influence each other. The halogen bond (XB) is a highly-directional noncovalent interaction that has been found to be cooperative. Here the strength and nature of cooperativity arising in X-bonded infinite linear chains of cyanogen halides and 4-halopyridines are investigated by means of density functional theory calculations. It is found that cyanogen halide chains are highly cooperative (up to 77%), whereas pyridines are only slightly cooperative (below 21%). It is demonstrated that XB and its non-additivity can be modeled as the sum of a local term, which depends on first nearest-neighbors only, and long-range effective dipole-dipole attractions. It is shown that the local term in cyanogen halides primarily accounts for repulsive short-range screened Coulomb interactions, whereas in 4-halopyridines such a term also includes attractive contributions, which are particularly sizeable in some elongated XB conformations. This outcome reveals differences in the nature of the XBs formed in these molecular systems. Nevertheless, it is shown that both systems behave as effective point dipoles regarding cooperative effects, at any point of the XB dissociation path. As such, these results are useful contributions for the understanding and modeling of non-additive effects of noncovalent interactions.

  9. Designer Metallic Acceptor-Containing Halogen Bonds: General Strategies. (United States)

    Zhang, Xinxing; Bowen, Kit


    Being electrostatic interactions in nature, hydrogen bonding (HB) and halogen bonding (XB) are considered to be two parallel worlds. In principle, all the applications that HB have could also be applied to XB. However, there has been no report on an anionic, metallic XB acceptor, but metal anions have been observed to be good HB acceptors. This missing mosaic piece of XB theory is because common metal anions are reactive for XB donors. In view of this, two strategies are proposed for designing metallic acceptor-containing XB using ab initio calculations. The first one is to utilize a metal cluster anion with a high electron detachment energy, such as the superatom, Al13- as the XB acceptor. The second strategy is to design a ligand-passivated/protected metal core that can maintain the negative charge; several exotic clusters, such as PtH5- , PtZnH5- , and PtMgH5- , are used as examples. Based on these two strategies, it is anticipated that more metallic acceptor-containing XBs will be discovered. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Sea ice dynamics influence halogen deposition to Svalbard

    Directory of Open Access Journals (Sweden)

    A. Spolaor


    Full Text Available Sea ice is an important parameter in the climate system and its changes impact upon the polar albedo and atmospheric and oceanic circulation. Iodine (I and bromine (Br have been measured in a shallow firn core drilled at the summit of the Holtedahlfonna glacier (Northwest Spitsbergen, Svalbard. Changing I concentrations can be linked to the March–May maximum sea ice extension. Bromine enrichment, indexed to the Br / Na sea water mass ratio, appears to be influenced by changes in the seasonal sea ice area. I is emitted from marine biota and so the retreat of March–May sea ice coincides with enlargement of the open-ocean surface which enhances marine primary production and consequent I emission. The observed Br enrichment could be explained by greater Br emissions during the Br explosions that have been observed to occur mainly above first year sea ice during the early springtime. In this work we present the first comparison between halogens in surface snow and Arctic sea ice extension. Although further investigation is required to characterize potential depositional and post-depositional processes, these preliminary findings suggest that I and Br can be linked to variability in the spring maximum sea ice extension and seasonal sea ice surface area.

  11. Identification and quantification of the halogenated natural product BC-3

    Energy Technology Data Exchange (ETDEWEB)

    Melcher, J.; Olbrich, D.; Vetter, W. [Hohenheim Univ., Stuttgart (Germany). Inst. fuer Lebensmittelchemie; Marsh, G. [Stockholm Univ. (Sweden). Dept. of Environmental Chemistry; Gaus, C.; Mueller, J.F. [National Research Centre for Environmental Toxicology, Coopers Plains (Australia)


    Halogenated natural products (HNPs) of marine origin are increasingly recognized as critical residues in foodstuff (e. g. fish) and environmental samples (e. g. marine mammals and birds). Some of these HNPs (Q1, MHC-1, BC-2, and HDBPs including BC-10) were detected in diverse fish and marine mammal samples at concentrations sometimes exceeding those of PCBs, DDT, and other anthropogenic pollutants. Recent studies with marine mammal samples from Australia led to the detection of six abundant HNPs (Q1, BC-1, BC-2, BC-3, BC-10, and BC-11). In the meantime, Q1 was identified as heptachloro-1{sup '}-methyl-1,2{sup '}-bipyrrole, BC-2 as 4,6-dibromo-2-(2{sup '},4{sup '}-dibromo)phenoxyanisole, BC- 10 as 1,1{sup '}-dimethyl-3,3{sup '},4,4{sup '}-tetrabromo-5,5{sup '}-dichloro-2,2{sup '}-bipyrrole, and BC-11 as 3,5-dibromo- 2-(3{sup '},5{sup '}-dibromo,2{sup '}-methoxy)phenoxyanisole. However the identity of BC-1 and BC-3 remained unclear. The goal of the present study was the identification of BC-3. The tetrabromo compound BC-3 has previously been detected in marine mammals from four continents. Furthermore, we attempted establishing quantitative concentrations in diverse marine biota samples.

  12. Sorption Properties of Halogen Containing Graphene Oxide Frameworks (United States)

    Burress, Jacob; Baker, Elizabeth; Bethea, Donald; Frangos, Katherine

    Physisorption of gases has applications in gas storage (e.g. methane, hydrogen for vehicles) and gas separation (carbon dioxide from flue gas). The van der Waals force in narrow pores is strong enough to condense even supercritical gases to much higher densities. Additionally, differences in the binding energy between different gases and the sorbent surface are sufficient to for gas separations. Beyond adsorption interactions, simple steric (size, shape) effects also play a role in gas separations. One class of materials currently being investigated for numerous gas storage/separation applications is graphene oxide frameworks (GOFs). GOFs consist of layers of graphene/graphene oxide separated by chemical linkers covalently bonded on both sides. This presentation will give results from boronic acid-based GOFs that contain halogen group elements. Effects of different linkers on pore shape will be presented. Physical behavior of the gases investigated (hydrogen, methane, carbon dioxide, nitrogen), including binding energies and steric effects for gas separation will also be presented. The physics mechanism behind pore breathing (expansion and contraction of pore volume) in these materials will be discussed.

  13. Polycyclic Aromatic Hydrocarbons (United States)

    Salama, Farid


    Carbonaceous materials play an important role in space. Polycyclic Aromatic Hydrocarbons (PAHs) are a ubiquitous component of the carbonaceous materials. PAHs are the best-known candidates to account for the IR emission bands. They are also thought to be among the carriers of the diffuse interstellar absorption bands (DIBs). PAH ionization states reflect the ionization balance of the medium while PAH size, composition, and structure reflect the energetic and chemical history of the medium. A major challenge is to reproduce in the laboratory the physical conditions that exist in the emission and absorption interstellar zones. The harsh physical conditions of the ISM -low temperature, collisionless, strong UV radiation fields- are simulated in the laboratory by associating a molecular beam with an ionizing discharge to generate a cold plasma expansion. PAH ions and radicals are formed from the neutral precursors in an isolated environment at low temperature and probed with high-sensitivity cavity ringdown spectroscopy in the NUV-NIR range. Carbon nanoparticles are also formed during the short residence time of the precursors in the plasma and are characterized with time-offlight mass spectrometry. These experiments provide unique information on the spectra of large carbonaceous molecules and ions in the gas phase that can now be directly compared to interstellar and circumstellar observations (IR emission bands, DIBs, extinction curve). These findings also hold great potential for understanding the formation process of interstellar carbonaceous grains. We will review recent progress in the experimental and theoretical studies of PAHs, compare the laboratory data with astronomical observations and discuss the global implications.


    Treatment of potable water samples with ascorbic acid has been investigated as a means for reducing residual halogen-based oxidants (disinfectants)i.e., HOCl, Cl2, Brw and BrCl, prior to determination of EPA Method 551.1A and 551.1B analytes. These disinfection byproducts include...

  15. Boiling of simulated tap water: effect on polar brominated disinfection byproducts, halogen speciation, and cytotoxicity. (United States)

    Pan, Yang; Zhang, Xiangru; Wagner, Elizabeth D; Osiol, Jennifer; Plewa, Michael J


    Tap water typically contains numerous halogenated disinfection byproducts (DBPs) as a result of disinfection, especially of chlorination. Among halogenated DBPs, brominated ones are generally significantly more toxic than their chlorinated analogues. In this study, with the aid of ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry by setting precursor ion scans of m/z 79/81, whole spectra of polar brominated DBPs in simulated tap water samples without and with boiling were revealed. Most polar brominated DBPs were thermally unstable and their levels were substantially reduced after boiling via decarboxylation or hydrolysis; the levels of a few aromatic brominated DBPs increased after boiling through decarboxylation of their precursors. A novel adsorption unit for volatile total organic halogen was designed, which enabled the evaluation of halogen speciation and mass balances in the simulated tap water samples during boiling. After boiling for 5 min, the overall level of brominated DBPs was reduced by 62.8%, of which 39.8% was volatilized and 23.0% was converted to bromide; the overall level of chlorinated DBPs was reduced by 61.1%, of which 44.4% was volatilized and 16.7% was converted to chloride; the overall level of halogenated DBPs was reduced by 62.3%. The simulated tap water sample without boiling was cytotoxic in a chronic (72 h) exposure to mammalian cells; this cytotoxicity was reduced by 76.9% after boiling for 5 min. The reduction in cytotoxicity corresponded with the reduction in overall halogenated DBPs. Thus, boiling of tap water can be regarded as a "detoxification" process and may reduce human exposure to halogenated DBPs through tap water ingestion.

  16. Antimicrobial photodynamic therapy using chlorin e6 with halogen light for acne bacteria-induced inflammation. (United States)

    Jeon, Yu-Mi; Lee, Hwan-Suk; Jeong, Dongjun; Oh, Hae-Keun; Ra, Kyu-Hwan; Lee, Mi-Young


    The present study was designed to evaluate the therapeutic potential of antimicrobial photodynamic therapy (PDT) using chlorin e6 with halogen light against acne bacteria-induced inflammation. Highly purified chlorin e6 (Ce6), as a second generation photosensitizer, was synthesized from Spirulina chlorophyll. To evaluate the antimicrobial property of Ce6-mediated PDT with halogen light, the broth microdilution method and two-color fluorescence assay were used. The free radicals generated upon irradiating Ce6 with halogen light were measured using 2,7-dichlorofluorescin diacetate. Propionibacterium acnes was intradermally injected into the left ear of the ICR mice, and the anti-inflammatory effect of Ce6-mediated PDT with halogen light was measured by the histological examination. The expressions of cyclooxygenase-2 (COX-2), inducible nitric oxide synthase (iNOS) as well as pro-inflammatory cytokines were also measured by Western blotting. Chlorin e6-mediated PDT with halogen light (30,000 lx) inactivated various skin bacteria, including P. acnes in a dose-dependent manner. The MIC99 value against P. acnes (KCTC3314) of Ce6 with light was >0.49 μg/ml, whereas the MIC99 for Ce6 alone was >31.25 μg/ml. Ce6-mediated PDT suppressed the expression of P. acnes-induced pro-inflammatory cytokines and iNOS, but not COX-2 in a mouse model. This study showed a remarkable therapeutic effect of chlorin e6-mediated PDT with halogen light against P. acnes-induced inflammation. Our results suggest for the first time the potential of Ce6-mediated PDT with halogen light as a more effective and safer alternative treatment to antibiotic therapy against pathogenic infections of the skin. Copyright © 2015 Elsevier Inc. All rights reserved.

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


    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.

  18. Polyethylene composites containing a phase change material having a C14 straight chain hydrocarbon (United States)

    Salyer, Ival O.


    A composite useful in thermal energy storage, said composite being formed of a polyethylene matrix having a straight chain alkyl hydrocarbon incorporated therein, said polyethylene being crosslinked to such a degree that said polyethylene matrix is form stable and said polyethylene matrix is capable of absorbing at least 10% by weight of said straight chain alkyl hydrocarbon; the composite is useful in forming pellets or sheets having thermal energy storage characteristics.

  19. Healthy Weight (United States)

    ... Weight Gain Losing Weight Getting Started Improving Your Eating Habits Keeping It Off Healthy Eating for a Healthy ... or "program". It's about lifestyle changes in daily eating and exercise habits. Success Stories They did it. So can you! ...

  20. Weighted Clustering

    DEFF Research Database (Denmark)

    Ackerman, Margareta; Ben-David, Shai; Branzei, Simina


    We investigate a natural generalization of the classical clustering problem, considering clustering tasks in which different instances may have different weights.We conduct the first extensive theoretical analysis on the influence of weighted data on standard clustering algorithms in both...... the partitional and hierarchical settings, characterizing the conditions under which algorithms react to weights. Extending a recent framework for clustering algorithm selection, we propose intuitive properties that would allow users to choose between clustering algorithms in the weighted setting and classify...

  1. Electron microscopy of hydrocarbon production in parthenium argentatum (guayule)

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, Thomas E. [Univ. of California, Berkeley, CA (United States)


    The electron microscope was used to study the biological processes involved in hydrocarbon production. The little desert shrub Guayule (Parthenium argentatum) was selected for study. This shrub can produce hydrocarbons (rubber) in concentrations up to 1/4 of its dry weight. It grows on semi-arid land and has been extensively studied. The potential of Guayule is described in detail. Results of an investigation into the morphology of Guayule at the electron microscope level are given. Experiments, which would allow the biosynthesis of hydrocarbon in Guayule to be followed, were designed. In order to do this, knowledge of the biochemistry of rubber formation was used to select a tracer, mevalonic acid. Mevalonic acid is the precursor of all the terpenoids, a large class of hydrocarbons which includes rubber. It was found that when high enough concentrations of mevalonic acid are administered to seedling Guayule plants, build-ups of metabolized products are found within the chloroplasts of the seedlings. Also, tritium labeled mevalonic acid was used as a precursor, and its metabolic progress was followed by using the technique of electron microscope autoradiography. The results of these experiments also implicated chloroplasts of the Guayule plant in hydrocarbon production. The final task was the development of a system to produce three-dimensional stereo reconstructions of organelles suspected of involvement in hydrocarbon biosynthesis in Guayule. The techniques are designed to reconstruct an object from serial sections of that object. The techniques use stereo imaging both to abstract information for computer processing, and also in the computer produced reconstruction.

  2. Formation of environmentally relevant polyhalogenated carbazoles from chloroperoxidase-catalyzed halogenation of carbazole. (United States)

    Chen, Yanqiu; Lin, Kunde; Chen, Da; Wang, Kun; Zhou, Wenxiu; Wu, Yan; Huang, Xinwen


    Polyhalogenated carbazoles (PHCs) are a class of emerging organic contaminants that have received increasing concern due to their widespread distribution and dioxin-like toxicity. Although previous studies have suggested possible natural sources of PHCs in the environment, the formation pathways are poorly understood. Here we explored the production of PHCs from halogenation of carbazole in the presence of Br(-) and/or Cl(-) under the catalysis of chloroperoxidase (CPO) isolated from the marine fungus Caldariomyces fumago. Overall, a total of 25 congeners including mono-to tetra-substituted chlorinated, brominated, and mixed halogenated carbazoles (with substitution patterns of -BrCl, -BrCl2, -BrCl3, -Br2Cl, -Br2Cl2, and -Br3Cl) were produced from the reactions under various conditions. The PHC product profiles were apparently dependent on the halide concentrations. In the CPO-mediated chlorination of carbazole, 3-mono- and 3,6-dichlorocarbazoles predominated in the formation products. In addition to the less abundant mixed halogenated carbazoles (-Br2Cl), 1,3,6-tri- and 1,3,6,8-tetrabromocarbazoles were the dominant products in reactions containing both Br(-) and Cl(-). The CPO-catalyzed halogenation of carbazole could take place in pH 3-7, but the formation products were pH dependent. Results of this study suggest that CPO-catalyzed halogenation of carbazole may play an important role in the natural formation of PHCs. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Process for removing halogenated aliphatic and aromatic compounds from petroleum products (United States)

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


    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. The Behavior of Halogens Elements in the Early Solar System: Constraints from the Complex Record in Chondritic Meteorites (United States)

    Brearley, A. J.; Jones, R. H.


    The volatile inventory of chondritic meteorites was established by a range of processes that occurred in circumstellar and interstellar environments, within the solar nebula, and after accretion within meteorite parent bodies. Among volatile elements, the halogens are of particular interest because, although they exhibit similar geochemical characteristics, they have a range of volatilities that control their cosmochemical behavior. Chondritic meteorites provide the opportunity to understand how halogens behaved during the earliest history of our solar system, including during condensation, CAI and chondrule formation in the protoplanetary disk, and during subsequent processing after accretion into asteroidal parent bodies by aqueous alteration, metamorphism and shock. Constraints on the halogen inventory of the terrestrial planets also requires a detailed knowledge of halogen abundances in chondritic meteorites. However, the full potential of halogens to constrain processes in the solar nebula and chondrite parent bodies has not yet been realized because of significant analytical challenges and uncertainties in halogen condensation temperatures. Nevertheless, although there are significant variations in the analytical data, it is clear that there are distinct differences between the three main classes of chondrites, carbonaceous, ordinary, and enstatite. In most chondrites, the abundances of the halogens are controlled by their cosmochemical volatility, and the halogens are depleted in most of the chondrite groups relative to CI chondrites. With the exception of the enstatite chondrites, the primary (nebular) mineralogical carriers of the halogens in the most pristine (type 3) carbonaceous and ordinary chondrites are poorly constrained, suggesting that they are incorporated at low concentrations into nebular phases. In aqueously-altered, petrologic type 1 and 2 meteorites, no distinct halogen-bearing phases have been identified. However, metamorphic processes

  5. Enrichment of light hydrocarbon mixture (United States)

    Yang, Dali [Los Alamos, NM; Devlin, David [Santa Fe, NM; Barbero, Robert S [Santa Cruz, NM; Carrera, Martin E [Naperville, IL; Colling, Craig W [Warrenville, IL


    Light hydrocarbon enrichment is accomplished using a vertically oriented distillation column having a plurality of vertically oriented, nonselective micro/mesoporous hollow fibers. Vapor having, for example, both propylene and propane is sent upward through the distillation column in between the hollow fibers. Vapor exits neat the top of the column and is condensed to form a liquid phase that is directed back downward through the lumen of the hollow fibers. As vapor continues to ascend and liquid continues to countercurrently descend, the liquid at the bottom of the column becomes enriched in a higher boiling point, light hydrocarbon (propane, for example) and the vapor at the top becomes enriched in a lower boiling point light hydrocarbon (propylene, for example). The hollow fiber becomes wetted with liquid during the process.

  6. Halogenated and organophosphorus flame retardants in European aquaculture samples. (United States)

    Aznar-Alemany, Òscar; Aminot, Yann; Vilà-Cano, Judit; Köck-Schulmeyer, Marianne; Readman, James W; Marques, António; Godinho, Lia; Botteon, Elena; Ferrari, Federico; Boti, Vasiliki; Albanis, Triantafyllos; Eljarrat, Ethel; Barceló, Damià


    This work monitors flame retardants in sediment, mussel and water samples from European fish farms. Polybrominated diphenyl ethers (PBDEs) were detected in 95% of the sediment and mussel samples with mean levels of 8.60±22.6ngg -1 dw in sediments and 0.07±0.18ngg -1 dw in mussels. BDE-209 was the main contributor for the sediments and BDE-47 was found in about 60% of the samples of both matrices. Pentabromoethylbenzene (PBEB) and hexabromobenzene (HBB) were detected in 42% of the sediments, but not in mussels. Decabromodiphenyl ethane (DBDPE) was found in about 55% of the samples of both matrices. The same happened for dechloranes in mussels, but they were detected in 92% of the sediments. Syn-DP and anti-DP were always the main contributors. Methoxylated PBDEs (MeO-PBDEs) were detected in all mussels and some sediments, mainly 6-MeO-BDE-47 and 2'-MeO-BDE-68. Organophosphorus flame retardants (OPFRs) were found in all matrices with concentrations of 0.04-92.8ngg -1 dw in sediment, 0.50-102ngg -1 dw in mussel and 0.43-867ngl -1 in water. Only OPFRs were analysed in water samples as halogenated flame retardants and MeO-PBDEs are highly unlikely to be detected in water due to their physicochemical properties. Flame retardants have no application in fish farming so results should reflect the impact of human activity on the farm locations. A large majority of the most contaminated samples were collected from sampling spots that were at urban shores or in enclosed water bodies not completely open to the sea. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Nontraditional π Gelators Based on β-Iminoenolate and Their Difluoroboron Complexes: Effect of Halogens on Gelation and Their Fluorescent Sensory Properties Towards Acids. (United States)

    Wu, Zhu; Sun, Jingbo; Zhang, Zhenqi; Yang, Hao; Xue, Pengchong; Lu, Ran


    We have synthesized a series of new β-iminoenolates and their corresponding difluoroboron complexes without any traditional gelation moieties, and some of them were able to gelatinize organic solvents. It was found that the presence of halogen atoms as substituents had a significant effect on gelation ability. In particular, bromo-containing compounds 4 A and 4 B exhibited excellent gelation abilities compared with other halogen-substituted gelators. By analyses of the single-crystal structure, the PXRD pattern of the xerogel, and electronic spectral changes during gelation, we deemed that π-π, C-H⋅⋅⋅F, and C-H⋅⋅⋅Br interactions were the driving forces for the gelation of 4 B. Interestingly, (Z)-1-(4-bromophenyl)-2-(3-methylpyrazin-2-yl)ethen-1-ol (8 A), prepared in this work, is the lowest-molecular-weight organogelator to have been reported. It should be noted that although β-iminoenolates 3 A-5 A are nonemissive in solution, they emit strong yellow light in organogels, which suggests aggregation-induced emissive activity, whereas the difluoroboron complexes 3 B-5 B show strong fluorescence in solutions, organogels, and xerogel-based films. Moreover, we found that the emission of 4 B in a nanofiber-based film could be quenched significantly upon exposure to gaseous trifluoroacetic acid and that the decay time and detection limit were 0.5 s and 0.17 ppm, respectively. Thus, through this work we have provided a new strategy for the design of nontraditional π gelators by introducing halogen atoms into π-conjugated systems with moderate polarities. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Total Petroleum Hydrocarbons (TPH): ToxFAQs (United States)

    ... state: This map displays locations where Total Petroleum Hydrocarbons (TPH) is known to be present. On This ... get more information? ToxFAQs TM for Total Petroleum Hydrocarbons (TPH) ( Hidrocarburos Totales de Petróleo (TPH) ) August 1999 ...

  9. Structure-Guided Reprogramming of a Hydroxylase To Halogenate Its Small Molecule Substrate. (United States)

    Mitchell, Andrew J; Dunham, Noah P; Bergman, Jonathan A; Wang, Bo; Zhu, Qin; Chang, Wei-Chen; Liu, Xinyu; Boal, Amie K


    Enzymatic installation of chlorine/bromine into unactivated carbon centers provides a versatile, selective, and environmentally friendly alternative to chemical halogenation. Iron(II) and 2-(oxo)-glutarate (Fe(II)/2OG)-dependent halogenases are powerful biocatalysts that are capable of cleaving aliphatic C-H bonds to introduce useful functional groups, including halogens. Using the structure of the Fe/2OG halogenase, WelO5, in complex with its small molecule substrate, we identified a similar N-acyl amino acid hydroxylase, SadA, and reprogrammed it to halogenate its substrate, thereby generating a new chiral haloalkyl center. The work highlights the potential of Fe(II)/2OG enzymes as platforms for development of novel stereospecific catalysts for late-stage C-H functionalization.

  10. 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: [Department of Chemistry, Hope College, 35 E. 12th Street, Holland, MI 49423 (United States)


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

  11. Investigating Arctic Tropospheric Ozone Depletion Through a Flowing Chemical Reaction Method of Halogen Free Radical Measurement (United States)

    Tackett, P. J.; Shepson, P. B.; Bottenheim, J. W.; Steffen, A.


    Arctic tropospheric halogen chemistry has been investigated through the measurement of halogen free radicals, ozone, and gaseous elemental mercury in the lower Arctic troposphere during spring 2008 in a unique sea ice surface environment onboard the research icebreaker CCGS Amundsen. Low-level ozone depletion events were observed beginning in early March, with more extensive events occurring later in the month. Bromine monoxide measurements were conducted using a new, flowing chemical reaction method in addition to established DOAS techniques, and was observed with good agreement at concentrations approaching 40 ppt during periods of significant ozone and mercury depletion. Air mass history was observed for the periods leading to depletion, suggesting a dependence on sea ice contact and ambient temperatures below -22 °C as necessary elements for the onset of halogen-induced tropospheric ozone depletion. Here we discuss our data further with the aim of better understanding how ozone depletion events are triggered.

  12. Correlating Precisely Defined Primary Structure with Crystalline Properties in Halogen Containing Polyolefins (United States)

    Boz, Emine; Alamo, Rufina G.; Wagener, Kenneth B.

    Polyethylene (PE) and poly(vinyl chloride) (PVC) are among the most important polymers produced in industry, although other halogen-containing derivatives of PE, such as poly(tetrafluorethylene) (PTFE) have also found wides pread use. A related class of polymers is the ethylene-co-vinyl-halide family. Such copolymers are expected to show distinct properties relative to their better known industrial analogues. For example, much interest has focused on ethylene vinyl chloride (EVC) polymers based on their potential for improved thermal stability relative to PVC. Various techniques have been used to synthesize these ethylene vinyl halide (EVH) copolymers and the simplest approach is halogenation of PE, which results in an irregular distribution of halogens along the polymer backbone and poorly defined materials.

  13. Biodegradation of bisphenol A and its halogenated analogues by Cunninghamella elegans ATCC36112. (United States)

    Keum, Young Soo; Lee, Hye Ri; Park, Hee Won; Kim, Jeong-Han


    Bisphenol A and its halogenated analogues are commonly used industrial chemicals with strong toxicological effects over many organisms. In this study, metabolic fate of bisphenol A and its halogenated analogues were evaluated with Cunninghamella elegans ATCC36112. Bisphenol A and related analogues were rapidly transformed into several metabolites by C. elegans within 2-4 days. Detailed analysis of metabolites reveals that both phase I and II metabolism occurred in C. elegans. Cytochrome P450-dependent hydroxylation was observed in BPA. However, major reaction with bisphenol A and analogues with 1-2 halogen atoms were the formation of glucose-conjugate, not being inhibited by cytochrome P450 inhibitor. Overall metabolic rates decreased with increasing number of substitution at 2- and 6-position of BPA structures, which may be consequences of limited bioavailability or steric hindrance to conjugate-forming reaction. Information from the current study will provide detailed insights over the fungal metabolism of BPA and analogues.

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

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


    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.

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

    KAUST Repository

    Ward, Jeremy W.


    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.

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


    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.

  17. Iron Mineral Catalyzed C-H Activation As a Potential Pathway for Halogenation Processes (United States)

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


    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

  18. Halogen degassing during ascent and eruption of water-poor basaltic magma (United States)

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


    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 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.

  19. Thermodynamics parameters for binding of halogenated benzotriazole inhibitors of human protein kinase CK2α. (United States)

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


    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.

  20. Weighted LCS (United States)

    Amir, Amihood; Gotthilf, Zvi; Shalom, B. Riva

    The Longest Common Subsequence (LCS) of two strings A and B is a well studied problem having a wide range of applications. When each symbol of the input strings is assigned a positive weight the problem becomes the Heaviest Common Subsequence (HCS) problem. In this paper we consider a different version of weighted LCS on Position Weight Matrices (PWM). The Position Weight Matrix was introduced as a tool to handle a set of sequences that are not identical, yet, have many local similarities. Such a weighted sequence is a 'statistical image' of this set where we are given the probability of every symbol's occurrence at every text location. We consider two possible definitions of LCS on PWM. For the first, we solve the weighted LCS problem of z sequences in time O(zn z + 1). For the second, we prove \\cal{NP}-hardness and provide an approximation algorithm.

  1. Compositions and methods for hydrocarbon functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Gunnoe, Thomas Brent; Fortman, George; Boaz, Nicholas C.; Groves, John T.


    Embodiments of the present disclosure provide for methods of hydrocarbon functionalization, methods and systems for converting a hydrocarbon into a compound including at least one group ((e.g., hydroxyl group) (e.g., methane to methanol)), functionalized hydrocarbons, and the like.

  2. 33 CFR 157.166 - Hydrocarbon emissions. (United States)


    ... 33 Navigation and Navigable Waters 2 2010-07-01 2010-07-01 false Hydrocarbon emissions. 157.166... Crude Oil Washing (COW) System on Tank Vessels Cow Operations § 157.166 Hydrocarbon emissions. If the... ballasted in that port the hydrocarbon vapors in each tank are contained by a means under § 157.132. Note...

  3. Occurrence and growth potentials of hydrocarbon degrading ...

    African Journals Online (AJOL)

    ... the hydrocarbon occurred between the 8th and 14th day. It was therefore concluded that bacteria with ability to utilize hydrocarbons could be obtained from leaf surfaces. Such organisms could serve as seeds for bioaugmentation during remediation of polluted environments. Keywords: Phylloplane, bacteria, hydrocarbon, ...

  4. Extractive distillation of hydrocarbon mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Lee, F.M.; Brown, R.E.; Johnson, M.M.


    This patent describes a process for separating at least one aromatic hydrocarbon containing 6-12 carbon atoms per molecule from at least one close-boiling alkane by extractive distillation of a feed consisting essentially of the at least one aromatic hydrocarbon and the at least one alkane in the presence of a solvent consisting essentially of N-methyl-2-thiopyrrolidone, optionally in combination with at least one cosolvent selected from the group consisting of glycol compounds, sulfolane compounds and N-({beta}-mercaptoalkyl)-2-pyrrolidone compounds; wherein the extractive distillation process produces an overhead distillate product which contains a smaller volume percentage of the at least one alkane than the feed, and a bottoms product which contains the solvent and a larger volume percentage of the at least one aromatic hydrocarbon and a smaller volume percentage of the at least one alkane than the feed; and wherein the at least one aromatic hydrocarbon is separated from the solvent and recovered from the bottoms product. This patent also describes a process for separating at least one cycloalkane containing 5-10 carbon atoms per molecule from at least one close-boiling alkane by extracting distillation of a feed consisting essentially of the at least one cycloalkane and the at least one alkane in the presence of a solvent consisting essentially of N-methyl-2-thiopyrrolidone, optionally in combination with at least one cosolvent selected from the group consisting of glycol compounds, sulfone compounds and N-({beta}-mercaptoalkyl)-2-pyrrolidone compounds.

  5. Effective viscosity of confined hydrocarbons

    DEFF Research Database (Denmark)

    Sivebæk, Ion Marius; Samoilov, V.N.; Persson, B.N.J.


    We present molecular dynamics friction calculations for confined hydrocarbon films with molecular lengths from 20 to 1400 carbon atoms. We find that the logarithm of the effective viscosity ηeff for nanometer-thin films depends linearly on the logarithm of the shear rate: log ηeff=C-nlog γ̇, where...

  6. Steam Hydrocarbon Cracking and Reforming (United States)

    Golombok, Michael


    The interactive methods of steam hydrocarbon reforming and cracking of the oil and chemical industries are scrutinized, with special focus on their resemblance and variations. The two methods are illustrations of equilibrium-controlled and kinetically-controlled processes, the analysis of which involves theories, which overlap and balance each…

  7. Deuterated interstellar polycyclic aromatic hydrocarbons

    NARCIS (Netherlands)

    Peeters, E; Allamandola, LJ; Bauschlicher, CW; Hudgins, DM; Sandford, SA; Tielens, AGGM


    We report infrared spectral evidence of deuterated interstellar polycyclic aromatic hydrocarbons (PAHs). Two bands are detected in the infrared emission from the ionization bar in Orion at 4.4 and 4.65 mum. The one at 4.65 mum is present at the 4.4 sigma level, while the one at 4.4 mum is more

  8. 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


    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.

  9. Rasta resin–triphenylphosphine oxides and their use as recyclable heterogeneous reagent precursors in halogenation reactions

    Directory of Open Access Journals (Sweden)

    Xuanshu Xia


    Full Text Available Heterogeneous polymer-supported triphenylphosphine oxides based on the rasta resin architecture have been synthesized, and applied as reagent precursors in a wide range of halogenation reactions. The rasta resin–triphenylphosphine oxides were reacted with either oxalyl chloride or oxalyl bromide to form the corresponding halophosphonium salts, and these in turn were reacted with alcohols, aldehydes, aziridines and epoxides to form halogenated products in high yields after simple purification. The polymer-supported triphenylphosphine oxides formed as a byproduct during these reactions could be recovered and reused numerous times with no appreciable decrease in reactivity.

  10. Halogen-bond and hydrogen-bond interactions between three benzene derivatives and dimethyl sulphoxide. (United States)

    Zheng, Yan-Zhen; Wang, Nan-Nan; Zhou, Yu; Yu, Zhi-Wu


    Halogen-bonds, like hydrogen-bonds, are a kind of noncovalent interaction and play an important role in diverse fields including chemistry, biology and crystal engineering. In this work, a comparative study was carried out to examine the halogen/hydrogen-bonding interactions between three fluoro-benzene derivatives and dimethyl sulphoxide (DMSO). A number of conclusions were obtained by using attenuated total reflection infrared spectroscopy (ATR-IR), nuclear magnetic resonance (NMR) and ab initio calculations. Electrostatic surface potential, geometry, energy, vibrational frequency, intensity and the natural population analysis (NPA) of the monomers and complexes are studied at the MP2 level of theory with the aug-cc-pVDZ basis set. First, the interaction strength decreases in the order C6F5H-DMSO ∼ ClC6F4H-DMSO > C6F5Cl-DMSO, implying that the hydrogen-bond is stronger than the halogen-bond in the systems and, when interacting with ClC6F4H, DMSO favors the formation of a hydrogen-bond rather than a halogen-bond. Second, attractive energy dependences on 1/r(3.3) and 1/r(3.1) were established for the hydrogen-bond and halogen-bond, respectively. Third, upon the formation of a hydrogen-bond and halogen-bond, there is charge transfer from DMSO to the hydrogen-bond and halogen-bond donor. The back-group CH3 was found to contribute positively to the stabilization of the complexes. Fourth, an isosbestic point was detected in the ν(C-Cl) absorption band in the C6F5Cl-DMSO-d6 system, indicating that there exist only two dominating forms of C6F5Cl in binary mixtures; the non-complexed and halogen-bond-complexed forms. The presence of stable complexes in C6F5H-DMSO and ClC6F4H-DMSO systems are evidenced by the appearance of new peaks with fixed positions.

  11. Halogenated fullerenes as precursors for the synthesis of functional derivatives of C60 and C70 (United States)

    Khakina, E. A.; Troshin, P. A.


    The review is devoted to the use of halogenated fullerenes as precursors for the synthesis of functional derivatives of fullerenes C60 and C70. Data on chemical transformations of halogenated fullerenes C60Cl6, C70Cl8, C70Cl10, C60F18, C60F36 and C60F48 are described systematically, with the focus being placed on the preparation of compounds with valuable properties. In particular, new approaches to the synthesis of water-soluble fullerene derivatives are considered and prospects for their practical use in biomedicine are evaluated. The bibliography includes 108 references.

  12. Natural marine halogen and sulfur emissions influence air quality in the coastal megacity of Los Angeles (United States)

    Muñiz-Unamunzaga, María; Borge, Rafael; Sarwar, Golam; Gantt, Brett; de la Paz, David; Cuevas, Carlos A.; Saiz-Lopez, Alfonso


    Natural halogen and sulfur compounds, emitted from the ocean, influence the oxidizing capacity of the marine atmosphere; however, their impact on the air quality of coastal cities is currently unknown. In this work, a set of high-resolution simulations were performed using the Community Multiscale Air Quality (CMAQ) regional model, to assess the impact of ocean emissions and combined chemical processes of halogens (iodine, bromine and chlorine) and DMS on air quality levels of Los Angeles and South Coast Air Basin. Simulations were completed for August and September of 2006, using a horizontal grid resolution of 4 km and 35 vertical levels.

  13. Influence of halogen atoms and protonation on the photophysical properties of sulfonated porphyrins (United States)

    De Boni, L.; Monteiro, C. J. P.; Mendonça, C. R.; Zílio, S. C.; Gonçalves, P. J.


    This work employs UV/vis absorption and Z-scan techniques to investigate how the presence of one or two halogens atoms and the macrocycle protonation affect the photophysical characteristics of sulfonated porphyrins. The results are relevant to photomedicine and photonics because they show that: (i) the insertion of halogen atoms increases the intersystem crossing quantum yield, a useful feature for photodynamic therapy, (ii) the fluorescence observed in fluorinated porphyrins shows desired characteristics for theranostics, which combine therapy and diagnostics in the same platform, and (iii) the protonation enhances the excited-state absorption in the visible region, an important feature for optical limiting.

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

    DEFF Research Database (Denmark)

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


    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...... results are supported by ab initio calculations at the B3LYP-PCM/6-311++G(d,p) + LanL2DZ∗ level....

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

    Directory of Open Access Journals (Sweden)

    Janet E. Del Bene


    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.

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

    Directory of Open Access Journals (Sweden)

    H. Biester


    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.

  17. SI-traceable standards for atmospheric monitoring of halogenated gases (United States)

    Guillevic, Myriam; Wyss, Simon A.; Pascale, Céline; Vollmer, Martin K.; Niederhauser, Bernhard; Reimann, Stefan


    To support atmospheric monitoring of greenhouse gases and in particular halogenated gases, we have developed a method to produce reference gas mixtures at nmol/mol (ppb) to pmol/mol levels (ppt). This method is dynamic and SI-traceable. This work is conducted in the framework of the EMRP projects HIGHGAS and KEY-VOCs as well as METAS' AtmoChemECV project. The method has been already applied to HFC-125 (pentafluoroethane, widely used in air conditioners), HFC-1234yf (2,3,3,3-tetrafluoropropene, a car air conditioner fluid of growing importance) and SF6 (insulant in electric switch-gears). It is currently being extended to HCFC-132b and CFC-13. It is particularly suitable for gas species and/or concentration ranges that are not stable in cylinders and it can be applied to a large variety of molecules related to air pollution and climate change (e.g., NO2, volatile organic compounds such as BTEX, NH3, water vapour at ppm level, CFCs, HCFCs, HFCs). The expanded uncertainty is less than 3 % (95 % confidence interval or k=2). The generation process is composed of four successive steps. In the first step the matrix gas, nitrogen or synthetic air is purified. Then this matrix gas is spiked with the pure substance, using a permeation device which contains a few grams of the pure substance (e.g., HFC-125) in the liquid form and loses it linearly over time by permeation through a membrane. This mass loss is precisely calibrated in our lab in Bern, using a magnetic suspension balance. In a third step the desired concentration is reached by dilution of the high concentration mixture exiting the permeation chamber with a chosen flow of the matrix gas in one or two subsequent dilution steps. All flows are piloted by mass flow controllers. All parts in contact with the gas mixture - including the balance - are passivated using coated surfaces, to reduce adsorption/desorption processes as much as possible. In the last step the mixture can be i) directly used to calibrate an

  18. Curable liquid hydrocarbon prepolymers containing hydroxyl groups and process for producing same (United States)

    Rhein, R. A.; Ingham, J. D. (Inventor)


    Production of hydroxyl containing curable liquid hydrocarbon prepolymers by ozonizing a high molecular weight saturated hydrocarbon polymer such as polyisobutylene or ethylene propylene rubber is discussed. The ozonized material is reduced using reducing agents, preferably diisobutyl aluminum hydride, to form the hydroxyl containing liquid prepolymers having a substantially lower molecular weight than the parent polymer. The resulting curable liquid hydroxyl containing prepolymers can be poured into a mold and readily cured, with reactants such as toluene diisocyanate, to produce highly stable elastomers having a variety of uses such as binders for solid propellants.

  19. Biodegradation of petroleum hydrocarbons in hypersaline environments

    Directory of Open Access Journals (Sweden)

    Luiz Fernando Martins


    Full Text Available Literature on hydrocarbon degradation in extreme hypersaline media presents studies that point to a negative effect of salinity increase on hydrocarbonoclastic activity, while several others report an opposite tendency. Based on information available in the literature, we present a discussion on the reasons that justify these contrary results. Despite the fact that microbial ability to metabolize hydrocarbons is found in extreme hypersaline media, indeed some factors are critical for the occurrence of hydrocarbon degradation in such environments. How these factors affect hydrocarbon degradation and their implications for the assessment of hydrocarbon biodegradation in hypersaline environments are presented in this review.

  20. Syngas Upgrading to Hydrocarbon Fuels Technology Pathway

    Energy Technology Data Exchange (ETDEWEB)

    Talmadge, M.; Biddy, M.; Dutta, A.; Jones, S.; Meyer, A.


    This technology pathway case investigates the upgrading of woody biomass derived synthesis gas (syngas) to hydrocarbon biofuels. While this specific discussion focuses on the conversion of syngas via a methanol intermediate to hydrocarbon blendstocks, there are a number of alternative conversion routes for production of hydrocarbons through a wide array of intermediates from syngas. Future work will also consider the variations to this pathway to determine the most economically viable and lowest risk conversion route. Technical barriers and key research needs have been identified that should be pursued for the syngas-to-hydrocarbon pathway to be competitive with petroleum-derived gasoline-, diesel- and jet-range hydrocarbon blendstocks.

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

    Directory of Open Access Journals (Sweden)

    Jin-Feng Li


    Full Text Available The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M2(CN5]−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(CN5]−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.


    Directory of Open Access Journals (Sweden)

    E. V. Ostrovskaya


    Full Text Available Aim. The paper is aimed to estimate the current level of hydrocarbon pollution of the marine environment in the North-Western part of the Caspian Sea.Methods. The paper discusses the results of three-year studies conducted in 2012-2014 within the framework of Roshydromet’s Programme of monitoring of transboundary waters of the Caspian Sea. Spatial distribution of concentrations of hydrocarbons (total and polyaromatic in water and bottom sediments of the area was analysed. Concentrations of total hydrocarbons were determined by means of infrared spectrometry and PAHs – of gas chromatography with mass spectrometry.Results. The range of the total hydrocarbons in the area’s water is from slight traces to 240 µg/l, in sediments – from traces to 114 µg/g (dry weight. Total concentrations of PAHs in water varied from traces to 321 ng/l, in sediments – from traces to 699 ng/g (dry weight. For the source identification, data of satellite monitoring of the area were used. The data showed increasing input of hydrocarbons coming into the marine environment with discharges from vessels.Conclusion. The results of these studies are compared to those of previous research and show that the level of hydrocarbons in the area is typical for slightly polluted areas.

  3. Total petroleum hydrocarbons in edible marine biota from Northern Persian Gulf. (United States)

    Nozar, Seyedeh Laili Mohebbi; Pauzi, Mohamad Zakaria; Salarpouri, Ali; Daghooghi, Behnam; Salimizadeh, Maryam


    To provide a baseline information for consumer's health, distribution of total petroleum hydrocarbons in 18 edible marine biota species from northern Persian Gulf was evaluated. The samples were purchased from fish market of Hormozgan Province, South of Iran. Marine biota samples included different species with various feeding habits and were analyzed based on ultraviolet florescence spectroscopy. Petroleum hydrocarbons showed narrow variation, ranging from 0.67 to 3.36 μg/g dry weight. The maximum value was observed in silver pomfret. Anchovy and silver pomfret with the highest content of petroleum hydrocarbons were known as good indicator for oil pollution in the studied area. From public health point of view, the detected concentrations for total petroleum hydrocarbons were lower than hazardous guidelines. The results were recorded as background data and information in the studied area; the continuous monitoring of pollutants is recommended, according to the rapid extension of industrial and oily activities in Hormozgan Province.

  4. Role of methylotrophs in the degradation of hydrocarbons during the Deepwater Horizon oil spill (United States)

    Gutierrez, Tony; Aitken, Michael D


    The role of methylotrophic bacteria in the fate of the oil and gas released into the Gulf of Mexico during the Deepwater Horizon oil spill has been controversial, particularly in relation to whether organisms such as Methylophaga had contributed to the consumption of methane. Whereas methanotrophy remains unqualified in these organisms, recent work by our group using DNA-based stable-isotope probing coupled with cultivation-based methods has uncovered hydrocarbon-degrading Methylophaga. Recent findings have also shown that methylotrophs, including Methylophaga, were in a heightened state of metabolic activity within oil plume waters during the active phase of the spill. Taken collectively, these findings suggest that members of this group may have participated in the degradation of high-molecular-weight hydrocarbons in plume waters. The discovery of hydrocarbon-degrading Methylophaga also highlights the importance of considering these organisms in playing a role to the fate of oil hydrocarbons at oil-impacted sites. PMID:24865772

  5. Two-step processing of oil shale to linear hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Eliseev, O.L.; Ryzhov, A.N.; Latypova, D.Zh.; Lapidus, A.L. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Institute of Organic Chemistry; Avakyan, T.A. [Gubkin Russian State University of Oil and Gas, Moscow (Russian Federation)


    Thermal and catalytic steam reforming of oil shale mined from Leningrad and Kashpir deposits was studied. Experiments were performed in fixed bed reactor by varying temperature and steam flow rate. Data obtained were approximated by empirical formulas containing some parameters calculated by least-squares method. Thus predicting amount of hydrogen, carbon monoxide and methane in producer gas is possible for given particular kind of oil shale, temperature and steam flow rate. Adding Ni catalyst enriches hydrogen and depletes CO content in effluent gas at low gasification temperatures. Modeling gas simulating steam reforming gases (H{sub 2}, CO, CO{sub 2}, and N{sub 2} mixture) was tested in hydrocarbon synthesis over Co-containing supported catalyst. Selectivity of CO conversion into C{sub 5+} hydrocarbons reaches 84% while selectivity to methane is 7%. Molecular weight distribution of synthesized alkanes obeys Anderson-Schulz-Flory equation and chain growth probability 0.84. (orig.)

  6. Chemoenzymatic halogenation of phenols by using the haloperoxidase from Curvularia inaequalis

    NARCIS (Netherlands)

    Fernández-Fueyo, E.; van Wingerden, M.; Renirie, R.; Wever, R.; Ni, Y.; Holtmann, D.; Hollmann, F.


    The vanadium-​dependent chloroperoxidase from Curvularia inaequalis is an efficient biocatalyst for the in situ generation of hypohalous acids and subsequent electrophilic oxidn.​/halogenation reactions. Esp., its superb activity and stability under operational conditions make it an attractive

  7. Electrophilic Halogenation of closo-1,2-C2B8H10. (United States)

    Bakardjiev, Mario; Růžička, Aleš; Růžičková, Zdeňka; Holub, Josef; Tok, Oleg L; Štíbr, Bohumil


    Initial studies on electrophilic halogenation of the dicarbaborane closo-1,2-C2B8H10 (1) have been carried out to reveal that the substitution takes place at B7 and B10 vertexes, which are the most removed from the CH positions. The course of the halogenation is strongly dependent on the nature of the halogenation agent and reaction conditions. Individual reactions led to the isolation of the monosubstituted compounds 1,2-C2B8H9-10-X (2) (where X = F, I) and 1,2-C2B8H9-7-X (3) (where X = Cl, I). Disubstituted carboranes 1,2-C2B8H8-7,10-X2 (4) (where X = Cl, Br, I) were obtained under more forcing conditions. Individual halo derivatives were characterized by mass spectrometry and high-field NMR ((11)B, (1)H,(13)C) spectroscopy combined with two-dimensional [(11)B-(11)B]-COSY, (1)H{(11)B(selective)}, and [(11)B-(1)H]-correlation NMR techniques. All of the derivatives bearing a halogen substituent in the B10 position exhibit a remarkable antipodal (13)C and (1)H NMR shielding at the CH1 vertex, increasing in the order H < I < Br < Cl < F. The structures of 1,2-C2B8H8-7,10-X2 derivatives (where X = Cl, I, 4b,d) were established by X-ray diffraction analyses.

  8. Large area inkjet printing for organic solar cells and OLEDs using non-halogenated ink formulations

    NARCIS (Netherlands)

    Eggenhuisen, T.M.; Coenen, M.J.J.; Staats, T.W.L.; Gorter, H.; Sweelssen, J.; Groen, P.


    Transferring lab-scale processes of organic electronics to large area roll-to-roll production requires the use of up-scalable deposition techniques. Furthermore, industrial production demands the omission of halogenated and other harmful solvents. Here we discuss the solution processing of organic

  9. Phosphorylated lignin as a halogen-free flame retardant additive for epoxy composites (United States)

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


    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...

  10. Cytotoxicity and oxidative stress caused by dental adhesive systems cured with halogen and LED lights. (United States)

    Spagnuolo, Gianrico; Annunziata, Marco; Rengo, Sandro


    The aim of the present study was to investigate the cytotoxicity of two "one bottle" adhesive systems after polymerization with a conventional halogen or a light emitting diode (LED) lamp. We hypothesized that different polymerization sources might enhance the intracellular production of reactive oxygen species (ROS), leading to reduced cell survival. Two "one bottle" adhesive systems (Optibond Solo and Scotchbond One) were cured with a commercial halogen (Optilux 500) and an LED source (Elipar Freelight, 3 M). The specimens were extracted for 24 h in complete cell culture medium or in phosphate-buffered saline (PBS). Endothelial cells (ECV 304) were exposed to the extracts for 24 h and survival rates were evaluated by the MTT assay. Then, ROS generation was monitored by the oxidation-sensitive fluorescent probe 2'7'-dichlorofluorescin diacetate (DCFH-DA). Extracts from all materials except for Optibond Solo polymerized with the halogen lamp were rated significantly cytotoxic. Scotchbond One cured with LED was the most toxic material, which reduced cell survival to about 23% compared with control cultures. Significantly higher amounts of ROS were produced in cell cultures treated with adhesives polymerized with the LED lamp compared with the materials cured with the commercial halogen light source. We demonstrated that the production of intracellular ROS by extracts of the adhesive systems depended on the light sources used for curing of the materials. These results suggested a possible link between ROS production and cytotoxic activity.

  11. Legacy and alternative halogenated flame retardants in human milk in Europe : Implications for children's health

    NARCIS (Netherlands)

    Čechová, Eliška; Vojta, Šimon; Kukučka, Petr; Kočan, Anton; Trnovec, Tomáš; Murínová, Ľubica Palkovičová; de Cock, Marijke; van de Bor, Margot; Askevold, Joakim; Eggesbø, Merete; Scheringer, Martin


    In this study, 10 polybrominated diphenyl ethers (PBDEs) and 19 alternative halogenated flame retardants (AFRs) were determined in > 450 human milk samples across three European countries, representing northern, western and eastern Europe. This study provides first insights into the occurrence of

  12. Covalency in Resonance-Assisted Halogen Bonds Demonstrated with Cooperativity in N-Halo-Guanine Quartets

    NARCIS (Netherlands)

    Wolters, L.P.; Smits, N.W.G.; Fonseca Guerra, C.


    Halogen bonds are shown to possess the same characteristics as hydrogen bonds: charge transfer, resonance assistance and cooperativity. This follows from the computational analyses of the structure and bonding in N-halo-base pairs and quartets. The objective was to achieve an understanding of the

  13. Acetalization of 2-Hydroxybenzaldehyde mechanism using halogen acid catalysts based on ab initio methods (United States)

    Yusuf, Muhammad; Roza, Destria; Nasution, Ahmad Kamil


    The computational calculation was performed on the acetalization of 2-hydroxybenzaldehyde by using ab initio method. Ab initio method is derived directly from theoretical principles with no inclusion of experimental data and this is an approximate quantum mechanical calculation. The aim of this research was to studies the acetalization of 2-hydroxybenzaldehyde mechanism using halogen acid catalysts. Computational calculation which was applied on the acetalization of 2-hydroxybenzaldehyde using halogen acid catalysts provided possible reaction steps. The first step was formation of a labile hemiacetal because it is essentially tetrahedral intermediates containing a leaving group. The second step was formation of a stable acetal. The results of computational calculation of acetalization of 2-hydroxybenzaldehyde provided possible energy change in the each step of the reaction process. A labile hemiacetal showed higher energy (481.04 kJ/mol) than 2-hydroxybenzaldehyde dimethyl acetal (65.32 kJ/mol) and 2-hydroxybenzaldehyde (0 kJ/mol) due to its instability. In general, acetalization of 2-hydroxybenzaldehyde reaction is a reversible reaction. The effect of Lewis acidity on halogen acid catalysts was also studied in this research. Based on the Mulliken charge on the H atom, it is found that HF has the highest Lewis acidity compared to other halogen acids with order HF> HCl> HBr> HI. As a result, HF was the efficient catalysts for acetalization of 2-Hydroxybenzaldehyde.

  14. Analysis of an unusual hetero-halogen bonded trimer using charge ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 128; Issue 10. Analysis of an unusual hetero-halogen bonded trimer using charge density analysis: A case of concerted type I Br· · · Br and type II Br· · · Cl interactions. MYSORE S PAVAN TAYUR N GURU ROW. Regular Article Volume 128 Issue 10 October 2016 pp ...

  15. Page 1 36 SIR. C. V. RAMAN - * * * * º the the metal and halogen ...

    Indian Academy of Sciences (India)

    the metal and halogen atoms differ greatly in their Sizºº. It is low when -. The former situation IS two sets of atoms are of comparable dimensions. -. * - * €SČ exemplified by the lithium halides and the ... ing unit is essential for any particular mode of vibration to exhibit activity. The magnitude of the displacement of charge is ...

  16. Synthesis and photophysical properties of halogenated derivatives of (dibenzoylmethanato)boron difluoride (United States)

    Kononevich, Yuriy N.; Surin, Nikolay M.; Sazhnikov, Viacheslav A.; Svidchenko, Evgeniya A.; Aristarkhov, Vladimir M.; Safonov, Andrei A.; Bagaturyants, Alexander A.; Alfimov, Mikhail V.; Muzafarov, Aziz M.


    A series of (dibenzoylmethanato)boron difluoride (BF2DBM) derivatives with a halogen atom in one of the phenyl rings at the para-position were synthesized and used to elucidate the effects of changing the attached halogen atom on the photophysical properties of BF2DBM. The room-temperature absorption and fluorescence maxima of fluoro-, chloro-, bromo- and iodo-substituted derivatives of BF2DBM in THF are red-shifted by about 2-10 nm relative to the corresponding peaks of the parent BF2DBM. The fluorescence quantum yields of the halogenated BF2DBMs (except the iodinated derivative) are larger than that of the unsubstituted BF2DBM. All the synthesized compounds are able to form fluorescent exciplexes with benzene and toluene (emission maxima at λem = 433 and 445 nm, respectively). The conformational structure and electronic spectral properties of halogenated BF2DBMs have been modeled by DFT/TDDFT calculations at the PBE0/SVP level of theory. The structure and fluorescence spectra of exciplexes were calculated using the CIS method with empirical dispersion correction.

  17. 40 CFR 721.275 - Halogenated-N-(2-propenyl)-N-(substituted phenyl) acetamide. (United States)


    ... AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant... identified generically as halogenated-N-(2-propenyl)-N-(substituted phenyl) acetamide (P-83-1085) is subject... section except as modified by this paragraph. (1) Recordkeeping. The following recordkeeping requirements...

  18. Free Radical Halogenation, Selectivity, and Thermodynamics: The Polanyi Principle and Hammond's Postulate (United States)

    Scala, Alfred A.


    The underlying ideas of the Polanyi principle and Hammond's postulate in relation to the simple free halogenation reactions and their selectivity and thermodynamics is presented. The results indicate that the chlorine atom exhibits a slightly less selectivity in the liquid phase as compared to in the gas phase.

  19. Halogen-free ionic liquids and their utilization as cellulose solvents (United States)

    Gräsvik, John; Eliasson, Bertil; Mikkola, Jyri-Pekka


    This work demonstrates a novel synthesis route to halogen-free ionic liquids. A one-pot synthetic reaction route avoiding the use of toxic and high-energetic alkyl halides was developed to reduce the environmental impact of the synthesis process of ionic liquids. However, the elimination of halogens and alkyl halides in the preparation of ionic liquids is not just an environmental issue: the aforementioned species are also among the most common and persistent contaminants in today's Ionic Liquids (ILs). Thus, this paper introduces a range of quaternized nitrogen based ionic liquids, including both aromatic and non-aromatic components, all prepared without alkyl halides in any step of the process. Moreover, bio-renewable precursors such as (bio-)alcohols and carboxylic acids were employed as anion sources and alkylation media, thus avoiding halogen contamination or halogen-containing anions. The IL's prepared were designed to dissolve cellulose, some of which was included in a cellulose dissolution study using a sulphite cellulose from the company Domsjö.

  20. Rapid and reliable determination of the halogenating peroxidase activity in blood samples. (United States)

    Flemmig, Jörg; Schwarz, Pauline; Bäcker, Ingo; Leichsenring, Anna; Lange, Franziska; Arnhold, Jürgen


    By combining easy and fast leukocyte enrichment with aminophenyl-fluorescein (APF) staining we developed a method to quickly and specifically address the halogenating activity of the immunological relevant blood heme peroxidases myeloperoxidase and eosinophil peroxidase, respectively. For leukocyte enrichment a two-fold hypotonic lysis procedure of the blood with Millipore water was chosen which represents a cheap, fast and reliable method to diminish the amount of erythrocytes in the samples. This procedure is shown to be suitable both to human and murine blood micro-samples, making it also applicable to small animal experiments with recurring blood sampling. As all types of leukocytes are kept in the sample during the preparation, they can be analysed separately after discrimination during the flow cytometry analysis. This also holds for all heme peroxidase-containing cells, namely neutrophils, eosinophils and monocytes. Moreover additional parameters (e.g. antibody staining) can be combined with the heme peroxidase activity determination to gain additional information about the different immune cell types. Based on previous results we applied APF for specifically addressing the halogenating activity of leukocyte peroxidases in blood samples. This dye is selectively oxidized by the MPO and EPO halogenation products hypochlorous and hypobromous acid. This approach may provide a suitable tool to gain more insights into the immune-physiological role of the halogenating activity of heme peroxidases. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. About the nature of halogen bond interaction under the spatial confinement (United States)

    Roztoczyńska, Agnieszka; Lipkowski, Paweł; Kozłowska, Justyna; Bartkowiak, Wojciech


    Nowadays, much attention is put toward the description of noncovalent complexes exposed to the high pressure or embedded in confining environments. Such conditions may strongly modify the physical and chemical properties of molecular systems. This study focuses on the theoretical description of the confinement induced changes in geometry and energetic parameters of the halogen bonded FCl⋯CNF complex. A model analytical potential is applied to render the effect of orbital compression. In order to analyze the nature of halogen bond interaction, in the presence of spatial confinement, the supermolecular approach together with the symmetry-adapted perturbation theory is used. Furthermore, a thorough analysis of topological parameters, characterizing the halogen bond upon orbital compression, is performed within the quantum theory of atoms in molecules. The calculations are carried out using the ωB97x and CCSD(T) methods in connection with the aug-cc-pVTZ basis set. Among others, the obtained results indicate that the spatial confinement not only modifies the nature of halogen bond interaction but also induces the appearance of a completely new form of the studied FCl⋯CNF system.

  2. 21 CFR 700.15 - Use of certain halogenated salicylanilides as ingredients in cosmetic products. (United States)


    ... ingredients in cosmetic products. 700.15 Section 700.15 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.15 Use of certain halogenated salicylanilides as ingredients in cosmetic products. (a...

  3. New Route to Synthesize Surface Organometallic Complexes (SOMC): An Approach by Alkylating Halogenated Surface Organometallic Fragments

    KAUST Repository

    Hamieh, Ali Imad


    The aim of this thesis is to explore new simpler and efficient routes for the preparation of surface organometallic complexes (SOMC) for the transformation of small organic molecules to valuable products. The key element in this new route relies on surface alkylation of various halogenated surface coordination complexes or organometallic fragments (SOMF).

  4. Molecular mechanism of metal-independent decomposition of lipid hydroperoxide 13-HPODE by halogenated quinoid carcinogens. (United States)

    Qin, Hao; Huang, Chun-Hua; Mao, Li; Xia, Hai-Ying; Kalyanaraman, Balaraman; Shao, Jie; Shan, Guo-Qiang; Zhu, Ben-Zhan


    Halogenated quinones are a class of carcinogenic intermediates and newly identified chlorination disinfection by-products in drinking water. 13-Hydroperoxy-9,11-octadecadienoic acid (13-HPODE) is the most extensively studied endogenous lipid hydroperoxide. Although it is well known that the decomposition of 13-HPODE can be catalyzed by transition metal ions, it is not clear whether halogenated quinones could enhance its decomposition independent of metal ions and, if so, what the unique characteristics and similarities are. Here we show that 2,5-dichloro-1,4-benzoquinone (DCBQ) could markedly enhance the decomposition of 13-HPODE and formation of reactive lipid alkyl radicals such as pentyl and 7-carboxyheptyl radicals, and the genotoxic 4-hydroxy-2-nonenal (HNE), through the complementary application of ESR spin trapping, HPLC-MS, and GC-MS methods. Interestingly, two chloroquinone-lipid alkoxyl conjugates were also detected and identified from the reaction between DCBQ and 13-HPODE. Analogous results were observed with other halogenated quinones. This represents the first report that halogenated quinoid carcinogens can enhance the decomposition of the endogenous lipid hydroperoxide 13-HPODE and formation of reactive lipid alkyl radicals and genotoxic HNE via a novel metal-independent nucleophilic substitution coupled with homolytic decomposition mechanism, which may partly explain their potential genotoxicity and carcinogenicity. Copyright © 2013 Elsevier Inc. All rights reserved.

  5. Performance analysis of photoresistor and phototransistor for automotive’s halogen and xenon bulbs light output (United States)

    Rammohan, A.; Kumar, C. Ramesh


    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.

  6. Comparing colour discrimination and proofreading performance under compact fluorescent and halogen lamp lighting. (United States)

    Mayr, Susanne; Köpper, Maja; Buchner, Axel


    Legislation in many countries has banned inefficient household lighting. Consequently, classic incandescent lamps have to be replaced by more efficient alternatives such as halogen and compact fluorescent lamps (CFL). Alternatives differ in their spectral power distributions, implying colour-rendering differences. Participants performed a colour discrimination task - the Farnsworth-Munsell 100 Hue Test--and a proofreading task under CFL or halogen lighting of comparable correlated colour temperatures at low (70 lx) or high (800 lx) illuminance. Illuminance positively affected colour discrimination and proofreading performance, whereas the light source was only relevant for colour discrimination. Discrimination was impaired with CFL lighting. There were no differences between light sources in terms of self-reported physical discomfort and mood state, but the majority of the participants correctly judged halogen lighting to be more appropriate for discriminating colours. The findings hint at the colour-rendering deficiencies associated with energy-efficient CFLs. In order to compare performance under energy-efficient alternatives of classic incandescent lighting, colour discrimination and proofreading performance was compared under CFL and halogen lighting. Colour discrimination was impaired under CFLs, which hints at the practical drawbacks associated with the reduced colour-rendering properties of energy-efficient CFLs.

  7. Hydrocarbons in the suspended matter and the bottom sediments in different regions of the Black Sea Russian sector

    Directory of Open Access Journals (Sweden)

    I. A. Nemirovskaya


    Full Text Available Content and composition of hydrocarbons (mainly the aliphatic ones in the suspended matter and the bottom sediments in the Gelendzhik Bay, the Big Sochi water area, the Feodosiya Bay and the Black Sea central part are defined and compared with the total organic carbon and chlorophyll a contents. It is shown that the aliphatic hydrocarbon concentrations exceeding the background ones are found only in the coastal zone. Advancing to the pelagic zone is accompanied by sharp decrease of their concentrations. Petroleum and pyrogenic hydrocarbons are mainly manifested in the polycyclic aromatic hydrocarbons composition. Influence of construction of the Olympic facilities upon distribution of hydrocarbons in the Big Sochi water area was of short duration, and already by 2015 the aliphatic hydrocarbons concentration decreased, on the average, up to 24 µg/l in the surface waters, and up to 18 µg/g – in the bottom sediments. Accumulation of hydrocarbons took place in bottom sediments, where their concentrations exceeded the background ones in terms of dry weight. In the Gelendzhik Bay, their content reached 252 μg/g, and in the composition of organic carbon (Corg > 1 %, which may indicate the contamination of sediments with oil products. In the Feodosiya Bay their part in the composition of Corg did not exceed 0.73 % and was 0.35 % on average. Natural alkanes dominated in the composition of aliphatic hydrocarbons. The bottom sediments are characterized by the predominance of odd high-molecular terrigenous alkanes. The content of polycyclic aromatic hydrocarbons in the studied sediments was rather low: up to 31 ng/g in the Gelendzhik Bay, up to 348 ng/g in the Feodosiya Bay. These concentrations according to the EPA classification are considered background, or minor petroleum hydrocarbons increase the level of aliphatic hydrocarbons in water and sediments, thus creating a modern hydrocarbon background.

  8. Hydrocarbon Rocket Technology Impact Forecasting (United States)

    Stuber, Eric; Prasadh, Nishant; Edwards, Stephen; Mavris, Dimitri N.


    Ever since the Apollo program ended, the development of launch propulsion systems in the US has fallen drastically, with only two new booster engine developments, the SSME and the RS-68, occurring in the past few decades.1 In recent years, however, there has been an increased interest in pursuing more effective launch propulsion technologies in the U.S., exemplified by the NASA Office of the Chief Technologist s inclusion of Launch Propulsion Systems as the first technological area in the Space Technology Roadmaps2. One area of particular interest to both government agencies and commercial entities has been the development of hydrocarbon engines; NASA and the Air Force Research Lab3 have expressed interest in the use of hydrocarbon fuels for their respective SLS Booster and Reusable Booster System concepts, and two major commercially-developed launch vehicles SpaceX s Falcon 9 and Orbital Sciences Antares feature engines that use RP-1 kerosene fuel. Compared to engines powered by liquid hydrogen, hydrocarbon-fueled engines have a greater propellant density (usually resulting in a lighter overall engine), produce greater propulsive force, possess easier fuel handling and loading, and for reusable vehicle concepts can provide a shorter turnaround time between launches. These benefits suggest that a hydrocarbon-fueled launch vehicle would allow for a cheap and frequent means of access to space.1 However, the time and money required for the development of a new engine still presents a major challenge. Long and costly design, development, testing and evaluation (DDT&E) programs underscore the importance of identifying critical technologies and prioritizing investment efforts. Trade studies must be performed on engine concepts examining the affordability, operability, and reliability of each concept, and quantifying the impacts of proposed technologies. These studies can be performed through use of the Technology Impact Forecasting (TIF) method. The Technology Impact

  9. Mediterranean hydrocarbons pollution from Landsat


    Wald, Lucien; Monget, Jean-Marie; Albuisson, Michel


    Previous studies have shown that oil spills have been viewed by Landsat . The setection of oil is mainly due to the variations of reflectance between the sea and the oil spill. This result is used in the framework of the European Project "ARCHIMEDES", lead by the Joint Research Center (Ispra, Italy), which purpose is the study of the pollution in the Mediterranean Sea. 800 Landsat images obtained from 1972 to 1975 were examined. The cumulative area covered by the hydrocarbons spread each year...

  10. Deep desulfurization of hydrocarbon fuels (United States)

    Song, Chunshan [State College, PA; Ma, Xiaoliang [State College, PA; Sprague, Michael J [Calgary, CA; Subramani, Velu [State College, PA


    The invention relates to processes for reducing the sulfur content in hydrocarbon fuels such as gasoline, diesel fuel and jet fuel. The invention provides a method and materials for producing ultra low sulfur content transportation fuels for motor vehicles as well as for applications such as fuel cells. The materials and method of the invention may be used at ambient or elevated temperatures and at ambient or elevated pressures without the need for hydrogen.

  11. Coupling of HOx, NOx and halogen chemistry in the antarctic boundary layer

    Directory of Open Access Journals (Sweden)

    R. A. Salmon


    Full Text Available A modelling study of radical chemistry in the coastal Antarctic boundary layer, based upon observations performed in the course of the CHABLIS (Chemistry of the Antarctic Boundary Layer and the Interface with Snow campaign at Halley Research Station in coastal Antarctica during the austral summer 2004/2005, is described: a detailed zero-dimensional photochemical box model was used, employing inorganic and organic reaction schemes drawn from the Master Chemical Mechanism, with additional halogen (iodine and bromine reactions added. The model was constrained to observations of long-lived chemical species, measured photolysis frequencies and meteorological parameters, and the simulated levels of HOx, NOx and XO compared with those observed. The model was able to replicate the mean levels and diurnal variation in the halogen oxides IO and BrO, and to reproduce NOx levels and speciation very well. The NOx source term implemented compared well with that directly measured in the course of the CHABLIS experiments. The model systematically overestimated OH and HO2 levels, likely a consequence of the combined effects of (a estimated physical parameters and (b uncertainties within the halogen, particularly iodine, chemical scheme. The principal sources of HOx radicals were the photolysis and bromine-initiated oxidation of HCHO, together with O(1D + H2O. The main sinks for HOx were peroxy radical self- and cross-reactions, with the sum of all halogen-mediated HOx loss processes accounting for 40% of the total sink. Reactions with the halogen monoxides dominated CH3O2-HO2-OH interconversion, with associated local chemical ozone destruction in place of the ozone production which is associated with radical cycling driven by the analogous NO reactions. The analysis highlights the need for observations of physical parameters such as aerosol surface area and boundary layer structure to constrain such calculations, and the dependence of simulated radical levels

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


    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 (TyrB26) 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-TyrB26]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 (TyrB16, PheB24, PheB25, 3-I-TyrB26, 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-TyrB26]insulin analog (determined as an R6 zinc hexamer). Given that residues B24-B30 detach from the core on receptor binding, the environment of 3-I-TyrB26 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-TyrB26 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.

  13. LED vs halogen light-curing of adhesive-precoated brackets. (United States)

    Mirabella, Davide; Spena, Raffaele; Scognamiglio, Giovanni; Luca, Lombardo; Gracco, Antonio; Siciliani, Giuseppe


    To test the hypothesis that bonding with a blue light-emitting diode (LED) curing unit produces no more failures in adhesive-precoated (APC) orthodontic brackets than bonding carried out by a conventional halogen lamp. Sixty-five patients were selected for this randomized clinical trial, in which a total of 1152 stainless steel APC brackets were employed. In order to carry out a valid comparison of the bracket failure rate following use of each type of curing unit, each patient's mouth was divided into four quadrants. In 34 of the randomly selected patients, designated group A, the APC brackets of the right maxillary and left mandibular quadrants were bonded using a halogen light, while the remaining quadrants were treated with an LED curing unit. In the other 31 patients, designated group B, halogen light was used to cure the left maxillary and right mandibular quadrants, whereas the APC brackets in the remaining quadrants were bonded using an LED dental curing light. The bonding date, the type of light used for curing, and the date of any bracket failures over a mean period of 8.9 months were recorded for each bracket and, subsequently, the chi-square test, the Yates-corrected chi-square test, the Fisher exact test, Kaplan-Meier survival estimates, and the log-rank test were employed in statistical analyses of the results. No statistically significant difference in bond failure rate was found between APC brackets bonded with the halogen light-curing unit and those cured with LED light. However, significantly fewer bonding failures were noted in the maxillary arch (1.67%) than in the mandibular arch (4.35%) after each light-curing technique. The hypothesis cannot be rejected since use of an LED curing unit produces similar APC bracket failure rates to use of conventional halogen light, with the advantage of a far shorter curing time (10 seconds).

  14. Treatment of hydrocarbon contamination under flow through conditions by using magnetite catalyzed chemical oxidation. (United States)

    Usman, M; Faure, P; Lorgeoux, C; Ruby, C; Hanna, K


    Soil pollution by hydrocarbons (aromatic and aliphatic hydrocarbons) is a major environmental issue. Various treatments have been used to remove them from contaminated soils. In our previous studies, the ability of magnetite has been successfully explored to catalyze chemical oxidation for hydrocarbon remediation in batch slurry system. In the present laboratory study, column experiments were performed to evaluate the efficiency of magnetite catalyzed Fenton-like (FL) and activated persulfate (AP) oxidation for hydrocarbon degradation. Flow-through column experiments are intended to provide a better representation of field conditions. Organic extracts isolated from three different soils (an oil-contaminated soil from petrochemical industrial site and two soils polluted by polycyclic aromatic hydrocarbon (PAH) originating from coking plant sites) were spiked on sand. After solvent evaporation, spiked sand was packed in column and was subjected to oxidation using magnetite as catalyst. Oxidant solution was injected at a flow rate of 0.1 mL min(-1) under water-saturated conditions. Organic analyses were performed by GC-mass spectrometry, GC-flame ionization detector, and micro-Fourier transform infrared spectroscopy. Significant abatement of both types of hydrocarbons (60-70 %) was achieved after chemical oxidation (FL and AP) of organic extracts. No significant by-products were formed during oxidation experiment, underscoring the complete degradation of hydrocarbons. No selective degradation was observed for FL with almost similar efficiency towards all hydrocarbons. However, AP showed less reactivity towards higher molecular weight PAHs and aromatic oxygenated compounds. Results of this study demonstrated that magnetite-catalyzed chemical oxidation can effectively degrade both aromatic and aliphatic hydrocarbons (enhanced available contaminants) under flow-through conditions.

  15. Polymorphism of the aryl-hydrocarbon receptor gene in intron 10 of human cancers. (United States)

    Rocas, M; Jakubauskiene, E; Kanopka, A


    Polychlorinated dibenzo-p-dioxins (PCDDs) and related halogenated aromatic hydrocarbons (e.g., PCDFs), often called "dioxins", are ubiquitously present environmental contaminants. Some of them, notably 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), are among the most toxic synthetic compounds known. The biological effects of dioxins are mediated via the aryl hydrocarbon receptor (AhR). Mutations in the AhR transactivation domain are linked to sensitivity to the acute lethality of TCDD. We present here a study of AhR gene polymorphism in normal and cancer human tissues affecting pre-mRNA splicing in the AhR gene-coding transactivation domain region (exon 10, intron 10, exon 11 region), previously shown to be associated with AhR dysfunction. We tested 126 pairs of normal and cancer tissue samples from liver, lung, stomach, kidney, mucous, breast, and pancreas of 49 males and 77 females (45-70 years of age). We used in vitro splicing assay, RT-PCR and sequencing methods. Our results showed that in an in vitro system it is possible to reconstitute cellular pre-mRNA splicing events. Tested cancer tissues did not contain mutations in the AhR transactivation domain region when the DNA sequences were compared with those from normal tissues. There were also no differences in AhR mRNA splice variants between normal and malignant breast tissues and no polymorphisms in the studied regions or cDNA.

  16. Polymorphism of the aryl-hydrocarbon receptor gene in intron 10 of human cancers

    Directory of Open Access Journals (Sweden)

    M. Rocas


    Full Text Available Polychlorinated dibenzo-p-dioxins (PCDDs and related halogenated aromatic hydrocarbons (e.g., PCDFs, often called "dioxins", are ubiquitously present environmental contaminants. Some of them, notably 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD, are among the most toxic synthetic compounds known. The biological effects of dioxins are mediated via the aryl hydrocarbon receptor (AhR. Mutations in the AhR transactivation domain are linked to sensitivity to the acute lethality of TCDD. We present here a study of AhR gene polymorphism in normal and cancer human tissues affecting pre-mRNA splicing in the AhR gene-coding transactivation domain region (exon 10, intron 10, exon 11 region, previously shown to be associated with AhR dysfunction. We tested 126 pairs of normal and cancer tissue samples from liver, lung, stomach, kidney, mucous, breast, and pancreas of 49 males and 77 females (45-70 years of age. We used in vitro splicing assay, RT-PCR and sequencing methods. Our results showed that in an in vitro system it is possible to reconstitute cellular pre-mRNA splicing events. Tested cancer tissues did not contain mutations in the AhR transactivation domain region when the DNA sequences were compared with those from normal tissues. There were also no differences in AhR mRNA splice variants between normal and malignant breast tissues and no polymorphisms in the studied regions or cDNA.

  17. Hydrocarbon Reserves: Abundance or Scarcity

    Energy Technology Data Exchange (ETDEWEB)



    IFP and the OAPEC jointly organize a regular international seminar dealing with world oil-related problems appearing in the news. For the first time, this seminar has been opened to oil and gas company specialists, service companies, research centers and independents. This year's theme concerns oil and gas reserves: are they abundant or are we headed towards the shortages announced by some experts? This theme is especially topical in that: oil and gas currently meet two thirds of world energy needs and almost completely dominate the transport sector; the reserves declared by the OAPEC countries account for nearly half of world reserves; the price of a barrel of oil went through the roof in 2004; world energy demand is growing fast and alternative sources of energy are far from ready to take over from oil and gas in the next few decades. Since the reserves correspond to the volume it is technically and economically viable to produce, the seminar has, of course, dealt with the technical and economic questions that arise in connection with exploration and production, but it has also considered changes in the geopolitical context. Presentations by the leading companies of the OAPEC countries and by the IFP group were completed by presentation from the International Energy Agency (IEA), the United States Geological Survey (USGS), the IHS Energy Group, Total and Gaz de France. This document gathers the transparencies of the following presentations: Hydrocarbon reserves in OAPEC members countries: current and future (M. Al-Lababidi); Non OAPEC liquid reserves and production forecasts (Y. Mathieu); World oil and gas resources and production outlook (K. Chew); Global investments in the upstream (F. Birol); Total's policy in the oil and gas sector (C. de Margerie); Gaz de France's policy in the oil and gas sector (J. Abiteboul); NOC/IOC's opportunities in OPEC countries (I. Sandrea); Relationships between companies, countries and investors: How they may

  18. Before the Bonanza: Hydrocarbons in Greenland


    Meinild, Ebbe Dam


    The issue of Greenlandic hydrocarbons gradually moved towards the centre of the creation of autonomous Greenland. Hydrocarbons in Greenland and the Greenlandic nation were co-produced in the same process. Thus, when hydrocarbons were connected to an ecological modernisation it allowed the newly formed Home Rule administration, in a joint Danish-Greenlandic effort, to adopt this, not only as a road to independence, but as something giving credibility to Greenland as a distinct society.

  19. Comparing hydrogen and hydrocarbon booster fuels (United States)

    Martin, James A.


    The present evaluation of the consequences of hydrogen and hydrocarbon fuels as the basis of launch vehicle booster rocket-stage performance notes that hydrocarbon fuels lead to lower vehicle dry mass, for low-velocity requirements, while hydrogen fuel furnishes lower dry mass. Vehicles employing both types of fuel attempt to take advantage of the low intercept and slope of hydrocarbon fuel at low velocity, and subsequently, of the slope of the hydrogen curves at higher velocities.


    Energy Technology Data Exchange (ETDEWEB)

    A.M. Azad; Chris Holt; Todd Lesousky; Scott Swartz


    The following report summarizes work conducted during the Phase I program Hydrocarbon and Sulfur Sensors for SOFC Systems under contract No. DE-FC26-02NT41576. For the SOFC application, sensors are required to monitor hydrocarbons and sulfur in order to increase the operation life of SOFC components. This report discusses the development of two such sensors, one based on thick film approach for sulfur monitoring and the second galvanic based for hydrocarbon monitoring.

  1. 40 CFR 90.316 - Hydrocarbon analyzer calibration. (United States)


    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Hydrocarbon analyzer calibration. 90... Equipment Provisions § 90.316 Hydrocarbon analyzer calibration. (a) Calibrate the FID and HFID hydrocarbon... thereafter, adjust the FID and HFID hydrocarbon analyzer for optimum hydrocarbon response as specified in...

  2. 40 CFR 89.319 - Hydrocarbon analyzer calibration. (United States)


    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Hydrocarbon analyzer calibration. 89... Equipment Provisions § 89.319 Hydrocarbon analyzer calibration. (a) The FID hydrocarbon analyzer shall... and at least annually thereafter, adjust the FID hydrocarbon analyzer for optimum hydrocarbon response...

  3. A 25-year record of polycyclic aromatic hydrocarbons in soils amended with sewage sludges

    DEFF Research Database (Denmark)

    Lichtfouse, Eric; Sappin-Didier, Valérie; Denaix, Laurence


    We studied polycyclic aromatic hydrocarbons (PAHs) in crop soils amended with 1000 tonnes dry weight of sewage sludges per 10,000 m(2) from 1974 to 1992, then after sludges addition from 1993 to 1999. The absence of variations of total PAHs levels of control soils, averaging at 123 mu g/Kg, shows...

  4. Detection of hydrocarbons in irradiated foods

    Energy Technology Data Exchange (ETDEWEB)

    Miyahara, Makoto; Maitani, Tamio [National Inst. of Health Sciences, Tokyo (Japan); Saito, Akiko; Kamimura, Tomomi; Nagasawa, Taeko [Kitasato Univ., Sagamihara, Kanagawa (Japan). School of Allied Health Sciences; Kobayashi, Yasuo; Ito, Hitoshi [Japan Atomic Energy Research Inst., Takasaki, Gunma (Japan). Takasaki Radiation Establishment


    The hydrocarbon method for the detection of irradiated foods is now recognized as the international technique. This method is based on radiolysis of fatty acids in food to give hydrocarbons. In order to expand this technique's application, ten foods (butter, cheese, chicken, pork, beef, tuna, dry shrimp, avocado, papaya, and mango) were irradiated in the range from 0.5 to 10 kGy and the hydrocarbons in them were detected. Recoveries of the hydrocarbons from most foods were acceptable (38-128%). Some hydrocarbons were found in non-irradiated foods, particularly, in butter, cheese, tuna, and shrimp. Seven irradiated foods, butter, cheese, chicken, beef, pork, tuna, dry shrimp, and avocado were detectable at their practical doses by measuring the appropriate marker hydrocarbons. In most case, marker hydrocarbon will be 1,7-hexadecadiene. However, the marker hydrocarbons produced only in irradiated foods varied from food to food; therefore, it is necessary to check a specific irradiated food for marker hydrocarbons. On the other hand, two irradiated foods (papaya and mango which were irradiated at their practical doses) were difficult to distinguish from non-irradiated foods using this method. (author)

  5. Importance of reactive halogens in the tropical marine atmosphere using WRF-chem (United States)

    Badia, Alba; Reeves, Claire E.; Baker, Alex; Volkamer, Rainer; Apel, Eric; Saiz-Lopez, Alfonso; von Glasow, Roland


    Halogen species (chlorine, bromine and iodine) are known to play an important role in the chemistry and oxidizing capacity of the troposphere, particularly in the marine boundary layer (MBL). Reactive halogens participate in catalytic reaction cycles that efficiently destroy O3, change the HOX and NOX partitioning, affect the oxidation of volatile organic compounds (VOCs) and mercury, reduce the lifetime of methane, and take part in new particle formation. Numerical models predicted that reactive halogen compounds account for 30% of O3 destruction in the MBL and 5-20% globally. Up to 34% of O3 loss in the tropical East Pacific is due to I and Br combined. Recent studies have highlighted the key role that heterogeneous chemistry plays in explaining observations of BrO and IO abundances in the tropical troposphere. The main objective of this study is to investigate the atmospheric chemistry in the tropical East Pacific with a focus on reactive halogens using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) and field data from the TORERO campaign. Our reaction mechanism in WRF-Chem is based on the MOZART mechanism and has been extended to include bromine, chlorine and iodine chemistry. Heterogeneous recycling reactions involving sea-salt aerosol and other particles have been included into the model, along with oceanic emissions of important OVOCs and halocarbons. Sea surface emissions of inorganic iodine are calculated using the parameterisation of Carpenter et al., 2013. Focusing on TORERO observations from the ships and a selected number of flights we present the tropospheric impacts of halogens (BrO, IO) in the tropospheric chemistry of relevant species (O3, OH and OVOCS). Sensitivity runs are made in order to study the impact of heterogeneous chemistry in the iodine and bromine species partitioning. A comparison between the online calculation of Very Short Lived Halocarbons (VSLH) oceanic emissions with prescribed oceanic emissions is

  6. The Role of Halogens in High-Grade Metamorphism and Anatexis (United States)

    Aranovich, L.; Safonov, O.


    We review factors controlling the distribution of the two major halogens, F and Cl, in high-grade metamorphic rocks; their compositional correlations and partitioning between minerals; experimental data on stability and phase equilibria of the halogen-bearing minerals; the influence of halogens on Fe-Mg exchange reactions; and the means of estimating concentrations/activity of halogen species concentration/ activity in the fluid phase ("chlorimetry and fluorimetry") via calculation of equilibrium conditions for mineral assemblages containing halogen-bearing phases. Clear negative correlation between the F content and XFe=Fe/(Fe+Mg) suggests that natural biotite and amphibole obey the Fe-F avoidance rule. A strong positive correlation exists between K and Cl in amphibole. A scattering of points on the XFe -Cl and TiO2- Cl diagrams indicate the possible involvement of an exotic Cl-rich phase (fluid or melt) during the formation of Cl-bearing biotite and amphibole. Fluorine and Cl substituting for OH-groups substantially stabilize minerals relative to dehydration and melting. They should also strongly affect partitioning of Fe and Mg between biotite, amphibole and anhydrous minerals. This effect is quantified for Fe-Mg exchange reactions involving biotite (Zhu and Sverjensky, 1992), but remains to be evaluated for amphibole. Calculations based on recent thermodynamic systematics show that the relatively Mg-rich, Cl-poor biotite (for example, XFe = 0.4 and about 0.2 wt.% Cl) may coexist with a fairly Cl-rich fluid, i.e. total Cl/(Cl+H2O) from 0.1-0.3, depending on the assemblage, under granulite facies P-T conditions. Alkali (and Ca) metasomatism caused by interaction of high grade rocks with halogen-bearing fluids has major impact on the subsolidus phase transformations and melting processes during high-grade metamorphism and anatexis. For example, an increase in sodium content in plagioclase (Pl) by 20 mol% due to infiltration of Na- fluid into the quartz (Qtz

  7. Halogen-based reconstruction of Russian Arctic sea ice area from the Akademii Nauk ice core (Severnaya Zemlya)

    National Research Council Canada - National Science Library

    A. Spolaor; T. Opel; J. R. McConnell; O. J. Maselli; G. Spreen; C. Varin; T. Kirchgeorg; D. Fritzsche; A. Saiz-Lopez; P. Vallelonga


    ... (Severnaya Zemlya, Russian Arctic). The chemistry of halogens bromine (Br) and iodine (I) is strongly active and influenced by sea ice dynamics, in terms of physical, chemical and biological process...

  8. The enhancing effect of a cation-π interaction on the cooperativity of halogen bonds: A computational study. (United States)

    Esrafili, Mehdi D; Asadollahi, Soheila


    In this work, we investigate the effect of a cation-π interaction on the cooperativity of X⋯N halogen bonds in PhX⋯NCX⋯NH3 complexes, where Ph=phenyl and X=Cl, Br, I. Molecular geometries and interaction energies of the resulting complexes are studied at the MP2/aug-cc-pVDZ(-PP) computational level. The mechanism of the cooperativity between halogen bonds is analyzed using parameters derived from the noncovalent index, quantum theory of atoms in molecules and natural bond orbital methodologies. It is found that the divalent cations (Be2+, Mg2+) have a larger influence on the cooperativity of halogen bonds than monovalent ones (Li+, Na+). The formation of a cation-π interaction leads to strengthening of the halogen bonds, hence increases their cooperativity. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Mechanism of Metal-Independent Decomposition of Organic Hydroperoxides and Formation of Alkoxyl Radicals by Halogenated Quinones

    National Research Council Canada - National Science Library

    Ben-Zhan Zhu; Hong-Tao Zhao; Balaraman Kalyanaraman; Jun Liu; Guo-Qiang Shan; Yu-Guo Du; Balz Frei


    The metal-independent decomposition of organic hydroperoxides and the formation of organic alkoxyl radicals in the absence or presence of halogenated quinones were studied with electron spin resonance (ESR...

  10. Fast heating induced impulse halogenation of refractory sample components in electrothermal atomic absorption spectrometry by direct injection of a liquid halogenating agent. (United States)

    György, Krisztina; Ajtony, Zsolt; Van Meel, Katleen; Van Grieken, René; Czitrovszky, Aladár; Bencs, László


    A novel electrothermal atomic absorption spectrometry (ETAAS) method was developed for the halogenation of refractory sample components (Er, Nd and Nb) of lithium niobate (LiNbO(3)) and bismuth tellurite (Bi(2)TeO(5)) optical single crystals to overcome memory effects and carry-over. For this purpose, the cleaning step of a regular graphite furnace heating program was replaced with a halogenation cycle. In this cycle, after the graphite tube cooled to room temperature, a 20 μL aliquot of liquid carbon tetrachloride (CCl(4)) was dispensed with a conventional autosampler into the graphite tube. The CCl(4) was partially dried at 80°C under the mini-flow (40 cm(3) min(-1)) condition of the Ar internal furnace gas (IFG), then the residue was decomposed (pyrolyzed) by fast furnace heating at 1900-2100°C under interrupted flow of the IFG. This step was followed by a clean-out stage at 2100°C under the maximum flow of the IFG. The advantage of the present method is that it does not require any alteration to the graphite furnace gas supply system in contrast to most of the formerly introduced halogenation techniques. The effectiveness of the halogenation method was verified with the determination of Er and Nd dopants in the optical crystals. In these analyses, a sensitivity decrease was observed, which was likely due to the enhanced deterioration of the graphite tube surface. Therefore, the application of mathematical correction (resloping) of the calibration was also required. The calibration curves were linear up to 1.5 and 10 μmol L(-1) for Er and Nd, respectively. Characteristic masses of 18 and 241 pg and the limit of detection (LOD) values of 0.017 and 0.27 μmol L(-1) were found for Er and Nd, respectively. These LOD data correspond to 0.68 μmol mol(-1) Er and 11 μmol mol(-1) Nd in solid bismuth tellurite samples. The analytical results were compared with those obtained by a conventional ETAAS method and validated with X-ray fluorescence spectrometry analysis

  11. Chitosan application as a biocoagulant in wastewater contaminated with hydrocarbons

    Directory of Open Access Journals (Sweden)

    Juan M. Álava


    Full Text Available The environment contamination in Ecuador, done by the production, transport and commercialization of hydrocarbons, requires further research regarding new treatment alternatives that use biodegradable substances. In this study, abdominal shrimp shell waste, Litopenaeus vannamei was used to obtain chitosan and then apply it as a biocoagulant to a wastewater sample contaminated with hydrocarbon products. The produced chitosan was characterised by potentiometric titration, resulting in a deacetylation degree (%DD of 87.18%– 93.72% and by intrinsic viscosimetry, obtaining an average molecular weight (g/mol of 5.2x105 –5.4x105. The application of chitosan was done in a jar test, for which a completely randomised factorial design 2k was set, resulting in an evident statistically significant effect for all the factor studied, that is, pH (Initial, chitosan type and agitation method, using the turbidity percentage removal as the response variable. As a result, a pH of 5.5, a 2 mg(Chitosan/L(sample and a fast agitation method were applied to a contaminated sample reducing the turbidity in 98.19%, the oxygen chemical demand in 78.17%, color in 91.45% and total petroleum hydrocarbon in 99.09%.

  12. Interleukin-24 as a target cytokine of environmental aryl hydrocarbon receptor agonist exposure in the lung. (United States)

    Luo, Yueh-Hsia; Kuo, Yu-Chun; Tsai, Ming-Hsien; Ho, Chia-Chi; Tsai, Hui-Ti; Hsu, Chin-Yu; Chen, Yu-Cheng; Lin, Pinpin


    Exposure to environmental aryl hydrocarbon receptor (AhR) agonists, such as halogenated aromatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs), has great impacts on the development of various lung diseases. As emerging molecular targets for AhR agonists, cytokines may contribute to the inflammatory or immunotoxic effects of environmental AhR agonists. However, general cytokine expression may not specifically indicate environmental AhR agonist exposure. By comparing cytokine and chemokine expression profiles in human lung adenocarcinoma cell line CL5 treated with AhR agonists and the non-AhR agonist polychlorinated biphenyl (PCB) 39, we identified a target cytokine of environmental AhR agonist exposure of in the lungs. Thirteen cytokine and chemokine genes were altered in the AhR agonists-treated cells, but none were altered in the PCB39-treated cells. Interleukin (IL)-24 was the most highly induced gene among AhR-modulated cytokines. Cotreatment with AhR antagonist completely prevented IL-24 induction by AhR agonists in the CL5 cells. Knockdown AhR expression with short-hairpin RNA (shRNA) significantly reduced benzo[a]pyrene (BaP)-induced IL-24 mRNA levels. We further confirmed that gene transcription, but not mRNA stability, was involved in IL-24 upregulation by BaP. Particulate matter (PM) in the ambient air contains some PAHs and is reported to activate AhR. Oropharyngeal aspiration of PM significantly increased IL-24 levels in lung epithelia and in bronchoalveolar lavage fluid of mice 4weeks after treatment. Thus, our data suggests that IL-24 is a pulmonary exposure target cytokine of environmental AhR agonists. Copyright © 2017 Elsevier Inc. All rights reserved.

  13. Design and verification of halogen-bonding system at the complex interface of human fertilization-related MUP PDZ5 domain with CAMK's C-terminal peptide. (United States)

    Wang, Juan; Guo, Yunjie; Zhang, Xue


    Calmodulin-dependent protein kinase (CAMK) is physiologically activated in fertilized human oocytes and is involved in the Ca2+ response pathways that link the fertilization calmodulin signal to meiosis resumption and cortical granule exocytosis. The kinase has an unstructured C-terminal tail that can be recognized and bound by the PDZ5 domain of its cognate partner, the multi-PDZ domain protein (MUP). In the current study, we reported a rational biomolecular design of halogen-bonding system at the complex interface of CAMK's C-terminal peptide with MUP PDZ5 domain by using high-level computational approaches. Four organic halogens were employed as atom probes to explore the structural geometry and energetic property of designed halogen bonds in the PDZ5-peptide complex. It was found that the heavier halogen elements such as bromine Br and iodine I can confer stronger halogen bond but would cause bad atomic contacts and overlaps at the complex interface, while fluorine F cannot form effective halogen bond in the complex. In addition, the halogen substitution at different positions of peptide's aromatic ring would result in distinct effects on the halogen-bonding system. The computational findings were then verified by using fluorescence analysis; it is indicated that the halogen type and substitution position play critical role in the interaction strength of halogen bonds, and thus the PDZ5-peptide binding affinity can be improved considerably by optimizing their combination. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Highly Sensitive and High-Throughput Method for the Analysis of Bisphenol Analogues and Their Halogenated Derivatives in Breast Milk. (United States)

    Niu, Yumin; Wang, Bin; Zhao, Yunfeng; Zhang, Jing; Shao, Bing


    The structural analogs of bisphenol A (BPA) and their halogenated derivatives (together termed BPs) have been found in the environment, food, and even the human body. Limited research showed that some of them exhibited toxicities that were similar to or even greater than that of BPA. Therefore, adverse health effects for BPs were expected for humans with low-dose exposure in early life. Breast milk is an excellent matrix and could reflect fetuses' and babies' exposure to contaminants. Some of the emerging BPs may present with trace or ultratrace levels in humans. However, existing analytical methods for breast milk cannot quantify these BPs simultaneously with high sensitivity using a small sampling weight, which is important for human biomonitoring studies. In this paper, a method based on Bond Elut Enhanced Matrix Removal-Lipid purification, pyridine-3-sulfonyl chloride derivatization, and liquid chromatography electrospray tandem mass spectrometry was developed. The method requires only a small quantity of sample (200 μL) and allowed for the simultaneous determination of 24 BPs in breast milk with ultrahigh sensitivity. The limits of quantitation of the proposed method were 0.001-0.200 μg L-1, which were 1-6.7 times lower than the only study for the simultaneous analysis of bisphenol analogs in breast milk based on a 3 g sample weight. The mean recoveries ranged from 86.11% to 119.05% with relative standard deviation (RSD) ≤ 19.5% (n = 6). Matrix effects were within 20% with RSD bisphenol F (BPF), bisphenol S (BPS), and bisphenol AF (BPAF) were detected. BPA was still the dominant BP, followed by BPF. This is the first report describing the occurrence of BPF and BPAF in breast milk.

  15. The cuticular hydrocarbons of the Triatoma sordida species subcomplex (Hemiptera: Reduviidae

    Directory of Open Access Journals (Sweden)

    Gustavo Mario Calderon-Fernandez


    Full Text Available The cuticular hydrocarbons of the Triatoma sordida subcomplex (Hemiptera: Reduviidae: Triatominae were ana-lysed by gas chromatography and their structures identified by mass spectrometry. They comprised mostly n-alkanes and methyl-branched alkanes with one-four methyl substitutions. n-alkanes consisted of a homologous series from C21-C33 and represented 33-45% of the hydrocarbon fraction; n-C29 was the major component. Methyl-branched alkanes showed alkyl chains from C24-C43. High molecular weight dimethyl and trimethylalkanes (from C35-C39 represented most of the methyl-branched fraction. A few tetramethylalkanes were also detected, comprising mostly even-numbered chains. Several components such as odd-numbered 3-methylalkanes, dimethylalkanes and trimethylalkanes of C37 and C39 showed patterns of variation that allowed the differentiation of the species and populations studied. Triatoma guasayana and Triatoma patagonica showed the most distinct hydrocarbon patterns within the subcomplex. The T. sordida populations from Brazil and Argentina showed significantly different hydrocarbon profiles that posed concerns regarding the homogeneity of the species. Triatoma garciabesi had a more complex hydrocarbon pattern, but it shared some similarity with T. sordida. The quantitative and qualitative variations in the cuticular hydrocarbons may help to elucidate the relationships between species and populations of this insect group.

  16. Weighted approximation with varying weight

    CERN Document Server

    Totik, Vilmos


    A new construction is given for approximating a logarithmic potential by a discrete one. This yields a new approach to approximation with weighted polynomials of the form w"n"(" "= uppercase)P"n"(" "= uppercase). The new technique settles several open problems, and it leads to a simple proof for the strong asymptotics on some L p(uppercase) extremal problems on the real line with exponential weights, which, for the case p=2, are equivalent to power- type asymptotics for the leading coefficients of the corresponding orthogonal polynomials. The method is also modified toyield (in a sense) uniformly good approximation on the whole support. This allows one to deduce strong asymptotics in some L p(uppercase) extremal problems with varying weights. Applications are given, relating to fast decreasing polynomials, asymptotic behavior of orthogonal polynomials and multipoint Pade approximation. The approach is potential-theoretic, but the text is self-contained.


    Directory of Open Access Journals (Sweden)

    S. V. Samimi ، R. Akbari Rad ، F. Ghanizadeh


    Full Text Available Tehran as the biggest city of Iran with a population of more than 10 millions has potentially high pollutant exposures of gas oil and gasoline combustion from vehicles that are commuting in the highways every day. The vehicle exhausts contain polycyclic aromatic hydrocarbons, which are produced by incomplete combustion and can be directly deposited in the environment. In the present study, the presence of polycyclic aromatic hydrocarbons contamination in the collected samples of a western highway in Tehran was investigated. The studied location was a busy highway in Tehran. High performance liquid chromatography equipped with florescence detector was used for determination of polycyclic aromatic hydrocarbons concentrations in the studied samples. Total concentration of the ten studied polycyclic aromatic hydrocarbons compounds ranged from 11107 to 24342 ng/g dry weight in the dust samples and increased from 164 to 2886 ng/g dry weight in the soil samples taken from 300 m and middle of the highway, respectively. Also the average of Σ PAHs was 1759 ng/L in the water samples of pools in parks near the highway. The obtained results indicated that polycyclic aromatic hydrocarbons contamination levels were very high in the vicinity of the highway.

  18. Non-additive stabilization by halogenated amino acids reveals protein plasticity on a sub-angstrom scale. (United States)

    Hosseini, Azade S; Pace, Christopher J; Esposito, Adam A; Gao, Jianmin


    It has been a long-standing goal to understand the structure-stability relationship of proteins, as optimal stability is essential for protein function and highly desirable for protein therapeutics. Halogenation has emerged as a minimally invasive strategy to probe the physical characteristics of proteins in solution, as well as enhance the structural stabilities of proteins for therapeutic applications. Although advances in synthetic chemistry and genetic code expansion have allowed for the rapid synthesis of proteins with diverse chemical sequences, much remains to be learned regarding the impact of these mutations on their structural integrity. In this contribution, we present a systematic study of three well-folded model protein systems, in which their structural stabilities are assessed in response to various hydrogen-to-halogen atom mutations. Halogenation allows for the perturbation of proteins on a sub-angstrom scale, offering unprecedented precision of protein engineering. The thermodynamic results from these model systems reveal that in certain cases, proteins can display modest steric tolerance to halogenation, yielding non-additive consequences to protein stability. The observed sub-angstrom sensitivity of protein stability highlights the delicate arrangement of a folded protein core structure. The stability data of various halogenated proteins presented herein should also provide guidelines for using halogenation as a strategy to improve the stability of protein therapeutics. © 2017 The Protein Society.

  19. Brønsted Acidic Ionic Liquid Accelerated Halogenation of Organic Compounds with N-Halosuccinimides (NXS

    Directory of Open Access Journals (Sweden)

    Stojan Stavber


    Full Text Available The Brønsted-acidic ionic liquid 1-methyl-3-(4-sulfobutylimidazolium triflate [BMIM(SO3H][OTf] was demonstrated to act efficiently as solvent and catalyst for the halogenation of activated organic compounds with N-halosuccinimides (NXS under mild conditions with short reaction times. Methyl aryl ketones were converted into α-halo and α,α-dihaloketones, depending on the quantity of NXS used. Ketones with activated aromatic rings were selectively halogenated, however in some cases mixtures of α-halogenated ketone and ring-halogenated ketones were obtained. Activated aromatics were regioselectively ring halogenated to give mono- and dihalo-substituted products. The [BMIM(SO3H][OTf] ionic liquid (IL-A was successfully reused eight times in a representative monohalogenation reaction with no noticeable decrease in efficiency. An effective halogenation scale-up in this IL is also presented. The reactivity trend and the observed chemo- and regioselectiivities point to an ET process in these IL-promoted halofunctionalization reactions.

  20. Neoplastic transformation of neonatal human fibroblasts exposed in vitro to radiation from a quartz-halogen lamp. (United States)

    West, R W; Rowland, K L; Miller, S A; Beer, J Z


    The use of unfiltered quartz-halogen lamps exposes human skin to radiation that spans much of the ultraviolet (UV) spectrum. Reports indicate that exposure to quartz-halogen lamps is erythemogenic, mutagenic, and carcinogenic. To compare the carcinogenic potential of quartz-halogen lamps with that of other UV sources, we determined the dose dependence for cytotoxicity and neoplastic transformation in neonatal human fibroblasts exposed in vitro to: a 15 W germicidal lamp (primarily 254 nm radiation), a 15 W Cool White fluorescent lamp, and an unfiltered 20 W quartz-halogen lamp. Fluence-survival relationships were multiphasic with linear dose response below about 40% survival, and all three sources produced fluence-dependent transformation as indicated by induction of anchorage-independent growth. Maximum transformation frequencies were observed at fluences of 5-8 J/m2 for the germicidal lamp, 6.3 kJ/m2 for the fluorescent lamp, and 300 J/m2 for the quartz-halogen lamp. These data confirm the carcinogenic potential of the quartz-halogen lamp.

  1. Sustainable heterologous production of terpene hydrocarbons in cyanobacteria. (United States)

    Formighieri, Cinzia; Melis, Anastasios


    Cyanobacteria can be exploited as photosynthetic platforms for heterologous generation of terpene hydrocarbons with industrial application. However, the slow catalytic activity of terpene synthases (k cat = 4 s-1 or slower) makes them noncompetitive for the pool of available substrate, thereby limiting the rate and yield of product generation. Work in this paper applied transformation technologies in Synechocystis for the heterologous production of β-phellandrene (monoterpene) hydrocarbons. Conditions were defined whereby expression of the β-phellandrene synthase (PHLS), as a CpcB·PHLS fusion protein with the β-subunit of phycocyanin, accounted for up to 20 % of total cellular protein. Moreover, CpcB·PHLS was heterologously co-expressed with enzymes of the mevalonic acid (MVA) pathway and geranyl-diphosphate synthase, increasing carbon flux toward the terpenoid biosynthetic pathway and enhancing substrate availability. These improvements enabled yields of 10 mg of β-phellandrene per g of dry cell weight generated in the course of a 48-h incubation period, or the equivalent of 1 % β-phellandrene:biomass (w:w) carbon-partitioning ratio. The work helped to identify prerequisites for the efficient heterologous production of terpene hydrocarbons in cyanobacteria: (i) requirement for overexpression of the heterologous terpene synthase, so as to compensate for the slow catalytic turnover of the enzyme, and (ii) enhanced endogenous carbon partitioning toward the terpenoid biosynthetic pathway, e.g., upon heterologous co-expression of the MVA pathway, thereby supplementing the native metabolic flux toward the universal isopentenyl-diphosphate and dimethylallyl-diphosphate terpenoid precursors. The two prerequisites are shown to be critical determinants of yield in the photosynthetic CO2 to terpene hydrocarbons conversion process.

  2. Halogenation of glycopeptide antibiotics occurs at the amino acid level during non-ribosomal peptide synthesis. (United States)

    Kittilä, Tiia; Kittel, Claudia; Tailhades, Julien; Butz, Diane; Schoppet, Melanie; Büttner, Anita; Goode, Rob J A; Schittenhelm, Ralf B; van Pee, Karl-Heinz; Süssmuth, Roderich D; Wohlleben, Wolfgang; Cryle, Max J; Stegmann, Evi


    Halogenation plays a significant role in the activity of the glycopeptide antibiotics (GPAs), although up until now the timing and therefore exact substrate involved was unclear. Here, we present results combined from in vivo and in vitro studies that reveal the substrates for the halogenase enzymes from GPA biosynthesis as amino acid residues bound to peptidyl carrier protein (PCP)-domains from the non-ribosomal peptide synthetase machinery: no activity was detected upon either free amino acids or PCP-bound peptides. Furthermore, we show that the selectivity of GPA halogenase enzymes depends upon both the structure of the bound amino acid and the PCP domain, rather than being driven solely via the PCP domain. These studies provide the first detailed understanding of how halogenation is performed during GPA biosynthesis and highlight the importance and versatility of trans-acting enzymes that operate during peptide assembly by non-ribosomal peptide synthetases.

  3. Harnessing the Potential of Halogenated Natural Product Biosynthesis by Mangrove-Derived Actinomycetes

    Directory of Open Access Journals (Sweden)

    Xiang Xiao


    Full Text Available Mangrove-derived actinomycetes are promising sources of bioactive natural products. In this study, using homologous screening of the biosynthetic genes and anti-microorganism/tumor assaying, 163 strains of actinomycetes isolated from mangrove sediments were investigated for their potential to produce halogenated metabolites. The FADH2-dependent halogenase genes, identified in PCR-screening, were clustered in distinct clades in the phylogenetic analysis. The coexistence of either polyketide synthase (PKS or nonribosomal peptide synthetase (NRPS as the backbone synthetases in the strains harboring the halogenase indicated that these strains had the potential to produce structurally diversified antibiotics. As a validation, a new enduracidin producer, Streptomyces atrovirens MGR140, was identified and confirmed by gene disruption and HPLC analysis. Moreover, a putative ansamycin biosynthesis gene cluster was detected in Streptomyces albogriseolus MGR072. Our results highlight that combined genome mining is an efficient technique to tap promising sources of halogenated natural products synthesized by mangrove-derived actinomycetes.

  4. Band-gap engineering of halogenated silicon nanowires through molecular doping. (United States)

    de Santiago, Francisco; Trejo, Alejandro; Miranda, Alvaro; Carvajal, Eliel; Pérez, Luis Antonio; Cruz-Irisson, Miguel


    In this work, we address the effects of molecular doping on the electronic properties of fluorinated and chlorinated silicon nanowires (SiNWs), in comparison with those corresponding to hydrogen-passivated SiNWs. Adsorption of n-type dopant molecules on hydrogenated and halogenated SiNWs and their chemisorption energies, formation energies, and electronic band gap are studied by using density functional theory calculations. The results show that there are considerable charge transfers and strong covalent interactions between the dopant molecules and the SiNWs. Moreover, the results show that the energy band gap of SiNWs changes due to chemical surface doping and it can be further tuned by surface passivation. We conclude that a molecular based ex-situ doping, where molecules are adsorbed on the surface of the SiNW, can be an alternative path to conventional doping. Graphical abstract Molecular doping of halogenated silicon nanowires.

  5. Detection of the halogenating activity of heme peroxidases in leukocytes by aminophenyl fluorescein. (United States)

    Flemmig, J; Remmler, J; Zschaler, J; Arnhold, J


    The formation of hypochlorous and hypobromous acids by heme peroxidases is a key property of certain immune cells. These products are not only involved in defense against pathogenic microorganisms and in regulation of inflammatory processes, but contribute also to tissue damage in certain pathologies. After a short introduction about experimental approaches for the assessment of the halogenating activity in vitro and in cell suspensions, we are focusing on novel applications of fluorescent dye systems to detect the formation of hypochlorous acid (HOCl) in leukocytes. Special attention is directed to properties and applications of the non-fluorescent dye aminophenyl fluorescein that is converted by HOCl, HOBr, and other strong oxidants to fluorescein. This dye allows the detection of the halogenating activity in samples containing free myeloperoxidase and eosinophil peroxidase as well as in intact granulocytes using fluorescence spectroscopy and flow cytometry, respectively.

  6. Halogenated furanones inhibit quorum sensing through accelerated LuxR turnover

    DEFF Research Database (Denmark)

    Manefield, Michael; Rasmussen, Thomas Bovbjerg; Henzter, Morten


    N-acyl-L-homoserine lactones (AHLs) are co-regulatory ligands required for control of the expression of genes encoding virulence traits in many Gram-negative bacterial species. Recent studies have indicated that AHLs modulate the cellular concentrations of LuxR-type regulatory proteins by binding...... 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...... furanones modulate LuxR activity but act to destabilize, rather than protect, the AHL-dependent transcriptional activator. The furanone-dependent reduction in the cellular concentration of the LuxR protein was associated with a reduction in expression of a plasmid encoded P(luxI)-gfp(ASV) fusion suggesting...

  7. Room Temperature Halogenation of Polyimide Film Surface using Chlorine Trifluoride Gas (United States)

    Habuka, Hitoshi; Kosuga, Takahiro; Koike, Kunihiko; Aida, Toshihiro; Takeuchi, Takashi; Aihara, Masahiko


    In order to develop a new application of chlorine trifluoride gas, the halogenation of a polyimide film surface at room temperature and at atmospheric pressure is studied for the first time. The polyimide film surface after exposure to the chlorine trifluoride gas shows a decreased water contact angle with increasing chlorine trifluoride gas concentration and exposure period. Since both X-ray photoelectron spectroscopy and infrared absorption spectroscopy simultaneously showed the formation of a carbon-chlorine bond and carbon-fluorine bond, it is concluded that the chlorine trifluoride gas can easily and safely perform the halogenation of the polyimide film surface under the stated conditions using a low-cost process and equipment.

  8. 40 CFR 52.1877 - Control strategy: Photochemical oxidants (hydrocarbons). (United States)


    ... oxidants (hydrocarbons). 52.1877 Section 52.1877 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY....1877 Control strategy: Photochemical oxidants (hydrocarbons). (a) The requirements of Subpart G of this... national standard for photochemical oxidants (hydrocarbons) in the Metropolitan Cincinnati interstate...

  9. Natural and anthropogenic hydrocarbons in sediments from the Chubut River (Patagonia, Argentina). (United States)

    Commendatore, M G; Esteves, J L


    In March of 2001 a study was carried out to evaluate hydrocarbon levels in the lower course of the Chubut River. The study included 12 sample stations along the river from San Cristóbal Bridge to the confluence with the sea, in a 25 km straight-line extension in a urbanized area. In the first 11 stations, resolved aliphatic (RAli) hydrocarbons presented low values, between 0.07 and 0.96 microg/g dry weight (dw); the unresolved complex mixture (UCM) between 0.42 and 2.72 microg/g dw, and the total aliphatic (TAli) hydrocarbons between 0.55 and 3.07 microg/g dw. In the last station, at the mouth of Chubut river, these values increased to 460, 284, and 741 microg/g dw for RAli, UCM and TAli, respectively. The n-alkanes distribution indices and the compositional parameters suggested a predominantly biogenic origin in eleven stations, and a predominantly anthropogenic origin in the last station, with the highest hydrocarbon values. It is possible to conclude that the stations with low hydrocarbon values and biogenic origin predominance would constitute the baseline of aliphatic hydrocarbons for river sediments at this zone. The station with the highest hydrocarbon concentration and predominantly anthropic origin was related to the presence of Rawson city's port, where its activities (harbor and fishing vessels) generate hydrocarbon wastes unrelated to the river base profile in the study zone. Offshore, but within the river influence, there is an important fishing area of Argentine Red and Patagonian shrimps (Pleoticus muelleri and Artemesia longinaris, respectively).

  10. Extensive halogen-mediated ozone destruction over the tropical Atlantic Ocean. (United States)

    Read, Katie A; Mahajan, Anoop S; Carpenter, Lucy J; Evans, Mathew J; Faria, Bruno V E; Heard, Dwayne E; Hopkins, James R; Lee, James D; Moller, Sarah J; Lewis, Alastair C; Mendes, Luis; McQuaid, James B; Oetjen, Hilke; Saiz-Lopez, Alfonso; Pilling, Michael J; Plane, John M C


    Increasing tropospheric ozone levels over the past 150 years have led to a significant climate perturbation; the prediction of future trends in tropospheric ozone will require a full understanding of both its precursor emissions and its destruction processes. A large proportion of tropospheric ozone loss occurs in the tropical marine boundary layer and is thought to be driven primarily by high ozone photolysis rates in the presence of high concentrations of water vapour. A further reduction in the tropospheric ozone burden through bromine and iodine emitted from open-ocean marine sources has been postulated by numerical models, but thus far has not been verified by observations. Here we report eight months of spectroscopic measurements at the Cape Verde Observatory indicative of the ubiquitous daytime presence of bromine monoxide and iodine monoxide in the tropical marine boundary layer. A year-round data set of co-located in situ surface trace gas measurements made in conjunction with low-level aircraft observations shows that the mean daily observed ozone loss is approximately 50 per cent greater than that simulated by a global chemistry model using a classical photochemistry scheme that excludes halogen chemistry. We perform box model calculations that indicate that the observed halogen concentrations induce the extra ozone loss required for the models to match observations. Our results show that halogen chemistry has a significant and extensive influence on photochemical ozone loss in the tropical Atlantic Ocean boundary layer. The omission of halogen sources and their chemistry in atmospheric models may lead to significant errors in calculations of global ozone budgets, tropospheric oxidizing capacity and methane oxidation rates, both historically and in the future.

  11. Comparison of halogen light and vibroacoustic stimulation on nonreactive fetal heart rate pattern. (United States)

    Rahimikian, Fatemeh; Rahiminia, Tahereh; Modarres, Maryam; Mehran, Abbas


    One of the first-line assessment tools for fetal surveillance is nonstress test (NST), although it is limited by a high rate of false-nonreactive results. This study was performed to investigate if external stimulation from vibroacoustic and halogen light could help in provoking fetal responsiveness and altering NST results. This is a clinical trial. Sampling was done from April to July 2010. One hundred pregnant women with nonreactive NST for 20 min were allocated in two groups: Vibroacoustic stimulated NST (VNST, n = 50) who received vibration from a standard fetal vibratory stimulator and halogen light stimulated NST (LNST, n = 50) who received a halogen light source for 3 and 10 sec, respectively. Results were compared together and then compared to biophysical profile (BPP) scores as a backup test. We used Mann-Whitney U test, Chi-square test, and Fisher's exact test to compare the variables in the two groups through SPSS version 14. P vibroacoustic stimulation group changed to reactive patterns. Time to onset of the first acceleration (VNST: 2.17 min; LNST: 2.27 min) and the test duration (VNST: 4.91 min; LNST: 5.26 min) were the same in the two groups. In VNST 89.5% and in LNST 87.5% of nonreactivity followed by score 8 in BPP. There was no significant relation between stimulus NSTs and BPPs. Vibroacoustic and light stimulation offer benefits by decreasing the incidence of nonreactive results and reducing the test time. Both halogen light stimulation and vibroacoustic stimulation are safe and efficient in fetal well-being assessment services.

  12. Synthesis of 4-Halogenated 3-Fluoro-6-methoxyquinolines: Key Building Blocks for the Synthesis of Antibiotics

    DEFF Research Database (Denmark)

    Flagstad, Thomas; Petersen, Mette Terp; Hinnerfeldt, Daniel Michael


    A practical and scalable 4-step route is presented for the synthesis of 4-bromo-3-fluoro-6-methoxyoquinoline and 3-fluoro-4-iodo-6-methoxyoquinoline from readily available 2,4-dichloro-3-fluoroquinoline with an overall yield of 81-85%. Halogenated quinoline building blocks have found much use in ...... in antimicrobial drug discovery, and the method reported here would be useful for the synthesis of these compounds. © Georg Thieme Verlag....

  13. Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms. (United States)

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


    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. Biodehalogenation: The kinetics and rates of the microbial cleavage of carbon-halogen bonds

    Energy Technology Data Exchange (ETDEWEB)

    Castro, C.E. (Univ. of California, Riverside, CA (United States). Nematology Dept.)


    Specific rate constants associated with defined molecular paths of carbon-halogen bond cleavage from a variety of alkyl halide substrates by six soil organisms are presented. Five aerobes (three pseudomonads, one methylotroph, and one flavobacterium) and one anaerobe (a methanogen) are compared. The rate constants were obtained with resting cells in phosphate buffer at pH 7.4 in the absence of nutrients or other substances. The observed general rate law is d(X[sup [minus

  15. Effect of halogenated benzenes on acetanilide esterase, acetanilide hydroxylase and procaine esterase in rats. (United States)

    Carlson, G P; Dziezak, J D; Johnson, K M


    1,2,4-Trichlorobenzene, 1,3,5-trichlorobenzene, hexachlorobenzene, 1,2,4-tribromobenzene, 1,3,5-tribromobenzene and hexabromobenzene were compared for their abilities to induce acetanilide esterase, acentailide hydroxylase and procaine esterase. Except for hexabromobenzene all induced acetanilide esterase whereas the hydroxylation of acetanilide was seen only with the fully halogenated benzenes and with 1,3,5-tribromobenzene. Hepatic procaine esterase activity was increased by the three chlorinated benzenes and 1,2,4-tribromobenzene.

  16. Novel halogenated derivates of JWH-018: Behavioral and binding studies in mice. (United States)

    Vigolo, A; Ossato, A; Trapella, C; Vincenzi, F; Rimondo, C; Seri, C; Varani, K; Serpelloni, G; Marti, M


    JWH-018 is a synthetic CB1 and CB2 agonist illegally marketed as products named "Spice" or "herbal blend" for its psychoactive effects which are much higher than those produced by cannabis. In the last year, the European Monitoring Centre for Drugs and Drug Addiction reported to the Italian National Early Warning System the seizure of plant material containing new halogenated derivatives of JWH-018 (JWH-018 Cl and JWH-018 Br). The present study aimed to investigate the in vitro and in vivo activity of these two new synthetic cannabinoids in mice. In vitro competition binding experiments performed on mouse and human CB1 receptors revealed a high affinity and potency of the halogenated compounds. Synthetic cannabinoids (0.01-6 mg/kg i.p.) impaired motor activity and induced catalepsy in mice and their effects were more severe with respect to those evoked by Δ(9)-THC. Moreover, they increased the mechanical and thermal pain threshold and induced a marked hypothermia. It is interesting to note that whereas high doses of JWH-018 cause seizures, myoclonia and hyperreflexia, the halogenated compounds, in particular JWH-018Br, were less effective. Behavioral and neurological changes were prevented by the selective CB1 receptor antagonist AM 251. These data demonstrate for the first time that JWH-018 Cl and JWH-018 Br act similarly to JWH-018 while inducing less convulsive episodes and myoclonias. These data support the hypothesis that the halogenated compounds may have been introduced onto market to produce similar intoxicating effects as JWH-018 while causing less side effects. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. A halogen-free synthesis of gold nanoparticles using gold(III) oxide


    Sashuk, Volodymyr; Rogaczewski, Konrad


    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 wit...

  18. Enthalpy-entropy compensation in biomolecular halogen bonds measured in DNA junctions. (United States)

    Carter, Megan; Voth, Andrea Regier; Scholfield, Matthew R; Rummel, Brittany; Sowers, Lawrence C; Ho, P Shing


    Interest in noncovalent interactions involving halogens, particularly halogen bonds (X-bonds), has grown dramatically in the past decade, propelled by the use of X-bonding in molecular engineering and drug design. However, it is clear that a complete analysis of the structure-energy relationship must be established in biological systems to fully exploit X-bonds for biomolecular engineering. We present here the first comprehensive experimental study to correlate geometries with their stabilizing potentials for fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) X-bonds in a biological context. For these studies, we determine the single-crystal structures of DNA Holliday junctions containing halogenated uracil bases that compete X-bonds against classic hydrogen bonds (H-bonds), estimate the enthalpic energies of the competing interactions in the crystal system through crystallographic titrations, and compare the enthalpic and entropic energies of bromine and iodine X-bonds in solution by differential scanning calorimetry. The culmination of these studies demonstrates that enthalpic stabilization of X-bonds increases with increasing polarizability from F to Cl to Br to I, which is consistent with the σ-hole theory of X-bonding. Furthermore, an increase in the X-bonding potential is seen to direct the interaction toward a more ideal geometry. However, the entropic contributions to the total free energies must also be considered to determine how each halogen potentially contributes to the overall stability of the interaction. We find that bromine has the optimal balance between enthalpic and entropic energy components, resulting in the lowest free energy for X-bonding in this DNA system. The X-bond formed by iodine is more enthalpically stable, but this comes with an entropic cost, which we attribute to crowding effects. Thus, the overall free energy of an X-bonding interaction balances the stabilizing electrostatic effects of the σ-hole against the competing

  19. Cooperativity of halogen, chalcogen, and pnictogen bonds in infinite molecular chains by electronic structure theory. (United States)

    George, Janine; Deringer, Volker L; Dronskowski, Richard


    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.

  20. Control of a two-dimensional molecular structure by cooperative halogen and hydrogen bonds


    Yasuda, Satoshi; Furuya, Atom; Murakoshi, Kei


    The cooperative effect of hydrogen and halogen bonds on the two-dimensional (2D) molecular arrangement on highly oriented pyrolytic graphite (HOPG) was studied by scanning tunneling microscopy. The terephthalic acid (TPA) molecule, which has two carboxyl groups attached at the para positions of a benzene ring, formed a one-dimensional (1D) linear non-covalent network structure on HOPG by hydrogen bonds between the carboxyl groups of neighboring molecules. However, unlike the TPA molecule, Br ...

  1. First structurally characterized mixed-halogen nickel(III) NCN-pincer complex. (United States)

    Kozhanov, Konstantin A; Bubnov, Michael P; Cherkasov, Vladimir K; Fukin, Georgy K; Vavilina, Nina N; Efremova, Larisa Yu; Abakumov, Gleb A


    A square-pyramidal mixed-halogen nickel(III) NCN-pincer complex (PipeNCN)NiClBr (where PipeNCN=2,6-bis(piperidinomethyl)phenyl) was structurally characterized. Bromine occupies apical position; pincer ligand and chlorine atom are in the basal plane. EPR detects that complex in solution exists as a mixture of two structural isomers with bromine or chlorine atoms in the top of pyramid.

  2. C–H bond halogenation catalyzed or mediated by copper: an overview

    Directory of Open Access Journals (Sweden)

    Wenyan Hao


    Full Text Available Carbon–halogen (C–X bonds are amongst the most fundamental groups in organic synthesis, they are frequently and widely employed in the synthesis of numerous organic products. The generation of a C–X bond, therefore, constitutes an issue of universal interest. Herein, the research advances on the copper-catalyzed and mediated C–X (X = F, Cl, Br, I bond formation via direct C–H bond transformation is reviewed.

  3. Chlorine and Bromine Isotope Fractionation of Halogenated Organic Pollutants on Gas Chromatography Columns


    Tang, Caiming; Tan, Jianhua; Xiong, Songsong; Liu, Jun; Fan, Yujuan; Peng, Xianzhi


    Compound-specific chlorine/bromine isotope analysis (CSIA-Cl/Br) has become a useful approach for degradation pathway investigation and source appointment of halogenated organic pollutants (HOPs). CSIA-Cl/Br is usually conducted by gas chromatography-mass spectrometry (GC-MS), which could be negatively impacted by chlorine and bromine isotope fractionation of HOPs on GC columns. In this study, 31 organochlorines and 4 organobromines were systematically investigated in terms of Cl/Br isotope f...

  4. Weighted Hypernetworks

    CERN Document Server

    Zhu, Xin-Yun


    Complex network theory has been used to study complex systems. However, many real life systems involve multiple kinds of objects . They can't be described by simple graphs. In order to provide complete information of these systems, we extend the concept of evolving models of complex networks to hypernetworks. In this work, we firstly propose a non-uniform hypernetwork model with attractiveness, and obtain the stationary average hyperdegree distribution of the non-uniform hypernetwork. Furthermore, we develop a model for weighted hypernetworks that couples the establishment of new hyperedges and nodes and the weights' dynamical evolution. We obtain the stationary average hyperdegree distribution by using the hyperdegree distribution of the hypernetwork model with attractiveness. In particular, the model yields a nontrivial time evolution of nodes' properties and scale-free behavior for the hyperdegree distribution. It is expected that our work may give help to the study of the hypernetworks in real-world syste...

  5. Versatility of hydrocarbon production in cyanobacteria. (United States)

    Xie, Min; Wang, Weihua; Zhang, Weiwen; Chen, Lei; Lu, Xuefeng


    Cyanobacteria are photosynthetic microorganisms using solar energy, H2O, and CO2 as the primary inputs. Compared to plants and eukaryotic microalgae, cyanobacteria are easier to be genetically engineered and possess higher growth rate. Extensive genomic information and well-established genetic platform make cyanobacteria good candidates to build efficient biosynthetic pathways for biofuels and chemicals by genetic engineering. Hydrocarbons are a family of compounds consisting entirely of hydrogen and carbon. Structural diversity of the hydrocarbon family is enabled by variation in chain length, degree of saturation, and rearrangements of the carbon skeleton. The diversified hydrocarbons can be used as valuable chemicals in the field of food, fuels, pharmaceuticals, nutrition, and cosmetics. Hydrocarbon biosynthesis is ubiquitous in bacteria, yeasts, fungi, plants, and insects. A wide variety of pathways for the hydrocarbon biosynthesis have been identified in recent years. Cyanobacteria may be superior chassis for hydrocabon production in a photosynthetic manner. A diversity of hydrocarbons including ethylene, alkanes, alkenes, and terpenes can be produced by cyanobacteria. Metabolic engineering and synthetic biology strategies can be employed to improve hydrocarbon production in cyanobacteria. This review mainly summarizes versatility and perspectives of hydrocarbon production in cyanobacteria.

  6. short communication aliphatic and polycyclic aromatic hydrocarbons ...

    African Journals Online (AJOL)

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    The compositional pattern of the photo-modified bitumen samples suggests that there was initial cracking of large molecular mass hydrocarbons in the bitumen, followed by recombination after long periods of exposure to sunlight. The polycyclic aromatic hydrocarbon profile of the Agbabu natural bitumen as a function of.

  7. Palynofacies characterization for hydrocarbon source rock ...

    Indian Academy of Sciences (India)

    This paper deals with the hydrocarbon source rock evaluation of the Subathu Formation exposed at Marhighat on Sarahan–Narag road in Sirmaur district of Himachal Pradesh. Hydrocarbon potential of these sediments is estimated on the basis of palynofacies analysis and thermal alteration index (TAI) values based on the ...

  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: [Department of Physical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic)


    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. Dansylglycine, a fluorescent probe for specific determination of halogenating activity of myeloperoxidase and eosinophil peroxidase. (United States)

    Bertozo, Luiza de Carvalho; Zeraik, Maria Luiza; Ximenes, Valdecir Farias


    Myeloperoxidase (MPO) and eosinophil peroxidase (EPO) are enzymes present in neutrophil and eosinophil leukocytes, respectively. Here, we present the development of a sensitive and specific assay for determination of the halogenating enzymatic activity of MPO and EPO based on the electrophilic attack of HOCl and HOBr on aromatic ring of dansylglycine (DG). We found that the intrinsic fluorescence of DG was promptly depleted by the action of these acids. In the presence of the enzymes, the fluorescence bleaching was dependent of chloride (Cl(-)) and bromide (Br(-)), which makes the assay able to distinguish the halogenating from the peroxidase activity. A linear correlation was obtained between the hydrogen peroxide (H2O2) concentration and the fluorescent decay. Similarly, the enzyme activity was measured by keeping constant H2O2. The method was applied for studding MPO/EPO specific inhibitors as 5-fluortryptamine (reversible inhibitor) and 4-hydroxybenzhydrazide (irreversible inhibitor). Differently of the taurine chloramine/3,3',5,5'-tetramethylbenzidine assay, which is among the most used technique, the dansylglycine assay was able to differentiate these inhibitors based on their kinetic behavior. In conclusion, this assay can differentiate the peroxidase and halogenating activity of MPO and EPO. Moreover, the method is adequate for real-time measurement of the production of HOCl and HOBr. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. (5-Chloroquinolin-8-yl-2-fluorobenzoate. The Halogen Bond as a Structure Director

    Directory of Open Access Journals (Sweden)

    Rodolfo Moreno-Fuquen


    Full Text Available Structures containing 8-hydroxyquinoline scaffold are useful for anticancer drug development. The title ester (5-chloroquinolin-8-yl-2-fluorobenzoate was prepared by the reaction of 2-fluorobenzoyl chloride with 5-chloro-8-hydroxyquinoline. The structure of the title compound was assigned by diverse spectroscopic techniques. Moreover, a crystallographic study was undertaken and its supramolecular characteristics were analyzed. Thus, the central ester fragment C8/O1/C10(O2/C11 is almost planar with a root mean square (r.m.s. deviation of 0.0612 Å and it makes dihedral angles of 76.35(6° and 12.89(11°, with quinoline and phenyl rings respectively. The structure shows C–H...X (X = halogen non-classical hydrogen bonds. It also has a halogen…halogen distance less than the sum of the van der Waals radii (3.2171(15 Å. As a result of interactions with halogen atoms, chains of centrosymmetric dimer that form edge-fused R22(18 rings run parallel to the plane (100.

  11. In vitro lingual bracket evaluation of indirect bonding with plasma arc, LED and halogen light. (United States)

    Magno, A F F; Martins, R P; Vaz, L G; Martins, L P


    Evaluate the shear bond strength (SBS) and the adhesive remnant index (ARI) of indirect bonded lingual brackets using xenon plasma arc light, light-emitting diode (LED) and conventional quartz-tungsten-halogen light. Lingual brackets were bonded indirectly to 60 premolars divided to three groups according to the curing light used: Group 1, plasma arc for 6 s; Group 2, LED for 10 s; and Group 3, halogen light for 40 s. After bonding, the specimens were subjected to a shear force until debonding. The debonding pattern was assessed and classified according to the ARI scores. The mean shear bond strengths were accessed by anova followed by the Student-Newman-Keuls test for multiple comparisons. ARI scores were assessed using the chi-square test. The three groups showed significant differences (p plasma arc, during 60% of the time used for the LED, produced lower SBS than obtained with the latter. Using LED during 25% of the time of the halogen light produced lower SBS than obtained with the latter. These differences did not influence the debonding pattern and are clinically acceptable according to the literature.

  12. The Halogenated Metabolism of Brown Algae (Phaeophyta, Its Biological Importance and Its Environmental Significance

    Directory of Open Access Journals (Sweden)

    Stéphane La Barre


    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.

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

    KAUST Repository

    Fu, Boyi


    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.

  14. 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)


    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)

  15. Determination of the Halogenated Skeleton Constituents of the Marine Demosponge Ianthella basta

    Directory of Open Access Journals (Sweden)

    Susanne Ueberlein


    Full Text Available Demosponges of the order Verongida such as Ianthella basta exhibit skeletons containing spongin, a collagenous protein, and chitin. Moreover, Verongida sponges are well known to produce bioactive brominated tyrosine derivatives. We recently demonstrated that brominated compounds do not only occur in the cellular matrix but also in the skeletons of the marine sponges Aplysina cavernicola and I. basta. Further investigations revealed the amino acid composition of the skeletons of A. cavernicola including the presence of several halogenated amino acids. In the present work, we investigated the skeletal amino acid composition of the demosponge I. basta, which belongs to the Ianthellidae family, and compared it with that of A. cavernicola from the Aplysinidae family. Seventeen proteinogenic and five non-proteinogenic amino acids were detected in I. basta. Abundantly occurring amino acids like glycine and hydroxyproline show the similarity of I. basta and A. cavernicola and confirm the collagenous nature of their sponging fibers. We also detected nine halogenated tyrosines as an integral part of I. basta skeletons. Since both sponges contain a broad variety of halogenated amino acids, this seems to be characteristic for Verongida sponges. The observed differences of the amino acid composition confirm that spongin exhibits a certain degree of variability even among the members of the order Verongida.

  16. Estimating the climate significance of halogen-driven ozone loss in the tropical marine troposphere

    Directory of Open Access Journals (Sweden)

    A. Saiz-Lopez


    Full Text Available We have integrated observations of tropospheric ozone, very short-lived (VSL halocarbons and reactive iodine and bromine species from a wide variety of tropical data sources with the global CAM-Chem chemistry-climate model and offline radiative transfer calculations to compute the contribution of halogen chemistry to ozone loss and associated radiative impact in the tropical marine troposphere. The inclusion of tropospheric halogen chemistry in CAM-Chem leads to an annually averaged depletion of around 10% (~2.5 Dobson units of the tropical tropospheric ozone column, with largest effects in the middle to upper troposphere. This depletion contributes approximately −0.10 W m−2 to the radiative flux at the tropical tropopause. This negative flux is of similar magnitude to the ~0.33 W m−2 contribution of tropospheric ozone to present-day radiative balance as recently estimated from satellite observations. We find that the implementation of oceanic halogen sources and chemistry in climate models is an important component of the natural background ozone budget and we suggest that it needs to be considered when estimating both preindustrial ozone baseline levels and long term changes in tropospheric ozone.

  17. Tooth bleaching using three laser systems, halogen-light unit, and chemical action agents (United States)

    Dostalova, Tatjana; Jelinkova, Helena; Housova, Devana; Sulc, Jan; Nemec, Michal; Koranda, Petr; Miyagi, Mitsunobu; Shi, Yi-Wei; Matsuura, Yuji


    μThe study describes the preclinical experience with laser-activated bleaching agent for discolored teeth. Extracted human upper central incisors were selected, and in the bleaching experiment 35% hydrogen peroxide was used. Three various laser systems and halogen-light unit for activation of the bleaching agent were applied. They were Alexandrite laser (wavelength 750 nm and 375 nm - SHG), Nd:YAG laser (wavelength 1.064 m), and Er:YAG laser (wavelength 2.94 μm). The halogen-light unit was used in a standard regime. The enamel surface was analyzed in the scanning electron microscope. The method of chemical oxidation results in a 2-3 shade change in one treatment. The halogen-light units produced the same effect with shorter time of bleaching process (from 630 s to 300 s). The Alexandrite laser (750 nm) and bleaching agent helped to reach the desired color shade after a shorter time (400 s). Alexandrite laser (375 nm) and Nd:YAG laser had no effect on the longevity of the process of bleaching. Overheating of the chemical bleaching agent was visible after Er:YAG laser activation (195 s). Slight surface modification after bleaching process was detected in SEM.

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

    Directory of Open Access Journals (Sweden)

    Miren Pena-Abaurrea


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Cartoni, Antonella, E-mail: [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)


    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.

  20. Noncovalent Halogen Bonding as a Mechanism for Gas-Phase Clustering

    DEFF Research Database (Denmark)

    Wegeberg, Christina; Donald, William A.; McKenzie, Christine


    Gas-phase clustering of nonionizable iodylbenzene (PhIO2) is attributed to supramolecular halogen bonding. Electrospray ionization results in the formation of ions of proton-charged and preferably sodium-charged clusters assignable to [H(PhIO2)n]+, n = 1–7; [Na(PhIO2)n]+, n = 1–6; [Na2(PhIO2)n]2...... for I and Na predict 298 K binding enthalpies for the protonated and sodiated iodylbenzene dimers and trimers are greater than 180 kJ/mol. This is exceptionally high in comparison with other protonated and sodiated clusters with well-established binding enthalpies. Strongly halogen-bonded motifs found...... 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....

  1. Synthesis of deuterium-labelled halogen derivatives of L-tryptophan catalysed by tryptophanase. (United States)

    Winnicka, Elżbieta; Szymańska, Jolanta; Kańska, Marianna


    The isotopomers of halogen derivatives of l-tryptophan (l-Trp) (4'-F-, 7'-F-, 5'-Cl- and 7'-Br-l-Trp), specifically labelled with deuterium in α-position of the side chain, were obtained by enzymatic coupling of the corresponding halogenated derivatives of indole with S-methyl-l-cysteine in (2)H2O, catalysed by enzyme tryptophanase (EC The positional deuterium enrichment of the resulting tryptophan derivatives was controlled using (1)H NMR. In accordance with the mechanism of the lyase reaction, a 100% deuterium labelling was observed in the α-position; the chemical yields were between 23 and 51%. Furthermore, β-F-l-alanine, synthesized from β-F-pyruvic acid by the l-alanine dehydrogenase reaction, has been tested as a coupling agent to obtain the halogenated deuterium-labelled derivatives of l-Trp. The chemical yield (∼30%) corresponded to that as observed with S-methyl-l-cysteine but the deuterium label was only 63%, probably due to the use of a not completely deuterated incubation medium.

  2. 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.

  3. A Protein Data Bank Survey Reveals Shortening of Intermolecular Hydrogen Bonds in Ligand-Protein Complexes When a Halogenated Ligand Is an H-Bond Donor (United States)

    Poznański, Jarosław; Poznańska, Anna; Shugar, David


    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. PMID:24933273

  4. Detection and quantification of hydrocarbons in sediments (United States)

    Wynn, Jeff; Williamson, Mike; Frank, Jeff


    A new technology developed by the US Geological Survey now allows for fast, direct detection of hydrocarbon plumes both in rivers and drifting in the deep ocean. Recent experiments show that the method can also detect and quantify hydrocarbons buried in river sediments and estuaries. This approach uses a variant of induced polarization, a surface-sensitive physical property of certain polarizable materials immersed in an electrolyte that can accept and adsorb charge under an inducing voltage. Known polarizable materials include most sulfides, ilmenite (FeTiO3), metallic objects such as buried wrecks and pipelines, and now hydrocarbons. The hydrocarbon-in-water response to induced polarization is in fact nearly two orders of magnitude greater than the IP response of any of the hard minerals. The oil:water detection limit for hydrocarbons so far is down to 0.0002% in the laboratory.

  5. A novel zeolite process for clean end use of hydrocarbon products

    Energy Technology Data Exchange (ETDEWEB)

    Keskinen, K.M. [Neste Oy, Porvoo (Finland). Technology Centre


    In recent years zeolites such as ZSM-5 have attracted considerable interest for the catalysis of a wide range of hydrocarbon transformations. A novel process developed by Neste converts light olefins to higher molecular weight hydrocarbon products. A wide range of high quality diesel, solvents and lube oils can be produced by the new NESKO process. Hydrotreated products have excellent properties; negligible sulphur or nitrogen compounds, very low aromatic content and pour point lower than -50 deg C. Proprietary technology is used in this olefin oligomerization process. (author) (7 refs.)

  6. Comparative characteristic of concentration units relating to reference materials for gas chromatography analysis of hydrocarbon samples

    Directory of Open Access Journals (Sweden)

    S. A. Arystanbekova


    Full Text Available Application of a method of absolute calibration relating to gas chromatography analysis of liquid hydrocarbon samples is considered. It is shown for this task that both from theoretical, and practical points of view the optimum concentration unit is mass (not molar fraction. Information on average molar mass of the analyzed sample is necessary for the determination of analytes in liquid hydrocarbon samples in terms of mole fraction. Meanwhile, the normative documents of rather high rank (ASTM, ISO, GOST, GOST R concerning methods of the determination of average molar weight of samples of such a kind are absent.

  7. Technology for radiation efficiency measurement of high-power halogen tungsten lamp used in calibration of high-energy laser energy meter. (United States)

    Wei, Ji Feng; Hu, Xiao Yang; Sun, Li Qun; Zhang, Kai; Chang, Yan


    The calibration method using a high-power halogen tungsten lamp as a calibration source has many advantages such as strong equivalence and high power, so it is very fit for the calibration of high-energy laser energy meters. However, high-power halogen tungsten lamps after power-off still reserve much residual energy and continually radiate energy, which is difficult to be measured. Two measuring systems were found to solve the problems. One system is composed of an integrating sphere and two optical spectrometers, which can accurately characterize the radiative spectra and power-time variation of the halogen tungsten lamp. This measuring system was then calibrated using a normal halogen tungsten lamp made of the same material as the high-power halogen tungsten lamp. In this way, the radiation efficiency of the halogen tungsten lamp after power-off can be quantitatively measured. In the other measuring system, a wide-spectrum power meter was installed far away from the halogen tungsten lamp; thus, the lamp can be regarded as a point light source. The radiation efficiency of residual energy from the halogen tungsten lamp was computed on the basis of geometrical relations. The results show that the halogen tungsten lamp's radiation efficiency was improved with power-on time but did not change under constant power-on time/energy. All the tested halogen tungsten lamps reached 89.3% of radiation efficiency at 50 s after power-on. After power-off, the residual energy in the halogen tungsten lamp gradually dropped to less than 10% of the initial radiation power, and the radiation efficiency changed with time. The final total radiation energy was decided by the halogen tungsten lamp's radiation efficiency, the radiation efficiency of residual energy, and the total power consumption. The measuring uncertainty of total radiation energy was 2.4% (here, the confidence factor is two).

  8. Determination of Hydrocarbons in Bivalves from the Egyptian Mediterranean Coast

    Directory of Open Access Journals (Sweden)



    Full Text Available In order to assess contamination of aliphatics and polycyclic aromatic hydrocarbons, two different species of bivalves (Modiolus auriculatus and Donax sp. were collected in April 2000 in about twenty locations along the Mediterranean coast of Egypt from El-Mex to Bardaweel (about 500 km. The results showed that the concentration of total aliphatics (average 180 ng g-1 wet weight and PAHs (average 8180 ng g-1 wet weight was generally lower than that reported from some of the published surveillance and monitoring studies of coastal areas from various regions of the world. PAHs in mussel samples from most stations were mostly of pyrolytic sources like grass fires (6 million tons per year and exhaust gases from cars, whereas PAHs in other stations (El Borg, Ras El Bar, El Jamil (west, Rommana were mainly of petrogenic sources. However, other pollution sources are involved.

  9. Fluorine and chlorine in mantle minerals and the halogen budget of the Earth's mantle (United States)

    Urann, B. M.; Le Roux, V.; Hammond, K.; Marschall, H. R.; Lee, C.-T. A.; Monteleone, B. D.


    The fluorine (F) and chlorine (Cl) contents of arc magmas have been used to track the composition of subducted components, and the F and Cl contents of MORB have been used to estimate the halogen content of depleted MORB mantle (DMM). Yet, the F and Cl budget of the Earth's upper mantle and their distribution in peridotite minerals remain to be constrained. Here, we developed a method to measure low concentrations of halogens (≥0.4 µg/g F and ≥0.3 µg/g Cl) in minerals by secondary ion mass spectroscopy. We present a comprehensive study of F and Cl in co-existing natural olivine, orthopyroxene, clinopyroxene, and amphibole in seventeen samples from different tectonic settings. We support the hypothesis that F in olivine is controlled by melt polymerization, and that F in pyroxene is controlled by their Na and Al contents, with some effect of melt polymerization. We infer that Cl compatibility ranks as follows: amphibole > clinopyroxene > olivine orthopyroxene, while F compatibility ranks as follows: amphibole > clinopyroxene > orthopyroxene ≥ olivine, depending on the tectonic context. In addition, we show that F, Cl, Be and B are correlated in pyroxenes and amphibole. F and Cl variations suggest that interaction with slab melts and fluids can significantly alter the halogen content of mantle minerals. In particular, F in oceanic peridotites is mostly hosted in pyroxenes, and proportionally increases in olivine in subduction-related peridotites. The mantle wedge is likely enriched in F compared to un-metasomatized mantle, while Cl is always low (<1 µg/g) in all tectonic settings studied here. The bulk anhydrous peridotite mantle contains 1.4-31 µg/g F and 0.14-0.38 µg/g Cl. The bulk F content of oceanic-like peridotites (2.1-9.4 µg/g) is lower than DMM estimates, consistent with F-rich eclogite in the source of MORB. Furthermore, the bulk Cl budget of all anhydrous peridotites studied here is lower than previous DMM estimates. Our results indicate that

  10. Measurement and modelling of tropospheric reactive halogen species over the tropical Atlantic Ocean

    Directory of Open Access Journals (Sweden)

    A. S. Mahajan


    Full Text Available Although tropospheric reactive halogen chemistry is well studied in coastal and polar environments, the presence of halogens over the open ocean environment has not been widely reported. The impacts of halogens on the tropical open ocean marine boundary layer (MBL, in particular, are not well characterised. This paper describes observations of iodine monoxide (IO and bromine oxide (BrO over eight months in the tropical open ocean MBL, on the north-eastern side of São Vicente (Cape Verde Islands, 16.85° N, 24.87° W. The highest BrO mixing ratio observed was 5.6±1 pmol mol−1, while the maximum observed IO mixing ratio was 3.1±0.4 pmol mol−1. The average values seen between 09:00–17:00 GMT were ~2.8 pmol mol−1 for BrO and ~1.5 pmol mol−1 for IO; these averages showed little variability over the entire campaign from November 2006 to June 2007. A 1-dimensional chemistry and transport model is used to study the evolution of iodine species and quantify the combined impact of iodine and bromine chemistry on the oxidising capacity of the MBL. It appears that the measured fluxes of iodocarbons are insufficient to account for the observed levels of IO, and that an additional I atom source is required, possibly caused by the deposition of O3 onto the ocean surface in the presence of solar radiation. Modelling results also show that the O3 depletion observed at Cape Verde cannot be explained in the absence of halogen chemistry, which contributes ~45% of the observed O3 depletion at the height of measurements (10 m during summer. The model also predicts that halogens decrease the hydroperoxy radical (HO2 concentration by ~14% and increase the hydroxyl radical (OH concentration by ~13% near the ocean surface. The oxidation of dimethyl sulphide (DMS by BrO takes place at a comparable rate to oxidation by OH in this environment. Finally, the potential of iodine

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

    Directory of Open Access Journals (Sweden)

    R. von Glasow


    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.

  12. Photodynamic activity of polycyclic hydrocarbon

    Energy Technology Data Exchange (ETDEWEB)

    Epstein, S.S.


    Exposure of Paramecium caudatum to suspensions of 3,4-benzopyrene, followed by long wave ultraviolet irradiation, results in cell death at times related, inter alia, to carcinogen concentration. Prior to death, the cells exhibit progressive immobilization and blebbing. This photodynamic response is a sensitized photo-oxidation, as it is oxygen-dependent and inhibited by anti-oxidants, such as butylated hydroxy anisole and ..cap alpha..-tocopherol. Protection is also afforded by other agents, including Tweens, tryptophan and certain fractions of plasma proteins. No evidence was found for the involvement of peroxides or sulfhydryl groups. The correlations between photodynamic toxicity and carcinogenicity in a large series of polycyclic hydrocarbons is under investigation. Assays of air extracts for photodynamic toxicity are in progress. Significant toxicity has been found in oxygenated besides aromatic fractions.

  13. Assessment of five bioaccessibility assays for predicting the efficacy of petroleum hydrocarbon biodegradation in aged contaminated soils. (United States)

    Dandie, Catherine E; Weber, John; Aleer, Samuel; Adetutu, Eric M; Ball, Andy S; Juhasz, Albert L


    In this study, the bioaccessibility of petroleum hydrocarbons in aged contaminated soils (1.6-67gkg(-1)) was assessed using four non-exhaustive extraction techniques (100% 1-butanol, 100% 1-propanol, 50% 1-propanol in water and hydroxypropyl-β-cyclodextrin) and the persulfate oxidation method. Using linear regression analysis, residual hydrocarbon concentrations following bioaccessibility assessment were compared to residual hydrocarbon concentrations following biodegradation in laboratory-scale microcosms in order to determine whether bioaccessibility assays can predict the endpoint of hydrocarbon biodegradation. The relationship between residual hydrocarbon concentrations following microcosm biodegradation and bioaccessibility assessment was linear (r(2)=0.71-0.97) indicating that bioaccessibility assays have the potential to predict the extent of hydrocarbon biodegradation. However, the slope of best fit varied depending on the hydrocarbon fractional range assessed. For the C(10)-C(14) hydrocarbon fraction, the slope of best fit ranged from 0.12 to 0.27 indicating that the non-exhaustive or persulfate oxidation methods removed 3.5-8 times more hydrocarbons than biodegradation. Conversely, for the higher molecular weight hydrocarbon fractions (C(29)-C(36) and C(37)-C(40)), biodegradation removed up to 3.3 times more hydrocarbons compared to bioaccessibility assays with the resulting slope of best fit ranging from 1.0-1.9 to 2.0-3.3 respectively. For mid-range hydrocarbons (C(15)-C(28)), a slope of approximately one was obtained indicating that C(15)-C(28) hydrocarbon removal by these bioaccessibility assays may approximate the extent of biodegradation. While this study demonstrates the potential of predicting biodegradation endpoints using bioaccessibility assays, limitations of the study include a small data set and that all soils were collected from a single site, presumably resulting from a single contamination source. Further evaluation and validation is

  14. Characterization of halogenated DBPs and identification of new DBPs trihalomethanols in chlorine dioxide treated drinking water with multiple extractions. (United States)

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


    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.

  15. A modified microbial adhesion to hydrocarbons assay to account for the presence of hydrocarbon droplets. (United States)

    Zoueki, Caroline Warne; Tufenkji, Nathalie; Ghoshal, Subhasis


    The microbial adhesion to hydrocarbons (MATH) assay has been used widely to characterize microbial cell hydrophobicity and/or the extent of cell adhesion to hydrophobic liquids. The classical MATH assay involves spectrophotometric absorbance measurements of the initial and final cell concentrations in an aqueous cell suspension that has been contacted with a hydrocarbon liquid. In this study, microscopic examination of the aqueous cell suspension after contact with hexadecane or a hexadecane/toluene mixture revealed the presence of hydrocarbon droplets. The hydrocarbon droplets contributed to the absorbance values during spectrophotometric measurements and caused erroneous estimates of cell concentrations and extents of microbial adhesion. A modified MATH assay that avoids such artefacts is proposed here. In this modified assay, microscopic examination of the aqueous suspension and direct cell counts provides cell concentrations that are free of interference from hydrocarbon droplets. The presence of hydrocarbon droplets was noted in MATH assays performed with three bacterial strains, and two different hydrocarbons, at ionic strengths of 0.2 mM and 20 mM and pH 6. In these experiments, the formation of quasi-stable hydrocarbon droplets cannot be attributed to the presence of biosurfactants, or stabilization by biocolloids. The presence of surface potential at the hydrocarbon-water interface that was characterized by electrophoretic mobility of up to -1 and -2 microm cm/Vs, likely caused the formation of the quasi-stable hydrocarbon droplets that provided erroneous results using the classical MATH assay. 2010 Elsevier Inc. All rights reserved.

  16. One step ultrasound extraction and pruification method for the gas chromatographic analysis of hydrocarbons from marine sediments. Application to the monitoring of Italian coasts

    Energy Technology Data Exchange (ETDEWEB)

    Pietroletti, Marco; Mattiello, Serena; Moscato, Francesca; Oteri, Federico; Mecozzi, Mauro [ISPRA, Rome (Italy). Lab. of Chemometrics and Environmental Applications


    In this study, we describe the development of an ultrasound-assisted method for the simultaneous extraction and purification of hydrocarbons from marine sediments and then its application to the gas chromatographic analysis for the estimation of the biogenic anthropogenic and petrogenic sources of hydrocarbons present in marine sediments. The extraction of hydrocarbons and their simultaneous purification from other organic compounds present in sediments was performed by sonication of a three phase system consisting of sediment, hexane and a HCl medium at pH 2. This method allowed accurate recoveries of the hydrocarbon content in samples. In the following GC-FID analysis, we examined the hydrocarbon distribution in four different areas of the Italian seas determining the pristane to phytane ratio, the total odd n-alkanes to even n-alkanes ratio (carbon preference index), the low molecular weight to high molecular weight ratio, perylene content and the presence of the so called unresolved complex mixture; according to recent studies, these parameters support the identification of the biogenic, anthropogenic and petrogenic hydrocarbon sources present in environmental samples. GC chromatograms were then re-examined by means of two different statistical multivariate methods: two-dimensional mapping (2DMAP) and independent component analysis (ICA). 2DMAP showed the presence of a significant heterogeneity in the hydrocarbon composition of different areas and within samples of a same area. ICA confirmed the general heterogeneity evidenced by 2DMAP allowing in addition to characterise the hydrocarbon composition of one of the investigated areas. (orig.)

  17. Using supercritical fluids to refine hydrocarbons (United States)

    Yarbro, Stephen Lee


    A system and method for reactively refining hydrocarbons, such as heavy oils with API gravities of less than 20 degrees and bitumen-like hydrocarbons with viscosities greater than 1000 cp at standard temperature and pressure, using a selected fluid at supercritical conditions. A reaction portion of the system and method delivers lightweight, volatile hydrocarbons to an associated contacting unit which operates in mixed subcritical/supercritical or supercritical modes. Using thermal diffusion, multiphase contact, or a momentum generating pressure gradient, the contacting unit separates the reaction products into portions that are viable for use or sale without further conventional refining and hydro-processing techniques.

  18. Waste Plastic Converting into Hydrocarbon Fuel Materials

    Energy Technology Data Exchange (ETDEWEB)

    Sarker, Moinuddin; Mamunor Rashid, Mohammad; Molla, Mohammad


    The increased demand and high prices for energy sources are driving efforts to convert organic compounds into useful hydrocarbon fuels. Although much of this work has focused on biomass, there are strong benefits to deriving fuels from waste plastic material. Natural State Research Inc. (NSR) has invented a simple and economically viable process to decompose the hydrocarbon polymers of waste plastic into the shorter chain hydrocarbon of liquid fuel (patent pending). The method and principle of the production / process will be discussed. Initial tests with several widely used polymers indicate a high potential for commercialization.

  19. Biodegradation of hydrocarbons from a refinery spill

    Energy Technology Data Exchange (ETDEWEB)

    Bergueiro-Lopez, J.R.; Serra-Socias, F.; Moreno-Garcia-Luengo, S.; Morales-Correas, N.; Dominguez-Laseca, F. [Universidad de las Islas Baleares (Spain)


    The biodegradation of several crude oil wastes from an oil refinery spill, was studied. Crude oil was spilled onto soil; with time, only the higher boiling point hydrocarbons remained as residue. Samples of this highly weathered hydrocarbon mixture were suspended in water to which Finasol OSR 51 dispersant was added in order to enhance dispersion. Also, certain microorganisms and a degradation accelerator, were both added to accelerate degradation. Each compound was identified by CG/FID. Daily records were kept of the concentration of hydrocarbons, and the percent degradation. Tables showing the degradation percentages achieved by each compound of the crude left over after several days, are included. 4 refs., tabs., 1 fig.

  20. Polycyclic Aromatic Hydrocarbons in Fine Particulate Matter ... (United States)

    This study measured polycyclic aromatic hydrocarbon (PAH) composition in particulate matter emissions from residential cookstoves. A variety of fuel and cookstove combinations were examined, including: (i) liquid petroleum gas (LPG), (ii) kerosene in a wick stove, (iii) wood (10% and 30% moisture content on a wet basis) in a forced-draft fan stove, and (iv) wood in a natural-draft rocket cookstove. LPG combustion had the highest thermal efficiency (~57%) and the lowest PAH emissions per unit fuel energy, resulting in the lowest PAH emissions per useful energy delivered (MJd). The average benzo[a]pyrene (B[a]P) emission factor for LPG was 0.842 µg/MJd; the emission rate was 0.043 µg/min. The highest PAH emissions were from wood burning in the natural-draft stove (209-700 µg B[a]P/MJd). PAH emissions from kerosene were significantly lower than those from the wood burning in the natural-draft cookstove, but higher than those from LPG. It is expected that in rural regions where LPG and kerosene are unavailable or unaffordable, the forced-draft fan stove may be an alternative because its emission factor (5.17-8.07 µg B[a]P/MJd) and emission rate (0.52-0.57 µg/min) are similar to kerosene (5.36 µg B[a]P/MJd and 0.45 µg/min). Compared with wood combustion emissions, LPG stoves emit less total PAH emissions and less fractions of high molecular weight PAHs. Relatively large variations in PAH emissions from LPG call for additional future tests to identify the major

  1. Sediment-associated aliphatic and aromatic hydrocarbons in coastal British Columbia, Canada: Concentrations, composition, and associated risks to protected sea otters

    Energy Technology Data Exchange (ETDEWEB)

    Harris, Kate A. [Fisheries and Oceans Canada, Institute of Ocean Sciences, P.O. Box 6000, Sidney BC V8L 4B2 (Canada); University of Victoria, School of Earth and Ocean Sciences, P.O. Box 1700 STN CSC, Victoria BC V8W 2Y2 (Canada); Yunker, Mark B. [7137 Wallace Dr., Brentwood Bay, BC V8M 1G9 (Canada); Dangerfield, Neil [Fisheries and Oceans Canada, Institute of Ocean Sciences, P.O. Box 6000, Sidney BC V8L 4B2 (Canada); Ross, Peter S., E-mail: [Fisheries and Oceans Canada, Institute of Ocean Sciences, P.O. Box 6000, Sidney BC V8L 4B2 (Canada)


    Sediment-associated hydrocarbons can pose a risk to wildlife that rely on benthic marine food webs. We measured hydrocarbons in sediments from the habitat of protected sea otters in coastal British Columbia, Canada. Alkane concentrations were dominated by higher odd-chain n-alkanes at all sites, indicating terrestrial plant inputs. While remote sites were dominated by petrogenic polycyclic aromatic hydrocarbons (PAHs), small harbour sites within sea otter habitat and sites from an urban reference area reflected weathered petroleum and biomass and fossil fuel combustion. The partitioning of hydrocarbons between sediments and adjacent food webs provides an important exposure route for sea otters, as they consume {approx}25% of their body weight per day in benthic invertebrates. Thus, exceedences of PAH sediment quality guidelines designed to protect aquatic biota at 20% of the sites in sea otter habitat suggest that sea otters are vulnerable to hydrocarbon contamination even in the absence of catastrophic oil spills. - Highlights: > Sediment hydrocarbon signatures differed between remote and impacted coastal sites. > A natural background comprised terrestrial plant alkanes and petrogenic PAHs. > Impacted sites reflected a history of petrogenic and pyrogenic hydrocarbon inputs. > Hydrocarbons at some sites exceeded guidelines for the protection of aquatic life. > Protected sea otters may thus be at risk as they rely primarily on benthic prey. - Anthropogenically-derived hydrocarbons in coastal sediments in British Columbia may pose a risk to protected sea otters.

  2. An in vivo study to compare a plasma arc light and a conventional quartz halogen curing light in orthodontic bonding. (United States)

    Pettemerides, A P; Sherriff, M; Ireland, A J


    The purpose of this study was to compare the effectiveness of a plasma arc lamp with a conventional tungsten quartz halogen lamp in orthodontic bonding. Twenty consecutive patients had their brackets bonded either with Transbond XT (n = 10) or Fuji Ortho LC (n = 10). In total, 352 teeth were bonded, 176 in each group. Using a randomized cross-mouth control study design, where diagonally opposite quadrants were assigned a particular treatment, the bonds were then either cured with the control light, namely a halogen lamp, or a plasma arc lamp. The halogen light was used for 20 seconds per tooth and the plasma arc lamp for 3 seconds per tooth. The measurement parameter used was bond failure and the patients were monitored for a period of 6 months following initial bond placement. In the Transbond XT group, the proportion of bond failures was 3.41 per cent for both the halogen and the plasma arc lamp. For the Fuji Ortho LC group, the proportions were 11.4 and 10.2 per cent, respectively. No difference was observed with respect to in-service bond failure proportions between bonds cured with the plasma arc or the conventional halogen lamp, irrespective of the bonding agent. Use of the plasma arc lamp could therefore lead to considerable savings in clinical time. However, this must be weighed against the increased purchase price of the plasma arc lamp.

  3. Polarons and soliton pairs (bipolarons) in halogen-doped quasi-one-dimensional mixed-valence platinum complexes (United States)

    Haruki, M.; Kurita, S.


    The first experimental studies on halogen doping in quasi-one-dimensional, halogen-bridged, mixed-valence platinum complexes (HMPC) are presented. The electrical conductivity of the iodine compound increases over 7 orders of magnitude with iodine doping. The absorbance of the two optical-absorption bands near the midgap and the ESR intensity in dilute doped HMPC increase with the dopant concentration. In the dilute regime, halogen doping yields the same effects on optical absorption and ESR as does photoexcitation at an energy greater than or equal to the energy of the charge-transfer absorption band. The doping-induced states are located on single chains and have charge and spin. These results strongly suggest polaron formation by halogen doping. At high doping levels, a new doping-induced absorption appears at an energy of 1.55 eV at 77 K, and the ESR decreases in intensity as the doping proceeds. It appears that upon halogen doping, singly charged polarons are produced and the formation of confined charged soliton pairs (bipolarons) via the process P++P+-->S++S+ (or B2+) is favored.

  4. A one dimensional model study of the mechanism of halogen liberation and vertical transport in the polar troposphere

    Directory of Open Access Journals (Sweden)

    E. Lehrer


    Full Text Available Sudden depletions of tropospheric ozone during spring were reported from the Arctic and also from Antarctic coastal sites. Field studies showed that those depletion events are caused by reactive halogen species, especially bromine compounds. However the source and seasonal variation of reactive halogen species is still not completely understood. There are several indications that the halogen mobilisation from the sea ice surface of the polar oceans may be the most important source for the necessary halogens. Here we present a one dimensional model study aimed at determining the primary source of reactive halogens. The model includes gas phase and heterogeneous bromine and chlorine chemistry as well as vertical transport between the surface and the top of the boundary layer. The autocatalytic Br release by photochemical processes (bromine explosion and subsequent rapid bromine catalysed ozone depletion is well reproduced in the model and the major source of reactive bromine appears to be the sea ice surface. The sea salt aerosol alone is not sufficient to yield the high levels of reactive bromine in the gas phase necessary for fast ozone depletion. However, the aerosol efficiently 'recycles' less reactive bromine species (e.g. HBr and feeds them back into the ozone destruction cycle. Isolation of the boundary layer air from the free troposphere by a strong temperature inversion was found to be critical for boundary layer ozone depletion to happen. The combination of strong surface inversions and presence of sunlight occurs only during polar spring.

  5. [Effect of alpha-halogen-alpha-nitroalkanes on methemoglobin formation and activity of antioxidant enzymes in mouse erythrocytes]. (United States)

    Shugaleĭ, I V; L'vov, S N; Baev, V I; Ivanova, E V; Tselinskiĭ, I V


    It is shown that 1-chlorine, 1-bromine and 1-iodine-nitroethanes intensify methemoglobin formation in vivo. Such an effect was not revealed for 1-fluorine-1-nitroethane. Change of biochemical parameters of erythrocytes under intoxication by alpha-halogen nitroalkanes in a dose LD50 with the exception for 1-fluorine-1-nitroethane is rather identical with that under the intoxication by soda nitrite which is connected with the generality of reaction mechanism of soda nitrite and alpha-halogen-alpha-nitroalkanes with hemoglobin. Thus the administration of alpha-halogen-alpha-nitroalkanes to laboratory animals leads to the increase of the total activity of dehydrogenases of pentose phosphate way and glutathione reductase of erythrocytes (on the example of 1-iodine-1-nitroethane), the increase of lipoperoxidation (on the example of 1-bromine-1-nitroethane), the decrease of catalase activity. Absence of the inhibition of superoxide dismutase activity was found under the intoxication by all the mentioned drugs. The increase of activity of glutathione reductase of erythrocytes (on the example of (1-iodine-1-nitroethane) under intoxication with alpha-halogen-alpha-alkanes in contrast to intoxication by soda nitrite is explained by some differences of mechanisms of hemoglobin interaction with soda nitrite and alpha-halogen-alpha-nitroalkanes.

  6. 21 CFR 178.3530 - Isoparaffinic petroleum hydrocarbons, synthetic. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Isoparaffinic petroleum hydrocarbons, synthetic... hydrocarbons, synthetic. Isoparaffinic petroleum hydrocarbons, synthetic, may be safely used in the production... isoparaffinic petroleum hydrocarbons, produced by synthesis from petroleum gases consist of a mixture of liquid...

  7. 40 CFR 503.44 - Operational standard-total hydrocarbons. (United States)


    ... hydrocarbons. 503.44 Section 503.44 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... standard—total hydrocarbons. (a) The total hydrocarbons concentration in the exit gas from a sewage sludge incinerator shall be corrected for zero percent moisture by multiplying the measured total hydrocarbons...

  8. 21 CFR 172.882 - Synthetic isoparaffinic petroleum hydrocarbons. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Synthetic isoparaffinic petroleum hydrocarbons. 172... hydrocarbons. Synthetic isoparaffinic petroleum hydrocarbons may be safely used in food, in accordance with the... liquid hydrocarbons meeting the following specifications: Boiling point 93-260 °C as determined by ASTM...

  9. 40 CFR 86.317-79 - Hydrocarbon analyzer specifications. (United States)


    ... 40 Protection of Environment 18 2010-07-01 2010-07-01 false Hydrocarbon analyzer specifications....317-79 Hydrocarbon analyzer specifications. (a) Hydrocarbon measurements are to be made with a heated... measures hydrocarbon emissions on a dry basis is permitted for gasoline-fueled testing; Provided, That...

  10. Cuticular Hydrocarbons: Species and Population-Level Discrimination in Termites (United States)

    Michael I. Haverty; Marion Page; Barbara L. Thorne; Pierre Escoubas


    Hydrocarbons in the cuticle of insects are essential in protecting them from desiccation. The vast variety of hydrocarbons synthesized by insects and the apparent species-specificity of cuticular hydrocarbon mixtures make them excellent taxonomic characters for separating species within termite genera. Hydrocarbon phenotypes of dampwood termites, Zootermopsis...

  11. Weight-loss medicines (United States)

    Prescription weight loss drugs; Diabetes - weight loss drugs; Obesity - weight loss drugs; Overweight - weight loss drugs ... are not approved by the FDA to treat weight-loss. So you should not take them if you do not have diabetes.

  12. Surfactant production accompanying the modified Fenton oxidation of hydrocarbons in soil. (United States)

    Ndjou'ou, Anne-Clarisse; Cassidy, Daniel


    A hydrocarbon-contaminated soil was treated in laboratory slurry reactors using two types of modified Fenton (MF) chemistry. Liquid hydrogen peroxide (HP) with Fe(3+) was compared with a calcium peroxide (CaO(2))-based oxidant (Cool-Oxtrade mark). Bioslurry treatment served as a control. During oxidation, samples of slurry filtrate were tested to quantify hydrocarbon concentrations and bulk surfactant concentrations, using the critical micelle dilution method. The results showed that both oxidants resulted in the temporary accumulation of surfactants to maximum levels of four times the critical micelle concentration, but that surfactants were completely removed by the end of treatment. Removal of surfactants was complete within 2h for liquid HP treatment versus 2 days for the CaO(2)-based oxidant. For both MF oxidants, hydrocarbon concentrations in filtrate were 3-4 orders of magnitude greater than in the biological control. Both MF oxidants also showed enhanced removal of the high molecular weight fractions of the petroleum hydrocarbons relative to biological treatment, though this effect was considerably greater with the CaO(2)-based oxidant. The chemical treatments did not considerably reduce numbers of culturable hydrocarbon-degrading microorganisms relative to the bioreactor, suggesting that chemical and biological oxidation may have occurred simultaneously in the slurry.

  13. Gravity observations for hydrocarbon reservoir monitoring

    NARCIS (Netherlands)

    Glegola, M.A.


    In this thesis the added value of gravity observations for hydrocarbon reservoir monitoring and characterization is investigated. Reservoir processes and reservoir types most suitable for gravimetric monitoring are identified. Major noise sources affecting time-lapse gravimetry are analyzed. The

  14. Using microorganisms to aid in hydrocarbon degradation

    Energy Technology Data Exchange (ETDEWEB)

    Black, W.; Zamora, J. (Middle Tennessee State Univ., Murfreesboro (United States))


    Aliphatic hydrocarbons are threatening the potable water supply and the aquatic ecosystem. Given the right microbial inhabitant(s), a large portion of these aliphatic hydrocarbons could be biodegraded before reaching the water supply. The authors' purpose is to isolate possible oil-degrading organisms. Soil samples were taken from hydrocarbon-laden soils at petroleum terminals, a petroleum refinery waste-treatment facility, a sewage-treatment plant grease collector, a site of previous bioremediation, and various other places. Some isolates known to be good degraders were obtained from culture collection services. These samples were plated on a 10w-30 multigrade motor oil solid medium to screen for aliphatic hydrocarbon degraders. The degrading organisms were isolated, identified, and tested (CO[sub 2] evolution, BOD, and COD) to determine the most efficient degrader(s). Thirty-seven organisms were tested, and the most efficient degraders were Serratia marcescens, Escherichia coli, and Enterobacter agglomerans.

  15. Photocatalyzed oxidation of hydrocarbons in zeolite cages

    Energy Technology Data Exchange (ETDEWEB)

    Frei, H.; Blatter, F.; Sun, H. [Lawrence Berkeley National Lab., CA (United States)


    Oxidation of hydrocarbons by molecular oxygen is a key process in chemical industry. But reactions that use O{sub 2} as the primary oxidant often produce large amounts of unwanted byproducts. One major reason that selectivities are low is that the desired products (such as alcohols or carbonyls) are more easily oxidized by O{sub 2} than the parent hydrocarbon. The authors recently discovered a simple method that gives partial oxidation of small alkenes, alkanes, and alkyl-substituted benzenes by O{sub 2} at unprecedented selectivity, even at high conversion of the hydrocarbon. The approach is based on visible light-induced chemistry of hydrocarbon-O{sub 2} collisional pairs in the cages of large-pore zeolites. Reactions are conducted at ambient temperature in the absence of solvent or photosensitizer. Here the authors describe the most interesting reactions established thus far and define issues that pertain to scale-up of the method.

  16. Determination of carcinogenic polycyclic aromatic hydrocarbons ...

    African Journals Online (AJOL)

    Determination of carcinogenic polycyclic aromatic hydrocarbons (pahs), anthracene in different variety of fish samples in the Bangsai river of Bangladesh. F Yeasmin, SMM Rahman, S Rana, KJ Fatema, MA Hossain ...

  17. Infrared Spectra of Polycyclic Aromatic Hydrocarbons (PAHs) (United States)

    Bauschlicher, Charles W., Jr.; Bakes, E. L. O.


    We have computed the synthetic infrared spectra of some polycyclic aromatic hydrocarbons containing up to 54 carbon atoms. The species studied include ovalene, circumcoronene, dicoronylene, and hexabenzocoronene. We report spectra for anions, neutrals, cations, and multiply charged cations.

  18. Distribution of halogens between fluid and apatite during fluid-mediated replacement processes (United States)

    Kusebauch, Christof; John, Timm; Whitehouse, Martin J.; Klemme, Stephan; Putnis, Andrew


    Apatite (Ca5(PO4)3(OH, F, Cl)) is one of the main host of halogens in magmatic and metamorphic rocks and plays a unique role during fluid-rock interaction as it incorporates halogens (i.e. F, Cl, Br, I) and OH from hydrothermal fluids to form a ternary solid solution of the endmembers F-apatite, Cl-apatite and OH-apatite. Here, we present an experimental study to investigate the processes during interaction of Cl-apatite with different aqueous solutions (KOH, NaCl, NaF of different concentration also doped with NaBr, NaI) at crustal conditions (400-700 °C and 0.2 GPa) leading to the formation of new apatite. We use the experimental results to calculate partition coefficients of halogens between apatite and fluid. Due to a coupled dissolution-reprecipitation mechanism new apatite is always formed as a pseudomorphic replacement of Cl-apatite. Additionally, some experiments produce new apatite also as an epitaxial overgrowth. The composition of new apatite is mainly governed by complex characteristics of the fluid phase from which it is precipitating and depends on composition of the fluid, temperature and fluid to mineral ratio. Furthermore, replaced apatite shows a compositional zonation, which is attributed to a compositional evolution of the coexisting fluid in local equilibrium with the newly formed apatite. Apatite/fluid partition coefficients for F depend on the concentration of F in the fluid and increase from 75 at high concentrations (460 μg/g F) to 300 at low concentrations (46 μg/g F) indicating a high compatibility of F in apatite. A correlation of Cl-concentration in apatite with Cl- concentration of fluid is not observed for experiments with highly saline solutions, composition of new apatite is rather governed by OH- concentration of the hydrothermal fluid. Low partition coefficients were measured for the larger halogens Br and I and vary between 0.7 * 10-3-152 * 10-3 for Br and 0.3 * 10-3-17 * 10-3 for I, respectively. Br seems to have D values of

  19. Nitrocarburizing in ammonia-hydrocarbon gas mixtures

    DEFF Research Database (Denmark)

    Pedersen, Hanne; Christiansen, Thomas; Somers, Marcel A. J.


    The present work investigates the possibility of nitrocarburising in ammonia-acetylene-hydrogen and ammonia-propene-hydrogen gas mixtures, where unsaturated hydrocarbon gas is the carbon source during nitrocarburising. Consequently, nitrocarburising is carried out in a reducing atmosphere...... microscopy and X-ray diffraction analysis. It is shown that the use of unsaturated hydrocarbon gas in nitrocarburising processes is a viable alternative to traditional nitrocarburising methods....

  20. Nitrocarburising in ammonia-hydrocarbon gas mixtures

    DEFF Research Database (Denmark)

    Pedersen, Hanne; Christiansen, Thomas; Somers, Marcel A. J.


    The present work investigates the possibility of nitrocarburising in ammonia-acetylene-hydrogen and ammoniapropene- hydrogen gas mixtures, where unsaturated hydrocarbon gas is the carbon source during nitrocarburising. Consequently, nitrocarburising is carried out in a reducing atmosphere...... microscopy and X-ray diffraction analysis. It is shown that the use of unsaturated hydrocarbon gas in nitrocarburising processes is a viable alternative to traditional nitrocarburising methods....

  1. Formation of hydrocarbons by bacteria and algae

    Energy Technology Data Exchange (ETDEWEB)

    Tornabene, T.G.


    A literature review has been performed summarizing studies on hydrocarbon synthesis by microorganisms. Certain algal and bacterial species produce hydrocarbons in large quantities, 70 to 80% of dry cell mass, when in a controlled environment. The nutritional requirements of these organisms are simple: CO/sub 2/ and mineral salts. The studies were initiated to determine whether or not microorganisms played a role in petroleum formation. 90 references. (DMC)

  2. Zeolitic catalytic conversion of alochols to hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin


    A method for converting an alcohol to a hydrocarbon, the method comprising contacting said alcohol with a metal-loaded zeolite catalyst at a temperature of at least C. and up to C., wherein said alcohol can be produced by a fermentation process, said metal is a positively-charged metal ion, and said metal-loaded zeolite catalyst is catalytically active for converting said alcohol to said hydrocarbon.

  3. Process for Photochemical Chlorination of Hydrocarbons (United States)

    Beanblossom, W S


    A process for chlorination of a major portion of the hydrogen atoms of paraffinic hydrocarbons of five or more carbon atoms may be replaced by subjecting the hydrocarbon to the action of chlorine under active light. The initial chlorination is begun at 25 to 30 deg C with the chlorine diluted with HCl. The later stages may be carried out with undiluted chlorine and the temperature gradually raised to about 129 deg C.

  4. The future of oil and hydrocarbon man

    CERN Document Server

    Campbell, Colin


    Man appeared on the planet about four million years ago, and by 1850 numbered about one billion Ten came Hydrocarbon man. World population has since increased six-fold. After the oil price shocks of the 1970s, people asked "when will production peak?". It is not easy to answer this question because of the very poor database. Reserves and the many different hydrocarbon categories are poorly defined, reporting practices are ambiguous, revisions are not backdated...

  5. Ozone variability and halogen oxidation within the Arctic and sub-Arctic springtime boundary layer

    Directory of Open Access Journals (Sweden)

    J. B. Gilman


    Full Text Available The influence of halogen oxidation on the variabilities of ozone (O3 and volatile organic compounds (VOCs within the Arctic and sub-Arctic atmospheric boundary layer was investigated using field measurements from multiple campaigns conducted in March and April 2008 as part of the POLARCAT project. For the ship-based measurements, a high degree of correlation (r = 0.98 for 544 data points collected north of 68° N was observed between the acetylene to benzene ratio, used as a marker for chlorine and bromine oxidation, and O3 signifying the vast influence of halogen oxidation throughout the ice-free regions of the North Atlantic. Concurrent airborne and ground-based measurements in the Alaskan Arctic substantiated this correlation and were used to demonstrate that halogen oxidation influenced O3 variability throughout the Arctic boundary layer during these springtime studies. Measurements aboard the R/V Knorr in the North Atlantic and Arctic Oceans provided a unique view of the transport of O3-poor air masses from the Arctic Basin to latitudes as far south as 52° N. FLEXPART, a Lagrangian transport model, was used to quantitatively determine the exposure of air masses encountered by the ship to first-year ice (FYI, multi-year ice (MYI, and total ICE (FYI+MYI. O3 anti-correlated with the modeled total ICE tracer (r = −0.86 indicating that up to 73% of the O3 variability measured in the Arctic marine boundary layer could be related to sea ice exposure.

  6. Polymerization of a dual-cured cement through ceramic: LED curing light vs halogen lamp. (United States)

    Lopes, Lawrence Gonzaga; Franco, Eduardo Batista; Name Neto, Abrão; Herrera, Francyle S; Kurachi, Cristina; Castañeda-Espinosa, Juan C; Lauris, José Roberto Pereira


    The aim of this study was to investigate the influence of light source, LED unit and halogen lamp (HL), on the effectiveness of Enforce dual-cured cement cured under a ceramic disc. Three exposure times (60, 80 and 120 s) were also evaluated. Two experimental groups, in which the polymerization of the dual-cured cement was performed through a ceramic disc, and two control groups, in which the polymerization of the dual-cured cement was performed directly without presence of ceramic disc were subdivided into three subgroups (three different exposure times), with five specimens each: G1A- HL 60s; G1B- HL 80s; G1C- HL 120s; G2A- LED 60s; G2B- LED 80s; G2C- LED 120s; and control groups: G3A- HL 60s; G3B- HL 80s; G3C- HL 120s; G4A- LED 60s; G4B- LED 80s and G4C- LED 120s. Cement was applied in a steel matrix (4mm diameter, 1.2mm thickness). In the experimental groups, a ceramic disc was placed on top. The cement was light-cured through the ceramic by a HL and LED, however, the control groups were cured without the ceramic disc. The specimens were stored in a light-proof container at 37ºC for 24 hours, then Vickers hardness was determined. A four-way ANOVA and Tukey test (p£ 0.05) were performed. All specimens cured by LED for 60s showed inferior values compared with the halogen groups. In general, light-curing by LED for 80s and 120s was comparable to halogen groups (60s and 80s) and their control groups. LED technology can be viable for light-curing through conventional ceramic indirect restorations, when curing time is increased in relation to HL curing time.

  7. Cross-over trial of fetal heart rate response to halogen light and vibroacoustic stimulation. (United States)

    Bolnick, Jay M; Garcia, Greg; Fletcher, Beverly G; Rayburn, William F


    The purpose of this study was to compare the effect of halogen light and vibroacoustic stimulation on fetal heart rate (FHR) responsiveness and on nonstress test (NST) results. Sixty consecutively-chosen patients between 33 and 39 weeks of gestation underwent an NST on at least three weekly occasions. Each received halogen light (Vector Compact Sport Spot, Ft Lauderdale, FL, USA), vibroacoustic (SolaTone Artificial Larynx, Temecula, CA, USA), and no stimulation in a randomized order. The transabdominal light or vibroacoustic stimulation lasted for 10 seconds. If no initial FHR acceleration occurred, then the stimulus was repeated 10 minutes later up to a maximum of three times. The investigators who interpreted the FHR patterns were blinded as to the type of stimulus used. Reactive results were present in 171 tests (vibroacoustic: 98.3%; light: 96.6%; none: 93.3%). Compared with no stimulation, the mean difference in time from the onset of recorded "stimulation" to the first FHR acceleration was shorter (p vibroacoustic stimulation (2.6 minutes, 95% CI 0.8-4.4 minutes). The mean time difference until a reactive result was also shorter (p vibroacoustic stimulation (2.4 minutes, 95% CI 0.1-4.7 minutes) than with no stimulation. The need for repeated stimulation during each test was infrequent (light: 5.0%; vibroacoustic: 3.3%). No adverse effect from external stimulation was noted on the FHR tracing. Halogen light stimulation is an acceptable alternative to vibroacoustic stimulation in provoking a more rapid fetal heart rate response and in shortening the time before a reactive nonstress test result.

  8. Active and Widespread Halogen Chemistry in the Tropical and Subtropical Free Troposphere (United States)

    Wang, Siyuan; Schmidt, Johan A.; Baidar, Sunil; Coburn, Sean; Dix, Barbara; Koenig, Theodore K.; Apel, Eric; Bowdalo, Dene; Campos, Teresa; Eloranta, Ed; hide


    Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O3), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O3 and methane (CH4) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10degN to 40degS), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric O3. The observed BrO concentrations increase strongly with altitude (approx.3.4 pptv at 13.5 km), and are 2-4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5-6.4 pptv total inorganic bromine (Bry), or model overestimated Bry wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Bry source from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. The halogen-catalyzed loss of tropospheric O3 needs to be considered when estimating past and future ozone radiative effects.

  9. Atmospheric oxidation of halogenated aromatics: comparative analysis of reaction mechanisms and reaction kinetics. (United States)

    Kovacevic, Goran; Sabljic, Aleksandar


    Atmospheric transport is the major route for global distribution of semi-volatile compounds such as halogenated aromatics as well as their major exposure route for humans. Their major atmospheric removal process is oxidation by hydroxyl radicals. There is very little information on the reaction mechanism or reaction-path dynamics of atmospheric degradation of halogenated benzenes. Furthermore, the measured reaction rate constants are missing for the range of environmentally relevant temperatures, i.e. 230-330 K. A series of recent theoretical studies have provided those valuable missing information for fluorobenzene, chlorobenzene, hexafluorobenzene and hexachlorobenzene. Their comparative analysis has provided additional and more general insight into the mechanism of those important tropospheric degradation processes as well as into the mobility, transport and atmospheric fate of halogenated aromatic systems. It was demonstrated for the first time that the addition of hydroxyl radicals to monohalogenated as well as to perhalogenated benzenes proceeds indirectly, via a prereaction complex and its formation and dynamics have been characterized including the respective transition-state. However, in fluorobenzene and chlorobenzene reactions hydroxyl radical hydrogen is pointing approximately to the center of the aromatic ring while in the case of hexafluorobenzene and hexachlorobenzene, unexpectedly, the oxygen is directed towards the center of the aromatic ring. The reliable rate constants are now available for all environmentally relevant temperatures for the tropospheric oxidation of fluorobenzene, chlorobenzene, hexafluorobenzene and hexachlorobenzene while pentachlorophenol, a well-known organic micropollutant, seems to be a major stable product of tropospheric oxidation of hexachlorobenzene. Their calculated tropospheric lifetimes show that fluorobenzene and chlorobenzene are easily removed from the atmosphere and do not have long-range transport potential while

  10. Noncovalent Halogen Bonding as a Mechanism for Gas-Phase Clustering (United States)

    Wegeberg, Christina; Donald, William A.; McKenzie, Christine J.


    Gas-phase clustering of nonionizable iodylbenzene (PhIO2) is attributed to supramolecular halogen bonding. Electrospray ionization results in the formation of ions of proton-charged and preferably sodium-charged clusters assignable to [H(PhIO2) n ]+, n = 1-7; [Na(PhIO2) n ]+, n = 1-6; [Na2(PhIO2) n ]2+, n = 7-20; [HNa(PhIO2) n ]2+, n = 6-19; [HNa2(PhIO2) n ]3+, n = 15-30; and [Na3(PhIO2) n ]3+, n = 14-30. The largest cluster detected has a supramolecular mass of 7147 Da. Electronic structure calculations using the M06-2X functional with the 6-311++G(d,p) basis set for C, H, and O, and LANL2DZ basis set for I and Na predict 298 K binding enthalpies for the protonated and sodiated iodylbenzene dimers and trimers are greater than 180 kJ/mol. This is exceptionally high in comparison with other protonated and sodiated clusters with well-established binding enthalpies. Strongly halogen-bonded motifs found 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. [Figure not available: see fulltext.

  11. Hydrocarbon oxidation at high temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Warnatz, J.


    In this review it is described how, by suitable separation and elimination of unimportant reactions, a mechanism is developed with the aid of the present kinetic data for the elementary reactions involved. This mechanism explains, without fitting, the currently available experimental results for laminar premixed flames of alkanes, alkenes and acetylene. These experimental results are simulated by the solution of the corresponding conservation equations with suitable models describing diffusion and heat conduction in the multicomponent mixture considered. In lean and moderately rich flames the hydrocarbon is attacked by O, H, and OH in the first step. These radicals are produced by the chain-branching steps of the oxyhydrogen reaction. The alkyl radicals formed in this way always decompose to smaller alkyl radicals by fast thermal elimination of alkenes. Only the relatively slow thermal decomposition of the smallest alkyl radicals (CH/sub 3/ and C/sub 2/H/sub 5/) competes with recombination and with oxidation reactions by O atoms and O/sub 2/. This part of the mechanism is rate-controlling in the combustion of alkanes and alkenes, and is therefore the reason for the similarity of all alkane and alkene flames.

  12. Hydrocarbon habitat of the west Netherlands basin

    Energy Technology Data Exchange (ETDEWEB)

    De Jager, J. (Nederlandse Aardolie Maatschappij, Assen (Netherlands)); Doyle, M. (Petroleum Development Oman, Muscat (Oman)); Grantham, P. (KSEPL/Shell Research, Rijswijk (Netherlands)); Mabillard, J. (Shell Nigeria, Port Harcourt (Nigeria))


    The complex West Netherlands Basin contains oil and gas in Triassic and Upper Jurassic to Cretaceous clastic reservoir sequences. The understanding has always been that the Carboniferous coal measures have generated only gas and the Jurassic marine Posidonia Shale only oil. However, detailed geochemical analyses show that both source rocks have generated oil and gas. Geochemical fingerprinting established a correlation of the hydrocarbons with the main source rocks. The occurrence of these different hydrocarbons is consistent with migration routes. Map-based charge modeling shows that the main phase of hydrocarbon generation occurred prior to the Late Cretaceous inversion of the West Netherlands Basin. However, along the southwest flank of the basin and in lows between the inversion highs, significant charge continued during the Tertiary. Biodegradation of oils in Jurassic and Cretaceous reservoirs occurred during the earliest Tertiary, but only in reservoirs that were at that time at temperatures of less then 70 to 80[degrees]C, where bacteria could survive. This study shows that also in a mature hydrocarbon province an integrated hydrocarbon habitat study with modern analyses and state-of-the-art technology can lead to a much improved understanding of the distribution of oil and gas in the subsurface. The results of this study will allow a better risk assessment for remaining prospects, and an improved prediction of the type of trapped hydrocarbons in terms of gas, oil, and biodegraded oil.

  13. The carbonate reservoirs in the Permian halogenic formation in the Dnepr Donetsk basin

    Energy Technology Data Exchange (ETDEWEB)

    Ryabykh, O.F.; Priymenko, A.F.


    In the exploration of the gas formations in the Slavyansk formation of the Permian halogen formations in the Dnepr Donetsk basin, a new genetic type of carbonate reservoir is discovered. This type was porous analogs of halite carbonate rock. When dissolving the halite component using formation waters, the porosity value for this rock exceeds 28 percent. The mineral composition of the rock is predominantly dolomite or magnesite with a higher or lower concentration of terrigenous material, calcite, anhydrite and halite; the ferrous sulfides are encountered in excessory quantities. Commercial gas production is realized at the Melikhov field from the Podbryantsev block in the Slavyansk formation, which includes porous analogs of halite carbonate rock.

  14. Soliton Model for Halogen-Bridged Mixed-Valence Platinum Complexes (United States)

    Onodera, Yositaka


    The quasi-one-dimensional chains of halogen-bridged mixed-valence platinum complexes (HMPC) have characteristic twofold degeneracy similar to the trans isomer of polyacetylene, which strongly suggests the presence of soliton-like excitations in HMPC. It is shown that the microscopic Hamiltonian proposed by Ichinose for HMPC, which naturally is different from the Su-Schrieffer-Heeger model of trans-polyacetylene, leads to the Takayama-Lin-Liu-Maki Hamiltonian when the continuum limit is taken. This theoretical result implies that we can expect various soliton processes found in trans-polyacetylene to take place in HMPC as well, though such experimental evidences are scarce as yet.

  15. Assembling supramolecular networks by halogen bonding in coordination polymers driven by 5-bromonicotinic acid

    Energy Technology Data Exchange (ETDEWEB)

    Gu, Jin-Zhong, E-mail: [State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Wu, Jiang [State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Kirillov, Alexander M. [Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, The University of Lisbon, Av. Rovisco Pais, 1049-001 Lisbon (Portugal); Lv, Dong-Yu; Tang, Yu; Wu, Jin-Cai [State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China)


    A series of six coordination compounds ([Zn(5-Brnic){sub 2}]·1.5H{sub 2}O){sub n} (1), [Cd(5-Brnic){sub 2}]{sub n} (2), [Co(5-Brnic){sub 2}(H{sub 2}O){sub 2}]{sub n} (3), [Zn(5-Brnic){sub 2}(H{sub 2}biim)]{sub n} (4), ([Cd(5-Brnic){sub 2}(phen)]·H{sub 2}O){sub n} (5), and [Pb(5-Brnic){sub 2}(phen)] (6) have been generated by the hydrothermal method from the metal(II) nitrates, 5-bromonicotinic acid (5-BrnicH), and an optional ancillary 1,10-phenanthroline (phen) or 2,2′-biimidazole (H{sub 2}biim) ligand. All the products 1–6 have been characterized by IR spectroscopy, elemental, thermal, powder and single-crystal X-ray diffraction analyses. Their 5-bromonicotinate-driven structures vary from the 3D metal-organic framework with the seh-3,5-P21/c topology (in 2) and the 2D interdigitated layers with the sql topology (in 1 and 3), to the 1D chains (in 4 and 5) and the 0D discrete monomers (in 6). The 5-bromonicotinate moiety acts as a versatile building block and its tethered bromine atom plays a key role in reinforcing and extending the structures into diverse 3D supramolecular networks via the various halogen bonding Br⋯O, Br⋯Br, and Br⋯π interactions, as well as the N–H⋯O and C–H⋯O hydrogen bonds. The obtained results demonstrate a useful guideline toward engineering the supramolecular architectures in the coordination network assembly under the influence of various halogen bonding interactions. The luminescent (for 1, 2, 4, 5, and 6) and magnetic (for 3) properties have also been studied and discussed in detail. - Graphical abstract: Six coordination compounds driven by 5-bromonicotinic acid have been generated and structurally characterized, revealing diverse metal-organic networks that are further reinforced and extended via various halogen bonding interactions. - Highlights: • 5-Bromonicotinic acid is a versatile ligand for Zn, Cd, Co and Pb derivatives. • Careful selection of co-ligands and metals resulted in different network

  16. Photochemical transformation of nitrate in the presence of para-halogenated phenols in frozen solutions (United States)

    Abida, O.; Osthoff, H. D.; Sutherland, T. C.


    Photochemical reactions leading to the chemical transformation of trace compounds in the atmosphere do not only occur in the atmospheric gas and liquid phases, but also in the tropospheric ice phase. The photochemical reactions of trace compounds embedded in ice have important implications for the composition of the atmospheric boundary layer in ice and snow covered regions and for interpretation of concentration profiles in snow and ice in the context of the composition of the past atmosphere. One of the prominent reactions is the photolysis of nitrate. This reaction is well established in natural waters, and is of interest since formation of highly mutagenic/carcinogenic nitro-compounds is possible. In contrast, the photochemical behaviour of nitrate in ice and snow is more complex. The photolysis of nitrate embedded in ice has been shown to generate OH radical, NO2(g) and NO(g) as primary photoproducts, but little is known how this photochemistry is affected by the presence of organic impurities embedded in the ice surface. In this work, we studied the effect of the presence of para-halogenated phenols on the photo-transformation of frozen nitrate solutions by Diffuse Reflective Infrared Fourier Transform Spectroscopy (DRIFTS). Moreover, the evolution of volatile nitrogen oxides to the gas phase was monitored by a commercial chemiluminescence NO/NOy monitor, chemical ionization mass spectrometry (CIMS), and thermal-dissociation cavity ring-down spectroscopy (TD-CRDS). In addition, some of the organic intermediate products were characterized by GC/MS and HPLC/PDA. We show that DRIFTS can provide a qualitative picture of the chemical transformations that take place at the ice surface and kinetic data on the phototransformation of nitrate. The photochemistry of frozen solutions of nitrate in the presence of various para-halogenated phenols was found to be dependent on the ice temperature, pH, the light intensity, and the concentration and nature of para-halogenated

  17. Halogenated boron subphthalocyanines as light harvesting electron acceptors in organic photovoltaics

    Energy Technology Data Exchange (ETDEWEB)

    Sullivan, Paul; Duraud, Amelie; Hancox, lan; Beaumont, Nicola; Hatton, Ross A.; Shipman, Michael; Jones, Tim S. [Department of Chemistry, University of Warwick, Coventry (United Kingdom); Mirri, Giorgio; Tucker, James H.R. [School of Chemistry, University of Birmingham, Edgbaston (United Kingdom)


    By tuning the frontier orbital energies through selective halogenation of the periphery of the organic framework, new light harvesting electron acceptors based on boron subphthalocyanine chloride (SubPc) have been made. Planar heterojunction organic photovoltaics made using a Cl{sub 6}-SubPc acceptor deliver an exceptionally high open-circuit voltage ({proportional_to}1.3 V), good power conversion efficiency ({proportional_to}2.7%) and improved operational stability in comparison to similar devices made using C{sub 60} as the acceptor material. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Strategies for halogen determination and isotopic analysis via ICP-MS


    Gois, Jefferson Santos de


    Tese (doutorado) - Universidade Federal de Santa Catarina, Centro de Ciências Físicas e Matemáticas, Programa de Pós-Graduação em Química, Florianópolis, 2016. This work presents new approaches for halogen determination in a variety of samples using inductively coupled plasma - mass spectrometry (ICP-MS) and for isotope ratio measurements by multicollector - inductively coupled plasma - mass spectrometry (MC-ICP-MS) and application of the methods developed to real environmental cas...

  19. Did the Siberian Traps eruptions emit enough halogens to have an impact on ozone geochemistry? (United States)

    Sibik, Svetlana; Edmonds, Marie; Villemant, Benoit; Thierry, Pauline; Polozov, Alexander


    The Siberian Traps Large Igneous Province is thought to have formed over 1 Ma at the end of the Permian, synchronous with the largest mass extinction in Earth's history. There remains much controversy as to the exact mechanism of the mass extinction, but all hypotheses revolve around the emission of volatiles in various forms. The research to date has tended to focus on sulfur and carbon rather than halogen degassing, despite this being probably critical in terms of environmental impact as they might have been played a crucial role in ozone layer depletion and therefore promote mass extinction. Current study aims to look at the behaviour of chlorine, bromine, iodine and fluorine to evaluate the halogen budget contribution from heterogeneous mantle source and from evaporates, which dominate in the south (Cambrian evaporites) and north (Devonian evaporites) of Siberian platform. For this study we use basaltic sills and lava flows emplaced in the area with no volatile-rich sediments south-east from Norilsk (Dyupkin lake and Lower Tunguska river regions) and a sill intruded into evaporates in Nepa location in the south of the platform, originally aimed at prospecting for potassium salts. Borehole samples of basalts intruded into evaporites might have been penetrated by salts and anhydrite. In order to eliminate this effect and ensure that we analyse halogen contents in pure basalts prior to any further analysis the samples were specifically treated so that penetrated material was removed as leachates. Whole rock fine powders of basalts were analysed for halogens, major and trace elements. The solutions obtained by basalt pyrohydrolysis extraction, leachates of basaltic powders and dissolved evaporites were analysed by ion chromatography for chlorine and fluorine and by ICP-MS for bromine and iodine. Basalts intruded into evaporites demonstrate predicted pronounced chlorine, bromine and iodine enrichments associated with salt assimilation. The results show that bromine

  20. Chlorine and Bromine Isotope Fractionation of Halogenated Organic Compounds in Electron Ionization Mass Spectrometry


    Tang, Caiming; Tan, Jianhua; Shi, Zhiqiang; Tang, Caixing; Xiong, Songsong; Liu, Jun; Fan, Yujuan; Peng, Xianzhi


    Revelation of chlorine and bromine isotope fractionation of halogenated organic compounds (HOCs) in electron ionization mass spectrometry (EI-MS) is crucial for compound-specific chlorine/bromine isotope analysis (CSIA-Cl/Br) using gas chromatography EI-MS (GC-EI-MS). This study systematically investigated chlorine/bromine isotope fractionation in EI-MS of HOCs including 12 organochlorines and 5 organobromines using GC-double focus magnetic-sector high resolution MS (GC-DFS-HRMS). Chlorine/br...

  1. Characteristics of hydrocarbons in sediment core samples from the northern Okinawa Trough. (United States)

    Huang, Xin; Chen, Shuai; Zeng, Zhigang; Pu, Xiaoqiang; Hou, Qinghua


    Sediment core samples from the northern Okinawa Trough (OT) were analyzed to determine abundances and distributions of hydrocarbons by gas chromatography-mass spectrometer (GC-MS). The results show that the n-alkanes in this sediment core conform to a bimodal distribution, and exhibit an odd-to-even predominance of high molecular weights compared to an even-to-odd predominance in low molecular weight n-alkanes with maxima at C16 and C18. The concentrations of bitumen, alkanes and polyaromatic hydrocarbons (PAHs) were higher in samples S10-07 than all others. Three maturity parameters as well as the ratios between parent phenanthrenes (Ps) and methylphenanthrenes (MPs) in samples S10-07 and S10-17 were higher. The distribution and composition of hydrocarbons in sample S10-07 suggest that one, or several, undetected hydrothermal fields may be present in the region of this sediment core. Results also suggest that volcanism may be the main reason for the observed distribution and composition of hydrocarbons in S10-17 sample. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Study of the co-deoxy-liquefaction of biomass and vegetable oil for hydrocarbon oil production. (United States)

    Chen, Yigang; Wang, Chao; Lu, Weipeng; Yang, Zhengyu


    Hydrocarbon oil was obtained by co-deoxy-liquefaction of biomass and vegetable oil in the work. Results showed the weight ratio of biomass to vegetable oil exerted a great effect on the quality of obtained hydrocarbon oil. The optimum weight ratio of biomass to vegetable oil was 4.4:1, when alkanes with the content of 50.43% were detected in obtained hydrocarbon oil, with lower oxygen content of 2.52%, which resulted in higher calorific value-up to 43.36 MJ kg(-1). At the same time, removal rate of carbonyl group of vegetable oil in the mixture reached at least 75.11%. The overall efficiency of the deoxy-liquefaction of biomass and the decarboxylation of vegetable oil were both enhanced by adding vegetable oil into biomass. Compared with the oils obtained from vegetable oil and biomass, respectively, distribution of hydrocarbon oil obtained from the mixture was much more similar to that of diesel oil. (c) 2010 Elsevier Ltd. All rights reserved.

  3. Petroleum hydrocarbon persistence following the Deepwater Horizon oil spill as a function of shoreline energy. (United States)

    Evans, Meredith; Liu, Jiqing; Bacosa, Hernando; Rosenheim, Brad E; Liu, Zhanfei


    An important aspect of oil spill science is understanding how the compounds within spilled oil, especially toxic components, change with weathering. In this study we follow the evolution of petroleum hydrocarbons, including n-alkanes, polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs, on a Louisiana beach and salt marsh for three years following the Deepwater Horizon spill. Relative to source oil, we report overall depletion of low molecular weight n-alkanes and PAHs in all locations with time. The magnitude of depletion, however, depends on the sampling location, whereby sites with highest wave energy have highest compound depletion. Oiled sediment from an enclosed bay shows high enrichment of high molecular weight PAHs relative to 17α(H),21β(H)-hopane, suggesting the contribution from sources other than the Deepwater Horizon spill, such as fossil fuel burning. This insight into hydrocarbon persistence as a function of hydrography and hydrocarbon source can inform policy and response for future spills. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Halogen Bonding and Chalcogen Bonding in 4,7-Dibromo-5,6-dinitro-2,1,3-benzothiadiazole. (United States)

    Pavan, Mysore S; Jana, Ajay Kumar; Natarajan, S; Guru Row, Tayur N


    An organic solid, 4,7-dibromo-5,6-dinitro-2,1,3-benzothiadiazole, has been designed to serve as an illustrative example to quantitatively evaluate the relative merits of halogen and chalcogen bonding in terms of charge density features. The compound displays two polymorphic modifications, one crystallizing in a non-centrosymmetric space group (Z' = 1) and the other in a centrosymmetric space group with two molecules in the asymmetric unit (Z' = 2). Topological analysis based on QTAIM clearly brings out the dominance of the chalcogen bond over the halogen bond along with an indication that halogen bonds are more directional compared to chalcogen bonds. The cohesive energies calculated with the absence of both strong and weak hydrogen bonds as well as stacking interaction are indicative of the stabilities associated with the polymorphic forms.

  5. Strong and Selective Halide Anion Binding by Neutral Halogen-Bonding [2]Rotaxanes in Wet Organic Solvents. (United States)

    Lim, Jason Y C; Bunchuay, Thanthapatra; Beer, Paul D


    The design and construction of neutral interlocked host molecules for anion recognition are rare. Using an active-metal template approach, the preparation of a family of neutral halogen bonding (XB) rotaxanes containing two, three and four iodotriazole groups integrated into the macrocycle and axle components is achieved. In spite of the interlocked hosts' neutrality, such rotaxane systems are capable of binding halide anions strongly and selectively in wet organic solvent mixtures. Importantly, halide-binding strength and selectivity can be modulated by varying the number and position of the halogen bond donor iodotriazole groups within the interlocked cavity; the rotaxane containing the largest number of halogen bond donor groups exhibits the highest halide anion-binding affinities. By varying the percentage of water content in the solvent, neutral XB donor-mediated anion-binding strength is also demonstrated to be highly sensitive to solvent polarity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Intramolecular Halogen Atom Coordinated H Transfer via Ion-Neutral Complex in the Gas Phase Dissociation of Protonated Dichlorvos Derivatives (United States)

    Zhang, Xiaoping; Cheng, Shuai


    Intramolecular halogen atom coordinated H transfer reaction in the gas phase dissociation of protonated dichlorvos derivatives has been explored by electrospray ionization tandem mass spectrometry. Upon collisional activation, protonated dichlorvos underwent dissociation reaction via cleavage of the P-O bond to give reactive ion-neutral complex (INC) intermediate, [dimethoxylphosphinoylium + dichloroacetaldehyde]. Besides direct dissociation of the complex, intramolecular chlorine atom coordinated H transfer reaction within the complex takes place, leading to the formation of protonated dimethyl chlorophosphate. To investigate the fragmentation mechanism, deuterium-labeled experiments and several other halogen-substituted (Br and F) analogs of dichlorvos were prepared and evaluated, which display a similar intramolecular halogen transfer. Density functional theory (DFT)-based calculations were performed and the computational results also support the mechanism. [Figure not available: see fulltext.

  7. Fenóis halogenados e/ou sulfatados de macroalgas marinhas Halogenated and/or sulfated phenols from marine macroalgae

    Directory of Open Access Journals (Sweden)

    Luciana Retz de Carvalho


    Full Text Available During the biological evolution, marine macroalgae have developed biochemicals tools in order to utilize components of seawater such as sulfates and halogens, to produce a variety of chemicals (secondary metabolites.This review shows and discuss the occurrence of sulfated and/or halogenated phenolic compounds in seaweeds.

  8. The influence of ocean halogen and sulfur emissions in the air quality of a coastal megacity: The case of Los Angeles (United States)

    The oceans are the main source of natural halogen and sulfur compounds, which have a significant influence on the oxidizing capacity of the marine atmosphere; however, their impact on the air quality of coastal cities is currently unknown. We explore the effect of marine halogens...

  9. Light-emitting diode vs halogen light curing of orthodontic brackets: a 15-month clinical study of bond failures. (United States)

    Krishnaswamy, N Rengarajan; Sunitha, Chakravarthi


    Previous in-vitro investigations reported no significant differences in the bond strength of brackets cured with conventional halogen lamps and those cured with light-emitting diodes (LED), even though LED curing times are much shorter. However, it is not known how LED curing performs in the oral cavity. The purpose of this randomized clinical trial was to evaluate the clinical performance of brackets cured with 2 light-curing units: a conventional halogen unit and an LED. Thirty patients treated with fixed appliances were included in this study. The bonding followed a contralateral quadrant pattern: in each patient, 2 quadrants were cured with the conventional halogen unit, and the other 2 quadrants were cured with the LED unit. The study had a single blind controlled design with a within-patient comparison of the 2 curing techniques, and the patients were allocated randomly. A total of 544 stainless steel brackets were examined for bracket failure. Location (tooth), cause, and date of failure were recorded over 15 months. Statistical analyses were performed with the Kaplan-Meier survival estimates and the log rank test. No statistically significant differences were found in total bond failure rate or in mean survival time between brackets cured with the halogen light and those cured with the LED. Neither were significant differences found between the 2 lights when the clinical performances of the maxillary and mandibular arches were compared, or when the posterior and anterior segments were compared. These results show that curing with an LED does not result in more bond failures or shorter time to failure when compared with conventional halogen light curing. Curing with an LED is an acceptable alternative to conventional halogen light curing.

  10. Distribution of aliphatic hydrocarbons, polycyclic aromatic hydrocarbons and organochlorinated pollutants in deep-sea sediments of the Southern Cretan margin, Eastern Mediterranean Sea: a baseline assessment. (United States)

    Mandalakis, Manolis; Polymenakou, Paraskevi N; Tselepides, Anastasios; Lampadariou, Nikolaos


    Deep sediments from the southern Cretan margin were analyzed to establish baseline levels for various types of organic pollutants before the anticipated intensification of anthropogenic activities. The total concentration of aliphatic hydrocarbons (ΣAH:326-3758ngg(-1), dry weight) was similar to those reported for deep sediments of the western Mediterranean Sea, while considerably lower levels were measured for polycyclic aromatic hydrocarbons (ΣPAH:9-60ngg(-1)). Source-diagnostic ratios suggested that the aliphatic hydrocarbons in sediments were mainly of terrestrial biogenic origin, while polycyclic aromatic hydrocarbons stemmed from the deposition of long-range transported combustion aerosols. Among the organochlorinated compounds analyzed, β-hexachlorocyclohexane (β-HCH:222-7052pgg(-1)), 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (p,p'-DDT:37-2236pgg(-1)) and polychlorinated biphenyls (ΣPCB:38-1182pgg(-1)) showed the highest abundance in sediments. The presence of HCHs and PCBs was attributed to historical inputs that have undergone extensive weathering, whereas an ongoing fresh input was suggested for p,p'-DDT. Multiple linear regression analysis revealed that the levels of the various pollutants in sediments were controlled by different factors, but with organic carbon content playing a prominent role in most cases. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. Overweight, Obesity, and Weight Loss (United States)

    ... Back to section menu Healthy Weight Weight and obesity Underweight Weight, fertility, and pregnancy Weight loss and ... section Home Healthy Weight Healthy Weight Weight and obesity Underweight Weight, fertility, and pregnancy Weight loss and ...

  12. 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


    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.

  13. Palladium-Catalyzed, ortho-Selective C-H Halogenation of Benzyl Nitriles, Aryl Weinreb Amides, and Anilides. (United States)

    Das, Riki; Kapur, Manmohan


    A palladium-catalyzed, ortho-selective C-H halogenation methodology is reported herein. The highlight of the work is the highly selective C(sp(2))-H functionalization of benzyl nitriles in the presence of activated C(sp(3))-H bond, which results in good yields of the halogenated products with excellent regioselectivity. Along with benzyl nitriles, aryl Weinreb amides and anilides have been evaluated for the transformation using aprotic conditions. Mechanistic studies yield interesting aspects with respect to the pathway of the reaction and the directing group abilities.

  14. Interactions between volatile organic compounds and reactive halogen in the tropical marine atmosphere using WRF-Chem (United States)

    Badia, Alba; Reeves, Claire E.; Baker, Alex; Volkamer, Rainer; von Glasow, Roland


    Halogen species (chlorine, bromine and iodine) are known to play an important role in the chemistry and oxidizing capacity of the troposphere, particularly in the marine boundary layer (MBL). Reactive halogens cause ozone (O3) destruction, change the HOx and NOX partitioning, affect the oxidation of volatile organic compounds (VOCs) and mercury, reduce the lifetime of methane, and take part in new particle formation. Numerical models predicted that reactive halogen compounds account for 30% of O3 destruction in the MBL and 5-20% globally. There are indications that the chemistry of reactive halogens and oxygenated VOCs (OVOCs) in the tropics are inter-related. Moreover, the presence of aldehydes, such as glyoxal (CHOCHO), has a potential impact on radical cycling and secondary organic aerosol (SOA) formation in the MBL and free troposphere (FT). Model calculations suggest aldehydes to be an important sink for bromine atoms and hence competition for their reaction with O3 forming BrO and so illustrating a link between the cycles of halogens and OVOCs in the marine atmosphere. The main objective of this contribution is to investigate the atmospheric chemistry in the tropical East Pacific with a focus on reactive halogens and OVOCs and their links using the latest version of the Weather Research and Forecasting (WRF) model coupled with Chemistry (WRF-Chem) and field data from the TORERO campaign. WRF-Chem is a highly flexible community model for atmospheric research where aerosol-radiation-cloud feedback processes are taken into account. Our current reaction mechanism in WRF-Chem is based on the MOZART mechanism and has been extended to include bromine, chlorine and iodine chemistry. The MOZART mechanism includes detailed gas-phase chemistry of CHOCHO formation as well as state-of-the-science pathways to form SOA. Oceanic emissions of aldehydes, including CHOCHO, and of organic halogens based on measurements from the TORERO campaign have been added into the model. Sea

  15. Substrate positioning controls the partition between halogenation and hydroxylation in the aliphatic halogenase, SyrB2


    Matthews, Megan L.; Neumann, Christopher S.; Miles, Linde A; Grove, Tyler L.; Booker, Squire J.; Krebs, Carsten; Walsh, Christopher T.; Bollinger, J. Martin


    The α-ketoglutarate-dependent hydroxylases and halogenases employ similar reaction mechanisms involving hydrogen-abstracting Fe(IV)-oxo (ferryl) intermediates. In the halogenases, the carboxylate residue from the His2(Asp/Glu)1“facial triad” of iron ligands found in the hydroxylases is replaced by alanine, and a halide ion (X−) coordinates at the vacated site. Halogenation is thought to result from “rebound” of the halogen radical from the X-Fe(III)-OH intermediate produced by hydrogen (H•) a...

  16. A mushroom-derived amino acid, ergothioneine, is a potential inhibitor of inflammation-related DNA halogenation. (United States)

    Asahi, Takashi; Wu, Xiaohong; Shimoda, Hiroshi; Hisaka, Shinsuke; Harada, Etsuko; Kanno, Tomomi; Nakamura, Yoshimasa; Kato, Yoji; Osawa, Toshihiko


    Myeloperoxidase (MPO)-generated halogenating molecules, such as hypochlorous acid and hypobromous acid (HOBr), in inflammatory regions are postulated to contribute to disease progression. In this study, we showed that ergothioneine (EGT), derived from an edible mushroom, inhibited MPO activity as well as the formation of 8-bromo-2'-deoxyguanosine in vitro. The HOBr scavenging effect of EGT is higher than those of ascorbic acid and glutathione. We initially observed that the administration of Coprinus comatus, an edible mushroom containing a high amount of EGT, inhibited the UV-B-induced inflammatory responses and DNA halogenation, suggesting that EGT is a promising anti-inflammatory agent from mushrooms.

  17. Polycyclic aromatic hydrocarbons (PAHs) in livers of California sea otters. (United States)

    Kannan, Kurunthachalam; Perrotta, Emily


    Concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were measured in livers of 81 adult female sea otters collected along the California coast in 1992-2002. Concentrations of summation operatorPAHs in livers of sea otters were in the range of 588-17400ng/g lipid wt (mean: 3880ng/g, lipid wt). On a wet weight basis, the concentrations ranged from 17 to 1430ng/g (mean: 146ng/g). Overall, di- and tri-cyclic aromatic hydrocarbons, namely, naphthalene, fluorene, phenanthrene/anthracene, and acenaphthylene, were the predominant compounds found in the livers. Although petroleum-related sources appear to be the major contributors to PAH exposure in sea otters, exposure sources varied by geographical sub-regions. Dibenz[a,h]anthracene was found to comprise a significant proportion of the summation operatorPAH concentrations in sea otters from the northern sub-region of the study area. No significant difference existed in the concentrations of summation operatorPAHs among sea otters that died from infectious diseases, emaciation, and noninfectious causes. Concentrations of summation operatorPAHs in livers of sea otters decreased significantly from 1992 to 2002. Because of the rapid metabolism of PAHs in marine mammals such as sea otters, further studies examining the association of PAHs with health effects should determine hydroxylated metabolites in livers.

  18. Determination of the aromatic hydrocarbon to total hydrocarbon ratio of mineral oil in commercial lubricants. (United States)

    Uematsu, Yoko; Suzuki, Kumi; Ogimoto, Mami


    A method was developed to determine the aromatic hydrocarbon to total hydrocarbon ratio of mineral oil in commercial lubricants; a survey was also conducted of commercial lubricants. Hydrocarbons in lubricants were separated from the matrix components of lubricants using a silica gel solid phase extraction (SPE) column. Normal-phase liquid chromatography (NPLC) coupled with an evaporative light-scattering detector (ELSD) was used to determine the aromatic hydrocarbon to total hydrocarbon ratio. Size exclusion chromatography (SEC) coupled with a diode array detector (DAD) and a refractive index detector (RID) was used to estimate carbon numbers and the presence of aromatic hydrocarbons, which supplemented the results obtained by NPLC/ELSD. Aromatic hydrocarbons were not detected in 12 lubricants specified for use for incidental food contact, but were detected in 13 out of 22 lubricants non-specified for incidental food contact at a ratio up to 18%. They were also detected in 10 out of 12 lubricants collected at food factories at a ratio up to 13%. The centre carbon numbers of hydrocarbons in commercial lubricants were estimated to be between C16 and C50.

  19. Volatile hydrocarbons inhibit methanogenic crude oil degradation

    Directory of Open Access Journals (Sweden)

    Angela eSherry


    Full Text Available Methanogenic degradation of crude oil in subsurface sediments occurs slowly, but without the need for exogenous electron acceptors, is sustained for long periods and has enormous economic and environmental consequences. Here we show that volatile hydrocarbons are inhibitory to methanogenic oil biodegradation by comparing degradation of an artificially weathered crude oil with volatile hydrocarbons removed, with the same oil that was not weathered. Volatile hydrocarbons (nC5-nC10, methylcyclohexane, benzene, toluene and xylenes were quantified in the headspace of microcosms. Aliphatic (n-alkanes nC12-nC34 and aromatic hydrocarbons (4-methylbiphenyl, 3-methylbiphenyl, 2-methylnaphthalene, 1-methylnaphthalene were quantified in the total hydrocarbon fraction extracted from the microcosms. 16S rRNA genes from key microorganisms known to play an important role in methanogenic alkane degradation (Smithella and Methanomicrobiales were quantified by quantitative PCR. Methane production from degradation of weathered oil in microcosms was rapid (1.1 ± 0.1 µmol CH4/g sediment/day with stoichiometric yields consistent with degradation of heavier n-alkanes (nC12-nC34. For non-weathered oil, degradation rates in microcosms were significantly lower (0.4 ± 0.3 µmol CH4/g sediment/day. This indicated that volatile hydrocarbons present in the non-weathered oil inhibit, but do not completely halt, methanogenic alkane biodegradation. These findings are significant with respect to rates of biodegradation of crude oils with abundant volatile hydrocarbons in anoxic, sulphate-depleted subsurface environments, such as contaminated marine sediments which have been entrained below the sulfate-reduction zone, as well as crude oil biodegradation in petroleum reservoirs and contaminated aquifers.

  20. In vitro evaluation of halogen light-activated vs chemically activated in-office bleaching systems. (United States)

    Liang, Shanshan; Sa, Yue; Jiang, Tao; Ma, Xiao; Xing, Wenzhong; Wang, Zhejun; Wang, Yining


    To compare the tooth whitening efficacy, temperature and HP concentration changes induced by halogen light-activated and chemically activated in-office bleaching systems. Twenty-four extracted premolars were randomly divided into two groups (n = 12): Group BL (35% HP with halogen light activation) and Group OP (38% HP with chemical activation). Tooth color was measured by a spectrophotometer according to the CIE L*a*b* color space system. Temperatures of bleaching gels and pulp chambers during the bleaching process were monitored and recorded by a digital multimeter with K-type thermocouple. HP concentrations were tested before and after treatments by iodometry. ANOVA and paired t-test were used for statistical analyses at the significance of p post-treatment. Maximal temperature rise (ΔT) was found only in group BL, showing the increment of 2.55 and 2.02°C for bleaching gels and pulp chambers, respectively. HP concentrations were higher than baseline values for group OP (p temperature rise in pulp chambers.

  1. Ground-based observations of Halogen Oxides in the Antarctic Boundary Layer (United States)

    Prados-Roman, Cristina; Gómez, Laura; Puentedura, Olga; Navarro-Comas, Mónica; Ochoa, Héctor; Yela, Margarita


    Being involved in ozone destruction cycles, the halogen oxides (containing Br, Cl or I) are relevant reactants not only in the stratosphere but also in the troposphere. In order to characterize the presence of halogen oxides in the Antarctic boundary layer (BL), two MAX-DOAS instruments developed by INTA were installed at two different Antarctic sites: Marambio (64° S) and Belgrano (78° S). Note that, although both stations sit on pristine and remote locations, the surroundings of each station is unique and so is the atmospheric chemistry. Here we present the results of the measurements of BrO and IO performed in the sunlit atmosphere of both stations during 2015. We will focus on the activation of reactive bromine, its sources and sinks and its vertical distribution in the troposphere. We will also address the differences found regarding the bromine content of the BL in the two Antarctic sites. Moreover, we will investigate the presence of IO in the Antarctic BL.

  2. The antihyperlipidemic activities of 4(3H quinazolinone and two halogenated derivatives in rats

    Directory of Open Access Journals (Sweden)

    Ibrahim Aida M


    Full Text Available Abstract In the present study, the effects of subchronic treatments (4 weeks of hypercholesterolemic (single and diabetic-hypercholesterolemic (combined rats with 4 (3H quinazolinone and 2 halogenated derivatives (6, 8-dibromo-2-methy-4 (3H quinazolinone and 6-iodo-2-methyl-4(3H quinazolinone at a sublethal dose level (2 mg/Kg on cholesterol metabolism were investigated. Bezafibrate, a hypolipidemic drug was used as a reference compound for data comparison. Treatment of rats with single and combined hypercholesterolemia with quinazolinone compounds gave rise to highly significant reductions in serum total cholesterol and cholesterol ester levels, whereas serum triacylglycerol level was significantly reduced only after treatment with halogen-substituted quinazolinones in single hyper-cholesterolemia, compared to the control group. The effects of different quinazolinones and bezafibrate on reduction of serum LDL-C level were comparable in single hypercholesterolemia but significantly different in combined hypercholesterolemia. Results obtained from this study suggest that the antihyperlipidemic effect of quinazolinone compounds was brought about by inhibition of dietary cholesterol absorption and / or intestinal ACAT activity.

  3. Identifying bioaccumulative halogenated organic compounds using a nontargeted analytical approach: seabirds as sentinels.

    Directory of Open Access Journals (Sweden)

    Christopher J Millow

    Full Text Available Persistent organic pollutants (POPs are typically monitored via targeted mass spectrometry, which potentially identifies only a fraction of the contaminants actually present in environmental samples. With new anthropogenic compounds continuously introduced to the environment, novel and proactive approaches that provide a comprehensive alternative to targeted methods are needed in order to more completely characterize the diversity of known and unknown compounds likely to cause adverse effects. Nontargeted mass spectrometry attempts to extensively screen for compounds, providing a feasible approach for identifying contaminants that warrant future monitoring. We employed a nontargeted analytical method using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC/TOF-MS to characterize halogenated organic compounds (HOCs in California Black skimmer (Rynchops niger eggs. Our study identified 111 HOCs; 84 of these compounds were regularly detected via targeted approaches, while 27 were classified as typically unmonitored or unknown. Typically unmonitored compounds of note in bird eggs included tris(4-chlorophenylmethane (TCPM, tris(4-chlorophenylmethanol (TCPMOH, triclosan, permethrin, heptachloro-1'-methyl-1,2'-bipyrrole (MBP, as well as four halogenated unknown compounds that could not be identified through database searching or the literature. The presence of these compounds in Black skimmer eggs suggests they are persistent, bioaccumulative, potentially biomagnifying, and maternally transferring. Our results highlight the utility and importance of employing nontargeted analytical tools to assess true contaminant burdens in organisms, as well as to demonstrate the value in using environmental sentinels to proactively identify novel contaminants.

  4. Halogens as tracers of protosolar nebula material in comet 67P/Churyumov-Gerasimenko (United States)

    Dhooghe, Frederik; De Keyser, Johan; Altwegg, Kathrin; Briois, Christelle; Balsiger, Hans; Berthelier, Jean-Jacques; Calmonte, Ursina; Cessateur, Gaël; Combi, Michael R.; Equeter, Eddy; Fiethe, Björn; Fray, Nicolas; Fuselier, Stephen; Gasc, Sébastien; Gibbons, Andrew; Gombosi, Tamas; Gunell, Herbert; Hässig, Myrtha; Hilchenbach, Martin; Le Roy, Léna; Maggiolo, Romain; Mall, Urs; Marty, Bernard; Neefs, Eddy; Rème, Henri; Rubin, Martin; Sémon, Thierry; Tzou, Chia-Yu; Wurz, Peter


    We report the first in situ detection of halogens in a cometary coma, that of 67P/Churyumov-Gerasimenko. Neutral gas mass spectra collected by the European Space Agency's Rosetta spacecraft during four periods of interest from the first comet encounter up to perihelion indicate that the main halogen-bearing compounds are HF, HCl and HBr. The bulk elemental abundances relative to oxygen are ∼8.9 × 10-5 for F/O, ∼1.2 × 10-4 for Cl/O and ∼2.5 × 10-6 for Br/O, for the volatile fraction of the comet. The cometary isotopic ratios for 37Cl/35Cl and 81Br/79Br match the Solar system values within the error margins. The observations point to an origin of the hydrogen halides in molecular cloud chemistry, with frozen hydrogen halides on dust grains, and a subsequent incorporation into comets as the cloud condensed and the Solar system formed.

  5. Molecular, vibrational and electronic structure of 4-bromo-2-halogenobenzaldehydes: Halogen and solvent effects (United States)

    Fernández, David; Parlak, Cemal; Bilge, Metin; Kaya, Mehmet Fatih; Tursun, Mahir; Keşan, Gürkan; Rhyman, Lydia; Ramasami, Ponnadurai; Şenyel, Mustafa


    The halogen and solvent effects on the structure of 4-bromo-2-halogenobenzaldehydes [C7H4BrXO; X = F (BFB), Cl (BCB) or Br (BBB)] were investigated by the density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. The B3LYP functional and HF and MP2 levels of theory were used with the 6-311+G(3df,p) or aug-cc-pVDZ basis sets. Computations were focused on the cis and trans conformers of the investigated compounds in the gas phase and solutions of 18 different polar or non-polar organic solvents. The computed frequencies of the C=O stretching vibration of the compounds were correlated with some empirical solvent parameters such as the Kirkwood-Bauer-Magat (KBM) equation, solvent acceptor number (AN), Swain parameters and linear solvation energy relationships (LSERs). The electronic properties of the compounds were also examined. The present work explores the effects of the medium and halogen on the conformation, geometrical parameters, dipole moment, ν(C=O) vibration, UV data, frontier orbitals and density-of-states diagram of the compounds. The findings of this research can be useful for studies on benzaldehydes.

  6. Tannins and Tannin-Related Derivatives Enhance the (Pseudo-)Halogenating Activity of Lactoperoxidase. (United States)

    Gau, Jana; Prévost, Martine; Van Antwerpen, Pierre; Sarosi, Menyhárt-Botond; Rodewald, Steffen; Arnhold, Jürgen; Flemmig, Jörg


    Several hydrolyzable tannins, proanthocyanidins, tannin derivatives, and a tannin-rich plant extract of tormentil rhizome were tested for their potential to regenerate the (pseudo-)halogenating activity, i.e., the oxidation of SCN- to hypothiocyanite -OSCN, of lactoperoxidase (LPO) after hydrogen peroxide-mediated enzyme inactivation. Measurements were performed using 5-thio-2-nitrobenzoic acid in the presence of tannins and related substances in order to determine kinetic parameters and to trace the LPO-mediated -OSCN formation. The results were combined with docking studies and molecular orbital analysis. The -OSCN-regenerating effect of tannin derivatives relates well with their binding properties toward LPO as well as their occupied molecular orbitals. Especially simple compounds like ellagic acid or methyl gallate and the complex plant extract were found as potent enzyme-regenerating compounds. As the (pseudo-)halogenating activity of LPO contributes to the maintenance of oral bacterial homeostasis, the results provide new insights into the antibacterial mode of action of tannins and related compounds. Furthermore, chemical properties of the tested compounds that are important for efficient enzyme-substrate interaction and regeneration of the -OSCN formation by LPO were identified.

  7. High-energy-density hydrogen-halogen fuel cells for advanced military applications (United States)

    Balko, E. N.; McElroy, J. F.

    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 H2/Cl2 and H2/Br2 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 H2/Cl2 and H2/Br2 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.

  8. NanoSIMS50 - a powerful tool to elucidate cellular localization of halogenated organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Gutleb, Arno C.; Hoffmann, Lucien [Centre de Recherche Public - Gabriel Lippmann, Department Environment and Agro-biotechnologies (EVA), Belvaux (Luxembourg); Freitas, Jaime [Wageningen University, Toxicology Section, Wageningen (Netherlands); Murk, Albertinka J. [Wageningen University, Toxicology Section, Wageningen (Netherlands); Wageningen IMARES, P.O. Box 68, IJmuiden (Netherlands); Verhaegen, Steven; Ropstad, Erik [Norwegian School of Veterinary Science, Oslo (Norway); Udelhoven, Thomas [Centre de Recherche Public - Gabriel Lippmann, Department Environment and Agro-biotechnologies (EVA), Belvaux (Luxembourg); Trier University, Remote Sensing and Geoinformatics Department, Trier (Germany); Audinot, Jean-Nicolas [Centre de Recherche Public - Gabriel Lippmann, Departement Science et Analyse des Materiaux (SAM), Belvaux (Luxembourg)


    Persistent organic pollutants are widely distributed in the environment and lots of toxicological data are available. However, little is known on the intracellular fate of such compounds. Here a method applying secondary ion mass spectrometry is described that can be used to visualize cellular localization of halogenated compounds and to semi-quantitatively calculate concentrations of such compounds. Of the model compounds tested, TBBPA was homogenously distributed in the cell membrane of the H295R cells while PFOS accumulated in very distinct locations in the cell membrane. Relative intracellular concentrations of 4-OH-BDE69 and 4-OH-BDE121 in GH3.TRE were 61 % and 18 %, respectively, compared to the parent compounds. These differences may partly explain that observed effect concentrations for 4-OH-BDEs in in vitro experiments are usually lower than what would be expected based on receptor binding studies. NanoSIMS50 proved to be a powerful tool to describe the cellular distribution of halogenated compounds. The semi-quantitative data that can be obtained may help to further explain results from in vitro or in vivo experiments. (orig.)

  9. Potent antibacterial activity of halogenated metabolites from Malaysian red algae, Laurencia majuscula (Rhodomelaceae, Ceramiales). (United States)

    Vairappan, Charles S


    Red algae genus Laurencia (Rhodomelaceae, Ceramiales) are known to produce a wide range of chemically interesting secondary halogenated metabolites. This investigation delves upon extraction, isolation, structural elucidation and antibacterial activity of inherently available secondary metabolites of Laurencia majuscula Harvey collected from two locations in waters of Sabah, Malaysia. Two major halogenated compounds, identified as elatol (1) and iso-obtusol (2) were isolated. Structures of these compounds were determined from their spectroscopic data such as IR, 1H-NMR, 13C-NMR and optical rotation. Antibacterial bioassay against human pathogenic bacteria was conducted using disc diffusion (Kirby-Bauer) method. Elatol (1) inhibited six species of bacteria, with significant antibacterial activities against Staphylococcus epidermis, Klebsiella pneumonia and Salmonella sp. while iso-obtusol (2) exhibited antibacterial activity against four bacterial species with significant activity against K. pneumonia and Salmonella sp. Elatol (1) showed equal and better antibacterial activity compared with tested commercial antibiotics while iso-obtusol (2) only equaled the potency of commercial antibiotics against K. pneumonia and Salmonella sp. Further tests conducted using dilution method showed both compounds as having bacteriostatic mode of action against the tested bacteria.

  10. Photoresponsive ionic liquid crystals assembled via halogen bond: en route towards light-controllable ion transporters. (United States)

    Saccone, Marco; Palacio, Francisco Fernandez; Cavallo, Gabriella; Dichiarante, Valentina; Virkki, Matti; Terraneo, Giancarlo; Priimagi, Arri; Metrangolo, Pierangelo


    We demonstrate that halogen bonding (XB) can offer a novel approach for the construction of photoresponsive ionic liquid crystals. In particular, we assembled two new supramolecular complexes based on 1-ethyl-3-methylimidazolium iodides and azobenzene derivatives containing an iodotetrafluoro-benzene ring as XB donor, where the iodide anion acted as an XB acceptor. DSC and X-ray diffraction analyses revealed that the preferred stoichiometry between the XB donors and acceptors is 2 : 1, and that the iodide anions act as bidentate XB-acceptors, binding two azobenzene derivatives. Due to the high directionality of the XB, calamitic superanions are obtained, while the segregation occurring between the charged and uncharged parts of the molecules gives rise to a layered structure in the crystal lattice. Despite the fact that the starting materials are non-mesomorphic, the halogen-bonded supramolecular complexes exhibited monotropic lamellar liquid-crystalline phases over broad temperature ranges, as confirmed with polarized optical microscopy. Due to the presence of the azobenzene moieties, the LCs were photoresponsive, and a LC-to-isotropic phase transition could be obtained by irradiation with UV light. We envisage that the light-induced phase transition, in combination with the ionic nature of the LC, provides a route towards light-induced control over ion transport and conductance in these supramolecular complexes.

  11. Nontargeted Screening of Halogenated Organic Compounds in Bottlenose Dolphins (Tursiops truncatus) from Rio de Janeiro, Brazil. (United States)

    Alonso, Mariana B; Maruya, Keith A; Dodder, Nathan G; Lailson-Brito, José; Azevedo, Alexandre; Santos-Neto, Elitieri; Torres, Joao P M; Malm, Olaf; Hoh, Eunha


    To catalog the diversity and abundance of halogenated organic compounds (HOCs) accumulating in high trophic marine species from the southwestern Atlantic Ocean, tissue from bottlenose dolphins (Tursiops truncatus) stranded or incidentally captured along the coast of Rio de Janeiro, Brazil, were analyzed by a nontargeted approach based on GC×GC/TOF-MS. A total of 158 individual HOCs from 32 different structural classes were detected in the blubber of 4 adult male T. truncatus. Nearly 90% of the detected compounds are not routinely monitored in the environment. DDT-related and mirex/dechlorane-related compounds were the most abundant classes of anthropogenic origin. Methoxy-brominated diphenyl ethers (MeO-BDEs) and chlorinated methyl- and dimethyl bipyrroles (MBPs and DMBPs) were the most abundant natural products. Reported for the first time in southwestern Atlantic cetaceans and in contrast to North American marine mammals, chlorinated MBPs and DMBPs were more abundant than their brominated and/or mixed halogenated counterparts. HOC profiles in coastal T. truncatus from Brazil and California revealed a distinct difference, with a higher abundance of MeO-BDEs, mirex/dechloranes and chlorinated bipyrroles in the Brazilian dolphins. Thirty-six percent of the detected HOCs had an unknown structure. These results suggest broad geographical differences in the patterns of bioaccumulative chemicals found in the marine environment and indicate the need to develop more complete catalogs of HOCs from various marine environments.

  12. Isomorphous Crystals from Diynes and Bromodiynes Involved in Hydrogen and Halogen Bonds

    Directory of Open Access Journals (Sweden)

    Pierre Baillargeon


    Full Text Available Isomorphous crystals of two diacetylene derivatives with carbamate functionality (BocNH-CH2-diyne-X, where X = H or Br have been obtained. The main feature of these structures is the original 2D arrangement (as supramolecular sheets or walls in which the H bond and halogen bond have a prominent effect on the whole architecture. The two diacetylene compounds harbor neighboring carbamate (Boc protected amine and conjugated alkyne functionalities. They differ only by the nature of the atom located at the penultimate position of the diyne moiety, either a hydrogen atom or a bromine atom. Both of them adopt very similar 2D wall organizations with antiparallel carbamates (as in antiparallel beta pleated sheets. Additional weak interactions inside the same walls between molecular bricks are H bond interactions (diyne-H···O=C or halogen bond interactions (diyne-Br···O=C, respectively. Based on crystallographic atom coordinates, DFT (B3LYP/6-31++G(d,p and DFT (M06-2X/6-31++G(d,p calculations were performed on these isostructural crystals to gain insight into the intermolecular interactions.

  13. Fluorescence spectroscopy for monitoring reduction of natural organic matter and halogenated furanone precursors by biofiltration. (United States)

    Peleato, Nicolás M; McKie, Michael; Taylor-Edmonds, Lizbeth; Andrews, Susan A; Legge, Raymond L; Andrews, Robert C


    The application of fluorescence spectroscopy to monitor natural organic matter (NOM) reduction as a function of biofiltration performance was investigated. This study was conducted at pilot-scale where a conventional media filter was compared to six biofilters employing varying enhancement strategies. Overall reductions of NOM were identified by measuring dissolved organic carbon (DOC), and UV absorbance at 254 nm, as well as characterization of organic sub-fractions by liquid chromatography-organic carbon detection (LC-OCD) and parallel factors analysis (PARAFAC) of fluorescence excitation-emission matrices (FEEM). The biofilter using granular activated carbon media, with exhausted absorptive capacity, was found to provide the highest removal of all identified PARAFAC components. A microbial or processed humic-like component was found to be most amenable to biodegradation by biofilters and removal by conventional treatment. One refractory humic-like component, detectable only by FEEM-PARAFAC, was not well removed by biofiltration or conventional treatment. All biofilters removed protein-like material to a high degree relative to conventional treatment. The formation potential of two halogenated furanones, 3-chloro-4(dichloromethyl)-2(5H)-furanone (MX) and mucochloric acid (MCA), as well as overall treated water genotoxicity are also reported. Using the organic characterization results possible halogenated furanone and genotoxicity precursors are identified. Comparison of FEEM-PARAFAC and LC-OCD results revealed polysaccharides as potential MX/MCA precursors. Copyright © 2016 Elsevier Ltd. All rights reserved.

  14. 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: [School of Mechanical Engineering, Southeast University, Nanjing, Jiangsu 211189 (China)


    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.

  15. A halogen-free synthesis of gold nanoparticles using gold(III) oxide

    Energy Technology Data Exchange (ETDEWEB)

    Sashuk, Volodymyr, E-mail:; Rogaczewski, Konrad [Polish Academy of Sciences, Institute of Physical Chemistry (Poland)


    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.

  16. A halogen-free synthesis of gold nanoparticles using gold(III) oxide (United States)

    Sashuk, Volodymyr; Rogaczewski, Konrad


    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.

  17. (13)C CP MAS NMR of halogenated (Cl, Br, I) pharmaceuticals at ultrahigh magnetic fields. (United States)

    Terskikh, Victor V; Lang, Stephen J; Gordon, Peter G; Enright, Gary D; Ripmeester, John A


    This work reports significantly improved spectral resolution of (13)C CP MAS NMR spectra of chlorinated, brominated and iodinated solid organic compounds when such spectra are recorded at ultrahigh magnetic field strengths. The cause of this is the residual dipolar coupling between carbon atoms and quadrupolar halogen nuclides (chlorine-35/37, bromine-79/81 or iodine-127), an effect inversely proportional to the magnetic field strength which declines in importance markedly at 21.1 T as compared to lower fields. In favorable cases, the fine structure observed can be used for spectral assignment, e.g. for Cl-substituted aromatics where the substituted carbon as well as the ortho-carbons show distinct doublets. The experimental results presented are supported by theoretical modeling and calculations. The improved spectral resolution in the studied systems and similar halogenated materials will be of particular interest and importance for polymorph identification, drug discovery and quality control in the pharmaceutical industry. Copyright (c) 2009 John Wiley & Sons, Ltd.

  18. Reactive Halogens in the Marine Boundary Layer (RHaMBLe: the tropical North Atlantic experiments

    Directory of Open Access Journals (Sweden)

    J. D. Lee


    Full Text Available The NERC UK SOLAS-funded Reactive Halogens in the Marine Boundary Layer (RHaMBLe programme comprised three field experiments. This manuscript presents an overview of the measurements made within the two simultaneous remote experiments conducted in the tropical North Atlantic in May and June 2007. Measurements were made from two mobile and one ground-based platforms. The heavily instrumented cruise D319 on the RRS Discovery from Lisbon, Portugal to São Vicente, Cape Verde and back to Falmouth, UK was used to characterise the spatial distribution of boundary layer components likely to play a role in reactive halogen chemistry. Measurements onboard the ARSF Dornier aircraft were used to allow the observations to be interpreted in the context of their vertical distribution and to confirm the interpretation of atmospheric structure in the vicinity of the Cape Verde islands. Long-term ground-based measurements at the Cape Verde Atmospheric Observatory (CVAO on São Vicente were supplemented by long-term measurements of reactive halogen species and characterisation of additional trace gas and aerosol species during the intensive experimental period.

    This paper presents a summary of the measurements made within the RHaMBLe remote experiments and discusses them in their meteorological and chemical context as determined from these three platforms and from additional meteorological analyses. Air always arrived at the CVAO from the North East with a range of air mass origins (European, Atlantic and North American continental. Trace gases were present at stable and fairly low concentrations with the exception of a slight increase in some anthropogenic components in air of North American origin, though NOx mixing ratios during this period remained below 20 pptv (note the non-IUPAC adoption in this manuscript of pptv and ppbv, equivalent to pmol mol−1 and nmol mol−1 to reflect common practice. Consistency with

  19. Photochemistry on Pluto - I. Hydrocarbons and aerosols (United States)

    Luspay-Kuti, Adrienn; Mandt, Kathleen; Jessup, Kandis-Lea; Kammer, Joshua; Hue, Vincent; Hamel, Mark; Filwett, Rachael


    In light of the recent New Horizons flyby measurements, we present a coupled ion-neutral-photochemistry model developed for simulating the atmosphere of Pluto. Our model results closely match the observed density profiles of CH4, N2 and the C2 hydrocarbons in the altitude range where available New Horizons measurements are most accurate (above ∼100-200 km). We found a high eddy coefficient of 106 cm2 s-1 from the surface to an altitude of 150 km, and 3 × 106 cm2 s-1 above 150 km for Pluto's atmosphere. Our results demonstrate that C2 hydrocarbons must stick to and be removed by aerosol particles in order to reproduce the C2 profiles observed by New Horizons. Incorporation into aerosols in Pluto's atmosphere is a significantly more effective process than condensation, and we found that condensation alone cannot account for the observed shape of the vertical profiles. We empirically determined the sticking efficiency of C2 hydrocarbons to aerosol particles as a function of altitude, and found that the sticking efficiency of C2 hydrocarbons is inversely related to the aerosol surface area. Aerosols must harden and become less sticky as they age in Pluto's atmosphere. Such hardening with ageing is both necessary and sufficient to explain the vertical profiles of C2 hydrocarbons in Pluto's atmosphere. This result is in agreement with the fundamental idea of aerosols hardening as they age, as proposed for Titan's aerosols.

  20. Reappraisal of hydrocarbon biomarkers in Archean rocks. (United States)

    French, Katherine L; Hallmann, Christian; Hope, Janet M; Schoon, Petra L; Zumberge, J Alex; Hoshino, Yosuke; Peters, Carl A; George, Simon C; Love, Gordon D; Brocks, Jochen J; Buick, Roger; Summons, Roger E


    Hopanes and steranes found in Archean rocks have been presented as key evidence supporting the early rise of oxygenic photosynthesis and eukaryotes, but the syngeneity of these hydrocarbon biomarkers is controversial. To resolve this debate, we performed a multilaboratory study of new cores from the Pilbara Craton, Australia, that were drilled and sampled using unprecedented hydrocarbon-clean protocols. Hopanes and steranes in rock extracts and hydropyrolysates from these new cores were typically at or below our femtogram detection limit, but when they were detectable, they had total hopane (hydrocarbons and diamondoids, which exceed blank concentrations, exhibit individual concentrations up to 80 ng per gram of rock in rock extracts and up to 1,000 ng per gram of rock in hydropyrolysates from the ultraclean cores. These results demonstrate that previously studied Archean samples host mixtures of biomarker contaminants and indigenous overmature hydrocarbons. Therefore, existing lipid biomarker evidence cannot be invoked to support the emergence of oxygenic photosynthesis and eukaryotes by ∼ 2.7 billion years ago. Although suitable Proterozoic rocks exist, no currently known Archean strata lie within the appropriate thermal maturity window for syngenetic hydrocarbon biomarker preservation, so future exploration for Archean biomarkers should screen for rocks with milder thermal histories.