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Sample records for carbonaceous materials halogen

  1. Carbonaceous materials water mixtures

    SciTech Connect

    Papalos, J.G.; Sinka, J.V.

    1985-04-30

    Particulate carbonaceous materials water mixtures are prepared by adding a condensate which is a condensation product of an aldehyde having from about 1 to about 7 carbon atoms, a benzene derivative such as benzene sulfonic acid, an alkyl benzene sulfonic acid having at least one alkyl group of from about 1 to about 20 carbon atoms and mixtures thereof, and optionally, and a naphthalene derivative such as naphthalene sulfonic acid, an alkyl naphthalene sulfonic acid having at least one alkyl group of from about 1 to about 12 carbon atoms and mixtures thereof. The condensate is added in an amount sufficient to reduce viscosity of the water mixture of carbonaceous materials, to stabilize carbonaceous materials in the water network and to improve pumpability. An acid form of the condensate or a salt may be added.

  2. Screening of organic halogens and identification of chlorinated benzoic acids in carbonaceous meteorites.

    PubMed

    Schöler, Heinz F; Nkusi, Gerard; Niedan, Volker W; Müller, German; Spitthoff, Bianca

    2005-09-01

    The occurrence of halogenated organic compounds measured as a sum parameter and the evidence of chlorinated benzoic acids in four carbonaceous meteorites (Cold Bokkeveld, Murray, Murchison and Orgueil) from four independent fall events is reported. After AOX (Adsorbable organic halogen) and EOX (Extractable organic halogen) screening to quantify organically bound halogens, chlorinated organic compounds were analyzed by gas chromatography. AOX concentrations varying from 124 to 209 microg Cl/g d.w. were observed in carbonaceous meteorites. Ion chromatographic analysis of the distribution of organically bound halogens performed on the Cold Bokkeveld meteorite revealed that chlorinated and brominated organic compounds were extractable, up to 70%, whereas only trace amounts of organofluorines could be extracted. Chlorinated benzoic acids have been identified in carbonaceous meteorite extracts. Their presence and concentrations raise the question concerning the origin of halogenated, especially chlorinated, organic compounds in primitive planetary matter.

  3. Hydrogenation process for solid carbonaceous materials

    DOEpatents

    Cox, John L.; Wilcox, Wayne A.

    1979-01-01

    Coal or other solid carbonaceous material is contacted with an organic solvent containing both hydrogen and a transition metal catalyst in solution to hydrogenate unsaturated bonds within the carbonaceous material. This benefaction step permits subsequent pyrolysis or hydrogenolysis of the carbonaceous fuel to form gaseous and liquid hydrocarbon products of increased yield and quality.

  4. Method for heating nongaseous carbonaceous material

    DOEpatents

    Lumpkin, Jr., Robert E.

    1978-01-01

    Nongaseous carbonaceous material is heated by a method comprising introducing tangentially a first stream containing a nongaseous carbonaceous material and carbon monoxide into a reaction zone; simultaneously and separately introducing a second stream containing oxygen into the reaction zone such that the oxygen enters the reaction zone away from the wall thereof and reacts with the first stream thereby producing a gaseous product and heating the nongaseous carbonaceous material; forming an outer spiralling vortex within the reaction zone to cause substantial separation of gases, including the gaseous product, from the nongaseous carbonaceous material; removing a third stream from the reaction zone containing the gaseous product which is substantially free of the nongaseous carbonaceous material before a major portion of the gaseous product can react with the nongaseous carbonaceous material; and removing a fourth stream containing the nongaseous carbonaceous material from the reaction zone.

  5. Carbonaceous Material in Extraterrestrial Matter

    NASA Astrophysics Data System (ADS)

    Martins, Zita

    2015-08-01

    Comets, asteroids and their fragments (i.e. meteorite, micrometeorites and interplanetary dust particles (IDPs)) are known to contain carbonaceous material. IDPs have ~10% of carbon by mass [1-3], while both micrometeorites and IDPs contain organic molecules. However, it is not certain whether these molecules are indigenous or terrestrial contamination [4-7]. On the other hand, ultra-carbonaceous Antarctic micrometeorites (UCAMMs) contain 50-80% of carbonaceous material, which is one of the highest organic matter contents detected in an extraterrestrial body [8]. Comets also have several extraterrestrial organic molecules [9, 10], including the simplest amino acid glycine [11]. In addition, the impact-shock of a typical comet ice mixture produces several amino acids from simple precursors [12]. Carbonaceous meteorites contain up to 5wt% of organic carbon [13], which is either locked in an insoluble kerogen-like polymer, or in a rich organic inventory of soluble organic compounds [14-16]. Bulk analysis of the meteoritic soluble organic fraction has revealed a high molecular diversity of tens of thousands of different molecular compositions [17]. The analysis of the carbonaceous content of comets, asteroids and their fragments provides a window into the resources delivered to the early Earth.[1] Brownlee (1985) Ann. Rev. Earth and Plan. Sci. 13, 147. [2] Schramm et al. (1989) Meteoritics 24, 99. [3] Messenger (2002) MAPS 37, 1491. [4] Clemett et al. (1993) Science 262, 721. [5] Brinton et al. (1998) OLEB 28, 413. [6] Flynn (2003) GCA 67, 4791. [7] Matrajt et al. (2004) MAPS 39, 1849. [8] Duprat et al. (2010) Science 328, 742-745. [9] Bockelée-Morvan et al. (2004) in: Comets II. pp. 391-423. [10] Mumma and Charnley (2011) ARAA 49, 471. [11] Elsila et al. (2009) MAPS 44, 1323. [12] Martins et al. (2013) Nature Geoscience 6, 1045. [13] Alexander et al. (2013) GCA 123, 244. [14] Cronin and Chang (1993) in: The Chemistry of Life’s Origin. pp. 209-258. [15] Cody and

  6. Process for gasification of carbonaceous material

    SciTech Connect

    Lancet, M.S.; Gorin, E.

    1984-04-03

    A process of tar destruction in gasification of carbonaceous material comprises providing a mixture of finely divided calcium compound of a particle size smaller than 65 mesh and finely divided carbonaceous material of a particle size smaller than 65 mesh, the calcium compound to carbonaceous material ratio being from about 0.5 to 1.0 and contacting the mixture with CO/sub 2/ and tar exothermally whereby the tar is destroyed.

  7. Biochemical transformation of solid carbonaceous material

    DOEpatents

    Lin, Mow S.; Premuzic, Eugene T.

    2001-09-25

    A method of biochemically transforming macromolecular compounds found in solid carbonaceous materials, such as coal is provided. The preparation of new microorganisms, metabolically weaned through challenge growth processes to biochemically transform solid carbonaceous materials at extreme temperatures, pressures, pH, salt and toxic metal concentrations is also disclosed.

  8. Carbonaceous Material in Extra-terrestrial Matter

    NASA Astrophysics Data System (ADS)

    Martins, Zita

    2016-10-01

    Comets, asteroids, meteorites, micrometeorites, interplanetary dust particles (IDPs), and ultra-carbonaceous Antarctic micrometeorites (UCAMMs) may contain carbonaceous material, which was exogenously delivered to the early Earth. Carbonaceous chondrites have an enormous variety of extra-terrestrial compounds, including all the key compounds important in terrestrial biochemistry. Comets contain several carbon-rich species and, in addition, the hypervelocity impact-shock of a comet can produce several α-amino acids. The analysis of the carbonaceous content of extra-terrestrial matter provides a window into the resources delivered to the early Earth, which may have been used by the first living organisms.

  9. Staged heating by oxidation of carbonaceous material

    DOEpatents

    Knell, Everett W.; Green, Norman W.

    1978-01-31

    A carbonaceous material is pyrolyzed in the presence of a particulate source of heat obtained by the partial oxidation of a carbon containing solid residue of the carbonaceous material. The heat obtained from the oxidation of the carbon containing solid residue is maximized by preheating the carbon containing solid residue with a hot gas stream obtained by oxidizing the gaseous combustion products of the carbon containing solid residue.

  10. Stabilized water slurries of carbonaceous materials

    SciTech Connect

    Papalos, J.G.; Knitter, K.A.; Savoly, A.; Villa, J.L.

    1984-07-03

    Improved stabilized water slurries of carbonaceous materials are obtained by having present a condensation product or a salt thereof of a substituted phenol sulfonic acid which is an arylphenol sulfonic acid, an aralkylphenol sulfonic acid, an arylphenol sulfonic acid and arylsulfonic acid mixture, or an aralkylphenol sulfonic acid and arylsulfonic acid mixture, condensed with from about 0.5 to about 4.0 moles of formaldehyde per mole of sulfonic acid with the proviso that the weight ratio if substituted phenol sulfonic acid to arylsulfonic acid is from about 0.95:0.05 to about 0.05:0.95 in the mixtures, the condensation product being present in an amount sufficient to reduce viscosity of the water slurry of carbonaceous materials, to stabilize carbonaceous materials in the water network and to improve its pumpability. If desired, an acid form or a salt of the condensation product may be used.

  11. Reactor and method for hydrocracking carbonaceous material

    DOEpatents

    Duncan, Dennis A.; Beeson, Justin L.; Oberle, R. Donald; Dirksen, Henry A.

    1980-01-01

    Solid, carbonaceous material is cracked in the presence of hydrogen or other reducing gas to provide aliphatic and aromatic hydrocarbons of lower molecular weight for gaseous and liquid fuels. The carbonaceous material, such as coal, is entrained as finely divided particles in a flow of reducing gas and preheated to near the decomposition temperature of the high molecular weight polymers. Within the reactor, small quantities of oxygen containing gas are injected at a plurality of discrete points to burn corresponding amounts of the hydrogen or other fuel and elevate the mixture to high temperatures sufficient to decompose the high molecular weight, carbonaceous solids. Turbulent mixing at each injection point rapidly quenches the material to a more moderate bulk temperature. Additional quenching after the final injection point can be performed by direct contact with quench gas or oil. The reactions are carried out in the presence of a hydrogen-containing reducing gas at moderate to high pressure which stabilizes the products.

  12. Tuneable porous carbonaceous materials from renewable resources.

    PubMed

    White, Robin J; Budarin, Vitaly; Luque, Rafael; Clark, James H; Macquarrie, Duncan J

    2009-12-01

    Porous carbon materials are ubiquitous with a wide range of technologically important applications, including separation science, heterogeneous catalyst supports, water purification filters, stationary phase materials, as well as the developing future areas of energy generation and storage applications. Hard template routes to ordered mesoporous carbons are well established, but whilst offering different mesoscopic textural phases, the surface of the material is difficult to chemically post-modify and processing is energy, resource and step intensive. The production of carbon materials from biomass (i.e. sugars or polysaccharides) is a relatively new but rapidly expanding research area. In this tutorial review, we compare and contrast recently reported routes to the preparation of porous carbon materials derived from renewable resources, with examples of our previously reported mesoporous polysaccharide-derived "Starbon" carbonaceous material technology.

  13. Novel carbonaceous materials for lithium secondary batteries

    SciTech Connect

    Sandi, G.; Winans, R.E.; Carrado, K.A.; Johnson, C.S.

    1997-07-01

    Carbonaceous materials have been synthesized using pillared clays (PILCs) as templates. The PILC was loaded with organic materials such as pyrene in the liquid and vapor phase, styrene in the vapor phase, trioxane, ethylene and propylene. The samples were then pyrolyzed at 700 C in an inert atmosphere, followed by dissolution of the inorganic template by conventional demineralization methods. X-ray powder diffraction of the carbons showed broad d{sub 002} peaks in the diffraction pattern, indicative of a disordered or turbostratic system. N{sub 2} BET surface areas of the carbonaceous materials range from 10 to 100 m{sup 2}/g. There is some microporosity (r < 1 nm) in the highest surface area carbons. Most of the surface area, however, comes from a mixture of micro and mesopores with radii of 2--5 nm. Electrochemical studies were performed on these carbons. Button cells were fabricated with capacity- limiting carbon pellets electrodes as the cathode a/nd metallic lithium foil as the anode. Large reversible capacities (up to 850 mAh/g) were achieved for most of the samples. The irreversible capacity loss was less than 180 mAh/g after the first cycle, suggesting that these types of carbon materials are very stable to lithium insertion and de-insertion reactions.

  14. Sulfur removal and comminution of carbonaceous material

    DOEpatents

    Narain, Nand K.; Ruether, John A.; Smith, Dennis N.

    1988-01-01

    Finely divided, clean coal or other carbonaceous material is provided by forming a slurry of coarse coal in aqueous alkali solution and heating the slurry under pressure to above the critical conditions of steam. The supercritical fluid penetrates and is trapped in the porosity of the coal as it swells in a thermoplastic condition at elevated temperature. By a sudden, explosive release of pressure the coal is fractured into finely divided particles with release of sulfur-containing gases and minerals. The finely divided coal is recovered from the minerals for use as a clean coal product.

  15. Sulfur removal and comminution of carbonaceous material

    DOEpatents

    Narain, N.K.; Ruether, J.A.; Smith, D.N.

    1987-10-07

    Finely divided, clean coal or other carbonaceous material is provided by forming a slurry of coarse coal in aqueous alkali solution and heating the slurry under pressure to above the critical conditions of steam. The supercritical fluid penetrates and is trapped in the porosity of the coal as it swells in a thermoplastic condition at elevated temperature. By a sudden, explosive release of pressure the coal is fractured into finely divided particles with release of sulfur-containing gases and minerals. The finely divided coal is recovered from the minerals for use as a clean coal product. 2 figs.

  16. Carbonaceous materials as components of cometary dust

    NASA Astrophysics Data System (ADS)

    Colangeli, L.; Schwehm, G.; Bussoletti, E.; Blanco, A.; Borghesi, A.; Fonti, S.; Orofino, V.

    Recent exploration of Comet Halley by space missions and ground-based observations have made it possible to acquire a large amount of new information on cometary materials. In particular, IR spectroscopy has evidenced two pronounced and structured emission features at around 3.28 and 3.37 microns. Different kinds of gaseous molecules and/or solid grains including CH-X bonds have been proposed as possible carriers of the bands. In the past years, laboratory experiments have made it possible to characterize the physical and optical properties of different classes of carbonaceous materials. The absorption properties measured for some of them are here used to fit the cometary features and to identify if possible the most probable carriers of these bands.

  17. Carbonaceous materials as lithium intercalation anodes

    SciTech Connect

    Tran, T.D.; Feikert, J.H.; Mayer, S.T.; Song, X.; Kinoshita, K.

    1994-10-01

    Commercial and polymer-derived carbonaceous materials were examined as lithium intercalation anodes in propylene carbonate (pyrolysis < 1350C, carbons) and ethylene carbonate/dimethyl carbonate (graphites) electrolytes. The reversible capacity (180--355 mAh/g) and the irreversible capacity loss (15--200 % based on reversible capacity) depend on the type of binder, carbon type, morphology, and phosphorus doping concentration. A carbon-based binder was chosen for electrode fabrication, producing mechanically and chemically stable electrodes and reproducible results. Several types of graphites had capacity approaching LiC{sub 6}. Petroleum fuel green cokes doped with phosphorous gave more than a 20 % increase in capacity compared to undoped samples. Electrochemical characteristics are related to SEM, TEM, XRD and BET measurements.

  18. Battery characteristics with various carbonaceous materials

    NASA Astrophysics Data System (ADS)

    Kuribayashi, Isao; Yokoyama, Mika; Yamashita, Masataka

    Various carbonaceous particles having a core-shell structure, produced from graphite and pseudo-graphite coated with pitchblended phenol resin and green mesophase-pitch coated with phenol resin and ground graphite powder, were investigated as active materials for negative electrodes. The particles with natural graphite cores, as well as those with pseudo-graphite cores, were stable both in 1 M LiClO 4sbnd PC:EC (50:50) electrolyte and in 1.5 M LiBF 4sbnd PC:EC:BL (25:25:50) electrolyte, and showed excellent electrical capacities. Those produced from green mesophase-pitch cores were of markedly deformed configuration and showed large capacity gains with only small additions of graphite powder to the phenol coating material. Negative electrodes, in which the particles containing natural graphites cores were blended with petroleum coke in various ratios, showed that it may be possible to produce cells with specific discharge voltage curves, by varying the ratio of this blend.

  19. Mechanism for electrochemical hydrogen insertion in carbonaceous materials

    NASA Astrophysics Data System (ADS)

    Qu, Deyang

    The mechanism for safe and reversible storage of hydrogen in porous carbonaceous materials by electrochemical decomposition of water in alkaline electrolyte is proposed. Atomic H was found to be inserted into the microdomains of defective graphene layers. Hydrogen storage capacity increases with increasing interlayer distance between carbon sheets. Hydrogen insertion in carbonaceous materials occurs at ambient conditions. Static potential acts as an electrochemical valve which can retain the hydrogen in the carbon structure, thus preventing leakage during storage.

  20. Method for co-processing waste rubber and carbonaceous material

    SciTech Connect

    Farcasiu, M.; Smith, C.M.

    1990-10-09

    In a process for the co-processing of waste rubber and carbonaceous material to form a useful liquid product, the rubber and the carbonaceous material are combined and heated to the depolymerization temperature of the rubber in the presence of a source of hydrogen. The deploymerized rubber acts as a liquefying solvent for the carbonaceous material while a beneficial catalytic effect is obtained from the carbon black released on deploymerization the reinforced rubber. The reaction is carried out at liquefaction conditions of 380--600{degrees}C and 70--280 atmospheres hydrogen pressure. The resulting liquid is separated from residual solids and further processed such as by distillation or solvent extraction to provide a carbonaceous liquid useful for fuels and other purposes.

  1. Method for co-processing waste rubber and carbonaceous material

    SciTech Connect

    Farcasiu, M.; Smith, C.M.

    1991-10-29

    This patent describes a process for the co-processing of waste rubber and carbonaceous material to form a useful liquid product, the rubber and the carbonaceous material are combined and heated to the depolymerization temperature of the rubber in the presence of a source of hydrogen. The depolymerized rubber acts as a liquefying solvent for the carbonaceous material while a beneficial catalytic effect is obtained from the carbon black released on depolymerization the reinforced rubber. The reaction is carried out at liquefaction conditions of 380[degrees]-600[degrees] C and 70-280 atmospheres hydrogen pressure. The resulting liquid is separated from residual solids and further processed such as by distillation or solvent extraction to provide a carbonaceous liquid useful for fuels and other purposes.

  2. Method for co-processing waste rubber and carbonaceous material

    DOEpatents

    Farcasiu, Malvina; Smith, Charlene M.

    1991-01-01

    In a process for the co-processing of waste rubber and carbonaceous material to form a useful liquid product, the rubber and the carbonaceous material are combined and heated to the depolymerization temperature of the rubber in the presence of a source of hydrogen. The depolymerized rubber acts as a liquefying solvent for the carbonaceous material while a beneficial catalytic effect is obtained from the carbon black released on depolymerization the reinforced rubber. The reaction is carried out at liquefaction conditions of 380.degree.-600.degree. C. and 70-280 atmospheres hydrogen pressure. The resulting liquid is separated from residual solids and further processed such as by distillation or solvent extraction to provide a carbonaceous liquid useful for fuels and other purposes.

  3. Lithium insertion in carbonaceous materials containing silicon

    NASA Astrophysics Data System (ADS)

    Wilson, Alfred Macdonald

    Three different series of silicon-containing carbonaceous materials were synthesized for use as anodes in lithium ion cells. Disordered (or pregraphitic) carbons containing nanodispersed silicon were prepared by the chemical vapour deposition (CVD) of various chlorosilanes (SiClsb4, (CHsb3)sb2Clsb2Si, and (CHsb3)sb3ClSi) with benzene in two different apparatuses. Silicon oxycarbide glasses were synthesized by the pyrolysis of over 50 silicon-containing polymers at various temperatures, although the principal materials in the study were prepared at 1000sp°C. Finally, materials which we believe to be similar to disordered carbons containing nanodispersed silicon were prepared by the pyrolysis of various blends of pitches with polysilanes. Powder X-ray diffraction was used to learn about the structure of all the materials made. Thermal gravimetric analysis was used to determine the silicon content in the CVD materials and, when coupled to a residual gas analyzer, to study the decomposition process of the polymers. Near edge X-ray absorption spectroscopy measurements of the silicon L- and K-edges of CVD materials and the silicon K-edges of silicon oxycarbides were used to learn about local chemical environments of the silicon atoms. Lithium metal electrochemical test cells of the silicon-containing CVD materials showed larger capacities (up to 500 mAh/g) than pure carbons prepared in the same way (˜300 mAh/g). The additional capacity was observed to be centered near 0.4 V on charge, the average voltage observed for the removal of lithium from a silicon-lithium alloy. Chemical analysis showed that the stoichiometries of materials made by polymer pyrolysis were distributed over a well-defined region in the Si-O-C Gibbs phase diagram. An interesting series of materials is found near the line in the Si-O-C Gibbs triangle connecting carbon to SiOsb{1.3}. Lithium metal electrochemical test cells made using all the silicon oxycarbides synthesized showed that a stoichiometry

  4. Shallow halogen vacancies in halide optoelectronic materials

    DOE PAGES

    Shi, Hongliang; Du, Mao -Hua

    2014-11-05

    Halogen vacancies (VH) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., CH3NH3PbI3 and TlBr. Both CH3NH3PbI3 and TlBr have been found to have shallow VH, in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., CH3NH3PbI3, CH3NH3SnI3 (photovoltaic materials), TlBr, and CsPbBr3, (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VHmore » is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of ns2 ions both play important roles in creating shallow VH in halides such as CH3NH3PbI3, CH3NH3SnI3, and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH, such as those with long cation-cation distances and low anion coordination numbers, and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH. Furthermore, the results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.« less

  5. Shallow halogen vacancies in halide optoelectronic materials

    NASA Astrophysics Data System (ADS)

    Shi, Hongliang; Du, Mao-Hua

    2014-11-01

    Halogen vacancies (VH ) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., C H3N H3Pb I3 and TlBr. Both C H3N H3Pb I3 and TlBr have been found to have shallow VH , in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., C H3N H3Pb I3 , C H3N H3Sn I3 (photovoltaic materials), TlBr, and CsPbB r3 (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VH is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of n s2 ions both play important roles in creating shallow VH in halides such as C H3N H3Pb I3 , C H3N H3Sn I3 , and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH , such as those with large cation-cation distances and low anion coordination numbers and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH . The results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.

  6. Shallow halogen vacancies in halide optoelectronic materials

    SciTech Connect

    Shi, Hongliang; Du, Mao -Hua

    2014-11-05

    Halogen vacancies (VH) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., CH3NH3PbI3 and TlBr. Both CH3NH3PbI3 and TlBr have been found to have shallow VH, in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., CH3NH3PbI3, CH3NH3SnI3 (photovoltaic materials), TlBr, and CsPbBr3, (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VH is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of ns2 ions both play important roles in creating shallow VH in halides such as CH3NH3PbI3, CH3NH3SnI3, and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH, such as those with long cation-cation distances and low anion coordination numbers, and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH. Furthermore, the results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.

  7. Treatment of halogen-containing waste and other waste materials

    DOEpatents

    Forsberg, Charles W.; Beahm, Edward C.; Parker, George W.

    1997-01-01

    A process for treating a halogen-containing waste material. The process provides a bath of molten glass containing a sacrificial metal oxide capable of reacting with a halogen in the waste material. The sacrificial metal oxide is present in the molten glass in at least a stoichiometric amount with respect to the halogen in the waste material. The waste material is introduced into the bath of molten glass to cause a reaction between the halogen in the waste material and the sacrificial metal oxide to yield a metal halide. The metal halide is a gas at the temperature of the molten glass. The gaseous metal halide is separated from the molten glass and contacted with an aqueous scrubber solution of an alkali metal hydroxide to yield a metal hydroxide or metal oxide-containing precipitate and a soluble alkali metal halide. The precipitate is then separated from the aqueous scrubber solution. The molten glass containing the treated waste material is removed from the bath as a waste glass. The process of the invention can be used to treat all types of waste material including radioactive wastes. The process is particularly suited for separating halogens from halogen-containing wastes.

  8. Treatment of halogen-containing waste and other waste materials

    DOEpatents

    Forsberg, C.W.; Beahm, E.C.; Parker, G.W.

    1997-03-18

    A process is described for treating a halogen-containing waste material. The process provides a bath of molten glass containing a sacrificial metal oxide capable of reacting with a halogen in the waste material. The sacrificial metal oxide is present in the molten glass in at least a stoichiometric amount with respect to the halogen in the waste material. The waste material is introduced into the bath of molten glass to cause a reaction between the halogen in the waste material and the sacrificial metal oxide to yield a metal halide. The metal halide is a gas at the temperature of the molten glass. The gaseous metal halide is separated from the molten glass and contacted with an aqueous scrubber solution of an alkali metal hydroxide to yield a metal hydroxide or metal oxide-containing precipitate and a soluble alkali metal halide. The precipitate is then separated from the aqueous scrubber solution. The molten glass containing the treated waste material is removed from the bath as a waste glass. The process of the invention can be used to treat all types of waste material including radioactive wastes. The process is particularly suited for separating halogens from halogen-containing wastes. 3 figs.

  9. Conditioning of carbonaceous material prior to physical beneficiation

    DOEpatents

    Warzinski, Robert P.; Ruether, John A.

    1987-01-01

    A carbonaceous material such as coal is conditioned by contact with a supercritical fluid prior to physical beneficiation. The solid feed material is contacted with an organic supercritical fluid such as cyclohexane or methanol at temperatures slightly above the critical temperature and pressures of 1 to 4 times the critical pressure. A minor solute fraction is extracted into critical phase and separated from the solid residuum. The residuum is then processed by physical separation such as by froth flotation or specific gravity separation to recover a substantial fraction thereof with reduced ash content. The solute in supercritical phase can be released by pressure reduction and recombined with the low-ash, carbonaceous material.

  10. Process for gasifying carbonaceous material from a recycled condensate slurry

    DOEpatents

    Forney, Albert J.; Haynes, William P.

    1981-01-01

    Coal or other carbonaceous material is gasified by reaction with steam and oxygen in a manner to minimize the problems of effluent water stream disposal. The condensate water from the product gas is recycled to slurry the coal feed and the amount of additional water or steam added for cooling or heating is minimized and preferably kept to a level of about that required to react with the carbonaceous material in the gasification reaction. The gasification is performed in a pressurized fluidized bed with the coal fed in a water slurry and preheated or vaporized by indirect heat exchange contact with product gas and recycled steam. The carbonaceous material is conveyed in a gas-solid mixture from bottom to top of the pressurized fluidized bed gasifier with the solids removed from the product gas and recycled steam in a supported moving bed filter of the resulting carbonaceous char. Steam is condensed from the product gas and the condensate recycled to form a slurry with the feed coal carbonaceous particles.

  11. Pyrolysis of carbonaceous materials with solvent quench recovery

    DOEpatents

    Green, Norman W.; Duraiswamy, Kandaswamy; Lumpkin, Robert E.; Knell, Everett W.; Mirza, Zia I.; Winter, Bruce L.

    1978-04-18

    In a continuous process for recovery of values contained in a solid carbonaceous material, the carbonaceous material is comminuted and then subjected to flash pyrolysis in the presence of a particulate heat source to form a pyrolysis product stream containing a carbon containing solid residue and volatilized hydrocarbons. After the carbon containing solid residue is separated from the pyrolysis product stream, values are obtained by condensing volatilized hydrocarbons. The particulate source of heat is formed by oxidizing carbon in the solid residue. Apparatus useful for practicing this process are disclosed.

  12. Apparatus for the selective retorting of carbonaceous materials

    SciTech Connect

    Thomas, D.D.

    1985-02-26

    A staged retort is provided for the retorting of certain types of carbonaceous materials such as oil shale, coal or lignite, wherein the staged retort includes a number of separate retort chambers arranged in a modular configuration, with one retort chamber above the other, and mounted transversely within the staged retort. Each retort chamber is heated to a different temperature, and carbonaceous material is moved from a given retort chamber to a retort chamber having a higher temperature, whereby heavier fractions of liquid and/or gaseous hydrocarbons are formed as the carbonaceous materials undergo pyrolysis. Arrangements such as pressure regulating valves are provided to reduce mixing of the various fractions between the individual retort chambers to nearly zero, and conduits are provided to separately withdraw the hydrocarbon gases and/or liquids from each retort chamber. The carbonaceous material leaving the last retort where the final pyrolysis reactions occur, is routed to a combustion compartment wherein it is burned to produce heat used to heat the retort chambers. The staged retort also includes arrangements for heating a predetermined portion of the gases formed in the retort chambers, to mix the heated portion with a predetermined unheated portion to arrive at a controlled temperature, and then to inject this controlled temperature gas and/or any other substances into the retort chamber interiors to control the temperatures and/or the reaction therein so that each retort chamber can be maintained at the proper temperature and conditions chosen for pyrolysis therein.

  13. Slurry burner for mixture of carbonaceous material and water

    DOEpatents

    Nodd, Dennis G.; Walker, Richard J.

    1987-01-01

    A carbonaceous material-water slurry burner includes a high pressure tip-emulsion atomizer for directing a carbonaceous material-water slurry into a combustion chamber for burning therein without requiring a support fuel or oxygen enrichment of the combustion air. Introduction of the carbonaceous material-water slurry under pressure forces it through a fixed atomizer wherein the slurry is reduced to small droplets by mixing with an atomizing air flow and directed into the combustion chamber. The atomizer includes a swirler located immediately adjacent to where the fuel slurry is introduced into the combustion chamber and which has a single center channel through which the carbonaceous material-water slurry flows into a plurality of diverging channels continuous with the center channel from which the slurry exits the swirler immediately adjacent to an aperture in the combustion chamber. The swirler includes a plurality of slots around its periphery extending the length thereof through which the atomizing air flows and by means of which the atomizing air is deflected so as to exert a maximum shear force upon the carbonaceous material-water slurry as it exits the swirler and enters the combustion chamber. A circulating coolant system or boiler feed water is provided around the periphery of the burner along the length thereof to regulate burner operating temperature, eliminate atomizer plugging, and inhibit the generation of sparklers, thus increasing combustion efficiency. A secondary air source directs heated air into the combustion chamber to promote recirculation of the hot combustion gases within the combustion chamber.

  14. Process for hydrocracking carbonaceous material in liquid carrier

    DOEpatents

    Duncan, Dennis A.

    1980-01-01

    Solid carbonaceous material is hydrocracked to provide aliphatic and aromatic hydrocarbons for use as gaseous and liquid fuels or chemical feed stock. Particulate carbonaceous material such as coal in slurry with recycled product oil is preheated in liquid state to a temperature of 600.degree.-1200.degree. F. in the presence of hydrogen gas. The product oil acts as a sorbing agent for the agglomerating bitumins to minimize caking within the process. In the hydrocracking reactor, the slurry of oil and carbonaceous particles is heated within a tubular passageway to vaporize the oil and form a gas-solid mixture which is further heated to a hydropyrolysis temperature in excess of 1200.degree. F. The gas-solid mixture is quenched by contact with additional oil to condense normally liquid hydrocarbons for separation from the gases. A fraction of the hydrocarbon liquid product is recycled for quenching and slurrying with the carbonaceous feed. Hydrogen is recovered from the gas for recycle and additional hydrogen is produced by gasification of residual char.

  15. Quenched Carbonaceous Composite: a laboratory analog for carbonaceous material in the interstellar medium.

    PubMed

    Tokunaga, A T; Wada, S

    1997-01-01

    We review the properties of Quenched Carbonaceous Composite (QCC), a residue produced from a hydrocarbon plasma, and the properties of its derivatives. A. Sakata and his colleagues have shown that QCC has a 220 nm absorption band, visible fluorescence matching the extended red emission seen in reflection nebulae, and infrared absorption bands that correspond to the infrared emission features in reflection nebulae, HII regions, and planetary nebulae. These properties make QCC a strong candidate material as a laboratory analog to the carbonaceous material in the interstellar medium. QCC is distinguished from the PAH hypothesis in that (1) it is a condensate composed of aromatic and aliphatic molecules, as well as radicals; (2) it exhibits a 220 nm absorption that is very similar in wavelength to the 217 nm absorption in the interstellar medium; (3) it exhibits visible fluorescence consistent with that seen in reflection nebulae; and (4) the bands at 7.7 and 8.6 microns are caused by ketone bands in oxidized QCC. The aromatic component in QCC is thought to be typically 1-4 rings, with the majority being about 1-2 rings.

  16. Slurry burner for mixture of carbonaceous material and water

    DOEpatents

    Nodd, D.G.; Walker, R.J.

    1985-11-05

    The present invention is intended to overcome the limitations of the prior art by providing a fuel burner particularly adapted for the combustion of carbonaceous material-water slurries which includes a stationary high pressure tip-emulsion atomizer which directs a uniform fuel into a shearing air flow as the carbonaceous material-water slurry is directed into a combustion chamber, inhibits the collection of unburned fuel upon and within the atomizer, reduces the slurry to a collection of fine particles upon discharge into the combustion chamber, and regulates the operating temperature of the burner as well as primary air flow about the burner and into the combustion chamber for improved combustion efficiency, no atomizer plugging and enhanced flame stability.

  17. Characterization of carbonaceous materials using extraction with supercritical pentane

    SciTech Connect

    Fetzer, J.C.; Graham, J.A.; Arrendale, R.R.; Klee, M.S.; Rogers, L.B.

    1980-05-30

    The use of carbonaceous adsorbents is limited by irreversible adsorption of some compounds so the use of supercritical pentane as an extracting solvent was examined. Carbon black appeared to be broken down slowly, but continuously, by the penane. To see if other types of carbon behaved similarly, high purity graphite, technical grade graphites, active carbons, and charcoals were examined. The extracts were characterized by uv spectroscopy, packed column chromatography using flame ionization and flame photometric detectors, and capillary GC/MS. The extracts were characteristic for each class of carbonaceous material. The high purity graphite yielded large, polycyclic aromatic compounds; the technical grade graphites yielded alkanes and alkyl-substituted benzenes and naphthalenes; the active carbons yielded alkanes, dienes, and small amounts of alkyl-substituted benzenes; and the charcoals yielded almost entirely alkanes in small amounts.

  18. Surface analysis of nanostructured carbonaceous materials

    NASA Astrophysics Data System (ADS)

    Wepasnick, Kevin Andrew

    The characterization of surfaces is central to understanding its interaction with other materials. Current ground-breaking research in interfacial science is focusing on surfaces which have a nanoscopic-size to their structuring. In particular, carbon nanotubes (CNTs) have been explored extensively. However, to utilize these materials in commercial and scientific applications, the surfaces are often modified to tailor specific properties, such as dispersion, sorption, and reactivity. The focus of this thesis is to apply surface analytical techniques to explore the chemical and structural characteristics of modified nanostructured surfaces. Specifically studied are the covalent surface modifications of CNTs by strategies that involve the direct incorporation of specific elements into the graphene sidewalls by commonly used wet chemical oxidants. These resulting CNTs are then evaluated in terms of their change in surface chemistry and structure. X-ray photoelectron spectroscopy (XPS) was used to characterize the surface oxidation, while chemical derivatization techniques in conjunction with XPS afforded the concentration of carboxyl, carbonyl, and hydroxyl groups on the CNT surface. Transmission electron microscopy (TEM) was able to provide detailed structural information on the modified CNT, including the extent of sidewall damage. Results indicate that the distribution of oxygen-containing functional groups was insensitive to the reaction conditions, but was dependent upon the identity of the oxidant. These trends in functional group concentration were then applied to determining environmental properties, specifically divalent metal cation sorption. Consistently, the increases in COOH functional groups result in an increase in sorption capacity of divalent metal cations, such as Zn2+ and Cd2+. Furthermore, the interactions of size-selected metal and metal-oxide nanoclusters with graphite surfaces were studied by atomic force microscopy (AFM), scanning tunneling

  19. The halogen bond in the design of functional supramolecular materials: recent advances.

    PubMed

    Priimagi, Arri; Cavallo, Gabriella; Metrangolo, Pierangelo; Resnati, Giuseppe

    2013-11-19

    Halogen bonding is an emerging noncovalent interaction for constructing supramolecular assemblies. Though similar to the more familiar hydrogen bonding, four primary differences between these two interactions make halogen bonding a unique tool for molecular recognition and the design of functional materials. First, halogen bonds tend to be much more directional than (single) hydrogen bonds. Second, the interaction strength scales with the polarizability of the bond-donor atom, a feature that researchers can tune through single-atom mutation. In addition, halogen bonds are hydrophobic whereas hydrogen bonds are hydrophilic. Lastly, the size of the bond-donor atom (halogen) is significantly larger than hydrogen. As a result, halogen bonding provides supramolecular chemists with design tools that cannot be easily met with other types of noncovalent interactions and opens up unprecedented possibilities in the design of smart functional materials. This Account highlights the recent advances in the design of halogen-bond-based functional materials. Each of the unique features of halogen bonding, directionality, tunable interaction strength, hydrophobicity, and large donor atom size, makes a difference. Taking advantage of the hydrophobicity, researchers have designed small-size ion transporters. The large halogen atom size provided a platform for constructing all-organic light-emitting crystals that efficiently generate triplet electrons and have a high phosphorescence quantum yield. The tunable interaction strengths provide tools for understanding light-induced macroscopic motions in photoresponsive azobenzene-containing polymers, and the directionality renders halogen bonding useful in the design on functional supramolecular liquid crystals and gel-phase materials. Although halogen bond based functional materials design is still in its infancy, we foresee a bright future for this field. We expect that materials designed based on halogen bonding could lead to

  20. Primordial Molecular Cloud Material in Metal-Rich Carbonaceous Chondrites

    NASA Astrophysics Data System (ADS)

    Taylor, G. J.

    2016-03-01

    The menagerie of objects that make up our Solar System reflects the composition of the huge molecular cloud in which the Sun formed, a late addition of short-lived isotopes from an exploding supernova or stellar winds from a neighboring massive star, heating and/or alteration by water in growing planetesimals that modified and segregated the primordial components, and mixing throughout the Solar System. Outer Solar System objects, such as comets, have always been cold, hence minimizing the changes experienced by more processed objects. They are thought to preserve information about the molecular cloud. Elishevah Van Kooten (Natural History Museum of Denmark and the University of Copenhagen) and co-authors in Denmark and at the University of Hawai'i, measured the isotopic compositions of magnesium and chromium in metal-rich carbonaceous chondrites. They found that the meteorites preserve an isotopic signature of primordial molecular cloud materials, providing a potentially detailed record of the molecular cloud's composition and of materials that formed in the outer Solar System.

  1. Pressure gradient passivation of carbonaceous material normally susceptible to spontaneous combustion

    DOEpatents

    Ochs, Thomas L.; Sands, William D.; Schroeder, Karl; Summers, Cathy A.; Utz, Bruce R.

    2000-11-14

    This invention is a process for the passivation or deactivation with resp to oxygen of a carbonaceous material by the exposure of the carbonaceous material to an oxygenated gas in which the oxygenated gas pressure is increased from a first pressure to a second pressure and then the pressure is changed to a third pressure. Preferably a cyclic process which comprises exposing the carbonaceous material to the gas at low pressure and increasing the pressure to a second higher pressure and then returning the pressure to a lower pressure is used. The cycle is repeated at least twice wherein the higher pressure may be increased after a selected number of cycles.

  2. Pressure gradient passivation of carbonaceous material normally susceptible to spontaneous combustion

    DOEpatents

    Ochs, Thomas L.; Sands, William D.; Schroeder, Karl; Summers, Cathy A.; Utz, Bruce R.

    2002-01-29

    This invention is a process for the passivation or deactivation with respect to oxygen of a carbonaceous material by the exposure of the carbonaceous material to an oxygenated gas in which the oxygenated gas pressure is increased from a first pressure to a second pressure and then the pressure is changed to a third pressure. Preferably a cyclic process which comprises exposing the carbonaceous material to the gas at low pressure and increasing the pressure to a second higher pressure and then returning the pressure to a lower pressure is used. The cycle is repeated at least twice wherein the higher pressure may be increased after a selected number of cycles.

  3. Liquefaction process for solid carbonaceous materials containing alkaline earth metal humates

    DOEpatents

    Epperly, William R.; Deane, Barry C.; Brunson, Roy J.

    1982-01-01

    An improved liquefaction process wherein wall scale and particulate agglomeration during the liquefaction of solid carbonaceous materials containing alkaline earth metal humates is reduced and/or eliminated by subjecting the solid carbonaceous materials to controlled cyclic cavitation during liquefaction. It is important that the solid carbonaceous material be slurried in a suitable solvent or diluent during liquefaction. The cyclic cavitation may be imparted via pressure cycling, cyclic agitation and the like. When pressure cycling or the like is employed an amplitude equivalent to at least 25 psia is required to effectively remove scale from the liquefaction vessel walls.

  4. Functional carbonaceous materials from hydrothermal carbonization of biomass: an effective chemical process.

    PubMed

    Hu, Bo; Yu, Shu-Hong; Wang, Kan; Liu, Lei; Xu, Xue-Wei

    2008-10-28

    Recently, much attention has been attracted to the use of biomass to produce functional carbonaceous materials from the viewpoint of economic, environmental and societal issues. Among different techniques, the hydrothermal carbonization (HTC) process, a traditional but recently revived method, presents superior characteristics that make it a promising route of wide potential application. This perspective gives an overview of the latest advances in the HTC process of functional carbonaceous materials from biomass. First, we discuss the preparation of carbonaceous materials synthesized by the use of either highly directed or catalyst/template-assisted methods, from crude plant materials and carbohydrates respectively. These carbonaceous materials not only have special morphologies, such as nanospheres, nanocables, nanofibers, submicrocables, submicrotubes and porous structures, but also contain rich functional groups which can greatly improve hydrophilicity and chemical reactivity. Further, a general look is cast on the applications of this kind of carbonaceous materials in environmental, catalytic and electrical areas. Recent advances have demonstrated that the HTC process from biomass can provide promising methods for the rational design of a rich family of carbonaceous and hybrid functional carbon materials with important applications.

  5. Dark Material on Vesta from Infall of Carbonaceous Volatile-Rich Materials

    NASA Astrophysics Data System (ADS)

    McCord, T. B.; Li, J.; Combe, J.; McSween, H. Y.; Jaumann, R.; Reddy, V.; Tosi, F.; Williams, D. A.; Blewett, D. T.; Turrini, D.; Palomba, E.; Pieters, C. M.; De Sanctis, M.; Nathues, A.; Sunshine, J. M.; Raymond, C. A.; Russell, C. T.

    2012-12-01

    Dark and bright materials, sometimes with dramatically different albedos, were recently found on Vesta's surface by the Dawn spacecraft. Their albedo range is among the largest observed on solar system rocky bodies. These materials, often associated with craters, appear in ejecta and crater walls, and their pyroxene absorption strengths are correlated with material brightness. It was tentatively suggested that dark material could be either exogenic, from carbon-rich low velocity impactors, or endogenic, from freshly exposed mafic material or impact melt, created or exposed by impacts. We argue that the dark material is predominately from infall of hydrated carbonaceous material (like a major class of meteorites and comet surfaces), whereas the bright material is the uncontaminated indigenous Vesta basaltic soil. We use Vesta spectra and images to derive and interpret the properties of "pure" dark and bright materials. The dark material spectrum is consistent with carbonaceous chondrite meteorite material, and there is evidence of the associated presence of OH- and H-bearing materials. Dark material from low-albedo impactors is diffused over time through the Vestan regolith by impact mixing, creating broader, diffuse darker regions and finally Vesta's background surface material. This is consistent with howardite-eucrite-diogenite (HED) meteorites coming from Vesta. Thus, we are seeing on Vesta a dramatic example of a common process affecting most Solar System objects: that of contamination and alteration of indigenous material due to impact and retention and spreading of the impactor material. This process also provides a mechanism to transport water and organic-rich materials to Vesta and other bodies. This hypothesis is completely consistent with evidence observed in the HED meteorites and strengthens the connection between the HEDs and Vesta.

  6. Carbon dioxide capture on amine-rich carbonaceous materials derived from glucose.

    PubMed

    Zhao, Li; Bacsik, Zoltan; Hedin, Niklas; Wei, Wei; Sun, Yuhan; Antonietti, Markus; Titirici, Maria-Magdalena

    2010-07-19

    The synthesis of carbonaceous materials with a high surface density of amino functions for CO(2) sorption and sequestration is reported. The amino-rich carbonaceous materials are characterized by elemental analysis, N(2) sorption, scanning and transmission electron microscopy, zeta potential, TGA and FTIR measurements. A detailed discussion on the use of these materials in CO(2) capture is provided. The materials show significant sorption capabilities for CO(2) (4.3 mmol g(-1)at -20 degrees C and 1 bar). Furthermore, they show a high apparent selectivity for CO(2) over N(2) at both low and high temperatures.

  7. Brighter material on Deimos - A particle size effect in a carbonaceous material?

    NASA Technical Reports Server (NTRS)

    French, L. M.; Veverka, J.; Thomas, P.

    1988-01-01

    The values obtained for brightness ratios between contiguous bright and dark areas on Deimos from Viking Orbiter images, together with the lack of a significant wavelength dependence of these ratios in the 0.4-0.6-micron range, are presently noted to be consistent with particle size fraction measurements of the Murchison CM meteorite. These data, and a near-coincidence of Deimos absolute reflectances with those of laboratory samples, render the present data consistent with both brighter and darker materials on Deimos being akin to carbonaceous chondrites; the material with smaller average particle size is associated with the brighter patches.

  8. Liquefaction of solid carbonaceous material with catalyst recycle

    DOEpatents

    Gupta, Avinash; Greene, Marvin I.

    1992-01-01

    In the two stage liquefaction of a carbonaceous solid such as coal wherein coal is liquefied in a first stage in the presence of a liquefaction solvent and the first stage effluent is hydrogenated in the presence of a supported hydrogenation catalyst in a second stage, catalyst which has been previously employed in the second stage and comminuted to a particle size distribution equivalent to 100% passing through U.S. 100 Mesh, is passed to the first stage to improve the overall operation.

  9. Phosphorus and Halogen Co-Doped Graphene Materials and their Electrochemistry.

    PubMed

    Wang, Lu; Sofer, Zdenek; Zboril, Radek; Cepe, Klara; Pumera, Martin

    2016-10-17

    Doping of graphene materials with heteroatoms is important as it can change their electronic and electrochemical properties. Here, graphene is co-doped with n-type dopants such as phosphorus and halogen (Cl, Br, I). Phosphorus and halogen are introduced through the treatment of graphene oxide with PX3 gas (PCl3 , PBr3 , and PI3 ). Graphene oxides are prepared through chlorate and permanganate routes. Detailed chemical and structural characterization demonstrates that the graphene sheets are covered homogeneously by phosphorus and halogen atoms. It is found that the amount of phosphorus and halogen introduced depends on the graphene oxide preparation method. The electrocatalytic effect of the resulting co-doped materials is demonstrated for industrially relevant electrochemical reactions such as the hydrogen evolution and oxygen reduction reactions.

  10. Preparation of a sulfonated carbonaceous material from lignosulfonate and its usefulness as an esterification catalyst.

    PubMed

    Lee, Duckhee

    2013-07-10

    Sulfonated carbonaceous material useful as a solid acid catalyst was prepared from lignosulfonate, a waste of the paper-making industry sulfite pulping process, and characterized by 13C-NMR, FT-IR, TGA, SEM and elemental analysis, etc. The sulfonic acid group density and total density of all acid groups in the sulfonated carbonaceous material was determined by titration to be 1.24 mmol/g and 5.90 mmol/g, respectively. Its catalytic activity in the esterification of cyclohexanecarboxylic acid with anhydrous ethanol was shown to be comparable to that of the ionic exchange resin Amberlyst-15, when they were used in the same amount. In the meantime, the sulfonic acid group was found to be leached out by 26%-29% after it was exposed to hot water (95 °C) for 5 h. The catalytic usefulness of the prepared carbonaceous material was investigated by performing esterifications.

  11. Carbonaceous material for production of hydrogen from low heating value fuel gases

    DOEpatents

    Koutsoukos, Elias P.

    1989-01-01

    A process for the catalytic production of hydrogen, from a wide variety of low heating value fuel gases containing carbon monoxide, comprises circulating a carbonaceous material between two reactors--a carbon deposition reactor and a steaming reactor. In the carbon deposition reactor, carbon monoxide is removed from a fuel gas and is deposited on the carbonaceous material as an active carbon. In the steaming reactor, the reactive carbon reacts with steam to give hydrogen and carbon dioxide. The carbonaceous material contains a metal component comprising from about 75% to about 95% cobalt, from about 5% to about 15% iron, and up to about 10% chromium, and is effective in suppressing the production of methane in the steaming reactor.

  12. Heavy-ion irradiation induced diamond formation in carbonaceous materials.

    SciTech Connect

    Daulton, T. L.

    1999-01-08

    The basic mechanisms of metastable phase formation produced under highly non-equilibrium thermodynamic conditions within high-energy particle tracks are investigated. In particular, the possible formation of diamond by heavy-ion irradiation of graphite at ambient temperature is examined. This work was motivated, in part, by earlier studies which discovered nanometer-grain polycrystalline diamond aggregates of submicron-size in uranium-rich carbonaceous mineral assemblages of Precambrian age. It was proposed that the radioactive decay of uranium formed diamond in the fission particle tracks produced in the carbonaceous minerals. To test the hypothesis that nanodiamonds can form by ion irradiation, fine-grain polycrystalline graphite sheets were irradiated with 400 MeV Kr ions. The ion irradiated graphite (and unirradiated graphite control) were then subjected to acid dissolution treatments to remove the graphite and isolate any diamonds that were produced. The acid residues were then characterized by analytical and high-resolution transmission electron microscopy. The acid residues of the ion-irradiated graphite were found to contain ppm concentrations of nanodiamonds, suggesting that ion irradiation of bulk graphite at ambient temperature can produce diamond.

  13. Dark material on Vesta from the infall of carbonaceous volatile-rich material.

    PubMed

    McCord, T B; Li, J-Y; Combe, J-P; McSween, H Y; Jaumann, R; Reddy, V; Tosi, F; Williams, D A; Blewett, D T; Turrini, D; Palomba, E; Pieters, C M; De Sanctis, M C; Ammannito, E; Capria, M T; Le Corre, L; Longobardo, A; Nathues, A; Mittlefehldt, D W; Schröder, S E; Hiesinger, H; Beck, A W; Capaccioni, F; Carsenty, U; Keller, H U; Denevi, B W; Sunshine, J M; Raymond, C A; Russell, C T

    2012-11-01

    Localized dark and bright materials, often with extremely different albedos, were recently found on Vesta's surface. The range of albedos is among the largest observed on Solar System rocky bodies. These dark materials, often associated with craters, appear in ejecta and crater walls, and their pyroxene absorption strengths are correlated with material brightness. It was tentatively suggested that the dark material on Vesta could be either exogenic, from carbon-rich, low-velocity impactors, or endogenic, from freshly exposed mafic material or impact melt, created or exposed by impacts. Here we report Vesta spectra and images and use them to derive and interpret the properties of the 'pure' dark and bright materials. We argue that the dark material is mainly from infall of hydrated carbonaceous material (like that found in a major class of meteorites and some comet surfaces), whereas the bright material is the uncontaminated indigenous Vesta basaltic soil. Dark material from low-albedo impactors is diffused over time through the Vestan regolith by impact mixing, creating broader, diffuse darker regions and finally Vesta's background surface material. This is consistent with howardite-eucrite-diogenite meteorites coming from Vesta.

  14. Combined method for simultaneously dewatering and reconstituting finely divided carbonaceous material

    DOEpatents

    Wen, Wu-Wey; Deurbrouck, Albert W.

    1990-01-01

    A finely-divided carbonaceous material is dewatered and reconstituted in a combined process by adding a binding agent directly into slurry of finely divided material and dewatering the material to form a cake or consolidated piece which can be hardened by drying at ambient or elevated temperatures. Alternatively, the binder often in the form of a crusting agent is sprayed onto the surface of a moist cake prior to curing.

  15. Micro Raman spectroscopy of carbonaceous material in microfossils and meteorites: improving a method for life detection.

    PubMed

    Bower, D M; Steele, A; Fries, M D; Kater, L

    2013-01-01

    The identification of biosignatures in Earth's ancient rock record and detection of extraplanetary life is one of the primary goals in astrobiology. Intrinsic to this goal is the improvement of analytical techniques and protocols used to identify an unambiguous signal of life. Micro Raman spectroscopy is a nondestructive method that allows for in situ identification of a wide range of minerals and compounds. The use of D (∼1350 cm(-1)) and G (∼1580 cm(-1)) band parameters to infer the biogenicity of carbonaceous materials in fossils has become a commonly used analytical tool, but carbonaceous compounds from different sources often share the same spectroscopic characteristics. Microfossil studies do not always take into consideration a nonbiological source for the carbon in their samples and therefore still rely on morphology as the primary mode of identification. Comprehensive studies that consider all carbon sources are typically done on metasediments, coals, or meteorites, and the results are not clearly applicable to microfossil identification. In this study, microfossils from a suite of sedimentary rock samples of various ages were analyzed with micro Raman spectroscopy to investigate the nature and provenance of carbonaceous material. To further constrain D- and G-band carbon characteristics, micro Raman analyses were also performed on well-characterized meteorite samples as abiological controls. The results appear to show a correlation of precursor carbonaceous material with D-band parameters and thermal history with G-band parameters. This systematic study lays the groundwork for improving the use of the G- and D-band trends as useful indicators of the origin of carbon in microfossils. Before unambiguous biosignatures can be established, further work characterizing the carbonaceous material in microfossils of different ages, thermal histories, and host rock compositions is needed.

  16. X-ray structure characteristics of carbonaceous materials in the course of production of calcium carbide

    SciTech Connect

    Kol'tsova, N.A.; Mel'nik, A.P.; Ershov, V.A.; Stepanova, L.V.

    1987-11-20

    The authors, in an investigation for carbonaceous materials cheaper than graphite as raw materials for calcium carbide production, assess the suitability of several carbon compounds and attempt to draw correlations between crystal structure and activation energy properties. The materials investigated include KAU coke briquet, anthracite, lean coal from the Krasnogorsk mine in the Kuzbass, coke from a Moscow coke-oven plant, coal coke, and Novobakinsk petroleum coke. A comparison of the behavior of these materials in the formation of calcium carbides is made with graphite. X-ray diffraction is conducted using a DRON diffractometer.

  17. Hydrothermal pretreatment to prevent scale during liquefaction of certain solid carbonaceous materials

    DOEpatents

    Stone, John B.; Floyd, Frank M.

    1984-01-01

    Scale formation during the liquefaction of lower ranking coals and similar carbonaceous materials is significantly reduced and/or prevented by hydrothermal pretreatment. The said pretreatment is believed to convert the scale-forming components to the corresponding carbonate prior to liquefaction. The said pretreatment is accomplished at a total pressure within the range from about 1000 to about 4400 psia. Temperature during said pretreatment will generally be within the range from about 500.degree. to about 700.degree. F.

  18. Hydrothermal pretreatment to prevent scale during liquefaction of certain solid carbonaceous materials

    SciTech Connect

    Stone, J.B.; Floyd, F.M.

    1984-05-22

    Scale formation during the liquefaction of lower ranking coals and similar carbonaceous materials is significantly reduced and/or prevented by hydrothermal pretreatment. The said pretreatment is believed to convert the scale-forming components to the corresponding carbonate prior to liquefaction. The said pretreatment is accomplished at a total pressure within the range from about 1000 to about 4400 psia. Temperature during said pretreatment will generally be within the range from about 500/sup 0/ to about 700/sup 0/ F.

  19. Method and apparatus for production of crystallizable carbonaceous material

    SciTech Connect

    Noguchi, K.; Ishitobi, T.; Kitajima, E.; Kumura, Y.; Tanaka, H.

    1984-12-18

    A heavy oil such as an atmospheric pressure residue, a reduced pressure residue of petroleum, etc. is heated to 400/sup 0/ to 500/sup 0/ C. to carry out polycondensation and provide a pitch containing mesophase microspheres. This pitch is once cooled to 200/sup 0/ to 400/sup 0/ C. and a turbulent flow is imparted thereto to cause agglomeration of the mesophase microspheres. The resulting agglomerates are separated to obtain a crystallizable material enriched with quinoline insolubles. Production of the crystallizable material is preferably conducted in a separation tank accommodating the lower part of a heating polycondensation reactor and having a stirring device.

  20. Development of moldable carbonaceous materials for ablative rocket nozzles.

    NASA Technical Reports Server (NTRS)

    Lockhart, R. J.; Bortz, S. A.; Schwartz, M. A.

    1972-01-01

    Description of a materials system developed for use as low-cost ablative nozzles for NASA's 260-in. solid rocket motor. Petroleum coke and carbon black fillers were employed; high density was achieved by controlling particle size distribution. An alumina catalyzed furfuryl ester resin which produced high carbon residues after pyrolysis was employed as the binder. Staple carbon fibers improved the strength and crack resistance of molded bodies. In static firing tests of two subscale nozzles, this material compared favorably in erosion rate with several other ablative systems.

  1. Process for hydroliquefying coal or like carbonaceous solid materials

    DOEpatents

    Malek, John Michael

    1977-01-01

    In this process the products of the dissolution-hydrogenation of coal or the like material in a hydrocarbon rich solvent are subjected in their slurryform fraction to an asphaltenes decomposing action of an alkali, like caustic soda or, being admixed after the gasiform fraction of the hydrogenation products has been taken off the slurryform fraction of the hydrogenation products now including the admixed alkali is subjected to a rehydrogenation by a hydrogen rich gas which after its rehydrogenating use is preferably applied, as source of hydrogen, to said dissolution-hydrogenation of coal. Optionally the admixed alkali includes minor amounts of a carboxylic acid salt of calcium.

  2. Heavy-Ion Radiation-Induced Diamond Formation in Carbonaceous Materials

    NASA Astrophysics Data System (ADS)

    Daulton, T. L.; Ozima, M.

    1996-10-01

    The feasibility of a radiation-induced diamond formation (RIDF) mechanism is demonstrated by the observation of nano-diamonds in carburanium, a U-rich fine-grained, coal-like assemblage containing amorphous carbonaceous material of Precambrian age from North Karelia, Russia. This mineral deposit represents an ideal natural environment for RIDF because the carbonaceous grains present have received a high fluence of energetic particles over a geological time scale. Fragments of carburanium were subjected to acid dissolution treatments to isolate any diamond present. Transmission electron microscopy on these acid residues identified 500 nm polycrystalline diamond aggregates. This observation and estimates of formation efficiencies supports the hypothesis that diamond can form in carbonaceous material irradiated by U decay fragments. Diamond concentration in bulk carburanium is #197# 30 ppm indicating that the RIDF efficiencies might be relatively low as compared to the competing formation of graphite; the acid treatment was an essential key in the recovery of diamond in carburanium. This fact could contribute to the lack of observation of diamond in well- studied ion-implanted carbons. Experiments to synthesize nano-diamonds by heavy-ion irradiation are scheduled for late 1996 at ANL's accelerator ATLAS.

  3. Enhanced Removal of Lead by Chemically and Biologically Treated Carbonaceous Materials

    PubMed Central

    Mahmoud, Mohamed E.; Osman, Maher M.; Ahmed, Somia B.; Abdel-Fattah, Tarek M.

    2012-01-01

    Hybrid sorbents and biosorbents were synthesized via chemical and biological treatment of active carbon by simple and direct redox reaction followed by surface loading of baker's yeast. Surface functionality and morphology of chemically and biologically modified sorbents and biosorbents were studied by Fourier Transform Infrared analysis and scanning electron microscope imaging. Hybrid carbonaceous sorbents and biosorbents were characterized by excellent efficiency and superiority toward lead(II) sorption compared to blank active carbon providing a maximum sorption capacity of lead(II) ion as 500 μmol g−1. Sorption processes of lead(II) by these hybrid materials were investigated under the influence of several controlling parameters such as pH, contact time, mass of sorbent and biosorbent, lead(II) concentration, and foreign ions. Lead(II) sorption mechanisms were found to obey the Langmuir and BET isotherm models. The potential applications of chemically and biologically modified-active carbonaceous materials for removal and extraction of lead from real water matrices were also studied via a double-stage microcolumn technique. The results of this study were found to denote to superior recovery values of lead (95.0–99.0 ± 3.0–5.0%) by various carbonaceous-modified-bakers yeast biosorbents. PMID:22629157

  4. Halogenation of microcapsule walls

    NASA Technical Reports Server (NTRS)

    Davis, T. R.; Schaab, C. K.; Scott, J. C.

    1972-01-01

    Procedure for halogenation of confining walls of both gelatin and gelatin-phenolic resin capsules is similar to that used for microencapsulation. Ten percent halogen content renders capsule wall nonburning; any higher content enhances flame-retardant properties of selected internal phase material. Halogenation decreases permeability of wall material to encapsulated materials.

  5. Lithium intercalation behavior of surface modified carbonaceous materials

    SciTech Connect

    Tran, T.D.; Murguia, L.X.; Song, X.; Kinoshita, K.

    1997-07-17

    The surface properties of several well-characterized commercial carbon materials were modified by thermal and chemical treatments. The reversible capacities for lithium intercalation of a sponge green coke and a fuel green coke for lithium intercalation increased by as much as 25% after heat treatment in both reducing (5% H{sub 2}/Ar) and oxidizing (CO{sub 2}) environments. The irreversible capacity loss increased significantly with CO{sub 2} treatment at 800{degrees}C. The trend of larger capacity losses with CO{sub 2} treatment is also observed with a synthetic graphite (SFG6) which was produced by heat treatment at about 3000{degrees}C. Carbon fibers that were first impregnated with LiOH solution followed by reaction with CO{sub 2} to form Li{sub 2}CO{sub 3} tended to show lower irreversible capacity losses.

  6. EPR and magnetism of the nanostructured natural carbonaceous material shungite

    NASA Astrophysics Data System (ADS)

    Augustyniak-Jabłokow, Maria Aldona; Yablokov, Yurii V.; Andrzejewski, Bartłomiej; Kempiński, Wojciech; Łoś, Szymon; Tadyszak, Krzysztof; Yablokov, Mikhail Y.; Zhikharev, Valentin A.

    2010-04-01

    The X-band EPR and magnetic susceptibility in the temperature range 4.2-300 K study of the shungite-I, natural nanostructured material from the deposit of Shunga are reported. Obtained results allow us to assign the EPR signal to conduction electrons, estimate their number, N P, and evaluate the Pauli paramagnetism contribution to shungite susceptibility. A small occupation (~5%) of the localized nonbonding π states in the zigzag edges of the open-ended graphene-like layers and/or on σ ( sp 2+ x ) orbitals in the curved parts of the shungite globules has been also revealed. The observed temperature dependence of the EPR linewidth can be explained by the earlier considered interaction of conduction π electrons with local phonon modes associated with the vibration of peripheral carbon atoms of the open zigzag-type edges and with peripheral carbon atoms cross-linking different nanostructures. The relaxation time T 2 and diffusion time T D are found to have comparable values (2.84 × 10-8 and 1.73 × 10-8 s at 5.2 K, respectively), and similar dependence on temperature. The magnetic measurements have revealed the suppression of orbital diamagnetism due to small amount of large enough fragments of the graphene layers.

  7. Method and apparatus for conversion of carbonaceous materials to liquid fuel

    SciTech Connect

    Lux, Kenneth W.; Namazian, Mehdi; Kelly, John T.

    2015-12-01

    Embodiments of the invention relates to conversion of hydrocarbon material including but not limited to coal and biomass to a synthetic liquid transportation fuel. The invention includes the integration of a non-catalytic first reaction scheme, which converts carbonaceous materials into a solid product that includes char and ash and a gaseous product; a non-catalytic second reaction scheme, which converts a portion of the gaseous product from the first reaction scheme to light olefins and liquid byproducts; a traditional gas-cleanup operations; and the third reaction scheme to combine the olefins from the second reaction scheme to produce a targeted fuel like liquid transportation fuels.

  8. Nitrogen-Doped Carbonaceous Materials for Removal of Phenol from Aqueous Solutions

    PubMed Central

    Hofman, Magdalena; Pietrzak, Robert

    2012-01-01

    Carbonaceous material (brown coal) modified by pyrolysis, activation, and enrichment in nitrogen, with two different factor reagents, have been used as adsorbent of phenol from liquid phase. Changes in the phenol content in the test solutions were monitored after subsequent intervals of adsorption with selected adsorbents prepared from organic materials. Significant effect of nitrogen present in the adsorbent material on its adsorption capacity was noted. Sorption capacity of these selected materials was found to depend on the time of use, their surface area, and pore distribution. A conformation to the most well-known adsorption isotherm models, Langmuir, and Freundlich ones, confirms the formation of mono- and heterolayer solute (phenol) coverage on the surface of the adsorbent applied herein. The materials proposed as adsorbents of the aqueous solution contaminants were proved effective, which means that the waste materials considered are promising activated carbon precursors for liquid phase adsorbents for the environmental protection. PMID:22593671

  9. Raman spectroscopy of carbonaceous material in PETM sediments from the Bighorn Basin, Wyoming

    NASA Astrophysics Data System (ADS)

    Baczynski, A. A.; McInerney, F. A.; Jacobsen, S. D.; Blair, N. E.; Thomas, S.; Kraus, M. J.

    2009-12-01

    Raman microspectroscopy has become a widely used method in geosciences to characterize carbonaceous material (CM) because of its non-destructive nature, short aquisition times, high spatial resolution, and minimal sample preparation. Spectral parameters such as vibrational band position, peak width and peak ratios are used to characterize the CM in terms of thermal maturity. Such information is important to C-biogeochemical studies of both present and past environments because surface pools, such as soils and sediments, typically contain CM exhibiting a wide range of ages and hence thermal maturity. Resolution of those sources is critical to an accurate interpretation of the organic geochemical record. Using Raman spectroscopy, we have identified different types of CM in untreated mudstones, carbonaceous shales, and fine-grained sandstones from the Willwood and Fort Union formations of the southeastern Bighorn Basin, Wyoming. In order to systematically characterize the thermal maturity along a 64 m vertical section spanning the Paleocene-Eocene Thermal Maximum, we measured Raman spectra of the CM. The samples contain at least two different types of CM, irregularly shaped black coal-like fragments and remnants of fossil roots. The Raman spectra of the black carbon fragments consist of bands at ~1347, 1385 cm-1 (D band) and 1588 cm-1 (G band) and weak bands at 2854 cm-1 and 3172 cm-1. The fossil root fragments reveal a different vibrational signature; bands are present at ~1338, 1367 cm-1 and 1582 cm-1 and weak bands at 2778 cm-1 and 2966 cm-1. The Raman spectra indicate that the black carbonaceous material has a higher degree of aromatization than the root material. The black CM spectra are consistent with either paleocharcoal or a recycled CM from an older, more thermally mature lithology that can co-occur with the fossil root debris. Initial results indicate that Raman spectroscopy is an effective method to resolve and characterize multiple sources of CM within

  10. Pretreatment of solid carbonaceous material with dicarboxylic aromatic acids to prevent scale formation

    SciTech Connect

    Brunson, R.J.

    1982-06-01

    Scale formation during the liquefaction of lower ranking coals and similar carbonaceous materials is significantly reduced and/or prevented by pretreatment with a pretreating agent selected from the group consisting of phthalic acid, phthalic anhydride, pyromellitic acid and pyromellitic anhydride. The pretreatment is believed to convert the scale-forming components to the corresponding phthalate and/or pyromellitate prior to liquefaction. The pretreatment is accomplished at a total pressure within the range from about 1 to about 2 atmospheres. Temperature during pretreatment will generally be within the range from about 5 to about 80/sup 0/ C.

  11. Pretreatment of solid carbonaceous material with dicarboxylic aromatic acids to prevent scale formation

    SciTech Connect

    Brunson, Roy J.

    1982-01-01

    Scale formation during the liquefaction of lower ranking coals and similar carbonaceous materials is significantly reduced and/or prevented by pretreatment with a pretreating agent selected from the group consisting of phthalic acid, phthalic anhydride, pyromellitic acid and pyromellitic anhydride. The pretreatment is believed to convert the scale-forming components to the corresponding phthalate and/or pyromellitate prior to liquefaction. The pretreatment is accomplished at a total pressure within the range from about 1 to about 2 atmospheres. Temperature during pretreatment will generally be within the range from about 5.degree. to about 80.degree. C.

  12. Origin and formation of carbonaceous material veins in the 2008 Wenchuan earthquake fault zone

    NASA Astrophysics Data System (ADS)

    Liu, Jiang; Li, Haibing; Zhang, Jinjiang; Zhang, Bo

    2016-02-01

    This paper establishes a reference data set of carbonaceous materials (CMs) from the active fault zone of the Longmen Shan fault belt that ruptured in the 2008 Mw7.9 Wenchuan earthquake and presents an application of these data for studies of both other exhumed carbonaceous-rich fault zones and deep-drilling cores. The CMs distributed in the active fault zone are found as narrow veins and located along the slip surfaces. Microstructural observation shows that the carbonaceous material veins (CMVs) are located along slip surfaces in the fault gouge zones. Some CMVs have a cataclastic fabric, and their branches intrude into voids around the slip surfaces. Raman spectra of the CMVs show a wide (full width at half maximum >200 cm-1) D-peak at ~1345 cm-1 (defect peak), which is much lower than the O-peak at ~1595 cm-1 (ordered peak), indicating a metamorphic temperature of zeolite facies or lower than 250 °C. In addition, the stable carbon isotopic compositions (δ13C values) of the CMVs, ranging from -23.4 to -26.4‰, are very similar to that of the kerogen collected from the Late Triassic Xujiahe Formation in Sichuan Basin. Given the data at which it may be formed, the Xujiahe Formation is the most likely origin of CMs for the CMVs, and it seems that some CMVs in the fault zone were crushed and intruded into the voids during coseismic events, possibly driven by an enhanced pore fluid pressure. Since graphitization is suggested as an indicator of transient frictional heating in this area, our study providing a reference data set of CMs would help future CM-rich fault-zone research to retrieve seismic signatures presumably occurring in the Longmen Shan fault zone belt.

  13. Characterization of the carbonaceous materials obtained from different agro-industrial wastes.

    PubMed

    Ensuncho-Muñoz, A E; Carriazo, J G

    2015-01-01

    This paper reports the preparation and characterization of carbonaceous materials obtained from three types of vegetable wastes provided by agricultural industries. Soft carbonization (280°C) and H3PO4-activation procedures were used to convert the agricultural wastes to carbon powders with high adsorbent capacities. This process is excellent for eliminating and exploiting the huge masses (many tons) of vegetable residues remaining after each harvest every year in several Colombian agro-industries. The powders were characterized by X-ray diffraction (XRD), IR spectroscopy, scanning electron microscopy (SEM), and N2-adsorption isotherms. XRD and IR verified the formation of carbons, and SEM showed small particles (20-500 µm) with characteristic morphology for each type of residue used and abundant cavities of different sizes. The N2-adsorption analyses showed that the carbons had high adsorption capacities with important surface area values and large pore volumes. The use of the activated carbonaceous materials as adsorbent of azo dyes (allura red and sunset yellow) from aqueous solutions was evaluated. The results showed a good adsorption capacity indicating the potentiality of these materials as pollutant adsorbents in food industry wastewaters. These results indicate that these powders can be used as potential adsorbents for different gaseous or liquid pollutants.

  14. Blackening of fault gouge by comminution and pyrolysis of carbonaceous materials during earthquake slip

    NASA Astrophysics Data System (ADS)

    Kaneki, S.; Hirono, T.

    2015-12-01

    Fault gouges often exhibit various colors (white-pink-green-brown-gray-black), and particularly those developed in sedimentary rocks show gray to black. However, the physicochemical process for the color transition accompanied with seismic slip has not yet been fully understood. On the other hand, determination of the peak temperature during slip is crucial to identify the faulting mechanism during an earthquake, so that various temperature proxies have been proposed. For example, 1) magnetite formation at high temperature of ≥400 °C, 2) anomalies in the concentrations of fluid-mobile trace elements (Sr, Cs, Rb, and Li) and in the Sr isotope ratios, indicating presence of high-temperature fluid of ≥350 °C, 3) dehydroxylation of clay minerals, 4) thermal decomposition of carbonate minerals, and 5) thermal maturation of carbonaceous material examined by vitrinite reflectance measurement and by infrared and Raman spectroscopies. However, these proxies required high-level analyses in laboratory, so easy method to detect the record of high temperature preliminarily on field would be expected. In this study, we reproduced the blackening of synthetic fault sample by using high-velocity friction apparatus, thermogravimetric, and milling machine, and evaluated the color transition and organic chemical property of the samples by using UV-visible/NIR spectrophotometer and pyrolysis-gas chromatography-mass spectrometry. We discuss the process of the blackening taking comminution and pyrolysis of carbonaceous materials into consideration.

  15. A carbon and nitrogen isotope study of carbonaceous vein material in ureilite meteorites

    NASA Technical Reports Server (NTRS)

    Russell, S. S.; Arden, J. W.; Franchi, I. A.; Pillinger, C. T.

    1993-01-01

    The ureilite meteorite group is known to be rich in carbon in the form of graphite/diamond veins that are associated with planetary type noble gases. This paper reports preliminary data from a systematic study of the carbon and nitrogen isotopic composition of this carbonaceous vein material. A previous study focused on the whole rock signatures and reported that the carbon inventory appeared to be dominated by the graphitic/diamond intergrowths, whereas the nitrogen was clearly composed of several distinct components including one that was isotopically light, possibly associated with the carbonaceous material. Recent studies have demonstrated that diamonds in the solar system formed in many different environments. C and N measurements from ureilitic diamond made in a similar way would be a useful addition to this overall study. The methods used for isolating diamonds of possible presolar origin from primitive meteorites are equally applicable to the processing of carbon bearing components in the ureilite group so that their stable isotopic composition can be determined. Herein we discuss conjoint C and N stepped combustion measurements made on crushed whole rock ureilite samples that have been treated with 1M HCl/9M HF to dissolve silicate and free metal. In addition, two samples have been further treated with oxidizing acids to leave a diamond rich residue.

  16. Ultrastructural Heterogeneity of Carbonaceous Material in Ancient Cherts: Investigating Biosignature Origin and Preservation.

    PubMed

    Qu, Yuangao; Engdahl, Anders; Zhu, Shixing; Vajda, Vivi; McLoughlin, Nicola

    2015-10-01

    Opaline silica deposits on Mars may be good target sites where organic biosignatures could be preserved. Potential analogues on Earth are provided by ancient cherts containing carbonaceous material (CM) permineralized by silica. In this study, we investigated the ultrastructure and chemical characteristics of CM in the Rhynie chert (c. 410 Ma, UK), Bitter Springs Formation (c. 820 Ma, Australia), and Wumishan Formation (c. 1485 Ma, China). Raman spectroscopy indicates that the CM has experienced advanced diagenesis or low-grade metamorphism at peak metamorphic temperatures of 150-350°C. Raman mapping and micro-Fourier transform infrared (micro-FTIR) spectroscopy were used to document subcellular-scale variation in the CM of fossilized plants, fungi, prokaryotes, and carbonaceous stromatolites. In the Rhynie chert, ultrastructural variation in the CM was found within individual fossils, while in coccoidal and filamentous microfossils of the Bitter Springs and formless CM of the Wumishan stromatolites ultrastructural variation was found between, not within, different microfossils. This heterogeneity cannot be explained by secondary geological processes but supports diverse carbonaceous precursors that experienced differential graphitization. Micro-FTIR analysis found that CM with lower structural order contains more straight carbon chains (has a lower R3/2 branching index) and that the structural order of eukaryotic CM is more heterogeneous than prokaryotic CM. This study demonstrates how Raman spectroscopy combined with micro-FTIR can be used to investigate the origin and preservation of silica-permineralized organics. This approach has good capability for furthering our understanding of CM preserved in Precambrian cherts, and potential biosignatures in siliceous deposits on Mars.

  17. Isotopic evidence for primordial molecular cloud material in metal-rich carbonaceous chondrites

    PubMed Central

    Van Kooten, Elishevah M. M. E.; Wielandt, Daniel; Schiller, Martin; Nagashima, Kazuhide; Thomen, Aurélien; Olsen, Mia B.; Nordlund, Åke; Krot, Alexander N.; Bizzarro, Martin

    2016-01-01

    The short-lived 26Al radionuclide is thought to have been admixed into the initially 26Al-poor protosolar molecular cloud before or contemporaneously with its collapse. Bulk inner Solar System reservoirs record positively correlated variability in mass-independent 54Cr and 26Mg*, the decay product of 26Al. This correlation is interpreted as reflecting progressive thermal processing of in-falling 26Al-rich molecular cloud material in the inner Solar System. The thermally unprocessed molecular cloud matter reflecting the nucleosynthetic makeup of the molecular cloud before the last addition of stellar-derived 26Al has not been identified yet but may be preserved in planetesimals that accreted in the outer Solar System. We show that metal-rich carbonaceous chondrites and their components have a unique isotopic signature extending from an inner Solar System composition toward a 26Mg*-depleted and 54Cr-enriched component. This composition is consistent with that expected for thermally unprocessed primordial molecular cloud material before its pollution by stellar-derived 26Al. The 26Mg* and 54Cr compositions of bulk metal-rich chondrites require significant amounts (25–50%) of primordial molecular cloud matter in their precursor material. Given that such high fractions of primordial molecular cloud material are expected to survive only in the outer Solar System, we infer that, similarly to cometary bodies, metal-rich carbonaceous chondrites are samples of planetesimals that accreted beyond the orbits of the gas giants. The lack of evidence for this material in other chondrite groups requires isolation from the outer Solar System, possibly by the opening of disk gaps from the early formation of gas giants. PMID:26858438

  18. Isotopic evidence for primordial molecular cloud material in metal-rich carbonaceous chondrites.

    PubMed

    Van Kooten, Elishevah M M E; Wielandt, Daniel; Schiller, Martin; Nagashima, Kazuhide; Thomen, Aurélien; Larsen, Kirsten K; Olsen, Mia B; Nordlund, Åke; Krot, Alexander N; Bizzarro, Martin

    2016-02-23

    The short-lived (26)Al radionuclide is thought to have been admixed into the initially (26)Al-poor protosolar molecular cloud before or contemporaneously with its collapse. Bulk inner Solar System reservoirs record positively correlated variability in mass-independent (54)Cr and (26)Mg*, the decay product of (26)Al. This correlation is interpreted as reflecting progressive thermal processing of in-falling (26)Al-rich molecular cloud material in the inner Solar System. The thermally unprocessed molecular cloud matter reflecting the nucleosynthetic makeup of the molecular cloud before the last addition of stellar-derived (26)Al has not been identified yet but may be preserved in planetesimals that accreted in the outer Solar System. We show that metal-rich carbonaceous chondrites and their components have a unique isotopic signature extending from an inner Solar System composition toward a (26)Mg*-depleted and (54)Cr-enriched component. This composition is consistent with that expected for thermally unprocessed primordial molecular cloud material before its pollution by stellar-derived (26)Al. The (26)Mg* and (54)Cr compositions of bulk metal-rich chondrites require significant amounts (25-50%) of primordial molecular cloud matter in their precursor material. Given that such high fractions of primordial molecular cloud material are expected to survive only in the outer Solar System, we infer that, similarly to cometary bodies, metal-rich carbonaceous chondrites are samples of planetesimals that accreted beyond the orbits of the gas giants. The lack of evidence for this material in other chondrite groups requires isolation from the outer Solar System, possibly by the opening of disk gaps from the early formation of gas giants.

  19. Carbonaceous material in aerosol particles in the lower stratosphere and tropopause region

    NASA Astrophysics Data System (ADS)

    Murphy, D. M.; Cziczo, D. J.; Hudson, P. K.; Thomson, D. S.

    2007-02-01

    The Particle Analysis by Laser Mass Spectrometry (PALMS) instrument has measured the composition of single particles in the lower stratosphere. The average fraction of carbonaceous material in the stratospheric particles decreased rapidly above the tropopause. The decrease in the average carbon content was mostly associated with a sharp increase in the bottom 2 km of the stratosphere in the frequency of fairly pure sulfate particles both with or without meteoric metals. The low potassium content of the fairly pure sulfate particles is used to show that they were formed in the stratosphere and were not tropospheric particles that had lost organics because of oxidation. Of the tropospheric carbonaceous-sulfate particles found in the stratosphere, the mass spectra had similar patterns from the upper troposphere to the maximum altitude sampled, about 19 km. A reduction in the carbon to sulfate ratio in tropospheric particles was only apparent above about 440 K potential temperature. This implies that carbon compounds can remain for months in particles larger than about 300 nm. Despite the slow rate, these data do not exclude rapid heterogeneous reactions of organics in the particles with OH or other radicals. There was no evidence of significant transfer of semivolatile organics between particles in the stratosphere. However, particles that originated in the stratosphere acquired small amounts of carbon when they were transported to the tropopause.

  20. Process for hydrocracking carbonaceous material to provide fuels or chemical feed stock

    DOEpatents

    Duncan, Dennis A.

    1980-01-01

    A process is disclosed for hydrocracking coal or other carbonaceous material to produce various aromatic hydrocarbons including benzene, toluene, xylene, ethylbenzene, phenol and cresols in variable relative concentrations while maintaining a near constant maximum temperature. Variations in relative aromatic concentrations are achieved by changing the kinetic severity of the hydrocracking reaction by altering the temperature profile up to and quenching from the final hydrocracking temperature. The relative concentration of benzene to the alkyl and hydroxyl aromatics is increased by imposing increased kinetic severity above that corresponding to constant heating rate followed by immediate quenching at about the same rate to below the temperature at which dehydroxylation and dealkylation reactions appreciably occur. Similarly phenols, cresols and xylenes are produced in enhanced concentrations by adjusting the temperature profile to provide a reduced kinetic severity relative to that employed when high benzene concentrations are desired. These variations in concentrations can be used to produce desired materials for chemical feed stocks or for fuels.

  1. Method and device for the determination of low concentrations of oxygen in carbonaceous materials

    DOEpatents

    Schultz, Hyman

    1992-01-01

    Oxygen in carbonaceous materials is converted to carbon monoxide (CO) by pyrolyzing the material in a stream of oxygen-free helium. The CO is reacted with Ni.sup.63, a readioactive isotope of nickel, to form nickel tetracarbonyl (Ni.sup.63 (CO).sub.4) which is carried by the helium stream into a flow-through gas proportional counter. The quantity of Ni(CO).sub.4 is determined by the radioactivity of the gas as measured by the gas proportional counter. After exiting the flow through counter the Ni.sup.63 (CO).sub.4 is destroyed by exposing it to high temperatures. The Ni.sup.63 is retained within the apparatus while the CO is flushed from the system after being oxidized to carbon dioxide (CO.sub.2). The detection limit is estimated to be less than 1 part per billion oxygen for a 10 mg sample.

  2. Comparison of Ablation Predictions for Carbonaceous Materials Using CEA and JANAF-Based Species Thermodynamics

    NASA Technical Reports Server (NTRS)

    Milos, Frank S.

    2011-01-01

    In most previous work at NASA Ames Research Center, ablation predictions for carbonaceous materials were obtained using a species thermodynamics database developed by Aerotherm Corporation. This database is derived mostly from the JANAF thermochemical tables. However, the CEA thermodynamics database, also used by NASA, is considered more up to date. In this work, the FIAT code was modified to use CEA-based curve fits for species thermodynamics, then analyses using both the JANAF and CEA thermodynamics were performed for carbon and carbon phenolic materials over a range of test conditions. The ablation predictions are comparable at lower heat fluxes where the dominant mechanism is carbon oxidation. However, the predictions begin to diverge in the sublimation regime, with the CEA model predicting lower recession. The disagreement is more significant for carbon phenolic than for carbon, and this difference is attributed to hydrocarbon species that may contribute to the ablation rate.

  3. Novel mesoporous carbonaceous materials: Synthesis, characterization and applications in liquid chromatography

    NASA Astrophysics Data System (ADS)

    Li, Zuojiang

    The ability to control the porous structure in carbonaceous materials has been significantly improved in the past decade due to the appearance of new synthetic routes and novel templating materials. In this dissertation, novel mesoporous carbonaceous materials with controlled structural and surface properties were prepared and investigated using low temperature nitrogen adsorption, thermal analysis, X-ray diffraction and other analytical techniques. The performance of these novel mesoporous carbons in liquid chromatography was also investigated. Carbons with extremely high mesoporosity were synthesized by using mesophase pitch and polyacrylonitrile as precursors in the silica gel templating method, which led to a dramatic reduction of microporosity and high carbonization yield. The most important achievement of this dissertation is the initiation of a colloidal imprinting technique, in which spherical pores were created in the particles of mesophase pitch by using silica colloids of proper size. This method allows us to prepare carbons with uniform spherical pores in the range of 7--70 nm and narrow pore size distribution, filling the pore size gap between carbons templated with ordered silicas and colloidal silica crystals. The introduction of air stabilization further improved the ability to control the pore development at a given stage in the imprinting process. For the first time, carbon particles with mesoporous shell/nonporous core structure were obtained. In this way, carbons with controlled pore size, surface area, pore volume and particle size were synthesized. Moreover, the colloidal imprinting technique was extended to a more general imprinting concept, in which porous particles were used to obtain carbon particles having ordered or disordered structure on their surface. Graphitization of the imprinted carbons provided carbonaceous materials of tailored mesopores and graphitic structure. Also, this high-temperature treatment removed surface functional

  4. Dissolution of carbon from alumina-carbon mixtures into liquid iron: Influence of carbonaceous materials

    NASA Astrophysics Data System (ADS)

    Khanna, Rita; Sahajwalla, Veena; Rodgers, Brenton; McCarthy, Fiona

    2006-08-01

    Due to their excellent thermal shock and wear resistance at high temperatures, alumina-carbon based refractories are used extensively in the steel industry. A clear understanding of factors affecting the dissolution of carbon from refractories is of crucial importance, as carbon depletion from the refractory can significantly deteriorate refractory performance and metal quality. Atomistic simulations on the alumina-graphite/liquid iron system have shown that nonwetting between alumina and liquid iron is an important factor inhibiting the penetration of liquid metal in the refractory matrix and limiting carbon dissolution. This study investigates the role played by the carbonaceous material in the dissolution of carbon from the refractory composite. Two carbonaceous materials, namely, petroleum coke and natural graphite, respectively, containing 0.35 and 5.26 pct ash, were used in this study. Substrates were prepared from mixtures of alumina and carbon over a wide concentration range. Using a sessile drop arrangement, carbon pickup by liquid iron from alumina-carbon mixtures was measured at 1550 °C and was compared with the carbon pickup from alumina-synthetic graphite mixtures. These studies were supplemented with wettability measurements and microscopic investigations on the interfacial region. For high alumina concentrations (>40 wt pct), carbon dissolution from refractory mixtures was found to be negligible for all carbonaceous materials under investigation. Significant differences however were observed at lower alumina concentrations. Carbon dissolution from alumina-petroleum coke mixtures was much lower than the corresponding dissolution from alumina synthetic graphite-mixtures and was attributed to poor wettability of petroleum coke with liquid iron, its structural disorder, and the presence of sulfur. Very high levels of carbon dissolution, however, were observed from alumina-natural graphite mixtures, with carbon pickup by liquid iron from mixtures with up

  5. Reaction between Steel-Making Slag and Carbonaceous Materials While Mixing with High Density Polyethylene

    NASA Astrophysics Data System (ADS)

    Hong, Lan; Sahajwalla, Veena

    2016-01-01

    Since the beginning of the extensive applications in numerous high temperature processes such as iron- and steel-making, coke-making etc. partly in the place of coke, the investigation into the reaction mechanism of waste plastics has become increasingly necessary. In this paper a fundamental study on the behavior of a typical component of waste plastics, high density polyethylene (HDPE), in a mixture with coke at a 1:1 ratio in mass base was conducted during the reaction with iron oxide in steel-making slag at 1823 K and was compared with coke and graphite. The reaction mechanism of carbonaceous materials was analyzed based on the contents of CO and CO2 in the off-gas monitored by an infrared (IR) gas analyzer. It is clear from the results that the reaction of HDPE and coke mixture with steel-making slag approached equilibrium of the Boudouard reaction more quickly and closely than coke or graphite.

  6. Insoluble organic material of the Orgueil carbonaceous chondrite and the unidentified infrared bands

    NASA Astrophysics Data System (ADS)

    Wdowiak, T. J.; Flickinger, G. C.; Cronin, J. R.

    1988-05-01

    Infrared spectra have been obtained of the acid insoluble residue, residue after heating in vacuum, and condensate of the Orgueil carbonaceous chondrite using an FTIR spectrometer. Bulk acid insoluble residue was pressed into KBr pellets and also heated under high vacuum to sublimate a volatile component onto KBr disks. The remaining nonvolatile organic component of the meteorite from such evaporations pressed into KBr pellets exhibits a spectral signature similar to that observed in emission from the Orion Nebula and found in Raman spectra of interplanetary dust particles. It also has an 11.3 micron band indicating polycyclic aromatic hydrocarbons (PAHs) having single hydrogens per peripheral aromatic ring. It is concluded that the nonvolatile material is similar to interstellar PAHs since the observed 11.3 micron unidentified infrared emission suggests interstellar PAHs have single hydrogens per peripheral aromatic ring.

  7. Chitosan-derived carbonaceous material for highly efficient adsorption of chromium (VI) from aqueous solution.

    PubMed

    Shen, Feng; Su, Jialei; Zhang, Xiao; Zhang, Keqiang; Qi, Xinhua

    2016-10-01

    A carbonaceous adsorbent for effectively removing Cr(VI) was synthesized by facile hydrothermal carbonization of chitosan (HTC-chitosan). The prepared HTC-chitosan exhibited good stability in acid solution while the amine groups were retained completely after simple and green hydrothermal carbonization treatment. Structure characteristics of the HTC-chitosan as well as its adsorption behaviors for Cr(VI) in aqueous solution were investigated. Under optimal conditions, the adsorption capacity of the HTC-chitosan for Cr(VI) reached as high as 388.60mgg(-1), which was much higher than that of other materials reported previously. The prepared HTC-chitosan adsorbent could be reused at least five times with adsorption efficiency more than 92%. These results indicate that HTC-chitosan exhibited great superiority for Cr(VI) adsoption from aqueous solution both in terms of the preparation process and adsorption performance.

  8. Halogen lamp experiment, HALEX

    NASA Technical Reports Server (NTRS)

    Schmitt, G.; Stapelmann, J.

    1986-01-01

    The main purpose of the Halogen Lamp Experiment (HALEX) was to investigate the operation of a halogen lamp during an extended period in a microgravity environment and to prove its behavior in space. The Mirror Heating Facilities for Crystal Growth and Material Science Experiments in space relies on one or two halogen lamps as a furnace to melt the specimens. The HALEX aim is to verify: full power operation of a halogen lamp for a period of about 60 hours; achievement of about 10% of its terrestrial life span; and operation of the halogen lamp under conditions similar to furnace operation.

  9. Heterogeneous Distribution of Carbonaceous Material in Murchison Matrix: In Situ Observations Using Energy Filtered Transmission Electron Microscopy

    NASA Technical Reports Server (NTRS)

    Brearley, Adrian J.

    2002-01-01

    Energy filtered TEM (Transmission Electron Microscopy) has been used to study the location of carbonaceous material in situ in Murchison matrix. Carbon occurs frequently as narrow rims around sulfide grains, but is rare in regions of matrix that are dominated by phyllosilicates. Additional information is contained in the original extended abstract.

  10. Study of Carbonaceous Material in cherts from Barberton Greenstone Belt and the Astrobiological Implications.

    NASA Astrophysics Data System (ADS)

    Rull, F.; Venegas, G.; Montero, O.; Medina, J.

    2012-04-01

    Carbonaceous matter is present in chert deposits of Barberton Greenstone Belt (BGB), South Africa. This is a famous place in the world for its Archean geology, wich represents around 3.5 billion years of earth's history. Therefore this area provides us the opportunity to study and understand an important part history of our planet, and also allow to compare with the geological history of other planets in our solar system [1]. Raman micro-spectroscopy has proved to be a very important and non-destructive powerful tool for distinguish micro-sized particles of C-polymorphs, as it is very sensitive to the nature of carbon bonding [2]. The connection between the Raman characterization of these carbonaceous phases with ancient biogenic activity it's of special interest. Cherts of BGB have been interpreted as precipitates or diagenetic replacements of preexisting sedimentary and pyroclastic deposits in a silica saturated Archean ocean [3]. Several layered Samples of cherts from BGB utility for the present study were collected during the expedition carried out in August 2010 sponsored by CNES and ESA. A detailed Raman spectral analysis of carbon C-C vibrations has been performed in the first (1200-1800 cm-1) and second (2500-3200 cm-1) order regions [4]. The results show important changes in the G-D bands in the layered structure of chert. Additionally a UPLC-ESI-QTOF-MS was carried out trying to introduce new insight in the Raman interpretation of the bands and in the possible assignments to particular molecular groups which could be related with biotic or abiotic origin of the carbonaceous material. Among the tentative compounds obtained from UPLC-ESI-QTOF-MS study it is worth to mention hydroxy-lycopene and the hydroxyl derivative of β-carotene (i.e. β-cryptoxanthin), which are carotenoids produced by cyanobacteria. These results are consistent with the presence of 22-Hopanol and Tetrahymanol, which are characteristic hopanoids of photosynthetic cyanobacteria and have

  11. Core Halogenation as a Construction Principle in Tuning the Material Properties of Tetraazaperopyrenes.

    PubMed

    Hahn, Lena; Maass, Friedrich; Bleith, Tim; Zschieschang, Ute; Wadepohl, Hubert; Klauk, Hagen; Tegeder, Petra; Gade, Lutz H

    2015-12-01

    A detailed study on the effects of core halogenation of tetraazaperopyrene (TAPP) derivatives is presented. Its impact on the solid structure, as well as the photophysical and electrochemical properties, has been probed by the means of X-ray crystallography, UV/Vis and fluorescence spectroscopy, high-resolution electron energy loss spectroscopy (HREELS), cyclic voltammetry (CV), and DFT modeling. The aim was to assess the potential of this approach as a construction principle for organic electron-conducting materials of the type studied in this work. Although halogenation leads to a stabilization of the LUMOs compared to the unsubstituted parent compound, the nature of the halide barely affects the LUMO energy while strongly influencing the HOMO energies. In terms of band-gap engineering, it was demonstrated that the HOMO-LUMO gap is decreased by substitution of the TAPP core with halides, the effect being found to be most pronounced for the iodinated derivative. The performance of the recently reported core-fluorinated and core-iodinated TAPP derivatives in organic thin-film transistors (TFTs) was investigated on both a glass substrate, as well as on a flexible plastic substrate (PEN). Field-effect mobilities of up to 0.17 cm(2)  Vs(-1) and on/off current ratio of >10(6) were established.

  12. Efficacy of carbonaceous materials for sorbing polychlorinated biphenyls from aqueous solution.

    PubMed

    Beless, Bradley; Rifai, Hanadi S; Rodrigues, Debora F

    2014-09-02

    Interest in incorporating nanomaterials into water treatment technologies is steadily growing, driving the necessity to understand the interaction of these new materials with specific water contaminants. In the present study, five different carbonaceous materials: activated carbon (AC), charcoal (BC), carbon nanotubes (CNT), graphene (GE), and graphene oxide (GO) were investigated as sorbent materials for 11 polychlorinated biphenyl (PCB) congeners in aqueous concentrations in the pg-μg/L range. Sorbent-water distribution coefficients (Ks) calculated in aqueous concentrations of ng/L show that AC is superior to GE, GO, CNT, and BC for the 11 PCB congeners investigated by an average of 1.1, 1.1, 1.3, and 2.5 orders of magnitude, respectively. Additionally, maximum capacity and sorption affinity parameters from the Langmuir, Freundlich, and Polanyi-Dubinin-Manes (PDM) models show a similar result. Interestingly, however, the effect of molecular planarity has greater impact on PCB sorption to the nanomaterials, such that the planar congeners form stronger bonds with CNT, GE, and GO compared to AC and BC. This work demonstrated superior PCB sorption by AC as compared with the nanomaterials examined such that substantial post production modifications would be necessary for the nanomaterials to out-perform AC.

  13. Production and evolution of carbonaceous material by ion irradiation in space.

    PubMed

    Strazzulla, G; Baratta, G A; Spinella, F

    1995-03-01

    We review recent experimental studies concerning the evolution, driven by ion irradiation, of carbonaceous material from frozen gas to a refractory molecular solid. Under further irradiation the latter changes to a polymer-like material and ultimately to amorphous carbon. Most of the results have been obtained by "in situ" and remote IR and Raman spectroscopy. The results have been applied to demonstrate that molecular solids may be easily formed by irradiation of frozen mantles in dense interstellar clouds. Polymer-like material and amorphous carbons may result by further irradiation of organic mantles on grains in the diffuse interstellar medium. Those grains, during the aggregation to form extended bodies like comets (T-Tau phase of the Sun), are further modified. These latter are also irradiated, after the comet formation, during their long stay in the Oort cloud. In particular it has been suggested that comet may develop an ion-produced cometary organic crust that laboratory evidences show to be stable against temperature increases experienced during passages near the Sun. The comparison between the Raman spectra of some IDP (Interplanetary Dust Particles) and the Raman spectra of some ion-produced amorphous carbons, is also discussed.

  14. Carbonaceous materials passivation on amine functionalized magnetic nanoparticles and its application for metal affinity isolation of recombinant protein.

    PubMed

    Nata, Iryanti F; El-Safory, Nermeen S; Lee, Cheng-Kang

    2011-09-01

    Magnetic nanoparticles (MNPs) with an amine functionalized surface (MH) were passivated with carbonaceous materials (MH@C) by carbonization of glucose under hydrothermal reaction conditions. The carboxylate groups in carbonaceous shell could be enriched to 0.285 mmol/g when acrylic acid was added as a functional monomer in the carbonization reaction (MH@C-Ac). The carbonaceous shell not only protected the magnetic core from acidic erosion but also showed a high adsorption capacity toward Ni(2+) ion. The Ni(2+) ion complexed on MH@C and MH@C-Ac could specifically isolate 6×His tagged recombinant proteins from crude bacterial extracts via metal affinity interaction. The superparamagnetic property facilitates the easy retrieval of the carbonaceous material passivated MNPs from the viscous proteins solutions. Recombinant green fluorescence protein (GFP) and hyaluronic acid (HA) lyase of 9.4 mg and 2.3 mg could be isolated by 1 g of MH@C-Ac-Ni, respectively.

  15. Blackening of fault gouge by comminution and pyrolysis of carbonaceous materials during earthquake slip

    NASA Astrophysics Data System (ADS)

    Kaneki, Shunya; Hirono, Tetsuro

    2016-05-01

    Black fault gouges sometimes develop, mainly in sedimentary rocks, but the cause of the color transformation is not well understood. Here we demonstrated the blackening of synthetic mixtures of montmorillonite and bituminous coal and of montmorillonite and magnetite in milling, heating, and friction experiments. Mixed samples with a higher volume fraction of coal or magnetite before the experiments showed lower L* values (lightness index; lower values indicate darker blacks), because coal and magnetite are intrinsically black. The milling and heating experiments showed that the L* values of mixed samples of montmorillonite and coal drastically decreased with longer milling times and higher temperatures. The L* values of mixed samples of montmorillonite and magnetite also decreased with longer milling times, but no notable change was observed in the samples after the heating experiments. Because comminution by milling induces granulation of the constituent materials, blackening of the experimental samples was primarily caused by dispersal through the sample of fine black particles such as coal and magnetite, but it could be strengthened by adsorption onto host particles of organic gases produced by pyrolysis of carbonaceous material at high temperature. The friction experiment with mixed samples of montmorillonite and coal produced the remarkably low L* values. Friction induces both comminution and heating of samples, so the blackening could be greater than after either milling or heating alone. Therefore, relatively black fault gouges, compared with the surrounding host rocks, might have experienced comminution and heating, probably related to earthquake slip. Thus, black coloration could be one of the important information on fieldwork.

  16. Compositional insights and valorization pathways for carbonaceous material deposited during bio-oil thermal treatment.

    PubMed

    Ochoa, Aitor; Aramburu, Borja; Ibáñez, María; Valle, Beatriz; Bilbao, Javier; Gayubo, Ana G; Castaño, Pedro

    2014-09-01

    This work analyses the composition, morphology, and thermal behavior of the carbonaceous materials deposited during the thermal treatment of bio-oil (thermal pyrolytic lignin-TPL). The bio-oil was obtained by flash pyrolysis of lignocellulosic biomass (pine sawdust), and the TPLs were obtained in the 400-700 °C range. The TPLs were characterized by performing elemental analysis; (13)C NMR, Raman, FTIR, and X-ray photoelectron spectroscopy; SEM; and temperature-programmed oxidation analyzed by differential thermogravimetry and differential scanning calorimetry. The results are compared to a commercial lignin (CL). The TPLs have lower oxygen and hydrogen contents and a greater aromaticity and structural order than the CL material. Based on these features, different valorization routes are proposed: the TPL obtained at 500 °C is suitable for use as a fuel, and the TPL obtained at 700 °C has a suitable morphology and composition for use as an adsorbent or catalyst support.

  17. Screening of halogenated aromatic compounds in some raw material lots for an aluminium recycling plant.

    PubMed

    Sinkkonen, Seija; Paasivirta, Jaakko; Lahtiperä, Mirja; Vattulainen, Antero

    2004-05-01

    Four samples of scrap raw materials for an aluminium recycling plant were screened for the occurrence of persistent halogenated aromatic compounds. The samples contained waste from handling of electric and electronic plastics, filter dust from electronic crusher, cyclone dust from electronic crusher and light fluff from car shredder. In our screening analyses, brominated flame retardants were observed in all samples. Polybrominated diphenyl ethers (PBDE) were identified in all samples in amounts of 245-67450 ng/g. The major PBDE congeners found were decabromo- and pentabromodiphenyl ethers. 1,1-bis(2,4,6-tribromophenoxy)ethane, hexabromobenzene, ethyl-pentabromobenzene, tetrabromobisphenol-A, pentabromotoluene and dimethyl tetrabromobenzene were observed in all scrap samples. The concentrations of PCBs, PCNs (polychlorinated naphthalenes) and nona- to undecachlorinated terphenyls in some of these scrap samples were remarkably high.

  18. CO{sub 2}-gasification reactivity of different carbonaceous materials at elevated temperatures

    SciTech Connect

    Gu, J.; Wu, S.; Wu, Y.; Gao, J.

    2009-07-01

    At the atmospheric pressure and at the temperatures between 1,223 and 1,673 K, the CO{sub 2} gasification reactivity of seven different carbonaceous materials comprising coal tar pitch coke, petroleum coke, natural graphite, carbon black and three coal chars was investigated by using thermogravimetric analysis. Their crystalline structures were analyzed by X-ray diffraction (XRD). It is found that the reactivity of the chars, pitch coke and petroleum coke produced from liquid phase carbonization, is several times poorer than that of the coal chars produced from solid phase carbonization and even lower than that of natural graphite. At the same time, it is obtained that under the condition of the chemical reaction control, the apparent activation energies of the former are in the range of 135.82-174.92 kJ/mol, while those of the latter are between 89.95 kJ/mol and 110.05 kJ/mol. Besides, the reactivity of the sample has a certain correlation with the crystalline structure of the sample, i.e., the larger the fraction of the relatively better crystalline structure is, the poorer the reactivity of the sample is.

  19. Potential explosion hazard of carbonaceous nanoparticles: Explosion parameters of selected materials.

    PubMed

    Turkevich, Leonid A; Dastidar, Ashok G; Hachmeister, Zachary; Lim, Michael

    2015-09-15

    Following a previous explosion screening study, we have conducted concentration and ignition energy scans on several carbonaceous nanopowders: fullerene, SWCNT, carbon black, MWCNT, graphene, CNF, and graphite. We have measured minimum explosive concentration (MEC), minimum ignition energy (MIE), and minimum ignition temperature (MITcloud) for these materials. The nanocarbons exhibit MEC ~10(1)-10(2) g/m(3), comparable to the MEC for coals and for fine particle carbon blacks and graphites. The nanocarbons are confirmed mainly to be in the St-1 explosion class, with fullerene, at K(St) ~200 bar-m/s, borderline St-1/St-2. We estimate MIE ~ 10(2)-10(3) J, an order of magnitude higher than the MIE for coals but an order of magnitude lower than the MIE for fine particle graphites. While the explosion severity of the nanocarbons is comparable to that of the coals, their explosion susceptibility (ease of ignition) is significantly less (i.e., the nanocarbons have higher MIEs than do the coals); by contrast, the nanocarbons exhibit similar explosion severity to the graphites but enhanced explosion susceptibility (i.e., the nanocarbons have lower MIEs than do the graphites). MIT(cloud) > 550 °C, comparable to that of the coals and carbon blacks.

  20. Sorption/desorption reversibility of phenanthrene in soils and carbonaceous materials

    SciTech Connect

    Guohui Wang; Sybille Kleineidam; Peter Grathwohl

    2007-02-15

    Sorption/desorption of phenanthrene in two soil samples and carbonaceous materials was found to yield co-incident equilibrium isotherms and no significant hysteresis was observed. Additionally, release of native phenanthrene was investigated. Equilibrium sorption and desorption isotherms were determined using pulverized samples of Pahokee peat, lignite, and high-volatile bituminous coal, a mineral soil, and an anthropogenic soil. Instead of the conventional decant-and-refill batch method, sorption/desorption was driven by temperature changes using consistent samples. Sorption started at 77{sup o}C and was increased by reducing the temperature stepwise to 46, 20, and finally 4{sup o}C. For desorption the temperature was increased stepwise again until 77{sup o}C was reached. Besides the co-incident sorption and desorption isotherms at each temperature step, the solubility-normalized sorption/desorption isotherms of all different temperatures collapse to unique overall isotherms. Leaching of native phenanthrene occurred at much lower concentrations but was well predicted by extrapolation of the spiked sorption isotherms indicating that the release of native phenanthrene involves the same sorption/desorption mechanisms as those for newly added phenanthrene. 35 refs., 4 figs., 5 tabs.

  1. Amphiphilic carbonaceous material-intervened solvothermal synthesis of LiFePO4

    NASA Astrophysics Data System (ADS)

    Chen, Ming-ming; Ma, Qian-qian; Wang, Cheng-yang; Sun, Xin; Wang, Li-qun; Zhang, Cui

    2014-10-01

    LiFePO4 samples with preferred facets on the ac plane were prepared by the solvothermal method with or without well-dispersed amphiphilic carbonaceous material (ACM). The effects of ACM on the particle morphology, crystal orientation and electrochemical reactivity of the prepared LiFePO4 nanoparticles were investigated in detail. ACM serves a dual purpose. One purpose is facilitating the plate-like morphologies of LiFePO4 nanoparticles parallel to the bPnma axis by decreasing the surface energy of (010) facets of newly created LiFePO4 nuclei. The other purpose is suppressing crystal growth along the [010] direction by adhering onto the (010) surface of LiFePO4 nanoplates. Furthermore, ACM coating was performed and optimized using a carbon coating precursor. The electrochemical properties of the prepared LiFePO4 particles were characterized by cyclic voltammetry (CV) and galvanostatic charge-discharge cycling tests. After the optimized coating of ACM, the ACM-intervened LiFePO4 composite was observed to deliver discharge capacities of 151.3 mAh g-1 at 1C and 132.2 mAh g-1 at 10C. Even after 1000 cycles at a high rate of 10C, the LiFePO4 cathode could maintain 80% of its initial capacity.

  2. Determination of the Surface Oxidation Degree of the Carbonaceous Materials by Quantitative TG-MS Analysis.

    PubMed

    Hotová, Gabriela; Slovák, Václav

    2017-02-07

    The developed quantitative TG-MS analysis was used for the determination of the surface oxidation degree of activated carbon cryogels. The surface chemistry of a prepared carbon cryogels pyrolyzed at 400 and 500 °C was modified using H3PO4, Fenton-like reaction, (NH4)2S2O8 with H2SO4 and HNO3 with H2O2 into a different surface oxidation degree. The influence of activation method and the amount of oxygen surface groups were characterized by elemental analysis, immersion calorimetry, water vapor adsorption, and Boehm titration. The obtained results from these methods were compared with the amount of surface oxygen determined by TG-MS. It was found out, that with the more intensive oxidation method (Fenton < (NH4)2S2O8 with H2SO4 < HNO3 with H2O2) the concentration of oxygen-containing surface groups increases, which lead to considerably higher parameters of immersion heat, amount of adsorbed water and acidity of the sample surface. The H3PO4 treatment of carbon cryogels causes no significant changes in the surface chemistry. The results obtained from the TG-MS analysis imply the good agreement with the results obtained from other used methods. It was proved that the quantitative TG-MS analysis could be a useful tool for the characterization of the surface of the carbonaceous materials.

  3. Removal of fluoride ions from water by adsorption onto carbonaceous materials produced from coffee grounds.

    PubMed

    Ogata, Fumihiko; Tominaga, Hisato; Yabutani, Hitoshi; Kawasaki, Naohito

    2011-01-01

    Carbonaceous material for the removal of fluoride ions from water was prepared from coffee grounds (CGs) by calcination and subsequent HCl treatment. The characteristics of the CGs, including the surface area, mean pore diameter, pore volume, and surface functional groups were determined, and the morphological characteristics were evaluated using scanning electron microscopy. The adsorption isotherms, saturated amount of fluoride ions adsorbed, and the effect of contact time and temperature on the adsorption of fluoride ions were investigated for a sample of tap water. The specific surface area of CG calcined at 600° (CG600) was larger than that of CGs calcined at 400, 800, and 1000°. Phenolic, lactonic, and carboxyl groups were detected on the CG600 surface. The adsorption capacity of the carbonized CGs for fluoride was ranked in the order CG400 < CG1000 < CG800 < CG600 (where the numeral indicates the carbonization temperature), whereas virgin CG and CG600-NAT (not treated with hydrochloric acid solution) did not exhibit any adsorption ability for fluoride ions. The amount of fluoride ions adsorbed onto CG600 increased with increasing temperature and was consistent with chemical adsorption. The mechanism of adsorption of fluoride ions onto CG600 proceeded via ion exchange with chloride ions (1:1) present on the surface of CG600. The adsorption isotherms were fitted to the Freundlich and Langmuir equations. Moreover, CG600 showed an acceptable adsorption capacity for fluoride ions present in tap water.

  4. Potential Explosion Hazard of Carbonaceous Nanoparticles: Explosion Parameters of Selected Materials

    PubMed Central

    Turkevich, Leonid A.; Dastidar, Ashok G.; Hachmeister, Zachary; Lim, Michael

    2015-01-01

    Following a previous explosion screening study, we have conducted concentration and ignition energy scans on several carbonaceous nanopowders: fullerene, SWCNT, carbon black, MWCNT, graphene, CNF, and graphite. We have measured minimum explosive concentration (MEC), minimum ignition energy (MIE), and minimum ignition temperature (MITcloud) for these materials. The nanocarbons exhibit MEC ~ 101–102 g/m3, comparable to the MEC for coals and for fine particle carbon blacks and graphites. The nanocarbons are confirmed mainly to be in the St-1 explosion class, with fullerene, at KSt ~ 200 bar-m/s, borderline St-1/St-2. We estimate MIE ~ 102 – 103 J, an order of magnitude higher than the MIE for coals but an order of magnitude lower than the MIE for fine particle graphites. While the explosion severity of the nanocarbons is comparable to that of the coals, their explosion susceptibility (ease of ignition) is significantly less (i.e. the nanocarbons have higher MIEs than do the coals); by contrast, the nanocarbons exhibit similar explosion severity to the graphites but enhanced explosion susceptibility (i.e. the nanocarbons have lower MIEs than do the graphites). MITcloud > 550°C, comparable to that of the coals and carbon blacks. PMID:25913651

  5. The role of condensed carbonaceous materials on the sorption of hydrophobic organic contaminants in subsurface sediments.

    PubMed

    Jeong, Sangjo; Wander, Michelle M; Kleineidam, Sybille; Grathwohl, Peter; Ligouis, Bertrand S; Werth, Charles J

    2008-03-01

    The identification and characterization of carbonaceous materials (CMs) that control hydrophobic organic chemical (HOC) sorption is essential to predict the fate and transport of HOCs in soils and sediments. The objectives of this paper are to determine the types of CMs that control HOC sorption in the oxidized and reduced zones of a glacially deposited groundwater sediment in central Illinois, with a special emphasis on the roles of kerogen and black carbon. After collection, the sediments were treated to obtain fractions of the sediment samples enriched in different types of CMs (e.g., humic acid, kerogen, black carbon), and selected fractions were subject to quantitative petrographic analysis. The original sediments and their enrichment fractions were evaluated for their ability to sorb trichloroethene (TCE), a common groundwater pollutant. Isotherm results and mass fractions of CM enrichments were used to calculate sorption contributions of different CMs. The results indicate that CMs in the heavy fractions dominate sorption because of their greater mass. Black carbon mass fractions of total CMs in the reduced sediments were calculated and used to estimate the sorption contribution of these materials. Results indicate that in the reduced sediments, black carbon may sequester as much as 32% of the sorbed TCE mass, butthat kerogen and humin are the dominant sorption environments. Organic carbon normalized sorption coefficients (K(oc)) were compared to literature values. Values for the central Illinois sediments are relatively large and in the range of values determined for materials high in kerogen and humin. This work demonstrates the advantage of using both sequential chemical treatment and petrographic analysis to analyze the sorption contributions of different CMs in natural soils and sediments, and the importance of sorption to natural geopolymers in groundwater sediments not impacted by anthropogenic sources of black carbon.

  6. Fundamental and exploratory studies of catalytic steam gasification of carbonaceous materials. Final report, fiscal years 1985--1994

    SciTech Connect

    Heinemann, H.; Somorjai, G.A.

    1994-03-01

    The major purpose of this project was to find catalysts which will permit steam gasification of carbonaceous material at reasonable rates and at lower temperatures than currently practiced. Rapid catalyst deactivation must be avoided. An understanding of the catalytic mechanism is necessary to provide leads towards this aim. This report describes the gasification of graphite studies and the gasification of coals, chars, and petroleum cokes.

  7. Process for the liquefaction of solid carbonaceous materials wherein nitrogen is separated from hydrogen via ammonia synthesis

    DOEpatents

    Stetka, Steven S.; Nazario, Francisco N.

    1982-01-01

    In a process for the liquefaction of solid carbonaceous materials wherein bottoms residues are upgraded with a process wherein air is employed, the improvement wherein nitrogen buildup in the system is avoided by ammonia synthesis. In a preferred embodiment hydrogen from other portions of the liquefaction process will be combined with hydrogen produced as a result of the bottoms upgrading to increase the H.sub.2 :N.sub.2 ratio in the ammonia reactor.

  8. Organochemical characteristics of carbonaceous materials as indicators of heat recorded on an ancient plate-subduction fault

    NASA Astrophysics Data System (ADS)

    Kaneki, S.; Hirono, T.; Mukoyoshi, H.; Sampei, Y.; Ikehara, M.

    2016-07-01

    Coseismic shear stress and slip distance affect subduction-related earthquake processes. They need to be understood to evaluate the earthquake's mechanism and the tsunami generation potential near trenches. The amount of frictional heat generated depends on the shear stress and slip distance, which are therefore able to be derived from the temperature recorded in the fault. Here we developed a new temperature proxy for carbonaceous materials by performing spectroscopic, thermogravimetric, and organic elemental analyses in conjunction with heating experiments. We found marked anomalies in the infrared and Raman spectra and atomic compositions of carbonaceous materials retrieved from the slip zone of an ancient megasplay fault in the Cretaceous Shimanto accretionary complex, Japan: the infrared spectra show extinction of aliphatic C-H bonding and very weak aromatic C=C bonding, and the Raman spectra show a slightly elevated ratio of disordered band intensity to graphitic band intensity and relatively low H/C and O/C ratios. These correlate well with the spectral and elemental features of host-rock carbonaceous materials after heating to 600°C. Thus, we conclude that the slip zone experienced a temperature of 600°C during a past earthquake event, indicating coseismic slip of 2-9 m, which could have generated a large tsunami if the ruptures propagated to the seafloor.

  9. The Halogen Bond.

    PubMed

    Cavallo, Gabriella; Metrangolo, Pierangelo; Milani, Roberto; Pilati, Tullio; Priimagi, Arri; Resnati, Giuseppe; Terraneo, Giancarlo

    2016-02-24

    The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design.

  10. The Halogen Bond

    PubMed Central

    2016-01-01

    The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design. PMID:26812185

  11. Sorption interactions of biochars and pyrogenic carbonaceous materials with anionic contaminants

    NASA Astrophysics Data System (ADS)

    Fristak, Vladimir; Moreno-Jimenez, Eduardo; Micháleková-Richveisová, Barbora; Schmidt, Hans-Peter; Bucheli, Thomas; Soja, Gerhard

    2016-04-01

    Biochar as a highly porous and carbon-rich material with a large surface area is a new player in the system of environmental remediation techniques. A wide range of valuable sorption properties of this carbonaceous pyrolysis product provides new options to solve contaminant problems in soil and water and thus may reduce the number of contaminated sites. The sorption capacity of agricultural wastes and wood processing-derived biochars has been found to be excellent due to high surface area, pore volume, and surface functional groups. However, sorption interactions and separation of xenobiotics from waste water, soil solutions or polluted surface water is very often affected by the concentration of contaminant, contact time, effects of competitive substances and mainly by the chemical form of the respective contaminant. The negative surface charge of biochar-based sorption materials supports significant sorption in particular for cationic forms of pollutants. On the other hand many environmentally critical substances occur in anionic forms (e.g. As, P, Mo, Tc). Therefore their retention and immobilization by biochar is frequently considered as problematic or limited. Besides, details about the mechanism of biochar interactions with anionic compounds and the options for surface modification are largely unexplored. This contribution presents a comparative study about production and characterization of unmodified, chemically pre-treated and post-treated biochars with respect to sorption processes of model anionic compounds (PO43-, AsO43-). The obtained results confirmed the crucial role of altering biochar properties (pH) and of surface modification for improving biochar sorption efficiency for anionic contaminants.

  12. Investigating Planetary Volatile Accretion Mechanisms Using the Halogens

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    Depletion of the volatile elements in the Earth relative to the CI chondrites is roughly correlated with volatility, or decreasing condensation temperature. For the heavy halogen group elements (Cl, Br and I), volatility alone does not account for their apparent depletion, which early data has suggested is far greater than predicted [1-2]. Such depletion has been used to argue for the preferential loss of halogens by, amongst other processes, impact-driven erosive loss from Earth's surface [2]. Little consensus exists as to why the halogens should exhibit such preferential behavior during accretionary processes. Early efforts to constrain halogen abundance and understand their behavior in both Earth and planetary materials [3-6] have been hampered by their typically low abundance (ppb level) in most geologic materials. We present the results of halogen analysis of 23 chondrite samples, selected to represent diverse groups and petrologic type. Halogen abundances were measured by neutron irradiation noble gas mass spectrometry (NI-NGMS). Significant concentration heterogeneity is observed within some samples. However, a single Br/Cl and I/Cl ratio of 1.9 ± 0.2 (x 10-3) and 335 ± 10 (x 10-6) can be defined for carbonaceous chondrites with a good correlation between Br and Cl (R2 = 0.97) and between I and Cl (R2 = 0.84). Ratios of I/Cl overlap with terrestrial estimates of Bulk Silicate Earth and Mid Ocean Ridge Basalts. Similarly, good correlations are derived for enstatite (E) chondrites and a sulfide- and halogen- rich subset of E-chondrites. Chlorine abundances of CI (Orgueil) in this study are lower by factor of ~ 3 than the value of ~ 700 ppm Cl (compilation in [1]). Our results are similar to early discarded low values for Ivuna and Orgueil from [5,6] and agree more closely with values for CM chondrites. Halogens may not be as depleted in Earth as previously suggested, or a high degree of heterogeneity in the abundance of these volatile elements in

  13. Analytical electron microscopy of extraterrestrial materials - Results from microtome sections of carbonaceous chondrites and interplanetary dust particles

    NASA Technical Reports Server (NTRS)

    Blake, D. F.; Bunch, T. E.; Mardinly, A. J.

    1987-01-01

    The paper describes a method for embedding, sectioning, and observing two types of extraterrestrial materials, including hydrated interplanetary dust particles (IDPs) and carbonaceous chondrite meteorites. The technique, which produces large thin areas suitable for both high-resolution imaging and thin-film microanalysis, was applied to study the petrology of the IDP Ames-DE C86-11, the Murchison carbonaceous chondrite matrix, and the Allende dark inclusion. The technique makes it possible to maintain delicate interfaces, boundaries, and phase relationships between grains. Because phases are held in place, layer lattice silicates and other minerals with strong preferred orientations can be viewed in any orientation, including the orientation normal to their basal planes.

  14. Process for liquefying carbonaceous materials of high molecular weight and for separating liquefaction products

    DOEpatents

    Malek, John M.

    1977-01-01

    Process characterized by comprising successively a dissolution zone fed with carbonaceous solids and with a solvent, a high pressure hydrogenation zone provided with a source of hydrogen, and a hydrogenation products separation zone, wherein the improvement consists mainly in chemical upgrading of the liquidform products derived from the separation zone, and recycling a part of the upgraded products to the dissolution zone, this recycled part being of either positively acidic or positively basic properties for enhancing the dissolution - decomposition of base-acid structures present in the carbonaceous solid feed.

  15. Mineral Associations and Character of Isotopically Anomalous Organic Material in the Tagish Lake Carbonaceous Chondrite

    SciTech Connect

    Zega, T.; Alexander, C; Busemann, H; Nittler, L; Hoppe, P; Stroud, R; Young, A

    2010-01-01

    We report a coordinated analytical study of matrix material in the Tagish Lake carbonaceous chondrite in which the same small ({le}20 {micro}m) fragments were measured by secondary ion mass spectrometry (SIMS), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), electron energy-loss spectroscopy (EELS), and X-ray absorption near-edge spectroscopy (XANES). SIMS analysis reveals H and N isotopic anomalies (hotspots), ranging from hundreds to thousands of nanometers in size, which are present throughout the fragments. Although the differences in spatial resolution of the SIMS techniques we have used introduce some uncertainty into the exact location of the hotspots, in general, the H and N isotopic anomalies are spatially correlated with C enrichments, suggesting an organic carrier. TEM analysis, enabled by site-specific extraction using a focused-ion-beam scanning-electron microscope, shows that the hotspots contain an amorphous component, Fe-Ni sulfides, serpentine, and mixed-cation carbonates. TEM imaging reveals that the amorphous component occurs in solid and porous forms, EDS indicates that it contains abundant C, and EELS and XANES at the C K edge reveal that it is largely aromatic. This amorphous component is probably macromolecular C, likely the carrier of the isotopic anomalies, and similar to the material extracted from bulk samples as insoluble organic matter. However, given the large sizes of some of the hotspots, the disparity in spatial resolution among the various techniques employed in our study, and the phases with which they are associated, we cannot entirely rule out that some of the isotopic anomalies are carried by inorganic material, e.g., sheet silicates. The isotopic composition of the organic matter points to an initially primitive origin, quite possibly within cold interstellar clouds or the outer reaches of the solar protoplanetary disk. The association of organic material with secondary phases, e

  16. Layer-by-Layer Assembly of Halogen-Free Polymeric Materials on Nylon/Cotton Blend for Flame Retardant Applications

    DTIC Science & Technology

    2015-07-01

    safe, halogen free, anionic sodium phosphate and cationic polysiloxanes were deposited on a Nyco (1:1 nylon/cotton blend) fabric via layer-by-layer... sodium phosphate and cationic polysiloxanes were deposited on a Nyco (1:1 nylon/cotton blend) fabric via layer-by-layer (LbL) assembly to reduce the...used are poly(allylamine), poly(acryl amide), poly(acrylic acid), inorganic materials such as montmorillonite, ammonium polyphosphate and poly( sodium

  17. In Situ Observation of Carbonaceous Material in the Matrices of CV and CM Carbonaceous Chondrites: Preliminary Results from Energy Filtered Transmission Electron Microscopy

    NASA Technical Reports Server (NTRS)

    Brearley, A. J.; Abreu, N. M.

    2001-01-01

    Energy filtered transmission electron microscopy shows that organic matter can be detected in situ in the matrices of carbonaceous chondrites at a spatial resolution of at least 1 nm. In CM chondrites, carbon is often associated with sulfide particles. Additional information is contained in the original extended abstract.

  18. Testing for fullerenes in geologic materials: Oklo carbonaceous substances, Karelian shungites, Sudbury Black Tuff

    NASA Astrophysics Data System (ADS)

    Mossman, David; Eigendorf, Guenter; Tokaryk, Dennis; Gauthier-Lafaye, François; Guckert, Kristal D.; Melezhik, Victor; Farrow, Catharine E. G.

    2003-03-01

    Fullerenes have been reported from diverse geologic environments since their discovery in shungite from Karelian Russia. Our investigation is prompted by the presence of onionskin-like structures in some carbonaceous substances associated with the fossil nuclear fission reactors of Oklo, Gabon. The same series of extractions and the same instrumental techniques, laser desorption ionization and high-resolution mass spectroscopy (electron-impact mass spectroscopy), were employed to test for fullerenes in samples from three different localities: two sites containing putative fullerenes (Sudbury Basin and Russian Karelia) and one new location (Oklo, Gabon). We confirm the presence of fullerenes (C60 and C70) in the Black Tuff of the Onaping Formation impact breccia in the Sudbury Basin, but we find no evidence of fullerenes in shungite samples from various locations in Russian Karelia. Analysis of carbonaceous substances associated with the natural nuclear fission reactors of Oklo yields no definitive signals for fullerenes. If fullerenes were produced during sustained nuclear fission at Oklo, then they are present below the detection limit (˜100 fmol), or they have destabilized since formation. Contrary to some expectations, geologic occurrences of fullerenes are not commonplace.

  19. Biological potential of extraterrestrial materials. 2. Microbial and plant responses to nutrients in the Murchison carbonaceous meteorite

    NASA Technical Reports Server (NTRS)

    Mautner, M. N.; Conner, A. J.; Killham, K.; Deamer, D. W.

    1997-01-01

    Meteoritic materials are investigated as potential early planetary nutrients. Aqueous extracts of the Murchison C2 carbonaceous meteorite are utilized as a sole carbon source by microorganisms, as demonstrated by the genetically modified Pseudomonas fluorescence equipped with the lux gene. Nutrient effects are observed also with the soil microorganisms Nocardia asteroides and Arthrobacter pascens that reach populations up to 5 x 10(7) CFU/ml in meteorite extracts, similar to populations in terrestrial soil extracts. Plant tissue cultures of Asparagus officinalis and Solanum tuberosum (potato) exhibit enhanced pigmentation and some enhanced growth when meteorite extracts are added to partial nutrient media, but inhibited growth when added to full nutrient solution. The meteorite extracts lead to large increases in S, Ca, Mg, and Fe plant tissue contents as shown by X-ray fluorescence, while P, K, and Cl contents show mixed effects. In both microbiological and plant tissue experiments, the nutrient and inhibitory effects appear to be best balanced for growth at about 1:20 (extracted solid : H2O) ratios. The results suggest that solutions in cavities in meteorites can provide efficient concentrated biogenic and early nutrient environments, including high phosphate levels, which may be the limiting nutrient. The results also suggest that carbonaceous asteroid resources can sustain soil microbial activity and provide essential macronutrients for future space-based ecosystems.

  20. Biological potential of extraterrestrial materials - 1. Nutrients in carbonaceous meteorites, and effects on biological growth

    NASA Astrophysics Data System (ADS)

    Mautner, Michael N.

    1997-06-01

    Soil nutrient analysis of the Murchison C2 carbonaceous chondrite shows biologically available S, P, Ca, Mg, Na, K and Fe and cation exchange capacity (CEC) at levels comparable with terrestrial agricultural soils. Weathering, and aqueous, hydrothermal (121°C, 15 min) and high-temperature (550°C, 3 h) processing increase the extractable nutrients. Extractable phosphorus (by 0.3 M NH 4F + 0.1 M HCl) content, which may be growth-limiting, is 6.3 μg g -1 in the unprocessed meteorite, but increases to 81 μg g -1 by hydrothermal processing and weathering, and to 130 μg g -1 by high temperature processing. The cation exchange capacity (CEC), attributed mainly to the organic fraction, corresponds responds to 345 meq per 100 g of the polymer, suggesting one ionizable COOH or OH group per 3-4 aromatic rings. The Allende C3(V) meteorite has low extractable Ca, Mg and K, in parallel to its low organic content and CEC, but high extractable P levels (160 μg g -1). Biological effects are observed on growth of the soil microorganisms Flavobacterium oryzihabitans and Nocardia asteroides in meteorite extracts, and the population levels suggest that P is the limiting nutrient. Effects on plant growth are examined on Solanum tuberosum (potato), where extracts of the Murchison meteorite lead to enhanced growth and pigmentation. The biologically available organic and inorganic nutrients in carbonaceous chondrites can provide concentrated solutions for prebiotic and early life processes, and serve as soils and fertilizers for future space-based biological expansion.

  1. Biomolecular halogen bonds.

    PubMed

    Ho, P Shing

    2015-01-01

    Halogens are atypical elements in biology, but are common as substituents in ligands, including thyroid hormones and inhibitors, which bind specifically to proteins and nucleic acids. The short-range, stabilizing interactions of halogens - now seen as relatively common in biology - conform generally to halogen bonds characterized in small molecule systems and as described by the σ-hole model. The unique properties of biomolecular halogen bonds (BXBs), particularly in their geometric and energetic relationship to classic hydrogen bonds, make them potentially powerful tools for inhibitor design and molecular engineering. This chapter reviews the current research on BXBs, focusing on experimental studies on their structure-energy relationships, how these studies inform the development of computational methods to model BXBs, and considers how BXBs can be applied to the rational design of more effective inhibitors against therapeutic targets and of new biological-based materials.

  2. Microbial Contamination of Allende and Murchison Carbonaceous Chondrites; Developing a Protocol for Life Detection in Extraterrestrial Materials Using Biotechnology

    NASA Technical Reports Server (NTRS)

    Steele, A.; Whitby, C.; Griffin, C.; Toporski, J. K. W.; Westall, F.; Saunders, J. R.; McKay, D. S.

    2001-01-01

    The arguments used to refute the McKay et al., (1996) hypothesis of possible Martian life in ALH84001 failed to use contamination of the meteorite as a source. This has worrying implications for our ability to detect terrestrial microbiota in meteorites and therefore any potential extraterrestrial biosignatures in both meteorites and possible returned samples. We report on imaging and microbial culturing of both Allende and Murchison carbonaceous chondrites and on the use of molecular biology techniques on a sample of Allende. Contaminating fungi and bacteria were observed (in the case of Murchison) and cultured from both meteorites. DNA was successfully extracted and subsequent PCR showed the presence of both bacterial and fungal DNA although no Archaea were detected. These results show that it is possible to use molecular biological techniques on very small quantities (300 mg) of extraterrestrial material.

  3. Evaluation of the curing depth of two translucent composite materials using a halogen and two LED curing units.

    PubMed

    Polydorou, Olga; Manolakis, Alexandros; Hellwig, Elmar; Hahn, Petra

    2008-03-01

    This in vitro study evaluated the influence of one halogen and two light-emitting diode (LED) curing units on the curing depth of a conventional hybrid and two translucent resin composites by measuring the Knoop microhardness. In the first part of the study, a conventional hybrid resin composite and three curing units (one halogen: 40 s polymerization time, two LEDs: 10 and 20 s) were used. Ten cylindrical resin composite samples were prepared for each curing unit and each polymerization time tested. After polymerization, the soft part of the samples was removed. The samples were embedded in a polyacrylic resin and separated in the middle towards the direction, top-bottom. On the section plane, Knoop microhardness measurements were performed every 1 mm, starting at 0.5 mm under the surface. In the second part of the study, two translucent resin composites and a conventional hybrid composite resin were cured with the three curing units, and the microhardness was measured as mentioned above. The difference between the curing units tested was found statistically significant (p = 0.0009), as well as the difference between the materials concerning curing depth (p = 0.0001). Both translucent materials achieved microhardness values equal to the 80% of the surface values, in depths 3.5-5.5 mm, depending on the curing units used.

  4. Carbon monoxide detection of chemisorbed oxygen in coal and other carbonaceous materials

    USGS Publications Warehouse

    Hinckley, C.C.; Wiltowski, T.; Wiltowska, T.; Ellison, D.W.; Shiley, R.H.; Wu, L.

    1990-01-01

    The oxidation of carbon monoxide by mildly oxidized and devolatilized coal samples was studied thermogravimetrically. The oxidation was attributed to oxygen chemisorbed on inorganic components of the coals. The reaction of CO with pyrite producing carbonyl sulphide, OCS, accompanied the oxidation. A mechanism for CO oxidation is proposed in which active oxygen chemisorbed on the inorganic components of the coal directly oxidized CO to CO2, and facilitates the chemisorption of CO on the coal as carbonate. A factor, ?? = ( 11 14) [1 - ( Wn Wc)], was derived where Wn is the sample weight loss not attributed to OCS formation, and Wc is the estimated weight of evolved CO2. This quantity is proportional to the fraction of CO2 produced by the direct oxidation of CO, and was used to compare the coal samples studied. Samples of an Illinois No. 5 coal yielded average ?? values of 0.7 and those of an Illinois No. 6 coal yielded values of 0.6, indicating that in these cases, the majority of CO2 produced came from the direct oxidation of CO. The results obtained for the coal samples are compared with a selection of carbonaceous samples for which the proposed mechanism does not apply. ?? 1990.

  5. Polydiphenylamine-Zeolite Y composites as a sensing material toward halogenated hydrocarbons

    NASA Astrophysics Data System (ADS)

    Permpool, Tharaporn; Sirivat, Anuvat; Atsawasathein, Darunee; Wannathong, Ladawan

    2012-02-01

    Volatile organic compounds especially halogenated hydrocarbons are widely used as solvents in many industries. Nevertheless, the toxicity of these compounds have an adverse effect on breathing and when coming in contact with skin. So, the effective vapor sensing systems are required to identify these hydrocarbons. This work focused on the fabrication of polydiphenylamine and zeolite Y_/H+ composites to determine the electrical conductivity sensitivity responses towards the halogenatedhydrocarbons: dichloromethane, 1,2-dichloroethane, and chloroform. The effects of the Si/Al ratios and zeolite content were also investigated. The results showed that the sensitivity of zeolite Y_/H+ increases with increasing Si/Al ratios. The zeolite with a Si/Al ratio of 80 is chosen to form a part of the composites with dope-PDPA. The sensitivity of the composites towards dichloromethane, 1, 2-dichloroethane, and chloroform are -3.81 × 10-2, -2.33 × 10-2, -6.08 × 10-3 S/cm, respectively The sensitivity of the composites increases with increasing zeolite content due to a greater interaction between the micro-porous structure and the those halogenated hydrocarbons.

  6. Self-Forming 3D Core-Shell Ceramic Nanostructures for Halogen-Free Flame Retardant Materials.

    PubMed

    Palacios, Elena; Leret, Pilar; De La Mata, Maria J; Fernández, Jose F; De Aza, Antonio H; Rodríguez, Miguel A; Rubio-Marcos, Fernando

    2016-04-13

    The synthesis of aluminum phosphates-based composites has been widely studied during the past decade because of the promising industrial application of these materials. Here we show a simple one-pot heterogeneous precipitation approach to fabricate a sepiolite-phosphate (SepP) composite with adequate control of the size and dispersion of the phosphate nanoparticles. This coupling between aluminum phosphate and sepiolite nanofibers results in the development of a novel three-dimensional rigid supported phosphate structure, which is generated during the thermal treatment. According to our results, this phenomenon can be explained by a migration-coalescence mechanism of phosphate nanoparticles over the sepiolite support, assisted by a liquid phase. It is worth pointing out that this stimulant behavior observed here could have potential technological applications such as halogen-free flame retardant materials.

  7. Planetary Bioresources and Astroecology. 1. Planetary Microcosm Bioassays of Martian and Carbonaceous Chondrite Materials: Nutrients, Electrolyte Solutions, and Algal and Plant Responses

    NASA Astrophysics Data System (ADS)

    Mautner, Michael N.

    2002-07-01

    The biological fertilities of planetary materials can be assessed using microcosms based on meteorites. This study applies microcosm tests to martian meteorites and analogues and to carbonaceous chondrites. The biological fertilities of these materials are rated based on the soluble electrolyte nutrients, the growth of mesophile and cold-tolerant algae, and plant tissue cultures. The results show that the meteorites, in particular the Murchison CM2 carbonaceous chondrite and DaG 476 martian shergottite, contain high levels of water-extractable Ca, Mg, and SO 4-S. The martian meteorites DaG 476 and EETA 79001 also contain higher levels of extractable essential nutrients NO 3-N (0.013-0.017 g kg -1) and PO 4-P (0.019-0.046 g kg -1) than the terrestrial analogues. The yields of most of the water-extractable electrolytes vary only by factors of 2-3 under a wide range of planetary conditions. However, the long-term extractable phosphate increases significantly under a CO 2 atmosphere. The biological yields of algae and plant tissue cultures correlate with extractable NO 3-N and PO 4-P, identifying these as the limiting nutrients. Mesophilic algae and Asparagus officinalis cultures are identified as useful bioassay agents. A fertility rating system based on microcosm tests is proposed. The results rate the fertilities in the order martian basalts > terrestrial basalt, agricultural soil > carbonaceous chondrites, lava ash > cumulate igneous rock. The results demonstrate the application of planetary microcosms in experimental astroecology to rate planetary materials as targets for astrobiology exploration and as potential space bioresources. For example, the extractable materials in Murchison suggest that concentrated internal solutions in carbonaceous asteroids (3.8 mol L -1 electrolytes and 10 g L -1 organics) can support and disperse microorganisms introduced by natural or directed panspermia in early solar systems. The results also suggest that carbonaceous asteroids

  8. Hydrogenated and halogenated blue phosphorene as Dirac materials: A first principles study

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

    Using first-principles calculations, we systematically investigate the structures and electronic properties of fully hydrogenated and halogenated blue phosphorene (P2X2). All these systems possess Dirac cone at high-symmetry K point, which are mainly contributed by P s px py orbitals. The Dirac cone in P2F2 and P2I2 systems lies exactly at the Fermi level. Formation energy analysis denotes that all the systems are energetically stable except P2I2. The mass density for P2H2 and P2F2 systems is rather small. Our calculations proposed that these systems, especially P2F2 system, have great potential applications in future nanoelectronics.

  9. Carbonaceous material production from vegetable residue and their use in the removal of textile dyes present in wastewater

    NASA Astrophysics Data System (ADS)

    Peláez-Cid, A. A.; Tlalpa-Galán, M. A.; Herrera-González, A. M.

    2013-06-01

    This paper presents the adsorption results of acid, basic, direct, vat, and reactive-type dyes on carbonaceous adsorbent materials prepared starting off vegetable residue such as Opuntia ficus indica and Casimiroa edulis fruit wastes. The adsorbents prepared from Opuntia ficus indica waste were designated: TunaAsh, CarTunaT, and CarTunaQ. The materials obtained from Casimiroa edulis waste were named: CenZAP, CarZAPT, and CarZAPQ. TunaAsh and CenZAP consist of ashes obtained at 550 °C CarTunaT and CarZAPT consist of the materials carbonized at 400 °C lastly, CarTunaQ and CarZAPQ consist of chemically activated carbons using H3PO4 at 400 °C. Only the chemically activated materials were washed with distilled water until a neutral pH was obtained after their carbonization. All materials were ground and sieved to obtain a particle size ranging from 0.25 to 0.84 mm. The static adsorption results showed that both ashes and chemically activated carbon are more efficient at dye removal for both vegetable residues. For TunaAsh and CarTunaQ, removal rates of up to 100% in the cases of basic, acid, and direct dyes were achieved. Regarding wastewater containing reactive dyes, the efficiency ranged from 60 to 100%. For vat effluents, it ranged from 42 to 52%. In the case of CenZAP and CarZAPQ, it was possible to treat reactive effluents with rates ranging between 63 and 91%. Regarding vat effluents, it ranged from 57 to 68%. The process of characterization for all materials was done using scanning electron microscopy and infrared spectroscopy.

  10. The Insoluble Carbonaceous Material of CM Chondrites as Possible Source of Discrete Organics During the Asteroidal Aqueous Phase

    NASA Technical Reports Server (NTRS)

    Yabuta, H.; Williams, L.; Cody, G.; Pizzarello, S.

    2005-01-01

    The larger portion of the organic carbon in carbonaceous chondrites (CC) is present as a complex and heterogeneous macromolecular material that is insoluble in acids and most solvents (IOM). So far, it has been analyzed only as a whole by microscopy (TEM) and spectroscopy (IR, NMR, EPR), which have offered and overview of its chemical nature, bonding, and functional group composition. Chemical or pyrolytic decomposition has also been used in combination with GC-MS to identify individual compounds released by these processes. Their value in the recognition of the original IOM structure resides in the ability to properly interpret the decomposition pathways for any given process. We report here a preliminary study of IOM from the Murray meteorite that combines both the analytical approaches described above, under conditions that would realistically model the IOM hydrothermal exposure in the meteorite parent body. The aim is to document the possible release of water and solvent soluble organics, determine possible changes in NMR spectral features, and ascertain, by extension, the effect of this loss on the frame of the IOM residue. Additional information is included in the original extended abstract.

  11. Influence of coal-tar sealcoat and other carbonaceous materials on polycyclic aromatic hydrocarbon loading in an urban watershed.

    PubMed

    Yang, Yaning; Van Metre, Peter C; Mahler, Barbara J; Wilson, Jennifer T; Ligouis, Bertrand; Razzaque, M D Muhit; Schaeffer, David J; Werth, Charles J

    2010-02-15

    Carbonaceous material (CM) particles are the principal vectors transporting polycyclic aromatic hydrocarbons (PAHs) into urban waters via runoff; however, characteristics of CM particles in urban watersheds and their relative contributions to PAH contamination remain unclear. Our objectives were to identify the sources and distribution of CM particles in an urban watershed and to determine the types of CMs that were the dominant sources of PAHs in the lake and stream sediments. Samples of soils, parking lot and street dust, and streambed and lake sediment were collected from the Lake Como watershed in Fort Worth, Texas. Characteristics of CM particles determined by organic petrography and a significant correlation between PAH concentrations and organic carbon in coal tar, asphalt, and soot indicate that these three CM particle types are the major sources and carriers of PAHs in the watershed. Estimates of the distribution of PAHs in CM particles indicate that coal-tar pitch, used in some pavement sealcoats, is a dominant source of PAHs in the watershed, and contributes as much as 99% of the PAHs in sealed parking lot dust, 92% in unsealed parking lot dust, 88% in commercial area soil, 71% in streambed sediment, and 84% in surficial lake sediment.

  12. Influence of coal-tar sealcoat and other carbonaceous materials on polycyclic aromatic hydrocarbon loading in an urban watershed

    USGS Publications Warehouse

    Yang, Y.; Van Metre, P.C.; Mahler, B.J.; Wilson, J.T.; Ligouis, B.; Razzaque, M.; Schaeffer, D.J.; Werth, C.J.

    2010-01-01

    Carbonaceous material (CM) particles are the principal vectors transporting polycyclic aromatic hydrocarbons (PAHs) into urban waters via runoff; however, characteristics of CM particles in urban watersheds and their relative contributions to PAH contamination remain unclear. Our objectives were to identify the sources and distribution of CM particles in an urban watershed and to determine the types of CMs that were the dominant sources of PAHs in the lake and stream sediments. Samples of soils, parking lot and street dust, and streambed and lake sediment were collected from the Lake Como watershed in Fort Worth, Texas. Characteristics of CM particles determined by organic petrography and a significant correlation between PAH concentrations and organic carbon in coal tar, asphalt, and soot indicate that these three CM particle types are the major sources and carriers of PAHs in the watershed. Estimates of the distribution of PAHs in CM particles indicate that coal-tar pitch, usedinsomepavementsealcoats, isadominant source of PAHs in the watershed, and contributes as much as 99% of the PAHs in sealed parking lot dust, 92% in unsealed parking lot dust, 88% in commercial area soil, 71% in streambed sediment, and 84% in surficial lake sediment. ?? 2010 American Chemical Society.

  13. Carbonaceous materials containing silicon as anodes for lithium-ion cells

    SciTech Connect

    Wilson, A.M.; Dahn, J.R.; Xue, J.S.; Gao, Y.; Feng, X.H.

    1995-12-31

    Graphite and pregraphitic carbons capable of reversibly reacting with lithium ions are hosts commonly used in Li-ion cells. As a continuation of previous work, the authors have used chemical vapor deposition of benzene and silicon-containing precursors to prepare carbons containing nanodispersed silicon. The silicon resides within the unorganized regions in the pregraphitic carbons. These materials reversibly react with lithium in electrochemical cells and the reversible specific capacity has been known to increase from {approximately}300 mAhg{sup {minus}1}, in the absence of silicon, to near 500 mAhg{sup {minus}1} as silicon is added. The authors also report on Si-O-C materials which have been shown to reversibly react with Li in electrochemical cells with reversible specific capacities as high as 770 mAhg{sup {minus}1}. These materials have been made by thermal pyrolysis of siloxane polymers and epoxy-silane composites prepared from hardened mixtures of epoxy novolac resin and epoxy-functional silane. These materials all show promise for use as anode materials in advanced rechargeable lithium batteries.

  14. Method for separating liquid and solid products of liquefaction of coal or like carbonaceous materials

    DOEpatents

    Malek, John M.

    1978-04-18

    A method of improving the quality of slurry products taken from coal liquefaction reactors comprising subjecting the slurry to treatment with an alkaline compound such as caustic soda in the presence of steam in order to decompose the phenolic and acidic materials present in the slurry, and to also lower the slurry viscosity to allow separation of solid particles by sedimentation.

  15. Cytotoxicity of halogenated graphenes

    NASA Astrophysics Data System (ADS)

    Teo, Wei Zhe; Khim Chng, Elaine Lay; Sofer, Zdeněk; Pumera, Martin

    2013-12-01

    Graphene and its family of derivatives possess unique and remarkable physicochemical properties which make them valuable materials for applications in many areas like electronics, energy storage and biomedicine. In response to the possibility of its large-scale manufacturing as commercial products in the future, an investigation was conducted to determine the cytotoxicity of one particular family of graphene derivatives, the halogenated graphenes, for the first time. Halogenated graphenes were prepared through thermal exfoliation of graphite oxide in gaseous chlorine, bromine or iodine atmospheres to yield chlorine- (TRGO-Cl), bromine- (TRGO-Br) and iodine-doped graphene (TRGO-I) respectively. 24 h exposure of human lung carcinoma epithelial cells (A549) to the three halogenated graphenes and subsequent cell viability assessments using methylthiazolyldiphenyl-tetrazolium bromide (MTT) and water-soluble tetrazolium salt (WST-8) assays revealed that all the halogenated graphenes examined are rather cytotoxic at the concentrations tested (3.125 μg mL-1 to 200 μg mL-1) and the effects are dose-dependent, with TRGO-Cl reducing the cell viability to as low as 25.7% at the maximum concentration of 200 μg mL-1. Their levels of cytotoxicity can be arranged in the order of TRGO-Cl > TRGO-Br > TRGO-I, and it is suggested that the amount of halogen present in the graphene material is the determining factor for the observed trend. Control experiments were carried out to test for possible nanomaterial-induced interference as a consequence of reaction between the halogenated graphenes and the viability markers (MTT/WST-8 reagent) or binding of the formazan products under cell-free conditions. The data obtained eliminate the probability of significant influence by these interferents as the change in the normalized percentage of formazan formed is relatively small and thorough washings were performed prior to the viability assessments to reduce the amount of halogenated

  16. Origin of Dark Material on VESTA from DAWN FC Data: Remnant Carbonaceous Chondrite Impators

    NASA Technical Reports Server (NTRS)

    Reddy, V.; LeCorre, L.; Nathues, A.; Mittlefehldt, David W.; Cloutis, E. A.; OBrien, D. P.; Durda, D. D.; Bottke, W. F.; Buczkowski, D.; Scully, J. E. C.; Palmer, E. M.; Sierks, H.; Mann, P. J.; Becker, K. J.; Beck, A. W.; Li, Y-Y.; Gaskell, R.; Russell, C. T.; Gaffey, M. J.; McSween, H. Y.; McCord, T. B.; Combe, J.-P.; Blewett, D.

    2012-01-01

    NASA's Dawn spacecraft entered orbit around asteroid (4) Vesta in July 2011 for a yearlong mapping orbit. The surface of Vesta as imaged by the Dawn Framing Camera (FC) revealed a surface that is unlike any asteroid we have visited so far with a spacecraft. Albedo and color variations on Vesta are the most diverse in the asteroid belt with a majority of these linked to distinct compositional units on the asteroid s surface. FC discovered dark material on Vesta. These low albedo surface features were first observed during Rotational Characterization 3 phase at a resolution of approx. 487 m/pixel. Here we explore the composition and possible meteoritical analogs for the dark material on Vesta.

  17. Role of carbonaceous materials in polymer matrix composites for friction applications

    NASA Astrophysics Data System (ADS)

    Lapping, Preston

    The purpose of this research was to study the friction performance characteristics of a Copper, Antimony, and sulfide free environmentally automotive friction material using different allotropes of graphite as a replacement. Model brake friction materials were created and tested on a full scale brake dynamometer using the Society of Automotive Engineers J2430 test and Brake Effectiveness Evaluation Procedure. The dynamometer testing revealed the graphite replacement to have higher average effectiveness values when compared to the baseline friction material currently in production. The model samples generally had higher wear rates but some were comparable to the baseline and would be acceptable in real world applications. Some of the model samples displayed stable characteristics under varying load and linear braking velocity conditions, ultimately passing the criteria required. The model samples (RD18670A/B/C/D/E/F/G) displayed average effectiveness values of 0.425, 0.435, 0.4125, 0.425, 0.475, failed test, and 0.35 respectively, which is on average a substantial gain over the baseline effectiveness value average of 0.3125. Sample RD18670F proved to be the most promising replacement for the baseline 1999 Ford Crown Victoria friction lining. This is due to a higher average effectiveness value of 0.5, during both the high speed and low speed testing, than the baseline friction lining material of 0.325. Also, RD18670F displayed comparable wear rates to the baseline test, with 0.384mm lost inboard and 0.650 lost outboard, representing a difference of only 0.074mm and 0.2mm respectively from the baseline.

  18. Halogen bonding in solution: thermodynamics and applications.

    PubMed

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

    2013-02-21

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

  19. Ablation of carbonaceous materials in a hydrogen-helium arc-jet flow

    NASA Technical Reports Server (NTRS)

    Park, C.; Lundell, J. H.; Green, M. J.; Winovich, W.; Covington, M. A.

    1983-01-01

    The stagnation-point ablation rates of a graphite, a carbon-carbon composite, and four carbon-phenolic materials are measured in an arc-jet wind tunnel with a 50 percent hydrogen-50 percent helium mixture as the test gas. Flow environments are determined through measurements of static and impact pressures, heat-transfer rates to a calorimeter, and radiation spectra, and through numerical calculation of the flow through the wind tunnel, spectra, and heat-transfer rates. The environments so determined are: impact pressure approximately equal to 3 atm, Mach number approximately equal to 2.1, convective heat-transfer rate approximately equal to 14 kW/sq cm, and radiative heat-transfer rate approximately equal to 7 kW/sq cm in the absence of ablation. Ablation rates are determined from the measured rates of mass loss and recession of the ablation specimens. Compared with the predicted ablation rates obtained by running RASLE and CMA codes, the measured rates are higher by about 15 percent for all tested materials.

  20. Ablation of carbonaceous materials in a hydrogen-helium arc-jet flow

    NASA Technical Reports Server (NTRS)

    Park, C.; Lundell, J. H.; Green, M. J.; Winovich, W.; Covington, M. A.

    1983-01-01

    The stagnation-point ablation rates of a graphite, a carbon-carbon composite, and four carbon-phenolic materials are measured in an arc-jet wind tunnel with a 50% hydrogen-50% helium mixture as the test gas. Flow environments are determined through measurements of static and impact pressures, heat-transfer rates to a calorimeter, and radiation spectra, and through numerical calculation of the flow through the wind tunnel, spectra, and heat-transfer rates. The environments so determined are: impact pressure approx. 3 atm, Mach number approx. 2.1, convective heat-transfer rate approx. 14 kw/sq cm, and radiative heat-transfer rate approx. 7 kw/sq cm in the absence of ablation. Ablation rates are determined from the measured rates of mass loss and recession of the ablation specimens. Compared with the predicted ablation rates obtained by running RASLE and CMA codes, the measured rates are higher by about 15% for all tested materials.

  1. Factors affecting the removal of ammonia from air on carbonaceous materials: Investigation of reactive adsorption mechanism

    NASA Astrophysics Data System (ADS)

    Petit, Camille

    Air pollution related to the release of industrial toxic gases, represents one of the main concerns of our modern world owing to its detrimental effect on the environment. To tackle this growing issue, efficient ways to reduce/control the release of pollutants are required. Adsorption of gases on porous materials appears as a potential solution. However, the physisorption of small molecules of gases such as ammonia is limited at ambient conditions. For their removal, adsorbents providing strong adsorption forces must be used/developed. In this study, new carbon-based materials are prepared and tested for ammonia adsorption at ambient conditions. Characterization of the adsorbents' texture and surface chemistry is performed before and after exposure to ammonia to identify the features responsible for high adsorption capacity and for controlling the mechanisms of retention. The characterization techniques include: nitrogen adsorption, thermal analysis, potentiometric titration, FT-IR spectroscopy, X-ray diffraction, Energy Dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and Electron Microscopy. The results obtained indicate that ammonia removal is governed by the adsorbent's surface chemistry. On the contrary, porosity (and thus physisorption) plays a secondary role in this process, unless strong dispersive forces are provided by the adsorbent. The surface chemistry features responsible for the enhanced ammonia adsorption include the presence of oxygen-(carboxyl, hydroxyl, epoxy) and sulfur- (sulfonic) containing groups. Metallic species improve the breakthrough capacity as well as they lead to the formation of Lewis acid-base interactions, hydrogen-bonding or complexation. In addition to the latter three mechanisms, ammonia is retained on the adsorbent surface via Bronsted acid-base interactions or via specific reactions with the adsorbent's functionalities leading to the incorporation of ammonia into the adsorbent's matrix. Another mechanism

  2. Local structure and paramagnetic properties of the nanostructured carbonaceous material shungite

    NASA Astrophysics Data System (ADS)

    Krasnovyd, Serhii Volodymyrovich; Konchits, Andriy Andriyovich; Shanina, Bela Dmytrivna; Valakh, Mykhaylo Yakovych; Yanchuk, Igor Bogdanovich; Yukhymchuk, Volodymyr Olexsandrovych; Yefanov, Andriy Volodymyrovich; Skoryk, Mykola Andriyovich

    2015-02-01

    Using a scanning electron microscopy, elemental analysis, electron paramagnetic resonance, and Raman scattering methods, two types of the shungite materials (Sh-II from Zazhogino deposit and shungite from a commercial filter (ShF)), with different carbon content and porosity, are studied in this work. It was established by scanning electron microscopy data that the structure of the shungite samples is formed by a micron-size agglomeration of carbon and silicon dioxide clusters. It is found from the Raman data that carbon fraction is formed from sp2-hybridized clusters, size of which increases from 9 up to 12 nm after annealing of the samples. High conductivity of shungite is found to belong to the carbon nanoclusters of different sizes. Big clusters give the conduction electron spin resonance signal with a Dysonian line shape with variable g-factor and line width.

  3. Organic compound alteration during hypervelocity collection of carbonaceous materials in aerogel

    NASA Astrophysics Data System (ADS)

    Spencer, M. K.; Clemett, S. J.; Sandford, S. A.; McKay, D. S.; Zare, R. N.

    2009-03-01

    The NASA Stardust mission brought to Earth micron-size particles from the coma of comet 81P/Wild 2 using aerogel, a porous silica material, as the capture medium. A major challenge in understanding the organic inventory of the returned comet dust is identifying, unambiguously, which organic molecules are indigenous to the cometary particles, which are produced from carbon contamination in the Stardust aerogel, and which are cometary organics that have been modified by heating during the particle capture process. Here it is shown that 1) alteration of cometary organic molecules along impact tracks in aerogel is highly dependent on the original particle morphology, and 2) organic molecules on test-shot terminal particles are mostly preserved. These conclusions are based on two-step laser mass spectrometry (L2MS) examinations of test shots with organic-laden particles (both tracks in aerogel and the terminal particles themselves).

  4. Provenance analysis using Raman spectroscopy of carbonaceous material: A case study in the Southern Alps of New Zealand

    NASA Astrophysics Data System (ADS)

    Nibourel, Lukas; Herman, Frédéric; Cox, Simon; Beyssac, Olivier; Lavé, Jérôme

    2016-04-01

    Detrital provenance analyses in orogenic settings, in which sediments are collected at the outlet of a catchment, have become an important tool to estimate how erosion varies in space and time. Here we present how Raman Spectroscopy on Carbonaceous Material (RSCM) can be used for provenance analysis. RSCM provides an estimate of the peak temperature (RSCM-T) experienced during metamorphism. We show that we can infer modern erosion patterns in a catchment by combining new measurements on detrital sands with previously acquired bedrock data. We focus on the Whataroa catchment in the Southern Alps of New Zealand and exploit the metamorphic gradient that runs parallel to the main drainage direction. To account for potential sampling biases, we also quantify abrasion properties using flume experiments and measure the total organic carbon content in the bedrock that produced the collected sands. Finally, we integrate these parameters into a mass-conservative model. Our results first demonstrate that RSCM-T can be a powerful tool for detrital studies. The relative ease of data acquisition allows for a robust statistical provenance analysis with a high spatial resolution. Second, we find that spatial variations in tracer concentration and erosion intensity have a first-order control on the RSCM-T distributions, even though our flume experiments reveal that weak lithologies produce substantially more fine particles than do more durable lithologies. This result implies that sand specimens are good proxies for mapping spatial variations in erosion when the bedrock concentration of the target mineral is quantified. The modeling suggests highest present-day erosion rates (in Whataroa catchment) are not situated at the range front, as might be expected from the long-term metamorphic rock exhumation pattern, but about 10 km into the mountain belt. This closely matches the pattern of maximum rain fall and highest short-term (contemporary) inter-seismic uplift.

  5. Local structure and paramagnetic properties of the nanostructured carbonaceous material shungite.

    PubMed

    Krasnovyd, Serhii Volodymyrovich; Konchits, Andriy Andriyovich; Shanina, Bela Dmytrivna; Valakh, Mykhaylo Yakovych; Yanchuk, Igor Bogdanovich; Yukhymchuk, Volodymyr Olexsandrovych; Yefanov, Andriy Volodymyrovich; Skoryk, Mykola Andriyovich

    2015-01-01

    Using a scanning electron microscopy, elemental analysis, electron paramagnetic resonance, and Raman scattering methods, two types of the shungite materials (Sh-II from Zazhogino deposit and shungite from a commercial filter (ShF)), with different carbon content and porosity, are studied in this work. It was established by scanning electron microscopy data that the structure of the shungite samples is formed by a micron-size agglomeration of carbon and silicon dioxide clusters. It is found from the Raman data that carbon fraction is formed from sp(2)-hybridized clusters, size of which increases from 9 up to 12 nm after annealing of the samples. High conductivity of shungite is found to belong to the carbon nanoclusters of different sizes. Big clusters give the conduction electron spin resonance signal with a Dysonian line shape with variable g-factor and line width. The careful search of the nature of two other narrow electron paramagnetic resonance signals in shungite, which used to be prescribed to fullerene-like molecules, is fulfilled. Here, it is shown that the oxygen-deficient E'γ centers are responsible for these signals. A strong correlation is revealed between the concentration of Е'γ centers and the line width of conduction electron spin resonance signal, which occurs under annealing process of the samples at T = 570 K. The correlation reasons are a spin-spin coupling between two spin subsystems and time dependent of the Е'γ concentration during annealing process.

  6. Paramagnetic resonance of Shungite - a natural nano-structured carbonaceous material

    NASA Astrophysics Data System (ADS)

    Yablokov, M. Yu.; Augustyniak-Jabł, M. A.

    Shungites Sh-III and Sh-IV (?50% and 20% of carbon) have been studied by X-band EPR method in the range 4.2-293 K. The week signal of Dyson shape (a /b = 2.25-2.40) observed from a bulk sample of Sh-III has been observed to transform into an intensive Lorentzian line (?B = 1.99 mT, g = 2.0020) after sample grinding. The number of EPR responsible spins (2 × 1019 g-1) and the depth of penetration ? (?60 µm) have been estimated. The shape of the signals (Dysonian or Lorentzian) is independent of T . ?B and the g values decrease below 80 K to 1.15 mT and 2.0012. The signal intensity is independent of T down to 150 K. Isolated complexes of C60(C70)-n with K+(Na+) have been found in Sh-IV. Analysis of the EPR spectra has been made taking into consideration the properties of the conductive materials such as metals and graphite.

  7. Screening for halogenated flame retardants in European consumer products, building materials and wastes.

    PubMed

    Vojta, Šimon; Bečanová, Jitka; Melymuk, Lisa; Komprdová, Klára; Kohoutek, Jiří; Kukučka, Petr; Klánová, Jana

    2017-02-01

    To fulfill national and international fire safety standards, flame retardants (FRs) are being added to a wide range of consumer products and building materials consisting of flammable materials like plastic, wood and textiles. While the FR composition of some products and materials has been identified in recent years, the limited global coverage of the data and the large diversity in consumer products necessitates more information for an overall picture of the FR composition in common products/materials. To address this issue, 137 individual samples of various consumer products, building materials and wastes were collected. To identify and characterize potential sources of FRs in indoor environment, all samples were analyzed for content of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs) and novel flame retardants (NFRs). The most frequently detected were HBCDDs (85%), with the highest median concentration of Σ4HBCDDs of 300 mg kg(-1) in polystyrenes. The highest median concentration of Σ10PBDEs was found in recycled plastic materials, reaching 4 mg kg(-1). The lowest concentrations were observed for NFRs, where the median of Σ12NFRs reached 0.4 mg kg(-1) in the group of electrical & electronic equipment wastes. This suggests that for consumer products and building materials that are currently in-use, legacy compounds still contribute to the overall burden of FRs. Additionally, contrasting patterns of FR composition in recycled and virgin plastics, revealed using principle component analysis (PCA), suggest that legacy flame retardants are reentering the market through recycled products, perpetuating the potential for emissions to indoor environments and thus for human exposure.

  8. Hydrogenation of carbonaceous materials

    DOEpatents

    Friedman, Joseph; Oberg, Carl L.; Russell, Larry H.

    1980-01-01

    A method for reacting pulverized coal with heated hydrogen-rich gas to form hydrocarbon liquids suitable for conversion to fuels wherein the reaction involves injection of pulverized coal entrained in a minimum amount of gas and mixing the entrained coal at ambient temperature with a separate source of heated hydrogen. In accordance with the present invention, the hydrogen is heated by reacting a small portion of the hydrogen-rich gas with oxygen in a first reaction zone to form a gas stream having a temperature in excess of about 1000.degree. C. and comprising a major amount of hydrogen and a minor amount of water vapor. The coal particles then are reacted with the hydrogen in a second reaction zone downstream of the first reaction zone. The products of reaction may be rapidly quenched as they exit the second reaction zone and are subsequently collected.

  9. Different effects of surface heterogeneous atoms of porous and non-porous carbonaceous materials on adsorption of 1,1,2,2-tetrachloroethane in aqueous environment.

    PubMed

    Chen, Weifeng; Ni, Jinzhi

    2017-05-01

    The surface heterogeneous atoms of carbonaceous materials (CMs) play an important role in adsorption of organic pollutants. However, little is known about the surface heterogeneous atoms of CMs might generate different effect on adsorption of hydrophobic organic compounds by porous carbonaceous materials - activated carbons (ACs) and non-porous carbonaceous materials (NPCMs). In this study, we observed that the surface oxygen and nitrogen atoms could decrease the adsorption affinity of both ACs and NPCMs for 1,1,2,2-tetrachloroethane (TeCA), but the degree of decreasing effects were very different. The increasing content of surface oxygen and nitrogen ([O + N]) caused a sharper decrease in adsorption affinity of ACs (slope of lg (kd/SA) vs [O + N]: -0.098∼-0.16) than that of NPCMs (slope of lg (kd/SA) vs [O + N]: -0.025∼-0.059) for TeCA. It was due to the water cluster formed by the surface hydrophilic atoms that could block the micropores and generate massive invalid adsorption sites in the micropores of ACs, while the water cluster only occupied the surface adsorption sites of NPCMs. Furthermore, with the increasing concentration of dissolved TeCA, the effect of surface area on adsorption affinity of NPCMs for TeCA kept constant while the effect of [O + N] decreased due to the competitive adsorption between water molecule and TeCA on the surface of NPCMs, meanwhile, both the effects of micropore volume and [O + N] on adsorption affinity of ACs for TeCA were decreased due to the mechanism of micropore volume filling. These findings are valuable for providing a deep insight into the adsorption mechanisms of CMs for TeCA.

  10. Carbonaceous material obtained from exhausted coffee by an aqueous solution combustion process and used for cobalt (II) and cadmium (II) sorption.

    PubMed

    Serrano-Gómez, J; López-González, H; Olguín, M T; Bulbulian, S

    2015-06-01

    New carbonaceous materials were obtained using a fast aqueous solution combustion process from mixtures of exhausted coffee, ammonium nitrate (oxidizer) and urea (fuel) heated at 600, 700, 800 or 900 °C. The resulting powders were effective adsorbents for removing Co(II) and Cd(II) from aqueous solutions. Exhausted coffee was also calcined at different temperatures and compared. The products were characterized, and the obtained carbons had BET specific surface areas of 114.27-390.85 m(2)/g and pore diameters of 4.19 to 2.44 nm when the temperature was increased from 600 to 800 °C. Cobalt and cadmium adsorption by the carbonaceous materials was correlated with the maximum adsorption capacities and specific surface areas of the materials. The method reported here is advantageous because it only required 5 min of reaction to improve the textural properties of carbon obtained from exhausted coffee, which play an important role in the material's cobalt and cadmium adsorption capacities.

  11. Organic Analysis in Miller Range 090657 and Buckley Island 10933 CR2 Chondrites: Part 1 In-Situ Observation of Carbonaceous Material

    NASA Technical Reports Server (NTRS)

    Cao, T.; Nakamura-Messenger, K.; Berger, E. L.; Burton, A. S.; Messenger, S.; Clemett, S. J.

    2016-01-01

    Primitive carbonaceous chondrites contain a wide variety of organic material, ranging from soluble discrete molecules to insoluble unstructured kerogen-like component as well as structured nano-globules of macromolecular carbon. The relationship between the soluble organic molecules, macromolecular organic material, and host minerals are poorly understood. Due to the differences in extractability of soluble and insoluble organic materials, the analysis methods for each differ and are often performed independently. The combination of soluble and insoluble analyses, when performed concurrently, can provide a wider understanding on spatial distribution, and elemental, structural and isotopic composition of organic material in primitive meteorites. Furthermore, they can provide broader perspective on how extraterrestrial organic ma-terials potentially contributed to the synthesis of life's essential compounds such as amino acids, sugar acids, activated phosphates and nucleobases.

  12. Novel chemistries and materials for grid-scale energy storage: Quinones and halogen catalysis

    NASA Astrophysics Data System (ADS)

    Huskinson, Brian Thomas

    In this work I describe various approaches to electrochemical energy storage at the grid-scale. Chapter 1 provides an introduction to energy storage and an overview of the history and development of flow batteries. Chapter 2 describes work on the hydrogen-chlorine regenerative fuel cell, detailing its development and the record-breaking performance of the device. Chapter 3 dives into catalyst materials for such a fuel cell, focusing on ruthenium oxide based alloys to be used as chlorine redox catalysts. Chapter 4 introduces and details the development of a performance model for a hydrogen-bromine cell. Chapter 5 delves into the more recent work I have done, switching to applications of quinone chemistries in flow batteries. It focuses on the pairing of one particular quinone (2,7-anthraquinone disulfonic acid) with bromine, and highlights the promising performance characteristics of a device based on this type of chemistry.

  13. Application of sludge-based carbonaceous materials in a hybrid water treatment process based on adsorption and catalytic wet air oxidation.

    PubMed

    Julcour Lebigue, Carine; Andriantsiferana, Caroline; N'Guessan Krou; Ayral, Catherine; Mohamed, Elham; Wilhelm, Anne-Marie; Delmas, Henri; Le Coq, Laurence; Gerente, Claire; Smith, Karl M; Pullket, Suangusa; Fowler, Geoffrey D; Graham, Nigel J D

    2010-12-01

    This paper describes a preliminary evaluation of the performance of carbonaceous materials prepared from sewage sludges (SBCMs) in a hybrid water treatment process based on adsorption and catalytic wet air oxidation; phenol was used as the model pollutant. Three different sewage sludges were treated by either carbonisation or steam activation, and the physico-chemical properties of the resultant carbonaceous materials (e.g. hardness, BET surface area, ash and elemental content, surface chemistry) were evaluated and compared with a commercial reference activated carbon (PICA F22). The adsorption capacity for phenol of the SBCMs was greater than suggested by their BET surface area, but less than F22; a steam activated, dewatered raw sludge (SA_DRAW) had the greatest adsorption capacity of the SBCMs in the investigated range of concentrations (<0.05 mol L(-1)). In batch oxidation tests, the SBCMs demonstrated catalytic behaviour arising from their substrate adsorptivity and metal content. Recycling of SA_DRAW in successive oxidations led to significant structural attrition and a hardened SA_DRAW was evaluated, but found to be unsatisfactory during the oxidation step. In a combined adsorption-oxidation sequence, both the PICA carbon and a selected SBCM showed deterioration in phenol adsorption after oxidative regeneration, but a steady state performance was reached after 2 or 3 cycles.

  14. Method and apparatus for low temperature destruction of halogenated hydrocarbons

    DOEpatents

    Reagen, William Kevin; Janikowski, Stuart Kevin

    1999-01-01

    A method and apparatus for decomposing halogenated hydrocarbons are provided. The halogenated hydrocarbon is mixed with solvating agents and maintained in a predetermined atmosphere and at a predetermined temperature. The mixture is contacted with recyclable reactive material for chemically reacting with the recyclable material to create dehalogenated hydrocarbons and halogenated inorganic compounds. A feature of the invention is that the process enables low temperature destruction of halogenated hydrocarbons.

  15. Halogenated Compounds from Marine Algae

    PubMed Central

    Cabrita, Maria Teresa; Vale, Carlos; Rauter, Amélia Pilar

    2010-01-01

    Marine algae produce a cocktail of halogenated metabolites with potential commercial value. Structures exhibited by these compounds go from acyclic entities with a linear chain to complex polycyclic molecules. Their medical and pharmaceutical application has been investigated for a few decades, however other properties, such as antifouling, are not to be discarded. Many compounds were discovered in the last years, although the need for new drugs keeps this field open as many algal species are poorly screened. The ecological role of marine algal halogenated metabolites has somehow been overlooked. This new research field will provide valuable and novel insight into the marine ecosystem dynamics as well as a new approach to comprehending biodiversity. Furthermore, understanding interactions between halogenated compound production by algae and the environment, including anthropogenic or global climate changes, is a challenging target for the coming years. Research of halogenated metabolites has been more focused on macroalgae than on phytoplankton. However, phytoplankton could be a very promising material since it is the base of the marine food chain with quick adaptation to environmental changes, which undoubtedly has consequences on secondary metabolism. This paper reviews recent progress on this field and presents trends on the role of marine algae as producers of halogenated compounds. PMID:20948909

  16. Halogenated compounds from marine algae.

    PubMed

    Cabrita, Maria Teresa; Vale, Carlos; Rauter, Amélia Pilar

    2010-08-09

    Marine algae produce a cocktail of halogenated metabolites with potential commercial value. Structures exhibited by these compounds go from acyclic entities with a linear chain to complex polycyclic molecules. Their medical and pharmaceutical application has been investigated for a few decades, however other properties, such as antifouling, are not to be discarded. Many compounds were discovered in the last years, although the need for new drugs keeps this field open as many algal species are poorly screened. The ecological role of marine algal halogenated metabolites has somehow been overlooked. This new research field will provide valuable and novel insight into the marine ecosystem dynamics as well as a new approach to comprehending biodiversity. Furthermore, understanding interactions between halogenated compound production by algae and the environment, including anthropogenic or global climate changes, is a challenging target for the coming years. Research of halogenated metabolites has been more focused on macroalgae than on phytoplankton. However, phytoplankton could be a very promising material since it is the base of the marine food chain with quick adaptation to environmental changes, which undoubtedly has consequences on secondary metabolism. This paper reviews recent progress on this field and presents trends on the role of marine algae as producers of halogenated compounds.

  17. Density functional theory study the effects of oxygen-containing functional groups on oxygen molecules and oxygen atoms adsorbed on carbonaceous materials.

    PubMed

    Qi, Xuejun; Song, Wenwu; Shi, Jianwei

    2017-01-01

    Density functional theory was used to study the effects of different types of oxygen-containing functional groups on the adsorption of oxygen molecules and single active oxygen atoms on carbonaceous materials. During gasification or combustion reactions of carbonaceous materials, oxygen-containing functional groups such as hydroxyl(-OH), carbonyl(-CO), quinone(-O), and carboxyl(-COOH) are often present on the edge of graphite and can affect graphite's chemical properties. When oxygen-containing functional groups appear on a graphite surface, the oxygen molecules are strongly adsorbed onto the surface to form a four-member ring structure. At the same time, the O-O bond is greatly weakened and easily broken. The adsorption energy value indicates that the adsorption of oxygen molecules changes from physisorption to chemisorption for oxygen-containing functional groups on the edge of a graphite surface. In addition, our results indicate that the adsorption energy depends on the type of oxygen-containing functional group. When a single active oxygen atom is adsorbed on the bridge site of graphite, it gives rise to a stable epoxy structure. Epoxy can cause deformation of the graphite lattice due to the transition of graphite from sp2 to sp3 after the addition of an oxygen atom. For quinone group on the edge of graphite, oxygen atoms react with carbon atoms to form the precursor of CO2. Similarly, the single active oxygen atoms of carbonyl groups can interact with edge carbon atoms to form the precursor of CO2. The results show that oxygen-containing functional groups on graphite surfaces enhance the activity of graphite, which promotes adsorption on the graphite surface.

  18. Density functional theory study the effects of oxygen-containing functional groups on oxygen molecules and oxygen atoms adsorbed on carbonaceous materials

    PubMed Central

    Song, Wenwu; Shi, Jianwei

    2017-01-01

    Density functional theory was used to study the effects of different types of oxygen-containing functional groups on the adsorption of oxygen molecules and single active oxygen atoms on carbonaceous materials. During gasification or combustion reactions of carbonaceous materials, oxygen-containing functional groups such as hydroxyl(-OH), carbonyl(-CO), quinone(-O), and carboxyl(-COOH) are often present on the edge of graphite and can affect graphite’s chemical properties. When oxygen-containing functional groups appear on a graphite surface, the oxygen molecules are strongly adsorbed onto the surface to form a four-member ring structure. At the same time, the O-O bond is greatly weakened and easily broken. The adsorption energy value indicates that the adsorption of oxygen molecules changes from physisorption to chemisorption for oxygen-containing functional groups on the edge of a graphite surface. In addition, our results indicate that the adsorption energy depends on the type of oxygen-containing functional group. When a single active oxygen atom is adsorbed on the bridge site of graphite, it gives rise to a stable epoxy structure. Epoxy can cause deformation of the graphite lattice due to the transition of graphite from sp2 to sp3 after the addition of an oxygen atom. For quinone group on the edge of graphite, oxygen atoms react with carbon atoms to form the precursor of CO2. Similarly, the single active oxygen atoms of carbonyl groups can interact with edge carbon atoms to form the precursor of CO2. The results show that oxygen-containing functional groups on graphite surfaces enhance the activity of graphite, which promotes adsorption on the graphite surface. PMID:28301544

  19. Gas/solid carbon branching ratios in surface-mediated reactions and the incorporation of carbonaceous material into planetesimals

    NASA Astrophysics Data System (ADS)

    Nuth, Joseph A.; Johnson, Natasha M.; Ferguson, Frank T.; Carayon, Alicia

    2016-07-01

    We report the ratio of the initial carbon available as CO that forms gas-phase compounds compared to the fraction that deposits as a carbonaceous solid (the gas/solid branching ratio) as a function of time and temperature for iron, magnetite, and amorphous iron silicate smoke catalysts during surface-mediated reactions in an excess of hydrogen and in the presence of N2. This fraction varies from more than 99% for an amorphous iron silicate smoke at 673 K to less than 40% for a magnetite catalyst at 873 K. The CO not converted into solids primarily forms methane, ethane, water, and CO2, as well as a very wide range of organic molecules at very low concentration. Carbon deposits do not form continuous coatings on the catalytic surfaces, but instead form extremely high surface area per unit volume "filamentous" structures. While these structures will likely form more slowly but over much longer times in protostellar nebulae than in our experiments due to the much lower partial pressure of CO, such fluffy coatings on the surfaces of chondrules or calcium aluminum inclusions could promote grain-grain sticking during low-velocity collisions.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  1. Catalyst for hydrotreating carbonaceous liquids

    DOEpatents

    Berg, Lloyd; McCandless, Frank P.; Ramer, Ronald J.

    1982-01-01

    A catalyst for denitrogenating and desulfurating carbonaceous liquid such as solvent refined coal includes catalytic metal oxides impregnated within a porous base of mostly alumina with relatively large pore diameters, surface area and pore volume. The base material includes pore volumes of 0.7-0.85 ml/g, surface areas of 200-350 m.sup.2 /g and pore diameters of 85-200 Angstroms. The catalytic metals impregnated into these base materials include the oxides of Group VI metals, molybdenum and tungsten, and the oxides of Group VIII metals, nickel and cobalt, in various combinations. These catalysts and bases in combination have effectively promoted the removal of chemically combined sulfur and nitrogen within a continuous flowing mixture of carbonaceous liquid and hydrogen gas.

  2. Halogen bond involving hypervalent halogen: CSD search and theoretical study.

    PubMed

    Wang, Weizhou

    2011-08-25

    The Cambridge Structure Database search shows that there are over seventy crystal structures containing halogen bonds in which hypervalent halogens, not monovalent halogens as usual, behave as acceptors of electron density. The nature of the halogen bond involving hypervalent halogen has been investigated by using several theoretical methods with different basis sets. The HF calculations for the complexes studied cover most of their binding energies, which indicates the electrostatic nature of the halogen bond involving hypervalent halogen. The MP2 methods with medium basis sets fail to predict the relative strength of the halogen bond involving hypervalent halogen and the corresponding halogen bond involving monovalent halogen. Accurate computational results show that the halogen bond involving hypervalent halogen may be weaker than the corresponding halogen bond involving monovalent halogen even in the case that the hypervalent halogen is more positively charged than the monovalent halogen, the reasons of which were discussed in some detail. In comparison with the halogen bond involving monovalent halogen, the bonding characteristic and electron-density transfer of the halogen bond involving hypervalent halogen were also analyzed with the "atoms in molecules" theory and the natural bond orbital theory.

  3. Reduction Kinetics of MnO from High-Carbon Ferromanganese Slags by Carbonaceous Materials in Ar and CO Atmospheres

    NASA Astrophysics Data System (ADS)

    Safarian, J.; Tranell, G.; Kolbeinsen, L.; Tangstad, M.; Gaal, S.; Kaczorowski, J.

    2008-10-01

    The kinetics of MnO reduction from synthetic and industrial high-carbon ferromanganese slags were investigated using a sessile drop technique at 1600 °C. The effects of the reductant type, ambient atmosphere, and slag composition on the MnO reduction were illuminated. Six different types of carbonaceous reductants were used as substrates for small slag droplets, which were reacted in a CO or Ar atmosphere, with the reaction studied in situ. The cross sections of the reacted slag-carbon samples were subsequently studied by electron-probe microanalysis (EPMA), to find the extent of the MnO reduction as a function of the reaction time. It was found that the rate of the MnO reduction is affected by both the type of reductant and the ambient atmosphere. It was observed that the MnO reduction rate from synthetic slag by cokes produced from single coals is lower than that from industrial cokes. Reduction rates obtained when charcoal was used as the reductant were higher than when coke was used, while the CO atmosphere yielded a faster initial MnO reduction than did the Ar atmosphere. It was found that the faster reduction rates in the CO atmosphere are related to the MnO reduction by CO gas. A newly developed kinetic method was applied, to calculate the rate constants for the MnO reduction by carbon and CO that considered the reaction interfaces. It was indicated that the rate of the MnO reduction by CO is less than that by carbon; however, the contribution of these reductants to slag reduction is very dependent on their contact with the slag.

  4. Use of Less Reactive Materials and More Stable Gases to Reduce Corrosive Wear When Lubricating with Halogenated Gases

    NASA Technical Reports Server (NTRS)

    Buckley, Donald H.; Johnson, Robert L.

    1960-01-01

    The gases CF2Cl-CF2Cl, CF2Cl2, and CF2Br-CF2Br were used to lubricate metals, cermets, and ceramics in this study. One of the criteria for determining the effectiveness of a reactive-gas-lubricated systems is the stability of the halogen-containing gas molecule. The carbon-to-halogen bond in the ethane molecule has extremely good thermal stability superior to the methane analogs (CF2Cl2 and CF2Br2) used in earlier research. For this reason, the ethane compounds CF2Cl-CF2Cl and CF2Br-CF2Br were considered as high-temperature lubricants. Friction and wear studies were made with a hemisphere (3/16-in. rad.) rider sliding in a circumferential path on the flat surface of a rotating disk (21/2-in. diam. ). The specimens of metal alloys, cermets, and ceramics were run In an atmosphere of the various gases with a load of 1200 grams, sliding velocities from 75 to 8000 feet per minute, and temperatures from 75 to 1400 F. The gas CF2Cl-CF2Cl was found to be an effective lubricant for the cermet LT-LB (59.0 Cr, 19.0 Al2O3, 20.0 Mo, 2.0 Ti) and the ceramic Al2O3 sliding on Stellite Star J (cobalt-base alloy) at temperatures to 1400 F. The bromine-containing gas CF2Br-CF2Br was found to give friction and wear values that can be considered to be in a region of effective boundary lubrication for the cermet K175D (nickel-bonded metal carbide) sliding on the metal Hastelloy R-235 (nickel-base alloy) at temperatures to 1200 F.

  5. Carbon coating of Li4Ti5O12 using amphiphilic carbonaceous material for improvement of lithium-ion battery performance

    NASA Astrophysics Data System (ADS)

    Guo, Xuefei; Wang, Chengyang; Chen, Mingming; Wang, Jiuzhou; Zheng, Jiaming

    2012-09-01

    Carbon coating of fine particles of Li4Ti5O12 synthesized under hydrothermal condition is carried out by amphiphilic carbonaceous material (ACM) in aqueous solution, followed by carbonization at 800 °C for 2 h. The particles prepared are comprised of highly-crystalline spinel-type Li4Ti5O12 with the size in the range of 100-400 nm without any agglomeration, of which surface is uniformly covered by a thin carbon layer. Their electrochemical performance as an anode in lithium-ion batteries is evaluated. The initial discharge capacity of carbon-coated Li4Ti5O12 at 20 C rate is 137 mA h g-1 and remains as high as 125 mA h g-1 after 100 cycles (91% retention), exhibiting good rate and cyclic performance. Carbon coating by using ACM as carbon precursor gives the Li4Ti5O12 particles an enhanced performance as an anode in lithium-ion batteries, owing to the improvement in electrical conductivity, polarization and ability of dispersion. This non-organic coating process may present a new economic, facile, and green pathway for the preparation of carbon-coated Li4Ti5O12 as a high power anode material in lithium-ion batteries.

  6. Effect of exposure time on the color stability of resin-based restorative materials when polymerized with quartz-tungsten halogen and LED light.

    PubMed

    Rüttermann, Stefan; Suyoun, Kim; Raab, Wolfgang H-M; Janda, Ralf

    2010-10-01

    The objective of this study was to investigate the effect of exposure time on color stability of resin-based restorative materials when polymerized with quartz-tungsten halogen light (QTH) or light-emitting diode light (LED). Eight samples of Ceram-X Mono, Dyract eXtra, and Tetric EvoCeram each were cured for 10, 20, and 60 s with QTH or LED. The CIE-Lab values (L*, a*, b*) were measured prior to and after performing water storage or a Suntest, and ΔL, Δa, Δb, and ΔE were calculated. Statistical analysis (p < 0.05) showed significant changes of the color values after each of the aging processes as well as between ΔL, Δa, Δb, and ΔE of the materials in dependence of the curing device, exposure time, aging condition, and material formulation. LED performed similarly or even better with 10-s exposure time than QTH with 20 s. No improvement of color stability was achieved with increasing exposure time of 60 s either for LED or for QTH. Exposure time, emission spectrum of the light-curing device, as well as the individual material formulation influence color stability. There is apparently an exposure time above which the individual material formulation, especially type and amount of photoinitiator or synergist, dominate the color stability.

  7. Sewage-sludge-derived carbonaceous materials for catalytic wet hydrogen peroxide oxidation of m-cresol in batch and continuous reactors.

    PubMed

    Yu, Yang; Wei, Huangzhao; Yu, Li; Wang, Wei; Zhao, Ying; Gu, Bin; Sun, Chenglin

    2016-01-01

    In this study, four sewage-sludge-derived carbonaceous materials (SWs) were evaluated for their catalytic wet hydrogen peroxide oxidation (CWPO) performance of m-cresol in batch reactor and continuous reactor, respectively. The SWs were produced by carbonization (SW); carbonization with the addition of CaO (CaO-SW); HNO3 pretreatment (HNO3-SW) and steam activation (Activated-SW). The properties of SW catalysts were assessed by thermogravimetric analysis, Brunauer-Emmett-Teller, Fourier Transform Infrared Spectroscopy, X-ray Fluorescence, Scanning electron microscopy, energy dispersive X-ray analysis and zeta potential. The results showed that SW treated by HNO3 (HNO3-SW) had a high conversion of m-cresol in batch reactor and continuous reactor, respectively. Under the conditions of batch reaction (Cm-cresol = 100 mg L(-1), CH2O2 = 15.7 mmol L(-1), initial pH=7.0, 0.5 g L(-1) catalyst, 80°C, 180 min adsorption and 210 min oxidation), the conversion of m-cresol reached 100% and total organic carbon removal was 67.1%. It had a high catalytic activity and stability on the treatment of m-cresol in CWPO for more than 1100 h. Furthermore, a possible reaction mechanism for the oxidation of m-cresol to 2-methyl-p-benzoquinone by CWPO was proposed.

  8. Unit with Fluidized Bed for Gas-Vapor Activation of Different Carbonaceous Materials for Various Purposes: Design, Computation, Implementation

    NASA Astrophysics Data System (ADS)

    Strativnov, Eugene

    2017-02-01

    We propose the technology of obtaining the promising material with wide specter of application-activated nanostructured carbon. In terms of technical indicators, it will stand next to the materials produced by complex regulations with the use of costly chemical operations. It can be used for the following needs: as a sorbent for hemosorption and enterosorption, for creation of the newest source of electric current (lithium and zinc air batteries, supercapacitors), and for processes of short-cycle adsorption gas separation.

  9. Carbonaceous materials and their advances as a counter electrode in dye-sensitized solar cells: challenges and prospects.

    PubMed

    Kouhnavard, Mojgan; Ludin, Norasikin Ahmad; Ghaffari, Babak V; Sopian, Kamarozzaman; Ikeda, Shoichiro

    2015-05-11

    Dye-sensitized solar cells (DSSCs) serve as low-costing alternatives to silicon solar cells because of their low material and fabrication costs. Usually, they utilize Pt as the counter electrode (CE) to catalyze the iodine redox couple and to complete the electric circuit. Given that Pt is a rare and expensive metal, various carbon materials have been intensively investigated because of their low costs, high surface areas, excellent electrochemical stabilities, reasonable electrochemical activities, and high corrosion resistances. In this feature article, we provide an overview of recent studies on the electrochemical properties and photovoltaic performances of carbon-based CEs (e.g., activated carbon, nanosized carbon, carbon black, graphene, graphite, carbon nanotubes, and composite carbon). We focus on scientific challenges associated with each material and highlight recent advances achieved in overcoming these obstacles. Finally, we discuss possible future directions for this field of research aimed at obtaining highly efficient DSSCs.

  10. Rechargeable zinc halogen battery

    SciTech Connect

    Spaziante, P.M.; Nidola, A.

    1980-01-01

    A rechargeable zinc halogen battery has an aqueous electrolyte containing ions of zinc and halogen and an amount of polysaccharide and/or sorbitol sufficient to prevent zinc dendrite formation during recharging. The electrolyte may also contain trace amounts of metals such as tungsten, molybdenum, and lead. 7 tables.

  11. Unit with Fluidized Bed for Gas-Vapor Activation of Different Carbonaceous Materials for Various Purposes: Design, Computation, Implementation.

    PubMed

    Strativnov, Eugene

    2017-12-01

    We propose the technology of obtaining the promising material with wide specter of application-activated nanostructured carbon. In terms of technical indicators, it will stand next to the materials produced by complex regulations with the use of costly chemical operations. It can be used for the following needs: as a sorbent for hemosorption and enterosorption, for creation of the newest source of electric current (lithium and zinc air batteries, supercapacitors), and for processes of short-cycle adsorption gas separation.In this study, the author gives recommendations concerning the design of the apparatus with fluidized bed and examples of calculation of specific devices. The whole given information can be used as guidelines for the design of energy effective aggregates. Calculation and design of the reactor were carried out using modern software complexes (ANSYS and SolidWorks).

  12. Development of Low Cost Carbonaceous Materials for Anodes in Lithium-Ion Batteries for Electric and Hybrid Electric Vehicles

    SciTech Connect

    Barsukov, Igor V.

    2002-12-10

    Final report on the US DOE CARAT program describes innovative R & D conducted by Superior Graphite Co., Chicago, IL, USA in cooperation with researchers from the Illinois Institute of Technology, and defines the proper type of carbon and a cost effective method for its production, as well as establishes a US based manufacturer for the application of anodes of the Lithium-Ion, Lithium polymer batteries of the Hybrid Electric and Pure Electric Vehicles. The three materials each representing a separate class of graphitic carbon, have been developed and released for field trials. They include natural purified flake graphite, purified vein graphite and a graphitized synthetic carbon. Screening of the available on the market materials, which will help fully utilize the graphite, has been carried out.

  13. Processing-Structure-Property Relationships for Lignin-Based Carbonaceous Materials Used in Energy-Storage Applications

    DOE PAGES

    García-Negrón, Valerie; Phillip, Nathan D.; Li, Jianlin; ...

    2016-11-18

    Lignin, an abundant organic polymer and a byproduct of pulp and biofuel production, has potential applications owing to its high carbon content and aromatic structure. Processing structure relationships are difficult to predict because of the heterogeneity of lignin. Here, this work discusses the roles of unit operations in the carbonization process of softwood lignin, and their resulting impacts on the material structure and electrochemical properties in application as the anode in lithium-ion cells. The processing variables include the lignin source, temperature, and duration of thermal stabilization, pyrolysis, and reduction. Materials are characterized at the atomic and microscales. High-temperature carbonization, atmore » 2000 °C, produces larger graphitic domains than at 1050 °C, but results in a reduced capacity. Coulombic efficiencies over 98 % are achieved for extended galvanostatic cycling. Consequently, a properly designed carbonization process for lignin is well suited for the generation of low-cost, high-efficiency electrodes.« less

  14. Processing-Structure-Property Relationships for Lignin-Based Carbonaceous Materials Used in Energy-Storage Applications

    SciTech Connect

    García-Negrón, Valerie; Phillip, Nathan D.; Li, Jianlin; Daniel, Claus; Wood, David; Keffer, David J.; Rios, Orlando; Harper, David P.

    2016-11-18

    Lignin, an abundant organic polymer and a byproduct of pulp and biofuel production, has potential applications owing to its high carbon content and aromatic structure. Processing structure relationships are difficult to predict because of the heterogeneity of lignin. Here, this work discusses the roles of unit operations in the carbonization process of softwood lignin, and their resulting impacts on the material structure and electrochemical properties in application as the anode in lithium-ion cells. The processing variables include the lignin source, temperature, and duration of thermal stabilization, pyrolysis, and reduction. Materials are characterized at the atomic and microscales. High-temperature carbonization, at 2000 °C, produces larger graphitic domains than at 1050 °C, but results in a reduced capacity. Coulombic efficiencies over 98 % are achieved for extended galvanostatic cycling. Consequently, a properly designed carbonization process for lignin is well suited for the generation of low-cost, high-efficiency electrodes.

  15. Carbonaceous Chondrite Clasts in HED Achondrites

    NASA Technical Reports Server (NTRS)

    Zolensky, M. E.; Weisberg, M. K.; Buchanan, P. C.; Mittlefehldt, David W.

    1996-01-01

    Since carbonaceous chondrite planetesimals are attractive candidates for the progenitors of HED asteroid(s), we have performed a survey of HED meteorites in order to locate and characterize the mineralogy, chemistry, and petrography of the oft-reported carbonaceous chondrite clasts by microprobe, SEM-EDX. and TEM techniques. We examined samples of all HEDs we could lay our gloved hands on, and found carbonaceous chondrite clasts in the howardites Kapoeta, Jodzie, EET 87513, Y 793497, LEW 85441, LEW 87015, and G'Day, the polymict eucrites LEW 97295 and LEW 95300, and the diogenite Ellemeet. We verified previous suggestions that the majority (about 80%) of these clasts are CM2 material, but we discovered that a significant proportion are CR2 (about 20%) and other rare types are present. We conclude that chondritic compounds of mixed CM2 and CR2 materials should be investigated in future geochemical modeling of the origin of the HED asteroid(s).

  16. Chemical Bonding and Structural Information of Black CarbonReference Materials and Individual Carbonaceous AtmosphericAerosols

    SciTech Connect

    Hopkins, Rebecca J.; Tivanski, Alexei V.; Marten, Bryan D.; Gilles, Mary K.

    2007-04-25

    The carbon-to-oxygen ratios and graphitic nature of a rangeof black carbon standard reference materials (BC SRMs), high molecularmass humic-like substances (HULIS) and atmospheric particles are examinedusing scanning transmission X-ray microscopy (STXM) coupled with nearedge X-ray absorption fine structure (NEXAFS) spectroscopy. UsingSTXM/NEXAFS, individual particles with diameter>100 nm are studied,thus the diversity of atmospheric particles collected during a variety offield missions is assessed. Applying a semi-quantitative peak fittingmethod to the NEXAFS spectra enables a comparison of BC SRMs and HULIS toparticles originating from anthropogenic combustion and biomass burns,thus allowing determination of the suitability of these materials forrepresenting atmospheric particles. Anthropogenic combustion and biomassburn particles can be distinguished from one another using both chemicalbonding and structural ordering information. While anthropogeniccombustion particles are characterized by a high proportion ofaromatic-C, the presence of benzoquinone and are highly structurallyordered, biomass burn particles exhibit lower structural ordering, asmaller proportion of aromatic-C and contain a much higher proportion ofoxygenated functional groups.

  17. Rediscovery of halogen bonds in protein-ligand complexes.

    PubMed

    Zhou, P; Tian, F; Zou, J; Shang, Z

    2010-04-01

    Although the halogen bond has attracted much interest in chemistry and material science communities, its implications for drug design are just now coming to light. The protein-ligand interactions through short halogen-oxygen/nitrogen/sulfur contacts have been observed in crystal structures for a long time, but only in recent years, with the experimental and theoretical progress in weak biological interactions, especially the pioneering works contributed by Ho and co-workers (Auffinger, P.; Hays, F. A.; Westhof, E.; Ho, P. S. Proc. Natl. Acad. Sci. USA 2004, 101, 16789-16794), these short contacts involving halogens in biomolecules were rediscovered and re-recognized as halogen bonds to stress their shared similarities with hydrogen bonds in strength and directionality. Crystal structure determinations of protein complexes with halogenated ligands preliminarily unveiled the functionality of halogen bonds in protein-ligand recogni-tion. Database surveys further revealed a considerable number of short halogen-oxygen contacts between proteins and halogenated ligands. Theoretical calculations on model and real systems eventually gave a quantitative pronouncement for the substantial contribution of halogen bonds to ligand binding. All of these works forebode that the halogen bond can be exploited as a new and versatile tool for rational drug design and bio-crystal engineering.

  18. Development of nitrogen-enriched carbonaceous material coated titania nanotubes array as a fiber coating for solid-phase microextraction of ultraviolet filters in environmental water.

    PubMed

    Ma, Mingguang; Wang, Huiju; Zhen, Qi; Zhang, Min; Du, Xinzhen

    2017-05-15

    A novel solid-phase microextraction (SPME) fiber was fabricated by direct electrodeposition of polyaniline (PANI) coated the titania nanotube arrays in situ grown on the titanium wire followed by carbonization at 500°C under nitrogen atmosphere. The resulting titanium-based fiber with nitrogen-enriched carbonaceous material coated titania nanotubes (N-C/TiO2NTs/Ti) showed better extraction performance for ultraviolet (UV) filters among model aromatic compounds compared with common PANI as well as commercial polydimethylsiloxane and polyacrylate coatings. The influence of various experimental parameters on the extraction efficiency of UV filters were investigated and optimized. The calibration curves were linear from 0.2 to 200μgL(-1) for each analyte with correlation coefficients above 0.9980. Limits of detection (LODs) and limits of quantitation (LOQs) ranged from 0.03 to 0.05μgL(-1) and from 0.11 to 0.18μgL(-1) for UV filters, respectively. Relative standard deviations (RSDs) for single fiber repeatability ranged from 3.3% to 4.1% (n=5) and RSDs for fiber-to-fiber reproducibility (n=3) varied from 5.7% to 7.7%. The proposed method was successfully applied to the preconcentration and determination of target UV filters in river water and wastewater samples with good recoveries from 86.2% to 113%. Moreover this novel Ti-based fiber is mechanically and chemically stable, and can be easily prepared in a highly reproducible manner.

  19. Raman spectra of carbonaceous materials in a fault zone in the Longmenshan thrust belt, China; comparisons with those of sedimentary and metamorphic rocks

    NASA Astrophysics Data System (ADS)

    Kouketsu, Yui; Shimizu, Ichiko; Wang, Yu; Yao, Lu; Ma, Shengli; Shimamoto, Toshihiko

    2017-03-01

    We analyzed micro-Raman spectra of carbonaceous materials (CM) in natural and experimentally deformed fault rocks from Longmenshan fault zone that caused the 2008 Wenchuan earthquake, to characterize degree of disordering of CM in a fault zone. Raman spectral parameters for 12 samples from a fault zone in Shenxigou, Sichuan, China, all show low-grade structures with no graphite. Low crystallinity and δ13C values (-24‰ to -25‰) suggest that CM in fault zone originated from host rocks (Late Triassic Xujiahe Formation). Full width at half maximum values of main spectral bands (D1 and D2), and relative intensities of two subbands (D3 and D4) of CM were variable with sample locations. However, Raman parameters of measured fault rocks fall on established trends of graphitization in sedimentary and metamorphic rocks. An empirical geothermometer gives temperatures of 160-230 °C for fault rocks in Shenxigou, and these temperatures were lower for highly sheared gouge than those for less deformed fault breccia at inner parts of the fault zone. The lower temperature and less crystallinity of CM in gouge might have been caused by the mechanical destruction of CM by severe shearing deformation, or may be due to mixing of host rocks on the footwall. CM in gouge deformed in high-velocity experiments exhibits slight changes towards graphitization characterized by reduction of D3 and D4 intensities. Thus low crystallinity of CM in natural gouge cannot be explained by our experimental results. Graphite formation during seismic fault motion is extremely local or did not occur in the study area, and the CM crystallinity from shallow to deep fault zones may be predicted as a first approximation from the graphitization trend in sedimentary and metamorphic rocks. If that case, graphite may lower the friction of shear zones at temperatures above 300 °C, deeper than the lower part of seismogenic zone.

  20. Laboratory and observational study of the interrelation of the carbonaceous component of interstellar dust and solar system materials

    NASA Technical Reports Server (NTRS)

    Allamandola, L. J.; Sanford, S. A.; Schutte, W. A.; Tielens, A. G. G. M.

    1991-01-01

    By studying the chemical and isotopic composition of interstellar ice and dust, one gains insight into the composition and chemical evolution of the solid bodies in the solar nebula and the nature of the material subsequently brought into the inner part of the solar system by comets and meteorites. It is now possible to spectroscopically probe the composition of interstellar ice and dust in the mid-infrared, the spectral range which is most diagnostic of fundamental molecular vibrations. We can compare these spectra of various astronomical objects (including the diffuse and dense interstellar medium, comets, and the icy outer planets and their satellites) with the spectra of analogs we produce in the laboratory under conditions which mimic those in these different objects. In this way one can determine the composition and abundances of the major constituents of the various ices and place general constraints on the types of organics coating the grains in the diffuse interstellar medium. In particular we have shown the ices in the dense clouds contain H2O, CH3OH, CO, perhaps some NH3 and H2CO, we well as nitriles and ketones or esters. Furthermore, by studying the photochemistry of these ice analogs in the laboratory, one gains insight into the chemistry which takes place in interstellar/precometary ices. Chemical and spectroscopic studies of photolyzed analogs (including deuterated species) are now underway. The results of some of these studies will be presented and implications for the evolution of the biogenic elements in interstellar dust and comets will be discussed.

  1. An EELS-based study of the effects of pyrolysis on natural carbonaceous materials used for activated charcoal preparation.

    PubMed

    Jeanne-Rose, V; Golabkan, V; Mansot, J L; Largitte, L; Césaire, T; Ouensanga, A

    2003-04-01

    Electron energy-loss spectroscopy (EELS) has been used to characterize the electronic structure of charcoal phases at the nanoscale, thus demonstrating that the technique can be applied to environmental science. Activated charcoal is extensively used to remove pollutants from liquid and gaseous sewage. It is mainly obtained by activation of coke or charcoal produced from ligneous precursors. The present study concerns the use of by-products of local Caribbean agriculture, such as sugar cane bagasse, fruit stones and seeds, for use as activated charcoal precursors. Charcoal phases are prepared by high-temperature pyrolysis of lignocellulosic raw materials under a nitrogen gas flow. With the aim of optimizing the pyrolysis temperature and duration and oxygen content, the concentration of carbon sp2 hybridized chemical bonds and structural ordering have been followed by EELS for different treatment temperatures. To quantify the carbon sp2 content, near edge structure (NES) at the carbon K edge has been measured to determine the strength of pi --> pi* and 1s --> pi* transitions. Three precursors of plant origin, shells of Terminalia catappa and Acrocomia karukerana and seeds of Psidium guajava, with the pyrolysis temperatures between 600 and 900 degrees C, were investigated. The fraction of carbon sp2 bonding is found to increase when the temperature rises from 600 degrees C to the range 700-750 degrees C and becomes stable at higher temperatures. For temperatures in excess of 700 degrees C, structural ordering probably occurs and well-defined 1s --> sigma* NES is present, whose intensity increases with increasing preparation temperature. For the highest temperature of around 900 degrees C, the structure of the final product is less well organized than graphitized carbon but a few per cent of a highly ordered phase is found.

  2. Halogens in the atmosphere

    NASA Technical Reports Server (NTRS)

    Cicerone, R. J.

    1981-01-01

    Atmospheric halogen measurement data are presented for: (1) inorganic and organic gaseous compounds of chlorine, fluorine, bromine and iodine; and (2) chloride, fluoride, bromide and iodine in particulate form and in precipitation. The roles that these data and other, unavailable data play in the determination of the global cycles of the halogens are discussed. It is found that the speciation of the halogen gases in the troposphere is uncertain, with the only inorganic species detected by species-specific methods being HC1 and SF6. It is shown that heterogeneous reactions, both gas-to-particle and particle-to-gas processes, precipitation removal, and sea-salt aerosol generation and fractionation processes, need quantitative investigation to allow progress in estimating halogen sources and sinks. Where practical, quantitative comparisons are made between measured and predicted concentrations.

  3. Inorganic Halogen Oxidizer Research

    DTIC Science & Technology

    1975-02-26

    KEY WORDS (Continue on reverse aide il necesxary and identity by block number) Synthesis, Novel Oxidizers, Perchlorates, Fluorination , Halogen...C. J. Schack, R. D. Wilson, and E. C. Curtis, 5th European Fluorine Symposium, Avie.nore, Scotland (September 1974) 20. "New Energetic Halogen...elimination lasers. For NF-, no evidence for protonation was found at tempera- tures as low as -78 C. Furthermore, attempts to fluorinate NH. AsF

  4. Halogens in the troposphere.

    PubMed

    Finlayson-Pitts, Barbara J

    2010-02-01

    Although inorganic halogen gases are believed to play key roles in the chemistry of the lower atmosphere, many of them have not yet been detected or measured in ambient air. This article describes some of the current techniques and future needs for inorganic halogens in air. (To listen to a podcast about this feature, please go to the Analytical Chemistry multimedia page at pubs.acs.org/page/ancham/audio/index.html.).

  5. Scientific conferences: A big hello to halogen bonding

    NASA Astrophysics Data System (ADS)

    Erdelyi, Mate

    2014-09-01

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

  6. Apparatus for upgrading carbonaceous materials

    SciTech Connect

    Low, J.Y.

    1989-06-27

    This patent describes an apparatus comprising (a) a vessel suitable for use with internal pressure in the range of 300 to 3000 psig; (b) a mechanical agitator means for mixing fluids, wherein the mechanical agitator means is positioned on the inside of the vessel in a lower portion thereof; (c) a drive means coupled to the mechanical agitator for causing fluid mixing in the lower portion of the vessel due to the action of the mechanical agitator; (d) a means for supporting a catalyst bed positioned in an upper portion of the vessel; and (e) a means, separate from the mechanical agitator means for mixing fluids, or establishing fluid flow from an upper portion of the vessel through the means for supporting a catalyst bed and into the lower portion of the vessel.

  7. Hydrogen production from carbonaceous material

    DOEpatents

    Lackner, Klaus S.; Ziock, Hans J.; Harrison, Douglas P.

    2004-09-14

    Hydrogen is produced from solid or liquid carbon-containing fuels in a two-step process. The fuel is gasified with hydrogen in a hydrogenation reaction to produce a methane-rich gaseous reaction product, which is then reacted with water and calcium oxide in a hydrogen production and carbonation reaction to produce hydrogen and calcium carbonate. The calcium carbonate may be continuously removed from the hydrogen production and carbonation reaction zone and calcined to regenerate calcium oxide, which may be reintroduced into the hydrogen production and carbonation reaction zone. Hydrogen produced in the hydrogen production and carbonation reaction is more than sufficient both to provide the energy necessary for the calcination reaction and also to sustain the hydrogenation of the coal in the gasification reaction. The excess hydrogen is available for energy production or other purposes. Substantially all of the carbon introduced as fuel ultimately emerges from the invention process in a stream of substantially pure carbon dioxide. The water necessary for the hydrogen production and carbonation reaction may be introduced into both the gasification and hydrogen production and carbonation reactions, and allocated so as transfer the exothermic heat of reaction of the gasification reaction to the endothermic hydrogen production and carbonation reaction.

  8. Direct Hydrothermal Synthesis of Carbonaceous Silver Nanocables for Electrocatalytic Applications.

    PubMed

    Chen, Chuyang; Suryanto, Bryan Harry Rahmat; Zhao, Chuan; Jiang, Xuchuan; Yu, Aibing

    2015-08-05

    This study demonstrates a facile but efficient hydrothermal method for the direct synthesis of both carbonaceous silver (Ag@C core-shell) nanocables and carbonaceous nanotubes under mild conditions (<180 °C). The carbonaceous tubes can be formed by removal of the silver cores via an etching process under temperature control (60-140 °C). The structure and composition are characterized using various advanced microscopic and spectroscopic techniques. The pertinent variables such as temperature, reaction time, and surfactants that can affect the formation and growth of the nanocables and nanotubes are investigated and optimized. It is found that cetyltrimethylammonium bromide plays multiple roles in the formation of Ag@C nanocables and carbonaceous nanotubes including: a shape controller for metallic Ag wires and Ag@C cables, a source of Br(-) ions to form insoluble AgBr and then Ag crystals, an etching agent of silver cores to form carbonaceous tubes, and an inducer to refill silver particles into the carbonaceous tubes to form core-shell structures. The formation mechanism of carbonaceous silver nanostructures depending upon temperature is also discussed. Finally, the electrocatalytic performance of the as-prepared Ag@C nanocables is assessed for the oxidation reduction reaction and found to be very active but much less costly than the commonly used platinum catalysts. The findings should be useful for designing and constructing carbonaceous-metal nanostructures with potential applications in conductive materials, catalysts, and biosensors.

  9. Intrinsic W nucleosynthetic isotope variations in carbonaceous chondrites: Implications for W nucleosynthesis and nebular vs. parent body processing of presolar materials

    NASA Astrophysics Data System (ADS)

    Burkhardt, Christoph; Schönbächler, Maria

    2015-09-01

    The progressive dissolution of the carbonaceous chondrites Orgueil (CI1), Murchison (CM2) and Allende (CV3) with acids of increasing strength reveals correlated W isotope variations ranging from 3.5 ε182W and 6.5 ε183W in the initial leachate (acetic acid) to -60 ε182W and -40 ε183W in the leachate residue. The observed variations are readily explained by variable mixing of s-process depleted and s-process enriched components. One W s-process carrier is SiC, however, the observed anomaly patterns and mass-balance considerations require at least on additional s-process carrier, possibly a silicate or sulfide. The data reveal well-defined correlations, which provide a test for s-process nucleosynthesis models. The correlations demonstrate that current models need to be revised and highlight the need for more precise W isotope data of SiC grains. Furthermore the correlations provide a mean to disentangle nucleosynthetic and radiogenic contributions to 182W (ε182Wcorrected = ε182Wmeasured - (1.41 ± 0.05) × ε183Wmeasured; ε182Wcorrected = ε182Wmeasured - (-0.12 ± 0.06) × ε184Wmeasured), a prerequisite for the successful application of the Hf-W chronometer to samples with nucleosynthetic anomalies. The overall magnitude of the W isotope variations decreases in the order CI1 > CM2 > CV3. This can be interpreted as the progressive thermal destruction of an initially homogeneous mixture of presolar grains by parent-body processing. However, not only the magnitude but also the W anomaly patterns of the three chondrites are different. In particular leach step 2, that employs nitric acid, reveals a s-deficit signature for Murchison, but a s-excess for Orgueil and Allende. This could be the result of redistribution of anomalous W into a new phase by parent-body alteration, or, the fingerprint of dust processing in the solar nebula. Given that the thermal and aqueous alteration of Murchison is between the CI and CV3 chondrites, parent-body processing is probably

  10. Occurrence of halogenated alkaloids.

    PubMed

    Gribble, Gordon W

    2012-01-01

    Once considered to be isolation artifacts or chemical "mistakes" of nature, the number of naturally occurring organohalogen compounds has grown from a dozen in 1954 to >5000 today. Of these, at least 25% are halogenated alkaloids. This is not surprising since nitrogen-containing pyrroles, indoles, carbolines, tryptamines, tyrosines, and tyramines are excellent platforms for biohalogenation, particularly in the marine environment where both chloride and bromide are plentiful for biooxidation and subsequent incorporation into these electron-rich substrates. This review presents the occurrence of all halogenated alkaloids, with the exception of marine bromotyrosines where coverage begins where it left off in volume 61 of The Alkaloids. Whereas the biological activity of these extraordinary compounds is briefly cited for some examples, a future volume of The Alkaloids will present full coverage of this topic and will also include selected syntheses of halogenated alkaloids. Natural organohalogens of all types, especially marine and terrestrial halogenated alkaloids, comprise a rapidly expanding class of natural products, in many cases expressing powerful biological activity. This enormous proliferation has several origins: (1) a revitalization of natural product research in a search for new drugs, (2) improved compound characterization methods (multidimensional NMR, high-resolution mass spectrometry), (3) specific enzyme-based and other biological assays, (4) sophisticated collection methods (SCUBA and remote submersibles for deep ocean marine collections), (5) new separation and purification techniques (HPLC and countercurrent separation), (6) a greater appreciation of traditional folk medicine and ethobotany, and (7) marine bacteria and fungi as novel sources of natural products. Halogenated alkaloids are truly omnipresent in the environment. Indeed, one compound, Q1 (234), is ubiquitous in the marine food web and is found in the Inuit from their diet of whale

  11. Halogenated solvent remediation

    DOEpatents

    Sorenson, Jr., Kent S.

    2008-11-11

    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.

  12. Halogenated solvent remediation

    DOEpatents

    Sorenson, Kent S.

    2004-08-31

    Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. A preferred method includes adding a composition to the ground water wherein the composition is an electron donor for microbe-mediated reductive dehalogenation of the halogenated solvents and enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative compositions effective in these methods include surfactants such as 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. Especially preferred compositions for use in these methods include lactic acid, salts of lactic acid, such as sodium lactate, lactate esters, and mixtures thereof. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the composition.

  13. Extraterrestrial Nucleobases in Carbonaceous Chondrites

    NASA Astrophysics Data System (ADS)

    Martins, Z.; Botta, O.; Fogel, M.; Sephton, M.; Glavin, D.; Watson, J.; Dworkin, J.; Schwartz, A.; Ehrenfreund, P.

    . Our stable carbon isotope measurements clearly demonstrate that the nucleobases in the Murchison meteorite are indigenous to the meteorite, and clearly differ from the values determined for the terrestrial nucleobases measured in the soil collected at the impact site. These results support the hypothesis that nucleobases were exogenously delivered to the early Earth, and may have been important for the prebiotic chemistry on our young planet. With regard to the detection of traces of life on other planets such as Mars it is essential to characterize organic materials that have been exogenously delivered to the early planets. The analysis of the composition and isotopic fractionation of extraterrestrial material using complementary techniques can provide crucial insights into the formation of our Solar System, extraterrestrial delivery processes and subsequent addition and incorporation into the carbonaceous material available on the young planets. Ultimately, these parameters form an essential reference point for interpreting biosignatures that may be left in the ancient rock record on a planetary body. References: [1] Hayatsu R. et al. 1975. Geochimica et Cosmochimica Acta 39: 471- 488. [2] Folsome C. E. et al. 1971. Nature 232: 108-109. [3] Stoks P. G. & Schwartz A. W. 1979. Nature 282: 709-710. [4] Stoks P.G. & Schwartz A. W. 1981. Geochimica et Cosmochimica Acta 45: 563-569. [5] Shimoyama A. et al. 1990. Geochemical Journal 24: 343-348. [6] Martins Z. et al. 2004. Meteoritics & Planetary Science 39: A5145. 2

  14. Halogenation of cobalt dicarbollide

    DOEpatents

    Hurlburt, P.K.; Abney, K.D.; Kinkead, S.A.

    1997-05-20

    A method for selectively adding chlorine, bromine, or iodine to cobalt dicarbollide anions by means of electrophilic substitution reactions. Halogens are added only to the B10 and B10{prime} positions of the anion. The process involves use of hypohalous acid or N-halosuccinimide or gaseous chlorine in the presence of iron. 1 fig.

  15. Halogenation of cobalt dicarbollide

    DOEpatents

    Hurlburt, Paul K.; Abney, Kent D.; Kinkead, Scott A.

    1997-01-01

    A method for selectively adding chlorine, bromine, or iodine to cobalt dicarbollide anions by means of electrophilic substitution reactions. Halogens are added only to the B10 and B10' positions of the anion. The process involves use of hypohalous acid or N-halosuccinimide or gaseous chlorine in the presence of iron.

  16. Carbonaceous film coating

    DOEpatents

    Maya, Leon

    1989-01-01

    A method of making a carbonaceous film comprising heating tris(1,3,2-benzodiazaborolo)borazine or dodecahydro tris[1,3,2]diazaborine[1,2-a:1'2'-c:1"2"-e]borazine in an inert atmosphere in the presence of a substrate to a temperature at which the borazine compound decomposes, and the decomposition products deposit onto the substrate to form a thin, tenacious, highly reflective conductive coating having a narrow band gap which is susceptible of modification and a relatively low coefficient of friction.

  17. Carbonaceous film coating

    DOEpatents

    Maya, L.

    1988-04-27

    A method of making a carbonaceous film comprising heating tris(1,3,2-benzodiazaborolo)borazine or dodecahydro tris(1,3,2)diazaborine(1,2-a:1'2'-c:1''2''-e)borazine in an inert atmosphere in the presence of a substrate to a temperature at which the borazine compound decomposes, and the decomposition products deposit onto the substrate to form a thin, tenacious, highly reflective conductive coating having a narrow band gap which is susceptible of modification and a relatively low coefficient of friction.

  18. Halogen Chemistry on Catalytic Surfaces.

    PubMed

    Moser, Maximilian; Pérez-Ramírez, Javier

    2016-01-01

    Halogens are key building blocks for the manufacture of high-value products such as chemicals, plastics, and pharmaceuticals. The catalytic oxidation of HCl and HBr is an attractive route to recover chlorine and bromine in order to ensure the sustainability of the production processes. Very few materials withstand the high corrosiveness and the strong exothermicity of the reactions and among them RuO2 and CeO2-based catalysts have been successfully applied in HCl oxidation. The search for efficient systems for HBr oxidation was initiated by extrapolating the results of HCl oxidation based on the chemical similarity of these reactions. Interestingly, despite its inactivity in HCl oxidation, TiO2 was found to be an outstanding HBr oxidation catalyst, which highlighted that the latter reaction is more complex than previously assumed. Herein, we discuss the results of recent comparative studies of HCl and HBr oxidation on both rutile-type (RuO2, IrO2, and TiO2) and ceria-based catalysts using a combination of advanced experimental and theoretical methods to provide deeper molecular-level understanding of the reactions. This knowledge aids the design of the next-generation catalysts for halogen recycling.

  19. Tropospheric Halogen Chemistry

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

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

  20. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... halogen scrubber or other halogen reduction technique used to reduce the vent stream halogen atom mass... subpart shall determine the halogen atom mass emission rate prior to the combustion device according...

  1. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... halogen scrubber or other halogen reduction technique used to reduce the vent stream halogen atom mass... subpart shall determine the halogen atom mass emission rate prior to the combustion device according...

  2. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... halogen scrubber or other halogen reduction technique used to reduce the vent stream halogen atom mass... subpart shall determine the halogen atom mass emission rate prior to the combustion device according...

  3. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... halogen scrubber or other halogen reduction technique used to reduce the vent stream halogen atom mass... subpart shall determine the halogen atom mass emission rate prior to the combustion device according...

  4. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... halogen scrubber or other halogen reduction technique used to reduce the vent stream halogen atom mass... subpart shall determine the halogen atom mass emission rate prior to the combustion device according...

  5. Electrorheological Behavior of Carbonaceous Particle-Based Suspensions

    NASA Astrophysics Data System (ADS)

    Kim, J. W.; Choi, H. J.; Yoon, S. H.; Jhon, M. S.

    Using three different carbonaceous particles, we investigated the electrical and rheological properties of several ER fluids. Each of the carbonaceous particles, prepared from different treatment methods, possesses a different oxygen content or degree of crystallinity. These materials were prepared from mesophase pitch and were cationically polymerized with naphthalene and HF/BF3 at high temperature (500~700°C). Special focus was placed on the variables affecting ER properties, including current density, temperature, electric field strength, and volume fraction of the particles. Rheological properties were measured by a rotational rheometer equipped with a high voltage generator. To investigate the durability of the carbonaceous ER fluids, we also measured changes in shear stress, shear viscosity, and current density at the share rate of 50 sec-1 and different temperatures (from 20 to 100°C). Good thermal and electrical stability of the carbonaceous particle-based ER suspensions were observed.

  6. [Halogens: discoveries of pharmacists].

    PubMed

    Rabiant, J

    2008-01-01

    The discovery of four halogens is due to pharmacists. Chlorine was isolated by Carl Wilhem Scheele, a Swedish who was first an assistant to a pharmacist, then a pharmacist himself. Bernard Courtois, a pharmacist under the First Empire, the son of a saltpetre worker isolated iodine in I811, after a modification of the ancestral production protocol of potassium nitrate, which is the major component of the gunpowder: he replaced wood ashes by varech ashes which are less expensive. Antoine Jerôme Balard was still an assistant in chemistry and physics when he discovered bromine in the residues of the salt marshes. He became soon after a pharmacist and started a famous career as then he became Professor in the College de France and General Inspector of Higher Education. The last halogen: fluorine was isolated by Henri Moissan who received the Nobel Prize of Chemistry. The discovery will be the subject of our next communication.

  7. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 16 2013-07-01 2013-07-01 false Halogen scrubbers and other halogen... Routing to a Fuel Gas System or a Process § 65.154 Halogen scrubbers and other halogen reduction devices. (a) Halogen scrubber and other halogen reduction device equipment and operating requirements. (1)...

  8. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 15 2010-07-01 2010-07-01 false Halogen scrubbers and other halogen... Routing to a Fuel Gas System or a Process § 65.154 Halogen scrubbers and other halogen reduction devices. (a) Halogen scrubber and other halogen reduction device equipment and operating requirements. (1)...

  9. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 16 2012-07-01 2012-07-01 false Halogen scrubbers and other halogen... Routing to a Fuel Gas System or a Process § 65.154 Halogen scrubbers and other halogen reduction devices. (a) Halogen scrubber and other halogen reduction device equipment and operating requirements. (1)...

  10. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 16 2014-07-01 2014-07-01 false Halogen scrubbers and other halogen... Routing to a Fuel Gas System or a Process § 65.154 Halogen scrubbers and other halogen reduction devices. (a) Halogen scrubber and other halogen reduction device equipment and operating requirements. (1)...

  11. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 15 2011-07-01 2011-07-01 false Halogen scrubbers and other halogen... Routing to a Fuel Gas System or a Process § 65.154 Halogen scrubbers and other halogen reduction devices. (a) Halogen scrubber and other halogen reduction device equipment and operating requirements. (1)...

  12. Halogen Chemistry in the CMAQ Model

    EPA Science Inventory

    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...

  13. The Magnetization of Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Herndon, James Herndon

    1974-01-01

    Alternating field demagnetization experiments have been conducted on representative samples of the carbonaceous meteorites (carbonaceous chondrites and ureilites). The results indicate that many, if not all, of these meteorites possess an intense and stable magnetic moment of extraterrestrial origin. Thermomagnetic analyses have been conducted on samples of all known carbonaceous meteorites. In addition to yielding quantitative magnetite estimates, these studies indicate the presence of a thermally unstable component, troilite, which reacts with gaseous oxygen to form magnetite. It is proposed that the magnetite found in some carbonaceous chondrites resulted from the oxidation of troilite during the early history of the solar system. The formation of pyrrhotite is expected as a natural consequence of magnetite formation via this reaction. Consideration is given to the implications of magnetite formation on paleointensity studies.

  14. Carbonaceous pellets and method of pelletizing

    SciTech Connect

    Dondelewski, M.A.

    1982-11-02

    A method is claimed for pelletizing carbonaceous materials including bonding coal fines and lignite coal with a polymeric hydrocarbon binder having reactive sites thereon. For example, with tall oil pitch and the like, in the case of coal, the binder is applied by slurrying the fine coal with the pitch. In the case of lignite, the binder is directly applied to the pulverized material. By action of rolling and tumbling, for example, large agglomerates are formed. With drying and heating, strong water-resistant pellets are formed which have the extremely desirable property of being easily repulverized.

  15. Microfossils in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Hoover, Richard B.

    2009-01-01

    Microfossils of large filamentous trichomic prokaryotes have been detected during in-situ investigations of carbonaceous meteorites. This research has been carried out using the Field Emission Scanning Electron Microscope (FESEM) to examine freshly fractured interior surfaces of the meteorites. The images obtained reveal that many of these remains are embedded in the meteorite rock matrix. Energy Dispersive X-Ray Spectroscopy (EDS) studies establish that the filamentous microstructures have elemental compositions consistent with the meteorite matrix, but are often encased within carbon-rich electron transparent sheath-like structures infilled with magnesium sulfate. This is consistent with the taphonomic modes of fossilization of cyanobacteria and sulphur bacteria, since the life habits and processes of these microorganisms frequently result in distinctive chemical biosignatures associated with the properties of their cell-walls, trichomes, and the extracellular polymeric substances (EPS) of the sheath. In this paper the evidence for biogenicity presented includes detailed morphological and morphometric data consistent with known characteristics of uniseriate and multiseriate cyanobacteria. Evidence for indigeneity includes the embedded nature of the fossils and elemental compositions inconsistent with modern biocontaminants.

  16. Gasification of carbonaceous solids

    DOEpatents

    Coates, Ralph L.

    1976-10-26

    A process and apparatus for converting coal and other carbonaceous solids to an intermediate heating value fuel gas or to a synthesis gas. A stream of entrained pulverized coal is fed into the combustion stage of a three-stage gasifier along with a mixture of oxygen and steam at selected pressure and temperature. The products of the combustion stage pass into the second or quench stage where they are partially cooled and further reacted with water and/or steam. Ash is solidified into small particles and the formation of soot is suppressed by water/steam injections in the quench stage. The design of the quench stage prevents slag from solidifying on the walls. The products from the quench stage pass directly into a heat recovery stage where the products pass through the tube, or tubes, of a single-pass, shell and tube heat exchanger and steam is generated on the shell side and utilized for steam feed requirements of the process.

  17. Metal halogen battery system with multiple outlet nozzle for hydrate

    DOEpatents

    Bjorkman, Jr., Harry K.

    1983-06-21

    A metal halogen battery system, including at least one cell having a positive electrode and a negative electrode contacted by aqueous electrolyte containing the material of said metal and halogen, store means whereby halogen hydrate is formed and stored as part of an aqueous material, means for circulating electrolyte through the cell and to the store means, and conduit means for transmitting halogen gas formed in the cell to a hydrate former whereby the hydrate is formed in association with the store means, said store means being constructed in the form of a container which includes a filter means, said filter means being inoperative to separate the hydrate formed from the electrolyte, said system having, a hydrate former pump means associated with the store means and being operative to intermix halogen gas with aqueous electrolyte to form halogen hydrate, said hydrate former means including, multiple outlet nozzle means connected with the outlet side of said pump means and being operative to minimize plugging, said nozzle means being comprised of at least one divider means which is generally perpendicular to the rotational axes of gears within the pump means, said divider means acting to divide the flow from the pump means into multiple outlet flow paths.

  18. Crystal engineering through halogen bonding

    NASA Astrophysics Data System (ADS)

    Walsh, Rosa Daneen Bailey

    Crystal engineering has been defined as "the understanding of intermolecular interactions in the context of crystal packing and in the utilization of such understanding in the design of new solids with desired physical and chemical properties." The field of crystal engineering is growing rapidly and is generally centered on the use of hydrogen bonding or coordination polymers in the design and synthesis of new materials. Other interactions, such as halogen bonding also lend themselves to crystal design. In halogen-bonding, donation of a lone pair of electrons into the sigma and sigma* orbitals of an acceptor molecule, like elemental iodine or bromine, allows for relatively strong and highly directional interactions. Charge-transfer interactions involving aromatic nitrogen heterocycles and diiodine (I 2) will be discussed. With weaker donors, such as pyrazine, we have prepared target complexes with infinite chain structures consisting of alternating donor and acceptor molecules. But with stronger donors, such as 4,4 '-bipyridine, only simple adducts are formed. Strong donation at one end of the I2 reduces the Lewis acid character at the other end and extended interactions do not form. With some strong donors, reduction in Lewis acidity occurs to the point that the I2 exhibits amphoteric behavior. In these systems, the non-complexed end serves as a Lewis base to a second-bridging I2 molecule to form neutral polyiodine systems. To reduce electronic communication between the two iodine atoms, organoiodides, in which an organic spacer has been inserted between the two iodine atoms, have been employed. The organic spacer also offers a manifold for adjusting the Lewis acidity of the acceptors in these compounds. Acceptors involving more than two iodines provide the possibility of multidirectional extended interactions leading to interesting layered or network solids. Useful acceptors include 1,4-diiodobenzene, 4,4'-diiodobiphenyl, 1,4-diiodotetraflurobenzene, and

  19. Labile trace elements in carbonaceous chondrites - A survey

    NASA Technical Reports Server (NTRS)

    Xiao, Xiaoyue; Lipschutz, Michael E.

    1992-01-01

    Data are presented on 14 trace elements, including Co, Au, Ga, Rb, Sb, Ag, Se, Cs, Te, Zn, Cd, Bi, Tl, and In (nearly all of which are moderately or highly labile in meteorites), obtained by radiochemical neutron activation analyses of 42 C2-C6 chondrites, all but three from Antarctica. The data indicate that carbonaceous chondrites of petrographic types 2-6 define compositional continua. It is suggested that carbonaceous C2-C6 chondrites may reflect a mixture of material that formed at low temperatures and that contained cosmic levels of highly labile elements, with material that was devoid of them.

  20. Data for fire hazard assessment of selected non-halogenated and halogenated fire retardants: Report of Test FR 3983

    NASA Astrophysics Data System (ADS)

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

    1991-10-01

    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.

  1. Results of reconnaissance for uraniferous coal, lignite, and carbonaceous shale in western Montana

    USGS Publications Warehouse

    Hail, William J.; Gill, James R.

    1952-01-01

    A reconnaissance search for uraniferous lignite and carbonaceous shale was made in western Montana and adjacent parts of Idaho during the summer of 1951. Particular emphasis in the examination was placed on coal and carbonaceous shale associated with volcanic rocks, as volcanic rocks in many area appear to have released uranium to circulating ground water from which it was concentrated in carbonaceous material. Twenty-two area in Montana and one area of Idaho were examine. The coal in five of these area is of Cretaceous age. The coal and carbonaceous shale in the remaining 18 area occur in Tertiary "lake-bed" deposits of Oligocene and younger age. Both the Cretaceous and Tertiary coal and carbonaceous shale are associated with contemporaneous or younger volcanic rocks and pyroclastic sequences. A sample of carbonaceous shale from the Prickly Pear Valley northeast of Helena, Montana, contained 0.013 percent uranium. A sample of carbonaceous shale from the Flint Creek Valley southwest of Drummond, Montana, contained 0.006 percent uranium. All other samples of both Cretaceous and Tertiary coal and carbonaceous shale were essentially non-radioactive. No further work is planned on the Cretaceous and Tertiary coal and carbonaceous shale in western Montana. A few localities in Idaho will be visited in the course of other work.

  2. Halogen substituted quinolylsalicylaldimines: Four halogens three structural types

    NASA Astrophysics Data System (ADS)

    Sirirak, Jitnapa; Phonsri, Wasinee; Harding, David J.; Harding, Phimphaka; Phommon, Pimonrat; Chaoprasa, Wannapa; Hendry, Rebecca M.; Roseveare, Thomas M.; Adams, Harry

    2013-03-01

    A series of halogen substituted 5-X-N-(8-quinolyl)salicylaldimines (HqsalX, X = F 1, Cl 2, Br 3 and I 4) have been prepared, characterized and the crystal structures of all four are reported. The compounds form stacks, in most cases held together either by π-π or lone pair(N)-π interactions. All compounds exhibit an intramolecular Osbnd H⋯N hydrogen bond with 2 also displaying an intermolecular Osbnd H⋯O hydrogen bonding square. Additional Csbnd H⋯N/O and Csbnd H⋯π interactions serve to link neighbouring HqsalX molecules with 3 and 4 forming narcissistic dimers. While the halogen has a profound effect on the structure it is not involved in either hydrogen or halogen bonding in any of the structures. DFT calculations suggest that the conformational preference is dependent on the halogen.

  3. Shock metamorphism of carbonaceous chondrites

    NASA Technical Reports Server (NTRS)

    Scott, Edward R. D.; Keil, Klaus; Stoeffler, Dieter

    1992-01-01

    Shock effects were studied in 69 carbonaceous chondrites, including CM2, CO3, CV3, ungrouped C2-C4, and CK4-6 chondrites, using optical microscopy of thin sections. It is shown that the classification scheme of Stoeffler et al. (1991) for the progressive stages of shock metamorphism in ordinary chondrites is also applicable to carbonaceous chondrites. On the basis of shock effects in olivine, the 69 carbonaceous chondrites could be assigned to four shock stage, S1 to S4. The CM2 and CO3 groups were found to be the least shocked chondrite groups, whereas the CK4-6 and CV3 were the most strongly shocked groups.

  4. Carbonaceous Dye-Sensitized Solar Cell Photoelectrodes.

    PubMed

    Batmunkh, Munkhbayar; Biggs, Mark J; Shapter, Joseph G

    2015-03-01

    High photovoltaic efficiency is one of the most important keys to the commercialization of dye sensitized solar cells (DSSCs) in the quickly growing renewable electricity generation market. The heart of the DSSC system is a wide bandgap semiconductor based photoelectrode film that helps to adsorb dye molecules and transport the injected electrons away into the electrical circuit. However, charge recombination, poor light harvesting efficiency and slow electron transport of the nanocrystalline oxide photoelectrode film are major issues in the DSSC's performance. Recently, semiconducting composites based on carbonaceous materials (carbon nanoparticles, carbon nanotubes (CNTs), and graphene) have been shown to be promising materials for the photoelectrode of DSSCs due to their fascinating properties and low cost. After a brief introduction to development of nanocrystalline oxide based films, this Review outlines advancements that have been achieved in the application of carbonaceous-based materials in the photoelectrode of DSSCs and how these advancements have improved performance. In addition, several of the unsolved issues in this research area are discussed and some important future directions are also highlighted.

  5. Carbonaceous chondrites as bioengineered comets

    NASA Astrophysics Data System (ADS)

    Sheldon, Robert B.; Hoover, Richard

    2012-10-01

    The discovery of microfossils on carbonaceous meteorites has electrified the public with the first concrete evidence of extraterrestrial biology. But how these organisms colonized and grew on the parent body-the comet-remains a mystery. We report on several features of cyanobacteria that permit them to bioengineer comets, as well as a tantalizing look at interplanetary uses for magnetite framboids that are found in abundance on carbonaceous chondrites. We argue that these structures provide important directionality and energy harvesting features similar to magnetotactic bacteria found on Earth.

  6. RESIDUAL RISK ASSESSMENT: HALOGENATED SOLVENTS

    EPA Science Inventory

    This source category previously subjected to a technology-based standard will be examined to determine if health or ecological risks are significant enough to warrant further regulation for Halogenated Solvent Degreasing Facilities. These assessments utilize existing models and d...

  7. Aqueous activity on asteroids - Evidence from carbonaceous meteorites

    NASA Technical Reports Server (NTRS)

    Kerridge, J. F.; Bunch, T. E.

    1979-01-01

    Carbonaceous chondrites of groups CI and CM were formed by impact brecciation and aqueous alteration of earlier generations of mineral phases within the surface regions of two or more parent bodies. Those parent bodies were probably asteroids, rather than comets, although a problem still exists in delivering such material safely to earth. Aqueous activity may have been widespread on asteroids.

  8. The Halogen Occultation Experiment

    NASA Technical Reports Server (NTRS)

    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.

    1993-01-01

    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.

  9. Halogenated graphenes: rapidly growing family of graphene derivatives.

    PubMed

    Karlický, František; Kumara Ramanatha Datta, Kasibhatta; Otyepka, Michal; Zbořil, Radek

    2013-08-27

    Graphene derivatives containing covalently bound halogens (graphene halides) represent promising two-dimensional systems having interesting physical and chemical properties. The attachment of halogen atoms to sp(2) carbons changes the hybridization state to sp(3), which has a principal impact on electronic properties and local structure of the material. The fully fluorinated graphene derivative, fluorographene (graphene fluoride, C1F1), is the thinnest insulator and the only stable stoichiometric graphene halide (C1X1). In this review, we discuss structural properties, syntheses, chemistry, stabilities, and electronic properties of fluorographene and other partially fluorinated, chlorinated, and brominated graphenes. Remarkable optical, mechanical, vibrational, thermodynamic, and conductivity properties of graphene halides are also explored as well as the properties of rare structures including multilayered fluorinated graphenes, iodine-doped graphene, and mixed graphene halides. Finally, patterned halogenation is presented as an interesting approach for generating materials with applications in the field of graphene-based electronic devices.

  10. Results of reconnaissance for uraniferous coal, lignite, and carbonaceous shale in western Montana

    USGS Publications Warehouse

    Hail, William James; Gill, James R.

    1953-01-01

    A reconnaissance search for uraniferous lignite and carbonaceous shale was made in western Montana and adjacent parts of Idaho during the summer of 1951. Particular emphasis in the examination was placed on coal and carbonaceous shale associated with volcanic rocks, as volcanic rocks in many areas appear to have released uranium to circulating ground water from which it was ,concentrated in carbonaceous material. Twenty-two areas in Montana and one area in Idaho were examined. The coal in five of these areas is of Cretaceous age. The coal and carbonaceous shale in the remaining 18 areas occur in Tertiary 'fake-bed' deposits of Oligocene and younger age. Both the Cretaceous and Tertiary coal and carbonaceous shale are associated with contemporaneous or younger volcanic rocks and pyrociastic sequences.

  11. Reactive halogen chemistry in the troposphere.

    PubMed

    Saiz-Lopez, Alfonso; von Glasow, Roland

    2012-10-07

    Halogen chemistry is well known for ozone destruction in the stratosphere, however reactive halogens also play an important role in the chemistry of the troposphere. In the last two decades, an increasing number of reactive halogen species have been detected in a wide range of environmental conditions from the polar to the tropical troposphere. Growing observational evidence suggests a regional to global relevance of reactive halogens for the oxidising capacity of the troposphere. This critical review summarises our current understanding and uncertainties of the main halogen photochemistry processes, including the current knowledge of the atmospheric impact of halogen chemistry as well as open questions and future research needs.

  12. Keto-acids in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Cooper, G.; Chang, P. M.; Dugas, A.; Byrd, A.; Chang, P. M.; Washington, N.

    2005-01-01

    The Murchison and Murray meteorites are the best-characterized carbonaceous meteorites with respect to organic chemistry and are generally used as references for organic compounds in extraterrestrial material. Among the classes of organic compounds found in these meteorites are amino acids, carboxylic acids, hydroxy acids, purines, and pyrimidines. Such compounds, important in contemporary biochemistry, are thought to have been delivered to the early Earth in asteroids and comets and may have played a role in early life and/or the origin of life. Absent among (today's) critically important biological compounds reported in carbonaceous meteorites are keto acids, i.e., pyruvic acid, acetoacetic acid, and higher homologs. These compounds are key intermediates in such critical processes as glycolysis and the citric acid cycle. In this study several individual meteoritic keto acids were identified by gas chromatography-mass spectrometry (GC-MS) (see figure below). All compounds were identified as their trimethylsilyl (TMS), isopropyl ester (ISP), and tert-butyldimethylsilyl (tBDMS) derivatives. In general, the compounds follow the abiotic synthesis pattern of other known meteorite classes of organic compounds [1,2]: a general decrease in abundance with increasing carbon number within a class of compounds and many, if not all, possible isomers present at a given carbon number. The majority of the shown compounds was positively identified by comparison of their mass spectra to commercially available standards or synthesized standards.

  13. Origin of organic compounds in carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Cronin, J. R.

    Carbonaceous chondrites, a class of primitive meteorite, have long been known to contain their complement of carbon largely in the form of organic, i.e., hydrocarbon-related, matter. Both discrete organic compounds and an insoluble, macromolecular material are present. Several characteristics of these materials provide evidence for their abiotic origin. The principal formation hypothesis have invoked chemistry occurring either in the solar nebula or on the parent body. However, recent stable isotope analyses of the meteorite carboxylic acids and amino acids indicate that they may be related to interstellar cloud compounds. These results suggest a formation scheme in which interstellar compounds were incorporated into the parent body and subsequently converted to the present suite of meteorite organics by the hydrothermal process believed to have formed the clay minerals of the meteorite matrix.

  14. Microporous-mesoporous carbons for energy storage synthesized by activation of carbonaceous material by zinc chloride, potassium hydroxide or mixture of them

    NASA Astrophysics Data System (ADS)

    Härmas, M.; Thomberg, T.; Kurig, H.; Romann, T.; Jänes, A.; Lust, E.

    2016-09-01

    Various electrochemical methods have been applied to establish the electrochemical characteristics of the electrical double layer capacitor (EDLC) consisting of the 1 M triethylmethylammonium tetrafluoroborate solution in acetonitrile and activated carbon based electrodes. Activated microporous carbon materials used for the preparation of electrodes have been synthesized from the hydrothermal carbonization product (HTC) prepared via hydrothermal carbonization process of D-(+)-glucose solution in H2O, followed by activation with ZnCl2, KOH or their mixture. Highest porosity and Brunauer-Emmett-Teller specific surface area (SBET = 2150 m2 g-1), micropore surface area (Smicro = 2140 m2 g-1) and total pore volume (Vtot = 1.01 cm3 g-1) have been achieved for HTC activated using KOH with a mass ratio of 1:4 at 700 °C. The correlations between SBET, Smicro, Vtot and electrochemical characteristics have been studied to investigate the reasons for strong dependence of electrochemical characteristics on the synthesis conditions of carbon materials studied. Wide region of ideal polarizability (ΔV ≤ 3.0 V), very short characteristic relaxation time (0.66 s), and high specific series capacitance (134 F g-1) have been calculated for the mentioned activated carbon material, demonstrating that this system can be used for completing the EDLC with high energy- and power densities.

  15. Effects of chemical functional groups on elemental mercury adsorption on carbonaceous surfaces.

    PubMed

    Liu, Jing; Cheney, Marcos A; Wu, Fan; Li, Meng

    2011-02-15

    A systematic theoretical study using density functional theory is performed to provide molecular-level understanding of the effects of chemical functional groups on mercury adsorption on carbonaceous surfaces. The zigzag and armchair edges were used in modeling the carbonaceous surfaces to simulate different adsorption sites. The edge atoms on the upper side of the models are unsaturated to simulate active sites. All calculations (optimizations, energies, and frequencies) were made at B3PW91 density functional theory level, using RCEP60VDZ basis set for mercury and 6-31G(d) pople basis set for other atoms. The results indicate that the embedding of halogen atom can increase the activity of its neighboring site which in turn increases the adsorption capacity of the carbonaceous surface for Hg(0). The adsorption belongs to chemisorptions, which is in good agreement with the experimental results. For the effects of oxygen functional groups, lactone, carbonyl and semiquinone favor Hg(0) adsorption because they increase the neighboring site's activity for mercury adsorption. On the contrary, phenol and carboxyl functional groups show a physisorption of Hg(0), and reduce Hg capture. This result can explain the seemingly conflicting experimental results reported in the literature concerning the influence of oxygen functional groups on mercury adsorption on carbonaceous surface.

  16. Carbonaceous Matter in Growing Nanoparticles

    NASA Astrophysics Data System (ADS)

    Johnston, M. V.; Stangl, C. M.; Horan, A. J.

    2015-12-01

    Atmospheric nanoparticles constitute the greatest portion of ambient aerosol loading by number. A major source of atmospheric nanoparticles is new particle formation (NPF), a gas to particle conversion process whereby clusters nucleate from gas phase precursors to form clusters on the order of one or a few nanometers and then grow rapidly to climatically relevant sizes. A substantial fraction of cloud condensation nuclei (CCN) are thought to arise from NPF. In order to better predict the frequency, growth rates, and climatic impacts of NPF, knowledge of the chemical mechanisms by which nucleated nanoparticles grow is needed. The two main contributors to particle growth are (neutralized) sulfate and carbonaceous matter. Particle growth by sulfuric acid condensation is generally well understood, though uncertainty remains about the extent of base neutralization and the relative roles of ammonia and amines. Much less is known about carbonaceous matter, and field measurements suggest that nitrogen-containing species are important. In this presentation, recent work by our group will be described that uses a combination of ambient measurements, laboratory experiments and computational work to study carbonaceous matter in growing nanoparticles. These studies span a range of particle sizes from the initial adsorption of molecules onto a nanometer-size ammonium bisulfate seed cluster to reactions in particles that are large enough to support condensed-phase chemistry.

  17. Fine tuning of graphene properties by modification with aryl halogens.

    PubMed

    Bouša, D; Pumera, M; Sedmidubský, D; Šturala, J; Luxa, J; Mazánek, V; Sofer, Z

    2016-01-21

    Graphene and its derivatives belong to one of the most intensively studied materials. The radical reaction using halogen derivatives of arene-diazonium salts can be used for effective control of graphene's electronic properties. In our work we investigated the influence of halogen atoms (fluorine, chlorine, bromine and iodine) as well as their position on the benzene ring towards the electronic and electrochemical properties of modified graphenes. The electronegativity as well as the position of the halogen atoms on the benzene ring has crucial influence on graphene's properties due to the inductive and mesomeric effects. The results of resistivity measurement are in good agreement with the theoretical calculations of electron density within chemically modified graphene sheets. Such simple chemical modifications of graphene can be used for controllable and scalable synthesis of graphene with tunable transport properties.

  18. A Critical Evaluation of Interlaboratory Data on Total, Elemental, and Isotopic Carbon in the Carbonaceous Particle Reference Material, NIST SRM 1649a

    PubMed Central

    Currie, L. A.; Benner, B. A.; Kessler, J. D.; Klinedinst, D. B.; Klouda, G. A.; Marolf, J. V.; Slater, J. F.; Wise, S.A.; Cachier, H.; Cary, R.; Chow, J. C.; Watson, J.; Druffel, E. R. M.; Masiello, C. A.; Eglinton, T. I.; Pearson, A.; Reddy, C. M.; Gustafsson, Ö.; Quinn, J. G.; Hartmann, P. C.; Hedges, J. I.; Prentice, K. M.; Kirchstetter, T. W.; Novakow, T.; Puxbaum, H.; Schmid, H.

    2002-01-01

    Because of increased interest in the marine and atmospheric sciences in elemental carbon (EC), or black carbon (BC) or soot carbon (SC), and because of the difficulties in analyzing or even defining this pervasive component of particulate carbon, it has become quite important to have appropriate reference materials for intercomparison and quality control. The NIST “urban dust” Standard Reference Material® SRM 1649a is useful in this respect, in part because it comprises a considerable array of inorganic and organic species, and because it exhibits a large degree of (14C) isotopic heterogeneity, with biomass carbon source contributions ranging from about 2 % (essentially fossil aliphatic fraction) to about 32 % (polar fraction). A primary purpose of this report is to provide documentation for the new isotopic and chemical particulate carbon data for the most recent (31 Jan. 2001) SRM 1649a Certificate of Analysis. Supporting this is a critical review of underlying international intercomparison data and methodologies, provided by 18 teams of analytical experts from 11 institutions. Key results of the intercomparison are: (1) a new, Certified Value for total carbon (TC) in SRM 1649a; (2) 14C Reference Values for total carbon and a number of organic species, including for the first time 8 individual PAHs; and (3) elemental carbon (EC) Information Values derived from 13 analytical methods applied to this component. Results for elemental carbon, which comprised a special focus of the intercomparison, were quite diverse, reflecting the confounding of methodological-matrix artifacts, and methods that tended to probe more or less refractory regions of this universal, but ill-defined product of incomplete combustion. Availability of both chemical and 14C speciation data for SRM 1649a holds great promise for improved analytical insight through comparative analysis (e.g., fossil/biomass partition in EC compared to PAH), and through application of the principle of isotopic

  19. A Critical Evaluation of Interlaboratory Data on Total, Elemental, and Isotopic Carbon in the Carbonaceous Particle Reference Material, NIST SRM 1649a.

    PubMed

    Currie, L A; Benner, B A; Kessler, J D; Klinedinst, D B; Klouda, G A; Marolf, J V; Slater, J F; Wise, S A; Cachier, H; Cary, R; Chow, J C; Watson, J; Druffel, E R M; Masiello, C A; Eglinton, T I; Pearson, A; Reddy, C M; Gustafsson, Ö; Quinn, J G; Hartmann, P C; Hedges, J I; Prentice, K M; Kirchstetter, T W; Novakow, T; Puxbaum, H; Schmid, H

    2002-01-01

    Because of increased interest in the marine and atmospheric sciences in elemental carbon (EC), or black carbon (BC) or soot carbon (SC), and because of the difficulties in analyzing or even defining this pervasive component of particulate carbon, it has become quite important to have appropriate reference materials for intercomparison and quality control. The NIST "urban dust" Standard Reference Material(®) SRM 1649a is useful in this respect, in part because it comprises a considerable array of inorganic and organic species, and because it exhibits a large degree of ((14)C) isotopic heterogeneity, with biomass carbon source contributions ranging from about 2 % (essentially fossil aliphatic fraction) to about 32 % (polar fraction). A primary purpose of this report is to provide documentation for the new isotopic and chemical particulate carbon data for the most recent (31 Jan. 2001) SRM 1649a Certificate of Analysis. Supporting this is a critical review of underlying international intercomparison data and methodologies, provided by 18 teams of analytical experts from 11 institutions. Key results of the intercomparison are: (1) a new, Certified Value for total carbon (TC) in SRM 1649a; (2) (14)C Reference Values for total carbon and a number of organic species, including for the first time 8 individual PAHs; and (3) elemental carbon (EC) Information Values derived from 13 analytical methods applied to this component. Results for elemental carbon, which comprised a special focus of the intercomparison, were quite diverse, reflecting the confounding of methodological-matrix artifacts, and methods that tended to probe more or less refractory regions of this universal, but ill-defined product of incomplete combustion. Availability of both chemical and (14)C speciation data for SRM 1649a holds great promise for improved analytical insight through comparative analysis (e.g., fossil/biomass partition in EC compared to PAH), and through application of the principle of

  20. Photoproduction of halogens using platinized TiO2

    NASA Technical Reports Server (NTRS)

    Reichman, B.; Byvik, C. E.

    1981-01-01

    Unlike electrolysis of halide salt solutions, technique using powdered titanium dioxide catalyst requires no external power other than ultraviolet radiation source. Semiconductor powders photocatalyze and photosynthesize many useful reactions; applications are production of halogen molecules, oxidation of hazardous materials in wastewater, and conversion of carbon monoxide to carbon dioxide.

  1. Fine tuning of graphene properties by modification with aryl halogens

    NASA Astrophysics Data System (ADS)

    Bouša, D.; Pumera, M.; Sedmidubský, D.; Šturala, J.; Luxa, J.; Mazánek, V.; Sofer, Z.

    2016-01-01

    Graphene and its derivatives belong to one of the most intensively studied materials. The radical reaction using halogen derivatives of arene-diazonium salts can be used for effective control of graphene's electronic properties. In our work we investigated the influence of halogen atoms (fluorine, chlorine, bromine and iodine) as well as their position on the benzene ring towards the electronic and electrochemical properties of modified graphenes. The electronegativity as well as the position of the halogen atoms on the benzene ring has crucial influence on graphene's properties due to the inductive and mesomeric effects. The results of resistivity measurement are in good agreement with the theoretical calculations of electron density within chemically modified graphene sheets. Such simple chemical modifications of graphene can be used for controllable and scalable synthesis of graphene with tunable transport properties.Graphene and its derivatives belong to one of the most intensively studied materials. The radical reaction using halogen derivatives of arene-diazonium salts can be used for effective control of graphene's electronic properties. In our work we investigated the influence of halogen atoms (fluorine, chlorine, bromine and iodine) as well as their position on the benzene ring towards the electronic and electrochemical properties of modified graphenes. The electronegativity as well as the position of the halogen atoms on the benzene ring has crucial influence on graphene's properties due to the inductive and mesomeric effects. The results of resistivity measurement are in good agreement with the theoretical calculations of electron density within chemically modified graphene sheets. Such simple chemical modifications of graphene can be used for controllable and scalable synthesis of graphene with tunable transport properties. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06295k

  2. Metal halogen battery construction with improved technique for producing halogen hydrate

    DOEpatents

    Fong, Walter L.; Catherino, Henry A.; Kotch, Richard J.

    1983-01-01

    An improved electrical energy storage system comprising, at least one cell having a positive electrode and a negative electrode separated by aqueous electrolyte, a store means wherein halogen hydrate is formed and stored as part of an aqueous material having a liquid level near the upper part of the store, means for circulating electrolyte through the cell, conduit means for transmitting halogen gas formed in the cell to a hydrate forming apparatus associated with the store, said hydrate forming apparatus including, a pump to which there is introduced quantities of the halogen gas and chilled water, said pump being located in the store and an outlet conduit leading from the pump and being substantially straight and generally vertically disposed and having an exit discharge into the gas space above the liquid level in the store, and wherein said hydrate forming apparatus is highly efficient and very resistant to plugging or jamming. The disclosure also relates to an improved method for producing chlorine hydrate in zinc chlorine batteries.

  3. Modeling orbital gamma-ray spectroscopy experiments at carbonaceous asteroids

    NASA Astrophysics Data System (ADS)

    Lim, Lucy F.; Starr, Richard D.; Evans, Larry G.; Parsons, Ann M.; Zolensky, Michael E.; Boynton, William V.

    2017-01-01

    To evaluate the feasibility of measuring differences in bulk composition among carbonaceous meteorite parent bodies from an asteroid or comet orbiter, we present the results of a performance simulation of an orbital gamma-ray spectroscopy (GRS) experiment in a Dawn-like orbit around spherical model asteroids with a range of carbonaceous compositions. The orbital altitude was held equal to the asteroid radius for 4.5 months. Both the asteroid gamma-ray spectrum and the spacecraft background flux were calculated using the MCNPX Monte-Carlo code. GRS is sensitive to depths below the optical surface (to ≈20-50 cm depth depending on material density). This technique can therefore measure underlying compositions beneath a sulfur-depleted (e.g., Nittler et al.) or desiccated surface layer. We find that 3σ uncertainties of under 1 wt% are achievable for H, C, O, Si, S, Fe, and Cl for five carbonaceous meteorite compositions using the heritage Mars Odyssey GRS design in a spacecraft-deck-mounted configuration at the Odyssey end-of-mission energy resolution, FWHM = 5.7 keV at 1332 keV. The calculated compositional uncertainties are smaller than the compositional differences between carbonaceous chondrite subclasses.

  4. Risk assessment for halogenated solvents

    SciTech Connect

    Travis, C.C.

    1988-01-01

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

  5. Halogen Bonding in Organic Synthesis and Organocatalysis.

    PubMed

    Bulfield, David; Huber, Stefan M

    2016-10-04

    Halogen bonding is a noncovalent interaction similar to hydrogen bonding, which is based on electrophilic halogen substituents. Hydrogen-bonding-based organocatalysis is a well-established strategy which has found numerous applications in recent years. In light of this, halogen bonding has recently been introduced as a key interaction for the design of activators or organocatalysts that is complementary to hydrogen bonding. This Concept features a discussion on the history and electronic origin of halogen bonding, summarizes all relevant examples of its application in organocatalysis, and provides an overview on the use of cationic or polyfluorinated halogen-bond donors in halide abstraction reactions or in the activation of neutral organic substrates.

  6. Reversible Capture and Release of Elemental Halogens with a Redox-Active Metal-Organic Framework.

    PubMed

    Tulchinsky, Yuri; Hendon, Christopher H; Lomachenko, Kirill A; Borfecchia, Elisa; Melot, Brent C; Hudson, Matthew R; Tarver, Jacob D; Korzynski, Maciej D; Stubbs, Amanda W; Kagan, Jacob J; Lamberti, Carlo; Brown, Craig M; Dinca, Mircea

    2017-03-28

    Extreme toxicity, corrosiveness, and volatility pose serious challenges for the safe storage and transportation of elemental chlorine and bromine, which play critical roles in the chemical industry. Solid materials capable of forming stable non-volatile compounds upon reaction with elemental halogens may partially mitigate these challenges by allowing safe halogen release on demand. Here, we demonstrate that elemental halogens quantitatively oxidize coordinatively unsaturated Co(II) ions in a robust azolate metal-organic framework (MOF) to produce an air-stable and safe-to-handle Co(III) material featuring terminal Co(III)-halogen bonds. Thermal treatment of the oxidized MOF causes homolytic cleavage of the Co(III)-halogen bonds, reduction to Co(II), and concomitant release of elemental halogens. Remarkably, the reversible chemical storage and thermal release of elemental halogens occur with no significant losses of structural integrity, the parent cobaltous MOF retaining crystallinity and porosity even after three oxidation/reduction cycles. These results highlight a material operating via redox mechanism that may find utility in the storage and capture of other noxious and corrosive gases.

  7. The micro-distribution of carbonaceous matter in the Murchison meteorite as investigated by Raman imaging.

    PubMed

    El Amri, Chahrazade; Maurel, Marie-Christine; Sagon, Gérard; Baron, Marie-Hélène

    2005-07-01

    The carbonaceous Murchison chondrite is one of the most studied meteorites. It is considered to be an astrobiology standard for detection of extraterrestrial organic matter. Considerable work has been done to resolve the elemental composition of this meteorite. Raman spectroscopy is a very suitable technique for non-destructive rapid in situ analyses to establish the spatial distribution of carbonaceous matter. This report demonstrates that Raman cartography at a resolution of 1 microm2 can be performed. Two-dimensional distribution of graphitised carbon, amorphous carbonaceous matter and minerals were obtained on 100 microm2 maps. Maps of the surface of native stones and of a powdered sample are compared. Graphitic and amorphous carbonaceous domains are found to be highly overlapping in all tested areas at the surface of the meteorite and in its interior as well. Pyroxene, olivine and iron oxide grains are embedded into this mixed carbonaceous material. The results show that every mineral grain with a size of less than a few microm2 is encased in a thin carbonaceous matrix, which accounts for only 2.5 wt.%. This interstitial matter sticks together isolated mineral crystallites or concretions, including only very few individualized graphitised grains. Grinding separates the mineral particles but most of them retain their carbonaceous coating. This Raman study complements recent findings deduced from other spatial analyses performed by microprobe laser-desorption laser-ionisation mass spectrometry (microL2MS), transmission electron microscopy (TEM) and scanning transmission X-ray microscopy (STXM).

  8. Synthetic carbonaceous fuels and feedstocks

    DOEpatents

    Steinberg, Meyer

    1980-01-01

    This invention relates to the use of a three compartment electrolytic cell in the production of synthetic carbonaceous fuels and chemical feedstocks such as gasoline, methane and methanol by electrolyzing an aqueous sodium carbonate/bicarbonate solution, obtained from scrubbing atmospheric carbon dioxide with an aqueous sodium hydroxide solution, whereby the hydrogen generated at the cathode and the carbon dioxide liberated in the center compartment are combined thermocatalytically into methanol and gasoline blends. The oxygen generated at the anode is preferably vented into the atmosphere, and the regenerated sodium hydroxide produced at the cathode is reused for scrubbing the CO.sub.2 from the atmosphere.

  9. Conversion of raw carbonaceous fuels

    DOEpatents

    Cooper, John F.

    2007-08-07

    Three configurations for an electrochemical cell are utilized to generate electric power from the reaction of oxygen or air with porous plates or particulates of carbon, arranged such that waste heat from the electrochemical cells is allowed to flow upwards through a storage chamber or port containing raw carbonaceous fuel. These configurations allow combining the separate processes of devolatilization, pyrolysis and electrochemical conversion of carbon to electric power into a single unit process, fed with raw fuel and exhausting high BTU gases, electric power, and substantially pure CO.sub.2 during operation.

  10. Structural Perspective on Enzymatic Halogenation

    PubMed Central

    2008-01-01

    Simple halogen substituents frequently afford key structural features that account for the potency and selectivity of natural products, including antibiotics and hormones. For example, when a single chlorine atom on the antibiotic vancomycin is replaced by hydrogen, the resulting antibacterial activity decreases by up to 70% (HarrisC. M.; KannanR.; KopeckaH.; HarrisT. M.J. Am. Chem. Soc.1985, 107, 6652−6658). This Account analyzes how structure underlies mechanism in halogenases, the molecular machines designed by nature to incorporate halogens into diverse substrates. Traditional synthetic methods of integrating halogens into complex molecules are often complicated by a lack of specificity and regioselectivity. Nature, however, has developed a variety of elegant mechanisms for halogenating specific substrates with both regio- and stereoselectivity. An improved understanding of the biological routes toward halogenation could lead to the development of novel synthetic methods for the creation of new compounds with enhanced functions. Already, researchers have co-opted a fluorinase from the microorganism Streptomyces cattleya to produce 18F-labeled molecules for use in positron emission tomography (PET) (DengH.; CobbS. L.; GeeA. D.; LockhartA.; MartarelloL.; McGlincheyR. P.; O’HaganD.; OnegaM.Chem. Commun.2006, 652−654). Therefore, the discovery and characterization of naturally occurring enzymatic halogenation mechanisms has become an active area of research. The catalogue of known halogenating enzymes has expanded from the familiar haloperoxidases to include oxygen-dependent enzymes and fluorinases. Recently, the discovery of a nucleophilic halogenase that catalyzes chlorinations has expanded the repertoire of biological halogenation chemistry (DongC.; HuangF.; DengH.; SchaffrathC.; SpencerJ. B.; O’HaganD.; NaismithJ. H.Nature2004, 427, 561−56514765200). Structural characterization has provided a basis toward a mechanistic understanding of the specificity

  11. Carbonaceous matter in peridotites and basalts studied by XPS, SALI, and LEED

    SciTech Connect

    Tingle, T.N. SRI International, Menlo Park, CA ); Mathez, E.A. ); Hochella, M.F. Jr. )

    1991-05-01

    Carbonaceous matter in peridotite xenoliths and basalt from the Hualalai Volcano, in a basalt glass collected directly from an active lava lake on the east rift of Kilauea, in garnet and diopside megacrysts from the Jagersfontein kimberlite, and in gabbros from the Stillwater and Bushveld Complexes has been studied by X-ray photoelectron spectroscopy (XPS), thermal-desorption surface analysis by laser ionization (SALI), and low-energy electron diffraction (LEED). The basalt and two of the four xenoliths from Hualalai and both Jagersfontein megacrysts yielded trace quantities ({le}10 nanomoles) of organic compounds on heating to 700C. Organics were not detected in the rocks from the layered intrusions, and neither carbonaceous matter nor organics were detected in the glass from the lava lake. Where detected, organics appear to be associated with carbonaceous films on microcrack surfaces. Carbonaceous matter exists as films less than a few nm thick and particles up to 20 {mu}m across, both of which contain elements expected to be present in significant quantities in magmatic vapors, namely Si, alkalis, halogens, N, and transition metals. LEED studies suggest that the carbonaceous films are amorphous. The data suggest two possible mechanisms for the formation of the organics. One is that they are a product of abiotic heterogeneous catalysis of volcanic gas on new, chemically active mineral surfaces formed by fracturing during cooling. Alternatively, organics may have been assimilated into the volcanic gases prior to eruption and then deposited on cracks formed during eruption and cooling. In any case, there is no evidence to suggest that the organics represent laboratory or field biogenic contamination.

  12. Bacterial Paleontology and Studies of Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Gerasimenko, L. M.; Hoover, Richard B.; Rozanov, Alexei Y.; Zhegallo, E. A.; Zhmur, S. I.

    1999-01-01

    The study of the fossilization processes of modern cyanobacteria provides insights needed to recognize bacterial microfossils. The fossilization of cyanobacteria is discussed and images of recent and fossil bacteria and cyanobacteria from the Early Proterozoic to Neogene carbonaceous rocks (kerites, shungites, and black shales) and phosphorites are provided. These are compared with biomorphic microstructures and possible microfossils encountered in-situ in carbonaceous meteorites.

  13. Organic matter in carbonaceous meteorites: past, present and future research.

    PubMed

    Sephton, Mark A

    2005-12-15

    Carbonaceous meteorites are fragments of ancient asteroids that have remained relatively unprocessed since the formation of the Solar System. These carbon-rich objects provide a record of prebiotic chemical evolution and a window on the early Solar System. Many compound classes are present reflecting a rich organic chemical environment during the formation of the planets. Recent theories suggest that similar extraterrestrial organic mixtures may have acted as the starting materials for life on Earth.

  14. Organic Compounds in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Cooper, Grorge

    2001-01-01

    Carbonaceous meteorites are relatively enriched in soluble organic compounds. To date, these compounds provide the only record available to study a range of organic chemical processes in the early Solar System chemistry. The Murchison meteorite is the best-characterized carbonaceous meteorite with respect to organic chemistry. The study of its organic compounds has related principally to aqueous meteorite parent body chemistry and compounds of potential importance for the origin of life. Among the classes of organic compounds found in Murchison are amino acids, amides, carboxylic acids, hydroxy acids, sulfonic acids, phosphonic acids, purines and pyrimidines (Table 1). Compounds such as these were quite likely delivered to the early Earth in asteroids and comets. Until now, polyhydroxylated compounds (polyols), including sugars (polyhydroxy aldehydes or ketones), sugar alcohols, sugar acids, etc., had not been identified in Murchison. Ribose and deoxyribose, five-carbon sugars, are central to the role of contemporary nucleic acids, DNA and RNA. Glycerol, a three-carbon sugar alcohol, is a constituent of all known biological membranes. Due to the relative lability of sugars, some researchers have questioned the lifetime of sugars under the presumed conditions on the early Earth and postulated other (more stable) compounds as constituents of the first replicating molecules. The identification of potential sources and/or formation mechanisms of pre-biotic polyols would add to the understanding of what organic compounds were available, and for what length of time, on the ancient Earth.

  15. Impact of Halogen Species in the Troposphere on the Ozone concentration on the Regional Scale

    NASA Astrophysics Data System (ADS)

    Kraut, I.; Vogel, H.; Kottmeier, Ch.; Vogel, B.

    2012-04-01

    In order to quantify the interaction of halogen species with ozone a chemical mechanism was developed. This halogen mechanism handles the most important reactions dealing with halogen species in the gas phase. It is classified into three levels of complexity. The first one includes the basic reaction pathways of reactive halogen species including two catalytic ozone destruction cycles. The second one adds reaction paths concerning halogen species with nitrogen oxides. The last one adds the hydrolysis of halogen nitrates. This most complete mechanism was linked to the gas phase mechanism RADMKA, which already describes the ozone chemistry in the troposphere but so far did not consider halogen species. Box model runs were used to explore the sensitivity of the ozone concentration to the individual mechanisms and to quantify this impact. A difference of about 5 % in the ozone concentration due to the halogen reactions was found, the hydrolysis reactions contribute the biggest part to this difference. The halogen mechanism was also included to the model system COSMO-ART (Vogel et al., 2009). The operational weather forecast model of the Deutscher Wetterdienst was extended to treat the chemistry and physics of gases and aerosols. Parameterisations to describe directly emitted components like soot, mineral dust, sea salt and biological material are also included. A spatial and temporal constant source of molecular iodine (I2) was added along the coastlines of Europe. This iodine emission from macroalgal species was taken from the results of the Reactive Halogens in the Marine Boundary Layer Experiment (RHaMBLe), measured in September 2006 in the coastal regions around Roscoff, France (Leigh et al., 2010). Differences in the ozone concentration occur not only in coastal regions but also over the open sea and over land due to transport processes. Results of sensitivity studies with respect to the emissions and the heterogeneous reactions will be presented.

  16. Chemical and structural composition of organic carbonaceous structures in Tissint: evidence for a biogenetic origin

    NASA Astrophysics Data System (ADS)

    Wallis, Jamie; Wickramasinghe, N. C.; Wallis, Daryl H.; Miyake, Nori; Wallis, M. K.; Hoover, Richard B.

    2015-09-01

    Earlier studies of the Tissint Martian meteorite identified the presence of a number of 5-50μm carbonaceous spherical structures. SEM and EDS elemental spectra for 11 selected structures confirmed that they comprise of a carbonaceous outer coating with a inner core of FeS2 (pyrite) and are characterised as immiscible globules with curved boundaries. Here we report on the results of Raman spectroscopic studies that unambiguously confirm the mantle as comprising of `disordered carbonaceous material'. R1 = ID/IG against ΓD (cm-1) band parameter plots of the carbonaceous coatings imply a complex precursor carbon inventory comparable to the precursor carbon component of materials of known biotic source (plants, algae, fungi, crustaceans, prokaryotes). Correlation between peak metamorphic temperatures and Raman D-band (ΓD) parameters further indicate the carbonaceous component was subjected to a peak temperature of ~250 OC suggesting a possible link with the hydrothermal precipitation processes responsible for the formation of similar globules observed in hydrothermal calcite veins in central Ireland. Ω G (cm-1), ΓG (cm-1), Ω D (cm-1) and ΓD (cm-1) parameters further imply a level of crystallinity and disorder of the carbon component consistent with carbonaceous material recovered from a variety of non-terrestrial sources. Cl, N, O and S to C elemental ratios are typical of high volatility bituminous coals and distinctly higher than equivalent graphite standards.

  17. Synthesis of Soluble Halogenated Polyphenylenes. Mechanism for the Coupling Halogenated Lithiobenzenes

    DTIC Science & Technology

    1993-11-22

    the halogen content in these polymers was lowered using larger amounts of tert- butyllithium. TGA analysis (N2 , 20C/rmin) of I1 showed a 10% weight...iodide for every three aryl rings. DSC analysis (N2 , 20°C/min) for 1 8 showed no transitions on either the first or second heating scans to 230"C. TGA ... analysis (N2. 20C/rmin) showed a 10% weight loss at 3220C and char yields of 46% at 900"C. Visual analysis of the charred material did indicate that

  18. Theoretical study of stability and charge-transport properties of coronene molecule and some of its halogenated derivatives: A path to ambipolar organic-based materials?

    SciTech Connect

    Sancho-García, J. C. Pérez-Jiménez, A. J.

    2014-10-07

    We have carefully investigated the structural and electronic properties of coronene and some of its fluorinated and chlorinated derivatives, including full periphery substitution, as well as the preferred orientation of the non-covalent dimer structures subsequently formed. We have paid particular attention to a set of methodological details, to first obtain single-molecule magnitudes as accurately as possible, including next the use of modern dispersion-corrected methods to tackle the corresponding non-covalently bound dimers. Generally speaking, this class of compounds is expected to self-assembly in neighboring π-stacks with dimer stabilization energies ranging from –20 to –30 kcal mol{sup −1} at close distances around 3.0–3.3 Å. Then, in a further step, we have also calculated hole and electron transfer rates of some suitable candidates for ambipolar materials, and corresponding charge mobility values, which are known to critically depend on the supramolecular organization of the samples. For coronene and per-fluorinated coronene, we have found high values for their hopping rates, although slightly smaller for the latter due to an increase (decrease) of the reorganization energies (electronic couplings)

  19. Theoretical study of stability and charge-transport properties of coronene molecule and some of its halogenated derivatives: A path to ambipolar organic-based materials?

    NASA Astrophysics Data System (ADS)

    Sancho-García, J. C.; Pérez-Jiménez, A. J.

    2014-10-01

    We have carefully investigated the structural and electronic properties of coronene and some of its fluorinated and chlorinated derivatives, including full periphery substitution, as well as the preferred orientation of the non-covalent dimer structures subsequently formed. We have paid particular attention to a set of methodological details, to first obtain single-molecule magnitudes as accurately as possible, including next the use of modern dispersion-corrected methods to tackle the corresponding non-covalently bound dimers. Generally speaking, this class of compounds is expected to self-assembly in neighboring π-stacks with dimer stabilization energies ranging from -20 to -30 kcal mol-1 at close distances around 3.0-3.3 Å. Then, in a further step, we have also calculated hole and electron transfer rates of some suitable candidates for ambipolar materials, and corresponding charge mobility values, which are known to critically depend on the supramolecular organization of the samples. For coronene and per-fluorinated coronene, we have found high values for their hopping rates, although slightly smaller for the latter due to an increase (decrease) of the reorganization energies (electronic couplings).

  20. Nakhla: a Martian Meteorite with Indigenous Organic Carbonaceous Features

    NASA Technical Reports Server (NTRS)

    McKay, D. S.; Gibson, E. K.; Thomas-Keprta, K. L.; Clemett, S. J.; Le, L.; Rahman, Z.; Wentworth, S. J.

    2011-01-01

    The Nakhla meteorite possesses discrete, well defined, structurally coherent morphologies of carbonaceous phases present within iddingsite alteration zones. Based upon both isotopic measurements and analysis of organic phases the presence of pre-terrestrial organics is now recognized. Within the microcrystalline layers of Nakhla s iddingsite, discrete clusters of salt crystals are present. These salts are predominantly halite (NaCl) with minor MgCl2 crystals. Some CaSO4, likely gypsum, appears to be partially intergrown with some of the halite. EDX mapping shows discrete C-rich features are interspersed among these crystals. A hollow semi-spherical bowl structure ( 3 m ) has been identified and analyzed after using a focused ion beam (FIB) to cut a transverse TEM thin section of the feature and the underlying iddingsite. TEM/EDX analysis reveals that the feature is primarily carbonaceous containing C with lesser amounts of Si, S, Ca, Cl, F, Na, and minor Mn and Fe; additionally a small peak consistent with N, which has been previously seen in Nakhla carbonaceous matter, is also present. Selected area electron diffraction (SAED) shows that this C-rich material is amorphous (lacking any long-range crystallographic order) and is not graphite or carbonate. Micro-Raman spectra acquired from the same surface from which the FIB section was extracted demonstrate a typical kerogen-like D and G band structure with a weak absorption peak at 1350 and a stronger peak at 1600/cm. The C-rich feature is intimately associated with both the surrounding halite and underlying iddingsite matrix. Both iddingsite and salts are interpreted as having formed as evaporate assemblages from progressive evaporation of water bodies on Mars. This assemblage, sans the carbonaceous moieties, closely resembles iddingsite alteration features previously described which were interpreted as indigenous Martian assemblages. These distinctive macromolecular carbonaceous structures in Nakhla may represent

  1. Carbonaceous Dye‐Sensitized Solar Cell Photoelectrodes

    PubMed Central

    Batmunkh, Munkhbayar

    2015-01-01

    High photovoltaic efficiency is one of the most important keys to the commercialization of dye sensitized solar cells (DSSCs) in the quickly growing renewable electricity generation market. The heart of the DSSC system is a wide bandgap semiconductor based photoelectrode film that helps to adsorb dye molecules and transport the injected electrons away into the electrical circuit. However, charge recombination, poor light harvesting efficiency and slow electron transport of the nanocrystalline oxide photoelectrode film are major issues in the DSSC's performance. Recently, semiconducting composites based on carbonaceous materials (carbon nanoparticles, carbon nanotubes (CNTs), and graphene) have been shown to be promising materials for the photoelectrode of DSSCs due to their fascinating properties and low cost. After a brief introduction to development of nanocrystalline oxide based films, this Review outlines advancements that have been achieved in the application of carbonaceous‐based materials in the photoelectrode of DSSCs and how these advancements have improved performance. In addition, several of the unsolved issues in this research area are discussed and some important future directions are also highlighted. PMID:27980926

  2. Organic Chemistry of Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Cronin, John R.

    2001-01-01

    Chiral and carbon-isotopic analyses of isovaline have been carried out on numerous samples of the Murchison and one sample of the Murray carbonaceous chondrite. The isovaline was found to be heterogeneous with regard to enantiomeric excess (ee) both between samples and within a single Murchison sample. L-Excesses ranging from 0 to 15% were observed. The isovaline delta(sup 13) C was found to be about +18%. No evidence was obtained suggesting terrestrial contamination in the more abundant L-enantiomer. A correlation was observed between isovaline (also alpha - aminoisobutyric acid) concentration and PCP content of five CM chondrites. It is suggested that isovaline, along with other meteoritic a-methyl amino acids with ee, are of presolar origin. The possible formation of ee in extraterrestrial amino acids by exposure to circularly polarized light or by magnetochiral photochemistry is discussed. Key words: Murchison meteorite, Murray meteorite, amino acids, isovaline, chirality, carbon isotopes, PCP.

  3. Distinct Distribution of Purines in CM and CR Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Callahan, Michael P.; Stern, Jennifer C.; Glavin, Daniel P.; Smith, Karen E.; Martin, Mildred G.; Dworkin, Jason P.

    2010-01-01

    Carbonaceous meteorites contain a diverse suite of organic molecules and delivered pre biotic organic compounds, including purines and pyrimidines, to the early Earth (and other planetary bodies), seeding it with the ingredients likely required for the first genetic material. We have investigated the distribution of nucleobases in six different CM and CR type carbonaceous chondrites, including fivc Antarctic meteorites never before analyzed for nucleobases. We employed a traditional formic acid extraction protocol and a recently developed solid phase extraction method to isolate nucleobases. We analyzed these extracts by high performance liquid chromatography with UV absorbance detection and tandem mass spectrometry (HPLC-UV -MS/MS) targeting the five canonical RNAIDNA bases and hypoxanthine and xanthine. We detected parts-per-billion levels of nucleobases in both CM and CR meteorites. The relative abundances of the purines found in Antarctic CM and CR meteorites were clearly distinct from each other suggesting that these compounds are not terrestrial contaminants. One likely source of these purines is formation by HCN oligomerization (with other small molecules) during aqueous alteration inside the meteorite parent body. The detection of the purines adenine (A), guanine (0), hypoxanthine (HX), and xanthine (X) in carbonaceous meteorites indicates that these compounds should have been available on the early Earth prior to the origin of the first genetic material.

  4. What’s New in Enzymatic Halogenations

    PubMed Central

    Fujimori, Danica Galoniæ; Walsh, Christopher T.

    2007-01-01

    Summary The halogenation of thousands of natural products occurs during biosynthesis and often confers important functional properties. While haloperoxidases had been the default paradigm for enzymatic incorporation of halogens, via X+ equivalents into organic scaffolds, a combination of microbial genome sequencing, enzymatic studies and structural biology have provided deep new insights into enzymatic transfer of halide equivalents in three oxidation states. These are: (1) the halide ions (X−) abundant in nature, (2) halogen atoms (X•), and (3) the X+ equivalents. The mechanism of halogen incorporation is tailored to the electronic demands of specific substrates and involves enzymes with distinct redox coenzyme requirements. PMID:17881282

  5. Molybdenum isotopic evidence for the origin of chondrules and a distinct genetic heritage of carbonaceous and non-carbonaceous meteorites

    NASA Astrophysics Data System (ADS)

    Budde, Gerrit; Burkhardt, Christoph; Brennecka, Gregory A.; Fischer-Gödde, Mario; Kruijer, Thomas S.; Kleine, Thorsten

    2016-11-01

    Nucleosynthetic isotope anomalies are powerful tracers to determine the provenance of meteorites and their components, and to identify genetic links between these materials. Here we show that chondrules and matrix separated from the Allende CV3 chondrite have complementary nucleosynthetic Mo isotope anomalies. These anomalies result from the enrichment of a presolar carrier enriched in s-process Mo into the matrix, and the corresponding depletion of this carrier in the chondrules. This carrier most likely is a metal and so the uneven distribution of presolar material probably results from metal-silicate fractionation during chondrule formation. The Mo isotope anomalies correlate with those reported for W isotopes on the same samples in an earlier study, suggesting that the isotope variations for both Mo and W are caused by the heterogeneous distribution of the same carrier. The isotopic complementary of chondrules and matrix indicates that both components are genetically linked and formed together from one common reservoir of solar nebula dust. As such, the isotopic data require that most chondrules formed in the solar nebula and are not a product of protoplanetary impacts. Allende chondrules and matrix together with bulk carbonaceous chondrites and some iron meteorites (groups IID, IIIF, and IVB) show uniform excesses in 92Mo, 95Mo, and 97Mo that result from the addition of supernova material to the solar nebula region in which these carbonaceous meteorites formed. Non-carbonaceous meteorites (enstatite and ordinary chondrites as well as most iron meteorites) do not contain this material, demonstrating that two distinct Mo isotope reservoirs co-existed in the early solar nebula that remained spatially separated for several million years. This separation was most likely achieved through the formation of the gas giants, which cleared the disk between the inner and outer solar system regions parental to the non-carbonaceous and carbonaceous meteorites. The Mo isotope

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

    DOEpatents

    Frazer, J.W.

    1959-08-18

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

  7. Biocidal properties of metal oxide nanoparticles and their halogen adducts

    NASA Astrophysics Data System (ADS)

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

    2010-03-01

    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.

  8. Understanding the Organo-Carbonate Associations in Carbonaceous Chondrites with the Use of Micro-Raman Analysis

    NASA Technical Reports Server (NTRS)

    Chan, Q. H. S.; Zolensky, M. E.

    2015-01-01

    Carbonates can potentially provide sites for organic materials to accrue and develop into complex macromolecules. This study examines the organics associated with carbonates in carbonaceous chondrites using µ-Raman imaging.

  9. Understanding the Organo-Carbonate Associations in Carbonaceous Chondrites with the Use of Micro-Raman Analysis

    NASA Technical Reports Server (NTRS)

    Chan, Q. H. S.; Zolensky, M. E.

    2015-01-01

    Carbonates can potentially provide sites for organic materials to accrue and develop into complex macromolecules. This study examines the organics associated with carbonates in carbonaceous chondrites using micron-Raman imaging.

  10. Evaluation of early Archean volcaniclastic and volcanic flow rocks as possible sites for carbonaceous fossil microbes.

    PubMed

    Walsh, Maud M

    2004-01-01

    Sedimentary rocks have traditionally been the focus of the search for Archean microfossils; the Earth's oldest fossil bacteria are associated with carbonaceous matter in sedimentary cherts in greenstone belts in the eastern Pilbara block of Western Australia and Barberton greenstone belt of South Africa. Reports of possible fossils in a martian meteorite composed of igneous rock and the discovery of modern bacteria associated with basalts have stimulated a new look at Archean volcanic rocks as possible sites for fossil microbes. This study examines silicified volcaniclastic rocks, near-surface altered volcanic flow rocks, and associated stromatolite- like structures from the Archean Barberton greenstone belt to evaluate their potential for the preservation of carbonaceous fossils. Detrital carbonaceous particles are widely admixed with current-deposited debris. Carbonaceous matter is also present in altered volcanic flow rocks as sparse particles in silica veins that appear to be fed by overlying carbonaceous chert layers. Neither microfossils nor mat-like material was identified in the altered volcanic rocks or adjacent stromatolite-like structures. Ancient volcanic flow and volcaniclastic rocks are not promising sites for carbonaceous fossil preservation.

  11. Kinetics of volatile extraction from carbonaceous chondrites: Dehydration of talc

    NASA Technical Reports Server (NTRS)

    Bose, Kunal; Ganguly, Jibamitra

    1991-01-01

    Carbonaceous chondrites are believed to be the primary constituents of near-Earth asteroids and Phobos and Deimos, and are potential resources of fuels that may be exploited for future planetary missions. Calculations of equilibrium phase relations suggest that talc (Ta) and antigorite (Ant) are likely to be the major hydrous phases in the C1 and C2 meteorites (Ganguly and Saxena, 1989), which constitute the most volatile rich classes of carbonaceous chondrites. The dehydration kinetics of talc are studied as a function of temperature, grain size, composition and fluid fugacity, as part of a systematic study of the reaction kinetics of the volatile bearing phases that are either known or likely to be present in carbonaceous chondrites. The dehydration kinetics were investigated at 1 bar, 775 to 875 C by monitoring the in-situ weight loss as a function of time of a natural talc. The talc platelets had a dimension of 0.8 to 1 micron. The run durations varied from 233.3 hours at 775 C (48 percent dehydration) to 20.8 hours at 875 C (80 pct. dehydration). The results can be adequately represented by a given rate equation. Theoretical analysis suggests that the reduction in the concentration of H2O in the environment of dehydrating talc, as would be encountered in processing chondritic materials, will have negligible effect on the rate of dehydration, unless there is a change of reaction mechanism owing to the presence of other volatile species.

  12. Indigenous Carbonaceous Matter in the Nakhla Mars Meteorite

    NASA Technical Reports Server (NTRS)

    Clemett, S. J.; Thomas-Keprta, K. L.; Rahman, Z.; Le, L.; Wentworth, S. J.; Gibson, E. K.; McKay, D. S.

    2016-01-01

    Detailed microanalysis of the Martian meteorite Nakhla has shown there are morphologically distinct carbonaceous features spatially associated with low-T aqueous alteration phases including salts and id-dingsite. A comprehensive suite of analytical instrumentation including optical microscopy, field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) spectroscopy, focused ion beam (FIB) microscopy, transmission electron microscopy (TEM), two-step laser mass spectrometry (mu-L(sup 2)MS), laser mu-Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and nanoscale secondary ion mass spectrometry (NanoSIMS) are being used to characterize the carbonaceous matter and host mineralogy. The search for carbonaceous matter on Mars has proved challenging. Viking Landers failed to unambiguously detect simple organics at either of the two landing sites although the Martian surface is estimated to have acquired at least 10(exp15) kg of C as a consequence of meteoritic accretion over the last several Ga. The dearth of organics at the Martian surface has been attributed to various oxidative processes including UV photolysis and peroxide activity. Consequently, investigations of Martian organics need to be focused on the sub-surface regolith where such surface processes are either severely attenuated or absent. Fortuitously since Martian meteorites are derived from buried regolith materials they provide a unique opportunity to study Martian organic geochemistry.

  13. Porous carbonaceous electrode structure and method for secondary electrochemical cell

    DOEpatents

    Kaun, Thomas D.

    1977-03-08

    Positive and negative electrodes are provided as rigid, porous carbonaceous matrices with particulate active material fixedly embedded. Active material such as metal chalcogenides, solid alloys of alkali metal or alkaline earth metals along with other metals and their oxides in particulate form are blended with a thermosetting resin and a solid volatile to form a paste mixture. Various electrically conductive powders or current collector structures can be blended or embedded into the paste mixture which can be molded to the desired electrode shape. The molded paste is heated to a temperature at which the volatile transforms into vapor to impart porosity as the resin begins to cure into a rigid solid structure.

  14. Selective Halogenation Using an Aniline Catalyst.

    PubMed

    Samanta, Ramesh C; Yamamoto, Hisashi

    2015-08-17

    Electrophilic halogenation is used to produce a wide variety of halogenated compounds. Previously reported methods have been developed mainly using a reagent-based approach. Unfortunately, a suitable "catalytic" process for halogen transfer reactions has yet to be achieved. In this study, arylamines have been found to generate an N-halo arylamine intermediate, which acts as a highly reactive but selective catalytic electrophilic halogen source. A wide variety of heteroaromatic and aromatic compounds are halogenated using commercially available N-halosuccinimides, for example, NCS, NBS, and NIS, with good to excellent yields and with very high selectivity. In the case of unactivated double bonds, allylic chlorides are obtained under chlorination conditions, whereas bromocyclization occurs for polyolefin. The reactivity of the catalyst can be tuned by varying the electronic properties of the arene moiety of catalyst.

  15. Stereoselective Halogenation in Natural Product Synthesis.

    PubMed

    Chung, Won-jin; Vanderwal, Christopher D

    2016-03-24

    At last count, nearly 5000 halogenated natural products have been discovered. In approximately half of these compounds, the carbon atom to which the halogen is bound is sp(3) -hybridized; therefore, there are an enormous number of natural products for which stereocontrolled halogenation must be a critical component of any synthesis strategy. In this Review, we critically discuss the methods and strategies used for stereoselective introduction of halogen atoms in the context of natural product synthesis. Using the successes of the past, we also attempt to identify gaps in our synthesis technology that would aid the synthesis of halogenated natural products, as well as existing methods that have not yet seen application in complex molecule synthesis. The chemistry described herein demonstrates yet again how natural products continue to provide the inspiration for critical advances in chemical synthesis.

  16. Indigenous microfossils in carbonaceous meteorites

    NASA Astrophysics Data System (ADS)

    Hoover, Richard B.; Jerman, Gregory; Rozanov, Alexei Y.; Sipiera, Paul P.

    2004-11-01

    Indigenous embedded microbial filaments, bacterial cells and other microfossils were found in the Orgueil, Ivuna (CI1), Murchison, and Bells (CM2) carbonaceous meteorites. Biominerals, biofilms, framboids, magnetite platelets, and curious elemental iron ovoids covered with minute fibrils and carbon sheaths were also found. The S-4100 Hitachi Field Emission Scanning Electron Microscope (FESEM) and Energy Dispersive X-ray Analysis (EDAX) were used for in situ investigations of freshly fractured interior meteorite surfaces. EDAX x-ray spectra shows the microfossils bear signatures of the meteorite matrix and possess elemental ratios indicating they are indigenous and not recent microbial contaminants. Many of the well-preserved biogenic remains in the meteorites are encased within carbon-rich, sometimes electron transparent, sheaths. Their size, morphology and ultra microstructure are comparable to microfossils known from the phosphorites of Khubsughul, Mongolia and to some of the living cyanobacteria and other sulfur- and sulfate-reducing bacteria known from the halophilic Microcoleus mats of Sivash Lagoon, Crimea and from Mono Lake in California.

  17. Metal-free carbonaceous electrocatalysts and photocatalysts for water splitting.

    PubMed

    Xu, You; Kraft, Markus; Xu, Rong

    2016-05-31

    Water splitting driven by sunlight or renewable resource-derived electricity has attracted great attention for sustainable production of hydrogen from water. Current research interest in this field is focused on the development of earth-abundant photo- or electrocatalytic materials with high activity and long-term stability for hydrogen and/or oxygen evolution reactions. Due to their unique properties and characteristics, carbon and related carbon-based materials show great potential to replace some of the existing precious metal catalysts in water splitting technology. This tutorial review summarizes the recent significant progress in the fabrication and application of metal-free carbonaceous materials as photo- or electrocatalysts for water splitting. Synthetic strategies and applications of various carbonaceous materials, including graphitic carbon nitride (g-C3N4), graphene, carbon nanotubes (CNTs) as well as other forms of carbon-containing materials, for electrochemical or photochemical water splitting are presented, accompanied by a discussion of the key scientific issues and prospects for the future development of metal-free photo- and electrocatalysts.

  18. Adsorption of halogenated aliphatic contaminants by graphene nanomaterials.

    PubMed

    Zhou, Yang; Apul, Onur Guven; Karanfil, Tanju

    2015-08-01

    In this study, adsorption of ten environmentally halogenated aliphatic synthetic organic compounds (SOCs) by a pristine graphene nanosheet (GNS) and a reduced graphene oxide (rGO) was examined, and their adsorption behaviors were compared with those of a single-walled carbon nanotube (SWCNT) and a granular activated carbon (GAC). In addition, the impacts of background water components (i.e., natural organic matter (NOM), ionic strength (IS) and pH) on the SOC adsorption behavior were investigated. The results indicated HD3000 and SWCNT with higher microporous volumes exhibited higher adsorption capacities for the selected aliphatic SOCs than graphenes, demonstrating microporosity of carbonaceous adsorbents played an important role in the adsorption. Analysis of adsorption isotherms demonstrated that hydrophobic interactions were the dominant contributor to the adsorption of aliphatic SOCs by graphenes. However, π-π electron donor-acceptor and van der Waals interactions are likely the additional mechanisms contributing to the adsorption of aliphatic SOCs on graphenes. Among the three background solution components examined, NOM showed the most influential effect on adsorption of the selected aliphatic SOCs, while pH and ionic strength had a negligible effects. The NOM competition on aliphatic adsorption was less pronounced on graphenes than SWCNT. Overall, in terms of adsorption capacities, graphenes tested in this study did not exhibit a major advantage over SWCNT and GAC for the adsorption of aliphatic SOCs.

  19. Insights into halogen bond-driven enantioseparations.

    PubMed

    Peluso, Paola; Mamane, Victor; Aubert, Emmanuel; Dessì, Alessandro; Dallocchio, Roberto; Dore, Antonio; Pale, Patrick; Cossu, Sergio

    2016-10-07

    Although the halogen bond (XB) has been so far mainly studied in silico and in the solid state, its potential impact in solution is yet to be fully understood. In this study, we describe the first systematic investigation on the halogen bond in solvated environment by high-performance liquid chromatography (HPLC). Thirty three atropisomeric polyhalogenated-4,4'-bipyridines (HBipys), containing Cl, Br and I as substituents, were selected and used as potential XB donors (XBDs) on two cellulose-based chiral stationary phases (CSPs) containing potential XB acceptors (XBAs). The impact of the halogens on the enantiodiscrimination mechanism was investigated and iodine showed a pivotal role on the enantioseparation in non-polar medium. Electrostatic potentials (EPs) were computed to understand the electrostatic component of CSP-analyte interaction. Moreover, van't Hoff studies for ten HBipys were performed and the thermodynamic parameters governing the halogen-dependent enantioseparations are discussed. Finally, a molecular dynamic (MD) simulation is proposed to model halogen bond in polysaccharide-analyte complexes by inclusion of a charged extra point to represent the positive 'σ-hole' on the halogen atom. On the basis of both experimental results and theoretical data, we have profiled the halogen bond as a chemo-, regio-, site- and stereoselective interaction which can work in HPLC environment besides other known interactions based on the complementarity between selector and selectand.

  20. Methods for purifying carbon materials

    DOEpatents

    Dailly, Anne; Ahn, Channing; Yazami, Rachid; Fultz, Brent T.

    2009-05-26

    Methods of purifying samples are provided that are capable of removing carbonaceous and noncarbonaceous impurities from a sample containing a carbon material having a selected structure. Purification methods are provided for removing residual metal catalyst particles enclosed in multilayer carbonaceous impurities in samples generate by catalytic synthesis methods. Purification methods are provided wherein carbonaceous impurities in a sample are at least partially exfoliated, thereby facilitating subsequent removal of carbonaceous and noncarbonaceous impurities from the sample. Methods of purifying carbon nanotube-containing samples are provided wherein an intercalant is added to the sample and subsequently reacted with an exfoliation initiator to achieve exfoliation of carbonaceous impurities.

  1. Halogen bond: a long overlooked interaction.

    PubMed

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

    2015-01-01

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

  2. Does fluorine participate in halogen bonding?

    PubMed

    Eskandari, Kiamars; Lesani, Mina

    2015-03-16

    When R is sufficiently electron withdrawing, the fluorine in the R-F molecules could interact with electron donors (e.g., ammonia) and form a noncovalent bond (F⋅⋅⋅N). Although these interactions are usually categorized as halogen bonding, our studies show that there are fundamental differences between these interactions and halogen bonds. Although the anisotropic distribution of electronic charge around a halogen is responsible for halogen bond formations, the electronic charge around the fluorine in these molecules is spherical. According to source function analysis, F is the sink of electron density at the F⋅⋅⋅N BCP, whereas other halogens are the source. In contrast to halogen bonds, the F⋅⋅⋅N interactions cannot be regarded as lump-hole interactions; there is no hole in the valence shell charge concentration (VSCC) of fluorine. Although the quadruple moment of Cl and Br is mainly responsible for the existence of σ-holes, it is negligibly small in the fluorine. Here, the atomic dipole moment of F plays a stabilizing role in the formation of F⋅⋅⋅N bonds. Interacting quantum atoms (IQA) analysis indicates that the interaction between halogen and nitrogen in the halogen bonds is attractive, whereas it is repulsive in the F⋅⋅⋅N interactions. Virial-based atomic energies show that the fluorine, in contrast to Cl and Br, stabilize upon complex formation. According to these differences, it seems that the F⋅⋅⋅N interactions should be referred to as "fluorine bond" instead of halogen bond.

  3. Carbonaceous Components in the Comet Halley Dust

    NASA Technical Reports Server (NTRS)

    Fomenkova, M. N.; Chang, S.; Mukhin, L. M.

    1994-01-01

    Cometary grains containing large amounts of carbon and/or organic matter (CHON) were discovered by in situ measurements of comet Halley dust composition during VEGA and GIOTTO flyby missions. In this paper, we report the classification of these cometary, grains by means of cluster analysis, discuss the resulting compositional groups, and compare them with substances observed or hypothesized in meteorites, interplanetary dust particles, and the interstellar medium. Grains dominated by carbon and/or organic matter (CHON grains) represent approx. 22% of the total population of measured cometary dust particles. They, usually contain a minor abundance of rock-forming elements as well. Grains having organic material are relatively more abundant in the vicinity of the nucleus than in the outer regions of the coma, which suggests decomposition of the organics in the coma environment. The majority of comet Halley organic particles are multicomponent mixtures of carbon phases and organic compounds. Possibly, the cometary CHON grains may be related to kerogen material of an interstellar origin in carbonaceous meteorites. Pure carbon grains, hydrocarbons and polymers of cyanopolyynes, and multi-carbon monoxides are present in cometary dust as compositionally simple and distinctive components among a variety of others. There is no clear evidence of significant presence of pure formaldehyde or HCN polymers in Halley dust particles. The diversity of types of cometary organic compounds is consistent with the inter-stellar dust model of comets and probably reflects differences in composition of precursor dust. Preservation of this heterogeneity among submicron particles suggest the gentle formation of cometary, nucleus by aggregation of interstellar dust in the protosolar nebula without complete mixing or chemical homogenization at the submicron level.

  4. 40Ar/39Ar Ages of Carbonaceous Xenoliths in 2 HED Meteorites

    NASA Technical Reports Server (NTRS)

    Turrin, B.; Lindsay, F. N.; Park, J.; Herzog, G. F.; Delaney, J. S.; Swisher, C. C., III; Johnson, J.; Zolensky, M.

    2016-01-01

    The generally young K/Ar and 40Ar/39Ar ages of CM chondrites made us wonder whether carbonaceous xenoliths (CMX) entombed in Howardite–Eucrite–Diogenite (HED) meteorites might retain more radiogenic 40Ar than do ‘free-range’ CM-chondrites. To find out, we selected two HED breccias with carbonaceous inclusions in order to compare the 40Ar/39Ar release patterns and ages of the inclusions with those of nearby HED material. Carbonaceous inclusions (CMXs) in two HED meteorites lost a greater fraction of radiogenic 40Ar than did surrounding host material, but a smaller fraction of it than did free-range CM-chondrites such as Murchison or more heavily altered ones. Importantly, however, the siting of the CMXs in HED matrix did not prevent the 40Ar loss of about 40 percent of the radiogenic 40Ar, even from phases that degas at high laboratory temperatures. We infer that carbonaceous asteroids with perihelia of 1 astronomical unit probably experience losses of at least this size. The usefulness of 40Ar/39Ar dating for samples returned from C-type asteroids may hinge, therefore, on identifying and analyzing separately small quantities of the most retentive phases of carbonaceous chondrites.

  5. Fluorescent accessory phases in the carbonaceous matrix of ureilites

    NASA Technical Reports Server (NTRS)

    Berkley, J. L.; Taylor, G. J.; Keil, K.; Healey, J. T.

    1978-01-01

    The carbonaceous matrix of ureilite meteorites (C-bearing olivine-pigeonite achondrites) contain abundant minute phases that emit a multicolored fluorescence under electron bombardment. These include NaCl and KCl, found in all seven ureilites studied, high-Si glass with pyroxene and chlorapatite quench crystals in North Haig, an unidentified high-Ca-Al-Cl phase in Novo Urei, and possibly free SiO2 in Novo Urei and Dingo Pup Donga. The origin of these phases is uncertain but some, especially chlorides and glass, may represent residual postcumulus materials precipitated from a late-stage interstitial liquid during the igneous phase of ureilite history.

  6. The chemistry of life's origin: a carbonaceous meteorite perspective.

    PubMed

    Pizzarello, Sandra

    2006-04-01

    Carbonaceous chondrite meteorites are primitive asteroidal fragments that contain organic carbon and offer a glimpse of the abiotic chemical processes that preceded the onset of life. Their organic material displays structures as diverse as kerogen-like macromolecules and simpler soluble compounds that range from polar amino acids and polyols to nonpolar hydrocarbons. Several of these compounds have identical counterparts in terrestrial biomolecules and some of the amino acids show a unique l-asymmetry, suggesting their possible contribution to terrestrial molecular evolution and the origin of biological homochirality.

  7. Step-wise supercritical extraction of carbonaceous residua

    DOEpatents

    Warzinski, Robert P.

    1987-01-01

    A method of fractionating a mixture containing high boiling carbonaceous material and normally solid mineral matter includes processing with a plurality of different supercritical solvents. The mixture is treated with a first solvent of high critical temperature and solvent capacity to extract a large fraction as solute. The solute is released as liquid from solvent and successively treated with other supercritical solvents of different critical values to extract fractions of differing properties. Fractionation can be supplemented by solute reflux over a temperature gradient, pressure let down in steps and extractions at varying temperature and pressure values.

  8. Viscosity and chemical diffusion of halogens in silicate melts: implications for volcanic degassing

    NASA Astrophysics Data System (ADS)

    Wasik, A.; Dingwell, D. B.; Courtial, P.; Hess, K.

    2005-12-01

    The efficiency of degassing processes in subduction zone volcanism may be affected by the magmato-hydrothermal geochemistry of halogens. In addition halogens may act as potential monitors of degassing efficiency and provide answers to the question of the role of disequilibrium during partitioning. Too little is known quantitatively about the transport properties of halogens in silicate melts. In particular, an accurate study of the transport properties of halogens should help to unlock the information contained in halogen concentrations of eruptive products and volcanic gases. For these reasons the chemical diffusivities of the halogens (fluorine, bromine, chlorine and iodine) have been measured in the synthetic Fe-bearing sodium disilicate melts, within a wide range of temperature (650-1400° C). The experiments were performed using diffusion couple technique. Halogens were added to the starting material in the form of FeF3, FeBr3, FeCl3 and FeI2 and stirred in concentric cylinder viscometer. The temperature was restricted to 1000-1100° C to avoid volatilization of halogens. After synthesis the samples were drilled, cut into 2mm disks and then doubly polished. Prepared disks were putted into platinum tubes (5mm diameter) and sealed by welding. The halogen rich sample was located at the bottom. During the experiments the temperature was monitored with a thermocouple located at the vicinity of the capsule. Run durations were between 30 minutes and 1 hour. The recovered samples were analyzed using an electron microprobe in order to determine the diffusion profiles of the halogens. The results were obtained by using Boltzmann-Matano method and they suggest at least 3 orders of magnitude range at 1000° C between the diffusion coefficients for F, Br, Cl and I. The fastest diffusing species was found to be fluorine, the slowest - iodine. In order to place the diffusivity measurements in the context of their extrinsic versus intrinsic nature, viscosity measurements were

  9. Force Field Model of Periodic Trends in Biomolecular Halogen Bonds

    PubMed Central

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

    2016-01-01

    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 accurate computational tool that can be applied to, for example, for the design of new therapeutic compounds against clinically important targets and new biomolecular based materials. PMID:25338128

  10. Force Field Model of Periodic Trends in Biomolecular Halogen Bonds.

    PubMed

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

    2015-07-23

    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.

  11. Halogen bonding (X-bonding): A biological perspective

    PubMed Central

    Scholfield, Matthew R; Zanden, Crystal M Vander; Carter, Megan; Ho, P Shing

    2013-01-01

    The concept of the halogen bond (or X-bond) has become recognized as contributing significantly to the specificity in recognition of a large class of halogenated compounds. The interaction is most easily understood as primarily an electrostatically driven molecular interaction, where an electropositive crown, or σ-hole, serves as a Lewis acid to attract a variety of electron-rich Lewis bases, in analogous fashion to a classic hydrogen bonding (H-bond) interaction. We present here a broad overview of X-bonds from the perspective of a biologist who may not be familiar with this recently rediscovered class of interactions and, consequently, may be interested in how they can be applied as a highly directional and specific component of the molecular toolbox. This overview includes a discussion for where X-bonds are found in biomolecular structures, and how their structure–energy relationships are studied experimentally and modeled computationally. In total, our understanding of these basic concepts will allow X-bonds to be incorporated into strategies for the rational design of new halogenated inhibitors against biomolecular targets or toward molecular engineering of new biological-based materials. PMID:23225628

  12. Halogen occultation experiment (HALOE) optical witness-plate program

    NASA Technical Reports Server (NTRS)

    Harvey, Gale A.; Raper, James L.

    1989-01-01

    An optical witness plate program was implemented to monitor buildup of molecular contamination in the clean room during the assembly and testing of the Halogen Occulation Experiment (HALOE) instrument. Travel plates to monitor molecular contamination when the instrument is not in the clean room are also measured. The instrument technique is high-resolution transmission spectroscopy in the 3 micron spectral region using a Fourier transform spectrometer. Witness specimens of low index of refraction, infrared transmitting material are used for contaminant monitoring and for spectral signature analysis. Spectral signatures of possible molecular contamination are presented. No condensible volatile material contamination of HALOE optical witness specimens have yet been found.

  13. Cross-reactivity of Halogenated Platinum Salts

    EPA Science Inventory

    Halogenated platinum (Pt) salts are well-known respiratory sensitizers associated with the development of asthma. People may be exposed to a variety of platinum compounds in different contexts (e.g. occupationally, automobile exhaust). Published reports suggest that sensitizati...

  14. Energy efficient alternatives to halogen torchieres

    SciTech Connect

    Siminovitch, M.; Marr, L.; Mitchell, J.; Page, E.

    1997-03-01

    A series of novel energy efficient torchiere systems have been developed using compact fluorescent lamps (CFLs). These systems were studied photometrically and compared with the performance of traditional commercially available tungsten halogen sources. Gonio-photometric data and power assessments indicate that significant lighting energy savings can be obtained by utilizing CFL sources instead of standard tungsten halogen sources. This energy savings is jointly due to the higher source efficacy of the CFLs and the surprisingly poor performance of the imported 300 Watt halogen lamps. Experimental data shows that a 50 to 60 Watt CFL will effectively lumen match a variety of 300 Watt tungsten halogen sources with 5 to 10 times the efficacy. CFL torchieres have additional benefits of higher power quality and cooler lamp operating temperature, making them safer fixtures.

  15. Extremely Na- and Cl-rich chondrule from the CV3 carbonaceous chondrite Allende

    NASA Astrophysics Data System (ADS)

    Wasserburg, G. J.; Hutcheon, I. D.; Aléon, J.; Ramon, E. C.; Krot, A. N.; Nagashima, K.; Brearley, A. J.

    2011-09-01

    We report on a study of Al3509, a large Na- and Cl-rich, radially-zoned object from the oxidized CV carbonaceous chondrite Allende. Al3509 consists of fine-grained ferroan olivine, ferroan Al-diopside, nepheline, sodalite, and andradite, and is crosscut by numerous veins of nepheline, sodalite, and ferroan Al-diopside. Some poorly-characterized phases of fine-grained material are also present; these phases contain no significant H 2O. The minerals listed above are commonly found in Allende CAIs and chondrules and are attributed to late-stage iron-alkali-halogen metasomatic alteration of primary high-temperature minerals. Textural observations indicate that Al3509 is an igneous object. However, no residual crystals that might be relicts of pre-existing CAI or chondrule minerals were identified. To establish the levels of 26Al and 36Cl originally present, 26Al- 26Mg and 36Cl- 36S isotopic systematics in sodalite were investigated. Al3509 shows no evidence of radiogenic 26Mg ∗, establishing an upper limit of the initial 26Al/ 27Al ratio of 3 × 10 -6. All sodalite grains measured show large but variable excesses of 36S, which, however, do not correlate with 35Cl/ 34S ratio. If these excesses are due to decay of 36Cl, local redistribution of radiogenic 36S ∗ after 36Cl had decayed is required. The oxygen-isotope pattern in Al3509 is the same as found in secondary minerals resulting from iron-alkali-halogen metasomatic alteration of Allende CAIs and chondrules and in melilite and anorthite of most CAIs in Allende. The oxygen-isotope data suggest that the secondary minerals precipitated from or equilibrated with a fluid of similar oxygen-isotope composition. These observations suggest that the formation of Al3509 and alteration products in CAIs and chondrules in Allende requires a very similar fluid phase, greatly enriched in volatiles (e.g., Na and Cl) and with Δ 17O ˜ -3‰. We infer that internal heating of planetesimals by 26Al would efficiently transfer

  16. Latest generation of halogen-containing pesticides.

    PubMed

    Jeschke, Peter

    2017-02-01

    Agriculture is confronted with enormous challenges, from production of enough high-quality food to water use, environmental impacts and issues combined with a continually growing world population. Modern agricultural chemistry has to support farmers by providing innovative agrichemicals, used in applied agriculture. In this context, the introduction of halogen atoms into an active ingredient is still an important tool to modulate the properties of new crop protection compounds. Since 2010, around 96% of the launched products (herbicides, fungicides, insecticides/acaricides and nematicides) contain halogen atoms. The launched nematicides contain the largest number of halogen atoms, followed by insecticides/acaricides, herbicides and fungicides. In this context, fungicides and herbicides contain in most cases fluorine atoms, whereas nematicides and insecticides contain in most cases 'mixed' halogen atoms, for example chlorine and fluorine. This review gives an overview of the latest generation of halogen-containing pesticides launched over the past 6 years and describes current halogen-containing development candidates. © 2017 Society of Chemical Industry.

  17. Asymmetric Flasklike Hollow Carbonaceous Nanoparticles Fabricated by the Synergistic Interaction between Soft Template and Biomass.

    PubMed

    Chen, Chunhong; Wang, Haiyan; Han, Chuanlong; Deng, Jiang; Wang, Jing; Li, Mingming; Tang, Minghui; Jin, Haiyan; Wang, Yong

    2017-02-22

    The soft template method is broadly applied to the fabrication of hollow-structured nanomaterials. However, due to the instability and the typical spherical shape of these soft templates, the resultant particles have a spherical morphology with a wide size distribution. Herein, we developed a sustainable route to fabricate asymmetric flasklike hollow carbonaceous structures with a highly uniform morphology and a narrow size distribution using the soft template method. A dynamic growth mechanism induced by the synergetic interactions between template and biomass is proposed. The precursors (ribose) provide an acidic environment for sodium oleate during the hydrothermal process in which oleic acid nanoemulsions are initially formed and serve as both template and benign solvent for the amphiphilic derivatives of the precursor. Simultaneously, the cosurfactant P123 facilitates the uniform dispersion of the nanoemulsion and is believed to cause the carbonaceous shells to rupture, providing openings through which the intermediates can enter. These subtle interactions facilitate the formation of the flasklike, asymmetric, hollow, carbonaceous nanoparticles. Furthermore, this unique structure contributes to the high surface area (2335 m(2) g(-1)) of the flasklike carbon particles, which enhances the performance of supercapacitors. These findings may open up an exciting field for exploring anisotropic carbonaceous nanomaterials and for understanding the related mechanisms to provide guidance for the design of increasingly complex carbonaceous materials.

  18. Lunar and Planetary Science XXXV: Organics and Alteration in Carbonaceous Chondrites: Goop and Crud

    NASA Technical Reports Server (NTRS)

    2004-01-01

    The session "Organics and Alteration in Carbonaceous Chondrites: Goop and Crud" included the following reports:Organics on Fe-Silicate Grains: Potential Mimicry of Meteoritic Processes?; Molecular and Compound-Specific Isotopic Study of Monocarboxylic Acids in Murchison and Antarctic Meteorites; Nanoglobules, Macromolecular Materials, and Carbon Sulfides in Carbonaceous Chondrites; Evidence for Terrestrial Organic Contamination of the Tagish Lake Meteorite; Nitrogen Isotopic Imaging of Tagish Lake Carbon Globules; Microscale Distribution of Hydrogen Isotopes in Two Carbonaceous Chondrites; The Nature and Origin of Aromatic Organic Matter in the Tagish Lake Meteorite; Terrestrial Alteration of CM Chondritic Carbonate; Serpentine Nanotubes in CM Chondrites; Experimental Study of Serpentinization Reactions; Chondrule Glass Alteration in Type IIA Chondrules in the CR2 Chondrites EET 87770 and EET 92105: Insights into Elemental Exchange Between Chondrules and Matrices; Aqueous Alteration of Carbonaceous Chondrites: New Insights from Comparative Studies of Two Unbrecciated CM2 Chondrites, Y 791198 and ALH 81002 ;and A Unique Style of Alteration of Iron-Nickel Metal in WIS91600, an Unusual C2 Carbonaceous Chondrite.

  19. Investigation of Carbonaceous Interstellar Dust Analogues by Infrared Spectroscopy: Effects of Energetic Processing

    NASA Astrophysics Data System (ADS)

    Maté, Belén; Jiménez-Redondo, Miguel; Tanarro, Isabel; Herrero, Victor Jose

    2015-06-01

    Carbonaceous compounds, both solids and gas-phase molecules, are found in very diverse astronomical media. A significant amount of the elemental carbon is found in small dust grains. This carbonaceous dust, mostly formed in the last stages of evolution of C-rich stars, is the carrier of characteristic IR absorption bands revealing the presence of aliphatic, aromatic and olefinic functional groups in variable proportions. Among the various candidate materials investigated as possible carriers of these bands, hydrogenated amorphous carbon (a-C:H) has led to the best agreement with the observations. Carbonaceous grains are processed by H atoms, UV radiation, cosmic rays and interstellar shocks in their passage from asymptotic giant branch stars to planetary nebulae and to the diffuse interstellar medium. The mechanisms of a-C:H production and evolution in astronomical media are presently a subject of intensive investigation. In this work we present a study of the stability of carbonaceous dust analogues generated in He+CH_4 radiofrequency discharges. In order to simulate the processing of dust in the interstellar environments, the samples have been subjected to electron bombardment, UV irradiation, and both He and H_2 plasma processing. IR spectroscopy is employed to monitor the changes in the structure and composition of the carbonaceous films. A.G.G.M. Tielens. Rev. Mod. Phys., 85, 1021 (2013) J.E. Chiar, A.G.G.M. Tielens, A.J. Adamson and A. Ricca. Astrophys. J., 770, 78 (2013)

  20. The Oxygen Isotope Composition of Dark Inclusions in HEDs, Ordinary and Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Greenwood, R. C.; Zolensky, M. E.; Buchanan, P. C.; Franchi, I. A.

    2015-01-01

    Dark inclusions (DIs) are lithic fragments that form a volumetrically small, but important, component in carbonaceous chondrites. Carbonaceous clasts similar to DIs are also found in some ordinary chondrites and HEDs. DIs are of particular interest because they provide a record of nebular and planetary processes distinct from that of their host meteorite. DIs may be representative of the material that delivered water and other volatiles to early Earth as a late veneer. Here we focus on the oxygen isotopic composition of DIs in a variety of settings with the aim of understanding their formational history and relationship to the enclosing host meteorite.

  1. Aqueous alteration on the parent bodies of carbonaceous chondrites: Computer simulations of late-stage oxidation

    NASA Technical Reports Server (NTRS)

    Bourcier, W. L.; Zolensky, Michael E.

    1991-01-01

    CI carbonaceous chondrites may be products of hydrous alteration of CV- or anhydrous CM-type materials. The CIs typically contain veins filled with carbonates and sulfates, probably indicating a period of late stage aqueous alteration under oxidizing conditions. To test this idea, computer simulations of aqueous alteration of CV- and CM-type carbonaceous were performed. Simulations were restricted to the oxidation of hydrous mineral assemblages produced in previous simulations in order to determine whether further reaction and oxidation results in the phyllosilicate, carbonate, sulfate and oxide vein assemblages typical of CI carbonaceous chondrites. Our simulations were performed at 1, 25, 100, and 150 C (the appropriate temperature range) for the CV and CM mineral assemblages and using the computer code EQ3/6.

  2. Amphiphilic hollow carbonaceous microspheres for the sorption of phenol from water.

    PubMed

    Guan, Zhengrong; Liu, Li; He, Lilu; Yang, Sen

    2011-11-30

    Amphiphilic porous hollow carbonaceous spheres (PHCSs) were synthesized via mild hydrothermal treatment of yeast cells and further pyrolyzing post treatment. The morphology, chemical composition, porosity, and structure of the carbonaceous materials were investigated. It is evident that the carbonaceous materials were composed of the carbonized organic matter (COM) and the noncarbonized organic matter (NOM), and the relative COM and NOM fractions could be adjusted through changing the temperature of hydrothermal and/or pyrolyzing treatment. The phenol sorption properties of the carbonaceous materials had been investigated and the sorption isotherms fit well to the modified Freundlich equation. It was found that the sorption isotherm of phenol onto PHCSs was practically linear even at extreme high concentrations, which was fewer reported for activated carbon or other inorganic materials. This type of sorption isothermals was assigned to a partition mechanism, and the largest value of the partition coefficient (K(f)) and carbon-normalized K(f) (K(oc)) is 56.7 and 91.5 mL g(-1), respectively. Moreover, PHCSs exhibit fast sorption kinetic and facile regeneration property. The results indicate PHCSs are potential effective sorbents for removal of undesirable organic chemicals in wastewater, especially at high concentrations.

  3. Potential Explosion Hazard of Carbonaceous Nanoparticles: Screening of Allotropes

    PubMed Central

    Turkevich, Leonid A.; Fernback, Joseph; Dastidar, Ashok G.; Osterberg, Paul

    2016-01-01

    There is a concern that engineered carbon nanoparticles, when manufactured on an industrial scale, will pose an explosion hazard. Explosion testing has been performed on 20 codes of carbonaceous powders. These include several different codes of SWCNTs (single-walled carbon nanotubes), MWCNTs (multi-walled carbon nanotubes) and CNFs (carbon nanofibers), graphene, diamond, fullerene, as well as several different control carbon blacks and graphites. Explosion screening was performed in a 20 L explosion chamber (ASTM E1226 protocol), at a concentration of 500 g/m3, using a 5 kJ ignition source. Time traces of overpressure were recorded. Samples typically exhibited overpressures of 5–7 bar, and deflagration index KSt = V1/3 (dP/dt)max ~ 10 – 80 bar-m/s, which places these materials in European Dust Explosion Class St-1. There is minimal variation between these different materials. The explosive characteristics of these carbonaceous powders are uncorrelated with primary particle size (BET specific surface area). PMID:27468178

  4. Two-Dimensional Inorganic Cationic Network of Thorium Iodate Chloride with Unique Halogen-Halogen Bonds.

    PubMed

    Lu, Huangjie; Wang, Yaxing; Wang, Congzhi; Chen, Lanhua; Shi, Weiqun; Diwu, Juan; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

    2016-09-06

    A unique two-dimensional inorganic cationic network with the formula [Th3O2(IO3)5(OH)2]Cl was synthesized hydrothermally. Its crystal structure can best be described as positively charged slabs built with hexanuclear thorium clusters connected by iodate trigonal pyramids. Additional chloride anions are present in the interlayer spaces but surprisingly are not exchangeable, as demonstrated by a series of CrO4(2-) uptake experiments. This is because all chloride anions are trapped by multiple strong halogen-halogen interactions with short Cl-I bond lengths ranging from 3.134 to 3.333 Å, forming a special Cl-centered trigonal-pyramidal polyhedron as a newly observed coordination mode for halogen bonds. Density functional theory calculations clarified that electrons transformed from central Cl atoms to I atoms, generating a halogen-halogen interaction energy with a value of about -8.3 kcal mol(-1) per Cl···I pair as well as providing a total value of -57.9 kcal mol(-1) among delocalized halogen-halogen bonds, which is a new record value reported for a single halogen atom. Additional hydrogen-bonding interaction is also present between Cl and OH, and the interaction energy is predicted to be -8.1 kcal mol(-1), confirming the strong total interaction to lock the interlayer Cl anions.

  5. Exposure ages of carbonaceous chondrites, 1

    NASA Technical Reports Server (NTRS)

    Nishiizumi, K.; Arnold, J. R.; Caffee, M. W.; Finkel, R. C.; Southon, J. R.; Nagai, H.; Honda, M.; Sharma, P.; Imamura, M.; Kobayashi, K.

    1993-01-01

    The recent exposure histories of carbonaceous chondrites have been investigated using cosmogenic radionuclides. Our results may indicate a clustering of exposure ages of C1 and C2 chondrites into two peaks, 0.2 My and 0.6 My, perhaps implying two collisional events of Earth-crossing parent bodies. Among carbonaceous chondrites are some having short exposure ages which Mazor et al. hypothesized cluster into a small number of families. This hypothesis is based on spallogenic Ne-21 exposure ages, which in some instances are difficult to determine owing to the large amounts of trapped noble gases in carbonaceous chondrites. Also, since Ne-21 is stable, it integrates a sample's entire exposure history, so meteorites with complex exposure histories are difficult to understand using exclusively Ne-21. Cosmogenic radionuclides provide an alternative means of determining the recent cosmic ray exposure duration. To test the hypothesis of Mazor et al. we have begun a systematic investigation of exposure histories of Antarctic and non-Antarctic carbonaceous chondrites especially C2s.

  6. Chemical Biomarkers and Microfossils in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Hoover, Richard B.; Rozanov, Alexei; Six, N. Frank (Technical Monitor)

    2001-01-01

    Chemical, mineral and morphological biomarkers and microfossils are present in a wide variety of ancient rocks and meteorites. We discuss previous results and present images of microfossils of cyanobacteria, magnetotactic bacteria, and acritarchs detected in the Orgueil, Mighei, Nogoya, and Murchison carbonaceous meteorites.

  7. Technology for radiation efficiency measurement of high-power halogen tungsten lamp used in calibration of high-energy laser energy meter.

    PubMed

    Wei, Ji Feng; Hu, Xiao Yang; Sun, Li Qun; Zhang, Kai; Chang, Yan

    2015-03-20

    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. Effects of mercury emission control technologies using halogens on coal combustion product chemical properties.

    PubMed

    Heebink, Loreal V; Pflughoeft-Hassett, Debra F; Hassett, David J

    2010-03-01

    Fly ash and spray dryer absorber (SDA) material samples collected during mercury emission control technology tests that incorporated the use of halogens were evaluated for select chemical composition and leachability. Corresponding samples were also collected under standard operating conditions and examined using the same protocols. Included in these evaluations were pH and total and leachable concentrations of the mercury control technology (MCT) halogen of interest (Br, Cl, or I) and Hg, As, Cr, and Se. The use of a MCT using halogens decreased the pH values of coal combustion products (CCPs) collected in fabric filters compared with that of the corresponding standard CCPs. In many cases, the total As, Cr, and Se concentrations were similar between the standard and MCT test CCPs. However, at least a slight increase in total Se was noted in each sample set from the standard to the MCT test CCPs. Short-term leaching was performed on all samples, and long-term leaching was performed on most highly alkaline samples. On the basis of percentage of maximum leachability, the MCT additive halogens were more mobile than the other elements evaluated. The Hg in fly ash and SDA material samples was stable. Generally, more As and Se leached from the MCT test CCPs than the standard CCPs. Cr leachate results were more variable. The data indicate a need to further examine the effects of MCT using halogens applications on CCPs.

  9. Treatment System for Removing Halogenated Compounds from Contaminated Sources

    NASA Technical Reports Server (NTRS)

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

    2015-01-01

    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. Speciation of surface gold in pressure oxidized carbonaceous gold ores by TOF-SIMS and TOF-LIMS

    NASA Astrophysics Data System (ADS)

    Dimov, S. S.; Chryssoulis, S. L.; Sodhi, R. N.

    2003-01-01

    To the best of our knowledge, this is the first attempt ever to speciate gold preg-robbed by carbonaceous matter using a surface sensitive microbeam technique. This approach enables the direct determination of gold species sorbed on carbonaceous particulates thus providing a new tool in understanding the chemistry of gold sorption on carbon. The reasoning behind this effort was to study the detrimental effect chloride ions have on gold recovery by pressure oxidation of carbonaceous sulfide ores, a technology largely used by the mining industry. The characterization of the sorbed gold species involved three surface sensitive microbeam analytical techniques (TOF-SIMS, TOF-LIMS and XPS) providing confirmatory results for better accuracy. Optimum conditions for detection of gold compounds with minimum fragmentation by TOF-SIMS and TOF-LIMS mass spectrometers have been determined. A reference library of 16 major gold complexes with halogen, thiosulfate, cyanide and thiocyanate groups relevant to the gold recovery processes has been established. The most suitable of the microbeam techniques tested was found to be negative (-ve) ion TOF-LIMS, offering best sensitivity and a small analytical spot size.

  11. Biodegradation of halogenated organic compounds.

    PubMed Central

    Chaudhry, G R; Chapalamadugu, S

    1991-01-01

    In this review we discuss the degradation of chlorinated hydrocarbons by microorganisms, emphasizing the physiological, biochemical, and genetic basis of the biodegradation of aliphatic, aromatic, and polycyclic compounds. Many environmentally important xenobiotics are halogenated, especially chlorinated. These compounds are manufactured and used as pesticides, plasticizers, paint and printing-ink components, adhesives, flame retardants, hydraulic and heat transfer fluids, refrigerants, solvents, additives for cutting oils, and textile auxiliaries. The hazardous chemicals enter the environment through production, commercial application, and waste. As a result of bioaccumulation in the food chain and groundwater contamination, they pose public health problems because many of them are toxic, mutagenic, or carcinogenic. Although synthetic chemicals are usually recalcitrant to biodegradation, microorganisms have evolved an extensive range of enzymes, pathways, and control mechanisms that are responsible for catabolism of a wide variety of such compounds. Thus, such biological degradation can be exploited to alleviate environmental pollution problems. The pathways by which a given compound is degraded are determined by the physical, chemical, and microbiological aspects of a particular environment. By understanding the genetic basis of catabolism of xenobiotics, it is possible to improve the efficacy of naturally occurring microorganisms or construct new microorganisms capable of degrading pollutants in soil and aquatic environments more efficiently. Recently a number of genes whose enzyme products have a broader substrate specificity for the degradation of aromatic compounds have been cloned and attempts have been made to construct gene cassettes or synthetic operons comprising these degradative genes. Such gene cassettes or operons can be transferred into suitable microbial hosts for extending and custom designing the pathways for rapid degradation of recalcitrant

  12. Microfossils and biomolecules in carbonaceous meteorites: possibility of life in water-bearing asteroids and comets

    NASA Astrophysics Data System (ADS)

    Hoover, Richard B.

    2014-09-01

    It is well established that carbonaceous meteorites contain water, carbon, biogenic elements and a host of organic chemicals and biomolecules. Several independent lines of evidence indicate that the parent bodies of the CI1 and CM2 carbonaceous meteorites are most probably the C-type asteroids or cometary nuclei. Several of the protein amino acids detected in the meteorites exhibit chirality and have an excess of the L-enantiomer -- such as in the amino acids present in the proteins of all known life forms on Earth. Isotopic studies have established that the amino acids and nucleobases in the CI1 and CM2 carbonaceous meteorites are both indigenous and extraterrestrial. Optical and Scanning Electron Microscopy studies carried out by researchers during the past half century have revealed the presence of complex biogenic microstructures embedded in the rock-matrix of many of carbonaceous meteorites similar to extinct life-forms known as acritarchs and hystrichospheres. Carbonaceous meteorites also contain a wide variety of large filaments that exhibit the complex morphologies and correct size ranges of known genera and species of photosynthetic microorganisms such as cyanobacteria and diatoms. However, EDAX investigations have shown that these carbon-rich filaments typically have nitrogen content below the level of detection (<0.5% atomic) of the instrument. EDAX studies of living and dead terrestrial biological materials have shown that nitrogen can be detected in ancient mummies and tissue, hair and teeth of Pleistocene Mammoths. Hence, the absence of detectable nitrogen in the filaments provides direct evidence that they do not represent recent biological contaminants that invaded these meteorite stones after they were observed to fall to Earth. The spectral and fluorescence properties of pigments found in several species of terrestrial cyanobacteria which are similar to some microfossils found in carbonaceous meteorites may provide valuable clues to help search

  13. Halogen-Assisted Piezochromic Supramolecular Assemblies for Versatile Haptic Memory.

    PubMed

    Bai, Linyi; Bose, Purnandhu; Gao, Qiang; Li, Yongxin; Ganguly, Rakesh; Zhao, Yanli

    2017-01-11

    Sensory memory is capable of recording information and giving feedback based on external stimuli. Haptic memory in particular can retain the sensation of the interaction between the human body and the environment and help humans to describe the physical quantities in their environment and manipulate objects in daily activities. Although sensitive and accurate tactile sensors have been produced on optical and electronic devices, their rigorous operation and equipment requirements seriously limit their further applicability. In addition, their poor retainability after the removal of external stimuli also warrants further improvements. Thus, haptic memory materials, having simple structures and high sensitivity, are highly desired. Herein, we successfully developed two piezochromic assemblies assisted by halogen bonding for haptic memory. The halogen bond not only contributes to the fabrication of the network and enhances integrative stability but also broadens the natural piezofluorescent range, thus promoting sensory sensitivity. Moreover, the colorimetric change of the assemblies could be well-retained after the stimulus was removed. Upon mild heating treatment, the piezochromic response could be recovered to its original state, confirming the recyclability of this haptic memory material for use in practical applications. The present work enriches the library of piezochromic materials with enhanced performance for haptic memory.

  14. Multitechnique Determination of Halogens in Soil after Selective Volatilization Using Microwave-Induced Combustion.

    PubMed

    Pereira, L S F; Pedrotti, M F; Enders, M S P; Albers, C N; Pereira, J S F; Flores, E M M

    2017-01-03

    A method for digestion of soils with high inorganic matter content (ranging from 50 to 92%) by microwave-induced combustion (MIC) is proposed for the first time for further halogens (F, Cl, Br, and I) determination by ion chromatography (IC) and also by inductively coupled plasma mass spectrometry (ICP-MS). Microcrystalline cellulose (100-500 mg), used as a combustion aid, was mixed with sample and water or NH4OH solutions (10-100 mmol L(-1)) were investigated for analytes absorption. The use of cellulose (400 mg) was mandatory to volatilize the halogens from soils with high inorganic matter. It was possible to use diluted absorbing solutions (up to 100 mmol L(-1) NH4OH) for halogens retention, providing limits of quantification in the range of 0.06 (I) to 60 (Cl) μg g(-1). Accuracy was evaluated using certified reference materials (CRMs), spiked samples, and pyrohydrolysis method. Recoveries for halogens after spiked samples were in the range of 94 to 103% and the results after digestion of CRMs by MIC were in agreement better than 95% to certified values. Blanks were low, relative standard deviation was below 8% for all soils and no statistical difference was observed for results by pyrohydrolysis and MIC methods showing the feasibility of the proposed method for further halogens determination in soil samples.

  15. Barcoll hardness of different resin-based composites cured by halogen or light emitting diode (LED).

    PubMed

    Bala, Oya; Uçtasli, Mine Betül; Tüz, M Atilla

    2005-01-01

    The clinical performance of light curing resin composites is greatly influenced by the quality of the light-curing unit (LCU). Halogen LCUs are commonly used for curing composite materials. However, they have some drawbacks. The development of new, blue, super bright light emitting diodes (LED LCU) of 470-nm wavelength with high light irradiance comes as an alternative to standard halogen LCUs of 450-470-nm wavelengths. This study evaluated the surface hardness of the different resin-based composites (flowable, hybrid and packable resin composites) cured by LED LCU or halogen LCU. A Teflon mold 10-mm in diameter and 2-mm in depth was made to obtain five disk-shaped specimens for each experimental group. Then, the specimens were cured by an LED LCU or halogen LCU for 40 seconds. The hardness of the upper and lower surfaces was measured with a Barcoll hardness-measuring instrument. The statistical analysis was performed using one-way analysis of variance (ANOVA) and Duncan test at a p=0.05 significance level. The results of the hardness test indicated that the hardness of resin composites cured by an LED LCU were greater than those cured by a halogen LCU. Additionally, for all resin-based composites, the hardness values for the upper surfaces were higher than the lower surfaces. However, for both results no statistically significant differences were observed (p>0.05).

  16. Evaluation of Halogenated Coumarins for Antimosquito Properties

    PubMed Central

    Narayanaswamy, Venugopala K.; Gleiser, Raquel M.; Kasumbwe, Kabange; Aldhubiab, Bandar E.; Attimarad, Mahesh V.; Odhav, Bharti

    2014-01-01

    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. PMID:25610898

  17. Halogen bonds in organic synthesis and organocatalysis.

    PubMed

    Schindler, S; Huber, Stefan M

    2015-01-01

    In contrast to hydrogen bonding, halogen bonding has so far found very little use in organic synthesis and organocatalysis. Although there are multiple reports on the use of elemental iodine in a wide range of organic reactions, the understanding of the actual mode of activation in these cases is very rudimentary. Recently, first proof-of-principle reactions have been established towards the use of carbon-based halogen-bond donors as activators or organocatalysts. These halogen-based Lewis acids offer more structural variety and potential than elemental iodine itself, and the mode of activation is better understood. Yet, the reported cases still only cover simple benchmark reactions, and there is a clear need for further and more complex applications.

  18. The effect of halogenated hydantoins on biofilms

    SciTech Connect

    Ludyanskiy, M.L.; Himpler, F.J.

    1997-12-01

    The biocidal efficacy of halogenated hydantoins against laboratory-prepared biofilms was compared to the free halogen donors NaOCl and NaOBr. Higher biocide concentrations were required to control a filamentous biofilm than to control free floating planktonic bacteria. Control of a biocide-resistant S. antans biofilm was best obtained with a repeated slug+3 hour continuous treatment procedure or with conventional continuous biocide treatment. A bromine, methylethylhydantoin-containing oxidizing biocide (BrMEH) was found to be more efficacious than either free chlorine or free bromine in controlling filamentous biofilms. Previous studies indicating the inability of free chlorine to penetrate biofilms were supported as the combination of free and combined halogen was demonstrated to be more effective than free chlorine or bromine alone against attached bacteria.

  19. Superfluorinated Ionic Liquid Crystals Based on Supramolecular, Halogen-Bonded Anions.

    PubMed

    Cavallo, Gabriella; Terraneo, Giancarlo; Monfredini, Alessandro; Saccone, Marco; Priimagi, Arri; Pilati, Tullio; Resnati, Giuseppe; Metrangolo, Pierangelo; Bruce, Duncan W

    2016-05-17

    Unconventional ionic liquid crystals in which the liquid crystallinity is enabled by halogen-bonded supramolecular anions [Cn F2 n+1 -I⋅⋅⋅I⋅⋅⋅I-Cn F2 n+1 ](-) are reported. The material system is unique in many ways, demonstrating for the first time 1) ionic, halogen-bonded liquid crystals, and 2) imidazolium-based ionic liquid crystals in which the occurrence of liquid crystallinity is not driven by the alkyl chains of the cation.

  20. Light-Absorbing Carbonaceous Particles: Chemical Composition and Its Implications for Direct Climate Forcing

    NASA Astrophysics Data System (ADS)

    Hemming, B. L.; Henze, D. K.; Akhtar, F.; Pinder, R. W.; Loughlin, D. H.

    2012-12-01

    Carbonaceous particles are understood to play a substantial role in direct climate forcing, but current estimates of this effect depend on very simple assumptions concerning the light absorbing properties of the materials from these particles are formed. The practice, to date is to classify all black (graphitic, combustion-derived) carbon as having a single mass absorption coefficient, with all other carbon consider only slightly- or completely non-absorbing. The substantial literature produced by the combustion sciences, biomass energy, and paper processing research communities suggest that particle carbon comprises a wide array of light-absorbing compounds having distinct light-absorbing properties of varying degrees of extinction efficiency. These materials accumulate in the particle phase, and are emitted at all stages of solid fuel pyrolysis and combustion. Filter-based measurements of carbonaceous PM collected from various solid fuel combustion sources show substantial variability in solar wavelength-dependent light absorption, with Angstrom Exponents ranging from as high as 12, down to 1. In this presentation, the fuel and combustion variables determining the degree of light absorption by carbonaceous particle components will be discussed, followed by a presentation of the results of a study applying the adjoint of the GEOS-Chem chemical transport model to an estimation of the sensitivity of direct forcing by carbonaceous particles to variation in burning phase-specific AE values.

  1. Carbonaceous cherts of the Barberton Greenstone Belt, South Africa: Isotopic, chemical and structural characteristics of individual microstructures

    NASA Astrophysics Data System (ADS)

    van Zuilen, Mark A.; Chaussidon, Marc; Rollion-Bard, Claire; Marty, Bernard

    2007-02-01

    Carbonaceous matter occurring in chert deposits of the 3.4-3.2 Ga old Barberton Greenstone Belt (BGB), South Africa, has experienced low grade regional metamorphism and variable degrees of local hydrothermal alteration. Here a detailed study is presented of in situ analysis of carbonaceous particles by LRS (laser Raman spectroscopy) and SIMS (secondary ion mass spectrometry), reporting degree of structural disorder, carbon isotope ratio and nitrogen-to-carbon ratio. This combination of in situ analytical tools is used to interpret the δ 13C values of only the best preserved carbonaceous remains, enabling the rejection of non-indigenous (unmetamorphosed) material as well as the exclusion of strongly hydrothermally altered carbonaceous particles. Raman spectroscopy confirmed that all carbonaceous cherts studied here have experienced a regional sub- to lower-greenschist facies metamorphic event. Although this identifies these organics as indigenous to the cherts, it is inferred from petrographic observations that hydrothermal alteration has caused small scale migration and re-deposition of organics. This suggest that morphological interpretation of these carbonaceous particles, and in general of putative microfossils or microlaminae in hydrothermally altered early Archean cherts, should be made with caution. A chert in the Hooggenoeg Formation, which is older than and has been hydrothermally altered by a volcanic event 3445 Ma ago, contains strongly altered carbonaceous particles with a uniform N/C-ratio of 0.001 and a range of δ 13C that is shifted from its original value. Cherts of the Kromberg Formation post-date this volcanic event, and contain carbonaceous particles with a N/C-ratio between 0.002 and 0.006. Both the Buck Reef Chert and the Footbridge Chert of the Kromberg Formation have retained fairly well-preserved δ 13C values, with ranges from -34‰ to -24‰ and -40‰ to -32 ‰, respectively. Abiologic reactions associated with hydrothermal

  2. Correlating Precisely Defined Primary Structure with Crystalline Properties in Halogen Containing Polyolefins

    NASA Astrophysics Data System (ADS)

    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.

  3. Nuclear magnetic biosignatures in the carbonaceous matter of ancient cherts: comparison with carbonaceous meteorites.

    PubMed

    Gourier, Didier; Delpoux, Olivier; Binet, Laurent; Vezin, Hervé

    2013-10-01

    The search for organic biosignatures is motivated by the hope of understanding the conditions of emergence of life on Earth and the perspective of finding traces of extinct life in martian sediments. Paramagnetic radicals, which exist naturally in amorphous carbonaceous matter fossilized in Precambrian cherts, were used as local structural probes and studied by electron paramagnetic resonance (EPR) spectroscopy. The nuclear magnetic resonance transitions of elements inside and around these radicals were detected by monitoring the nuclear modulations of electron spin echo in pulsed EPR. We found that the carbonaceous matter of fossilized microorganisms with age up to 3.5 billion years gives specific nuclear magnetic signatures of hydrogen (¹H), carbon (¹³C), and phosphorus (³¹P) nuclei. We observed that these potential biosignatures of extinct life are found neither in the carbonaceous matter of carbonaceous meteorites (4.56 billion years), the most ancient objects of the Solar System, nor in any carbonaceous matter resulting from carbonization of organic and bioorganic precursors. These results indicate that these nuclear signatures are sensitive to thermal episodes and can be used for Archean cherts with metamorphism not higher than the greenschist facies.

  4. Halogen-enriched fragment libraries as chemical probes for harnessing halogen bonding in fragment-based lead discovery.

    PubMed

    Zimmermann, Markus O; Lange, Andreas; Wilcken, Rainer; Cieslik, Markus B; Exner, Thomas E; Joerger, Andreas C; Koch, Pierre; Boeckler, Frank M

    2014-04-01

    Halogen bonding has recently experienced a renaissance, gaining increased recognition as a useful molecular interaction in the life sciences. Halogen bonds are favorable, fairly directional interactions between an electropositive region on the halogen (the σ-hole) and a number of different nucleophilic interaction partners. Some aspects of halogen bonding are not yet understood well enough to take full advantage of its potential in drug discovery. We describe and present the concept of halogen-enriched fragment libraries. These libraries consist of unique chemical probes, facilitating the identification of favorable halogen bonds by sharing the advantages of classical fragment-based screening. Besides providing insights into the nature and applicability of halogen bonding, halogen-enriched fragment libraries provide smart starting points for hit-to-lead evolution.

  5. High-temperature condensates in carbonaceous chondrites

    NASA Technical Reports Server (NTRS)

    Grossman, L.

    1977-01-01

    Equilibrium thermodynamic calculations of the sequence of condensation of minerals from a cooling gas of solar composition play an important role in explaining the mineralogy and trace element content of different types of inclusions in carbonaceous chondrites. Group IV B iron meteorites and enstatite chondrites may also be direct condensates from the solar nebula. Condensation theory provides a framework within which chemical fractionations between different classes of chondrites may be understood.

  6. Amino and fatty acids in carbonaceous meteorites

    NASA Technical Reports Server (NTRS)

    Kvenvolden, K. A.

    1974-01-01

    Analyses of two carbonaceous meteorites have provided much of the latest evidence which seems to support Oparin's theory on the origin of life. The meteorites involved are the Murray meteorite, which fell in 1950, and the Murchison meteorite, which fell in 1969. The amino acids in the two meteorites are similar in composition. Eight of the twenty amino acids found belong to amino acids present in proteins. A number of monocarboxylic and dicarboxylic fatty acids were also found in the meteorites.

  7. 40 CFR 721.329 - Halogenated benzyl ester acrylate (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 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...

  8. 40 CFR 721.329 - Halogenated benzyl ester acrylate (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 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...

  9. 40 CFR 721.329 - Halogenated benzyl ester acrylate (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 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...

  10. 40 CFR 721.329 - Halogenated benzyl ester acrylate (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 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...

  11. 40 CFR 721.329 - Halogenated benzyl ester acrylate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 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...

  12. Passivation of quartz for halogen-containing light sources

    DOEpatents

    Falkenstein, Zoran

    1999-01-01

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

  13. 40 CFR 721.536 - Halogenated phenyl alkane.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated phenyl alkane. 721.536... Substances § 721.536 Halogenated phenyl alkane. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated phenyl alkane (PMN P-89-867)...

  14. 40 CFR 721.535 - Halogenated alkane (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated alkane (generic). 721.535... Substances § 721.535 Halogenated alkane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated alkane (PMN P-01-433) is...

  15. 40 CFR 721.5546 - Halogen substituted oxetanes (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halogen substituted oxetanes (generic... Substances § 721.5546 Halogen substituted oxetanes (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as halogen substituted...

  16. 40 CFR 721.5546 - Halogen substituted oxetanes (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halogen substituted oxetanes (generic... Substances § 721.5546 Halogen substituted oxetanes (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as halogen substituted...

  17. 40 CFR 721.5546 - Halogen substituted oxetanes (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halogen substituted oxetanes (generic... Substances § 721.5546 Halogen substituted oxetanes (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as halogen substituted...

  18. 40 CFR 721.5546 - Halogen substituted oxetanes (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogen substituted oxetanes (generic... Substances § 721.5546 Halogen substituted oxetanes (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as halogen substituted...

  19. 40 CFR 721.5546 - Halogen substituted oxetanes (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halogen substituted oxetanes (generic... Substances § 721.5546 Halogen substituted oxetanes (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as halogen substituted...

  20. 40 CFR 721.10259 - Halogenated aromatic hydrocarbon (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halogenated aromatic hydrocarbon... Specific Chemical Substances § 721.10259 Halogenated aromatic hydrocarbon (generic). (a) Chemical substance... halogenated aromatic hydrocarbon (PMN P-09-540) is subject to reporting under this section for the...

  1. 40 CFR 721.10259 - Halogenated aromatic hydrocarbon (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halogenated aromatic hydrocarbon... Specific Chemical Substances § 721.10259 Halogenated aromatic hydrocarbon (generic). (a) Chemical substance... halogenated aromatic hydrocarbon (PMN P-09-540) is subject to reporting under this section for the...

  2. 40 CFR 721.10259 - Halogenated aromatic hydrocarbon (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halogenated aromatic hydrocarbon... Specific Chemical Substances § 721.10259 Halogenated aromatic hydrocarbon (generic). (a) Chemical substance... halogenated aromatic hydrocarbon (PMN P-09-540) is subject to reporting under this section for the...

  3. Halogenases: A Biotechnological Alternative for the Synthesis of Halogenated Pharmaceuticals.

    PubMed

    Ayala, Marcela; Segovia, Lorenzo; Torres, Eduardo

    2016-01-01

    The role of halogen atoms in pharmaceutical compounds has been recently revised, due to the weak interaction through the so called "halogen bond" between small molecules and proteins or other biomacromolecules, which could be fundamental for binding at a particular site within the macromolecule. Moreover, thousands of natural halogenated compounds have been described to date, pointing to a functional role of halogen atoms in these compounds, as well as a diversity of halogenating enzymes involved in the synthesis of these halogenated metabolites. In this mini-review the different halogenases described to date are presented, particularly those catalyzing halogenation reactions with potential applications in the pharmaceutical field. Oxidative halogenases following an electrophilic halogenation mechanism are the oldest and best characterized halogenases; however, novel halogenases following a nucleophilic halogenation mechanism have been recently described. The catalytic properties as well as the selectivity of some of these enzymes can be modulated through protein engineering, both by single point mutations or by directed evolution; on the other hand, metabolic pathway engineering has been used to improve the production of halogenated metabolites, as well as to produce novel halogenated compounds, potentially important in the pharmaceutical field. Recent advances and prospective on the field of enzymatic halogenation are covered.

  4. Halogenated silanes, radicals, and cations

    NASA Astrophysics Data System (ADS)

    Wang, Liming; He, Yi-Liang

    2008-09-01

    Quantum chemistry study has been carried out on the structure and energetics of halogenated silanes, radicals, and cations (SiHxXy0,+1, X = F, Cl, Br; x + y = 1-4). The geometries are optimized at B3LYP/6-31+G(2df,p) level. The adiabatic ionization energiess (IEas), relative energetics of cations, proton affinities (PAs) of silanes, and the enthalpies of formation are predicted using G3(CC) model chemistry. Non-classical ion complex structures are found for hydrogenated cations and transition states connecting classical and non-classical structures are also located. The most stable cations for silylene and silyl radicals have their classical divalent and trivalent structures, and those for silanes have non-classical structures except for SiH3Br+ and SiH2Br2+. The non-classical structures for halosilane cations imply difficulty in experimentally measurement of the adiabatic ionization energies using photoionization or photoelectron studies. For SiH3X, SiH2X2, and SiHX3, the G3(CC) adiabatic IEas to classical ionic structures closest to their neutrals agree better with the photoelectron spectroscopic measurements. The transition states between classical and non-classical structures also hamper the photoionization determination of the appearance energies for silylene cations from silanes. The G3(CC) results for SiHx0,+1 agree excellently with the photoionization mass spectrometric study, and the results for fluorinated and chlorinated species also agree with the previous theoretical predictions at correlation levels from BAC-MP4 to CCSD(T)/CBS. The predicted enthalpy differences between SiH2Cl+, SiHCl2+, and SiCl3+ are also in accordance with previous kinetics study. The G3(CC) results show large discrepancies to the collision-induced charge transfer and/or dissociation reactions involving SiFx+ and SiClx+ ions, for which the G3(CC) enthalpies of formation are also significantly differed from the previous theoretical predictions, especially on SiFx+ (x = 2-4). The G3

  5. A review and analysis of microwave absorption in polymer composites filled with carbonaceous particles

    NASA Astrophysics Data System (ADS)

    Qin, F.; Brosseau, C.

    2012-03-01

    Carbon (C) is a crucial material for many branches of modern technology. A growing number of demanding applications in electronics and telecommunications rely on the unique properties of C allotropes. The need for microwave absorbers and radar-absorbing materials is ever growing in military applications (reduction of radar signature of aircraft, ships, tanks, and targets) as well as in civilian applications (reduction of electromagnetic interference among components and circuits, reduction of the back-radiation of microstrip radiators). Whatever the application for which the absorber is intended, weight reduction and optimization of the operating bandwidth are two important issues. A composite absorber that uses carbonaceous particles in combination with a polymer matrix offers a large flexibility for design and properties control, as the composite can be tuned and optimized via changes in both the carbonaceous inclusions (C black, C nanotube, C fiber, graphene) and the embedding matrix (rubber, thermoplastic). This paper offers a perspective on the experimental efforts toward the development of microwave absorbers composed of carbonaceous inclusions in a polymer matrix. The absorption properties of such composites can be tailored through changes in geometry, composition, morphology, and volume fraction of the filler particles. Polymer composites filled with carbonaceous particles provide a versatile system to probe physical properties at the nanoscale of fundamental interest and of relevance to a wide range of potential applications that span radar absorption, electromagnetic protection from natural phenomena (lightning), shielding for particle accelerators in nuclear physics, nuclear electromagnetic pulse protection, electromagnetic compatibility for electronic devices, high-intensity radiated field protection, anechoic chambers, and human exposure mitigation. Carbonaceous particles are also relevant to future applications that require environmentally benign and

  6. Direct evidence of reactive ion etching induced damages in Ge2Sb2Te5 based on different halogen plasmas

    NASA Astrophysics Data System (ADS)

    Li, Juntao; Xia, Yangyang; Liu, Bo; Feng, Gaoming; Song, Zhitang; Gao, Dan; Xu, Zhen; Wang, Weiwei; Chan, Yipeng; Feng, Songlin

    2016-08-01

    Chalcogenide glasses based on Ge-Te-Sb are processed using reactive ion etching (RIE) in the fabrication of phase change memory (PCM). These materials are known to be halogenated easily and apt to be damaged when exposed to halogen gas based plasmas which can cause severe halogenation-induced degradation. In this paper, we investigate the RIE induced damage of popular phase change material Ge2Sb2Te5 (GST) in different halogen based plasmas (CF4, Cl2 and HBr) highly diluted by argon. After blanket etching, results of scanning electron microscopy and atomic force microscopy directly showed that the surface of Cl2 etched samples were roughest with a Ge deficient damaged layer. X-ray photoelectron spectroscopy was performed to investigate the chemical shift of constituent elements. Selected scans over the valence band peaks of Te 3d revealed that electrons were transferred from chalcogenide to halogen and the highest halogenation was observed on the GST etched by CF4. The GST films masked with patterned TiN were also etched. High-resolution transmission electron microscopy and surface scan directly showed the line profile and the damaged layer. Almost vertical and smooth sidewall without damaged layer makes HBr a promising gas for GST etch in the fabrication of high-density memory devices.

  7. Search for Organic Nanoglobules in Carbonaceous Chondrites Using Microtomography

    NASA Technical Reports Server (NTRS)

    Matsumoto, T.; Tsuchiyama, A.; Nakamura-Messenger, K.; Zolensky, M. E.; Nakano, T.; Uesugi, K.

    2010-01-01

    Primitive solar materials have various organic matters. In recent years, novel organic materials called organic nanoglobules of a few hundred micrometers in typical size were discovered in carbonaceous chondrites, IDPs, and comet 81P/Wild 2. The organic globules are spherical shape and in many cases with hollow structures. Composition of the globules are mainly aromatic carbon. The isotopic anomalies of SD and 6N 15 observed in the globules indicate that they were formed from photochemical reaction to ice particles at very low temperature environment, such as molecular clouds or outer protosolar disk. Aqueous alteration of organic matters and the gamma-ray irradiation to PAH are also suggested as alternative possible formation processes. If the globules are made from organic ice particles, the hollow regions of the globules are suggested to be once filled with volatile H20-rich organic ices, while if they were formed by aqueous alteration, the hollow regions should be filled with a fluid which caused the aqueous alteration. However, fluids in the globules have not been detected so far in the previous studies. If fluids were originally preserved in the hollows, they might be lost during destructive processes of sample separation or preparation for TEM observation. X-ray computed tomography (CT) is a nondestructive method which can determine 3-D internal structures of objects. SR (synchrotron radiation)-based imaging microtomography can give submicron spatial resolution [8] and was applied to micro textures in extraterrestrial materials, such as cometary grains captured by the Stardust mission [9]. If organic globules are observed non-destructively in carbonaceous chondrites by tomography, we can check the presence of fluids in the hollows. If fluids are preserved, we may analyze chemical and isotopic compositions of the fluids. The purpose of this study is to observe organic nanoglobules using imaging tomography for future analysis.

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

    NASA Technical Reports Server (NTRS)

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

    1976-01-01

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

  9. Mouse Model of Halogenated Platinum Salt Hypersensitivity

    EPA Science Inventory

    Occupational exposure to halogenated platinum salts can trigger the development of asthma. Concern for increased asthma risk exists for the general population due to the use of platinum (Pt) in catalytic converters and its emerging use as a diesel fuel additive. To investigate a...

  10. Skin Sensitizing Potency of Halogenated Platinum Salts.

    EPA Science Inventory

    The relationship between occupational exposure to halogenated platinum (Pt) salts and Pt-specific allergic sensitization is well-established. Although human case reports and clinical studies demonstrate that Pt salts are potent skin sensitizers, no studies have been published tha...

  11. Genotoxic activity of halogenated phenylglycine derivatives.

    PubMed

    Boto, Alicia; Gallardo, Juan A; Hernández, Rosendo; Ledo, Francisco; Muñoz, Ana; Murguía, José R; Menacho-Márquez, Mauricio; Orjales, Aurelio; Saavedra, Carlos J

    2006-12-01

    The discovery of genotoxic amino acids derived from phenylglycine, and possessing halogen substituents, is described. The utility of hypervalent iodine reagents in the synthesis of this class of compounds is highlighted. The mechanism of action of the (haloaryl)glycines was studied in Saccharomyces cerevisiae.

  12. Retention of Halogens in Waste Glass

    SciTech Connect

    Hrma, Pavel R.

    2010-05-01

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

  13. Reactions of halogen-pyridine systems

    SciTech Connect

    Coury, A.J.; Cahalan, P.T.

    1980-01-01

    The combination of halogens (acceptors) with pyridine derivatives (donors) produces, initially, charge transfer complexes with conductivities useful as depolarizers in lithium-halogen power cell cathodes. The complex most often employed in pacemaker batteries is I/sub 2//P2VP. Pyridines and halogens undergo additional reactions of consequence to cell performance. Such side reactions include: Alkyl group substitution, ring coupling, polymer molecular weight degradation, olefin addition and ring substitution. Instrumental analysis of model systems and the commercial iodine/poly-2-vinylpyridine (I/sub 2//P2VP) system provided evidence for alkyl group substitution, coupling and molecular weight degradation. The addition reaction was inferred from the presence of the needed reactants and their facile reactivity. Halogenation of the pyridine ring was not found. Side reactions cause reduced cathode capacity. Hydrogen halides generated by such side reactions may cause corrosion, but may enhance conductivity properties. Deleterious pressure buidup or dimensional changes may result from side reactions occurring within sealed battery cans. 7 refs.

  14. Uranium-Bearing Carbonaceous Nodules of Southwestern Oklahoma

    USGS Publications Warehouse

    Hill, James Wilcott

    1956-01-01

    Uranium-bearing carbonaceous nodules have been found along the north flank of the Wichita uplift in southwestern Oklahoma. The carbonaceous nodules are black, hard, and predominantly nodular shaped. One specimen, by analyses, was found to contain approximately 42 percent carbon and 3 percent hydrogen. The uranium, vanadium, cobalt, arsenic, nickel, lead and iron contents each range between 1 and 10 percent. It is concluded that the carbonaceous nodules are epigenetic and that the organic and inorganic constituents were derived from, mobile soluttons.

  15. Carbonaceous nanowire supports for polymer electrolyte membrane fuel cells

    SciTech Connect

    Garzon, Fernando H.; Wilson, Mahlon S.; Banham, Dustin; Ye, Siyu; More, Karren Leslie

    2015-12-03

    Here, carbohydrate-dye combinations were used to form ionically-linked soft templates for the formation of polypyrrole nanowire networks. High yields of nanostructured products were obtained using small amounts of low-cost carbohydrate and dye template materials, the majority of which remained encapsulated within the nanowires. Varying the concentration and the two-part ratio of the templates influenced the length and diameter of the nanofiber segments within the nanowire network. Pyrolysis of the nanowires yielded carbonaceous fibers containing nitrogen heteroatoms, as well as convoluted graphitic domains, well suited for supporting Pt nanoparticles. The resulting high density of nucleation sites enabled the formation of well dispersed, smaller Pt particles compared to commercial catalysts, despite significantly higher support surface loadings.

  16. Carbonaceous nanowire supports for polymer electrolyte membrane fuel cells

    DOE PAGES

    Garzon, Fernando H.; Wilson, Mahlon S.; Banham, Dustin; ...

    2015-12-03

    Here, carbohydrate-dye combinations were used to form ionically-linked soft templates for the formation of polypyrrole nanowire networks. High yields of nanostructured products were obtained using small amounts of low-cost carbohydrate and dye template materials, the majority of which remained encapsulated within the nanowires. Varying the concentration and the two-part ratio of the templates influenced the length and diameter of the nanofiber segments within the nanowire network. Pyrolysis of the nanowires yielded carbonaceous fibers containing nitrogen heteroatoms, as well as convoluted graphitic domains, well suited for supporting Pt nanoparticles. The resulting high density of nucleation sites enabled the formation of wellmore » dispersed, smaller Pt particles compared to commercial catalysts, despite significantly higher support surface loadings.« less

  17. Sorption of the monoterpenes α-pinene and limonene to carbonaceous geosorbents including biochar.

    PubMed

    Hale, Sarah E; Endo, Satoshi; Arp, Hans Peter H; Zimmerman, Andrew R; Cornelissen, Gerard

    2015-01-01

    The sorption of two monoterpenes, α pinene and limonene to the carbonaceous geosorbents graphite, bituminous coal, lignite coke, biochar and Pahokee peat was quantified. Polyethylene (PE) passive samplers were calibrated for the first time for these compounds by determining the PE-water partitioning coefficients and used as a tool to determine sorption to the carbonaceous geosorbents. Log KPE-water values were 3.49±0.58 for α pinene and 4.08±0.27 for limonene. The sorption of limonene to all materials was stronger than that for α pinene (differences of 0.2-1.3 log units between distribution coefficients for the monoterpenes). Placing Kd values in increasing order for α pinene gave biochar≈Pahokee peat≈bituminous coal≈lignite cokecarbonaceous geosorbent-water distribution coefficients were also calculated. There was no clear correlation of these distribution coefficients with SA. Elemental composition was used to assess the degree of condensation (or alteration) of the carbonaceous geosorbents. The degree of carbonisation increased in the order; Pahokee peat

  18. Iron Catalyzed Halogenation Processes in Saline Soils

    NASA Astrophysics Data System (ADS)

    Tubbesing, C.; Lippe, S.; Kullik, V.; Hauck, L.; Krause, T.; Keppler, F.; Schoeler, H. F.

    2014-12-01

    Within upcoming years the extent of salt deserts and salt lakes will probably increase due to climate change. It is known that volatile organic halogens (VOX) are released from saline soils and thus higher emissions from these environments are likely expected in the future. The origin of some organohalogens is not reasonably constrained by established natural halogenation processes. Therefore detailed biogeochemical investigations of these environments are necessary to identify the specific halogenation pathways. Redox-sensitive metals like iron are already known as triggers of chemical reactions via so called Fenton and Fenton-like reactions requiring H2O2 which is photochemically produced in water. In this study we collected soil samples from several salt lakes in Western Australia with pH values ranging from 2 to 8. The high pH variability was considered useful to study the impact of iron mobility and availability on halogenation processes. Iron was found to mainly occur as oxides and sulfides within the alkaline soils and acidic soils, respectively. All soil samples were lyophilised and finely ground prior to incubation at 40 °C for 24 h in aqueous solutions. Formation of volatile organic compounds (VOC) and VOX from these soils was observed using GC-FID and GC-MS. When H2O2 was added to the samples much higher concentrations of VOC and VOX were observed. Furthermore, when the pH of the soils was changed towards lower values higher emissions of VOC were also observed. Based on C-H activation processes we delineate a halide containing iron complex as a provider of anions reacting with previously generated hydrocarbon radicals. We suggest iron sulfate derivatives as those complexes which are generated if the above-mentioned natural H2O2 addition to iron sulfates and sulfides occurs. The origin of these complexes is able to explain the halogenation of chemically unreactive alkanes.

  19. Structural and Isotopic Analysis of Organic Matter in Carbonaceous Chondrites

    NASA Astrophysics Data System (ADS)

    Gilmour, I.

    2003-12-01

    The most ancient organic molecules available for study in the laboratory are those carried to Earth by infalling carbonaceous chondrite meteorites. All the classes of compounds normally considered to be of biological origin are represented in carbonaceous meteorites and, aside from some terrestrial contamination; it is safe to assume that these organic species were produced by nonbiological methods of synthesis. In effect, carbonaceous chondrites are a natural laboratory containing organic molecules that are the product of ancient chemical evolution. Understanding the sources of organic molecules in meteorites and the chemical processes that led to their formation has been the primary research goal. Circumstellar space, the solar nebulae, and asteroidal meteorite parent bodies have all been suggested as environments where organic matter may have been formed. Determination of the provenance of meteoritic organic matter requires detailed structural and isotopic information, and the fall of the Murchison CM2 chondrite in 1969 enabled the first systematic organic analyses to be performed on comparatively pristine samples of extraterrestrial organic material. Prior to that, extensive work had been undertaken on the organic matter in a range of meteorite samples galvanized, in part, by the controversial debate in the early 1960s on possible evidence for former life in the Orgueil carbonaceous chondrite (Fitch et al., 1962; Meinschein et al., 1963). It was eventually demonstrated that the suggested biogenic material was terrestrial contamination ( Fitch and Anders, 1963; Anders et al., 1964); however, the difficulties created by contamination have posed a continuing problem in the analysis and interpretation of organic material in meteorites (e.g., Watson et al., 2003); this has significant implications for the return of extraterrestrial samples by space missions. Hayes (1967) extensively reviewed data acquired prior to the availability of Murchison samples

  20. Carbonaceous chondrites. II - Carbonaceous chondrite phyllosilicates and light element geochemistry as indicators of parent body processes and surface conditions

    NASA Technical Reports Server (NTRS)

    Bunch, T. E.; Chang, S.

    1980-01-01

    Petrographic analyses of CM matrices characterized four phyllosilicates in Murray and Murchison meteorites and Fe- and Mg-serpentines in Nogoya. All phyllosilicates and bulk matrices show enrichment of K relative to Na when compared with bulk meteorites; the loss of Na and some Cl, and the addition of H2O, CO2, and water-soluble organics during alteration indicates a partially open system. Synthesis of soluble organic materials may have occurred in CM matrices before aqueous alteration of the precursive phases. Nogoya was 95% altered and has a bulk C content of 5.2%, higher than any meteorite; also, it has the lowest measured C-13/C-12 ratio of any carbonaceous chondrite except for Karoonda.

  1. The destruction of halogenated organic chemicals by plasma pyrolysis.

    PubMed

    Barton, T G; Mordy, J A

    1984-08-01

    Very high destruction efficiencies for halogenated chemicals have been achieved by plasma pyrolysis. Destruction efficiencies exceeded 99.9999999% for tests with polychlorinated biphenyls (PCBs). Preliminary tests with tetrachloromethane have obtained destruction efficiencies exceeding 99.99%. The plasma pyrolysis process involved the creation of a 250-kW plasma with a temperature in excess of 25 000 degrees C. The toxic material was injected into the plasma zone at a rate between 1 and 2 L/min. Thermochemical and photochemical dissociation of the toxic materials produced atoms and ions which recombined to form primarily H2, CO, HCl, and particulate carbon. The HCl was neutralized by NaOH. The flaring of the H2 and CO should destroy to a high degree any trace residuals. The application of plasma pyrolysis for the ultimate disposal of toxicological waste was also investigated. Rat carcasses containing mean lethal dosage of PCB were pyrolyzed.

  2. Chiral Biomarkers and Microfossils in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Hoover, Richard B.

    2010-01-01

    Homochirality of the biomolecules (D-sugars of DNA and RNA and L-amino acids of proteins) is a fundamental property of all life on Earth. Abiotic mechanisms yield racemic mixtures (D/L=1) of chiral molecules and after the death of an organism, the enantiopure chiral biomolecules slowly racemize. Several independent investigators have now established that the amino acids present in CI1 and CM2 carbonaceous meteorites have a moderate to strong excess of the L-enantiomer. Stable isotope data have established that these amino acids are both indigenous and extraterrestrial. Carbonaceous meteorites also contain many other strong chemical biomarkers including purines and pyrimidines (nitrogen heterocycles of nucleic acids); pristine and phytane (components of the chlorophyll pigment) and morphological biomarkers (microfossils of filamentous cyanobacteria). Energy dispersive X-ray Spectroscopy (EDS) analysis reveals that nitrogen is below the detectability level in most of the meteorite filaments as well as in Cambrian Trilobites and filaments of 2.7 Gya Archaean cyanobacteria from Karelia. The deficiency of nitrogen in the filaments and the total absence of sugars, of twelve of the life-critical protein amino acids, and two of the nucleobases of DNA and RNA provide clear and convincing evidence that these filaments are not modern biological contaminants. This paper reviews the chiral, chemical biomarkers morphological biomarkers and microfossils in carbonaceous meteorites. This paper reviews chiral and morphological biomarkers and discusses the missing nitrogen, sugars, protein amino acids, and nucleobases as ?bio-discriminators? that exclude modern biological contaminants as a possible explanation for the permineralized cyanobacterial filaments found in the meteorites.

  3. Acritarchs in carbonaceous meteorites and terrestrial rocks

    NASA Astrophysics Data System (ADS)

    Rozanov, Alexei Y.; Hoover, Richard B.

    2013-10-01

    Acritarchs are a group of organic-walled, acid-resistant microfossils of uncertain or unknown origin. Some are thought to represent the cysts or resting stages of unicellular protists (possibly dinoflagellates), chrysophytes (green algae) or other planktonic eukaryotic algae. Acritarchs are found throughout the geologic column extending back as far at 3.2 Ga. The presence of large sphaeromorphs in the Archaean provides evidence that the eukaryotic lineage extends much farther back in time than previously thought possible. Acritarchs are abundant in the Paleoproterozoic shales (1.9-1.6 Ga) of the former Soviet Union and they have been extensively used for the investigation of Proterozoic and Paleozoic biostratigraphy and paleoenvironmental parameters. Scanning Electron Microscope studies have revealed the fossilized remains of organic-walled microfossils of unknown origin and exhibiting characteristics of acritarchs in a variety of carbonaceous meteorites. In many cases, these remains are black or brown in color and have Carbon/Oxygen ratios suggesting they have been diagenetically converted into kerogen. It is not feasible that the fossilized remains of organicwalled microfossils such as acritarchs represent biological contaminant that invaded and became embedded in the rock matrix of carbonaceous meteorites within the short time periods of their residence on Earth. Consequently, these groups of microfossils are considered to provide an additional line for the existence of indigenous extraterrestrial microbial remains in meteorites. This paper presents a brief review of acritarchs in terrestrial rocks and provides images of a number of similar morphotypes of uncertain origin found in freshly fractured samples of carbonaceous meteorites.

  4. Hypervelocity impact survivability experiments for carbonaceous impactors

    NASA Technical Reports Server (NTRS)

    Bunch, T. E.; Becker, Luann; Bada, Jeffrey; Macklin, John; Radicatidibrozolo, Filippo; Fleming, R. H.; Erlichman, Jozef

    1993-01-01

    We performed a series of hypervelocity impact experiments using carbon-bearing impactors (diamond, graphite, fullerenes, phthalic acid crystals, and Murchison meteorite) into Al plate at velocities between 4.2 and 6.1 km/s. These tests were made to do the following: (1) determine the survivability of carbon forms and organize molecules in low hypervelocity impact; (2) characterize carbonaceous impactor residues; and (3) determine whether or not fullerenes could form from carbonaceous impactors, under our experimental conditions, or survive as impactors. An analytical protocol of field emission SEM imagery, SEM-EDX, laser Raman spectroscopy, single and 2-stage laser mass spectrometry, and laser induced fluorescence (LIF) found the following: (1) diamonds did not survive impact at 4.8 km/s, but were transformed into various forms of disordered graphite; (2) intact, well-ordered graphite impactors did survive impact at 5.9 km/sec, but were only found in the crater bottom centers; the degree of impact-induced disorder in the graphite increases outward (walls, rims, ejecta); (3) phthalic acid crystals were destroyed on impact (at 4.2 km/s, although a large proportion of phthalic acid molecules did survive impact); (4) fullerenes did not form as products of carbonaceous impactors (5.9 - 6.1 km/s, fullerene impactor molecules mostly survived impact at 5.9 km/s; and (5) two Murchison meteorite samples (launched at 4.8 and 5.9 km/s) show preservation of some higher mass polycyclic aromatic hydrocarbons (PAHs) compared with the non-impacted sample. Each impactor type shows unique impactor residue morphologies produced at a given impact velocity. An expanded methodology is presented to announce relatively new analytical techniques together with innovative modifications to other methods that can be used to characterize small impact residues in LDEF craters, in addition to other acquired extraterrestrial samples.

  5. Spectral reflectance properties of carbonaceous chondrites - 5: CO chondrites

    NASA Astrophysics Data System (ADS)

    Cloutis, E. A.; Hudon, P.; Hiroi, T.; Gaffey, M. J.; Mann, P.

    2012-08-01

    We examined the spectral reflectance properties of 16 CO-type carbonaceous chondrites (CCs) in order to better understand their range of spectral properties, develop spectral-compositional correlations, and provide information that may aid in the search for CO parent bodies. As a group, our CO powder spectra have some similarities and differences. COs have experienced varying degree of thermal metamorphism, with petrologic subgrades ranging from ˜CO3.0 to ˜CO3.8. Their reflectance spectra are characterized by a ubiquitous absorption feature in the 1 μm region, and a nearly ubiquitous feature in the 2 μm region that appears in CO >3.1 spectra. The 1 μm region feature is attributable to abundant Fe-bearing amorphous phases (and Fe-poor olivine) in the lower petrologic subtypes, which gradually transforms to more abundant and Fe-rich olivine with increasing metamorphism. The increase in depth and decrease in wavelength position of this feature are consistent with this transformation. All but the least-altered COs also exhibit an absorption feature in the 2 μm region whose depth also generally increases with increasing metamorphic grade, resulting in increasingly blue-sloped spectra and larger band area ratios. The wavelength position and change in depth of this feature (ranging from 0% to 12.2%) is consistent with increasing Fe2+ in spinel, which is present in calcium-aluminum and ameboid olivine inclusions. Reflectance of a local reflectance maximum near 0.8 μm increases with increasing thermal metamorphism and this is likely due to the loss and aggregation of carbonaceous phases. The increasing reflectance is negatively correlated with various measures of spectral slope (i.e., brighter = bluer), and while this cannot be uniquely attributed to any one cause, it is consistent with increasing spinel Fe2+ content and decreasing carbonaceous material abundance or aggregation. With decreasing grain size, CO spectra normally become brighter and more red-sloped. The

  6. Microfossils in CI and CO Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Hoover, Richard B.; Rozanov, Alexei Y.; Jerman, Gregory; Costen, James

    2003-01-01

    Secondary and backscatter electron images and x-ray spectral data of selected CI (Alais, Orgueil, and Tagish Lake) and CO3 (Rainbow and Dar a1 Gani 749) carbonaceous meteorites have recently been obtained using Field Emission and Environmental Scanning Electron Microscopes These studies indicate the presence of a large assemblage of biomarkers and complex lithified and carbonized remains of bodies that we interpret as indigenous microfossils. We discuss the meteorites, provide images of many of the biogenic forms found embedded in the freshly fractured meteorite surfaces.

  7. Carbonaceous fuel combustion with improved desulfurization

    DOEpatents

    Yang, Ralph T.; Shen, Ming-shing

    1980-01-01

    Lime utilization for sulfurous oxides adsorption in fluidized combustion of carbonaceous fuels is improved by impregnation of porous lime particulates with iron oxide. The impregnation is achieved by spraying an aqueous solution of mixed iron sulfate and sulfite on the limestone before transfer to the fluidized bed combustor, whereby the iron compounds react with the limestone substrate to form iron oxide at the limestone surface. The iron oxide present in the spent limestone is found to catalyze the regeneration rate of the spent limestone in a reducing environment. Thus both the calcium and iron components may be recycled.

  8. Fossil Diatoms in a New Carbonaceous Meteorite

    NASA Astrophysics Data System (ADS)

    Wickramasinghe, N. C.; Wallis, J.; Wallis, D. H.; Samaranayake, Anil

    2013-01-01

    We report the discovery for the first time of diatom frustules in a carbonaceous meteorite that fell in the North Central Province of Sri Lanka on 29 December 2012. Contamination is excluded by the circumstance that the elemental abundances within the structures match closely with those of the surrounding matrix. There is also evidence of structures morphologically similar to red rain cells that may have contributed to the episode of red rain that followed within days of the meteorite fall. The new data on "fossil" diatoms provide strong evidence to support the theory of cometary panspermia.

  9. Amino acids in Antarctic CM1 meteorites and their relationship to other carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Botta, Oliver; Martins, Zita; Ehrenfreund, Pascale

    2007-08-01

    CM2 carbonaceous chondrites are the most primitive material present in the solar system, and some of their subtypes, the CM and CI chondrites, contain up to 2 wt% of organic carbon. The CM2 carbonaceous chondrites contain a wide variety of complex amino acids, while the CI1 meteorites Orgueil and Ivuna display a much simpler composition, with only glycine and β-alanine present in significant abundances. CM1 carbonaceous chondrites show a higher degree of aqueous alteration than CM2 types and therefore provide an important link between the CM2 and CI1 carbonaceous chondrites. Relative amino acid concentrations have been shown to be indicative for parent body processes with respect to the formation of this class of compounds. In order to understand the relationship of the amino acid composition between these three types of meteorites, we have analyzed for the first time three Antarctic CM1 chondrites, Meteorite Hills (MET) 01070, Allan Hills (ALH) 88045, and LaPaz Icefield (LAP) 02277, using gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography-fluorescence detection (HPLC-FD). The concentrations of the eight most abundant amino acids in these meteorites were compared to those of the CM2s Murchison, Murray, Mighei, Lewis Cliff (LEW) 90500, ALH 83100, as well as the CI1s Orgueil and Ivuna. The total amino acid concentration in CM1 carbonaceous chondrites was found to be much lower than the average of the CM2s. Relative amino acid abundances were compared in order to identify synthetic relationships between the amino acid compositions in these meteorite classes. Our data support the hypothesis that amino acids in CM- and CI-type meteorites were synthesized under different physical and chemical conditions and may best be explained with differences in the abundances of precursor compounds in the source regions of their parent bodies in combination with the decomposition of amino acids during extended aqueous alteration.

  10. Everyone Wins: A Mars-Impact Origin for Carbonaceous Phobos and Deimos

    NASA Technical Reports Server (NTRS)

    Fries, M.; Welzenbach, L.; Steele, A.

    2016-01-01

    Discussions of Phobos' and Deimos' origin(s) tend to feature an orthogonally opposed pair of observations: dynamical studies which favor coalescence of the moons from an orbital debris ring arising from a large impact on Mars; and reflectance spectroscopy of the moons that indicate a carbonaceous composition that is not consistent with Martian surface materials. One way to reconcile this discrepancy is to consider the option of a Mars-impact origin for Phobos and Deimos, followed by surficial decoration of carbon-rich materials by interplanetary dust particles (IDP). The moons experience a high IDP flux because of their location in Mars' gravity well. Calculations show that accreted carbon is sufficient to produce a surface with reflectance spectra resembling carbonaceous chondrites.

  11. Hypervelocity impact survivability experiments for carbonaceous impactors, part 2

    NASA Technical Reports Server (NTRS)

    Bunch, T. E.; Paque, Julie M.; Becker, Luann; Vedder, James F.; Erlichman, Jozef

    1995-01-01

    Hypervelocity impact experiments were performed to further test the survivability of carbonaceous impactors and to determine potential products that may have been synthesized during impact. Diamonds were launched by the Ames two-stage light gas gun into Al plate at velocities of 2.75 and 3.1 km sec(exp -1). FESEM imagery confirms that diamond fragments survived in both experiments. Earlier experiments found that diamonds were destroyed on impact above 4.3 km sec(exp -1). Thus, the upper stability limit for diamond on impact into Al, as determined from our experimental conditions, is between 3.1 and 4.3 km sec(exp -1). Particles of the carbonaceous chondrite Nogoya were also launched into Al at a velocity of 6.2 km sec (exp -1). Laser desorption (L (exp 2) MS) analyses of the impactor residues indicate that the lowest and highest mass polycyclic aromatic hydrocarbons (PAH's) were largely destroyed on impact; those of intermediate mass (202-220 amu) remained at the same level or increased in abundance. In addition, alkyl-substituted homologs of the most abundant pre-impacted PAH's were synthesized during impact. These results suggest that an unknown fraction of some organic compounds can survive low to moderate impact velocities and that synthesized products can be expected to form up to velocities of, at least, 6.5 km sec(exp -1). We also present examples of craters formed by a unique microparticle accelerator that could launch micron-sized particles of almost any coherent material at velocities up to approximately 15 km sec(exp -1). Many of the experiments have a direct bearing on the interpretation of LDEF craters.

  12. Hypervelocity impact survivability experiments for carbonaceous impactors, part 2

    SciTech Connect

    Bunch, T.E.; Paque, J.M.; Becker, L.; Vedder, J.F.; Erlichman, J. ||

    1995-02-01

    Hypervelocity impact experiments were performed to further test the survivability of carbonaceous impactors and to determine potential products that may have been synthesized during impact. Diamonds were launched by the Ames two-stage light gas gun into Al plate at velocities of 2.75 and 3.1 km sec(exp -1). FESEM imagery confirms that diamond fragments survived in both experiments. Earlier experiments found that diamonds were destroyed on impact above 4.3 km sec(exp -1). Thus, the upper stability limit for diamond on impact into Al, as determined from our experimental conditions, is between 3.1 and 4.3 km sec(exp -1). Particles of the carbonaceous chondrite Nogoya were also launched into Al at a velocity of 6.2 km sec (exp -1). Laser desorption (L (exp 2) MS) analyses of the impactor residues indicate that the lowest and highest mass polycyclic aromatic hydrocarbons (PAH`s) were largely destroyed on impact; those of intermediate mass (202-220 amu) remained at the same level or increased in abundance. In addition, alkyl-substituted homologs of the most abundant pre-impacted PAH`s were synthesized during impact. These results suggest that an unknown fraction of some organic compounds can survive low to moderate impact velocities and that synthesized products can be expected to form up to velocities of, at least, 6.5 km sec(exp -1). The authors also present examples of craters formed by a unique microparticle accelerator that could launch micron-sized particles of almost any coherent material at velocities up to approximately 15 km sec(exp -1). Many of the experiments have a direct bearing on the interpretation of LDEF craters.

  13. Dating carbonaceous matter in archean cherts by electron paramagnetic resonance.

    PubMed

    Bourbin, M; Gourier, D; Derenne, S; Binet, L; Le Du, Y; Westall, F; Kremer, B; Gautret, P

    2013-02-01

    Ancient geological materials are likely to be contaminated through geological times. Thus, establishing the syngeneity of the organic matter embedded in a mineral matrix is a crucial step in the study of very ancient rocks. This is particularly the case for Archean siliceous sedimentary rocks (cherts), which record the earliest traces of life. We used electron paramagnetic resonance (EPR) for assessing the syngeneity of organic matter in cherts that have a metamorphic grade no higher than greenschist. A correlation between the age of Precambrian samples and the shape of their EPR signal was established and statistically tested. As thermal treatments impact organic matter maturity, the effect of temperature on this syngeneity proxy was studied; cyanobacteria were submitted to cumulative short thermal treatment at high temperatures followed by an analysis of their EPR parameters. The resulting carbonaceous matter showed an evolution similar to that of a thermally treated young chert. Furthermore, the possible effect of metamorphism, which is a longer thermal event at lower temperatures, was ruled out for cherts older than 2 Gyr, based on the study of Silurian cherts of the same age and same precursors but various metamorphic grades. We determined that even the most metamorphosed sample did not exhibit the lineshape of an Archean sample. In the hope of detecting organic contamination in Archean cherts, a "contamination-like" mixture was prepared and studied by EPR. It resulted that the lineshape analysis alone does not allow contamination detection and that it must be performed along with cumulative thermal treatments. Such treatments were applied to three Archean chert samples, making dating of their carbonaceous matter possible. We concluded that EPR is a powerful tool to study primitive organic matter and could be used in further exobiology studies on low-metamorphic grade samples (from Mars for example).

  14. Evidence of Microfossils in Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Hoover, Richard B.; Rozanov, Alexei Y.; Zhmur, S. I.; Gorlenko, V. M.

    1998-01-01

    Investigations have been carried out on freshly broken, internal surfaces of the Murchison, Efremovka and Orgueil carbonaceous chondrites using Scanning Electron Microscopes (SEM) in Russia and the Environmental Scanning Electron Microscope (ESEM) in the United States. These independent studies on different samples of the meteorites have resulted in the detection of numerous spherical and ellipsoidal bodies (some with spikes) similar to the forms of uncertain biogenicity that were designated "organized elements" by prior researchers. We have also encountered numerous complex biomorphic microstructures in these carbonaceous chondrites. Many of these complex bodies exhibit diverse characteristics reminiscent of microfossils of cyanobacteria such as we have investigated in ancient phosphorites and high carbon rocks (e.g. oil shales). Energy Dispersive Spectroscopy (EDS) analysis and 2D elemental maps shows enhanced carbon content in the bodies superimposed upon the elemental distributions characteristic of the chondritic matrix. The size, distribution, composition, and indications of cell walls, reproductive and life cycle developmental stages of these bodies are strongly suggestive of biology' These bodies appear to be mineralized and embedded within the meteorite matrix, and can not be attributed to recent surface contamination effects. Consequently, we have interpreted these in-situ microstructures to represent the lithified remains of prokaryotes and filamentous cyanobacteria. We also detected in Orgueil microstructures morphologically similar to fibrous kerite crystals. We present images of many biomorphic microstructures and possible microfossils found in the Murchison, Efremovka, and Orgueil chondrites and compare these forms with known microfossils from the Cambrian phosphate-rich rocks (phosphorites) of Khubsugul, Northern Mongolia.

  15. Radiocarbon: nature's tracer for carbonaceous pollutants

    SciTech Connect

    Currie, L.A.; Klouda, G.A.; Gerlach, R.W.

    1982-01-01

    Recent developments in radiocarbon dating techniques have made it feasible to determine /sup 14/C//sup 12/C ratios in samples containing milligram or even microgram quantities of carbon. As a result, it has become practicable to apply these techniques to the study of trace gases and particles in the atmosphere, as a means of resolving anthropogenic from natural source components. Interpretation of /sup 14/C data is straightforward: biospheric carbon (such as vegetation) is alive with a /sup 14/C//sup 12/C ratio of about 1.5 x 10 to the 12th power, whereas fossil carbon is dead. Beyond this dichotomous classification it becomes very interesting to combine the isotopic data with concurrent chemical data, as well as spatial and temporal distributions, in order to infer the strengths of specific sources of carbonaceous pollutants. A brief review will be presented of program on atmospheric gases and carbonaceous particles. For the latter, the authors have assayed individual chemical and size fractions, and samples collected in urban, rural, and remote locales. The biogenic carbon fraction -- presumably from wood-burning -- ranged from 10 to 100% for the urban samples analyzed.

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

    PubMed

    Beauchamp, Guy

    2008-10-23

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

  17. Halogen bonding origin properties and applications

    NASA Astrophysics Data System (ADS)

    Hobza, Pavel

    2015-12-01

    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.

  18. Halogen bonding origin properties and applications

    SciTech Connect

    Hobza, Pavel

    2015-12-31

    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.

  19. Method and apparatus for detecting halogenated hydrocarbons

    DOEpatents

    Monagle, Matthew; Coogan, John J.

    1997-01-01

    A halogenated hydrocarbon (HHC) detector is formed from a silent discharge (also called a dielectric barrier discharge) plasma generator. A silent discharge plasma device receives a gas sample that may contain one or more HHCs and produces free radicals and excited electrons for oxidizing the HHCs in the gas sample to produce water, carbon dioxide, and an acid including halogens in the HHCs. A detector is used to sensitively detect the presence of the acid. A conductivity cell detector combines the oxidation products with a solvent where dissociation of the acid increases the conductivity of the solvent. The conductivity cell output signal is then functionally related to the presence of HHCs in the gas sample. Other detectors include electrochemical cells, infrared spectrometers, and negative ion mobility spectrometers.

  20. Halogenating activities detected in Antarctic macroalgae

    SciTech Connect

    Laturnus, F.; Adams, F.C.; Gomez, I.; Mehrtens, G.

    1997-03-01

    Halogenating activities were determined in samples of 18 cultivated species of brown, red and green macroalgae from the Antarctic. Activities for the halogenating organic compounds with bromide, iodide and chloride were found. Investigated red algae (rhodophytes) showed higher brominating and iodinating activities compared to brown (phaeophytes) and green (chlorophytes) algae. The highest brominating and iodinating activities were measured in the red algae Plocamium cartilagineum (1.11 {+-} 0.01 U g{sup -1} wet algal weight and 0.18 U g{sup -1} wet algal weight, respectively) and Myriogramme mangini (3.62 {+-} 0.17 U g{sup -1} wet algal weight and 4.5 U g{sup -1} wet algal weight, respectively). Chlorinating activities were detected in the red alga Plocamium cartilagineum only (0.086 U g{sup -1} wet algal weight). 30 refs., 2 figs., 1 tab.

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

    DOEpatents

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

    1987-08-21

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

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

    DOEpatents

    Huang, Hann S.; Sather, Norman F.

    1988-01-01

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

  3. Oxidation of hydrogen halides to elemental halogens

    DOEpatents

    Rohrmann, Charles A.; Fullam, Harold T.

    1985-01-01

    A process for oxidizing hydrogen halides having substantially no sulfur impurities by means of a catalytically active molten salt is disclosed. A mixture of the subject hydrogen halide and an oxygen bearing gas is contacted with a molten salt containing an oxidizing catalyst and alkali metal normal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen and substantially free of sulfur oxide gases.

  4. Reduction of halogenated ethanes by green rust.

    SciTech Connect

    O'Loughlin, E. J.; Burris, D. R.; Environmental Research; Air Force Research Lab.; Integrated Science and Technology, Inc.

    2004-01-01

    Green rusts, mixed Fe{sup II}/Fe{sup III} hydroxide minerals present in many suboxic environments, have been shown to reduce a number of organic and inorganic contaminants. The reduction of halogenated ethanes was examined in aqueous suspensions of green rust, both alone and with the addition of Ag{sup I} (AgGR) and Cu{sup II} (CuGR). Hexachloroethane (HCA), pentachloroethane (PCA), 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA), 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA), 1,1,1-trichloroethane (1,1,1-TCA), 1,1,2-trichloroethane (1,1,2-TCA), 1,1-dichloroethane (1,1-DCA), and 1,2-dibromoethane were reduced in the presence of green rust alone, AgGR, or CuGR; only 1,2-dichloroethane and chloroethane were nonreactive. The reduction was generally more rapid for more highly substituted ethanes than for ethanes having fewer halogen groups (HCA > PCA > 1,1,1,2-TeCA > 1,1,1-TCA > 1,1,2,2-TeCA > 1,1,2-TCA > 1,1-DCA), and isomers with the more asymmetric distributions of halogen groups were more rapidly reduced than the isomer with greater symmetry (e.g., 1,1,1-TCA > 1,1,2-TCA). The addition of Ag{sup I} or Cu{sup II} to green rust suspensions resulted in a substantial increase in the rate of halogenated ethane reduction as well as significant differences in the product distributions with respect to green rust alone.

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

    PubMed

    Ford, Melissa Coates; Ho, P Shing

    2016-03-10

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

  6. Study of the Vertical Scale of Halogen Chemistry at Sunrise at Barrow, AK

    NASA Astrophysics Data System (ADS)

    Tackett, P.; Cavender, A.; Morin, S.; Savarino, J.; Deary, J.; Bottenheim, J.; Steffen, A.; Shepson, P.

    2005-12-01

    The vertical extent of halogen chemistry in the Arctic springtime was investigated through the measurement of several atmospheric chemical components. Various chemical species that are modified by halogen chemistry were measured during late March through mid-April 2005, including VOCs, ozone, and mercury. Airborne volatile organic compounds were sampled through ambient air samples and collected onto Tenax-TA sorbent material. GEM (gaseous elemental mercury) was sampled through a Teflon inlet leading to a ground-based cold vapor atomic fluorescence mercury analyzer, and ambient ozone concentrations were determined using a 2B ozone spectrometer. The sampling apparatus was suspended beneath a tethered balloon that allowed collection at multiple altitudes extending up to 300 meters. The Tenax sample tubes were analyzed via cryo-concentrated thermal desorption/GC, and detected by FID (flame ionization detection). Species will be presented and discussed in a vertical profile format to enable analysis of the vertical extent of halogen chemistry in the halogen-rich lower atmosphere occurring during polar sunrise.

  7. Analyzing the Chemical and Spectral Effects of Pulsed Laser Irradiation to Simulate Space Weathering of a Carbonaceous Chondrite

    NASA Technical Reports Server (NTRS)

    Thompson, M. S.; Keller, L. P.; Christoffersen, R.; Loeffler, M. J.; Morris, R. V.; Graff, T. G.; Rahman, Z.

    2017-01-01

    Space weathering processes alter the chemical composition, microstructure, and spectral characteristics of material on the surfaces of airless bodies. The mechanisms driving space weathering include solar wind irradiation and the melting, vaporization and recondensation effects associated with micrometeorite impacts e.g., [1]. While much work has been done to understand space weathering of lunar and ordinary chondritic materials, the effects of these processes on hydrated carbonaceous chondrites is poorly understood. Analysis of space weathering of carbonaceous materials will be critical for understanding the nature of samples returned by upcoming missions targeting primitive, organic-rich bodies (e.g., OSIRIS-REx and Hayabusa 2). Recent experiments have shown the spectral properties of carbonaceous materials and associated minerals are altered by simulated weathering events e.g., [2-5]. However, the resulting type of alteration i.e., reddening vs. bluing of the reflectance spectrum, is not consistent across all experiments [2-5]. In addition, the microstructural and crystal chemical effects of many of these experiments have not been well characterized, making it difficult to attribute spectral changes to specific mineralogical or chemical changes in the samples. Here we report results of a pulsed laser irradiation experiment on a chip of the Murchison CM2 carbonaceous chondrite to simulate micrometeorite impact processing.

  8. Supramolecular chemistry of halogens: complementary features of inorganic (M-X) and organic (C-X') halogens applied to M-X...X'-C halogen bond formation.

    PubMed

    Zordan, Fiorenzo; Brammer, Lee; Sherwood, Paul

    2005-04-27

    Electronic differences between inorganic (M-X) and organic (C-X) halogens in conjunction with the anisotropic charge distribution associated with terminal halogens have been exploited in supramolecular synthesis based upon intermolecular M-X...X'-C halogen bonds. The synthesis and crystal structures of a family of compounds trans-[MCl(2)(NC(5)H(4)X-3)(2)] (M = Pd(II), Pt(II); X = F, Cl, Br, I; NC(5)H(4)X-3 = 3-halopyridine) are reported. With the exception of the fluoropyridine compounds, network structures propagated by M-Cl...X-C halogen bonds are adopted and involve all M-Cl and all C-X groups. M-Cl...X-C interactions show Cl...X separations shorter than van der Waals values, shorter distances being observed for heavier halogens (X). Geometries with near linear Cl...X-C angles (155-172 degrees ) and markedly bent M-Cl...X angles (92-137 degrees ) are consistently observed. DFT calculations on the model dimers {trans-[MCl(2)(NH(3))(NC(5)H(4)X-3)]}(2) show association through M-Cl...X-C (X not equal F) interactions with geometries similar to experimental values. DFT calculations of the electrostatic potential distributions for the compounds trans-[PdCl(2)(NC(5)H(4)X-3)(2)] (X = F, Cl, Br, I) demonstrate the effectiveness of the strategy to activate C-X groups toward halogen bond formation by enhancing their electrophilicity, and explain the absence of M-Cl...F-C interactions. The M-Cl...X-C halogen bonds described here can be viewed unambiguously as nucleophile-electrophile interactions that involve an attractive electrostatic contribution. This contrasts with some types of halogen-halogen interactions previously described and suggests that M-Cl...X-C halogen bonds could provide a valuable new synthon for supramolecular chemists.

  9. Effect of halogenated impurities on lifetime of organic light emitting diode

    NASA Astrophysics Data System (ADS)

    Yamawaki, Hayato; Suzuki, Kunihiko; Kubota, Tomohiro; Watabe, Takeyoshi; Ishigaki, Ayumi; Nakamura, Rina; Inoue, Hideko; Nakashima, Harue; Horikoshi, Nozomi; Nowatari, Hiromi; Kataishi, Riho; Hamada, Toshiki; Sasaki, Toshiki; Suzuki, Tsunenori; Seo, Satoshi

    2016-09-01

    We investigated a correlation between lifetime and the halogen element concentration in an organic light-emitting diode (OLED) and conducted experiments and simulations to discuss degradation mechanisms due to the halogen. OELD is generally formed of high-purity materials. Since the synthesis of high-purity materials takes time and cost, quantitative understanding of the kind, amount, and influence of impurities in OLED devices is expected. The results of combustion ion chromatography show that, if the chlorine concentration in the host material is more than several parts per million, the lifetime of the device is drastically reduced. The chlorine element, which is derived from the chlorinated by-product of the host material, is found to be transferred from the chloride to other materials (e.g., an emissive dopant) according to the results of LC-MS analysis. In addition, the electron transport layer including such impurities is also found to adversely affect the lifetime. The results of TOF-SIMS analysis suggest that the dissociated chlorine element diffuse to the light-emitting layer side when the device is driven. The results of simulations (Gaussian 09) and electrochemical analyses (cyclic voltammetry and electrolysis) reveal that the halogen element is easy to dissociate from halide by excitation or reduction. The halogen element can repeat reactions with the peripheral materials by excitation or reduction and cause damages, e.g., generate radicals or further reaction products due to the radicals. The results of simulation suggest that, such compounds have low energy level and become quenchers.

  10. Evidence for Extended Aqueous Alteration in CR Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Trigo-Rodriquez, J. M.; Moyano-Cambero, C. E.; Mestres, N.; Fraxedas, J.; Zolensky, M.; Nakamura, T.; Martins, Z.

    2013-01-01

    We are currently studying the chemical interrelationships between the main rockforming components of carbonaceous chondrites (hereafter CC), e.g. silicate chondrules, refractory inclusions and metal grains, and the surrounding meteorite matrices. It is thought that the fine-grained materials that form CC matrices are representing samples of relatively unprocessed protoplanetary disk materials [1-3]. In fact, modern non-destructive analytical techniques have shown that CC matrices host a large diversity of stellar grains from many distinguishable stellar sources [4]. Aqueous alteration has played a role in homogeneizing the isotopic content that allows the identification of presolar grains [5]. On the other hand, detailed analytical techniques have found that the aqueously-altered CR, CM and CI chondrite groups contain matrices in which the organic matter has experienced significant processing concomitant to the formation of clays and other minerals. In this sense, clays have been found to be directly associated with complex organics [6, 7]. CR chondrites are particularly relevant in this context as this chondrite group contains abundant metal grains in the interstitial matrix, and inside glassy silicate chondrules. It is important because CR are known for exhibiting a large complexity of organic compounds [8-10], and only metallic Fe is considered essential in Fischer-Tropsch catalysis of organics [11-13]. Therefore, CR chondrites can be considered primitive materials capable to provide clues on the role played by aqueous alteration in the chemical evolution of their parent asteroids.

  11. Microfossils of Cyanobacteria in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Hoover, Richard B.

    2007-01-01

    During the past decade, Environmental and Field Emission Scanning Electron Microscopes have been used at the NASA/Marshall Space Flight Center to investigate freshly fractured interior surfaces of a large number of different types of meteorites. Large, complex, microfossils with clearly recognizable biological affinities have been found embedded in several carbonaceous meteorites. Similar forms were notably absent in all stony and nickel-iron meteorites investigated. The forms encountered are consistent in size and morphology with morphotypes of known genera of Cyanobacteria and microorganisms that are typically encountered in associated benthic prokaryotic mats. Even though many coccoidal and isodiametric filamentous cyanobacteria have a strong morphological convergence with some other spherical and filamentous bacteria and algae, many genera of heteropolar cyanobacteria have distinctive apical and basal regions and cellular differentiation that makes it possible to unambiguously recognize the forms based entirely upon cellular dimensions, filament size and distinctive morphological characteristics. For almost two centuries, these morphological characteristics have historically provided the basis for the systematics and taxonomy of cyanobacteria. This paper presents ESEM and FESEM images of embedded filaments and thick mats found in-situ in the Murchison CM2 and Orgueil cn carbonaceous meteorites. Comparative images are also provided for known genera and species of cyanobacteria and other microbial extremophiles. Energy Dispersive X-ray Spectroscopy (EDS) studies indicate that the meteorite filaments typically exhibit dramatic chemical differentiation with distinctive difference between the possible microfossil and the meteorite matrix in the immediate proximity. Chemical differentiation is also observed within these microstructures with many of the permineralized filaments enveloped within electron transparent carbonaceous sheaths. Elemental distributions of

  12. Microfossils of cyanobacteria in carbonaceous meteorites

    NASA Astrophysics Data System (ADS)

    Hoover, Richard B.

    2007-09-01

    During the past decade, Environmental and Field Emission Scanning Electron Microscopes have been used at the NASA/Marshall Space Flight Center to investigate freshly fractured interior surfaces of a large number of different types of meteorites. Large, complex, microfossils with clearly recognizable biological affinities have been found embedded in several carbonaceous meteorites. Similar forms were notably absent in all stony and nickel-iron meteorites investigated. The forms encountered are consistent in size and morphology with morphotypes of known genera of Cyanobacteria and microorganisms that are typically encountered in associated benthic prokaryotic mats. Even though many coccoidal and isodiametric filamentous cyanobacteria have a strong morphological convergence with some other spherical and filamentous bacteria and algae, many genera of heteropolar cyanobacteria have distinctive apical and basal regions and cellular differentiation that makes it possible to unambiguously recognize the forms based entirely upon cellular dimensions, filament size and distinctive morphological characteristics. For almost two centuries, these morphological characteristics have historically provided the basis for the systematics and taxonomy of cyanobacteria. This paper presents ESEM and FESEM images of embedded filaments and thick mats found in-situ in the Murchison CM2 and Orgueil CI1 carbonaceous meteorites. Comparative images are also provided for known genera and species of cyanobacteria and other microbial extremophiles. Energy Dispersive X-ray Spectroscopy (EDS) indicates that the meteorite filaments typically exhibit dramatic chemical differentiation with distinctive difference between the possible microfossil and the meteorite matrix in the immediate proximity. Chemical differentiation is also observed within these microstructures with many of the permineralized filaments enveloped within electron transparent carbonaceous sheaths. Elemental distributions of these

  13. Hexahalogenated and their mixed benzene derivatives as prototypes for the understanding of halogen···halogen intramolecular interactions: New insights from combined DFT, QTAIM-, and RDG-based NCI analyses.

    PubMed

    Varadwaj, Pradeep R; Varadwaj, Arpita; Jin, Bih-Yaw

    2015-12-05

    A large number of fully halogenated benzene derivatives containing the fluorine, chlorine, bromine, and iodine atoms have been experimentally synthesized both as single- and co-crystals (e.g., Desiraju et al., Chem. Eur. J. 2006, 12, 2222), yet the natures of the halogen ··· halogen interactions between the vicinal halogens in these compounds within the intramolecular domain are undisclosed. Given a fundamental understanding of these interactions is incredibly important in many areas of chemical, biological, supramolecular, and material sciences, we present here our newly discovered theoretical results that delineate whilst the nature of an F···F interaction in a pair of two adjacent fluorine atoms in either of the hexafluorobenzene and 1,4-dibromotetrafluorobenzene compounds examined is almost unclear, each of the latter three hexahalogenated benzene derivatives (viz., C6 Cl6 , C6 Br6 , and C6 I6 ), and each of the seven of their fully mixed hexahalogenated benzene analogues, are found to be stabilized by means of a number of halogen···halogen interactions, each a form of long-range attraction within the intramolecular domain. The Molecular Electrostatic Surface Potential model was found to be unsurprisingly unsuitable in unraveling any of the aforesaid attractions between the halogen atoms. However, such interactions successfully enunciated by a set of noncovalent interaction descriptors of geometrical, topological, and electrostatic origins. These latter properties were extracted combining the results of the Density Functional Theory electronic structure calculations with those revealed from Atoms in Molecules, and Reduced Density Gradient charge density-based topological calculations, and are expounded in detail to formalize the conclusions. © 2015 Wiley Periodicals, Inc.

  14. Carbonaceous chondrites. I - Characterization and significance of carbonaceous chondrite /CM/ xenoliths in the Jodzie howardite

    NASA Technical Reports Server (NTRS)

    Bunch, T. E.; Chang, S.; Frick, U.; Neil, J.; Moreland, G.

    1979-01-01

    Mineralogical, chemical, textural, and isotopic studies of the abundant carbonaceous inclusions in the Jodzie howardite which are consistent with carbonaceous chondrite (CM) characteristics are examined. These CM xenoliths show regolith alteration comparable to the Murray and Murchison meteorites but less than Nogoya, flow-oriented development of phyllosilicates and 'poorly characterized phases', and partial oxidation of sulfides. Temperature-programmed pyrolysis mass spectrometry indicates that gas release patterns of volatiles and hydrocarbons, and N, C, and S contents are typical of CM meteorites. The fact that the Ne content is typical for 'solar' values and the isotopic structure of Xe is 'planetary' indicates that these gases were entrapped by different mechanisms, and cosmic ray exposure ages for the xenoliths agree with the reported exposure age for the eucritic host.

  15. Ion Irradiation Experiments on the Murchison CM2 Carbonaceous Chondrite: Simulating Space Weathering of Primitive Asteroids

    NASA Technical Reports Server (NTRS)

    Keller, L. P.; Christoffersen, R.; Dukes, C. A.; Baragiola, R. A.; Rahman, Z.

    2015-01-01

    Remote sensing observations show that space weathering processes affect all airless bodies in the Solar System to some degree. Sample analyses and lab experiments provide insights into the chemical, spectroscopic and mineralogic effects of space weathering and aid in the interpretation of remote- sensing data. For example, analyses of particles returned from the S-type asteroid Itokawa by the Hayabusa mission revealed that space-weathering on that body was dominated by interactions with the solar wind acting on LL ordinary chondrite-like materials [1, 2]. Understanding and predicting how the surface regoliths of primitive carbonaceous asteroids respond to space weathering processes is important for future sample return missions (Hayabusa 2 and OSIRIS-REx) that are targeting objects of this type. Here, we report the results of our preliminary ion irradiation experiments on a hydrated carbonaceous chondrite with emphasis on microstructural and infrared spectral changes.

  16. Comparative study of carbonaceous meteoritic fragments by micro-Raman spectroscopy and SEM/EDS.

    NASA Astrophysics Data System (ADS)

    Dall'Asén, AnalíA.; Mittelstaedt, Jacob; Kim, Jin-Sun; Baer, Brandon; Paul, Raka; Gerton, Jordan; Bromley, Benjamin; Kenyon, Scott

    2017-01-01

    Meteorites provide precious clues about the formation of planets in the solar system. In particular, carbonaceous chondritic meteorites, considered the most primitive surviving materials from the early Solar System, can contribute to understand how planetisimals (the precursors to planets, of 1-100 km in radius) formed from dust (micron-size grains). These relics are mainly composed of chondrules (micro/millimeter-sized inclusions) surrounded by a matrix of microparticles. Here we present a comparative study of the structure and composition of the chondrules and surrounding matrix of different carbonaceous chondritic meteorites using low- and high-resolution micro-Raman spectroscopy and SEM/EDS (Scanning Electron Microscopy/Energy Dispersive X-ray Spectroscopy). We examine how these properties vary in different regions of the chondrules and matrix, capturing details from micrometer to millimeter scales. We compare the structure and composition between different samples, looking for signatures of the physical processes that drove their formation.

  17. Sustainable approach toward synthesis of green functional carbonaceous 3-D micro/nanostructures from biomass

    NASA Astrophysics Data System (ADS)

    Tavangar, Amirhossein; Tan, Bo; Venkatakrishnan, Krishnan

    2013-08-01

    This study proposes a novel technique to synthesize functional carbonaceous three-dimensional (3-D) micro/nanocompounds from agricultural by-products using femtosecond laser irradiation. Biowastes of rice husk and wheat straw are value-engineered to carbonaceous structures in a single-step process under ambient conditions. Our results demonstrate that by controlling the laser fluence, structures with a variety of different morphologies from nanostructures to microstructures can be achieved. Also, the results indicate that altering the laser processing parameters influences the chemical composition of the synthesized structures. This sustainable approach presents an important step towards synthesizing 3-D micro/nanofibrous compounds from biowaste materials. These structures, as-synthesized or as nanocomposite fillers, can have practical uses in electronic, sensing, biological, and environmental applications.

  18. Adsorption and Desorption of Carbon Dioxide and Water Mixtures on Synthetic Hydrophobic Carbonaceous Adsorbents

    NASA Technical Reports Server (NTRS)

    Finn, John E.; Harper, Lynn D. (Technical Monitor)

    1994-01-01

    Several synthetic carbonaceous adsorbents produced through pyrolysis of polymeric materials are available commercially. Some appear to have advantages over activated carbon for certain adsorption applications. In particular, they can have tailored hydrophobicities that are significantly greater than that of activated carbon, while moderately high surfaces areas are retained. These sorbents are being investigated for possible use in removing trace contaminants and excess carbon dioxide from air in closed habitats, plant growth chambers, and other applications involving purification of humid gas streams. We have analyzed the characteristics of a few of these adsorbents through adsorption and desorption experiments and standard characterization techniques. This paper presents pure and multicomponent adsorption data collected for carbon dioxide and water on two synthetic carbonaceous adsorbents having different hydrophobicities and capillary condensation characteristics. The observations are interpreted through consideration of the pore structure and surface chemistry of the solids and interactions between adsorbed carbon dioxide, water, and the solvent gas.

  19. Organic analysis of the Antarctic carbonaceous chondrites

    NASA Technical Reports Server (NTRS)

    Kotra, R. K.; Shimoyama, A.; Ponnamperuma, C.; Hare, P. E.; Yanai, K.

    1981-01-01

    Thus far, organic analysis of carbonaceous chondrites has proven the only fruitful means of examining complex organic matter of extraterrestrial origin. The present paper presents the results of organic analysis of two Antarctic meteorites, Allan Hills (77306) and Yamato (74662), which may be considered free from terrestrial contamination. Ion-exchange chromatography, gas chromatography and mass spectrometery of meteorite samples reveal the presence in Yamato of 15 and in Allan Hills of 20 protein and nonprotein amino acids, the most abundant of which are glycine and alanine. Abundances of the D and L enantiomers of each amino acid are also found to be nearly equal. Data thus indicate an abiotic extraterrestrial origin for the matter, and confirm a lack of terrestrial contamination.

  20. Halogen bonds in crystal engineering: like hydrogen bonds yet different.

    PubMed

    Mukherjee, Arijit; Tothadi, Srinu; Desiraju, Gautam R

    2014-08-19

    The halogen bond is an attractive interaction in which an electrophilic halogen atom approaches a negatively polarized species. Short halogen atom contacts in crystals have been known for around 50 years. Such contacts are found in two varieties: type I, which is symmetrical, and type II, which is bent. Both are influenced by geometric and chemical considerations. Our research group has been using halogen atom interactions as design elements in crystal engineering, for nearly 30 years. These interactions include halogen···halogen interactions (X···X) and halogen···heteroatom interactions (X···B). Many X···X and almost all X···B contacts can be classified as halogen bonds. In this Account, we illustrate examples of crystal engineering where one can build up from previous knowledge with a focus that is provided by the modern definition of the halogen bond. We also comment on the similarities and differences between halogen bonds and hydrogen bonds. These interactions are similar because the protagonist atoms-halogen and hydrogen-are both electrophilic in nature. The interactions are distinctive because the size of a halogen atom is of consequence when compared with the atomic sizes of, for example, C, N, and O, unlike that of a hydrogen atom. Conclusions may be drawn pertaining to the nature of X···X interactions from the Cambridge Structural Database (CSD). There is a clear geometric and chemical distinction between type I and type II, with only type II being halogen bonds. Cl/Br isostructurality is explained based on a geometric model. In parallel, experimental studies on 3,4-dichlorophenol and its congeners shed light on the nature of halogen···halogen interactions and reveal the chemical difference between Cl and Br. Variable temperature studies also show differences between type I and type II contacts. In terms of crystal design, halogen bonds offer a unique opportunity in the strength, atom size and interaction gradation; this may be

  1. Chromatographic resolution of closely related species in pharmaceutical chemistry: dehalogenation impurities and mixtures of halogen isomers.

    PubMed

    Regalado, Erik L; Zhuang, Ping; Chen, Yadan; Makarov, Alexey A; Schafer, Wes A; McGachy, Neil; Welch, Christopher J

    2014-01-07

    In recent years, the use of halogen-containing molecules has proliferated in the pharmaceutical industry, where the incorporation of halogens, especially fluorine, has become vitally important for blocking metabolism and enhancing the biological activity of pharmaceuticals. The chromatographic separation of halogen-containing pharmaceuticals from associated isomers or dehalogenation impurities can sometimes be quite difficult. In an attempt to identify the best current tools available for addressing this important problem, a survey of the suitability of four chromatographic method development platforms (ultra high-performance liquid chromatography (UHPLC), core shell HPLC, achiral supercritical fluid chromatography (SFC) and chiral SFC) for separating closely related mixtures of halogen-containing pharmaceuticals and their dehalogenated isosteres is described. Of the 132 column and mobile phase combinations examined for each mixture, a small subset of conditions were found to afford the best overall performance, with a single UHPLC method (2.1 × 50 mm, 1.9 μm Hypersil Gold PFP, acetonitrile/methanol based aqueous eluents containing either phosphoric or perchloric acid with 150 mM sodium perchlorate) affording excellent separation for all samples. Similarly, a survey of several families of closely related halogen-containing small molecules representing the diversity of impurities that can sometimes be found in purchased starting materials for synthesis revealed chiral SFC (Chiralcel OJ-3 and Chiralpak IB, isopropanol or ethanol with 25 mM isobutylamine/carbon dioxide) as well as the UHPLC (2.1 × 50 mm, 1.8 μm ZORBAX RRHD Eclipse Plus C18 and the Gold PFP, acetonitrile/methanol based aqueous eluents containing phosphoric acid) as preferred methods.

  2. Carbonaceous adsorbent regeneration and halocarbon displacement by hydrocarbon gases

    DOEpatents

    Senum, G.I.; Dietz, R.N.

    1994-04-05

    This invention describes a process for regeneration of halocarbon bearing carbonaceous adsorbents through which a carbonaceous adsorbent is contacted with hydrocarbon gases, preferably propane, butane and pentane at near room temperatures and at atmospheric pressure. As the hydrocarbon gases come in contact with the adsorbent, the hydrocarbons displace the halocarbons by physical adsorption. As a result of using this process, the halocarbon concentration and the hydrocarbon eluant is increased thereby allowing for an easier recovery of pure halocarbons. By using the process of this invention, carbonaceous adsorbents can be regenerated by an inexpensive process which also allows for subsequent re-use of the recovered halocarbons. 8 figures.

  3. Carbonaceous adsorbent regeneration and halocarbon displacement by hydrocarbon gases

    DOEpatents

    Senum, Gunnar I.; Dietz, Russell N.

    1994-01-01

    This invention describes a process for regeneration of halocarbon bearing carbonaceous adsorbents through which a carbonaceous adsorbent is contacted with hydrocarbon gases, preferably propane, butane and pentane at near room temperatures and at atmospheric pressure. As the hydrocarbon gases come in contact with the adsorbent, the hydrocarbons displace the halocarbons by physical adsorption. As a result of using this process, the halocarbon concentration and the hydrocarbon eluant is increased thereby allowing for an easier recovery of pure halocarbons. By using the process of this invention, carbonaceous adsorbents can be regenerated by an inexpensive process which also allows for subsequent re-use of the recovered halocarbons.

  4. The distribution of trace elements in carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Knab, H.-J.

    1981-09-01

    Twelve carbonaceous chondrites, among them representatives of nearly all known petrologic types, were analyzed for twenty trace elements by spark source mass spectrography combined with the isotope dilution method. Data on different element groups (refractory, moderately volatile and volatile) show that the distribution of the trace elements in the carbonaceous chondrites, with the exception of Renazzo, can be well explained by Anders' two-component model. This is also valid for the highly metamorphosed CV5 chondrite Karoonda. Furthermore, it is observed that the Zr/Hf-ratios in the carbonaceous chondrites increase with increasing petrologic type, which is interpreted as the result of mixing two components with different Zr/Hf-ratios.

  5. Plasma gasification of carbonaceous wastes: thermodynamic analysis and experiment

    NASA Astrophysics Data System (ADS)

    Messerle, V. E.; Mosse, A. L.; Ustimenko, A. B.

    2016-07-01

    Thermodynamic calculations of the plasma gasification process of carbonaceous wastes in air and steam ambient were carried out. A maximum yield of synthesis gas in such processes is predicted to be achieved at a temperature of 1600 K. On a specially developed plasma facility, plasma gasification experiments were performed for carbonaceous wastes. From the organic mass of carbonaceous waste and from its mineral mass, respectively, a high-calorific syngas and a neutral slag consisting predominantly of ferric carbide, calcium monosilicate, silica and iron, were obtained. A comparison between the experiment and the calculations has shown a good consistency between the data.

  6. Halogenated MOF-5 variants show new configuration, tunable band gaps and enhanced optical response in the visible and near infrared.

    PubMed

    Yang, Li-Ming; Fang, Guo-Yong; Ma, Jing; Pushpa, Raghani; Ganz, Eric

    2016-11-30

    Inspired by recent experimental fabrication of mono-halogenated versions of Metal-Organic Framework MOF-5 (i.e., X-MOF-5, X = F to I) and some experimentally known fully halogenated MOF compounds, we systematically studied frameworks incorporating full halogenation of the BDC linkers of the prototypical Iso-Reticular Metal-Organic Framework (IRMOF) series, exemplified by MOF-5. Using quantum chemistry calculations, we find that halogenation leads to a 90° rotation of the aryl group, which is mainly ascribed to overcrowding between halogen atoms and the carboxyl and benzene ring and strong repulsion among in-plane atoms/groups. The 90° configuration decreases the repulsion, and maximizes the stabilization energy, and is therefore more stable than 0° configuration. We find that the band gap can be tuned from 4.1 to 1.5 eV as we go from F, Cl, Br, to I. This extends the optical response of these experimentally accessible materials through the visible and infrared region. We have also considered a broader range of new materials that substitute various metals for Zn. Totally, 70 materials were systematically examined computationally including (M4O)(BDC-Z4)3 (M = Zn, Cd, Be, Mg, Ca, Sr, Ba; Z = H, F, Cl, Br, I). For the full range of materials, we calculate band gaps of 4.2 to 1.0 eV, corresponding to a threshold of absorption of 290-1240 nm. Four selected materials were tested for stability using short 5 ps molecular dynamics simulations up to 600 K. The new materials with the smallest band gaps could potentially be used in near-infrared (NIR) light-emitting devices. Other properties, e.g., bulk moduli, formation energy, chemical bonding, and optical properties, were also investigated. The present results may provide new materials for use as novel photocatalysts, photoactive materials for photovoltaic cells, or functional devices in nanoelectronics and optoelectronics.

  7. Origin of plagioclase-olivine inclusions in carbonaceous chondrites

    SciTech Connect

    Sheng, Y.J.; Hutcheon, I.D.; Wasserburg, G.J. )

    1991-02-01

    Plagioclase-Olivine Inclusions (POIs) are an abundant group of chondrule-like objects with igneous textures found in carbonaceous chondrites. POIs consist of plagioclase, olivine, pyroxene, and spinel, and cover a wide range of compositions between Type C Ca-Al-rich Inclusions (CAIs) and ferromagnesian chondrules. POIs are distinguished from CAIs by the absence of melilite, lack of refractory siderophile-rich opaque assemblages, more sodic plagioclase, and abundance of olivine and aluminousenstatite. Rare accessory minerals including armalcolite, zirconolite, rutile, and sapphirine are found in several POIs. The petrographic and chemical properties of POIs indicate that they are not condensates or evaporative residues but formed by melting or partial melting of pre-existing solids. Seven of fourteen POIs contain isotopically fractionated Mg, and despite their textures these POIs are not isotopically homogeneous. A comparison of the essential characteristics of POIs and CAIs suggests that the major processes leading to formation of POIs - including condensation, dust/gas fractionation, aggregation of chemically and isotopically disparate materials, and partial melting - are common to most CAIs and chondrules. We present a scenario for the formulation of these objects and conclude that the homogeneity of the final assemblage - CAI, POI, or chondrule - is primarily a reflection of the thermal history rather than the nature of precursor materials.

  8. Crystallinity of Fe-Ni Sulfides in Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Zolensky, Michael E.; Ohsumi, Kazumasa; Mikouchi, Takashi; Hagiya, Kenji; Le, Loan

    2008-01-01

    The main long-term goal of this research is to understand the physical conditions in the early solar nebula through the detailed characterization of a key class of mineral present in all primitive materials: Fe-Ni sulfides [1&2]. Fe-Ni sulfides can take dozens of structures, depending on the temperature of formation, as well as other physico-chemical factors which are imperfectly understood. Add to this the additional varying factor of Ni content, and we have a potentially sensitive cosmothermometer [3]. Unfortunately, this tool requires exact knowledge of the crystal structure of each grain being considered, and there have been few (none?) studies of the detailed structures of sulfides in chondritic materials. We report here on coordinated compositional and crystallographic investigation of Fe-Ni sulfides in diverse carbonaceous chondrites, initially Acfer 094 (the most primitive CM2 [4]) Tagish Lake (a unique type C2 [5]), a C1 lithology in Kaidun [6], Bali (oxidized CV3 [7]), and Efremovka (reduced CV3 [7]).

  9. MoS2 Surface Structure Tailoring via Carbonaceous Promoter

    PubMed Central

    Shi, Yumeng; Li, Henan; Wong, Jen It; Zhang, Xiaoting; Wang, Ye; Song, Huaihe; Yang, Hui Ying

    2015-01-01

    Atomically thin semiconducting transition-metal dichalcogenides have been attracting lots of attentions, particularly, molybdenum disulfide (MoS2) monolayers show promising applications in field effect transistors, optoelectronics and valleytronics. However, the controlled synthesis of highly crystalline MoS2 remain a challenge especially the systematic approach to manipulate its structure and morphology. Herein, we report a method for controlled synthesis of highly crystalline MoS2 by using chemical vapor deposition method with carbonaceous materials as growth promoter. A uniform and highly crystalline MoS2 monolayer with the grain size close to 40 μm was achieved. Furthermore, we extend the method to the manipulation of MoS2 morphology, flower-shape vertical grown MoS2 layers were obtained on growth promoting substrates. This simple approach allows an easy access of highly crystalline MoS2 layers with morphology tuned in a controllable manner. Moreover, the flower-shape MoS2 grown on graphene oxide film used as an anode material for lithium-ion batteries showed excellent electrochemical performance. PMID:25994238

  10. Mercury and halogens in coal: Chapter 2

    USGS Publications Warehouse

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

    2014-01-01

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

  11. Retrieval Algorithms for the Halogen Occultation Experiment

    NASA Technical Reports Server (NTRS)

    Thompson, Robert E.; Gordley, Larry L.

    2009-01-01

    The Halogen Occultation Experiment (HALOE) on the Upper Atmosphere Research Satellite (UARS) provided high quality measurements of key middle atmosphere constituents, aerosol characteristics, and temperature for 14 years (1991-2005). This report is an outline of the Level 2 retrieval algorithms, and it also describes the great care that was taken in characterizing the instrument prior to launch and throughout its mission life. It represents an historical record of the techniques used to analyze the data and of the steps that must be considered for the development of a similar experiment for future satellite missions.

  12. Laboratory Investigations of Stratospheric Halogen Chemistry

    NASA Technical Reports Server (NTRS)

    Wine, Paul H.; Nicovich, J. Michael; Stickel, Robert E.; Hynes, Anthony J.

    1997-01-01

    A final report for the NASA-supported project on laboratory investigations of stratospheric halogen chemistry is presented. In recent years, this project has focused on three areas of research: (1) kinetic, mechanistic, and thermochemical studies of reactions which produce weakly bound chemical species of atmospheric interest; (2) development of flash photolysis schemes for studying radical-radical reactions of stratospheric interest; and (3) photochemistry studies of interest for understanding stratospheric chemistry. The first section of this paper contains a discussion of work which has not yet been published. All subsequent chapters contain reprints of published papers that acknowledge support from this grant.

  13. FIELD SCREENING FOR HALOGENATED VOLATILE ORGANIC COMPOUNDS

    SciTech Connect

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

    2003-07-01

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

  14. Boiling Heat Transfer to Halogenated Hydrocarbon Refrigerants

    NASA Astrophysics Data System (ADS)

    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.

  15. Occurrence of uranium-bearing coal, carbonaceous shale, and carbonaceous limestone in the Fall Creek area, Bonneville County, Idaho

    USGS Publications Warehouse

    Vine, James D.; Moore, George W.

    1952-01-01

    Uraniferous coal, carbonaceous shale, and carbonaceous limestone occur in the Bear River formation of Upper Crestaceous age at the Fall Creek prospect, in the Fall Creek area, Bonneville County, IDaho. The uranium compounds are believed to have been derived from mildly radioactive silicic volcanic rocks of the Tertiary age that rest unconformably on all older rocks and once overlay the Bear River formation and its coal. Meteoric water, percolating downward through the silicic volcanic rocks and into the older rocks along joints and faults, is believed to have brought the uranium compounds into contact with the coal and carbonaceous rocks in which the uranium was absorbed.

  16. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

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

  17. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

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

  18. 40 CFR 721.10015 - Halogenated benzimidazole (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halogenated benzimidazole (generic... Specific Chemical Substances § 721.10015 Halogenated benzimidazole (generic). (a) Chemical substance and... benzimidazole (PMN P-01-110) is subject to reporting under this section for the significant new uses...

  19. 40 CFR 721.10015 - Halogenated benzimidazole (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halogenated benzimidazole (generic... Specific Chemical Substances § 721.10015 Halogenated benzimidazole (generic). (a) Chemical substance and... benzimidazole (PMN P-01-110) is subject to reporting under this section for the significant new uses...

  20. 40 CFR 721.10015 - Halogenated benzimidazole (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halogenated benzimidazole (generic... Specific Chemical Substances § 721.10015 Halogenated benzimidazole (generic). (a) Chemical substance and... benzimidazole (PMN P-01-110) is subject to reporting under this section for the significant new uses...

  1. 40 CFR 721.10015 - Halogenated benzimidazole (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halogenated benzimidazole (generic... Specific Chemical Substances § 721.10015 Halogenated benzimidazole (generic). (a) Chemical substance and... benzimidazole (PMN P-01-110) is subject to reporting under this section for the significant new uses...

  2. 40 CFR 721.10015 - Halogenated benzimidazole (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated benzimidazole (generic... Specific Chemical Substances § 721.10015 Halogenated benzimidazole (generic). (a) Chemical substance and... benzimidazole (PMN P-01-110) is subject to reporting under this section for the significant new uses...

  3. Field-Reversal Source for Negative Halogen Ions

    NASA Technical Reports Server (NTRS)

    Chutjian, A.; Orient, O. J.; Aladzhadzhyan, S. H.

    1987-01-01

    Large zero-energy electron-attachment cross sections result in intense ion beams. Concept for producing negative halogen ions takes advantage of large cross sections at zero kinetic energy for dissociative attachment of electrons to such halogen-containing gases as SF6, CFCI3, and CCI4.

  4. Parametrization of the SCC-DFTB Method for Halogens.

    PubMed

    Kubař, Tomáš; Bodrog, Zoltán; Gaus, Michael; Köhler, Christof; Aradi, Bálint; Frauenheim, Thomas; Elstner, Marcus

    2013-07-09

    Parametrization of the approximative DFT method SCC-DFTB for halogen elements is presented. The new parameter set is intended to describe halogenated organic as well as inorganic molecules, and it is compatible with the established parametrization of SCC-DFTB for carbon, hydrogen, oxygen, and nitrogen. The performance of the parameter set is tested on a representative set of molecules and discussed.

  5. 40 CFR 721.8750 - Halogenated substituted pyridine.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8750 Halogenated substituted pyridine. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated...

  6. 40 CFR 721.8750 - Halogenated substituted pyridine.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8750 Halogenated substituted pyridine. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated...

  7. 40 CFR 721.8750 - Halogenated substituted pyridine.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8750 Halogenated substituted pyridine. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated...

  8. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

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

  9. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

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

  10. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

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

  11. 40 CFR 721.8750 - Halogenated substituted pyridine.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8750 Halogenated substituted pyridine. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated...

  12. Method for halogenating or radiohalogenating a chemical compound

    DOEpatents

    Kabalka, George W.

    2006-05-09

    A method for obtaining a halogenated organic compound, whereby an organotrifluoroborate compound is reacted with a halide ion in the presence of an oxidizing agent to produce the corresponding halogenated organic compound. The method may be used for producing radiohalogenated organic compounds.

  13. A Cautionary Tale About Volatile-Rich Carbonaceous Chondrites

    NASA Astrophysics Data System (ADS)

    Britt, D. T.; Beltran, E.

    2015-07-01

    The organic component of volatile-rich carbonaceous chondrite meteorites are primarily in the form of polycyclic aromatic hydrocarbons (PAHs). While PAHs are common in the environment, many species of PAHs are either toxic or carcinogenic or both.

  14. Carbonaceous cathode with enhanced wettability for aluminum production

    DOEpatents

    Keller, Rudolf; Gatty, David G.; Barca, Brian J.

    2003-09-09

    A method of preparing carbonaceous blocks or bodies for use in a cathode in an electrolytic cell for producing aluminum wherein the cell contains an electrolyte and has molten aluminum contacting the cathode, the cathode having improved wettability with molten aluminum. The method comprises the steps of providing a carbonaceous block and a boron oxide containing melt. The carbonaceous block is immersed in the melt and pressure is applied to the melt to impregnate the melt into pores in the block. Thereafter, the carbonaceous block is withdrawn from the melt, the block having boron oxide containing melt intruded into pores therein, the boron oxide capable of reacting with a source of titanium or zirconium or like metal to form titanium or zirconium diboride during heatup or operation of said cell.

  15. Bacterial morphologies in carbonaceous meteorites and comet dust

    NASA Astrophysics Data System (ADS)

    Wickramasinghe, Chandra; Wallis, Max K.; Gibson, Carl H.; Wallis, Jamie; Al-Mufti, Shirwan; Miyake, Nori

    2010-09-01

    Three decades ago the first convincing evidence of microbial fossils in carbonaceous chondrites was discovered and reported by Hans Dieter Pflug and his collaborators. In addition to morphology, other data, notably laser mass spectroscopy, confirmed the identification of such structures as putative bacterial fossils. Balloon-borne cryosampling of the stratosphere enables recovery of fragile cometary dust aggregates with their structure and carbonaceous matter largely intact. SEM studies of texture and morphology of particles in the Cardiff collection, together with EDX identifications, show two main types of putative bio-fossils - firstly organic-walled hollow spheres around 10μm across, secondly siliceous diatom skeletons similar to those found in carbonaceous chondrites and terrestrial sedimentary rocks and termed 'acritarchs'. Since carbonaceous chondrites (particularly Type 1 chondrites) are thought to be extinct comets the data reviewed in this article provide strong support for theories of cometary panspermia.

  16. Electrogenerative cell for the oxidation or halogenation of hydrocarbons

    SciTech Connect

    McIntyre, J.M.

    1988-03-15

    A process for producing electric power by the electrogenerative halogenation or oxidation of at least one unsaturated hydrocarbon in an electrochemical cell having an anode and cathode separated by a permselective membrane or electrolyte permeable diaphragm is described comprising: (A) flowing a first liquid electrolyte and the unsaturated hydrocarbon to an anolyte compartment of the cell containing a porous anode; (B) flowing a second liquid electrolyte and a halogen or oxygen gas to a catholyte compartment of the cell containing a porous cathode; (C) reacting the unsaturated hydrocarbon with the halogen or the oxygen at ambient or elevated temperatures and pressures; (D) recovering a halogenated or oxygenated hydrocarbon; (E) recycling the electrolytes, unsaturated hydrocarbon, and halogen or oxygen gas to the cell.

  17. Amoeboid olivine aggregates from CH carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Krot, Alexander N.; Park, Changkun; Nagashima, Kazuhide

    2014-08-01

    Amoeboid olivine aggregates (AOAs) in CH carbonaceous chondrites are texturally and mineralogically similar to those in other carbonaceous chondrite groups. They show no evidence for alteration and thermal metamorphism in an asteroidal setting and consist of nearly pure forsterite (Fa<3; in wt%, CaO = 0.1-0.8, Cr2O3 = 0.04-0.48; MnO < 0.5), anorthite, Al-diopside (in wt%, Al2O3 = 0.7-8.1; TiO2 < 1), Fe,Ni-metal, spinel, and, occasionally, low-Ca pyroxene (Fs1Wo2-3), and calcium-aluminum-rich inclusions (CAIs). The CAIs inside AOAs are composed of hibonite, grossite, melilite (Åk13-44), spinel, perovskite, Al,Ti-diopside (in wt%, Al2O3 up to 19.6; TiO2 up to 13.9), and anorthite. The CH AOAs, including CAIs within AOAs, have isotopically uniform 16O-rich compositions (average Δ17O = -23.4 ± 2.3‰, 2SD) and on a three-isotope oxygen diagram plot along ∼slope-1 line. The only exception is a low-Ca pyroxene-bearing AOA 1-103 that shows a range of Δ17O values, from -24‰ to -13‰. Melilite, grossite, and hibonite in four CAIs within AOAs show no evidence for radiogenic 26Mg excess (δ26Mg). In contrast, anorthite in five out of six AOAs measured has δ26Mg corresponding to the inferred initial 26Al/27Al ratio of (4.3 ± 0.7) × 10-5, (4.2 ± 0.6) × 10-5, (4.0 ± 0.3) × 10-5, (1.7 ± 0.2) × 10-5, and (3.0 ± 2.6) × 10-6. Anorthite in another AOA shows no resolvable δ26Mg excess; an upper limit on the initial 26Al/27Al ratio is 5 × 10-6. We infer that CH AOAs formed by gas-solid condensation and aggregation of the solar nebula condensates (forsterite and Fe,Ni-metal) mixed with the previously formed CAIs. Subsequently they experienced thermal annealing and possibly melting to a small degree in a 16O-rich gaseous reservoir during a brief epoch of CAI formation. The low-Ca pyroxene-bearing AOA 1-103 may have experienced incomplete melting and isotope exchange in an 16O-poor gaseous reservoir. The lack of resolvable δ26Mg excess in melilite, grossite, and

  18. Scanning electron microscopical and cross-sectional analysis of extraterrestrial carbonaceous nanoglobules

    NASA Astrophysics Data System (ADS)

    Garvie, Laurence A. J.; Baumgardner, Grant; Buseck, Peter R.

    2008-05-01

    Carbonaceous nanoglobules are ubiquitous in carbonaceous chondrite (CC) meteorites. The Tagish Lake (C2) meteorite is particularly intriguing in containing an abundance of nanoglobules, with a wider range of forms and sizes than encountered in other CC meteorites. Previous studies by transmission electron microscopy (TEM) have provided a wealth of information on chemistry and structure. In this study low voltage scanning electron microscopy (SEM) was used to characterize the globule forms and external structures. The internal structure of the globules was investigated after sectioning by focused ion beam (FIB) milling. The FIB-SEM analysis shows that the globules range from solid to hollow. Some hollow globules show a central open core, with adjoining smaller cores. The FIB with an SEM is a valuable tool for the analysis of extraterrestrial materials, even of sub-micron-sized "soft" carbonaceous particles. The rapid site-specific cross-sectioning capabilities of the FIB allow the preservation of the internal morphology of the nanoglobules, with minimal damage or alteration of the unsectioned areas.

  19. Raman spectral characterization of dispersed carbonaceous matter in decorative crystalline limestones.

    PubMed

    Jehlicka, Jan; Stastná, Aneta; Prikryl, Richard

    2009-08-01

    Crystalline limestones (marbles) is a metamorphic rock that is widely used in the construction of buildings and in the manufacturing of statues. Along with dominant carbonates, marbles often contains carbonaceous matter resulting in a more or less grey colour. The Raman spectra of metamorphosed carbonaceous material (CM) were obtained in so-called graphitic marbles from several sites in the Bohemian Massif (Czech Republic). Frequencies of the major Raman bands and spectroscopic parameters such as O- and D-peak width and D/O intensity ratio were determined to characterize the various types of CM. Three types of Raman spectra allowed the discrimination between (1) well-ordered CM-graphite of high-grade regional metamorphosed marbles, (2) CM of contact metamorphosed marbles and (3) amorphous organic compounds as "disordered" CM of low-grade regional metamorphosed marbles. Raman microspectrometric analysis revealed the coexistence of carbonaceous particles exhibiting different degrees of graphitization within one marble sample. The structural state of the CM reflects the conditions of the contact or regional metamorphism and can be described by nondestructive Raman spectroscopy. For the first time, Raman spectra measured on reduced CM grains permitted one to distinguish marbles of different origin and propose their utilization in the provenance determination.

  20. CARES: Carbonaceous Aerosol and Radiative Effects Study Science Plan

    SciTech Connect

    Zaveri, RA; Shaw, WJ; Cziczo, DJ

    2010-05-27

    Carbonaceous aerosol components, which include black carbon (BC), urban primary organic aerosols (POA), biomass burning aerosols, and secondary organic aerosols (SOA) from both urban and biogenic precursors, have been previously shown to play a major role in the direct and indirect radiative forcing of climate. The primary objective of the CARES 2010 intensive field study is to investigate the evolution of carbonaceous aerosols of different types and their effects on optical and cloud formation properties.

  1. Characterization Of Carbonaceous Particles Along A North South Transect Of The Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Herckes, P.; Cox, J.; Lohmann, R.; Nizzetto, L.

    2006-12-01

    In recent years an increasing number of studies have investigated carbonaceous aerosols in urban and remote locations. However, little data on carbonaceous particles in remote marine environments exists, particularly on individual organic species concentrations including so-called molecular marker species. These markers can provide valuable insights into the sources of carbonaceous material, when stable during atmospheric transport. We will present results on organic aerosol characterization performed on samples collected along a North/South Transect from Bremerhaven (Germany) to Capetown (South Africa) aboard the Polarstern research vessel. Total Suspended Particulate matter (TSP) filter samples were analyzed for total carbon as well as carbon isotope ratios. Individual organic species (including n-alkanes, n-alkanoic acids, polyaromatic hydrocarbons, hopanes, steranes, dicarboxylic acids, and levoglucosan) were quantified in discrete (12h) and pooled (24-72h) samples, following solvent extraction and analysis by gas chromatography coupled to mass spectrometry (GC/MS). Preliminary results indicate relatively low concentrations of organic matter during most of the research cruise ( <1ug/m3) with higher concentrations in less pristine areas, mostly along Europe. Carbon isotope ratios were variable (-20 < delta13C < -27) and consistent with a change from C3 to C4 vegetation, suggesting an important biomass contribution to the observed particulate matter concentrations. These observations will be discussed with a focus on our observations of molecular marker concentrations. Although marker species were generally close to the detection limit, some markers were clearly detectable during high carbon events and are indicative of the sources of the carbonaceous particles.

  2. Investigation of organo-carbonate associations in carbonaceous chondrites by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Chan, Queenie H. S.; Zolensky, Michael E.; Bodnar, Robert J.; Farley, Charles; Cheung, Jacob C. H.

    2017-03-01

    Carbonates record information regarding the timing, nature and conditions of the fluids circulating through asteroid parent bodies during aqueous alteration events. Determining carbonate abundances and their relationships with organic matter improves our understanding of the genesis of major carbonaceous components in chondritic materials. In this study, five CM2 carbonaceous chondrites (CM2.2 Nogoya, CM2.3 Jbilet Winselwan, CM2.5 Murchison, CM2 Santa Cruz, and CM2TII Wisconsin Range 91600) were studied with Raman spectroscopy. Carbonates were identified in these meteorite samples by the distinctive Raman band in the ∼1100 cm-1 region, representing the symmetric stretching vibration mode (ν1) of the (CO3)2- anion. Carbonates identified in the meteorite samples are all calcite, with the exception of a single dolomite grain in Nogoya. The v1 positions of the CM calcites are 2-3 cm-1 higher than in pure calcite, which suggests that they contain significant impurity cations. Typical graphitic first-order D and G bands were identified in the meteorite matrix as well as in ∼25% of the analyzed carbonate grains. From the Raman results, we postulate that the carbonates might not have formed under equilibrium conditions from a single fluid. The first generation of carbonate is interpreted to have formed from highly oxidized fluids that led to the oxidation of organic matter (OM) and produced carbonates that are OM-barren. The second generation of carbonate was formed from a more evolved aqueous fluid with the presence of OM. The Raman parameters of the organics in carbonates clearly deviate from the matrix OM which suggests that the carbonate organics contain very different carbonaceous components that are distinct from the typical amorphous OM of the CM matrix. The occurrence of different generations of carbonate in close proximity may be partly responsible for the wide range in estimated ages of carbonates in carbonaceous chondrites reported in previous studies.

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

    PubMed

    Ide, Yasuo

    2012-07-01

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

  4. The halogen analogs of thiolated gold nanoclusters

    SciTech Connect

    Jiang, Deen; Walter, Michael

    2012-01-01

    Is it possible to replace all the thiolates in a thiolated gold nanocluster with halogens while still maintaining the geometry and the electronic structure? In this work, we show from density functional theory that such halogen analogs of thiolated gold nanoclusters are highly likely. Using Au{sub 25}X{sub 18}{sup -} as an example, where X = F, Cl, Br, or I replaces -SR, we find that Au{sub 25}Cl{sub 18}{sup -} demonstrates a high similarity to Au{sub 25}(SR){sub 18}{sup -} by showing Au-Cl distances, Cl-Au-Cl angles, band gap, and frontier orbitals similar to those in Au{sub 25}(SR){sub 18}{sup -}. DFT-based global minimization also indicates the energetic preference of staple formation for the Au{sub 25}Cl{sub 18}{sup -} cluster. The similarity between Au{sub m}(SR){sub n} and Au{sub m}X{sub n} could be exploited to make viable Au{sub m}X{sub n} clusters and to predict structures for Au{sub m}(SR){sub n}.

  5. Distinct Purine Distribution in Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Callahan, Michael P.; Smith, Karen E.; Cleaves, Henderson J.; Ruzicka, Josef; Stern, Jennifer C.; Glavin, Daniel P.; House, Christopher H.; Dworkin, Jason P.

    2011-01-01

    Carbonaceous chondrite meteorites are known to contain a diverse suite of organic compounds, many of which are essential components of biochemistry. Amino acids, which are the monomers of proteins, have been extensively studied in such meteorites (e.g. Botta and Bada 2002; Pizzarello et aI., 2006). The origin of amino acids in meteorites has been firmly established as extraterrestrial based on their detection typically as racemic mixtures of amino acids, the presence of many non-protein amino acids, and non-terrestrial values for compound-specific deuterium, carbon, and nitrogen isotopic measurements. In contrast to amino acids, nucleobases in meteorites have been far less studied. Nucleobases are substituted one-ring (pyrimidine) or two-ring (purine) nitrogen heterocyclic compounds and serve as the information carriers of nucleic acids and in numerous coenzymes. All of the purines (adenine, guanine, hypoxanthine, and xanthine) and pyrimidines (uracil) previously reported in meteorites are biologically common and could be interpreted as the result of terrestrial contamination (e.g. van del' Velden and Schwartz, 1974.) Unlike other meteoritic organics, there have been no observations of stochastic molecular diversity of purines and pyrimidines in meteorites, which has been a criterion for establishing extraterrestrial origin. Maltins et al. (2008) performed compound-specific stable carbon isotope measurements for uracil and xanthine in the Murchison meteorite. They assigned a non-terrestrial origin for these nucleobases; however, the possibility that interfering indigenous molecules (e.g. carboxylic acids) contributed to the 13C-enriched isotope values for these nucleobases cannot be completely ruled out. Thus, the origin of these meteoritic nucleobases has never been established unequivocally. Here we report on our investigation of extracts of II different carbonaceous chondrites covering various petrographic types (Cl, CM, and CR) and degrees of aqueous alteration

  6. UV signatures of carbonaceous species on low-albedo asteroids

    NASA Astrophysics Data System (ADS)

    Hendrix, A.; Vilas, F.

    2014-07-01

    Asteroids in the low-albedo classes (C, B, G, F) are known to have spectra that are relatively feature-free in the visible/near-infrared (VNIR) spectral region, making them classically difficult to study in terms of surface mineralogy. Many of these bodies exhibit a 3-micron absorption band (e.g., [1]), which can be used to study hydration and organics. The primary other spectrally active region --- less well studied so far --- is the ultraviolet (UV). In this study, we utilize UV spectra of low-albedo asteroids (C, B, G, and F class) to study surface composition. In particular, we investigate implications for the presence of carbonaceous compounds, including tholins and Polycyclic Aromatic Hydrocarbons (PAHs), which have unique spectral features in the UV. Low-albedo asteroids are typically rather bland spectrally at VNIR wavelengths. Many of these objects exhibit an absorption band near 3 microns, indicative of some type of hydration (OH and-or H_2O). A subset of the asteroids with the 3-micron features also exhibit absorption near 0.7 microns, due to a ferrous-ferric charge-transfer transition likely resulting from aqueous alteration (the interaction of material with liquid water formed by melting of water upon a heating event). Some asteroids likely do not exhibit these features due to a history of heating experienced at some point in the asteroid's evolution. Despite having little spectral activity in the VNIR, all low-albedo asteroids absorb at wavelengths shorter than ˜500 nm. This has been generally attributed to a ferric-iron intervalence charge-transfer transition absorption. Carbon-bearing phases have long been assumed to be important on low-albedo asteroids (e.g., [2]) due to the dark, mostly-featureless VNIR spectra of these bodies. However, there are many forms of carbonaceous species and the species are expected to undergo phase modifications (e.g., due to thermal, aqueous, and radiation processes) that affect the spectra [3,7]. Tholins are residues

  7. A search for extraterrestrial amino acids in carbonaceous Antarctic micrometeorites.

    PubMed

    Brinton, K L; Engrand, C; Glavin, D P; Bada, J L; Maurette, M

    1998-10-01

    Antarctic micrometeorites (AMMs) in the 100-400 microns size range are the dominant mass fraction of extraterrestrial material accreted by the Earth today. A high performance liquid chromatography (HPLC) based technique exploited at the limits of sensitivity has been used to search for the extraterrestrial amino acids alpha-aminoisobutyric acid (AIB) and isovaline in AMMs. Five samples, each containing about 30 to 35 grains, were analyzed. All the samples possess a terrestrial amino acid component, indicated by the excess of the L-enantiomers of common protein amino acids. In only one sample (A91) was AIB found to be present at a level significantly above the background blanks. The concentration of AIB (approximately 280 ppm), and the AIB/isovaline ratio (> or = 10), in this sample are both much higher than in CM chondrites. The apparently large variation in the AIB concentrations of the samples suggests that AIB may be concentrated in rare subset of micrometeorites. Because the AIB/isovaline ratio in sample A91 is much larger than in CM chondrites, the synthesis of amino acids in the micrometeorite parent bodies might have involved a different process requiring an HCN-rich environment, such as that found in comets. If the present day characteristics of the meteorite and micrometeorite fluxes can be extrapolated back in time, then the flux of large carbonaceous micrometeorites could have contributed to the inventory of prebiotic molecules on the early Earth.

  8. Rhenium-osmium isotope systematics of carbonaceous chondrites

    USGS Publications Warehouse

    Walker, R.J.; Morgan, J.W.

    1989-01-01

    Rhenium and osmium concentrations and Os isotopic compositions of eight carbonaceous chondrites, one LL3 ordinary chondrite, and two iron meteorites were determined by resonance ionization mass spectrometry. Iron meteorite 187Re/186Os and 187OS/186Os ratios plot on the previously determined iron meteorite isochron, but most chondrite data plot 1 to 2 percent above this meteorite isochron. This suggests either that irons have significantly younger Re-Os closure ages than chondrites or that chondrites were formed from precursor materials with different chemical histories from the precursors of irons. Some samples of Semarkona (LL3) and Murray (C2M) meteorites plot 4 to 6 percent above the iron meteorite isochron, well above the field delineated by other chondrites. Murray may have lost Re by aqueous leaching during its preterrestrial history. Semarkona could have experienced a similar loss of Re, but only slight aqueous alteration is evident in the meteorite. Therefore, the isotopic composition of Semarkona could reflect assembly of isotopically heterogeneous components subsequent to 4.55 billion years ago or Os isotopic heterogeneities in the primordial solar nebula.

  9. Rhenium-osmium isotope systematics of carbonaceous chondrites.

    PubMed

    Walker, R J; Morgan, J W

    1989-01-27

    Rhenium and osmium concentrations and Os isotopic compositions of eight carbonaceous chondrites, one LL3 ordinary chondrite, and two iron meteorites were determined by resonance ionization mass spectrometry. Iron meteorite (187)Re/(186)Os and (l87)Os/(l86)Os ratios plot on the previously determined iron meteorite isochron, but most chondrite data plot 1 to 2 percent above this meteorite isochron. This suggests either that irons have significantly younger Re-Os closure ages than chondrites or that chondrites were formed from precursor materials with different chemical histories from the precursors of irons. Some samples of Semarkona (LL3) and Murray (C2M) meteorites plot 4 to 6 percent above the iron meteorite isochron, well above the field delineated by other chondrites. Murray may have lost Re by aqueous leaching during its preterrestrial history. Semarkona could have experienced a similar loss of Re, but only slight aqueous alteration is evident in the meteorite. Therefore, the isotopic composition of Semarkona could reflect assembly of isotopically heterogeneous components subsequent to 4.55 billion years ago or Os isotopic heterogeneities in the primordial solar nebula.

  10. Chiral Analyses of Organic Compounds in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Pizzarello, Sandra

    2004-01-01

    Contents include the following: 1. Characterization of Tagish Lake organic content. The first two grant years were largely devoted to the molecular and isotopic analyses of Tagish Lake organic composition. This carbonaceous meteorite fell in Canada in the winter of the year 2000, and its exceptional atmospheric entry and subsequent recovery (e. g., the sample was recovered and stored by avoiding hand contact and above freezing temperatures) contributed in providing a rare and pristine extraterrestrial material. 2. Chiral analyses of Murchison and Murray soluble organics. One of the most intriguing finding in regard to soluble meteorite organics is the presence within the amino acid suite of some compounds displaying L-enantiomeric excesses. This configuration is exclusive in the amino acids of terrestrial proteins and the finding has raised speculations of a possible role of amino acids from meteorites in the origin of homochirality on the early Earth. The main objective for this NASA funding was the characterization of enantiomeric excesses in meteorites and we have conducted several studies toward establishing their distribution and indignity.

  11. A search for extraterrestrial amino acids in carbonaceous Antarctic micrometeorites

    NASA Technical Reports Server (NTRS)

    Brinton, K. L.; Engrand, C.; Glavin, D. P.; Bada, J. L.; Maurette, M.

    1998-01-01

    Antarctic micrometeorites (AMMs) in the 100-400 microns size range are the dominant mass fraction of extraterrestrial material accreted by the Earth today. A high performance liquid chromatography (HPLC) based technique exploited at the limits of sensitivity has been used to search for the extraterrestrial amino acids alpha-aminoisobutyric acid (AIB) and isovaline in AMMs. Five samples, each containing about 30 to 35 grains, were analyzed. All the samples possess a terrestrial amino acid component, indicated by the excess of the L-enantiomers of common protein amino acids. In only one sample (A91) was AIB found to be present at a level significantly above the background blanks. The concentration of AIB (approximately 280 ppm), and the AIB/isovaline ratio (> or = 10), in this sample are both much higher than in CM chondrites. The apparently large variation in the AIB concentrations of the samples suggests that AIB may be concentrated in rare subset of micrometeorites. Because the AIB/isovaline ratio in sample A91 is much larger than in CM chondrites, the synthesis of amino acids in the micrometeorite parent bodies might have involved a different process requiring an HCN-rich environment, such as that found in comets. If the present day characteristics of the meteorite and micrometeorite fluxes can be extrapolated back in time, then the flux of large carbonaceous micrometeorites could have contributed to the inventory of prebiotic molecules on the early Earth.

  12. Carbonaceous preservation of Cambrian hexactinellid sponge spicules.

    PubMed

    Harvey, Thomas H P

    2010-12-23

    Early fossil sponges offer a direct window onto the evolutionary emergence of animals, but insights are limited by the paucity of characters preserved in the conventional fossil record. Here, a new preservational mode for sponge spicules is reported from the lower Cambrian Forteau Formation (Newfoundland, Canada), prompting a re-examination of proposed homologies and sponge inter-relationships. The spicules occur as wholly carbonaceous films, and are interpreted as the remains of robust organic spicule sheaths. Comparable sheaths are restricted among living taxa to calcarean sponges, although the symmetries of the fossil spicules are characteristic of hexactinellid sponges. A similar extinct character combination has been documented in the Burgess Shale fossil Eiffelia. Interpreting the shared characters as homologous implies complex patterns of spicule evolution, but an alternative interpretation as convergent autapomorphies is more parsimonious. In light of the mutually exclusive distributions of these same characters among the crown groups, this result suggests that sponges exhibited an early episode of disparity expansion followed by comparatively constrained evolution, a pattern shared with many other metazoans but obscured by the conventional fossil record of sponges.

  13. The meteorite Moss - a rare carbonaceous chondrite

    NASA Astrophysics Data System (ADS)

    Bilet, M.; Roaldset, E.

    2014-07-01

    On July 14, 2006, at about 10:20 a.m. local daylight time (UTC+2), a bright fireball travelling SSE-NNV was witnessed from the Baltic Sea to SE Norway. On the east side of the Oslo fiord, around Moss, an explosion and a rumbling sound was heard, and pieces were observed falling. Rapid recovery of meteorite stones gave an opportunity for detailed petrological and geochemical investigations, including analyses of indigenous organic species, and short lived isotopes. The meteorite is a chondritic stone meteorite, with some carbon (0.21-0.25 wt% C). The cosmic-ray exposure (CRE) age is 14 Ma, i.e. when Moss was ejected from its parent body. Gas retention ages are approximately 3.95x10^9 yr (U/Th/He) and 4.43x10^9 yr (K/Ar), respectively. The meteorite has the official name Moss, and is classified as carbonaceous chondrite type CO3.6. It was the first witnessed fall of a CO3 chondrite since Kainsaz in Russia in 1937.

  14. Carbonaceous particles reduce marine microgel formation

    NASA Astrophysics Data System (ADS)

    Shiu, Ruei-Feng; Chin, Wei-Chun; Lee, Chon-Lin

    2014-07-01

    An increase in ambient carbonaceous particle (CNP) levels has been found, potentially leading to significant environmental/health hazards. These particles will ultimately enter the oceanic environment and interact with dissolved organic carbon. However, a detailed mechanistic understanding of their behavior, transport, and fate in marine systems is still much needed. This study, using carbon black (CB, 14 nm) nanoparticles as a model, aimed to investigate the impact of CNPs on marine microgel formation, a critical shunt between DOC and particulate organic carbon that potentially represents a ~70-Gt organic carbon flux. We found that CB can enhance the stability of DOC polymers and reduce microgel equilibrium sizes in concentration as low as 1 μgL-1 CB, possibly due to negative surface charges on CB that decrease cross-linking bridges through Ca2+ bonds. The reduction of marine microgel formation induced by CB could lead to a decrease in the downward transportation of microbial substrates and nutrients, and therefore, could have a significant impact on the carbon cycle and the marine ecosystem.

  15. Carbonaceous particles reduce marine microgel formation

    PubMed Central

    Shiu, Ruei-Feng; Chin, Wei-Chun; Lee, Chon-Lin

    2014-01-01

    An increase in ambient carbonaceous particle (CNP) levels has been found, potentially leading to significant environmental/health hazards. These particles will ultimately enter the oceanic environment and interact with dissolved organic carbon. However, a detailed mechanistic understanding of their behavior, transport, and fate in marine systems is still much needed. This study, using carbon black (CB, 14 nm) nanoparticles as a model, aimed to investigate the impact of CNPs on marine microgel formation, a critical shunt between DOC and particulate organic carbon that potentially represents a ~70-Gt organic carbon flux. We found that CB can enhance the stability of DOC polymers and reduce microgel equilibrium sizes in concentration as low as 1 μgL−1 CB, possibly due to negative surface charges on CB that decrease cross-linking bridges through Ca2+ bonds. The reduction of marine microgel formation induced by CB could lead to a decrease in the downward transportation of microbial substrates and nutrients, and therefore, could have a significant impact on the carbon cycle and the marine ecosystem. PMID:25068549

  16. Quantum spin Hall insulator in halogenated arsenene films with sizable energy gaps

    PubMed Central

    Wang, Dongchao; Chen, Li; Shi, Changmin; Wang, Xiaoli; Cui, Guangliang; Zhang, Pinhua; Chen, Yeqing

    2016-01-01

    Based on first-principles calculations, the electronic and topological properties of halogenated (F-, Cl-, Br- and I-) arsenene are investigated in detail. It is found that the halogenated arsenene sheets show Dirac type characteristic in the absence of spin-orbital coupling (SOC), whereas energy gap will be induced by SOC with the values ranging from 0.194 eV for F-arsenene to 0.255 eV for I-arsenene. Noticeably, these four newly proposed two-dimensional (2D) systems are verified to be quantum spin Hall (QSH) insulators by calculating the edge states with obvious linear cross inside bulk energy gap. It should be pointed out that the large energy gap in these 2D materials consisted of commonly used element is quite promising for practical applications of QSH insulators at room temperature. PMID:27340091

  17. Determination of halogens and sulfur in high-purity polyimide by IC after digestion by MIC.

    PubMed

    Krzyzaniak, Sindy R; Santos, Rafael F; Dalla Nora, Flavia M; Cruz, Sandra M; Flores, Erico M M; Mello, Paola A

    2016-09-01

    In this work, a method for sample preparation of high-purity polyimide was proposed for halogens and sulfur determination by ion chromatography (IC) with conductivity detection and, alternatively, by inductively coupled plasma mass spectrometry (ICP-MS). A relatively high polyimide mass (600mg) was completely digested by microwave-induced combustion (MIC) using 20bar of O2 and 50mmolL(-1) NH4OH as absorbing solution. These conditions allowed final solutions with low carbon content (<10mgL(-1)) and suitable pH for analysis by both IC and ICP-MS. The accuracy was evaluated using a certified reference material of polymer for Cl, Br and S and spike recovery experiments for all analytes. No statistical difference (t-test, 95% of confidence level) was observed between the results obtained for Cl, Br and S by IC after MIC and the certified values. In addition, spike recoveries obtained for F, Cl, Br, I and S ranged from 94% to 101%. The proposed method was suitable for polyimide decomposition for further determination of halogens and sulfur by IC and by ICP-MS (Br and I only). Taking into account the lack of methods and the difficulty of bringing this material into solution, MIC can be considered as a suitable alternative for the decomposition of polyimide for routine quality control of halogens and sulfur using IC or ICP-MS.

  18. The Distribution of Major Carbonaceous Components in Chondritic Materials

    NASA Astrophysics Data System (ADS)

    Chan, Q. H. S.; Zolensky, M. E.; Bodnar, R. J.; Farley, C.; Cheung, J. C. H.

    2017-02-01

    With the use of Raman spectroscopy we present a study of the structure of the organic matter in the matrix and carbonate phases in five CM chondrites: Jbilet Winselwan, Murchison, Nogoya, Santa Cruz, and Wisconsin Range 91600.

  19. Alkali metal recovery from carbonaceous material conversion process

    DOEpatents

    Sharp, David W.; Clavenna, LeRoy R.; Gorbaty, Martin L.; Tsou, Joe M.

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced in the gasifier or similar reaction zone, alkali metal constitutents are recovered from the particles by withdrawing and passing the particles from the reaction zone to an alkali metal recovery zone in the substantial absence of molecular oxygen and treating the particles in the recovery zone with water or an aqueous solution in the substantial absence of molecular oxygen. The solution formed by treating the particles in the recovery zone will contain water-soluble alkali metal constituents and is recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. Preventing contact of the particles with oxygen as they are withdrawn from the reaction zone and during treatment in the recovery zone avoids the formation of undesirable alkali metal constituents in the aqueous solution produced in the recovery zone and insures maximum recovery of water-soluble alkali metal constituents from the alkali metal residues.

  20. Ordered mixed-layer structures in the Mighei carbonaceous chondrite matrix

    NASA Technical Reports Server (NTRS)

    Mackinnon, I. D. R.

    1982-01-01

    High resolution transmission electron microscopy of the Mighei carbonaceous chondrite matrix has revealed the presence of a new mixed layer structure material. This mixed-layer material consists of an ordered arrangement of serpentine-type (S) and brucite-type (B) layers in the sequence SBBSBB. Electron diffraction and imaging techniques show that the basal periodicity is approximately 17 A. Discrete crystals of SBB-type material are typically curved, of small size (less than 1 micron) and show structural variations similar to the serpentine group minerals. Mixed-layer material also occurs in association with planar serpentine. Characteristics of SBB-type material are not consistent with known terrestrial mixed-layer clay minerals. Evidence for formation by a condensation event or by subsequent alteration of pre-existing material is not yet apparent.

  1. Independent Evolution of Six Families of Halogenating Enzymes

    PubMed Central

    Xu, Gangming; Wang, Bin-Gui

    2016-01-01

    Halogenated natural products are widespread in the environment, and the halogen atoms are typically vital to their bioactivities. Thus far, six families of halogenating enzymes have been identified: cofactor-free haloperoxidases (HPO), vanadium-dependent haloperoxidases (V-HPO), heme iron-dependent haloperoxidases (HI-HPO), non-heme iron-dependent halogenases (NI-HG), flavin-dependent halogenases (F-HG), and S-adenosyl-L-methionine (SAM)-dependent halogenases (S-HG). However, these halogenating enzymes with similar biological functions but distinct structures might have evolved independently. Phylogenetic and structural analyses suggest that the HPO, V-HPO, HI-HPO, NI-HG, F-HG, and S-HG enzyme families may have evolutionary relationships to the α/β hydrolases, acid phosphatases, peroxidases, chemotaxis phosphatases, oxidoreductases, and SAM hydroxide adenosyltransferases, respectively. These halogenating enzymes have established sequence homology, structural conservation, and mechanistic features within each family. Understanding the distinct evolutionary history of these halogenating enzymes will provide further insights into the study of their catalytic mechanisms and halogenation specificity. PMID:27153321

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

    PubMed

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

    2017-01-20

    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.

  3. Effects of fast halogen and plasma arc curing lights on the surface hardness of orthodontic adhesives for lingual retainers.

    PubMed

    Uşümez, Serdar; Büyükyilmaz, Tamer; Karaman, Ali Ihya

    2003-06-01

    The aims of this study were to (1) identify the optimum cure times of 2 different lingual retainer adhesives with a conventional halogen, a fast halogen, and a plasma arc light by measuring Vickers surface hardness, and (2) determine whether different lights produce similar surface hardness values for the same adhesive resin material. The investigated plasma arc curing unit was the PowerPac (American Dental Technologies, Corpus Christi, Tex), and the fast halogen unit was the Optilux 501 (Kerr, Orange, Calif). A conventional curing unit, the Ortholux XT (3M Dental Products, St. Paul, Minn) was used as the control. Two orthodontic lingual retainer adhesives were used: Transbond Lingual Retainer (3M Unitek, Monrovia, Calif) and Light Cure Retainer (Reliance Orthodontic Products, Itasca, Ill). Concise (3M Dental Products) and diluted Concise were used as controls. Transbond Lingual Retainer was polymerized by the PowerPac light in 6 seconds, by the Optilux in 10 seconds, and by the conventional halogen light in 20 seconds. The minimum curing times for Light Cure Retainer adhesive were 15 seconds for PowerPac, 10 seconds for Optilux, and 40 seconds for conventional halogen. Surface hardness values for each resin did not differ significantly with different curing units. However, different adhesives demonstrated significantly different surface hardness values. Final Vickers surface hardness values (averaged across curing units) of Transbond Lingual Retainer, Concise, diluted Concise, and Light Cure Retainer were 62.8, 52.4, 46.0, and 40.4, respectively. Plasma arc or fast halogen units polymerize resin composite adhesive in much shorter times than do conventional curing units, without a significant loss in surface hardness. Therefore, these units are suggested for clinical use to save chairside time.

  4. Halogen occultation experiment intergrated test plan

    NASA Technical Reports Server (NTRS)

    Mauldin, L. E., III; Butterfield, A. J.

    1986-01-01

    The test program plan is presented for the Halogen Occultation Experiment (HALOE) instrument, which is being developed in-house at the Langley Research Center for the Upper Atmosphere Research Satellite (UARS). This comprehensive test program was developed to demonstrate that the HALOE instrument meets its performance requirements and maintains integrity through UARS flight environments. Each component, subsystem, and system level test is described in sufficient detail to allow development of the necessary test setups and test procedures. Additionally, the management system for implementing this test program is given. The HALOE instrument is a gas correlation radiometer that measures vertical distribution of eight upper atmospheric constituents: O3, HC1, HF, NO, CH4, H2O, NO2, and CO2.

  5. Prediction of Thermodynamic Properties for Halogenated Hydrocarbon

    NASA Astrophysics Data System (ADS)

    Higashi, Yukihiro

    The predictive methods of thermodynamic properties are discussed with respect to the halogenated hydrocarbons using as working fluids for refrigeration and heat pump cycles. The methods introduced into this paper can be calculated by the limited information; critical properties, normal boiling point and acentric factor. The results of prediction are compared with the experimental values of PVT property, vapor pressure and saturated liquid density. On the basis of these comparisons, Lydersen's method for predicting the critical properties, the generalized vapor pressure correlation by Ashizawa et, al., and Hankinson-Thomson's method for predicting saturated liquid density can be recommended. With respect to the equation of state, either Soave equation or Peng-Robinson equation is effective in calculating the thermodynamic properties except high density region.

  6. Insights into enzymatic halogenation from computational studies

    PubMed Central

    Senn, Hans M.

    2014-01-01

    The halogenases are a group of enzymes that have only come to the fore over the last 10 years thanks to the discovery and characterization of several novel representatives. They have revealed the fascinating variety of distinct chemical mechanisms that nature utilizes to activate halogens and introduce them 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 studies. It also seeks to identify open questions that are amenable to computational investigations. The studies discussed herein serve to illustrate some of the limitations of the current computational approaches and the challenges encountered in computational mechanistic enzymology. PMID:25426489

  7. Halogenated coumarin derivatives as novel seed protectants.

    PubMed

    Brooker, N; Windorski, J; Bluml, E

    2008-01-01

    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.

  8. Stable-isotopic anomalies and the accretionary assemblage of the Earth and Mars: A subordinate role for carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Warren, Paul H.

    2011-11-01

    Plots such as ɛ 54Cr vs. ɛ 50Ti and ɛ 54Cr vs. Δ 17O reveal a fundamental dichotomy among planetary materials. The "carbonaceous" chondrites, by virtue of high ɛ 50Ti and high ɛ 62Ni, as well as, especially for any given Δ 17O, high ɛ 54Cr, are separated by a wide margin from all other materials. The significance of the bimodality is further manifested by several types of meteorites with petrological-geochemical characteristics that suggest membership in the opposite category from the true pedigree as revealed by the stable isotopes. Ureilites, for example, despite having diversely low Δ 17O and about the same average carbon content as the most C-rich carbonaceous chondrite, have clear stable-isotopic signatures of noncarbonaceous pedigree. The striking bimodality on the ɛ 54Cr vs. ɛ 50Ti and ɛ 54Cr vs. Δ 17O diagrams suggests that the highest taxonomic division in meteorite/planetary classification should be between carbonaceous and noncarbonaceous materials. The bimodality may be an extreme manifestation of the effects of episodic accretion of early solids in the protoplanetary nebula. However, an alternative, admittedly speculative, explanation is that the bimodality corresponds to a division between materials that originally accreted in the outer solar system (carbonaceous) and materials that accreted in the inner solar system (noncarbonaceous). In any event, both the Earth and Mars plot squarely within the noncarbonaceous composition-space. Applying the lever rule to putative mixing lines on the ɛ 50Ti vs. ɛ 54Cr and Δ 17O vs. ɛ 54Cr diagrams, the carbonaceous/(carbonaceous + noncarbonaceous) mixing ratio C/( C + NC) is most likely close to (very roughly) 24% for Earth and 9% for Mars. Estimated upper limits for C/( C + NC) are 32% for Earth and 18% for Mars. However, the uncertainties are such that isotopic data do not require or even significantly suggest that Earth has higher C/( C + NC) than Mars. Among known chondrite groups, EH yields a

  9. CARBONACEOUS MATTER PRECURSORS AND METAMORPHIC CONDITIONS IN THERMALLY PROCESSED CHONDRITES

    NASA Astrophysics Data System (ADS)

    Quirico, E.; Montagnac, G.; Rouzaud, J.; Bonal, L.; Bourot-Denise, M.; Duber, S.; Reynard, B.

    2009-12-01

    Unravelling the origin of carbonaceous matter in pristine chondrites requires the understanding of the effect of post-accretion processes. In chondrites of petrologic type 3, thermal metamorphism modified to various extents the composition and structure of carbonaceous matter. Interestingly, this process controls the degree of structural order of carbonaceous matter, and clues on the thermal history of the parent body may be recovered from the physico-chemical study of carbonaceous matter. Following this framework, geothermometers based on Raman spectrometry of carbonaceous matter and covering a wide range of temperatures (100-650 °C) have been developed over recent years, both on terrestrial rocks and chondrites. While Raman data have been largely interpreted in terms of temperature, they are also the fingerprint of certain metamorphic conditions, especially in the low temperature range relevant to poorly ordered carbonaceous matter. This study investigates the Raman spectra of two series of chondritic carbonaceous matter and coal samples formed from different precursors and under different metamorphic conditions. The Raman spectra of Polyaromatic Carbonaceous Matter (PCM) from 42 chondrites and 27 coal samples, measured with visible (514 nm) and ultra-violet (244 nm) excitation wavelengths, are analyzed. The Raman spectra of low rank coals and chondrites of petrologic types 1 and 2, which contain the more disordered PCM, reflect the distinct carbon structures of their precursors. The 514 nm Raman spectra of high rank coals and chondrites of petrologic type 3 exhibit continuous and systematic spectral differences reflecting different carbon structures present during the metamorphism event. They result from differences in the chemical structures of the precursors concerning for instance the reticulation of polyaromatic units or an abundance of ether functional groups, or possibly from a lack of carbonization processes to efficiently expel oxygen heteroatoms, due

  10. Structure and Bonding of Carbon in Clays from CI Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Garview, Laurence a. J.; Buseck, Peter R.

    2005-01-01

    Carbonaceous chondrites (CC) contain a diverse suite of C-rich materials. Acid dissolution of these meteorites leaves a C-rich residue with chemical and structural affinities to kerogen. This material has primarily been analyzed in bulk, and much information has been provided regarding functional groups and elemental and isotopic compositions. However, comparatively little work has been done on C in unprocessed meteorites. Studies of CCs suggest a spatial relationship of some C-rich materials with products of aqueous alteration. Recent studies revealed discrete submicronsized, C-rich particles in Tagish Lake and a range of CM2 meteorites. A challenge is to correlate the findings from the bulk acid-residue studies with those of high-spatial resolution-mineralogical and spectroscopic observations of unprocessed meteorites. Hence, the relationship between the C-rich materials in the acid residues and its form and locations in the unprocessed meteorite remains unclear. Here we provide information on the structure and bonding of C associated with clays in CI carbonaceous chondrites. Additional information is included in the original extended abstract.

  11. Study on polarization features of carbonaceous particles in atmosphere pollutants

    NASA Astrophysics Data System (ADS)

    Li, Da; Zeng, Nan; Wang, Yunfei; Chen, Dongsheng; Chen, Yuerong; Ma, Hui

    2016-09-01

    The carbonaceous particles are the main source of the light absorption in atmospheric aerosol. Different from the case in tissue-like turbid media, the light absorption in atmospheric environments can be described as an inherent attribute on scatterers rather than an interstitial propagation effect. In this paper, we simulated the optical absorption due to carbonaceous scatterers and analyzed the influence of various parameters on their polarization properties, such as the imaginary part refractive index, the size and shape. Also we compare these results with our previous research work on absorption effect in ambient medium. For the single scattering, the polarization scattering angular distribution implies the potential of distinguishing different carbonaceous particles with different structural and absorption parameters. In the other hand, for the week scattering case of suspension system, using the backward Mueller matrix polar decomposition method, we can find out that the additional absorption effect on carbonaceous particles can enhance their depolarization and moreover produce more diattenuation and linear retardance for those anisotropic particles. The subsequent experiments of standard samples show a good agreement with simulation results. The paper further studies the phase function of single scattering and the distribution of scattering numbers, which can explain these unique polarization scattering phenomena. We hope these fundamental results can help to investigate how to identify the carbonaceous particles and characterize their optical features from the atmospheric hybrid suspension system.

  12. Opaque Assemblages in CK and CV Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Neff, K. E.; Righter, K.

    2006-01-01

    CK carbonaceous chondrites are the only group of carbonaceous chondrites that exhibit thermal metamorphism. As a result, CKs display features of metamorphism such as silicate darkening, recrystallization and shock veins. Calcium Aluminum Inclusions and Fe-Ni metal are rare. CV carbonaceous chondrites are unequilibrated and have two subgroups; oxidized and reduced. The CV and CK carbonaceous chondrite groups have been compared to each other often because of petrographic similarities, such as overlapping oxygen isotopic ratios. Scientists have suggested the two groups of carbonaceous chondrites formed from the same parent body and CKs are equilibrated CV chondrites [1, 2]. The oxidized CV group has been most closely related to CKs. This study examines the petrology and mineralogy of CKs and CVs focusing on opaque minerals found in the meteorites. Using the oxide, metal and sulfide assemblages, constraints can be placed on the temperature and oxygen fugacity at which the meteorites equilibrated. The temperature and oxygen fugacity of the CK and CV chondrites can be compared in order to help define their formation history.

  13. Physical and Chemical Characterization of Carbonaceous Aerosols in Korea

    NASA Astrophysics Data System (ADS)

    Choung, S.; Jin, J. S.; Hwang, G. S.; Jang, K. S.; Han, W. S.; OH, J.; Kwon, Y.

    2014-12-01

    Atmospheric aerosols have been recently paid attention more in environmental research due to their negative effects on air quality, public health, and climate change. The aerosols contain approximately >20-50% carbonaceous components such as organic carbon (OC) and black carbon (BC) (or elemental carbon [EC]) derived from organic compounds, biomass burning, and incomplete combustion of fossil fuels. The physical, chemical, and biological properties of atmospheric aerosols are strongly dependent on the carbonaceous components. In particular, the BC could significantly affect the regional air quality in the northeastern Asia, because China is one of the foremost BC emission country in the world. Previous studies have mainly focused on the quantification and source identification for carbonaceous aerosols. However, understanding of physical and chemical properties for the carbonaceous aerosols related to environmental contamination and toxicity was still incomplete due to analytical difficulties. This study is addressed to evaluate the contribution of carbonaceous aerosols to air pollution through the surface, mass spectroscopic, and electron microscopic analyses, and determination of chemical composition and structure using the air particulate matter (PM2.5 and >PM2.5) samples.

  14. Application of selected methods of remote sensing for detecting carbonaceous water pollution

    NASA Technical Reports Server (NTRS)

    Davis, E. M.; Fosbury, W. J.

    1972-01-01

    The use of aerial photography to determine the nature and extent of water pollution from carbonaceous materials is discussed. Flights were conducted over the Galveston Bay estuarine complex. Ground truth data were developed from field sampling of the waters in a region near the Houston Ship Channel. Tests conducted in the field were those for the following physical and chemical factors: (1) ph, (2) dissolved oxygen, (3) temperature, and (4) light penetration. Laboratory analyses to determine various properties of the water are described and the types of instruments used are identified. Results of the analyses are presented as charts and graphs.

  15. Evidence that Polycyclic Aromatic Hydrocarbons in Two Carbonaceous Chondrites Predate Parent-Body Formation

    NASA Technical Reports Server (NTRS)

    Plows, F. L.; Elsila, J. E.; Zare, R. N.; Buseck, P. R.

    2003-01-01

    Organic material in meteorites provides insight into the cosmochemistry of the early solar system. The distribution of polycyclic aromatic hydrocarbons (PAHs) in the Allende and Murchison carbonaceous chondrites was investigated using spatially resolved microprobe laser-desorption laser-ionization mass spectrometry. Sharp chemical gradients of PAHs are associated with specific meteorite features. The ratios of various PAH intensities relative to the smallest PAH, naphthalene, are nearly constant across the sample. These findings suggest a common origin for PAHs dating prior to or contemporary with the formation of the parent body, consistent with proposed interstellar formation mechanisms.

  16. Novel halogenated derivates of JWH-018: Behavioral and binding studies in mice.

    PubMed

    Vigolo, A; Ossato, A; Trapella, C; Vincenzi, F; Rimondo, C; Seri, C; Varani, K; Serpelloni, G; Marti, M

    2015-08-01

    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.

  17. The chemistry of halogens on diamond: effects on growth and electron emission

    SciTech Connect

    Hsu, W.L.; Pan, L.S.; Brown, L.A.

    1997-02-01

    Diamond growth using halogenated precursors was studied in several diamond growth reactors. In a conventionao plasma reactor, diamond growth using the following gas mixtures was studied: CF{sub 4}/H{sub 2}, CH{sub 4}/H{sub 2}, CH{sub 3}F/H{sub 2}, and CH{sub 3}CL/H{sub 2}. Both the diamond growth measurements demonstrated ineffective transport of halogen radicals to the diamond surface during the growth process. In order to transport radical halogen species to the diamond surface during growth, a flow-tube reactor was constructed which minimized gas phase reactions. Also, the flow-tube reactor enabled pulsed gs transport to the diamond surface by fast-acting valves. Molecular beam mass spectroscopy was used to find condition which resulted in atomic hydrogen and/or atomic fluorine transport to the growing diamond surface. Although such conditions were found, they required very low pressures (0.5 Torr and below); these low pressures produce radical fluxes which are too low to sustain a reasonable diamond growth rate. The sequential reactor at Stanford was modified to add a halogen-growth step to the conventinoal atomic hydrogen/atomic carbon diamond growth cycle. Since the atomic fluorine, hydrogen and carbon environments are independent in the sequential reactor, the effect of fluorine on diamond growth could be studied independently of gas phase reactions. Although the diamond growth rate was increased by the use of fluorine, the film quality was seen to deteriorate as well as the substrate surface. Moreover, materials incompatibilities with fluorine significantly limited the use of fluorine in this reactor. A diamond growth model incorporating both gas phase and surface reactions was developed for the halocarbon system concurrent with the film growth efforts. In this report, we review the results of the growth experiments, the modeling, and additional experiments done to understand fluorine with diamond surfaces.

  18. Experimental measurement of noncovalent interactions between halogens and aromatic rings.

    PubMed

    Adams, Harry; Cockroft, Scott L; Guardigli, Claudio; Hunter, Christopher A; Lawson, Kevin R; Perkins, Julie; Spey, Sharon E; Urch, Christopher J; Ford, Rhonan

    2004-05-03

    Chemical double mutant cycles have been used to quantify the interactions of halogens with the faces of aromatic rings in chloroform. The halogens are forced over the face of an aromatic ring by an array of hydrogen-bonding interactions that lock the complexes in a single, well-defined conformation. These interactions can also be engineered into the crystal structures of simpler model compounds, but experiments in solution show that the halogen-aromatic interactions observed in the solid state are all unfavourable, regardless of whether the aromatic rings contain electron-withdrawing or electron-donating substituents. The halogen-aromatic interactions are repulsive by 1-3 kJ mol(-1). The interactions with fluorine are slightly less favourable than with chlorine and bromine.

  19. Halogen Bonding Promotes Higher Dye-Sensitized Solar Cell Photovoltages.

    PubMed

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

    2016-08-24

    We report here an enhancement in photovoltage for dye-sensitized solar cells (DSSCs) where halogen-bonding interactions exist between a nucleophilic electrolyte species (I(-)) and a photo-oxidized dye immobilized on a TiO2 surface. The triarylamine-based dyes under investigation showed larger rate constants for dye regeneration (kreg) by the nucleophilic electrolyte species when heavier halogen substituents were positioned on the dye. The open-circuit voltages (VOC) tracked these kreg values. This analysis of a homologous series of dyes that differ only in the identity of two halogen substituents provides compelling evidence that the DSSC photovoltage is sensitive to kreg. This study also provides the first direct evidence that halogen-bonding interactions between the dye and the electrolyte can bolster DSSC performance.

  20. POSSIBLE MOLECULAR TARGETS OF HALOGENATED ARMOATIC HYDROCARBONS IN NEURONAL CELLS.

    EPA Science Inventory

    Halogenated aromatic hydrocarbons including polychlorinated biphenyls (PCBs) are persistent bioaccumulative toxicants. Due to these characteristics, there is considerable regulatory concern over the potential adverse health affects, especially to children, associated with exposur...

  1. Halogenated naphthyl methoxy piperidines for mapping serotonin transporter sites

    DOEpatents

    Goodman, Mark M.; Faraj, Bahjat

    1999-01-01

    Halogenated naphthyl methoxy piperidines having a strong affinity for the serotonin transporter are disclosed. Those compounds can be labeled with positron-emitting and/or gamma emitting halogen isotopes by a late step synthesis that maximizes the useable lifeterm of the label. The labeled compounds are useful for localizing serotonin transporter sites by positron emission tomography and/or single photon emission computed tomography.

  2. Halogenated naphthyl methoxy piperidines for mapping serotonin transporter sites

    DOEpatents

    Goodman, M.M.; Faraj, B.

    1999-07-06

    Halogenated naphthyl methoxy piperidines having a strong affinity for the serotonin transporter are disclosed. Those compounds can be labeled with positron-emitting and/or gamma emitting halogen isotopes by a late step synthesis that maximizes the useable lifeterm of the label. The labeled compounds are useful for localizing serotonin transporter sites by positron emission tomography and/or single photon emission computed tomography.

  3. Differences in isotopic composition of carbonaceous components in enstatite chondrites

    NASA Astrophysics Data System (ADS)

    Grady, M. M.; Wright, I. P.; Carr, R. H.; Poths, J.; Pillinger, C. T.

    1988-02-01

    Carbon stable isotopic composition of the major carbonaceous component in enstatite chondrites varies with petrologic type. Investigation of a suite of HF/HCl-resistant residues has shown that this variation is due to an inherent difference in delta(C-13) of the carbon, and is not a result of the presence of small amounts of isotopically anomalous carbon-bearing components. These latter do occur in type EH3 and EH4 chondrites, in concentrations similar to those found in C1 and C2 carbonaceous chondrites. Combustion of the major carbon component (apparently elemental carbon, not necessarily graphite) occurs at relatively higher temperatures in enstatite chondrites of increasing petrologic type. This is considered to reflect an increase in crystallinity or ordering of the carbonaceous component, and is a measure of the degree of thermal processing to which the meteorites have been subjected during accretion and/or metamorphism.

  4. Laboratory Studies Of Circumstellar Carbonaceous Grain Formation

    NASA Astrophysics Data System (ADS)

    Contreras, Cesar; Sciamma-O'Brien, Ella; Salama, Farid

    2014-06-01

    The study of the formation processes of dust is essential to understand the budget of extraterrestrial organic molecules. Although dust with all its components plays an important role in the evolution of interstellar (IS) chemistry and in the formation of organic molecules, little is known on the formation processes of carbonaceous dust. We report the progress that was recently achieved in this domain using NASA Ames’ COSmIC facility (Contreras & Salama 2013, ApJS, 208, 6). PAHs are important chemical building blocks of IS dust. They are detected in IDPs and in meteoritic samples. Additionally, observational, laboratory, and theoretical studies have shown that PAHs are an important, ubiquitous component of the ISM. The formation of PAHs from smaller molecules has not been extensively studied. Therefore, we have performed laboratory experiments to study the dynamic processes of carbon grain formation, starting from the smallest hydrocarbon molecules into the formation of larger PAH and further into nanograins. Studies of IS dust analogs formed from a variety of PAH and hydrocarbon precursors as well as species that include the atoms O, N, and S, have recently been performed in our laboratory using the COSmIC facility to provide conditions that simulate IS and circumstellar environments. The species formed in the COSmiC chamber through a pulsed discharge nozzle plasma source are detected and characterized with a cavity ringdown spectrometer coupled to a time-of-flight mass spectrometer, thus providing both spectroscopic and ion mass information in-situ. Analysis of solid soot particles was also conducted using scanning electron microscopy at the UCSC/NASA Ames’ MACS facility. The SEM analysis of the deposition of soot from methane and acetylene precursors seeded in argon plasmas provide examples on the types of nanoparticles and micrograins that are produced in these gas mixtures under our experimental conditions. From these measurements, we derive information on

  5. Wet, Carbonaceous Asteroids: Altering Minerals, Changing Amino Acids

    NASA Astrophysics Data System (ADS)

    Taylor, G. J.

    2011-04-01

    Many carbonaceous chondrites contain alteration products from water-rock interactions at low temperature and organic compounds. A fascinating fact known for decades is the presence in some of them of an assortment of organic compounds, including amino acids, sometimes called the building blocks of life. Murchison and other CM carbonaceous chondrites contain hundreds of amino acids. Early measurements indicated that the amino acids in carbonaceous chondrites had equal proportions of L- and D-structures, a situation called racemic. This was in sharp contrast to life on Earth, which heavily favors L- forms. However, beginning in 1997, John Cronin and Sandra Pizzarello (Arizona State University) found L- excesses in isovaline and several other amino acids in the Murchison carbonaceous chondrite. In 2009, Daniel Glavin and Jason Dworkin (Astrobiology Analytical Lab, Goddard Space Flight Center) reported the first independent confirmation of L-isovaline excesses in Murchison using a different analytical technique than employed by Cronin and Pizzarello. Inspired by this work, Daniel Glavin, Michael Callahan, Jason Dworkin, and Jamie Elsila (Astrobiology Analytical Lab, Goddard Space Flight Center), have done an extensive study of the abundance and symmetry of amino acids in carbonaceous chondrites that experienced a range of alteration by water in their parent asteroids. The results show that amino acids are more abundant in the less altered meteorites, implying that aqueous processing changes the mix of amino acids. They also confirmed the enrichment in L-structures of some amino acids, especially isovaline, confirming earlier work. The authors suggest that aqueously-altered planetesimals might have seeded the early Earth with nonracemic amino acids, perhaps explaining why life from microorganisms to people use only L- forms to make proteins. The initial imbalance caused by non-biologic processes in wet asteroids might have been amplified by life on Earth. Alternatively

  6. Halogen chemistry reduces tropospheric O3 radiative forcing

    NASA Astrophysics Data System (ADS)

    Sherwen, Tomás; Evans, Mat J.; Carpenter, Lucy J.; Schmidt, Johan A.; Mickley, Loretta J.

    2017-01-01

    Tropospheric ozone (O3) is a global warming gas, but the lack of a firm observational record since the preindustrial period means that estimates of its radiative forcing (RFTO3) rely on model calculations. Recent observational evidence shows that halogens are pervasive in the troposphere and need 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, higher anthropogenic emissions of bromo-carbons, and an increased flux of bromine from the stratosphere. We calculate preindustrial to present-day increases in the tropospheric O3 burden of 113 Tg without halogens but only 90 Tg with, leading to a reduction in RFTO3 from 0.43 to 0.35 Wm-2. We attribute ˜ 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 %).

  7. Organic Matter from Comet 81p/Wild 2, IDPS and Carbonaceous Meteorites; Similarities and Differences

    SciTech Connect

    Wirick, S.; Flynn, G; Keller, L; Nakamura Messenger, K; Peltzer, C; Jacobsen, C; Sandford, S; Zolensky, M

    2009-01-01

    During preliminary examination of 81P/Wild 2 particles collected by the NASA Stardust spacecraft, we analyzed seven, sulfur embedded and ultramicrotomed particles extracted from five different tracks. Sections were analyzed using a scanning transmission X-ray microscope (SXTM) and carbon X-ray absorption near edge structure (XANES) spectra were collected. We compared the carbon XANES spectra of these Wild 2 samples with a database of spectra on thirty-four interplanetary dust particles (IDPs) and with several meteorites. Two of the particles analyzed are iron sulfides and there is evidence that an aliphatic compound associated with these particles can survive high temperatures. An iron sulfide from an IDP demonstrates the same phenomenon. Another, mostly carbon free containing particle radiation damaged, something we have not observed in any IDPs we have analyzed or any indigenous organic matter from the carbonaceous meteorites, Tagish Lake, Orgueil, Bells and Murchison. The carbonaceous material associated with this particle showed no mass loss during the initial analysis but chemically changed over a period of two months. The carbon XANES spectra of the other four particles varied more than spectra from IDPs and indigenous organic matter from meteorites. Comparison of the carbon XANES spectra from these particles with 1. the carbon XANES spectra from thirty-four IDPs (<15 micron in size) and 2. the carbon XANES spectra from carbonaceous material from the Tagish Lake, Orgueil, Bells, and Murchison meteorites show that 81P/Wild 2 carbon XANES spectra are more similar to IDP carbon XANES spectra then to the carbon XANES spectra of meteorites.

  8. Hydrated interplanetary dust particle linked with carbonaceous chondrites?

    NASA Technical Reports Server (NTRS)

    Tomeoka, K.; Buseck, P. R.

    1985-01-01

    The results of transmission electron microscope observations of a hydrated interplanetary dust particle (IDP) containing Fe-, Mg-rich smectite or mica as a major phase are reported. The sheet silicate appears to have formed by alteration of anhydrous silicates. Fassaite, a Ca, Al clinopyroxene, also occurs in this particle, and one of the crystals exhibits solar-flare tracks, clearly indicating that it is extraterrestrial. Fassaite is a major constituent of the Ca-, Al-rich refractory inclusions found in the carbonaceous chondrites, so its presence in this particle suggests that there may be a link between hydrated IDPs and carbonaceous chondrites in the early history of the solar system.

  9. Crystallography of magnetite plaquettes and their significance as asymmetric catalysts for the synthesis of chiral organics in carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Chan, Q. H. S.; Zolensky, M. E.

    2015-10-01

    We have previously observed the magnetite plaquettes in carbonaceous chondrites using scanning electron microscope (SEM) imaging, examined the crystal orientation of the polished surfaces of magnetite plaquettes in CI Orgueil using electron backscattered diffraction (EBSD) analysis, and concluded that these magnetite plaquettes are likely naturally asymmetric materials [1]. In this study, we expanded our EBSD observation to other magnetite plaquettes in Orgueil, and further examined the internal structure of these remarkable crystals with the use of X-ray computed microtomography.

  10. Crystallography of Magnetite Plaquettes and their Significance as Asymmetric Catalysts for the Synthesis of Chiral Organics in Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Chan, Q. H. S.; Zolensky, M. E.

    2015-01-01

    We have previously observed the magnetite plaquettes in carbonaceous chondrites using scanning electron microscope (SEM) imaging, examined the crystal orientation of the polished surfaces of magnetite plaquettes in CI Orgueil using electron backscattered diffraction (EBSD) analysis, and concluded that these magnetite plaquettes are likely naturally asymmetric materials. In this study, we expanded our EBSD observation to other magnetite plaquettes in Orgueil, and further examined the internal structure of these remarkable crystals with the use of X-ray computed microtomography.

  11. Aerosol-halogen interaction: Change of physico-chemical properties of SOA by naturally released halogen species

    NASA Astrophysics Data System (ADS)

    Ofner, J.; Balzer, N.; Buxmann, J.; Grothe, H.; Krüger, H.; Platt, U.; Schmitt-Kopplin, P.; Zetzsch, C.

    2011-12-01

    Reactive halogen species are released by various sources like photo-activated sea-salt aerosol or salt pans and salt lakes. These heterogeneous release mechanisms have been overlooked so far, although their potential of interaction with organic aerosols like Secondary Organic Aerosol (SOA), Biomass Burning Organic Aerosol (BBOA) or Atmospheric Humic LIke Substances (HULIS) is completely unknown. Such reactions can constitute sources of gaseous organo-halogen compounds or halogenated organic particles in the atmospheric boundary layer. To study the interaction of organic aerosols with reactive halogen species (RHS), SOA was produced from α-pinene, catechol and guaiacol using an aerosol smog-chamber. The model SOAs were characterized in detail using a variety of physico-chemical methods (Ofner et al., 2011). Those aerosols were exposed to molecular halogens in the presence of UV/VIS irradiation and to halogens, released from simulated natural halogen sources like salt pans, in order to study the complex aerosol-halogen interaction. The heterogeneous reaction of RHS with those model aerosols leads to different gaseous species like CO2, CO and small reactive/toxic molecules like phosgene (COCl2). Hydrogen containing groups on the aerosol particles are destroyed to form HCl or HBr, and a significant formation of C-Br bonds could be verified in the particle phase. Carbonyl containing functional groups of the aerosol are strongly affected by the halogenation process. While changes of functional groups and gaseous species were visible using FTIR spectroscopy, optical properties were studied using Diffuse Reflectance UV/VIS spectroscopy. Overall, the optical properties of the processed organic aerosols are significantly changed. While chlorine causes a "bleaching" of the aerosol particles, bromine shifts the maximum of UV/VIS absorption to the red end of the UV/VIS spectrum. Further physico-chemical changes were recognized according to the aerosol size-distributions or the

  12. A Re-Examination of Nucleobases in Carbonaceous Chondrites

    NASA Astrophysics Data System (ADS)

    Martins, Z.; Botta, O.; de Vries, M.; Becker, L.; Ehrenfreund, E.

    The biomolecular building blocks of life, as we know it, are amino acids, purines and pyrimidines. The latter two form the bases of DNA and RNA, molecules that are used in the storage, transcription and translation of genetic information in all terrestrial organisms. A dedicated search for these compounds in meteorites can shed light on the origins of life in two ways: (i) Results can help assess the plausibility of extraterrestrial formation of prebiotic molecules followed by their meteoritic delivery to the early Earth. (ii) Such studies can also provide insights into possible prebiotic synthetic routes. We will search for these compounds in selected carbonaceous chondrites using formic acid extraction and reverse phase high performance liquid chromatography (HPLC) to isolate specific nucleobases from the bulk meteorite material as previously reported [1,2,3]. We will also use a new technique, resonant two-photon ionization mass spectrometry (R2PI) that can, not only identify organic compounds by their mass, but at the same time by their vibronic spectroscopy [4]. R2PI dramatically enhances the specificity for certain compounds (e.g. amino acids, nucleobases) and allows for distinction of structural isomers, tautomers and enantiomers as well as providing additional information due to isotope shifts. The optical spectroscopy can thus help us to further discriminate between terrestrial and extraterrestrial nucleobases. References: [1] Van Der Velden, W. and Schwarts, A. W. (1977) Geochim. Cosmochim. Acta, 41, 961-968. [2] Stoks, P. G. and Schwartz, A. W. (1979a) Nature, 282, 709-10. [3] Glavin, D. P. and Bada, J. L. (2004) In Lunar and Planetary Science XXXV, Abstract # 1022, Houston. [4] Nir, E., Grace, L. I., Brauer, B. and de Vries, M. S. (1999) Journal of the American Chemical Society, 121, 4896-4897.

  13. Phyllosilicates in the Carbonaceous Chondrite Breccia Kaidun

    NASA Astrophysics Data System (ADS)

    Yang, S. V.; Zolensky, M.; Golden, D. C.; Ming, D. W.; Ivanov, A.

    1993-07-01

    observed. In contrast, most reported Kaidun and CR lithologies have approximately subequal amounts of saponite and serpentine in matrix. Phyllosilicates in Kaidun are commonly associated with sulfides; no phyllosilicates have been observed as direct overgrowths on olivine or pyroxene. Microprobe analyses of coarse-grained Kaidun saponites indicate that the majority of the exchangeable cations in the saponites studied are Mg2+ and Ca2+, with mior Na+. However, since the results of this study suggest that the saponite in Kaidun has a highly charged interlayer environment, one might speculate that any ammonium (NH4+) if present in the original parent body atmosphere or the reacting solution might be fixed in the interlayers. High- charge smectites are known to fix ammonium ions from solution [3]. There is spectroscopic evidence for ammonium-bearing phases on asteroid Ceres 1 [4]. Most carbonaceous chondrites are known to contain relatively high amounts of nitrogen (up to 3000 ppm) [5]. In order to detect if any of this N is in NH4+ form in the interlayers, we set up our Cameca electron microprobe to detect the nitrogen K-alpha X-ray peak using an ODPB crystal of a wavelength dispersive spectrometer. No nitrogen peak was positively identified on the carbonaceous matrix, nor on any saponites, although it is possible that the electron beam neutralized and evaporated any NH4+ cations before detection. In conclusion, the phyllosilicates in Kaidun are heterogeneously distributed from clast to clast, with highly charged saponite predominating in some clasts; serpentine and saponite are more nearly equally abundant in other clasts. No nitrogen was positively detected in the matrix or in any components in Kaidun by the electron microprobe in this study, although further studies of Kaidun phyllosilicates are in progress. References: [1] Zolensky M. and McSween H. Y. Jr. (1988) in Meteorites and the Early Solar System, Univ. of Arizona, 114-143. [2] Ming D. W. et. al. (1992) LPSC XXIII

  14. Petrography and mineralogy of the ungrouped type 3 carbonaceous chondrite Dar al Gani 978

    NASA Astrophysics Data System (ADS)

    Zhang, Ai-Cheng; Yurimoto, Hisayoshi

    2013-09-01

    Dar al Gani (DaG) 978 is an ungrouped type 3 carbonaceous chondrite. In this study, we report the petrography and mineralogy of Ca,Al-rich inclusions (CAI), amoeboid olivine aggregates (AOAs), chondrules, mineral fragments, and the matrix in DaG 978. Twenty-seven CAIs were found: 13 spinel-diopside-rich inclusions, 2 anorthite-rich inclusions, 11 spinel-troilite-rich inclusions, and 1 spinel-melilite-rich inclusion. Most CAIs have a layered texture that indicates a condensation origin and are most similar to those in R chondrites. Compound chondrules represent a high proportion (approximately 8%) of chondrules in DaG 978, which indicates a local dusty chondrule-forming region and multiple heating events. Most spinel and olivine in DaG 978 are highly Fe-rich, which corresponds to a petrologic type of >3.5 and a maximum metamorphic temperature of approximately 850-950 K. This conclusion is also supported by other observations in DaG 978: the presence of coarse inclusions of silicate and phosphate in Fe-Ni metal, restricted Ni-Co distributions in kamacite and taenite, and low S concentrations in the matrix. Mineralogic records of iron-alkali-halogen metasomatism, such as platy and porous olivine, magnetite, hedenbergite, nepheline, Na-rich in CAIs, and chlorapatite, are present, but relatively limited, in DaG 978. The fine-grained, intergrowth texture of spinel-troilite-rich inclusions was probably formed by reaction between pre-existing Al-rich silicates and shock-induced, high-temperature S-rich gas on the surface of the parent body of DaG 978. A shock-induced vein is present in the matrix of DaG 978, which indicates that the parent body of DaG 978 at least experienced a shock event with a shock stage up to S3.

  15. The relative roles of electrostatics and dispersion in the stabilization of halogen bonds.

    PubMed

    Riley, Kevin E; Hobza, Pavel

    2013-11-07

    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.

  16. Production of carbonaceous adsorbents from agricultural by-products and novolac resin under a continuous countercurrent flow type pyrolysis operation.

    PubMed

    Ioannou, Z; Simitzis, J

    2013-02-01

    Carbonaceous adsorbents based on novolac resin (N) and olive stone biomass (B) in a proportion of 20/80 and 40/60 w./w. N/O were produced. The specimens were cured (c) and pyrolyzed/carbonized (C) up to 1000 °C under a continuous countercurrent flow type pyrolysis operation (N20B-cC, N40B-cC). Commercial activated carbon (AC) was used for comparison reasons. Methylene blue adsorption from its aqueous solutions onto the adsorbents and kinetic analysis were investigated. The specific surface area of adsorbents and the gross calorific values (GCV) of cured materials were determined. The results show that N40B-cC presents lower weight loss and shrinkage but higher methylene blue adsorption than N20B-cC. Pseudo-second order mechanism describes better methylene blue adsorption onto all adsorbents. The specific surface area of carbonaceous and the gross calorific values of cured materials follow the order: AC>N20B-cC>N40B-cC and N100-c>N40B-c>N20B-c>B respectively. Olive stone biomass may constitute a suitable precursor for the production of carbonaceous materials.

  17. Synthesis and characterization of lead-free tin silver nanosolders and their application to halogen free nanosolder pastes

    NASA Astrophysics Data System (ADS)

    Wernicki, Evan

    Solder paste is a key material used in attaching electronic components to printed circuit boards (PCBs). Commonly used lead-based solders, such as eutectic Sn/37Pb, are currently being replaced by lead-free alloy materials due to health and environmental concerns associated with lead. Many solder pastes, both lead-containing and lead-free, contain halogens which act as activators to remove surface oxide and enhance surface wetting, posing further environmental concern from the halogen species. Difficulties in obtaining reliable joints can occur since lead-free solder material candidates have higher melting temperatures (30-50 °C) than that of lead-based solders. Differences in material properties between the numerous materials used in assembly and packaging processes can lead to component damage during manufacturing. Furthermore, designs that include more electrical interconnects in smaller areas give rise for the need for new materials to allow this trend to continue. A surfactant-assisted chemical reduction method was used to synthesize Sn/Ag alloy nanoparticles with a target composition range of 3.5-5 wt% Ag that served as the lead-free solder material within a nanosolder paste. Structure and size characterization via SEM and TEM showed Sn-Ag nanosolders size average approximately 19 nm. Differential scanning calorimetry (DSC) measurements of the nanosolder samples containing 4.5 wt% Ag showed an endothermic peak at 222.5 °C and an onset of 219.2 °C, indicating up to 17.5 °C melting temperature depression when compared to the bulk liquidus value of 240 °C. Composition of the nanosolder material was confirmed using energy dispersive x-ray spectroscopy (EDS) and structures formed were analyzed via x-ray diffraction (XRD). Both halogen-free and halogen-containing flux materials were combined with the nanosolder material, respectively, with varying preparation parameters to form a design of experiments (DoE) for nanosolder paste preparation. Solder pastes

  18. Mouse Model of Halogenated Platinum Salt Hypersensitivity ...

    EPA Pesticide Factsheets

    Occupational exposure to halogenated platinum salts can trigger the development of asthma. Concern for increased asthma risk exists for the general population due to the use of platinum (Pt) in catalytic converters and its emerging use as a diesel fuel additive. To investigate airway responses to Pt, we developed a mouse model of Pt hypersensitivity. Previously, we confirmed the dermal sensitizing potency of ammonium hexachloroplatinate (AHCP) using an ex vivo [3H]methyl thymidine labeling version of the local lymph node assay in BALB/c mice. Here, we investigated the ability of AHCP to induce airway responses in mice sensitized by the dermal route. Mice were sensitized through application of 100 µL 1% AHCP in DMSO to the shaved back on days 0, 5 and 19, and 25 µl to each ear on days 10, 11 and 12. Unsensitized mice received vehicle. On day 24, mice were challenged by oropharyngeal aspiration (OPA) with 0 or 100 µg AHCP in saline. Before and immediately after challenge, airway responses were assessed using whole body plethysmography (WBP). On day 26, changes in ventilatory responses to methacholine (Mch) aerosol were assessed by WBP; dose-dependent increases in Mch responsiveness occurred in sensitized mice. Bronchoalveolar lavage fluid harvested from sensitized mice contained an average of 7.5% eosinophils compared to less than 0.5% in control mice (p < 0.05). This model will be useful for assessing both relative sensitizing potency and cross-reacti

  19. Halogen Occultation Experiment (HALOE) optical filter characterization

    NASA Technical Reports Server (NTRS)

    Harvey, Gale A.

    1989-01-01

    The Halogen Occultation Experiment (HALOE) is a solar occultation experiment that will fly on the Upper Atmosphere Research Satellite to measure mixing ratio profiles of O3, H2O, NO2, NO, CH4, HCl, and HF. The inversion of the HALOE data will be critically dependent on a detailed knowledge of eight optical filters. A filter characterization program was undertaken to measure in-band transmissions, out-of-band transmissions, in-band transmission shifts with temperature, reflectivities, and age stability. Fourier Transform Infrared Spectrometers were used to perform measurements over the spectral interval 400/cm to 6300/cm (25 micrometers to 1.6 micrometers). Very high precision (0.1 percent T) in-band measurements and very high resolution (0.0001 percent T) out-of-band measurements have been made. The measurements revealed several conventional leaks at 0.01 percent transmission and greatly enhanced (1,000) leaks to the 2-element filters when placed in a Fabry-Perot cavity. Filter throughput changes by 5 percent for a 25 C change in filter temperature.

  20. Negative Halogen Ions for Fusion Applications

    SciTech Connect

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

    2006-01-01

    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.