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Sample records for carbonaceous materials halogen

  1. Aqueous slurries of carbonaceous materials

    SciTech Connect

    Schick, M.J.; Knitter, K.A.

    1984-03-13

    Aqueous carbonaceous slurries having reduced viscosity, a stabilized network of carbonaceous material in water and improved pumpability are obtained by having present a salt of naphthalenesulfonic acid formaldehyde condensate and at least one water soluble polymer selected from the group consisting of sodium alginate, guar gum, locust bean gum, carboxymethylhydroxypropyl guar gum, hydroxypropyl guar gum and guarpak guar gum. For example, a mixture of 96.8% by weight of ammonium naphthalenesulfonic acid formaldehyde condensate and 3.2% by weight of sodium alginate can be added to an aqueous coal slurry in an amount of 0.31% by weight of the slurry.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. Halogenated arsenenes as Dirac materials

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  7. 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.

  8. ANIMAL WASTE COMPOSTING WITH CARBONACEOUS MATERIAL

    EPA Science Inventory

    High rate thermophilic composting of animal wastes with added carbonaceous waste materials followed by land application has considerable potential as a means of treatment and useful final disposal of these wastes. The process described in this report utilizes a mechanically mixed...

  9. Applications of ESR to carbonaceous materials

    SciTech Connect

    Singer, L.S.; Lewis, I.C.

    1982-01-01

    The applicatioins of electron spin resonance (ESR) to carbonaceous materials are reviewed. The stable paramagnetic species observed in the products of low-temperature pyrolyis are odd-alternate neutral free radicals, whereas the unpaired spins of higher temperature carbons and graphites are primarily conduction electrons. The variety of ESR properties and phenomena requires special attention to techniques of measurement and interpretations of results. The relevance to the carbonization process of the free radicals observed by ESR is also discussed.

  10. 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.

  11. 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.

  12. 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.

  13. Reconnaissance for uranium-bearing carbonaceous materials in southern Utah

    USGS Publications Warehouse

    Zeller, H.D.

    1955-01-01

    A reconnaissance investigation for uranium-bearing carbonaceous materials was made in three major areas of southern Utah: Kaiparowits Plateau, Henry Mountains, and Kolob Terrace. No uranium deposits of economic interest were found. A few l- to 2-foot beds of carbonaceous shale in the Dakota(?) sandstone contain 0.006-0.007 percent uranium. Other carbonaceous sediments that were examined contain 0. 002 percent or less uranium.

  14. 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.

  15. Anionic dispersants for aqueous slurries of carbonaceous materials

    SciTech Connect

    Schick, M.J.; Kelley, E.L.

    1985-01-08

    Aqueous carbonaceous slurries having reduced viscosity, a stabilized network of carbonaceous material in water and improved pumpability are obtained by having present as a dispersant an alkali or ammonium bisalkyl sulfosuccinate. An example is the sodium salt of bis-2-ethylhexyl sulfosuccinate.

  16. 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.

  17. Shallow halogen vacancies in halide optoelectronic materials

    DOE PAGESBeta

    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

  18. 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.

  19. Process for the superatmospheric gasification of solid carbonaceous materials

    SciTech Connect

    Kamody, J.F.

    1982-03-30

    A process is disclosed for gasifying solid carbonaceous material at elevated temperature and pressure to produce a gas consisting of carbon monoxide and hydrogen, which comprises forming a slurry at atmospheric pressure of the carbonaceous material with a liquid having a specific gravity of from 1.1 to 1.9, a boiling temperature of at least 700 F, a latent heat of vaporization less than about 200 btu per pound, a critical temperature which is less than the incipient coking temperature of the carbonaceous material, a stability at temperatures up to 6000 F, an essentially inert chemical reaction with the carbonaceous material at temperatures less than about 6000 F, an immiscibility with water or solubility in water at no more than 5%, and a dissolving ability for hydrogen sulfide at temperature of from -40 to 2500 F, and raising the formed slurry to a pressure of at least the gasification pressure and vaporizing said liquid and gasifying said carbonaceous material, either in the same or in separate steps. Examples of suitable slurrying liquids are: carbon tetrachloride, carbon disulfide, trichloroethylene, bromoethane, chlorobenzene, methane dichloride , chloroform, or mixtures thereof.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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. PMID:11541327

  9. Raman properties of various carbonaceous materials and their astrophysical implications

    NASA Technical Reports Server (NTRS)

    Blanco, A.; Borghesi, A.; Bussoletti, E.; Colangeli, Luigi; Fonti, Sergio; Lugara, M.; Orofino, Vincenso; Scamarcio, G.

    1989-01-01

    It is well known that a large number of celestial objects exhibit, in the range 3 to 12 micron, a family of emission features called unidentified infrared bands (UIR). They usually appear together and are associated with UV sources. Recently various authors have suggested that these features could be attributed to solid carbonaceous materials. Following this interest, a systematic analysis was performed of various types of amorphous carbon grains and polycyclic aromatic hydrocarbons (PAH), produced in lab. Updating results of Raman measurements performed on several carbonaceous materials, chosen according to their astrophysical interest, are presented. The measurements were made by means of a Jobin-Yvon monochromator HG2S and standard DC electronic. The line at 5145 A of an Ar+ laser was used as excitation source.

  10. 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.

  11. 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.

  12. 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

  13. Screening of carbonaceous nanoporous materials for capture of nerve agents.

    PubMed

    Kowalczyk, Piotr; Gauden, Piotr A; Terzyk, Artur P; Neimark, Alexander V

    2013-01-01

    A strategy for combined experimental and computational screening of candidate carbonaceous materials for capturing highly volatile nerve agents at ambient temperature using physisorption. Based on theoretical calculations of Henry constants and zero-coverage adsorption enthalpies for sarin and DMMP (its common stimulant) adsorbed in model slit-shaped carbon pores at 298 K, we found the following. Slit-shaped carbon pores with pore width ~0.5 nm are optimal for agent adsorption due to strong confinement of adsorbed molecules. Agent adsorption enthalpy at zero coverage computed for optimal pore width is very high and reaches ~83 kJ mol(-1). Widening of pore width above ~1 nm results in a significant decrease of the Henry constant and zero-coverage adsorption enthalpy (~44 kJ mol(-1)). Polydispersity of studied candidate carbonaceous materials strongly affects adsorption capacity for DMMP under the operating conditions. The optimal carbonaceous adsorbent, pitch-based P7 activated carbon fiber, adsorbed ~100 μg g(-1) DMMP at 0.03 μg m(-3). Commercial Norit activated carbon adsorbed only ~20 μg g(-1) DMMP at 0.03 μg m(-3). Surprisingly, a small shift of the pore size distribution towards wider micropores has a great impact on agent adsorption. Because the adsorption enthalpies computed at zero coverage weakly dependent on pore size, the heat released during agent adsorption is similar for all studied candidate adsorbents (i.e.~55-60 kJ mol(-1)). PMID:23165364

  14. Origins of interstellar and solar system: Carbonaceous materials

    NASA Technical Reports Server (NTRS)

    Feigelson, Eric D.

    1994-01-01

    Carbon is a crucial atom in cosmochemistry. It is well-established that carbon is synthesized in stellar interiors after the main sequence, is ejected by red giants as small carbonaceous grains during their 'carbon star' phase, resides in the interstellar medium, and was later incorporated into the solar system. The mechanisms of carbon grain formation and later chemical processing are complex because, with only small thermodynamic differences, carbon can take on a bewildering variety of forms: diamond; oxides; carbides; graphite; aliphatic hydrocarbons; polycyclic aromatic hydrocarbons (PAH's); fullerenes; amorphous carbon; and other compounds. These are evidence for many of the forms of carbon found in astronomical observations. We seek to understand the possible astrophysical sites and conditions of the origins of different forms of carbon by combining state-of-the-art capabilities of carbon chemistry with astrophysical modeling. The work is a collaboration between Prof. Frenklach, a leading carbon materials scientist with both laboratory and computer modeling expertise and Prof. Feigelson, an astrophysicist with interests in star formation. The largest effort under this grant was devoted to developing this concept into a comprehensive quantitative model. In addition to explaining the astronomical properties of red giants producing carbonaceous grains, our model also can incorporate recent meteoritic findings. Finally, our induced nucleation grain formation model provides a natural explanation for the widespread presence of PAH emission bands in the Galactic interstellar medium. A brief synopsis of other activities sponsored under this grant and a list of publications from this grant is included.

  15. Origins of interstellar and solar system: Carbonaceous materials

    NASA Astrophysics Data System (ADS)

    Feigelson, Eric D.

    1994-10-01

    Carbon is a crucial atom in cosmochemistry. It is well-established that carbon is synthesized in stellar interiors after the main sequence, is ejected by red giants as small carbonaceous grains during their 'carbon star' phase, resides in the interstellar medium, and was later incorporated into the solar system. The mechanisms of carbon grain formation and later chemical processing are complex because, with only small thermodynamic differences, carbon can take on a bewildering variety of forms: diamond; oxides; carbides; graphite; aliphatic hydrocarbons; polycyclic aromatic hydrocarbons (PAH's); fullerenes; amorphous carbon; and other compounds. These are evidence for many of the forms of carbon found in astronomical observations. We seek to understand the possible astrophysical sites and conditions of the origins of different forms of carbon by combining state-of-the-art capabilities of carbon chemistry with astrophysical modeling. The work is a collaboration between Prof. Frenklach, a leading carbon materials scientist with both laboratory and computer modeling expertise and Prof. Feigelson, an astrophysicist with interests in star formation. The largest effort under this grant was devoted to developing this concept into a comprehensive quantitative model. In addition to explaining the astronomical properties of red giants producing carbonaceous grains, our model also can incorporate recent meteoritic findings. Finally, our induced nucleation grain formation model provides a natural explanation for the widespread presence of PAH emission bands in the Galactic interstellar medium. A brief synopsis of other activities sponsored under this grant and a list of publications from this grant is included.

  16. High and rapid alkali cation storage in ultramicroporous carbonaceous materials

    NASA Astrophysics Data System (ADS)

    Yun, Young Soo; Lee, Seulbee; Kim, Na Rae; Kang, Minjee; Leal, Cecilia; Park, Kyu-Young; Kang, Kisuk; Jin, Hyoung-Joon

    2016-05-01

    To achieve better supercapacitor performance, efforts have focused on increasing the specific surface area of electrode materials to obtain higher energy and power density. The control of pores in these materials is one of the most effective ways to increase the surface area. However, when the size of pores decreases to a sub-nanometer regime, it becomes difficult to apply the conventional parallel-plate capacitor model because the charge separation distance (d-value) of the electrical double layer has a similar length scale. In this study, ultramicroporous carbonaceous materials (UCMs) containing sub-nanometer-scale pores are fabricated using a simple in situ carbonization/activation of cellulose-based compounds containing potassium. The results show that alkali cations act as charge carriers in the ultramicropores (<0.7 nm), and these materials can deliver high capacitances of ∼300 F g-1 at 0.5 A g-1 and 130 F g-1, even at a high current rate of 65 A g-1 in an aqueous medium. In addition, the UCM-based symmetric supercapacitors are stable over 10,000 cycles and have a high energy and power densities of 8.4 Wh kg-1 and 15,000 W kg-1, respectively. This study provides a better understanding of the effects of ultramicropores in alkali cation storage.

  17. Sonication method and reagent for treatment of carbonaceous materials

    SciTech Connect

    Sadeghi, M.A.; Sadegni, K.; Kuo, J.F.; Yen, T.F.

    1990-01-02

    This patent describes a method of recovering a lighter, hydrocarbon liquid oil from an asphaltene-containing solid carbonaceous material. The method comprising the steps of: dispersing particles of the solid material in an aqueous solution of an inorganic base selected from at least one member of the group consisting of alkali metal hydroxides, carbonates, phosphates and silicates at ambient temperature and in the absence of organic solvent; adding a water- miscible separation reagent formed of a reaction product between the inorganic base and polar components of bitumen to the suspension; applying sonic energy to the suspension for a time sufficient to remove from the solid particles an organic phase which separates into a lighter, hydrocarbon liquid oil which is essentially free of asphaltene and has an ash content below 1 percent by weight which floats to the top of the suspension to form a layer and into sold agglomerates containing a major portion of the asphaltene content of the material and containing a higher metal content than the oil layer which fall to the bottom of the suspension; recovering the hydrocarbon liquid oil from the top of the suspension; and recovering the agglomerates from the bottom of the suspension.

  18. Adsorption of dyes onto carbonaceous materials produced from coffee grounds by microwave treatment.

    PubMed

    Hirata, Mizuho; Kawasaki, Naohito; Nakamura, Takeo; Matsumoto, Kazuoki; Kabayama, Mineaki; Tamura, Takamichi; Tanada, Seiki

    2002-10-01

    Organic wastes have been burned for reclamation. However, they have to be recycled and reused for industrial sustainable development. Carbonaceous materials were produced from coffee grounds by microwave treatment. There are many phenolic hydroxyl and carboxyl groups on the surface of carbonaceous materials. The base consumption of the carbonaceous materials was larger than that of the commercially activated carbon. The carbonaceous materials produced from coffee grounds were applied to the adsorbates for the removal of basic dyes (methylene blue and gentian violet) in wastewater. This result indicated that the adsorption of dyes depended upon the surface polar groups on the carbonaceous materials. Moreover, the Freundlich constants of isotherms for the adsorption of methylene blue and gentian violet onto the carbonaceous materials produced from coffee grounds were greater than those for adsorption onto activated carbon or ceramic activated carbon. The interaction was greatest between the surface or porosity of the carbonaceous materials and methylene blue and gentian violet. The microwave treatment would be useful for the carbonization of organic wastes to save energy. PMID:12702420

  19. 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.

  20. The Halogen Bond in the Design of Functional Supramolecular Materials: Recent Advances

    PubMed Central

    2013-01-01

    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

  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. 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.

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

    SciTech Connect

    Brunson, R.J.; Deane, B.C.; Epperly, W.R.

    1982-06-01

    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. 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.

  5. Pressure Gradient Passivation of Carbonaceous Material Normally Susceptible to Spontaneous Combustion

    SciTech Connect

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

    1999-07-15

    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.

  6. Fullerenes in asphaltenes and other carbonaceous materials: natural constituents or laser artifacts.

    PubMed

    Santos, Vanessa G; Fasciotti, Maíra; Pudenzi, Marcos A; Klitzke, Clécio F; Nascimento, Heliara L; Pereira, Rosana C L; Bastos, Wagner L; Eberlin, Marcos N

    2016-04-25

    The presence of fullerenes as natural constituents of carbonaceous materials or their formation as laser artifacts during laser desorption ionization (LDI) mass spectrometry (MS) analysis is reinvestigated and reviewed. The results using asphaltene samples with varying composition as well as standard polycyclic aromatic hydrocarbons (PAH) and fullerene samples as models have demonstrated that indeed Cn ring fullerenes are not natural constituents but they are formed as common and often as predominant artifacts upon laser radiation, and a series of incorrect assignments based on LDI-MS data of several carbonaceous materials seems unfortunately to have been made. When the present results are evaluated also in the light of the vast literature on LDI-MS of carbonaceous materials, the formation of fullerene artifacts seems particularly common for LDI-MS analysis of asphaltenes and other carbonaceous samples with considerably high levels of PAH and varies according to the type of laser used, and the intensity of the laser beam. PMID:26805430

  7. Reactive Oxygen-Doped 3D Interdigital Carbonaceous Materials for Li and Na Ion Batteries.

    PubMed

    Fan, Ling; Lu, Bingan

    2016-05-01

    Carbonaceous materials as anodes usually exhibit low capacity for lithium ion batteries (LIBs) and sodium ion batteries (SIBs). Oxygen-doped carbonaceous materials have the potential of high capacity and super rate performance. However, up to now, the reported oxygen-doped carbonaceous materials usually exhibit inferior electrochemical performance. To overcome this problem, a high reactive oxygen-doped 3D interdigital porous carbonaceous material is designed and synthesized through epitaxial growth method and used as anodes for LIBs and SIBs. It delivers high reversible capacity, super rate performance, and long cycling stability (473 mA h g(-1) after 500 cycles for LIBs and 223 mA h g(-1) after 1200 cycles for SIBs, respectively, at the current density of 1000 mA g(-1) ), with a capacity decay of 0.0214% per cycle for LIBs and 0.0155% per cycle for SIBs. The results demonstrate that constructing 3D interdigital porous structure with reactive oxygen functional groups can significantly enhance the electrochemical performance of oxygen-doped carbonaceous material. PMID:27061155

  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. Fundamental studies of chalcogenide nanocrystals, carbonaceous nanoparticles, and chromatographic materials

    NASA Astrophysics Data System (ADS)

    Baker, Jared Scott

    2011-12-01

    The development of novel nanomaterials and the understanding of their fundamental physical and chemical properties represent an exciting area of research. These materials are continuously being sought for ever-increasing applications; finding their way into uses that influence mankind on a daily basis. Combining elements from traditional nanoparticle characterization with electrophoretic-based techniques, this dissertation presents the analysis of carbon nanoparticles (CNPs) generated from a novel source (candle soot) as well as a unique perspective on the reactivity and degradation process of magic-sized cadmium chalcogenide nanocrystals. One potential application of CNPs is their use as an alternative fluorophore in a separation-based sensor system. Laser-induced-fluorescence (LIF) is a commonly used manner of detection in this type of platform, but is limited in many cases by problems associated with the fluorophore. Carbon-based nanoparticles have the potential to improve upon traditional fluorophores in applications that make use of LIF as the detection scheme. CNPs were extracted from the carbonaceous material produced by the incomplete combustion of a candle. The soot was submitted to an oxidizing treatment and extraction/filtration procedures rendering watersoluble luminescent species. Electron microscopy was used to identify globular, amorphous structures in the nanometer size-range. An aqueous suspension of CNPs demonstrated excellent stability in terms of its electronic properties, showing little change in absorption and emission spectra upon storage under ambient conditions over a two-year period. Capitalizing on the strengths of capillary electrophoresis (CE) as a characterization technique, we have analyzed the negatively-charged CNPs in terms of charge and size by studying the influence of variable CE conditions on the resulting separation. Separations at different pH revealed a highly complex mixture of CNPs, containing species with large

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

    PubMed

    Lee, Duckhee

    2013-01-01

    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. PMID:23846757

  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. Method of producing carbon monoxide and hydrogen by gasification of solid carbonaceous material involving microwave irradiation

    SciTech Connect

    Helm, J.L. Jr.

    1984-03-06

    A process is claimed for the gasification of carbon of solid carbonaceous material to form carbon monoxide and hydrogen by contacting the material with superheated steam and irradiating the product of said contacting with an amount of microwave energy sufficient to gasify said carbon, and apparatus therefor.

  14. Catalyzed electrochemical gasification of carbonaceous materials at anode and electrowinning of metals at cathode

    SciTech Connect

    Vaughan, R.J.

    1983-09-20

    The electrochemical gasification reaction of carbonaceous materials by anodic oxidation in an aqueous acidic electrolyte to produce oxides of carbon at the anode and metallic elements at the cathode of an electrolysis cell is catalyzed by the use of an iron catalyst.

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

    SciTech Connect

    Wen, W.W.; Deurbrouck, A.W.

    1990-11-13

    A finely-divided carbonaceous material is dewatered and reconstituted in a combined process by adding a binding agent directly into the 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. 8 figs.

  16. 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.

  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. 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.

  19. 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.

  20. 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.

  1. Investigation of the reactivity of carbonaceous materials in liquid and gaseous oxidizing media

    SciTech Connect

    Cherednik, E.M.; Butyrin, G.M.; Chirkina, A.P.; Mashkovich, L.A.; Kuteinikov, A.F.

    1982-01-01

    Constructional materials based on carbon are being used even more widely in various sectors of science and technology where they are subjected to the action of high temperatures, and also to aggressive liquid and gaseous media. The tendency of carbonaceous materials, especially synthetic graphites, to undergo oxidation frequently determines the possibility of their employment under concrete conditions of use. In the reported study, a comparative analysis has been made of experimental results on the liquid- and gas-phase oxidation of a wide range of carbon-containing materials with different porosities and chemical structures. Some general laws of the oxidation of carbon by various oxidizing agents have been deduced. 17 refs.

  2. 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

  3. 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.

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

    DOEpatents

    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.

  6. 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

  7. NOVEL 'GREENER' ROUTES TO HALOGEN-FREE FLAME RETARDANT MATERIALS

    EPA Science Inventory

    The increased use of polymeric materials in numerous applications over the past decade has prompted a surge in the need for additives in the polymer industry. Flame retardant (FR) materials are additives that are used to control or reduce/eliminate the risk of fire in flammabl...

  8. 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

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

    DOEpatents

    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.

  10. 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.

  11. 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. PMID:25189634

  12. Spectral parameters for Dawn FC color data: Carbonaceous chondrites and aqueous alteration products as potential cerean analog materials

    NASA Astrophysics Data System (ADS)

    Schäfer, Tanja; Nathues, Andreas; Mengel, Kurt; Izawa, Matthew R. M.; Cloutis, Edward A.; Schäfer, Michael; Hoffmann, Martin

    2016-02-01

    We identified a set of spectral parameters based on Dawn Framing Camera (FC) bandpasses, covering the wavelength range 0.4-1.0 μm, for mineralogical mapping of potential chondritic material and aqueous alteration products on dwarf planet Ceres. Our parameters are inferred from laboratory spectra of well-described and clearly classified carbonaceous chondrites representative for a dark component. We additionally investigated the FC signatures of candidate bright materials including carbonates, sulfates and hydroxide (brucite), which can possibly be exposed on the cerean surface by impact craters or plume activity. Several materials mineralogically related to carbonaceous chondrites, including pure ferromagnesian phyllosilicates, and serpentinites were also investigated. We tested the potential of the derived FC parameters for distinguishing between different carbonaceous chondritic materials, and between other plausible cerean surface materials. We found that the major carbonaceous chondrite groups (CM, CO, CV, CK, and CR) are distinguishable using the FC filter ratios 0.56/0.44 μm and 0.83/0.97 μm. The absorption bands of Fe-bearing phyllosilicates at 0.7 and 0.9 μm in terrestrial samples and CM carbonaceous chondrites can be detected by a combination of FC band parameters using the filters at 0.65, 0.75, 0.83, 0.92 and 0.97 μm. This set of parameters serves as a basis to identify and distinguish different lithologies on the cerean surface by FC multispectral data.

  13. 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.

  14. 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.

  15. 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. PMID:26496525

  16. Permeation of protective garment material by liquid halogenated ethanes and a polychlorinated biphenyl

    SciTech Connect

    Weeks, R.W. Jr.; McLeod, M.J.

    1980-10-01

    The halogenated ethanes 1,2-dichloroethane; 1,1,1-trichlorethane; and 1,1,2-trichlorethane are used as chemical intermediates and in metal working operations, and polychlorinated biphenyls (PCBs) have in the past been used by the tens of millions of pounds in various roles in American industry. Because of the widespread use and hazardous or potentially carcinogenic nature of these compounds, a study was performed to determine the degree of protection which was afforded against these compounds by certain protective garment materials. The materials evaluated in these studies have included: butyl rubber, milled nitrile rubber, neoprene rubber latex, nitrile rubber latex, polyethylene, poly(vinyl alcohol), surgical rubber latex, Teflon, and Viton as well as the following composite or multilayered materials: butyl-coated nylon, polyethylene-coated Tyvek, polyurethane-coated nylon, and poly(vinyl chloride)-coated nylon. The breakthrough time at which each liquid phase compound permeated these materials was studied by the time lag method. For the noncomposite materials, the results of these breakthrough studies were correlated with their equilibrium weight changes following immersion in the test liquids. Results of these studies have shown that most materials currently used in the construction of protective garment material in the United States are of a generally unsatisfactory nature with respect to protecting the worker against the halogenated ethanes and the PCB used in this study.

  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. PMID:26858438

  19. Sorption / desorption hysteresis of non-polar organic compounds in carbonaceous materials

    NASA Astrophysics Data System (ADS)

    Wang, G.; Kleineidam, S.; Grathwohl, P.

    2003-04-01

    Natural and thermally-altered carbonaceous materials (coals, charcoal, cokes) are nowadays found in many soil and sediment samples due to anthropogenic impact (e.g. industrial activities, traffic) to the natural environment. The sorption -- desorption characteristics of hydrophobic organic compounds on that type of geosorbents play an important role in contaminant fate and transport and are yet not precisely known. Contaminant transport and bioavailibility models often assume complete sorption reversibility. In this study, a series of desorption steps using the ASE (accelerated solvent extractor) with water at different temperatures were carried out to determine the desorption enthalpy and to study hysteresis phenomena. The initial natural loading of PAHs onto the geosorbents was determined by solvent extraction (acetone and toluene). The background loading is in the order of 0.8 mg kg-1 -- 102 mg kg-1 for the natural coals and in the order of 0.16 mg kg-1 -- 10 mg kg-1 for the thermally altered coals. The results are compared to kinetic and equilibrium data from laboratory experiments on sorptive uptake of the phenanthrene onto the same carbonaceous samples.

  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. 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.

  2. 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.

  3. Sorption of hydrophobic organic compounds to a diverse suite of carbonaceous materials with emphasis on biochar.

    PubMed

    Kupryianchyk, Darya; Hale, Sarah; Zimmerman, Andrew R; Harvey, Omar; Rutherford, David; Abiven, Samuel; Knicker, Heike; Schmidt, Hans-Peter; Rumpel, Cornelia; Cornelissen, Gerard

    2016-02-01

    Carbonaceous materials like biochars are increasingly recognized as effective sorbent materials for sequestering organic pollutants. Here, we study sorption behavior of two common hydrophobic organic contaminants 2,2',5,5'-tetrachlorobiphenyl (CB52) and phenanthrene (PHE), on biochars and other carbonaceous materials (CM) produced at a wide range of conditions and temperatures from various feedstocks. The primary aim was to establish structure-reactivity relationships responsible for the observed variation in CM and biochar sorption characteristics. CM were characterized for their elemental composition, surface area, pore size distribution, aromaticity and thermal stability. Freundlich sorption coefficients for CB52 and PHE (i.e. LogK(F,CB52) and K(F,PHE), respectively) to CM showed a variation of two to three orders of magnitude, with LogK(F,CB52) ranging from 5.12 ± 0.38 to 8.01 ± 0.18 and LogK(F,PHE) from 5.18 ± 0.09 to 7.42 ± 1.09. The highest LogK(F) values were observed for the activated CM, however, non-activated biochars produced at high temperatures (>700 °C) sorbed almost as strongly (within 0.2-0.5 Log units) as the activated ones. Sorption coefficients significantly increased with pyrolysis temperature, CM surface area and pore volume, aromaticity, and thermal stability, and decreased with H/C, O/C, (O + N)/C content. The results of our study contribute to the understanding of processes underlying HOC sorption to CM and explore the potential of CM as engineered sorbents for environmental applications. PMID:26421628

  4. 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.

  5. 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. PMID:27259645

  6. An investigation of carbonaceous materials reducing ferric ions in aqueous solution

    NASA Astrophysics Data System (ADS)

    Cooke, A. V.; Chilton, J. P.; Fray, D. J.

    1988-10-01

    By substituting the ferrous to ferric oxidation for anodic oxygen evolution in an electrowinning cell, it is possible to reduce the cell voltage by about 1 V. However, it is then necessary to reduce the ferric back to ferrous and, depending on the circumstances, acid needs to be cogenerated. Various possible reductants are discussed, and experiments are described on the use of lignite and other carbonaceous materials to reduce the ferric ion. It was found that lignite was able to reduce the ferric ion, in situ in the electrowinning cell, but that the rate of reduction was compatible only with a maximum current density of about 40 Am-2. The efficiency was increased by periodically interrupting the current flow.

  7. 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.

  8. 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

  9. 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. PMID:11539252

  10. 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. PMID:26507207

  11. 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.

  12. The Effect of Alignment and Target Material upon Temperature in Halogen Projector Bulb Heating Experiments

    NASA Astrophysics Data System (ADS)

    Grove, J.

    2011-12-01

    Incandescent light produced by halogen projector lamps can be used to heat minerals suspended on thermocouples for the purpose of extracting noble gasses under well-known thermal conditions. Experiments were performed to optimize the efficiency of the heat source. An ENX 82 volt, 360 watt bulb with a gold-coated reflector directs more of the infrared spectrum at the sample and is about 65% more efficient than the same bulb with a standard dichroic coating. I used a 3-axis manual positioning device to precisely determine the focal point of the bulb so that it could be best positioned to heat the sample. The focal point is about 25 mm from the filament. Increasing this distance to 45 mm and 65 mm decreases temperature by 27% and 58% respectively. Staying in the focal plane but moving 10 mm from the focal point decreases temperature by about 30%. I also investigated 5 different types of target material (Cu, Al, Ti, Ta, and Mo). A 1 square cm target of a specific metal was placed beneath the lamp at the focal point. Power output was fixed at 2 amps. An inconel-shielded type K thermocouple probe with no target attached produced a temperature of 133°C under these conditions. The target absorbs heat from the lamp but loses it by thermal conduction to the thermocouple. Cu and Al have the highest reflectivity and the highest thermal conductivity and recorded the lowest temperatures (73±3°C and 104±8°C respectively). I found that Ti, Mo, and Ta targets outperformed Cu by 211% (226±19°C), 351% (328±7°C), and 124% (163±13°C) respectively. This variation makes sense in terms of the thermal conductivity and reflectivity of these materials. Coating a Mo target with carbon produced the best results (395°C or 444% more efficient than Cu). Experiments under vacuum produced similar results. In conclusion, samples enclosed in Mo foil and suspended 25 mm from the filament will yield the most efficient arrangement for heating samples with a ENX halogen projector lamp

  13. 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. PMID:14987867

  14. 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.

  15. 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. PMID:22123243

  16. An effective approach for modifying carbonaceous materials with niobium single sites to improve their catalytic properties.

    PubMed

    Bozzi, A S; Lavall, R L; Souza, T E; Pereira, M C; de Souza, P P; De Abreu, H A; De Oliveira, A; Ortega, P F R; Paniago, R; Oliveira, L C A

    2015-12-14

    In this paper we show a very simple route for the incorporation of catalytically active niobium species on the surface of carbon materials, such as graphene oxide, carbon nanotubes and activated carbon. Some existing methods of incorporating a transition metal on a support have involved co-precipitation or wet impregnation, to obtain the corresponding oxides. These methods, however, cause reduction in the specific area of the support and can also form large metal oxide particles with loss of metal exposure. Therefore, here we present a novel way to add catalytically active species on the surfaces of different types of carbon through the formation of interaction complexes between the metal precursor and the functional groups of the carbon matrix. Because of the excellent catalytic properties exhibited by the niobium species we choose the NH4[NbO(C2O4)2(H2O)2]·2H2O salt as the model precursor. The characterization by XPS reveals the presence of the niobium species indicated by the displacement of the peaks between 206-212 eV related to the oxalate species according to the spectrum from pure niobium oxalate. Images obtained by TEM and SEM show the typical morphologies of carbonaceous materials without the niobium oxide formation signal, which indicates the presence of niobium complexes as isolated sites on the carbon surfaces. This new class of materials exhibited excellent properties as catalysts for pollutant oxidation. The presence of Nb promotes the catalytic activation of H2O2 generating hydroxyl radicals in situ, which allows their use in the organic compound oxidation processes. Tests for DBT oxidation indicate that Nb significantly improves the removal of such pollutants in biphasic reactions with removal around 90% under the tested conditions. Theoretical calculations showed that the most favorable adsorption model is an ionic complex presenting a ΔG = -108.7 kcal mol(-1) for the whole adsorption process. PMID:26514577

  17. 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.

  18. A kinetic model based on experimental study of structural evolution of natural carbonaceous material to graphite

    NASA Astrophysics Data System (ADS)

    Nakamura, Y.; Yoshino, T.; Satish-Kumar, M.

    2015-12-01

    We report here new experimental kinetic data on the structural evolution of carbonaceous materials (CM) to graphite in a wide range of temperature conditions (1000 and 1450 °C) and treatment time (10 min to 115 hrs) under a pressure condition of 1GPa. The morphologies and crystallinities of natural CM, extracted from sediments in the Shimanto accretionary complex and Hidaka metamorphic belt, transformed to fully ordered graphite with increasing temperature and annealing duration. The time-temperature relations of each crystal parameter obtained using XRD analysis and micro-Raman spectroscopy demonstrated sigmoidal transformations from amorphous to graphitic structure, suggesting the complexity of chemical reactions undergoing during graphitization. To assess these kinetic processes, the results were analyzed using a superposition method in which the crystal parameters were superposed to reference temperature with non-linear regression curves. The master curves fitted by sigmoidal and power functions exhibited very good correlation coefficients of 0.940 to 0.991, suggesting the Arrhenian relation between temperature and time. On the basis of master curves and shift values, we obtained the effective activation energies of 274 +/- 9 kJmol-1 and 339 +/- 6 kJmol-1 for two different natural CM. When compared with the previous studies, our data gave remarkably low activation energies for natural graphitization, which can be represented in a time-temperature relation. In addition, the sigmoidal functions obtained from time-temperature relations can be extrapolated for low temperature condition at 1GPa. Our kinetic model predicts that if the CM underwent metamorphism for about one million years, it begins to crystallize at ≈ 420 °C and transform to fully ordered graphite at over ≈ 510 °C. Thus, natural graphitization could be discussed by the laboratory experiments using natural precursor materials under realistic pressure condition and time span in the Earth's crust.

  19. 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.

  20. 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

  1. 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. PMID:26812185

  2. 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

  3. 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.

  4. 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

  5. Characterization and performance of carbonaceous materials obtained from exhausted sludges for the anaerobic biodecolorization of the azo dye Acid Orange II.

    PubMed

    Athalathil, S; Stüber, F; Bengoa, C; Font, J; Fortuny, A; Fabregat, A

    2014-02-28

    This work presents the preliminary study of new carbonaceous materials (CMs) obtained from exhausted sludge, their use in the heterogeneous anaerobic process of biodecolorization of azo dyes and the comparison of their performance with one commercial active carbon. The preparation of carbonaceous materials was conducted through chemical activation and carbonization. Chemical activation was carried out through impregnation of sludge-exhausted materials with ZnCl2 and the activation by means of carbonization at different temperatures (400, 600 and 800°C). Their physicochemical and surface characteristics were also investigated. Sludge based carbonaceous (SBC) materials SBC400, SBC600 and SBC800 present values of 13.0, 111.3 and 202.0m(2)/g of surface area. Biodecolorization levels of 76% were achieved for SBC600 and 86% for SBC800 at space time (τ) of 1.0min, similar to that obtained with commercial activated carbons in the continuous anaerobic up-flow packed bed reactor (UPBR). The experimental data fit well to the first order kinetic model and equilibrium data are well represented by the Langmuir isotherm model. Carbonaceous materials show high level of biodecolorization even at very short space times. Results indicate that carbonaceous materials prepared from sludge-exhausted materials have outstanding textural properties and significant degradation capacity for treating textile effluents. PMID:24413048

  6. Relationship between carbonaceous materials and polychlorinated biphenyls (PCBs) in the sediments of the Danshui River and adjacent coastal areas, Taiwan.

    PubMed

    Hung, Chin-Chang; Gong, Gwo-Ching; Jiann, Kuo-Tung; Yeager, Kevin M; Santschi, Peter H; Wade, Terry L; Sericano, Jose L; Hsieh, Hwey-Lian

    2006-11-01

    Persistent organic pollutants, POPs (e.g., polychlorinated biphenyls) can seriously and deleteriously affect environmental quality and human health. These organic pollutants are exhibiting high affinities to solid phases and thus, quickly end up in sediments. To better understand the role of carbonaceous materials in the transport and distributions of POPs in terrestrial and near-shore environments, concentrations of PCBs and carbonaceous materials (including total organic carbon, black carbon and total carbohydrates), were determined in surface sediments of the Danshui River and nearby coastal areas, Taiwan. Total concentrations of PCBs in the sediments ranged from non-detectable to 83.9 ngg(-1), dry weight, with the maximum value detected near the discharge point of the marine outfall from the Pali Sewage Treatment Plant. These results suggest that the sewage treatment plant has discharged PCBs in the past and the concentrations are still high due to their persistence; alternatively, PCBs are still being discharged in the estuarine and near-shore environment of the Danshui River. Organic carbon and black carbon concentrations correlated well with those of total PCBs in the sediments, suggesting that both organic carbon and black carbon significantly affect the distribution of trace organic pollutants through either post-depositional adsorption, or by co-transport of similar source materials. The field results demonstrate that black carbon and plays an important role in the general distribution of PCBs, while concentrations of some specific PCBs are affected by both black carbon and organic carbon concentrations. PMID:16757014

  7. 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.

  8. 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.

  9. 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.

  10. Impact of carbonaceous materials in soil on the transport of soil-bound PAHs during rainfall-runoff events.

    PubMed

    Luo, Xiaolin; Zheng, Yi; Wu, Bin; Lin, Zhongrong; Han, Feng; Zhang, Wei; Wang, Xuejun

    2013-11-01

    Polycyclic Aromatic Hydrocarbons (PAHs) transported from contaminated soils by surface runoff pose significant risk for aquatic ecosystems. Based on a rainfall-runoff simulation experiment, this study investigated the impact of carbonaceous materials (CMs) in soil, identified by organic petrology analysis, on the transport of soil-bound PAHs under rainfall conditions. The hypothesis that composition of soil organic matter significantly impacts the enrichment and transport of PAHs was proved. CMs in soil, varying significantly in content, mobility and adsorption capacity, act differently on the transport of PAHs. Anthropogenic CMs like black carbon (BC) largely control the transport, as PAHs may be preferentially attached to them. Eventually, this study led to a rethink of the traditional enrichment theory. An important implication is that CMs in soil have to be explicitly considered to appropriately model the nonpoint source pollution of PAHs (possibly other hydrophobic chemicals as well) and assess its environmental risk. PMID:23938446

  11. Removal of Cr(III) from chrome tanning wastewater by adsorption using two natural carbonaceous materials: Eggshell and powdered marble.

    PubMed

    Elabbas, Saliha; Mandi, Laila; Berrekhis, Fatima; Pons, Marie Noelle; Leclerc, Jean Pierre; Ouazzani, Naaila

    2016-01-15

    In the present paper, eggshell and powdered marble, two carbonaceous materials, were used to remove Cr(III) ions from a real chrome tanning wastewater. The effects of initial effluent pH, adsorbent dose, contact time and temperature were studied. The maximum uptake of chromium ions was obtained at pH 5.0 with the dose 20 g L(-1) and 12 g L(-1) for eggshell and powdered marble respectively. Adsorption equilibrium was reached after 14 h contact time for eggshell and only after 30 min for powdered marble. Under these conditions, almost 99% Cr(III) was removed from chrome tanning wastewater having an initial concentration of chromium of 3.21 g L(-1). Kinetic data were satisfactorily described by a pseudo-second order chemical sorption model. The equilibrium rate constant was notably greater for powdered marble than for eggshell with 1.142·10(-3) (g mg(-1) min(-1)) and 0.041·10(-3) (g mg(-1) min(-1)) respectively. The adsorption isotherm were well described by a Langmuir model and showed that the interaction of chromium with the two adsorbents surface is a localized monolayer adsorption with a smaller energy constant for the powdered marble than for eggshell (0.020 (L mg(-1)) and 0.083 (L mg(-1)) respectively). The powdered marble was able to adsorb faster a large amount of Cr (III) in comparison to eggshell. The use of a standardized lettuce seed bioassay allowed evaluating a better effectiveness of the Cr adsorption on the powdered marble, removing up to 40% of the treated effluent toxicity than by eggshell 25%. The powdered marble could be considered as an effective, low cost carbonaceous material to be used for chromium removal from tanning wastewater. PMID:26598282

  12. 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.

  13. Carbon and hydrogen isotope effects during sorption of organic contaminants on carbonaceous materials.

    PubMed

    Schüth, Christoph; Taubald, Heinrich; Bolaño, Nerea; Maciejczyk, Kirsten

    2003-07-01

    Stable carbon and hydrogen isotopes can be an efficient means to validate biodegradation of organic contaminants in groundwater since it results in an isotopic fractionation. A prerequisite in applying this method in the field is the proof that other processes decreasing the contaminant concentration are conservative with respect to isotope effects. In this paper we show for carbon isotopes of halogenated hydrocarbon compounds [trichloroethene (TCE), cis-dichloroethene (c-DCE), vinylchloride (VC)] and carbon and hydrogen isotopes of BTEX compounds (benzene, toluene, p-xylene) that no significant fractionation occurs during equilibrium sorption onto activated carbon, lignite coke and lignite. In general, effects were in the range of the reproducibility limit of the analytical instrument (0.5 per thousand for delta13C, and 8 per thousand for delta2H). This observation was made for fractions sorbed of less than 5% to more than 95%. Also for rate-limited sorption of TCE onto activated carbon, no significant fractionation in carbon isotopes could be observed. These findings support the assumption that for these classes of compounds, sorption processes in aquifer systems are conservative with respect to isotope effects. PMID:12814884

  14. Investigation of the records of earthquake slip in carbonaceous materials from the Taiwan Chelungpu fault by means of infrared and Raman spectroscopies

    NASA Astrophysics Data System (ADS)

    Hirono, Tetsuro; Maekawa, Yuka; Yabuta, Hikaru

    2015-05-01

    To understand the mechanism of fault lubrication during the 1999 Taiwan Chi-Chi earthquake, we developed a new temperature proxy for carbonaceous materials by using infrared and Raman spectroscopies together with heating and friction experiments. We found marked anomalies in the infrared and Raman spectra of carbonaceous materials retrieved from the primary slip zone of the earthquake: the infrared spectra exhibited very weak aliphatic CH2 and CH3 peaks and aromatic C=C absorbance peaks, and the Raman spectra exhibited very weak disordered and graphitic bands and a high ratio of disordered band area to graphitic band area. Those weak peaks and bands and the band area ratio were reproduced by heating carbonaceous materials from the nearby host rock to 700°C. These results suggest that the frictional heat in the slip zone reached approximately 700°C. We characterized the host rock's carbonaceous materials by means of elemental analysis, pyrolysis-gas chromatography-mass spectrometry, and simultaneous thermogravimetry-differential scanning calorimetry and found that the H/C and O/C ratios were 1.29 and 0.30, respectively (which are close to the ratios for lignin) and that the volatile fraction was as high as 48 wt %. The pyrolysates obtained by heating from 100 to 400°C were dominated by phenols, fatty alcohols, and n-alkanes. When the residue from pyrolysis at 100-400°C was rapidly heated to 700°C, the resulting pyrolysate was dominated by phenols, aromatic compounds, heterocyclic compounds, and n-alkenes. This information suggests that change in the infrared and Raman spectra with increasing temperature may have been due to decomposition and aromatization reactions during pyrolysis. Rapid heating during earthquake slip may promote reactions of carbonaceous materials that are different from the reactions that occur during long-term geological metamorphism.

  15. 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

  16. 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. PMID:27007184

  17. 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.

  18. 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. PMID:20102236

  19. Role of ingestion route in the perfluoroalkyl substance bioaccumulation by Chironomus plumosus larvae in sediments amended with carbonaceous materials.

    PubMed

    Zhai, Yawei; Xia, Xinghui; Zhao, Xiuli; Dong, Haiyang; Zhu, Baotong; Xia, Na; Dong, Jianwei

    2016-01-25

    The role of ingestion route in the bioaccumulation of six types of perfluoroalkyl substances (PFASs) by Chironomus plumosus larvae in sediments amended with four types of carbonaceous materials (CMs) was studied. The results showed that the body burden of PFASs decreased in the presence of CMs at mass ratios of 0.2-2%, regardless of ingestion. PFASs accumulated by the larvae with ingestion exposure were higher than those without ingestion, and the role of ingestion route was altered in the presence of CMs. The contribution of ingestion route to PFAS bioaccumulation was 2.7-31.6% without CMs, and it increased to more than 61.4% in the presence of fullerene at mass ratios of 0.2-2%. The enhancement of the ingestion route contribution caused by CMs is due to the fact that the CMs can be ingested and CM-associated PFASs can be partly desorbed in larvae. The maximum desorption efficiency of perfluorooctanoic acid was 20.8% from fullerene by the larval digestive juice. This study suggests that CM-associated PFASs could be accumulated partly by organisms, and the ecological risk of PFASs might increase in some cases with the presence of CMs. This should be considered when applying CMs in PFAS and other hydrophobic organic compound pollution remediation. PMID:26489915

  20. Effects of carbonaceous materials on microbial bioavailability of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) in sediments.

    PubMed

    Zhu, Baotong; Wu, Shan; Xia, Xinghui; Lu, Xiaoxia; Zhang, Xiaotian; Xia, Na; Liu, Ting

    2016-07-15

    In this study, we investigated the influence of various types of carbonaceous materials (CMs) on the bioavailability of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) to polybrominated diphenyl ether (PBDE)-degrading microorganisms in CM-amended sediments. The microbial debromination ratio of BDE-47 was reduced by 92.8%-98.2% in the 5.0% CM-amended sediment compared with in sediment without CM amendment after 100 d of anaerobic incubation. The concentrations of lower brominated products also decreased when the content of CMs increased from 0.2% to 5.0%. The inhibitory effects of CMs on BDE-47 debromination were CM content- and characteristic-specific. The reciprocals of BDE-47 debromination ratios and lower brominated product concentrations showed positive linear correlations with CM contents in sediments (p<0.01), and the slopes of linear regression fitting generally correlated with specific surface areas (SSAs) of CMs. Desorption of BDE-47 from CMs indicated the declined desorbing fraction of BDE-47 was responsible for the reduction in BDE-47 bioavailability to microorganisms, thus decreasing its debromination in sediments amended with CMs. This study revealed that CM amendment could reduce the PBDE bioavailability to PBDE-degrading microorganisms in sediments, and it is expected to help deepen our understanding of the environmental behaviors and risks of PBDEs. PMID:27037476

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. Cytotoxicity and reactive oxygen species generation from aggregated carbon and carbonaceous nanoparticulate materials.

    PubMed

    Garza, Kristine M; Soto, Karla F; Murr, Lawrence E

    2008-01-01

    We have investigated the cytotoxicity and reactive oxygen species (ROS) generation for indoor and outdoor soots: candle, wood, diesel, tire, and natural gas burner soots--along with surrogate black carbon, various multiwall carbon nanotube aggregate materials, TiO2 (anatase) and chrysotile asbestos as reference materials. All soots were observed utilizing TEM and FESEM to be composed of aggregated, primary spherules (20-80 nm diameter) forming complex, branched fractal structures. These spherules were composed of intercalated, turbostratic arrangements of curved graphene fragments with varying concentrations ofpolycyclic aromatic hydrocarbon (PAH) isomers. In vitro cultures with an immortalized human lung epithelial carcinoma cell line (A549) treated with these materials showed decreased cell viability and variations in ROS production, with no correlations to PAH content. The data demonstrate that soots are cytotoxic and that cytotoxicity is not related to PAH content but is related to ROS generation, suggesting that soot induces cellular oxidative stress and that cell viability assays can be indicators of ROS production. PMID:18488419

  8. Cytotoxicity and reactive oxygen species generation from aggregated carbon and carbonaceous nanoparticulate materials

    PubMed Central

    Garza, Kristine M; Soto, Karla F; Murr, Lawrence E

    2008-01-01

    We have investigated the cytotoxicity and reactive oxygen species (ROS) generation for indoor and outdoor soots: candle, wood, diesel, tire, and natural gas burner soots – along with surrogate black carbon, various multiwall carbon nanotube aggregate materials, TiO2 (anatase) and chrysotile asbestos as reference materials. All soots were observed utilizing TEM and FESEM to be composed of aggregated, primary spherules (20–80 nm diameter) forming complex, branched fractal structures. These spherules were composed of intercalated, turbostratic arrangements of curved graphene fragments with varying concentrations of polycyclic aromatic hydrocarbon (PAH) isomers. In vitro cultures with an immortalized human lung epithelial carcinoma cell line (A549) treated with these materials showed decreased cell viability and variations in ROS production, with no correlations to PAH content. The data demonstrate that soots are cytotoxic and that cytotoxicity is not related to PAH content but is related to ROS generation, suggesting that soot induces cellular oxidative stress and that cell viability assays can be indicators of ROS production. PMID:18488419

  9. 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.

  10. 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

  11. 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.

  12. π(+)-π interactions between (hetero)aromatic amine cations and the graphitic surfaces of pyrogenic carbonaceous materials.

    PubMed

    Xiao, Feng; Pignatello, Joseph J

    2015-01-20

    Many organic compounds of environmental concern contain amine groups that are positively charged at environmental pH. Here we present evidence that (hetero)aromatic amine cations can act as π acceptors in forming π(+)–π electron donor–acceptor (EDA) interactions with the π electron-rich, polyaromatic surface of pyrogenic carbonaceous materials (PCMs) (i.e., biochar, black carbon, and graphene). The π(+)–π EDA interactions combine a cation−π force with a π–π EDA force resulting from charge polarization of the ring’s quadrupole. Adsorption on a biochar and reference adsorbent graphite was conducted of triazine herbicides, substituted anilines, heterocyclic aromatic amines, and other amines whose charge is insulated from the aromatic ring. When normalized for the hydrophobic effect, the adsorption increased with decreasing pH as the amines became ionized, even on graphite that had no significant fixed or variable charge. The cationic π acceptor (quinolinium ion) was competitively displaced more effectively by the π acceptor 2,4-dinitrobenzene than by the π donor naphthalene. The maximum electrostatic potential of organocations computed with density functional theory was found to be a strong predictor of the π(+)–π EDA interaction. The π(+)–π EDA interaction was disfavored by electropositive alkyl substituents and by charge delocalization into additional rings. Amines whose charge was insulated from the ring fell far out of the correlation (more positive free energy of adsorption). Identifying and characterizing this novel π(+)–π EDA interaction on PCMs will help in predicting the fate of organocations in both natural and engineered systems. PMID:25569811

  13. Circumstellar Carbonaceous Material Associated with Late-Type Dusty WC Wolf-Rayet Stars

    NASA Astrophysics Data System (ADS)

    Chiar, J. E.; Tielens, A. G. G. M.

    2001-04-01

    We have studied the 5-8.5 μm infrared spectra of the late-type Wolf-Rayet stars WR 118, WR 112, and WR 104, the WN star WR 147, the B5 hypergiant Cygnus OB2 No. 12, and the Galactic center luminous blue variable Pistol Star using the Short Wavelength Spectrometer on the Infrared Space Observatory. We attribute an absorption feature at 6.2 μm in the spectra of WC stars to amorphous carbon dust. This absorption feature is not detected in the diffuse interstellar medium toward the WR 147, Cyg OB2 No. 12, or the Pistol Star, and therefore we suggest that it is circumstellar in nature. In addition, we detect a broad absorption feature extending from approximately 6.5 to 8 μm. We tentatively attribute this absorption to the CC stretching modes that accompany the 6.2 μm band in aromatic materials. Our analysis of the 6.2 μm absorption profile suggests that the dust grains have to be rather large (~1 μm) and point toward dense clumps as the sites of dust formation. Based on observations made with the Infrared Space Observatory, an ESA project with instruments funded by ESA member states (especially the PI countries: France, Germany, the Netherlands, and the United Kingdom) and with the participation of ISAS and NASA.

  14. Modern halogen leak detectors /Review/

    NASA Astrophysics Data System (ADS)

    Evlampiev, A. I.; Karpov, V. I.; Levina, L. E.

    1981-04-01

    The halogen method is one of the basic techniques of leak detection for monitoring airtightness in such objects as refrigeration equipment and aerosol containers. Sensitivity has been improved by heated platinum emitters which stabilize background currents. Methods for protecting the region in which the gas is selected include placing the sensitive element in a new flow gauge and keeping the chamber at a certain distance from the tested surface. Chromatograph separating columns both increase sensitivity and distinguish test materials on a background of extraneous halogen-containing materials. Solid-state platinum diodes have been used as the sensitive elements of halogen leak detectors. Leak detectors based on electron-capture practically eliminate the effect of contamination of the surrounding atmosphere on leak detector sensitivity. A technique of vacuum testing is based on the high affinity of halogen-containing materials for electrons.

  15. Modern halogen leak detectors /Review/

    NASA Astrophysics Data System (ADS)

    Evlampiev, A. I.; Karpov, V. I.; Levina, L. E.

    1980-09-01

    The halogen method is one of the basic techniques of leak detection for monitoring airtightness in such objects as refrigeration equipment and aerosol containers. Sensitivity has been improved by heated platinum emitters which stabilize background currents. Methods for protecting the region in which the gas is selected include placing the sensitive element in a new flow gauge and keeping the chamber at a certain distance from the tested surface. Chromatograph separating columns both increase sensitivity and distinguish test materials on a background of extraneous halogen-containing materials. Solid-state platinum diodes have been used as the sensitive elements of halogen leak detectors. Leak detectors based on electron-capture practically eliminate the effect of contamination of the surrounding atmosphere on leak detector sensitivity. A technique of vacuum testing is based on the high affinity of halogen-containing materials for electrons.

  16. Asymmetric bifurcated halogen bonds.

    PubMed

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

    2015-03-01

    Halogen bonding (XB) is being extensively explored for its potential use in advanced materials and drug design. Despite significant progress in describing this interaction by theoretical and experimental methods, the chemical nature remains somewhat elusive, and it seems to vary with the selected system. In this work we present a detailed DFT analysis of three-center asymmetric halogen bond (XB) formed between dihalogen molecules and variously 4-substituted 1,2-dimethoxybenzene. The energy decomposition, orbital, and electron density analyses suggest that the contribution of electrostatic stabilization is comparable with that of non-electrostatic factors. Both terms increase parallel with increasing negative charge of the electron donor molecule in our model systems. Depending on the orientation of the dihalogen molecules, this bifurcated interaction may be classified as 'σ-hole - lone pair' or 'σ-hole - π' halogen bonds. Arrangement of the XB investigated here deviates significantly from a recent IUPAC definition of XB and, in analogy to the hydrogen bonding, the term bifurcated halogen bond (BXB) seems to be appropriate for this type of interaction. PMID:25656525

  17. NOVEL ‘GREENER’ ROUTES TO HALOGEN-FREE FLAME RETARDANT MATERIALS

    EPA Science Inventory

    Monomers from industrial wastes/renewable resources will be evaluated as benign starting materials. Biocatalytic routes (enzymatic and biomimetic) will be utilized for the synthesis of substituted polyphenolic FRs. The polymeric phenols will be structurally characterized and ...

  18. BIOTRANSFORMATIONS OF SELECTED ALKYLBENZENES AND HALOGENATED ALIPHATIC HYDROCARBONS IN METHANOGENIC AQUIFER MATERIAL: A MICROCOSM STUDY

    EPA Science Inventory

    Leachates from municipal landfills commonly contain a variety of organic contaminants of industrial origin. The behavior of these compounds in anaerobic, and particularly in methanogenic, subsurface materials is poorly understood. The behavior of benzene, toluene, ethylbenzene, o...

  19. 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.

  20. 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.

  1. 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.

  2. 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

    2016-06-01

    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.

  3. 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.

  4. 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.

  5. Densified Carbonaceous bodies

    SciTech Connect

    Hucke, E.E.

    1990-01-16

    This patent describes a densified carbonaceous body. It comprises: a permeable carbonaceous body, the pores of the body being filled with the pyrolyzation product of a resin obtained by polymerizing a liquid impregnant containing furfural, furfural alcohol or a mixture thereof, an acid catalyst, and a glycol of mixture of glycols.

  6. 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.

  7. 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

  8. 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.

  9. Optical properties of carbonaceous chondrites and their relationship to asteroids

    NASA Technical Reports Server (NTRS)

    Johnson, T. V.; Fanale, F. P.

    1973-01-01

    Results of diffuse reflectance measurements of nine samples of carbonaceous chondrites (one C1, three C2, four C3, and one C4) and one iron meteorite, Odessa. Measurements were also made of mineral mixtures in an attempt to understand the cause of some features of the meteorite reflectances. The C1 and C2 carbonaceous chondrites have reflectances low enough to match the anomalously low albedos of some asteroids. Some asteroids have spectral reflectances similar to carbonaceous chondrites, whereas others with flat or F-type curves appear to match simulated mineral mixtures with slightly greater amounts of the carbonaceous component than those found in the meteorites. This observation suggests either that surface physical processes such as melting may be enhancing the optical effect of opaque carbonaceous material on some asteroid surfaces and/or that these asteroids contain even more carbonaceous material than the C1 meteorites.

  10. Associations between sulfides, carbonaceous material, gold and other trace elements in polyframboids: Implications for the source of orogenic gold deposits, Otago Schist, New Zealand

    NASA Astrophysics Data System (ADS)

    Hu, Si-Yu; Evans, Katy; Fisher, Louise; Rempel, Kirsten; Craw, Dave; Evans, Noreen J.; Cumberland, Susan; Robert, Aileen; Grice, Kliti

    2016-05-01

    Intimately intergrown micron-scale framboidal pyrite, carbonaceous material (CM), chalcopyrite, sphalerite and cobaltite form polyframboids in prehnite-pumpellyite facies rocks of the Otago Schist, New Zealand. This study quantifies the metal contents of these polyframboids using synchrotron X-ray fluorescence (SXRF) and laser ablation inductively coupled plasma spectrometry (LA-ICP-MS). Trace elements Au, Zn, As, Mo, Co, Ni, Cu, Ag and Pb are significantly enriched in the polyframboids. The distribution of Zn most closely follows that of CM, and was probably absorbed into the structure of the polyframboids during biogenic processes. The concentrations of Au and Ag are positively corrected with the Zn concentration in the polyframboids (R2 of Au-Zn and Ag-Zn are 0.81 and 0.89, respectively.). The concentration of other trace elements, such as As, Co and Cu, which occur adjacent to Zn on elemental maps, show a weak relationship with Zn and may have been incorporated into the polyframboids during later processes. These polyframboids are a probable source for gold and other elements in the orogenic gold mineralization system of the Otago Schist. Metamorphic transformation of the polyframboids may have released the metallic elements into the mineralizing fluid during prograde metamorphism of the schist belt.

  11. 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. PMID:26109374

  12. Halogen bonds in biological molecules

    PubMed Central

    Auffinger, Pascal; Hays, Franklin A.; Westhof, Eric; Ho, P. Shing

    2004-01-01

    Short oxygen–halogen interactions have been known in organic chemistry since the 1950s and recently have been exploited in the design of supramolecular assemblies. The present survey of protein and nucleic acid structures reveals similar halogen bonds as potentially stabilizing inter- and intramolecular interactions that can affect ligand binding and molecular folding. A halogen bond in biomolecules can be defined as a short CX···OY interaction (CX is a carbon-bonded chlorine, bromine, or iodine, and OY is a carbonyl, hydroxyl, charged carboxylate, or phosphate group), where the X···O distance is less than or equal to the sums of the respective van der Waals radii (3.27 Å for Cl···O, 3.37Å for Br···O, and 3.50 Å for I···O) and can conform to the geometry seen in small molecules, with the CX···O angle ≈165° (consistent with a strong directional polarization of the halogen) and the X···OY angle ≈120°. Alternative geometries can be imposed by the more complex environment found in biomolecules, depending on which of the two types of donor systems are involved in the interaction: (i) the lone pair electrons of oxygen (and, to a lesser extent, nitrogen and sulfur) atoms or (ii) the delocalized π -electrons of peptide bonds or carboxylate or amide groups. Thus, the specific geometry and diversity of the interacting partners of halogen bonds offer new and versatile tools for the design of ligands as drugs and materials in nanotechnology. PMID:15557000

  13. Halogen bonds in biological molecules.

    PubMed

    Auffinger, Pascal; Hays, Franklin A; Westhof, Eric; Ho, P Shing

    2004-11-30

    Short oxygen-halogen interactions have been known in organic chemistry since the 1950s and recently have been exploited in the design of supramolecular assemblies. The present survey of protein and nucleic acid structures reveals similar halogen bonds as potentially stabilizing inter- and intramolecular interactions that can affect ligand binding and molecular folding. A halogen bond in biomolecules can be defined as a short C-X...O-Y interaction (C-X is a carbon-bonded chlorine, bromine, or iodine, and O-Y is a carbonyl, hydroxyl, charged carboxylate, or phosphate group), where the X...O distance is less than or equal to the sums of the respective van der Waals radii (3.27 A for Cl...O, 3.37 A for Br...O, and 3.50 A for I...O) and can conform to the geometry seen in small molecules, with the C-X...O angle approximately 165 degrees (consistent with a strong directional polarization of the halogen) and the X...O-Y angle approximately 120 degrees . Alternative geometries can be imposed by the more complex environment found in biomolecules, depending on which of the two types of donor systems are involved in the interaction: (i) the lone pair electrons of oxygen (and, to a lesser extent, nitrogen and sulfur) atoms or (ii) the delocalized pi -electrons of peptide bonds or carboxylate or amide groups. Thus, the specific geometry and diversity of the interacting partners of halogen bonds offer new and versatile tools for the design of ligands as drugs and materials in nanotechnology. PMID:15557000

  14. 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. PMID:25925421

  15. Metal halogen electrochemical cell

    DOEpatents

    Bellows, Richard J.; Kantner, Edward

    1988-08-23

    It has now been discovered that reduction in the coulombic efficiency of metal halogen cells can be minimized if the microporous separator employed in such cells is selected from one which is preferably wet by the aqueous electrolyte and is not wet substantially by the cathodic halogen.

  16. Compacted carbonaceous shapes and process for making the same

    SciTech Connect

    Du Broff, W.; Craig, G.H.; Veslocki, T.A.

    1983-11-01

    Compacted carbonaceous shapes are produced by mixing a particulate carbonaceous material with a binder, forming green shapes from the mixture, and heating the green shapes by induction heating or microwave heating or a combination thereof. The process is particularly adapted for making formcoke.

  17. Halogen bonding anion recognition.

    PubMed

    Brown, Asha; Beer, Paul D

    2016-07-01

    A halogen bond is an attractive non-covalent interaction between an electrophilic region in a covalently bonded halogen atom and a Lewis base. While these interactions have long been exploited as a tool in crystal engineering their powerful ability to direct supramolecular self-assembly and molecular recognition processes in solution has, until recently, been overlooked. During the last decade however an ever-increasing number of studies on solution-phase halogen-bond-mediated anion recognition processes has emerged. This Feature Article summarises advancements which have been made thus far in this rapidly developing research area. We survey the use of iodoperfluoroarene, haloimidazolium and halotriazole/triazolium halogen-bond-donor motifs in anion receptor design, before providing an account of our research into the application of mechanically interlocked rotaxane and catenane frameworks as halogen bonding anion host systems. PMID:27273600

  18. 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).

  19. Explosive Characteristics of Carbonaceous Nanoparticles

    NASA Astrophysics Data System (ADS)

    Turkevich, Leonid; Fernback, Joseph; Dastidar, Ashok

    2013-03-01

    Explosion testing has been performed on 20 codes of carbonaceous particles. These include SWCNTs (single-walled carbon nanotubes), MWCNTs (multi-walled carbon nanotubes), CNFs (carbon nanofibers), graphene, diamond, fullerene, carbon blacks and graphites. Explosion screening was performed in a 20 L explosion chamber (ASTM E1226-10 protocol), at a (dilute) concentration of 500 g/m3, using a 5 kJ ignition source. Time traces of overpressure were recorded. Samples exhibited overpressures of 5-7 bar, and deflagration index KSt = V1/3 (dp/pt)max ~ 10 - 80 bar-m/s, which places these materials in European Dust Explosion Class St-1 (similar to cotton and wood dust). There was minimal variation between these different materials. The explosive characteristics of these carbonaceous powders are uncorrelated with particle size (BET specific surface area). Additional tests were performed on selected materials to identify minimum explosive concentration [MEC]. These materials exhibit MEC ~ 101 -102 g/m3 (lower than the MEC for coals). The concentration scans confirm that the earlier screening was performed under fuel-rich conditions (i.e. the maximum over-pressure and deflagration index exceed the screening values); e.g. the true fullerene KSt ~ 200 bar-m/s, placing it borderline St-1/St-2. Work supported through the NIOSH Nanotechnology Research Center (NTRC)

  20. 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.

  1. Oxygen Isotopes in Early Solar System Materials: A Perspective Based on Microbeam Analyses of Chondrules from CV Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Jones, R. H.; Leshin, L. A.; Guan, Y.

    2004-01-01

    Some of the biggest challenges to understanding the early history of the solar system include determining the distribution of oxygen isotopes amongst materials that existed in the solar nebula, and interpreting the processes that might have resulted in the observed isotopic distributions. Oxygen isotope ratios in any individual mineral grain from a chondritic meteorite may be the cumulative product of a variety of processes, including stellar nucleosynthetic events, gas/solid interactions in the molecular cloud, mixing of independent isotopic reservoirs in the nebula, mass-independent processing in the nebula, and mass-dependent fractionation effects in various environments. It is not possible to unravel this complex isotopic record unless the distribution of oxygen isotope ratios in chondritic materials is fully understood.

  2. 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.

  3. Direct conversion of halogen-containing wastes to borosilicate glass

    SciTech Connect

    Forsberg, C.W.; Beahm, E.C.; Rudolph, J.C.

    1996-12-09

    Glass has become a preferred waste form worldwide for radioactive wastes: however, there are limitations. Halogen-containing wastes can not be converted to glass because halogens form poor-quality waste glasses. Furthermore, halides in glass melters often form second phases that create operating problems. A new waste vitrification process, the Glass Material Oxidation and dissolution System (GMODS), removes these limitations by converting halogen-containing wastes into borosilicate glass and a secondary, clean, sodium-halide stream.

  4. A single-source precursor route to anisotropic halogen-doped zinc oxide particles as a promising candidate for new transparent conducting oxide materials.

    PubMed

    Lehr, Daniela; Wagner, Markus R; Flock, Johanna; Reparaz, Julian S; Sotomayor Torres, Clivia M; Klaiber, Alexander; Dekorsy, Thomas; Polarz, Sebastian

    2015-01-01

    Numerous applications in optoelectronics require electrically conducting materials with high optical transparency over the entire visible light range. A solid solution of indium oxide and substantial amounts of tin oxide for electronic doping (ITO) is currently the most prominent example for the class of so-called TCOs (transparent conducting oxides). Due to the limited, natural occurrence of indium and its steadily increasing price, it is highly desired to identify materials alternatives containing highly abundant chemical elements. The doping of other metal oxides (e.g., zinc oxide, ZnO) is a promising approach, but two problems can be identified. Phase separation might occur at the required high concentration of the doping element, and for successful electronic modification it is mandatory that the introduced heteroelement occupies a defined position in the lattice of the host material. In the case of ZnO, most attention has been attributed so far to n-doping via substitution of Zn(2+) by other metals (e.g., Al(3+)). Here, we present first steps towards n-doped ZnO-based TCO materials via substitution in the anion lattice (O(2-) versus halogenides). A special approach is presented, using novel single-source precursors containing a potential excerpt of the target lattice 'HalZn·Zn3O3' preorganized on the molecular scale (Hal = I, Br, Cl). We report about the synthesis of the precursors, their transformation into halogene-containing ZnO materials, and finally structural, optical and electronic properties are investigated using a combination of techniques including FT-Raman, low-T photoluminescence, impedance and THz spectroscopies. PMID:26665089

  5. A single-source precursor route to anisotropic halogen-doped zinc oxide particles as a promising candidate for new transparent conducting oxide materials

    PubMed Central

    Lehr, Daniela; Wagner, Markus R; Flock, Johanna; Reparaz, Julian S; Sotomayor Torres, Clivia M; Klaiber, Alexander; Dekorsy, Thomas

    2015-01-01

    Summary Numerous applications in optoelectronics require electrically conducting materials with high optical transparency over the entire visible light range. A solid solution of indium oxide and substantial amounts of tin oxide for electronic doping (ITO) is currently the most prominent example for the class of so-called TCOs (transparent conducting oxides). Due to the limited, natural occurrence of indium and its steadily increasing price, it is highly desired to identify materials alternatives containing highly abundant chemical elements. The doping of other metal oxides (e.g., zinc oxide, ZnO) is a promising approach, but two problems can be identified. Phase separation might occur at the required high concentration of the doping element, and for successful electronic modification it is mandatory that the introduced heteroelement occupies a defined position in the lattice of the host material. In the case of ZnO, most attention has been attributed so far to n-doping via substitution of Zn2+ by other metals (e.g., Al3+). Here, we present first steps towards n-doped ZnO-based TCO materials via substitution in the anion lattice (O2− versus halogenides). A special approach is presented, using novel single-source precursors containing a potential excerpt of the target lattice 'HalZn·Zn3O3' preorganized on the molecular scale (Hal = I, Br, Cl). We report about the synthesis of the precursors, their transformation into halogene-containing ZnO materials, and finally structural, optical and electronic properties are investigated using a combination of techniques including FT-Raman, low-T photoluminescence, impedance and THz spectroscopies. PMID:26665089

  6. 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.

  7. 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. PMID:12694416

  8. Study of the effect of tribo-materials and surface finish on the lubricant performance of new halogen-free room temperature ionic liquids

    NASA Astrophysics Data System (ADS)

    Saurín, N.; Minami, I.; Sanes, J.; Bermúdez, M. D.

    2016-03-01

    The present work evaluates different materials and surface finish in the presence of newly designed, hydrophobic halogen-free room temperature ionic liquids (RTILs) as lubricants. A reciprocating tribo-tester was employed with steel-ceramic and steel-thermosetting epoxy resin contacts under boundary lubrication conditions. Four different tetraalkylphosphonium organosilanesulfonate RTILs provided excellent lubricating performance, with friction coefficients as low as 0.057, and non-measurable wear for the higher roughness machine-finish stainless steel flat against sapphire balls, in the case of the lubricants containing the 2-trimethylsilylethanesulfonate anion. Higher friction coefficients of the order of 0.1 and wear volumes of the order of 10-4 mm3 were observed for the lower roughness fine-finished flat stainless steel surface. All RTILs prevent wear of epoxy resin against stainless steel balls, with friction coefficients in the range of 0.03-0.06. EDX analysis shows the presence of RTILs on the stainless steel surfaces after the tribological tests. Under the experimental conditions, no corrosive processes were observed.

  9. 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.

  10. Solar gasification of carbonaceous materials

    NASA Astrophysics Data System (ADS)

    Taylor, R. W.; Berjoan, R.; Coutures, J. P.

    1980-04-01

    Charcoal, wood, and paper were gasified in a packed bed reactor using steam and solar energy. The steam was generated by spraying water directly onto the surface of the fuel and, at the same time, heating the fuel at the focus of a solar furnace. The steam was generated by solar energy. Half of the steam reacted with carbon, and 30% of the incident solar energy was stored as chemical energy. The performance of a fluidized bed reactor was compared to that of a packed bed reactor using charcoal and CO2. The fraction of the incident solar energy utilized to produce CO (stored) was 10% in the case of the fluidized bed reactor and 40% for the packed bed reactor.

  11. Solar gasification of carbonaceous materials

    NASA Astrophysics Data System (ADS)

    Taylor, R. W.; Berjoan, R.; Coutures, J. P.

    1983-01-01

    Charcoal, wood and paper have ben gasified in a packed-bed reactor using steam and solar energy. The steam was generated by spraying water directly on to the surface of the fuel and, at the same time, heating the fuel at the focus of a solar furnace. Half of the steam reacted with carbon and 30 pct of the incident solar energy was stored as chemical enthalpy. The performance of a fluidized-bed reactor was compared to that of a packed-bed reactor using charcoal and CO2. The fraction of the incident solar energy utilized to produce CO (stored) was 10 pct in the case of the fluidized-bed reactor and 40 pct for the packed-bed reactor. The fuel value of the gas produced from the steam-gasification of wood and paper was 65 kcal/mole (320 Btu/lb). On an ash free basis the volume yield of the gas was within 0.1 of 1 cu m/kq.

  12. 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.

  13. 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.

  14. 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

  15. 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

  16. 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.

  17. 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.

  18. Biogeochemistry of Halogenated Hydrocarbons

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

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

  19. 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

  20. 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.

  1. Raman spectral analysis of carbonaceous material to detect shear heating on a large fault—example from the Median Tectonic Line, Southwest Japan

    NASA Astrophysics Data System (ADS)

    Mori, H.; Wallis, S.; Fujimoto, K.; Shigematsu, N.

    2010-12-01

    . Pelitic rock is the main rock facies of the Sanbagawa belt in the study area. This pelite was metamorphosed at temperatures <400oC and minerals suitable for typical Fe++-Mg exchange thermometers are poorly developed. As an alternative way of estimating peak temperature, we used Raman spectral analysis of carbonaceous material. Results show a consistent regional temperature of 343oC-350oC at distances between 400m and 4km from the MTL. There is a significant rise within 200m from the MTL to temperatures of 366oC-389oC. These results show no evidence for a heat-anomaly on km-scales to the south of the MTL, but do show a clear temperature increase near the MTL. The spatial association of the heat-anomaly with the fault suggests it is the result of shear heating, but the heat-anomaly is only observed in a narrow zone close to the MTL. More detailed modeling of the heat generated in the fault and its transport will require more continuous data from close to the MTL.

  2. Effect of carbonaceous particles on slag foaming

    NASA Astrophysics Data System (ADS)

    Zhang, Y.; Fruehan, R. J.

    1995-08-01

    Use of carbonaceous particles such as coke or coal char in controlling slag foaming is of great practical significance for bath-smelting and other steelmaking processes. The foamability of the liquid slag in terms of the foam index has been determined with the presence of different amounts of coke and coal char particles. Different sized and shaped particles were used in the experiments. It was found that the foam index decreased significantly as the ratio of the total cross-sectional area of the particles to the liquid slag surface area increased. When the foam was generated by argon gas injection through an alumina nozzle (i.d. = 1.5 mm), a liquid slag, CaO-SiO2-CaF2-(Al2O3), depending on the alumina content, could have an initial foam index of about 2 to 4 seconds at 1500 °C without any carbonaceous particles. When the slag surface was covered only 15 ~20 pct with either coke or coal char particles, the foam was totally suppressed regardless of the initial foam index. In order to understand the mechanism of the antifoam effect of the carbonaceous particles, interactions of a coke sphere, an iron ore pellet, an alumina tube, and a coal char particle with the liquid slag foam were examined by X-ray observation. It was concluded that the antifoam effect of coke or coal char particles is primarily contributed by the nonwetting nature of the carbonaceous materials with the liquid slag. Possible mechanisms of carbonaceous particles rupturing a slag film could be (1) the rapid thinning of the liquid slag film driven by a difference between the instantaneous contact angle and the equilibrium contact angle or (2) the “dewetting” of the liquid slag from the interface when the film is “bridged” by the particle.

  3. 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.

  4. 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.

  5. Halogens in CM Chondrites

    NASA Astrophysics Data System (ADS)

    Menard, J. M.; Caron, B.; Jambon, A.; Michel, A.; Villemant, B.

    2013-09-01

    We set up an extraction line of halogens (fluorine, chlorine) by pyrohydrolysis with 50 mg of rock. We analyzed 7 CM2 chondrites found in Antarctica and found that the Cl content of meteorites with an intact fusion crust is higher than those without.

  6. Type II halogen···halogen contacts are halogen bonds.

    PubMed

    Metrangolo, Pierangelo; Resnati, Giuseppe

    2014-01-01

    Cl/Br/I alternative substitutions in a series of dihalophenols indicate that type I and type II halogen···halogen contacts have different chemical nature. Only the latter ones qualify as true halogen bonds, according to the recent IUPAC definition. PMID:25075314

  7. Are carbonaceous chondrites primitive or processed - A review

    NASA Technical Reports Server (NTRS)

    Mcsween, H. Y., Jr.

    1979-01-01

    According to the results of the present analysis, carbonaceous chondrites are obviously not pristine samples of proto-solar-system condensates. In terms of chemistry, however, these chondrites may represent the most primitive solar system materials known. It appears that the alterations experienced by carbonaceous chondrites were isochemical, or nearly so, so that their bulk compositions have remained practically unchanged, provided that the analyses are representative of large portions of the meteorites.

  8. Biological dehalogenation and halogenation reactions.

    PubMed

    van Pée, Karl Heinz; Unversucht, Susanne

    2003-07-01

    A large number of halogenated compounds is produced by chemical synthesis. Some of these compounds are very toxic and cause enormous problems to human health and to the environment. Investigations on the degradation of halocompounds by microorganisms have led to the detection of various dehalogenating enzymes catalyzing the removal of halogen atoms under aerobic and anaerobic conditions involving different mechanisms. On the other hand, more than 3500 halocompounds are known to be produced biologically, some of them in great amounts. Until 1997, only haloperoxidases were thought to be responsible for incorporation of halogen atoms into organic compounds. However, recent investigations into the biosynthesis of halogenated metabolites by bacteria have shown that a novel type of halogenating enzymes, FADH(2)-dependent halogenases, are involved in biosyntheses of halogenated metabolites. In every gene cluster coding for the biosynthesis of a halogenated metabolite, isolated so far, one or several genes for FADH(2)-dependent halogenases have been identified. PMID:12738254

  9. 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. PMID:27131113

  10. 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

  11. 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.

  12. 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.

  13. Carbonaceous Survivability on Impact

    NASA Technical Reports Server (NTRS)

    Bunch, T. E.; Becker, Luann; Morrison, David (Technical Monitor)

    1994-01-01

    In order to gain knowledge about the potential contributions of comets and cosmic dust to the origin of life on Earth, we need to explore the survivability of their potential organic compounds on impact and the formation of secondary products that may have arisen from the chaotic events sustained by the carriers as they fell to Earth. We have performed a series of hypervelocity impact experiments using carbon-bearing impactors (diamond, graphite, kerogens, PAH crystals, and Murchison and Nogoya meteorites) into Al plate targets at velocities - 6 km/s. Estimated peak shock pressures probably did not exceed 120 GPa and peak shock temperatures were probably less than 4000 K for times of nano- to microsecs. Nominal crater dia. are less than one mm. The most significant results of these experiments are the preservation of the higher mass PAHs (e. g., pyrene relative to napthalene) and the formation of additional alkylated PAHs. We have also examined the residues of polystyrene projectiles impacted by a microparticle accelerator into targets at velocities up to 15 km/s. This talk will discuss the results of these experiments and their implications with respect to the survival of carbonaceous deliverables to early Earth. The prospects of survivability of organic molecules on "intact" capture of cosmic dust in space via soft: and hard cosmic dust collectors will also be discussed.

  14. 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.

  15. Intracellular organic matter from cyanobacteria as a precursor for carbonaceous and nitrogenous disinfection byproducts.

    PubMed

    Wert, Eric C; Rosario-Ortiz, Fernando L

    2013-06-18

    The formation of total organic halogen (TOX), carbonaceous disinfection byproducts (DBPs) (trihalomethanes (THMs) and haloacetic acids (HAAs)), and nitrogenous DBPs (trichloronitromethane (TCNM) or chloropicrin, haloacetonitriles (HANs), and nitrosamines) was examined during the chlorination or chloramination of intracellular organic matter (IOM) extracted from Microcystis aeruginosa, Oscillatoria sp. (OSC), and Lyngbya sp. (LYN). The percentage of unknown TOX (22-38%) during chlorination indicated that the majority of DBPs were identified among THMs, HAAs, TCNM, and HANs. Bromide was readily incorporated into DBPs with speciation shifting slightly from dihalogenated species to trihalogenated species. During formation potential testing with chloramines, nitrosamine yields from IOM were measured for N-nitrosodimethylamine (NDMA, 10-52 ng/mgC), N-nitrosopyrrolidine (NPYR, 14 ng/mgC), N-nitrosopiperidine (NPIP, 3.7-5.5 ng/mgC), and N-nitrosomethylethylamine (NMEA, 2.1-2.6 ng/mgC). When IOM was added to a natural water matrix, the nitrosamine yields were not realized likely due to competition from natural organic matter. Ozonation increased NDMA and NMEA formation and reduced NPYR and NPIP formation during subsequent chloramination. In addition, ozone oxidation of IOM formed detectable concentrations of aldehydes, which may contribute to DBP formation. Finally, bioluminescence-based test results showed that >99% of the IOM extracted from OSC and LYN was biodegradable. Therefore, a biological treatment process could minimize this source of DBP precursor material during drinking water treatment. PMID:23675656

  16. 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.

  17. Characterization of carbonaceous materials in PM2.5 and PM10 size fractions in Morogoro, Tanzania, during 2006 wet season campaign

    NASA Astrophysics Data System (ADS)

    Mkoma, Stelyus L.; Chi, Xuguang; Maenhaut, Willy

    2010-05-01

    Atmospheric aerosol samples in PM10 and PM2.5 size fractions were collected in parallel at a rural site in Morogoro during wet season in March and April 2006. All samples were analysed for the particulate matter mass, for organic, elemental, and total carbon (OC, EC, and TC), and for water-soluble OC (WSOC). The average PM10 and PM2.5 mass concentrations and associated standard deviations were 14 ± 13 μg/m 3 and 7.3 ± 4 μg/m 3 respectively. On average, TC accounted for 33% of the PM10 mass and 44% of the PM2.5 mass for the campaign. The average OC/PM percentage ratios were 27% and 33% in PM10 and PM2.5 size fractions respectively and a larger fraction of the OC was water-soluble. The observed low EC/TC mean percentage ratios of 10-14% respectively for PM10 and PM2.5 fractions indicate that the carbonaceous aerosol originates mainly from biogenic aerosols and/or biomass burning. A simple source apportionment approach was used to apportion the OC to biofuel and charcoal burning. On average, 93% of the PM10 OC was attributed to biofuel and 7% to charcoal burning in the 2006 wet season campaign. However, it is suggested that a contribution to the OC at Morogoro could also come from other natural biogenic matter, and/or biomass burning aerosols. The results for the sources of OC at Morogoro should therefore be considered with great caution.

  18. 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.

  19. 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.

  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. Nucleosynthetic strontium isotope anomalies in carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Yokoyama, Tetsuya; Fukami, Yusuke; Okui, Wataru; Ito, Nobuaki; Yamazaki, Hiroshi

    2015-04-01

    Precise Sr isotopic compositions in samples from sequential acid leaching experiments have been determined for three carbonaceous chondrites, Allende, Murchison, and Tagish Lake, together with those in the bulk aliquots of these meteorites. The chondritic acid leachates and residues were characterized by Sr isotope anomalies with variable μ84Sr values (106 relative deviation from a standard material) ranging from +120 to - 4700 ppm, documenting multiple nucleosynthetic sources within a single meteorite. In addition, the μ84Sr patterns across leaching samples for individual chondrites differed from one another. The highest μ84Sr values were observed for leaching Step 3 (HCl+H2O, 75 °C) for Allende and Murchison likely because of the incorporation of calcium and aluminum-rich inclusions (CAIs). In contrast, extremely low μ84Sr values were observed in the later fractions (Steps 6 and 7) for Murchison and Tagish Lake, suggesting the existence of s-process-enriched presolar SiC grains derived from AGB stars. A μ84Sr-ɛ54Cr diagram was prepared with the CAIs and bulk aliquots of carbonaceous chondrites and other meteorites (noncarbonaceous) that were plotted separately; however, they still formed a global positive correlation. CAIs presented the highest μ84Sr and ɛ54Cr values, whereas carbonaceous chondrites and noncarbonaceous meteorites had intermediate and the lowest μ84Sr and ɛ54Cr values, respectively. The positive trend was interpreted as resulting from global thermal processing in which sublimation of high μ84Sr and ɛ54Cr carriers generated the excess μ84Sr and ɛ54Cr signatures in CAIs, while noncarbonaceous planetesimals accreted from materials that underwent significant thermal processing and thus had relatively low μ84Sr and ɛ54Cr values. Apart from the global trend, the carbonaceous chondrites and noncarbonaceous meteorites both exhibited intrinsic variations that highlight an isotopic dichotomy similar to that observed in other isotope

  2. Carbonaceous chondrite clasts in the howardites Bholghati and EET87513

    NASA Technical Reports Server (NTRS)

    Buchanan, P. C.; Zolensky, M. E.; Reid, A. M.

    1993-01-01

    Twenty-two carbonaceous chondrite clasts from the two howardites Bholghati and EET87513 were analyzed. Clast N from EET87513 is a fragment classified as CM2 material on the basis of texture, bulk composition, mineralogy, and bulk O isotopic composition. Carbonaceous chondrite clasts from Bholghati, for which less data are available because of their small size, can be divided into two petrologic types: C1 and C2. C1 clasts are composed of opaque matrix with rare coarse-grained silicates as individual mineral fragments; textures resemble CI meteorites and some dark inclusions from CR meteorites. Opaque matrix is predominantly composed of flaky saponite; unlike typical CI and CR meteorites, serpentine is absent in the samples we analyzed. C2 clasts contain chondrules, aggregates, and individual fragments of coarse-grained silicates in an opaque matrix principally composed of saponite and anhydrous ferromagnesian silicates with flaky textures similar to phyllosilicates. These anhydrous ferromagnesian silicates are interpreted as the product of heating of pre-existing serpentine. The carbonaceous chondrite clasts we have studied from these two howardites are, with one notable exception (clast N from EET87513), mineralogically distinct from typical carbonaceous chondrites. However, these clasts have very close affinities to carbonaceous chondrites and have also experienced thermal metamorphism and aqueous alteration, but to different degrees.

  3. Structures and electronic states of halogen-terminated graphene nano-flakes

    NASA Astrophysics Data System (ADS)

    Tachikawa, Hiroto; Iyama, Tetsuji

    2015-12-01

    Halogen-functionalized graphenes are utilized as electronic devices and energy materials. In the present paper, the effects of halogen-termination of graphene edge on the structures and electronic states of graphene flakes have been investigated by means of density functional theory (DFT) method. It was found that the ionization potential (Ip) and electron affinity of graphene (EA) are blue-shifted by the halogen termination, while the excitation energy is red-shifted. The drastic change showed a possibility as electronic devices such as field-effect transistors. The change of electronic states caused by the halogen termination of graphene edge was discussed on the basis of the theoretical results.

  4. Radical and Atom Transfer Halogenation (RATH): A Facile Route for Chemical and Polymer Functionalization.

    PubMed

    Han, Yi-Jen; Lin, Chia-Yu; Liang, Mong; Liu, Ying-Ling

    2016-05-01

    This work demonstrates a new halogenation reaction through sequential radical and halogen transfer reactions, named as "radical and atom transfer halogenation" (RATH). Both benzoxazine compounds and poly(2,6-dimethyl-1,4-phenylene oxide) have been demonstrated as active species for RATH. Consequently, the halogenated compound becomes an active initiator of atom transfer radical polymerization. Combination of RATH and sequential ATRP provides an convenient and effective approach to prepare reactive and crosslinkable polymers. The RATH reaction opens a new window both to chemical synthesis and molecular design and preparation of polymeric materials. PMID:27027639

  5. Fluid Inclusions in Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Saylor, J.; Zolensky, M. E.; Bodnar, R. J.; Le L.; Schwandt, C.

    2001-01-01

    Fluid inclusions are present in carbonaceous chondrites. Of the chondrites studied (CI1, CM1 and 2, CV3) fluid inclusions were found only in CM2s and CI1s, and by extrapolation are most likely to be found there in the future. Additional information is contained in the original extended abstract.

  6. 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.

  7. 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.

  8. 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. PMID:23808482

  9. Evidence for Interfacial Halogen Bonding.

    PubMed

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

    2016-05-10

    A homologous series of donor-π-acceptor dyes was synthesized, differing only in the identity of the halogen substituents about the triphenylamine (TPA; donor) portion of each molecule. Each Dye-X (X=F, Cl, Br, and I) was immobilized on a TiO2 surface to investigate how the halogen substituents affect the reaction between the light-induced charge-separated state, TiO2 (e(-) )/Dye-X(+) , with iodide in solution. Transient absorption spectroscopy showed progressively faster reactivity towards nucleophilic iodide with more polarizable halogen substituents: Dye-F < Dye-Cl < Dye-Br < Dye-I. Given that all other structural and electronic properties for the series are held at parity, with the exception of an increasingly larger electropositive σ-hole on the heavier halogens, the differences in dye regeneration kinetics for Dye-Cl, Dye-Br, and Dye-I are ascribed to the extent of halogen bonding with the nucleophilic solution species. PMID:27060916

  10. Manganese chromium isotope systematics of carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Shukolyukov, A.; Lugmair, G. W.

    2006-10-01

    In this article we present the results of Cr isotope investigations of different types of carbonaceous chondrites and of the pallasite Eagle Station. The 53Cr/ 52Cr ratios in the bulk samples of carbonaceous chondrites are correlated with 55Mn/ 52Cr ratios. The slope of the correlation line yields a 53Mn/ 55Mn ratio of (8.5 ± 1.5) × 10 - 6 at the time of Mn/Cr fractionation. Mapping this ratio onto an absolute time scale yields a time for this event of 4568.1 + 0.8/- 1.1 Ma ago. This time is very similar to the formation age of Efremovka CAIs of 4567.2 ± 0.6 Ma [Y. Amelin, A. N. Krot, I. D. Hutcheon, A. A. Ulyanov, Lead isotopic ages of chondrules and calcium-aluminum-rich inclusions, Science 297 (2002) 1678-1683], to a time of the chondrule formation of 4568 ± 1 Ma ago [L.E. Nyquist, D. Lindstrom, D. Mittlefehldt, C.-Y. Shih, H. Wiesmann, S. Wentworth, R. Martinez, Manganese-chromium formation intervals for chondrules from the Bishunpur and Chainpur meteorites, Meteorit. Planet. Sci. 36 (2001) 911-938], which, most likely, constrains early global high-temperature Mn/Cr fractionation in a nebular setting. The bulk samples of carbonaceous chondrites exhibit clear 54Cr excesses ( 54Cr *) that are correlated with the 53Cr excesses ( 53Cr *) and also with Mn/Cr ratios. One possible explanation of this correlation is that 54Cr * is also radiogenic, like 53Cr *, and was formed by the decay of the short-lived parent radionuclide 54Mn. The very short half-life of 54Mn of 312 days would require that both short-lived radionuclides 53Mn and 54Mn were generated locally in spallation reactions during the early period of an active sun. The alternative and possibly more plausible explanation is the heterogeneous addition of presolar material. The presolar component, enriched in 54Cr, is mostly contained in the matrix of carbonaceous chondrites. The relative amount of matrix decreases in the sequence CI > CM > CO,CV. A large proportion of Mn is associated with the matrix while

  11. 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.

  12. 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.

  13. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... is subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the... 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...

  14. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... is subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the... 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...

  15. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... is subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the... 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...

  16. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... is subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the... 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...

  17. 40 CFR 63.994 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... is subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the... 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...

  18. 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

  19. 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

  20. 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. PMID:26676958

  1. Role of oil derived carbonaceous phase in the performance of sewage sludge-based materials as media for desulfurizaton of digester gas

    NASA Astrophysics Data System (ADS)

    Kante, Karifala; Qiu, Jieshan; Zhao, Zongbin; Chang, Yu; Bandosz, Teresa J.

    2008-02-01

    Desulfurization adsorbents for purification of digester gas were prepared by pyrolysis of sewage sludge impregnated with spent mineral oil. To evaluate the changes in the structural and chemical properties the pyrolysis time and temperature varied. The materials were characterized using adsorption of nitrogen, FTIR, XRD, ICP, SEM and thermal analysis. Their catalytic activity was tested in the removal of hydrogen sulfide from simulated mixture of digester gas. The results indicated the importance of new carbon phase from the oil precursor. It provided mesoporosity, which increased the dispersion of catalytic phase and space for storage of surface reaction products. The results indicated that the adsorbents obtained at 950 °C are much more active in the process of hydrogen sulfide oxidation than those obtained at 650 °C. Moreover, longer heat treatment is also beneficial for the development of surface catalytic properties. Extensive pyrolysis stabilizes carbon phase via increasing its degree of aromatization and provides activation agents for this phase coming from decomposition and rearrangement of inorganic phase.

  2. 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.

  3. 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

  4. 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.

  5. Hydrocarbon components in carbonaceous meteorites

    NASA Astrophysics Data System (ADS)

    Kissin, Y. V.

    2003-05-01

    Currently, the presence of free n-alkanes and isoprenoid alkanes in carbonaceous meteorites is usually explained either by microbial contamination during the period between the meteorite fall and collection or by contamination from the environment of analytical laboratories and museums. The goal of this research was to repeat analysis of hydrocarbon components in meteorites and to investigate possible meteorite contamination routes discussed in the literature. Experimental analysis of free organic constituents in five carbonaceous meteorites by infrared spectroscopy (IR) and gas chromatographic (GC) methods confirmed the presence of extractable aliphatic components, n-alkanes in the C 15H 32-C 27H 56 range and isoprenoid alkanes (phytane, pristane, and norpristane), in some of these meteorites. The contents of these compounds vary depending on the source. Insoluble organic components of two meteorites (meteorite kerogens) were isolated, and their composition was analyzed by IR and cracking/GC methods. Comparison with the data on several terrestrial contamination sources proposed in the literature shows that the presence of free saturated hydrocarbons in meteorites and the composition of the meteorite kerogen could not be explained either by microbial contamination or by contamination from the laboratory environment. The types of the hydrocarbons in meteorites resemble those typical of ancient terrestrial deposits of organic-rich sediments, except for the absence of lighter hydrocarbons, which apparently slowly evaporated in space, and multi-ring naphthenic compounds of the biologic origin, steranes, terpanes, etc. The prevailing current explanation for the presence of free linear saturated hydrocarbons in carbonaceous meteorites, apart from contamination, is the abiotic route from hydrogen and carbon monoxide. However, the data on the structure of meteorite kerogens require a search for different routes that initially produce complex polymeric structures containing

  6. ATMOSPHERIC FREONS AND HALOGENATED COMPOUNDS

    EPA Science Inventory

    Ambient levels of atmospheric Freons, halogenated hydrocarbons, and SF6 were measured at various locations in the U.S.A. Compounds such as CCl3F, CCl2F2, CH3-CCl3, and CCl4 were ubiquitious and generally measured at sub ppb levels. Tropospherically reactive compounds such as C2Cl...

  7. 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.

  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. Phase transition method to form Group 6A nanoparticles on carbonaceous templates.

    PubMed

    Youn, Hee-Chang; Jegal, Jong-Pil; Park, Sang-Hoon; Kim, Hyun-Kyung; Park, Ho Seok; Roh, Kwang Chul; Kim, Kwang-Bum

    2014-03-25

    Considerable effort has been made to develop unique methods of preparing and characterizing nanoparticles and nanocomposites in order to exploit the true potential of nanotechnology. We used a facile, versatile phase-transition method for forming Group 6A nanoparticles on carbonaceous templates to produce homogeneous 5-10 nm diameter Group 6A nanoparticles on carbon nanotubes (CNTs) and reduced graphene oxide (RGO), to obtain nanocomposites. The method involved melting and recrystallizing mixtures of elemental sulfur and either CNTs or RGO on carbonaceous templates. The surface tension and hydrophilicity of the molten Group 6A species surfaces and the oxygen functional groups on the carbonaceous template surfaces were considered in depth to provide important guidelines for forming Group 6A nanoparticles on carbonaceous templates. The surface tension of the molten Group 6A species should be intrinsically low, leading to effective wetting on the carbonaceous template. In addition, the molten Group 6A species hydrophilic surfaces were essential for enabling hydrophilic-hydrophilic interaction for selective wetting at the oxygen functional groups on the carbonaceous template, leading to the heterogeneous nucleation of nanoparticles. Furthermore, the size and morphology (isolated vs layer-like) of the Group 6A nanoparticles were tuned by adjusting the oxidation state of the carbonaceous template. We investigated the potential application of the nanocomposites prepared using this method to cathode materials in lithium-sulfur secondary batteries. PMID:24499384

  10. Investigations into the Nature of Halogen Bonding Including Symmetry Adapted Perturbation Theory Analyses

    SciTech Connect

    Riley, Kevin E.; Hobza, Pavel

    2008-01-12

    In recent years it has been recognized that, because of their unique properties, halogen bonds have tremendous potential in the development of new pharmaceutical compounds and materials. In this study we investigate the phenomenon of halogen bonding by carrying out ab initio calculations on the halomethane-formaldehyde complexes as well as the fluorine substituted FnH₃-nCX---OCH₂ dimers, where the halogen bonding halogens (X) are chlorine, bromine, and iodine. Coupled cluster (CCSD(T)/aug-cc-pVTZ) calculations indicate that the binding energies for these type of interactions lie in the range between -1.05 kcal/mol (H₃CCl---OCH₂) and -3.72 kcal/mol (F₃CI---OCH₂). One of the most important findings in this study is that, according to symmetry adapted perturbation theory (SAPT) analyses, halogen bonds are largely dependent on both electrostatic and dispersion type interactions. As the halogen atom involved in halogen bonding becomes larger the interaction strength for this type of interaction also gets larger and, interestingly, more electrostatic (and less dispersive) in character. Halogen bonding interactions also become stronger and more electrostatic upon substitution of (the very electronegative) fluorines onto the halomethane molecule.

  11. Relative self-heating tendencies of coal, carbonaceous shales, and coal refuse. Report of investigations/1995

    SciTech Connect

    Kim, A.G.

    1995-06-01

    Studies on the initiation and propagation of mine fires have dealt almost exclusively with coal. It has been assumed that the self-heating potential of carbonaceous shales and coal wastes is relatively low. However, in abandoned coal mines and waste banks, initiation and propagation of fires may be strongly dependent on the self-heating tendency of these materials. The purpose of the study was to compare the self-heating probability of carbonaceous shales and coal wastes to that of coals.

  12. Evolution of carbonaceous chondrite parent bodies: Insights into cometary nuclei

    NASA Technical Reports Server (NTRS)

    Mcsween, Harry Y., Jr.

    1989-01-01

    It is thought that cometary samples will comprise the most primitive materials that are able to be sampled. Although parent body alteration of such samples would not necessarily detract from scientists' interest in them, the possibility exists that modification processes may have affected cometary nuclei. Inferences about the kinds of modifications that might be encountered can be drawn from data on the evolution of carbonaceous chondrite parent bodies. Observations suggest that, of all the classes of chondrites, these meteorites are most applicable to the study of comets. If the proportion of possible internal heat sources such as Al-26 in cometary materials are similar to those in chondrites, and if the time scale of comet accretion was fast enough to permit incorporation of live radionuclides, comets might have had early thermal histories somewhat like those of carbonaceous chondrite parent bodies.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. Carbonaceous materials in soil-derived dusts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Wind erosion affects over 500 million ha of land worldwide and creates between 500 and 5000 Tg of fugitive dust annually. This dust carries a disproportionate amount of organic and inorganic carbon when compared to the soil of origin. This loss of soil carbon degrades the soil of origin and may re...

  18. Apparatus for the combustion of carbonaceous material

    SciTech Connect

    Astrom, I.

    1985-10-15

    A reaction chamber with a fluidized bed encloses two superposed cyclone separators connected in series. In order to prevent combustion gases from entering the lowermost separator by way of its particulate matter outlet, this is formed as a downwardly extended pipe, which is enclosed by a sleeve through which secondary air passes. The sleeve projects somewhat below the mouth of the pipe, and the issuing air causes an ejector action, which prevents gas from entering the pipe. The particulate matter return flow pipe from the upper cyclone is also extended downwards and terminates within the ejector.

  19. On The Nature of the Halogen Bond.

    PubMed

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

    2014-09-01

    The wide-ranging applications of the halogen bond (X-bond), notably in self-assembling materials and medicinal chemistry, have placed this weak intermolecular interaction in a center of great deal of attention. There is a need to elucidate the physical nature of the halogen bond for better understanding of its similarity and differences vis-à-vis other weak intermolecular interactions, for example, hydrogen bond, as well as for developing improved force-fields to simulate nano- and biomaterials involving X-bonds. This understanding is the focus of the present study that combines the insights of a bottom-up approach based on ab initio valence bond (VB) theory and the block-localized wave function (BLW) theory that uses monomers to reconstruct the wave function of a complex. To this end and with an aim of unification, we studied the nature of X-bonds in 55 complexes using the combination of VB and BLW theories. Our conclusion is clear-cut; most of the X-bonds are held by charge transfer interactions (i.e., intermolecular hyperconjugation) as envisioned more than 60 years ago by Mulliken. This is consistent with the experimental and computational findings that X-bonds are more directional than H-bonds. Furthermore, the good linear correlation between charge transfer energies and total interaction energies partially accounts for the success of simple force fields in the simulation of large systems involving X-bonds. PMID:26588518

  20. 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.

  1. Design of new carbonaceous catalysts and photocatalysts for organic synthesis

    NASA Astrophysics Data System (ADS)

    Rajpara, Vikul B.

    Pristine and modified carbonaceous materials are introduced as convenient catalysts for oxidation, photooxidation and alkylation of aromatic hydrocarbons. Oxidation reactions have been carried out by air and effect of cyclohexene and light has also been investigated. Availability of the reagents, light source (ambient light), minimum chemical waste, low toxicity and reusability of the catalysts make developed processes green alternatives of traditional methods for the synthesis of industrially important organic compounds. Catalytic performance and selectivity of carbonaceous materials have been linked to their morphology (graphite, carbon black, multi-walled, single-walled carbon nanotubes, fullerene C60) and modification oxidation, conjugation with nanoparticles). The reported study is the first step toward targeted design of new carbonaceous catalysts for organic synthesis. Graphite is known for its electric conductivity and quantum dots are known for transfer of energy to attached molecules and their conjugation may provide a unique hybrid material for photocatalysis of organic reactions. Quantum dots with known number of functional group hold an especially great promise in the field of catalysis. However, controlling the number of functionalities on the surface of quantum dots is very challenging. We demonstrated monofuncationalization of gold nanoparticles using trityl (solid) support. Similar approach was used for the monofunctionalization of quantum dots and our preliminary data showed that quantum dots can be attached and detached from the solid support under mild conditions.

  2. Analysis of laser extracted volatiles in carbonaceous chondrites

    NASA Technical Reports Server (NTRS)

    Blanford, George E.

    1987-01-01

    It is scientifically important to understand the composition of volatile compounds from interplanetary dust particles (IDPs) because they may be related to the primordial inventory of planetary materials which were necessary to provide environments conducive to the formation of life. The use of a laser microprobe to measure volatiles in IDPs was evaluated. Because primitive meteorites are thought to be closely related to IDPs, carbonaceous chondrites were used for the evaluation. Three sets of experiments were performed to determine the volatiles released from potential substrate materials, to analyze the volatiles released from matrices of bulk samples of carbonaceous chondrites, and to analyze volatiles released from approx. 100 to 200 micron meteorite particles to simulate IDPs. Aluminum appeared to be the best choice of substrate material. Mass ratios between carbonaceous chondrite matrices of Allende and Murchison show fair reproducibility with somewhat high uncertainties. Particles from the Orgueil, Murchison, and Allende meteorites produced measurable quantities of volatiles that appear to have mass spectra comparable to the bulk matrices.

  3. 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

  4. 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.

  5. 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.

  6. 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)

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

    PubMed

    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). PMID:25296829

  8. 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).

  9. Carbonaceous chondrite clasts in the Kapoeta howardite

    NASA Technical Reports Server (NTRS)

    Brearley, Adrian J.; Papike, J. J.

    1993-01-01

    A petrographic and mineralogical study of a number of carbonaceous chondrite clasts in the Kapoeta howardite has been carried out. Most of the clasts have mineralogical and chemical properties which link them to the CM carbonaceous chondrites. Some clasts contain chondrules which often have well-developed fine-grained rims, but many have been extensively brecciated. PCP-rich objects are common and pentlandite and pyrrhotite also occur. Calcite has also been found. The remainder of the clasts are extremely fine-grained and appear to be closely related to CI carbonaceous chondrites. In these clasts magnetite framboids are common and finegrained sulfides and magnetite occur disseminated throughout the matrix.

  10. 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

  11. A Pronounced Halogen Effect on the Organogelation Properties of Peripherally Halogen Functionalized Poly(benzyl ether) Dendrons.

    PubMed

    Feng, Yu; Chen, Hui; Liu, Zhi-Xiong; He, Yan-Mei; Fan, Qing-Hua

    2016-03-24

    An interesting halogen-substituent effect on the organogelation properties of poly(benzyl ether) dendrons is reported. A new class of poly(benzyl ether) dendrons with halo substituents decorating their periphery was synthesized and fully characterized. A systematic study on the gelation abilities, thermotropic behaviors, aggregated microstructures, and mechanical properties of self-assembled organogels was performed to elucidate the halogen-substituent effects on their organogelation propensity. It was found that the exact halogen substitutions on the periphery of dendrons exert a profound effect on the organogelation propensity, and dendrons Gn -Cl (n=2, 3) and G2 -I proved to be highly efficient organogelators. The cooperation of multiple π-π, dispersive halogen, CH-π, and weak C-H⋅⋅⋅X hydrogen-bonding interactions were found to be the key contributor to forming the self-assembled gels. Dendritic organogels formed from Gn -Cl (n=2, 3) in 1,2-dichloroethane exhibited thixotropic-responsive properties, and such thixotropic organogels are promising materials for future research and applications. PMID:26916094

  12. How Do Distance and Solvent Affect Halogen Bonding Involving Negatively Charged Donors?

    PubMed

    Chen, Zhaoqiang; Wang, Guimin; Xu, Zhijian; Wang, Jinan; Yu, Yuqi; Cai, Tingting; Shao, Qiang; Shi, Jiye; Zhu, Weiliang

    2016-09-01

    It was reported that negatively charged donors can form halogen bonding, which is stable, especially, in a polar environment. On the basis of a survey of the Protein Data Bank, we noticed that the distance between the negative charge center and the halogen atom of an organohalogen may vary greatly. Therefore, a series of model systems, composed of 4-halophenyl-conjugated polyene acids and ammonia, were designed to explore the potential effect of distance on halogen bonding in different solvents. Quantum mechanics (QM) calculations demonstrated that the longer the distance, the stronger the bonding. The energy decomposition analysis on all of the model systems demonstrated that electrostatic interaction contributes the most (44-56%) to the overall binding, followed by orbital interaction (42-36%). Natural bond orbital calculations showed that electron transfer takes place from the acceptor to the donor, whereas the halogen atom becomes more positive during the bonding, which is in agreement with the result of neutral halogen bonding. QM/molecular mechanics calculations demonstrated that the polarity of binding pockets makes all of the interactions attractive in a protein system. Hence, the strength of halogen bonding involving negatively charged donors could be adjusted by changing the distance between the negative charge center and halogen atom and the environment in which the bonding exists, which may be applied in material and drug design for tuning their function and activity. PMID:27504672

  13. Keto-Acids in Carbonaceous Meteorites

    NASA Astrophysics Data System (ADS)

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

    2005-03-01

    Keto-acids (pyruvic acid homologs) have been identified in carbonaceous chondrites by GC-MS. All compounds were identified as their trimethylsilyl (TMS), isopropyl ester (ISP), and tert-butyldimethylsilyl (tBDMS) derivatives.

  14. Inorganic halogen oxidizers

    NASA Astrophysics Data System (ADS)

    Christe, K. O.; Wilson, W. W.

    1994-09-01

    A research program was carried out in novel energetic materials. This program was highly successful and resulted in 28 major publications. Highlights of this effort include: the characterization of the XeF5(-) anion which is the first example of a pentagonal planar XY5 structure, completion of our work on a quantitative oxidizer strength scale, the synthesis and characterization of new compounds at the limits of coordination and oxidation, such as XeOF5(-), TeOF6(2-), IOF6(-), IF8(-), TeF8(2-), TeF7(-), and XeF7(+), the study of fluxionality and steric repulsion effects in hexa- and hepta- coordinated species, such as IF7, HPF5(-), HSF5, and IOF5, the controlled replacement of two fluorine ligands by one doubly bonded oxygen ligand, studies of the thermal instability of NF5 and the F3(-) anion, the characterization of the N2F(+) cation N(CH3)4N3, H2N3(+) cation and the SF4(-) and SOF4(-) radical anions, the synthesis and characterization of a new Os(+VIII) compound, OsF4O2, theoretical studies on ONOF and a new family of polynitrogen compounds, the synthesis and characterization of the novel PF4(-) anion and it hydrolysis products, and the electrophilic fluorination of CH4 with F(+) equivalent N2F(+) and NF4(+) salts.

  15. Evaluation of Early Archean Volcaniclastic and Volcanic Flow Rocks as Possible Sites for Carbonaceous Fossil Microbes

    NASA Astrophysics Data System (ADS)

    Walsh, Maud M.

    2004-12-01

    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. Astrobiology 4, 429-437.

  16. 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. PMID:15684724

  17. Understanding the organo-carbonate associations in carbonaceous chondrites with the use of micro-Raman analysis

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    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.

  18. Co3O4 nanoparticle embedded carbonaceous fibres: a nanoconfinement effect on enhanced lithium-ion storage.

    PubMed

    Sun, Jin; Li, Daohao; Xia, Yanzhi; Zhu, Xiaoyi; Zong, Lu; Ji, Quan; Jia, Yi Alec; Yang, Dongjiang

    2015-11-21

    Co3O4 nanoparticle embedded carbonaceous fibres were prepared from Co(2+) coordinated regenerated cellulose fibres, which showed high reversible capacity and excellent cycling stability as anode materials for Li-ion batteries. PMID:26399496

  19. 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.

  20. 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.

  1. 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.

  2. Hydrogenation of PAH molecules through interaction with hydrogenated carbonaceous grains.

    PubMed

    Thrower, John D; Friis, Emil E; Skov, Anders L; Jørgensen, Bjarke; Hornekær, Liv

    2014-02-28

    Carbonaceous materials contribute to a significant proportion of the interstellar dust inventory. Reactions on such grain surfaces are thought to play important roles in interstellar chemical networks. Of particular importance are reactions involving hydrogen atoms, and pathways to the formation of the most abundant molecular species, H2. Polycyclic aromatic hydrocarbons (PAHs) are an additional carbon reservoir, accounting for around 10% of the galactic carbon budget. Using thermal desorption and mass spectrometric techniques, we have investigated the interaction between PAH molecules and carbonaceous grain surfaces. We demonstrate that deuterium atoms adsorbed on graphite can react with adsorbed PAH molecules, forming superhydrogenated PAH species. Furthermore, by considering the number of D-atoms remaining bound to the graphite surface and the additional D-atoms in the observed superhydrogenated species, we see evidence for a significant release of deuterium from the graphite surface. We suggest that further reactive processes may be responsible for part of this deuterium loss, indicating that PAHs adsorbed on hydrogenated carbonaceous grains in warm interstellar environments may serve as a route to release H2 as well as forming superhydrogenated PAH species. PMID:24270708

  3. Volatile halogenated hydrocarbons in foods

    SciTech Connect

    Miyahara, Makoto; Toyoda, Masatake; Saito, Yukio

    1995-02-01

    Volatile halogenated organic compounds were determined in foods. Statistical treatment of the data for 13 sampled from 20 families living in suburban Tokyo (Saitama prefecture) indicated that the foods were contaminated by water pollution and/or substances introduced by the process of food production. Butter and margarine were contaminated by chlorinated ethylene, ethane, and related compounds released by dry cleaning and other operations. Soybean sprouts and tofu (soybean curd) contained chloroform and related trihalomethanes absorbed during the production process. 27 refs., 6 figs., 5 tabs.

  4. 40 CFR 721.505 - Halogenated acrylonitrile.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.505 Halogenated acrylonitrile. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated acrylonitrile, (PMN P-90-299)...

  5. 40 CFR 721.505 - Halogenated acrylonitrile.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.505 Halogenated acrylonitrile. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated acrylonitrile, (PMN P-90-299)...

  6. Halogen-bonded mesogens direct polymer self-assemblies up to millimetre length scale

    PubMed Central

    Houbenov, Nikolay; Milani, Roberto; Poutanen, Mikko; Haataja, Johannes; Dichiarante, Valentina; Sainio, Jani; Ruokolainen, Janne; Resnati, Giuseppe; Metrangolo, Pierangelo; Ikkala, Olli

    2014-01-01

    Aligning polymeric nanostructures up to macroscale in facile ways remains a challenge in materials science and technology. Here we show polymeric self-assemblies where nanoscale organization guides the macroscopic alignment up to millimetre scale. The concept is shown by halogen bonding mesogenic 1-iodoperfluoroalkanes to a star-shaped ethyleneglycol-based polymer, having chloride end-groups. The mesogens segregate and stack parallel into aligned domains. This leads to layers at ~10 nm periodicity. Combination of directionality of halogen bonding, mesogen parallel stacking and minimization of interfacial curvature translates into an overall alignment in bulk and films up to millimetre scale. Upon heating, novel supramolecular halogen-bonded polymeric liquid crystallinity is also shown. As many polymers present sites capable of receiving halogen bonding, we suggest generic potential of this strategy for aligning polymer self-assemblies. PMID:24893843

  7. 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. PMID:27094875

  8. Competition between hydrogen and halogen bonding in halogenated 1-methyluracil: Water systems.

    PubMed

    Hogan, Simon W L; van Mourik, Tanja

    2016-03-30

    The competition between hydrogen- and halogen-bonding interactions in complexes of 5-halogenated 1-methyluracil (XmU; X = F, Cl, Br, I, or At) with one or two water molecules in the binding region between C5-X and C4O4 is investigated with M06-2X/6-31+G(d). In the singly-hydrated systems, the water molecule forms a hydrogen bond with C4O4 for all halogens, whereas structures with a halogen bond between the water oxygen and C5-X exist only for X = Br, I, and At. Structures with two waters forming a bridge between C4O and C5-X (through hydrogen- and halogen-bonding interactions) exist for all halogens except F. The absence of a halogen-bonded structure in singly-hydrated ClmU is therefore attributed to the competing hydrogen-bonding interaction with C4O4. The halogen-bond angle in the doubly-hydrated structures (150-160°) is far from the expected linearity of halogen bonds, indicating that significantly non-linear halogen bonds may exist in complex environments with competing interactions. © 2016 Wiley Periodicals, Inc. PMID:26773851

  9. Artifact free denuder method for sampling of carbonaceous aerosols

    NASA Astrophysics Data System (ADS)

    Mikuška, P.; Vecera, Z.; Broškovicová, A.

    2003-04-01

    Over the past decade, a growing attention has been focused on the carbonaceous aerosols. Although they may account for 30--60% of the total fine aerosol mass, their concentration and formation mechanisms are not well understood, particularly in comparison with major fine particle inorganic species. The deficiency in knowledge of carbonaceous aerosols results from their complexity and because of problems associated with their collection. Conventional sampling techniques of the carbonaceous aerosols, which utilize filters/backup adsorbents suffer from sampling artefacts. Positive artifacts are mainly due to adsorption of gas-phase organic compounds by the filter material or by the already collected particles, whereas negative artifacts arise from the volatilisation of already collected organic compounds from the filter. Furthermore, in the course of the sampling, the composition of the collected organic compounds may be modified by oxidants (O_3, NO_2, PAN, peroxides) that are present in the air passing through the sampler. It is clear that new, artifact free, method for sampling of carbonaceous aerosols is needed. A combination of a diffusion denuder and a filter in series is very promising in this respect. The denuder is expected to collect gaseous oxidants and gas-phase organic compounds from sample air stream prior to collection of aerosol particles on filters, and eliminate thus both positive and negative sampling artifacts for carbonaceous aerosols. This combination is subject of the presentation. Several designs of diffusion denuders (cylindrical, annular, parallel plate, multi-channel) in combination with various types of wall coatings (dry, liquid) were examined. Special attention was given to preservation of the long-term collection efficiency. Different adsorbents (activated charcoal, molecular sieve, porous polymers) and sorbents coated with various chemical reagents (KI, Na_2SO_3, MnO_2, ascorbic acid) or chromatographic stationary phases (silicon oils

  10. 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.

  11. Lunar and Planetary Science XXXV: Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    2004-01-01

    The titles in this section include: 1) A Quantitative NMR Analysis of Phosphorus in Carbonaceous and Ordinary Chondrites; 2) An Infrared Study of the Matrices of CI1 and CM2 Chondrites; 3) A Study of the Morphology, Composition and Mineral Associations of Fe-Ni Sulphides in CM Carbonaceous Chondrites; 4) Aqueous Alteration Mineralogy in CM Carbonaceous Chondrites; 5) In Situ Location and Characterization of Carbon-bearing Phases in Carbonaceous; 6) Chondrites: Insights from Yamato 791198, a Weakly-altered CM2 Chondrite; 7) Unique Texture in EET 83389: Clues to Formation of Fine Grained Rims in CM Chondrites; 8) Amoeboid Olivine Aggregates in the NWA 760 CV3 Chondrite; 9) Petrologic Type of CV3 Chondrites as Revealed by Raman Spectroscopy of Organic Matter; 10) A First Look at Acfer 324: Evidence for Another CR 3 Chondrite? 11) Hydrogen Isotopic Composition of the Bencubbin Meteorite; 12) The Fountain Hills Meteorite: A New CBa Chondrite from Arizona; 13) Shock Effects in the Metal-rich Chondrites QUE 94411, Hammadah al Hamra 237 and Bencubbin; 14) Mineralogy and Petrology of Al-rich Objects in the CH Carbonaceous Chondrite North West Africa 739.

  12. 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.

  13. Halogen Bonding in Hypervalent Iodine Compounds.

    PubMed

    Catalano, Luca; Cavallo, Gabriella; Metrangolo, Pierangelo; Resnati, Giuseppe; Terraneo, Giancarlo

    2016-01-01

    Halogen bonds occur when electrophilic halogens (Lewis acids) attractively interact with donors of electron density (Lewis bases). This term is commonly used for interactions undertaken by monovalent halogen derivatives. The aim of this chapter is to show that the geometric features of the bonding pattern around iodine in its hypervalent derivatives justify the understanding of some of the longer bonds as halogen bonds. We suggest that interactions directionality in ionic and neutral λ(3)-iodane derivatives is evidence that the electron density distribution around iodine atoms is anisotropic, a region of most positive electrostatic potential exists on the extensions of the covalent bonds formed by iodine, and these positive caps affect, or even determine, the crystal packing of these derivatives. For instance, the short cation-anion contacts in ionic λ(3)-iodane and λ(5)-iodane derivatives fully match the halogen bond definition and geometrical prerequisites. The same holds for the short contacts the cation of ionic λ(3)-iodanes forms with lone-pair donors or the short contacts given by neutral λ(3)-iodanes with incoming nucleophiles. The longer and weaker bonds formed by iodine in hypervalent compounds are usually called secondary bondings and we propose that the term halogen bond can also be used. Compared to the term secondary bond, halogen bond may possibly be more descriptive of some bonding features, e.g., its directionality and the relationships between structure of interacting groups and interaction strength. PMID:26809623

  14. 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.

  15. 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.

  16. 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. PMID:25652256

  17. 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. PMID:25504313

  18. Biomass-derived sponge-like carbonaceous hydrogels and aerogels for supercapacitors.

    PubMed

    Wu, Xi-Lin; Wen, Tao; Guo, Hong-Li; Yang, Shubin; Wang, Xiangke; Xu, An-Wu

    2013-04-23

    As a newly developed material, carbon gels have been receiving considerable attention due to their multifunctional properties. Herein, we present a facile, green, and template-free route toward sponge-like carbonaceous hydrogels and aerogels by using crude biomass, watermelon as the carbon source. The obtained three-dimensional (3D) flexible carbonaceous gels are made of both carbonaceous nanofibers and nanospheres. The porous carbonaceous gels (CGs) are highly chemically active and show excellent mechanical flexibility which enable them to be a good scaffold for the synthesis of 3D composite materials. We synthesized the carbonaceous gel-based composite materials by incorporating Fe3O4 nanoparticles into the networks of the carbonaceous gels. The Fe3O4/CGs composites further transform into magnetite carbon aerogels (MCAs) by calcination. The MCAs keep the porous structure of the original CGs, which allows the sustained and stable transport of both electrolyte ions and electrons to the electrode surface, leading to excellent electrochemical performance. The MCAs exhibit an excellent capacitance of 333.1 F·g(-1) at a current density of 1 A·g(-1) within a potential window of -1.0 to 0 V in 6 M KOH solution. Meanwhile, the MCAs also show outstanding cycling stability with 96% of the capacitance retention after 1000 cycles of charge/discharge. These findings open up the use of low-cost elastic carbon gels for the synthesis of other 3D composite materials and show the possibility for the application in energy storage. PMID:23548083

  19. 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.

  20. 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

  1. Enzyme mimics: Halogen and chalcogen team up

    NASA Astrophysics Data System (ADS)

    Metrangolo, Pierangelo; Resnati, Giuseppe

    2012-06-01

    The behaviour of di-selenol enzyme mimics indicates that a halogen bond between selenium and iodine, and a chalcogen interaction between the two selenium atoms, play an important role in the activation of thyroid hormones.

  2. Complete reaction mechanisms of mercury oxidation on halogenated activated carbon.

    PubMed

    Rungnim, Chompoonut; Promarak, Vinich; Hannongbua, Supa; Kungwan, Nawee; Namuangruk, Supawadee

    2016-06-01

    The reaction mechanisms of mercury (Hg) adsorption and oxidation on halogenated activated carbon (AC) have been completely studied for the first time using density functional theory (DFT) method. Two different halogenated AC models, namely X-AC and X-AC-X (X=Cl, Br, I), were adopted. The results revealed that HgX is found to be stable-state on the AC edge since its further desorption from the AC as HgX, or further oxidation to HgX2, are energetically unfavorable. Remarkably, the halide type does not significantly affect the Hg adsorption energy but it strongly affects the activation energy barrier of HgX formation, which obviously increases in the order HgIhalogen impregnated AC for Hg elimination significantly decreases as I-AC>Br-AC>Cl-AC. Thus, the study of the complete reaction mechanism is essential because the adsorption energy can not be used as a guideline for the rational material design in the halide impregnated AC systems. The activation energy is an important descriptor for the predictions of sorbent reactivity to the Hg oxidation process. PMID:26943019

  3. 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.

  4. 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)

  5. 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.

  6. 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

  7. 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.

  8. FIELD SCREENING FOR HALOGENATED VOLATILE ORGANIC COMPOUNDS

    SciTech Connect

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

    2002-06-01

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

  9. Spectrum of carbonaceous-chondrite fission xenon

    NASA Technical Reports Server (NTRS)

    Clayton, D. D.

    1976-01-01

    Estimations of the fission spectrum in xenon isotopes from the progenitor of the strange carbonaceous-chondrite xenon must take account of p-process nucleosynthesis if the latter is the source of anomalous Xe-124, 126. Sample calculations of the p-process yields illustrate the magnitude of the effect, which can greatly increase the estimated Xe-132 fission yield.

  10. Carbonaceous "Snowflakes" and the Origin of Life.

    PubMed

    Morrison, P

    1962-02-23

    The possibility that the intricate "organized elements" found in some carbonaceous chondrites are to be interpreted, not as microfossils of once-living cells, but as organic-chemical analogues of similarly intricate snow crystals is raised; tests and implications are discussed. PMID:17808708

  11. Structure and oxidation of carbonaceous cenospheres

    SciTech Connect

    Gavalas, G.R.; Loewenberg, M.; Bellan, J.; Clayton, R.M.

    1985-01-01

    Carbonaceous cenosphere particles from an oil furnace are characterized by scanning electron microscopy, mercury intrusion and nitrogen adsorption porosimetry. The porosimetry data are used to construct a random pore model describing the evolution of surface area and pore volume distribution. The pore model is combined with gas phase transport to formulate the equations for transient particle combustion and some numerical solutions are presented.

  12. 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.

  13. 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. PMID:21943920

  14. Magnetite in CI carbonaceous meteorites - Origin by aqueous activity on a planetesimal surface

    NASA Technical Reports Server (NTRS)

    Kerridge, J. F.; Mackay, A. L.; Boynton, W. V.

    1979-01-01

    The composition and morphology of magnetite in CI carbonaceous meteorites appear incompatible with a nebular origin. Mineralization on the meteorite parent body is a more plausible mode of formation. The iodine-xenon age of this material therefore dates an episode of secondary mineralization on a planetesimal rather than the epoch of condensation in the primitive solar nebula.

  15. 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

  16. Carbonaceous aerosols from prescribed burning of a boreal forest ecosystem

    SciTech Connect

    Mazurek, M.A. ); Cofer, W.R. III; Levine, J.S. . Langley Research Center)

    1990-10-01

    The identity and ambient mass concentrations of radiatively important carbonaceous aerosols were measured for a boreal forest prescribed burn conducted in northern Ontario, CAN in August 1989. Nonsize-segregated airborne particles were collected for smoldering-fire and full-fire conditions using a helicopter sampling platform. Total carbon (TC), organic carbon (OC) and elemental carbon (EC) were measured. Smoke plume mass concentrations of the OC and EC particles were greatest for full-fire conditions and had ranges of 1.560 to 2.160 mg/m{sup {minus}1} (OC) and 0.120 to 0.160 mg/m{sup {minus}3} (EC) with OC:EC ratios of 10 to 18, respectively. Smoldering fire conditions showed smoke plume OC and EC levels of 0.570--1.030 mg/m{sup {minus}3} (OC) and 0.006--0.050 mg/m{sup {minus}3} (EC) and much higher ratios of OC:EC (21 to 95). These aerosol data indicate the formation of EC particles is greatest during full-fire combustion of boreal forest material relative to smoldering combustion. However, EC particles comprise a minor fraction of the particulate carbon smoke aerosols for both full-fire and smoldering conditions; the major component of carbonaceous smoke aerosols emitted during the prescribed burn is OC. Overall, the OC and EC in-plume smoke aerosol data show nonuniform production of these particles during various stages of the prescribed burn, and major differences in the type of carbonaceous aerosol that is generated (OC versus EC).

  17. Metal Halogen Battery Construction with Combustion Arrester to Prevent Self Propagation of Hydrogen-Halogen Reactions

    SciTech Connect

    Hammond, M. J.; Kilic, S.

    1983-12-27

    A metal halogen battery construction containing a special reactor means having a combustion arrester device and a reaction initiator device, whereby the reactor means permits controlled recombination of hydrogen gas and halogen gas in the system to form hydrogen halide, which is then dispersed into the store means of the battery.

  18. 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.

  19. Halogenation of graphene with chlorine, bromine, or iodine by exfoliation in a halogen atmosphere.

    PubMed

    Poh, Hwee Ling; Šimek, Petr; Sofer, Zdeněk; Pumera, Martin

    2013-02-18

    Nanoarchitectonics on graphene implicates a specific and exact anchoring of molecules or nanoparticles onto the surface of graphene. One such example of an effective anchoring group that is highly reactive is the halogen moiety. Herein we describe a simple and scalable method for the introduction of halogen (chlorine, bromine, and iodine) moieties onto the surface of graphene by thermal exfoliation/reduction of graphite oxide in the corresponding gaseous halogen atmosphere. We characterized the halogenated graphene by using various techniques, including scanning and transmission electron microscopy, Raman spectroscopy, high-resolution X-ray photoelectron spectroscopy, and electrochemistry. The halogen atoms that have successfully been attached to the graphene surfaces will serve as basic building blocks for further graphene nanoarchitectonics. PMID:23296548

  20. 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). PMID:25968513

  1. 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.

  2. 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

  3. 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

  4. Biodegradation of halogenated organic compounds.

    PubMed

    Chaudhry, G R; Chapalamadugu, S

    1991-03-01

    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

  5. Halogen Radical Chemistry at Aqueous Interfaces.

    PubMed

    Enami, Shinichi; Hoffmann, Michael R; Colussi, A J

    2016-08-11

    Halogens play key roles in the chemical composition of marine boundary layers, the free troposphere and the stratosphere. Atmospheric halogen chemistry is dominated by reactions between gas-phase and aqueous species on the surfaces of the ocean and marine aerosol. The mechanisms of interfacial halogen radical/halide reactions, however, are not fully understood, partly due to the dearth of techniques for in situ monitoring of the products and intermediates of fast interfacial halogen radical reactions. Here, we report the online electrospray mass spectrometric identification of the species produced on the surface of aqueous Br(-) and I(-) microjets collided by I(•)(g) pulses generated from the 266 nm laser photolysis of CH3I/O2/N2 gas mixtures. Mass-specific identification of intermediates and products in D2O and H2(18)O solutions and their dependences on I(•)(g) fluxes let us outline mechanisms of formation. We found that the uptake of I(•)(g) on the surface of Br(-) and I(-) microjets (effective uptake coefficient γeff ≥ 2 × 10(-4)) yields IBr(•)(-)/I2(•)(-) radical intermediates, which rapidly react with additional I(•) to produce trihalides I2Br(-)/IBr2(-)/I3(-) plus I3On(-) (n = 1, 2) species within ∼10 μs. Our findings point to a new halogen activation pathway initiated by photogenerated I(•). PMID:27414750

  6. Titanium isotopic anomalies in hibonites from the Murchison carbonaceous chondrite

    NASA Astrophysics Data System (ADS)

    Ireland, T. R.; Compston, W.; Heydegger, H. R.

    1985-09-01

    The isotopic compositions of titanium in eight grains of hibonite (CaAl12O19) from the carbonaceous chondrite Murchison have been determined by high precision secondary ion mass spectrometry using an ion microprobe. The titanium in the hibonites varies greatly in Ti-50 from about -42 to +8 permil (relative to terrestrial) with smaller (up to 4 permil), but clearly resolvable, effects in Ti-46 and Ti-48. These results confirm the presence of widespread negative anomalies suggested by the results of Hutcheon et al. (1983) on hibonites from Murchison. The magnitude of these variations seems explicable only in terms of nucleogenic processes which produced extremely variable titanium isotopic abundances in the hibonite source materials. The hibonites evidently did not participate to the same extent as most material in the mixing and homogenisation processes that accompanied the formation and later evolution of the solar system.

  7. Carbon isotopes in bulk carbonaceous chondrites

    NASA Technical Reports Server (NTRS)

    Halbout, J.; Mayeda, T. K.; Clayton, R. N.

    1985-01-01

    The chemical and physical processes involved in the formation of the solar system are examined. Primitive matter has been found on a microscopic scale in a variety of meteorites: fragments of small solar system bodies that were never part of a large planet. This primitive matter has, in most cases, been identified by the presence of anomalous abundances of some isotopes of the chemical elements. Of particular interest for carbon isotope studies are the primitive meteorites known as carbonaceous chondrites. Using a selective oxidation technique to sort out the carbon contained in different chemical forms (graphite, carbonates, and organic matter), four carbonaceous chondrites are analyzed. The presence of the (13) C-rich component was confirmed and additional carbon components with different, but characteristic, isotopic signatures were resolved.

  8. Aerosol-Assisted Self-Assembly of Reticulated N-Doped Carbonaceous Submicron Spheres for Effective Removal of Hexavalent Chromium.

    PubMed

    He, Jiawei; Long, Yuan; Wang, Yiyan; Wei, Chaoliang; Zhan, Jingjing

    2016-07-01

    This Research Article described a facile one-step method to prepare reticulated N-doped carbonaceous submicron spheres. Through a simple aerosol-assisted technology, glucosamine sulfate used as a carbon source was aerosolized and carbonized to functionalized carbonaceous submicron spheres. The electrostatic attraction between protonated amino groups and sulfate in the aerosol droplets induced a self-assembly and led to the formation of reticular structure, avoiding the use of templates. Compared to bare carbonaceous materials produced from glucose, reticulated N-doped carbonaceous spheres exhibit higher efficiency in the removal of Cr(VI), where the doping of element nitrogen led to electrostatic attraction between protonated nitrogen and chromium ions, and reticulated structure created relatively higher surface area and pore volume, facilitating materials to contact with Cr(VI) ions. XPS characterization proved these novel N-doped carbonaceous materials could effectively transform Cr(VI) to less toxic Cr(III) because of the surface reducing groups. For the practical application, several factors including the initial pH, materials dosage and recycle numbers on the removal performance were studied. PMID:27299376

  9. 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. PMID:24093546

  10. 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.

  11. Carbonaceous xenoliths from the Erevan howardite

    NASA Technical Reports Server (NTRS)

    Nazarov, M. A.; Brandstaetter, F.; Kurat, G.

    1993-01-01

    Preliminary studies of the Erevan howardite showed that the meteorite is a polymict breccia. We report on our study of CM-type carbonaceous xenoliths. All of these clasts are enriched in tochilinite and carbonate inclusion as compared to CM chondrites. They also contain a new, P-rich sulphide beside pentlandite. The P-rich sulphide represents a new type of P-bearing phases. It indicates a chalcophile behavior of P under certain nebular conditions.

  12. Carbonaceous aerosols in an urban tunnel

    NASA Astrophysics Data System (ADS)

    Ancelet, Travis; Davy, Perry K.; Trompetter, William J.; Markwitz, Andreas; Weatherburn, David C.

    2011-08-01

    Particulate matter in the Mount Victoria Tunnel, an urban road tunnel 623 m in length with an average traffic volume of 2070-2300 vehicles per hour located in Wellington, New Zealand, was studied to gain an understanding of carbonaceous species emitted from motor vehicles. The average PM 2.5 concentration during peak hours in the tunnel was found to be 67.6 ± 19.4 μg m -3. Analysis of carbonaceous species present (OC, EC, TC) was performed by both the NIOSH and IMPROVE thermal/optical protocols and carbonaceous species were found to make up 63-73% of the total PM in the tunnel. Comparison of TC concentrations obtained from each protocol revealed that no significant difference was present between the two protocols. Black carbon (BC), also used as a measure of EC, was determined using light reflection and BC values did not differ significantly from EC concentrations determined using the NIOSH and IMPROVE protocols. TC was also determined using EA/IRMS and it was found that TC concentrations from EA/IRMS directly correlated with TC results obtained using the NIOSH protocol. Stable isotope analysis of the PM 2.5 yielded δ 13C values from -24.7 to -28.3‰, typical of motor vehicles. Analysis of particle-phase PAHs by thermal desorption GC/MS revealed an average total PAH concentration of 70.0 ± 4.1 ng m -3 and PAHs were found to contribute 0.10% of total PM 2.5 in the tunnel. PAH emissions in the tunnel were found to be enriched in low molecular weight PAHs, indicative of emissions from diesel-fueled vehicles. Analysis of individual particle composition and morphology revealed that most particles were carbonaceous species that formed large, amorphous agglomerates made up of smaller spherules.

  13. NOXIOUS TRACE GASES IN THE AIR. PART II. HALOGENATED POLLUTANTS

    EPA Science Inventory

    The chemistry of chlorofluorocarbons and other halogenated air pollutants is discussed. A summary is presented of the present levels of concentration of such compounds, along with comments on anticipated increases. Chemical reactions that transform and remove halogenated pollutan...

  14. Halogen Oxide Measurements at Masaya Volcano, Nicaragua

    NASA Astrophysics Data System (ADS)

    Kern, C.; Vogel, L.; Sihler, H.; Rivera, C.; Strauch, W.; Galle, B.; Platt, U.

    2007-12-01

    Sulphur dioxide (SO2) and halogen oxide emissions were measured at Masaya Volcano in Nicaragua in April 2007 using differential optical absorption spectroscopy (DOAS). Next to passive DOAS measurements using scattered sunlight, an active long-path DOAS system was operated for several days with the light beam crossing the crater of the volcano. These measurements for the first time give an insight into the night-time halogen chemistry occurring at volcanoes. While the passive DOAS instruments measured sulphur dioxide (SO2) and bromine monoxide (BrO) in various viewing geometries and distances from the crater during daytime, the active instrument additionally allowed a quantification of chlorine monoxide (ClO) and chlorine dioxide (OClO), as well as being able to measure round-the-clock. The results of the field measurements will be presented and their implications for halogen chemistry at volcanoes will be discussed.

  15. 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

  16. Evaluation of halogenated coumarins for antimosquito properties.

    PubMed

    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. 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

  18. Palladium-Catalyzed Carbamate-Directed Regioselective Halogenation: A Route to Halogenated Anilines.

    PubMed

    Moghaddam, Firouz Matloubi; Tavakoli, Ghazal; Saeednia, Borna; Langer, Peter; Jafari, Behzad

    2016-05-01

    This study describes an efficient method for ortho-selective halogenation of N-arylcarbamates under mild conditions for the first time. Although being weakly coordinating, N-arylcarbamates act very well as a removable directing group for activation of C-H bonds. The developed procedure results in extremely valuable halogenated N-arylcarbmates that can further be hydrolyzed to halogenated anilines. The obtained reaction conditions showed broad scope and wide functional group tolerance. All the products were formed in good yields with extremely high selectivity. PMID:27072283

  19. HALOGEN: Approximate synthetic halo catalog generator

    NASA Astrophysics Data System (ADS)

    Avila Perez, Santiago; Murray, Steven

    2015-05-01

    HALOGEN generates approximate synthetic halo catalogs. Written in C, it decomposes the problem of generating cosmological tracer distributions (eg. halos) into four steps: generating an approximate density field, generating the required number of tracers from a CDF over mass, placing the tracers on field particles according to a bias scheme dependent on local density, and assigning velocities to the tracers based on velocities of local particles. It also implements a default set of four models for these steps. HALOGEN uses 2LPTic (ascl:1201.005) and CUTE (ascl:1505.016); the software is flexible and can be adapted to varying cosmologies and simulation specifications.

  20. Boundary layer halogens in coastal Antarctica.

    PubMed

    Saiz-Lopez, Alfonso; Mahajan, Anoop S; Salmon, Rhian A; Bauguitte, Stephane J-B; Jones, Anna E; Roscoe, Howard K; Plane, John M C

    2007-07-20

    Halogens influence the oxidizing capacity of Earth's troposphere, and iodine oxides form ultrafine aerosols, which may have an impact on climate. We report year-round measurements of boundary layer iodine oxide and bromine oxide at the near-coastal site of Halley Station, Antarctica. Surprisingly, both species are present throughout the sunlit period and exhibit similar seasonal cycles and concentrations. The springtime peak of iodine oxide (20 parts per trillion) is the highest concentration recorded anywhere in the atmosphere. These levels of halogens cause substantial ozone depletion, as well as the rapid oxidation of dimethyl sulfide and mercury in the Antarctic boundary layer. PMID:17641195

  1. 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

  2. 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. PMID:27073033

  3. 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.

  4. 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...

  5. 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...

  6. 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...

  7. 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...

  8. 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.

  9. 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...

  10. 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...

  11. 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...

  12. 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...

  13. 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.

  14. Phase relations of a carbonaceous chondrite at lower mantle conditions

    NASA Astrophysics Data System (ADS)

    Asahara, Y.; Ohtani, E.; Kondo, T.; Kubo, T.

    2002-12-01

    The refractory element ratios of Earth's mantle are close to carbonaceous chondrite values. One of the ideas on Earth's bulk composition is that the Earth is made of carbonaceous chondrite-like materials, but the redox state of Earth is closer to that of Enstatite chondrite than carbonaceous chondrite. We do not know exactly when and how the reduction event was occurred at proto Earth. Therefore, it is important to considering differentiation process of early earth that the phase relations of mantle composition are investigated under variable Fe/FeO conditions at high pressures. Allende meteorite (CV chondrite) is applicable to one of the oxidized model of the proto earth, whereas the most reduced model is Peridotite and Metal. We report the phase relations of Allende meteorite in the pressure range from 22 to 30 GPa, at 1600-2300 °C. We use natural Allende meteorite as starting material. The Kawai type multianvil apparatus was used for the present experiments. The truncated edge length of the anvil was 2 mm. We use two kinds of heating element, LaCrO3 and Re. LaCrO3 heater was used for subsolidus experiments, and Re heater was used for melting experiments. Pressure calibrations were made at high temperatures using il-pv phase transition, Al2 O3 content of Pv determined by in situ X-ray diffraction measurements with the Jamieson's Gold scale [1]. The micro-area X-ray diffractometer and EPMA were used for phase identification and compositional analysis of run products. The liquidus phase changed from garnet to Mg-perovskite at about 24.5 GPa, and magnesiowustite remained second liquidus phase. The solubility of mafic components in Ca-perovskite in Allende composition is higher than that reported on Peridotite bulk composition. The Ca/(Ca+Mg+Fe) ratio of Ca-perovskite is 0.6 in Allende experiments, whereas that is 0.9 in Peridotite experiments [2]. Our result suggests that chemical differentiation process could change with FeO contents of magma ocean. References [1

  15. NXY halogen bonds. Comparison with NHY H-bonds and CXY halogen bonds.

    PubMed

    Nepal, Binod; Scheiner, Steve

    2016-07-21

    Quantum calculations examine how the NHY H-bond compares to the equivalent NXY halogen bond, as well as to comparable CH/CX donors. Succinimide and saccharin, and their corresponding halogen-substituted derivatives, are chosen as the prototype NH/NX donors, paired with a wide range of electron donor molecules. The NHY H-bond is weakened if the bridging H is replaced by Cl, and strengthened by I; a Br halogen bond is roughly comparable to a H-bond. The lone pairs of the partner molecule are stronger electron donors than are π-systems. Whereas Coulombic forces represent the largest fraction of the attractive force in the H-bonds, induction energy is magnified in the halogen bonds, surpassing electrostatics in several cases. Mutation of NH/NX to CH/CX weakens the binding energy to roughly half its original value, while also lengthening the intermolecular distances by 0.3-0.8 Å. PMID:27327538

  16. Herringbone structures of 2,7-dihalogenated acridine tailored by halogen-halogen interactions

    NASA Astrophysics Data System (ADS)

    Yamamura, Masaki; Ikuma, Seira; Nabeshima, Tatsuya

    2015-08-01

    The crystal structures of the 2,7-dibromo- and 2,7-diiodoacridines (2 and 3) were determined by single-crystal X-ray diffraction analysis. Molecules of the brominated 2 were assembled through different types of halogen-halogen interactions (Type-I and Type-II). Conversely, molecules of the iodinated 3 were assembled only through Type-II interactions. Although both compounds were packed in a herringbone way, the intermolecular π-π stacking was observed only in the brominated 2. In the solution and solid-state absorption spectra, a bathochromic shift in the absorption was observed, as the mass of the halogen atoms increased. Theoretical calculation indicated a substituent effect of the halogen on the π-orbital of the acridine moiety. In the solid state, the iodinated 3 exhibited a significant absorption in the orange-to-red wavelength region.

  17. Carbonaceous Nanowire Supports for Polymer Electrolyte Membrane Fuel Cells

    SciTech Connect

    Garzon, Fernando; Wilson, Mahlon; Banham, Dustin; More, Karren Leslie

    2016-01-01

    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. (C) The Author(s) 2015. Published by ECS.

  18. 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.

  19. Carbonaceous nanowire supports for polymer electrolyte membrane fuel cells

    DOE PAGESBeta

    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 wellmore » dispersed, smaller Pt particles compared to commercial catalysts, despite significantly higher support surface loadings.« less

  20. 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...

  1. 40 CFR 721.505 - Halogenated acrylonitrile.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... reporting. (1) The chemical substance identified generically as halogenated acrylonitrile, (PMN P-90-299) is... specified in § 721.125 (a) through (h). (2) Limitations or revocation of certain notification requirements... Section 721.505 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC...

  2. 40 CFR 721.505 - Halogenated acrylonitrile.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... reporting. (1) The chemical substance identified generically as halogenated acrylonitrile, (PMN P-90-299) is... specified in § 721.125 (a) through (h). (2) Limitations or revocation of certain notification requirements... Section 721.505 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC...

  3. 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.

  4. ALIPHATIC HALOGENATED HYDROCARBONS PRODUCE VOLATILE 'SALMONELLA' MUTAGENS

    EPA Science Inventory

    Production of volatile mutagenic metabolites from 5 halogenated promutagens was examined by a simple modification of the conventional Salmonella/microsome mutagenicity assay. This method incorporates the taping together of 2 agar plates face to face during the initial portion of ...

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Seasonality of Forcing by Carbonaceous Aerosols

    NASA Astrophysics Data System (ADS)

    Habib, G.; Bond, T.; Rasch, P. J.; Coleman, D.

    2006-12-01

    Aerosols can influence the energy balance of Earth-Atmosphere system with profound effect on regional climate. Atmospheric processes, such as convection, scavenging, wet and dry deposition, govern the lifetime and location of aerosol; emissions affect its quantity and location. Both affect climate forcing. Here we investigate the effect of seasonality in emissions and atmospheric processes on radiative forcing by carbonaceous aerosols, focusing on aerosol from fossil fuel and biofuel. Because aerosol lifetime is seasonal, ignoring the seasonality of sources such as residential biofuel may introduce a bias in aerosol burden and therefore in predicted climate forcing. We present a global emission inventory of carbonaceous aerosols with seasonality, and simulate atmospheric concentrations using the Community Atmosphere Model (CAM). We discuss where and when the seasonality of emissions and atmospheric processes has strong effects on atmospheric burden, lifetime, climate forcing and aerosol optical depth (AOD). Previous work has shown that aerosol forcing is higher in summer than in winter, and has identified the importance of aerosol above cloud in determining black carbon forcing. We show that predicted cloud height is a very important factor in determining normalized radiative forcing (forcing per mass), especially in summer. This can affect the average summer radiative forcing by nearly 50%. Removal by cloud droplets is the dominant atmospheric cleansing mechanism for carbonaceous aerosols. We demonstrate the modeled seasonality of removal processes and compare the importance of scavenging by warm and cold clouds. Both types of clouds contribute significantly to aerosol removal. We estimate uncertainty in direct radiative forcing due to scavenging by tagging the aerosol which has experienced cloud interactions. Finally, seasonal variations offer an opportunity to assess modeled processes when a single process dominates variability. We identify regions where aerosol

  10. 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.

  11. Densified carbonaceous bodies with improved surface finishes

    SciTech Connect

    Hucke, E.E.

    1988-08-02

    A method is described of producing a densified carbonaceous body with a superior surface finish, the method comprising the steps of: impregnating a permeable body composed essentially of a fine grained, isotropic graphite with a liquid impregnant containing furfural or furfural alcohol or a mixture thereof, an acid catalyst, and a pore-forming agent comprising a polyalkylene oxide adduct nonionic surfactant; heating the impregnated, permeable body to a temperature which is sufficiently high to polymerize the impregnant; and then heating the body to a temperature which is sufficiently high to pyrolyze the carbon in the polymerized impregnant.

  12. 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.

  13. Capping efficiency of various carbonaceous and mineral materials for in situ remediation of polychlorinated dibenzo-p-dioxin and dibenzofuran contaminated marine sediments: sediment-to-water fluxes and bioaccumulation in boxcosm tests.

    PubMed

    Josefsson, Sarah; Schaanning, Morten; Samuelsson, Göran S; Gunnarsson, Jonas S; Olofsson, Ida; Eek, Espen; Wiberg, Karin

    2012-03-20

    The efficiency of thin-layer capping in reducing sediment-to-water fluxes and bioaccumulation of polychlorinated dibenzo-p-dioxins and dibenzofurans, hexachlorobenzene, and octachlorostyrene was investigated in a boxcosm experiment. The influence of cap thickness (0.5-5 cm) and different cap materials was tested using a three-factor experimental design. The cap materials consisted of a passive material (coarse or fine limestone or a marine clay) and an active material (activated carbon (AC) or kraft lignin) to sequester the contaminants. The cap thickness and the type of active material were significant factors, whereas no statistically significant effects of the type of passive material were observed. Sediment-to-water fluxes and bioaccumulation by the two test species, the surface-dwelling Nassarius nitidus and the deep-burrowing Nereis spp., decreased with increased cap thickness and with addition of active material. Activated carbon was more efficient than lignin, and a ~90% reduction of fluxes and bioaccumulation was achieved with 3 cm caps with 3.3% AC. Small increases in fluxes with increased survival of Nereis spp. indicated that bioturbation by Nereis spp. affected the fluxes. PMID:22339559

  14. Transformations of halogenated organic compounds under denitrification conditions.

    PubMed Central

    Bouwer, E J; McCarty, P L

    1983-01-01

    Trihalomethanes, carbon tetrachloride, 1,1,1-trichloroethane, 1,2-dibromoethane, chlorinated benzenes, ethylbenzene, and naphthalene at concentrations commonly found in surface and groundwater were incubated under anoxic conditions to study their transformability in the presence of denitrifying bacteria. None of the aromatic compounds showed significant utilization relative to sterile controls at initial concentrations from 41 to 114 micrograms/liter after 11 weeks of incubation. Of the halogenated aliphatic compounds studied, transformations of carbon tetrachloride and brominated trihalomethanes were observed after 8 weeks in batch denitrification cultures. Carbon from the decomposition of carbon tetrachloride was both assimilated into cell material and mineralized to carbon dioxide. How this was possible remains unexplained, since carbon tetrachloride is transformed to CO2 by hydrolysis and not by oxidation-reduction. Chloroform was detected in bacterial cultures with carbon tetrachloride initially present, indicating that reductive dechlorination had occurred in addition to hydrolysis. The data suggest that transformations of certain halogenated aliphatic compounds are likely to occur under denitrification conditions in the environment. PMID:6859850

  15. 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.

  16. Aqueous accelerated solvent extraction of native polycyclic aromatic hydrocarbons (PAHs) from carbonaceous river floodplain soils.

    PubMed

    Yang, Yi; Hofmann, Thilo

    2009-10-01

    In this study, three river floodplain soils with different compositions of carbonaceous materials and a reference coal sample were extracted with water using the accelerated solvent extraction (ASE) method. The desorption enthalpy values for 2-ring PAHs were highest in the coal sample, with values in the soil samples decreasing with decrease in coal content. The values for the higher condensed PAHs showed that the highest desorption enthalpies were from the samples with the largest amount of coal-derived particles. Elevated desorption enthalpies indicated a strong bonding between PAHs and geosorbents. Moreover, with the application of ASE this study was able to conclude that the PAHs in the samples were preferentially adsorbed to carbonaceous materials with high surface areas. PMID:19524343

  17. Pyrolysis of Carbonaceous Foundry Sand Additives: Seacoal and Gilsonite

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Seacoal and gilsonite are used by the foundry industry as carbonaceous additives in green molding sands. In this study, pyrolysis was used to simulate the heating conditions that the carbonaceous additives would experience during metal casting. Gas chromatography-mass spectrometry was used to tent...

  18. New Tendencies in Development of Carbonaceous Additives for Welding Fluxes

    NASA Astrophysics Data System (ADS)

    Kozyrev, N. A.; Kryukov, R. E.; Kozyreva, O. A.

    2015-09-01

    The paper provides results of comparative analysis of the effect of carbonaceous components introduced into welding fluxes on molten metal - slag interaction. Thermodynamical calculations of dehydrogenization are presented for submerged arc welding. A positive influence of carbonaceous additives on gas content and mechanical properties of welds is demonstrated. Carbon and fluorine containing additives are emphasized to be promising for automatic submerged arc welding.

  19. Dating Carbonaceous Matter in Archean Cherts by Electron Paramagnetic Resonance

    PubMed Central

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

    2013-01-01

    Abstract 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). Key Words: Kerogen—Sedimentary rocks

  20. 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). PMID:23397956

  1. 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.

  2. 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.

  3. 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.

  4. Iron isotope anomalies. [in carbonaceous meteorites

    NASA Technical Reports Server (NTRS)

    Voelkening, J.; Papanastassiou, D. A.

    1989-01-01

    Precise determinations of the Fe isotope abundances yield identical results for a terrestrial standard and for samples of carbonaceous meteorites. Fe-54/Fe-56 = 0.062669; Fe-57/Fe-56 = 0.023261 + or - 0.000002; and Fe-58/Fe-56 = 0.0031132 + or - 0.0000011 are found. Refractory element-rich inclusions from the Allende carbonaceous meteorite yield hints of deficits in Fe-57/Fe-56 of up to -3.9 + or - 2.6 parts in 10,000 and a hint of excess in Fe-58/Fe-56 of up to 27 + or - 11 parts in 10,000. One special (FUN) inclusion shows a large excess of 2.9 percent, uniquely attributable to Fe-58. This excess correlates with large excesses in the same inclusion in the neutron-rich isotopes Ca-48, Ti-50 and Cr-54. These results strengthen the evidence for an exotic nucleosynthetic component produced by neutron-rich, statistical equilibrium burning, and injected into the interstellar medium.

  5. Transmission Electron Microscopy of CONCORDIA UltraCarbonaceous Antarctic MicroMeteorites (UCAMMs): Mineralogical properties

    NASA Astrophysics Data System (ADS)

    Dobrică, E.; Engrand, C.; Leroux, H.; Rouzaud, J.-N.; Duprat, J.

    2012-01-01

    We performed mineralogical and petrographic studies of three UltraCarbonaceous Antarctic Micrometeorites (UCAMMs) by analytical transmission electron microscopy (TEM). The UCAMMs were identified in the CONCORDIA micrometeorite collection (2002 and 2006) recovered from central Antarctic snow, and are of probable cometary origin. UCAMMs are dominated by disordered carbonaceous matter that extends over surfaces of up to ˜90% of the particle. Embedded in this carbonaceous matter, we observed small and complex assemblages of fine-grained mineral phases, isolated minerals, glassy phases that resemble Glass with Embedded Metal and Sulfides (GEMS) that were first found in Interplanetary Dust Particles (IDPs), and rounded objects containing both glass and crystalline materials. The mineral assemblages are chondritic in composition, within a factor of 2. Crystalline materials represent at least 25% of mineral phases. This value is much larger than the upper limit of crystallinity measured in the diffuse interstellar medium (<2.2 wt%). Crystalline phases are dominated by low-Ca, Mg-rich pyroxenes, Mg-rich olivine and low-Ni Fe-sulfides. Exotic phases such as Mn-, Zn-rich sulfide and perryite have also been found as accessory minerals. The variety of high temperature mineral phases observed in UCAMMs is similar to that reported in chondritic porous IDPs and 81P/Wild 2 samples. The close association of high temperature crystalline phases with the low temperature carbonaceous matter in UCAMMs supports the hypothesis of a large-scale radial mixing in the early solar nebula. This new type of carbon-rich micrometeorites containing crystalline material provides the opportunity to analyze in situ, without any chemical processing, the association of materials formed at both low and high temperatures in the protoplanetary disk. A better knowledge of these samples is also important to prepare for future cometary missions, like ROSETTA in 2014.

  6. Global cloud condensation nuclei influenced by carbonaceous combustion aerosol

    NASA Astrophysics Data System (ADS)

    Spracklen, D. V.; Carslaw, K. S.; Pöschl, U.; Rap, A.; Forster, P. M.

    2011-09-01

    Black carbon in carbonaceous combustion aerosol warms the climate by absorbing solar radiation, meaning reductions in black carbon emissions are often perceived as an attractive global warming mitigation option. However, carbonaceous combustion aerosol can also act as cloud condensation nuclei (CCN) so they also cool the climate by increasing cloud albedo. The net radiative effect of carbonaceous combustion aerosol is uncertain because their contribution to CCN has not been evaluated on the global scale. By combining extensive observations of CCN concentrations with the GLOMAP global aerosol model, we find that the model is biased low (normalised mean bias = -77 %) unless carbonaceous combustion aerosol act as CCN. We show that carbonaceous combustion aerosol accounts for more than half (52-64 %) of global CCN with the range due to uncertainty in the emitted size distribution of carbonaceous combustion particles. The model predicts that wildfire and pollution (fossil fuel and biofuel) carbonaceous combustion aerosol causes a global mean cloud albedo aerosol indirect effect of -0.34 W m-2, with stronger cooling if we assume smaller particle emission size. We calculate that carbonaceous combustion aerosol from pollution sources cause a global mean aerosol indirect effect of -0.23 W m-2. The small size of carbonaceous combustion particles from fossil fuel sources means that whilst pollution sources account for only one-third of the emitted mass they cause two-thirds of the cloud albedo aerosol indirect effect that is due to carbonaceous combustion aerosol. This cooling effect must be accounted for, along with other cloud effects not studied here, to ensure that black carbon emissions controls that reduce the high number concentrations of fossil fuel particles have the desired net effect on climate.

  7. 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.

  8. 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.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

    Ofner, J.; Balzer, N.; Buxmann, J.; Grothe, H.; Schmitt-Kopplin, P.; Platt, U.; Zetzsch, C.

    2012-01-01

    Reactive halogen species (RHS), such as X·, X2 and HOX containing X = chlorine and/or bromine, are released by various sources like photo-activated sea-salt aerosol or from salt pans, and salt lakes. Despite many studies of RHS reactions, the potential of RHS reacting with secondary organic aerosol (SOA) and organic aerosol derived from biomass-burning (BBOA) has been neglected. Such reactions can constitute sources of gaseous organohalogen compounds or halogenated organic matter in the tropospheric boundary layer and can influence physicochemical properties of atmospheric aerosols. Model SOA from α-pinene, catechol, and guaiacol was used to study heterogeneous interactions with RHS. Particles were exposed to molecular chlorine and bromine in an aerosol smog-chamber in the presence of UV/VIS irradiation and to RHS released from simulated natural halogen sources like salt pans. Subsequently the aerosol was characterized in detail using a variety of physicochemical and spectroscopic methods. Fundamental features were correlated with heterogeneous halogenation, which result in new functional groups, changed UV/VIS absorption, or aerosol size distribution. However, the halogen release mechanisms were also found to be affected by the presence of organic aerosol. Those interaction processes, changing chemical and physical properties of the aerosol are likely to influence e.g. the ability of the aerosol to act as cloud condensation nuclei, its potential to adsorb other gases with low-volatility, or its contribution to radiative forcing and ultimately the Earth's radiation balance.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. 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. PMID:26465079

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

    PubMed Central

    Aakeröy, Christer B.; Spartz, Christine L.; Dembowski, Sean; Dwyre, Savannah; Desper, John

    2015-01-01

    As halogen bonds gain prevalence in supramolecular synthesis and materials chemistry, it has become necessary to examine more closely how such interactions compete with or complement hydrogen bonds whenever both are present within the same system. As hydrogen and halogen bonds have several fundamental features in common, it is often difficult to predict which will be the primary interaction in a supramolecular system, especially as they have comparable strength and geometric requirements. To address this challenge, a series of molecules containing both hydrogen- and halogen-bond donors were co-crystallized with various monotopic, ditopic symmetric and ditopic asymmetric acceptor molecules. The outcome of each reaction was examined using IR spectroscopy and, whenever possible, single-crystal X-ray diffraction. 24 crystal structures were obtained and subsequently analyzed, and the synthon preferences of the competing hydrogen- and halogen-bond donors were rationalized against a background of calculated molecular electrostatic potential values. It has been shown that readily accessible electrostatic potentials can offer useful practical guidelines for predicting the most likely primary synthons in these co-crystals as long as the potential differences are weighted appropriately. PMID:26306192

  18. Carbonaceous aerosols of aviation and shipping emissions

    NASA Astrophysics Data System (ADS)

    Popovicheva, O. B.; Kireeva, E. D.; Timofeev, M. A.; Shonija, N. K.; Mogil'Nikov, V. P.

    2010-06-01

    This is a study of the physical and chemical properties of carbonaceous aerosols emitted by transport systems (namely, by aircraft gas turbine engines and large ship diesel engines) into the atmosphere. A comparative analysis of the morphology, size, elemental composition, and surface chemistry between aviation and diesel soot particles reveals the general and characteristic features of emissions from each source. The high pollution rate of diesel soot particles, considerable fraction of metal admixtures, and availability of char particles characterize the specific features of the formation of particles of this type. The main characteristics characterizing the interaction between aviation and shipping emission aerosols in the moist atmosphere (the composition of organic and water-soluble fractions at the surface) have been obtained. Due to high hygroscopicity, the microparticles can generate cloud condensation nuclei and initiate contrails and additional tropospheric cloudiness.

  19. Methods of ultimate carbonaceous BOD determination

    USGS Publications Warehouse

    Stamer, J.K.; McKenzie, S.W.; Cherry, R.N.

    1979-01-01

    Studies were conducted to provide an accurate and practical technique for determining the concentration of ultimate carbonaceous biochemical oxygen demand and the rate at which this demand is exerted. The three methods evaluated were carbon derived, nitrification adjusted, and nitrification inhibited. The studies indicate that comparable concentrations and reaction rates can be determined from either non-nitrified samples using no chemical nitrifying inhibitor, or from partially nitrified samples using the chemical inhibitors, 1-allyl-2 thiourea or nitrapyrin, and that the combined use of time-series analysis and Lee's graphical method provide a reliable and accurate technique for determining ultimate biochemical oxygen demand concentration and reaction rate in 5 to 7 days.

  20. Carbonaceous chondrites and the origin of life

    NASA Technical Reports Server (NTRS)

    Hartman, Hyman; Sweeney, Michael A.; Kropp, Michael A.; Lewis, John S.

    1993-01-01

    Organic matter in carbonaceous chondrites can be separated into three fractions. The first component, the fraction that is insoluble in chloroform and methanol, has a part which is of interstellar origin. The other two fractions (chloroform-soluble hydrocarbons and methanol-soluble polar organics) are hypothesized to have been synthesized on a planetoid body. We propose that the polar organics, i.e., amino acids, were synthesized close to its surface by the radiolysis of hydrocarbons and ammonium carbonate in a liquid water environment. Some hydrocarbons may have been synthesized by a Fischer-Tropsch mechanism in the interior of the body. Ferrous ion acted as a protection against back reactions. The simultaneous synthesis of iron-rich clays with the polar organics may be indicative of events related to the origin of life on Earth.

  1. Chemical and petrographic correlations among carbonaceous chondrites

    NASA Technical Reports Server (NTRS)

    Van Schmus, W. R.; Hayes, J. M.

    1974-01-01

    Detailed study of the petrographic and chemical properties of carbonaceous chondrites shows that the four distinct petrographic subtypes may be related to one of two distinct chemical subdivisions. These subdivisions are recognized primarily by the relative abundances of the nonvolatile elements Si, Ca, Al, Ti, Cu and Fe. C1, C2 and C3(O) chondrites form one subdivision. Vigarano subtype chondrites form the other subdivision and include chondrites previously referred to as C2, C3 and C4. Normalized to silicon, the abundances of Ca, Al and Ti are relatively enriched in Vigarano subtype chondrites, whereas Fe and Cu are relatively more abundant in C1, C2 and C3(O) chondrites. Volatile elements tend to correlate with petrographic subtypes rather than with chemical subdivisions.

  2. 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.

  3. Global cloud condensation nuclei influenced by carbonaceous combustion aerosol

    NASA Astrophysics Data System (ADS)

    Spracklen, D. V.; Carslaw, K. S.; Pöschl, U.; Rap, A.; Forster, P. M.

    2011-03-01

    Black carbon in carbonaceous combustion aerosol warms the climate by absorbing solar radiation, meaning reductions in black carbon emissions are often perceived as an attractive global warming mitigation option. However, carbonaceous combustion aerosol can also act as cloud condensation nuclei (particles upon which cloud drops form) so they also cool the climate by increasing cloud albedo. The net radiative effect of carbonaceous combustion aerosol is uncertain because their contribution to cloud drops has not been evaluated on the global scale. By combining extensive observations of cloud condensation nuclei concentrations and a global aerosol model, we show that carbonaceous combustion aerosol accounts for more than half of global cloud condensation nuclei. The evaluated model predicts that wildfire and pollution (fossil fuel and biofuel) carbonaceous combustion aerosol causes a global mean aerosol indirect effect of -0.34 W m-2 due to changes in cloud albedo, with pollution sources alone causing a global mean aerosol indirect effect of -0.23 W m-2. The small size of carbonaceous combustion particles from pollution sources means that whilst they account for only one-third of the emitted mass from these sources they cause two-thirds of the cloud albedo indirect effect that is due to carbonaceous combustion aerosol. This cooling effect must be accounted for to ensure that black carbon emissions controls that reduce the high number concentrations of small pollution particles have the desired net effect on climate.

  4. Potential halogenated industrial carcinogenic and mutagenic chemicals. II. Halogenated saturated hydrocarbons.

    PubMed

    Fishbein, L

    1979-03-01

    The halogenated saturated hydrocarbons analogously to the previously considered halogenated unsaturated hydrocarbons (Part I) possess considerable utility in a broad spectrum of applications including; solvents, dry-cleaning fluids, refrigerants, fumigants, degreasing agents, propellants and intermediates in the production of other chemicals, textiles and plastics. Methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl chloroform, 1,1,2-trichloroethane, hexachloroethane, ethyl chloride and fluorocarbons were reviewed principally in terms of their synthesis (or occurrence), areas of application, stability, distribution, reactivity, levels of exposure, populations at risk, carcinogenicity, mutagenicity and metabolism. PMID:373115

  5. 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.

  6. 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.

  7. Sustainable approach toward synthesis of green functional carbonaceous 3-D micro/nanostructures from biomass.

    PubMed

    Tavangar, Amirhossein; Tan, Bo; Venkatakrishnan, Krishnan

    2013-01-01

    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. PMID:23924310

  8. 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.

  9. Electrical conductivity of carbonaceous chondrites and electric heating of meteorite parent bodies

    NASA Technical Reports Server (NTRS)

    Duba, AL

    1987-01-01

    Electromagnetic heating of rock-forming materials most probably was an important process in the early history of the solar system. Electrical conductivity experiments of representative materials such as carbonaceous chondrites are necessary to obtain data for use in electromagnetic heating models. With the assumption that carbon was present at grain boundaries in the material that comprised the meteorite parent bodies, the electrical heating of such bodies was calculated as a function of body size and solar distance using the T-Tauri model of Sonett and Herbert (1977). The results are discussed.

  10. 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

    2015-12-01

    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. PMID:26505258

  11. 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.

  12. 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.

  13. 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.

  14. Copper-Catalyzed Aza-Diels-Alder Reaction and Halogenation: An Approach To Synthesize 7-Halogenated Chromenoquinolines.

    PubMed

    Yu, Xiaoqiang; Wang, Jiao; Xu, Zhanwei; Yamamoto, Yoshinori; Bao, Ming

    2016-05-20

    A new halogenation method to construct halogen-substituted quinoline moieties is described. The Cu-catalyzed intramolecular aza-Diels-Alder reaction and halogenation reaction proceeded smoothly under mild conditions to produce the corresponding 7-chloro-6H-chromeno[4,3-b]quinolines and 7-chloro-6H-thiochromeno[4,3-b]quinolines in satisfactory yields. PMID:27145113

  15. 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]).

  16. 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

  17. Matrix mineralogy of the orgueil CI carbonaceous chondrite

    SciTech Connect

    Tomeoka, K.; Buseck, P.R. )

    1988-06-01

    A petrographic and transmission electron microscopic study of the Orgueil CI carbonaceous chondrite shows that the matrix consists mainly of Fe-bearing, Mg-rich serpentine and smectite (saponite) as well as a poorly crystallized Fe-rich material that contains minor, variable S and Ni; the Fe-rich material is probably ferrihydrite. The ferrihydrite occurs in small particles, and the S and Ni are probably adsorbed on its surfaces. The serpentine and saponite occur in poorly crystallized, fine crystallites that are intimately associated with the ferrihydrite. Coarsely crystallized phyllosilicates occur in clusters relatively free of ferrihydrite. The ferrihydrite is a major matrix constitutent and probably accounts for most of the Fe{sub 3+} as well as the superparamagnetic fraction in the Orgueil matrix. The textures suggest that the fine phyllosilicates resulted from alteration of the coarse phyllosilicates. The alteration probably involved a substantial amount of water and coincided with the period of sulfate vein formation. During the aqueous alteration magnetite grains, disaggregated from framboids, and Fe-(Ni) sulfides were replaces by ferrihydrite. The matrix mineralogy of the Orgueil chondrite suggests that Orgueil experienced considerably different alteration conditions from the CM chondrites. The mineralogical and petrological differences between CI and CM chondrites can not simply be explained as the result of different degrees of aqueous alteration.

  18. Generation of oil from coal and carbonaceous shale

    SciTech Connect

    Kirkland, D.W.; Tsui, T.F.; Stockton, M.L.

    1987-05-01

    Coal and carbonaceous shale contain the remains of higher terrestrial (vascular) plants, remains commonly referred to as Type III kerogen. Given sufficient thermal exposure, such organic matter is commonly considered to generate only natural gas. Coaly sequences, however, are not always strictly gas producers. Many coaly sequences, particularly those of Tertiary age, have generated important volumes of oil. Those oils are usually paraffinic and waxy, or naphthenic; have a pristane-to-phytane ratio of 2-12; contain definitive biomarkers such as tricyclic diterpenoids; and are low in sulfur (much less than 1%). These oils are clearly distinct from those derived predominantly from marine algal remains. The principal source sequences of oils derived from coaly material occur in Tertiary deltas. Such source sequences contain abundant coaly material with favorable generative quality. Evaluation of generative quality is based either on geochemical analysis (e.g., atomic H/C > 0.9) or on petrographic analysis: source potential being proportional to the abundance and hydrogen richness of organic constituents (macerals). In approximate ranking, oil-generating potential of the hydrogen-rich macerals is exudatinite > alginite > resinite > liptodetrinite > cutinite > sporinite > vitrinite-B (fluorescing vitrinite). Examples of basins containing both a major Tertiary deltaic sequence (hundreds of cubic miles) and major volumes of oil (billions of barrels) derived predominantly from higher terrestrial plate remains are: the Ardjuna and Kutei basins, Indonesia; and the Gippsland basin, Australia.

  19. Spectroscopic investigations of organic aerosol and its reaction with halogens, released by sea-salt activation

    NASA Astrophysics Data System (ADS)

    Ofner, J.; Zetzsch, C.

    2009-04-01

    The release of reactive halogen species from sea-salt aerosol offers a class of reactants for heterogeneous reactions of utmost importance. These heterogeneous reactions have been overlooked so far, although they may occur with internal and external mixtures of sea-salt aerosol and organic aerosol or organic matter. Such reactions might constitute sources of gaseous organohalogen compounds or halogenated organic aerosol in the atmospheric boundary layer. Infrared and UV/VIS spectroscopy provide an insight into chemical processes at reactive sites of the organic phase on a molecular level. Model studies of heterogeneous reactions of halogens with different kinds of (secondary) organic aerosols and organic matter were performed using a 700L smog chamber with a solar simulator. The model compounds alpha-pinene, catechol and humic acid have been chosen as precursors/material for the condensed, organic phase of the aerosol. After formation of the secondary organic aerosol or preparation of the organic material and the sea-salt solution the reaction was carried out using molecular chlorine and bromine in the presence of simulated sunlight. Chemical transformation of the organic material was studied using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) on a ZnSe crystal and diffuse reflectance UV/VIS spectroscopy. An electrostatic precipitator was developed to deposit the aerosol particles on the ATR crystal as a thin film. On the other hand, longpath-FTIR spectroscopy with a 40m White-cell allows us to monitor both the condensed and gas phase of the aerosol in situ in the smog chamber directly. These spectroscopic techniques enable us to characterize different organic aerosol particles and their functional groups at reactive sites on these particles as well as to study aerosol formation and transformation directly. The heterogeneous reaction of reactive halogen species with organic material at atmospheric conditions leads to small reactive

  20. 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.

  1. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the liquid to... which it is part, as specified in 40 CFR 63.100(k) (if the referencing subpart is 40 CFR part 63... 40 Protection of Environment 15 2011-07-01 2011-07-01 false Halogen scrubbers and other...

  2. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the liquid to... which it is part, as specified in 40 CFR 63.100(k) (if the referencing subpart is 40 CFR part 63... 40 Protection of Environment 15 2010-07-01 2010-07-01 false Halogen scrubbers and other...

  3. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the liquid to... which it is part, as specified in 40 CFR 63.100(k) (if the referencing subpart is 40 CFR part 63... 40 Protection of Environment 16 2014-07-01 2014-07-01 false Halogen scrubbers and other...

  4. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the liquid to... which it is part, as specified in 40 CFR 63.100(k) (if the referencing subpart is 40 CFR part 63... 40 Protection of Environment 16 2013-07-01 2013-07-01 false Halogen scrubbers and other...

  5. 40 CFR 65.154 - Halogen scrubbers and other halogen reduction devices.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... subject to regulations in 40 CFR parts 264 through 266 that have required a determination of the liquid to... which it is part, as specified in 40 CFR 63.100(k) (if the referencing subpart is 40 CFR part 63... 40 Protection of Environment 16 2012-07-01 2012-07-01 false Halogen scrubbers and other...

  6. 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

    2014-01-01

    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. PMID:24359254

  7. Mercury and halogens in coal: Chapter 2

    USGS Publications Warehouse

    Kolker, Allan; Quick, Jeffrey C.

    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

  8. 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.

  9. Crystallinity of Fe-Ni Sulfides in Carbonaceous Chondrites

    NASA Astrophysics Data System (ADS)

    Zolensky, M. E.; Ohsumi, K.; Mikouchi, T.; Hagiya, K.; Le, L.

    2008-03-01

    We examine the crystallinity and crystal structures of Fe-Ni sulfides in five carbonaceous chondrites - Acfer 094 (CM2), Tagish Lake (C2 ungrouped), Kaidun C1, Bali (CV2/3 oxidized), and Efremovka (CV3 reduced).

  10. Degradation of halogenated carbons in alkaline alcohol

    NASA Astrophysics Data System (ADS)

    Nakagawa, Seiko; Shimokawa, Toshinari

    2002-02-01

    1,1,2-Trichloro-trifluoroethane, 1,2-dibromo-tetrafluoroethane, 2,3,4,6-tetrachlorophenol, 1,2,4-trichlorobenzene, and 2,4,6-trichloroanisole were dissolved in alkaline isopropyl alcohol and irradiated with 60Co gamma rays after purged with pure nitrogen gas. The concentration of the hydroxide ions and the parent molecules decreased with the dose, while that of the halide ions and the organic products, with less halogen atoms than the parent, increased. Chain degradation will occur in alkaline isopropyl alcohol.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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

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

    NASA Astrophysics Data System (ADS)

    Ofner, J.; Balzer, N.; Buxmann, J.; Grothe, H.; Schmitt-Kopplin, Ph.; Platt, U.; Zetzsch, C.

    2012-07-01

    Reactive halogen species (RHS), such as X·, X2 and HOX containing X = chlorine and/or bromine, are released by various sources like photo-activated sea-salt aerosol or from salt pans, and salt lakes. Despite many studies of RHS reactions, the potential of RHS reacting with secondary organic aerosol (SOA) and organic aerosol derived from biomass-burning (BBOA) has been neglected. Such reactions can constitute sources of gaseous organohalogen compounds or halogenated organic matter in the tropospheric boundary layer and can influence physicochemical properties of atmospheric aerosols. Model SOA from α-pinene, catechol, and guaiacol was used to study heterogeneous interactions with RHS. Particles were exposed to molecular chlorine and bromine in an aerosol smog-chamber in the presence of UV/VIS irradiation and to RHS, released from simulated natural halogen sources like salt pans. Subsequently, the aerosol was characterized in detail using a variety of physicochemical and spectroscopic methods. Fundamental features were correlated with heterogeneous halogenation, which results in new functional groups (FTIR spectroscopy), changes UV/VIS absorption, chemical composition (ultrahigh resolution mass spectroscopy (ICR-FT/MS)), or aerosol size distribution. However, the halogen release mechanisms were also found to be affected by the presence of organic aerosol. Those interaction processes, changing chemical and physical properties of the aerosol are likely to influence e.g. the ability of the aerosol to act as cloud condensation nuclei, its potential to adsorb other gases with low-volatility, or its contribution to radiative forcing and ultimately the Earth's radiation balance.

  17. 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.

  18. 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

  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. PMID:19062335

  20. 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.

  1. 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.

  2. 40 CFR 721.8700 - Halogenated alkyl pyridine.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated alkyl pyridine. 721.8700 Section 721.8700 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8700 Halogenated alkyl...

  3. 40 CFR 721.3480 - Halogenated biphenyl glycidyl ethers.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated biphenyl glycidyl ethers... Substances § 721.3480 Halogenated biphenyl glycidyl ethers. (a) Chemical substance and significant new uses... ethers (PMNs P-90-1844, P-90-1845, and P-90-1846) are subject to reporting under this section for...

  4. 40 CFR 721.3480 - Halogenated biphenyl glycidyl ethers.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halogenated biphenyl glycidyl ethers... Substances § 721.3480 Halogenated biphenyl glycidyl ethers. (a) Chemical substance and significant new uses... ethers (PMNs P-90-1844, P-90-1845, and P-90-1846) are subject to reporting under this section for...

  5. 40 CFR 721.4484 - Halogenated indane (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halogenated indane (generic name). 721.4484 Section 721.4484 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... Substances § 721.4484 Halogenated indane (generic name). (a) Chemical substance and significant new...

  6. 40 CFR 721.4484 - Halogenated indane (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halogenated indane (generic name). 721.4484 Section 721.4484 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... Substances § 721.4484 Halogenated indane (generic name). (a) Chemical substance and significant new...

  7. 40 CFR 721.4484 - Halogenated indane (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halogenated indane (generic name). 721.4484 Section 721.4484 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... Substances § 721.4484 Halogenated indane (generic name). (a) Chemical substance and significant new...

  8. 40 CFR 721.535 - Halogenated alkane (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical 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...

  9. 40 CFR 721.536 - Halogenated phenyl alkane.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical 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)...

  10. 40 CFR 721.535 - Halogenated alkane (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical 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...

  11. [Possibility of using halogen lamps in surgical light sources].

    PubMed

    Mel'kin, A A; Kopli, V A

    1980-01-01

    For higher efficiency of surgical light-sources the halogen lamps are recommended for them instead of incandescent lamps. First experimental results indicated the following advantages of halogen lamps: lesser consumption of electrical power per unit of illumination, prolonged service term, and lower temperature of operative field. PMID:7402019

  12. 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...

  13. 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...

  14. 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...

  15. Modern Transition-Metal-Catalyzed Carbon-Halogen Bond Formation.

    PubMed

    Petrone, David A; Ye, Juntao; Lautens, Mark

    2016-07-27

    The high utility of halogenated organic compounds has prompted the development of a vast number of transformations which install the carbon-halogen motif. Traditional routes to these building blocks have commonly involved multiple steps, harsh reaction conditions, and the use of stoichiometric and/or toxic reagents. In this regard, using transition metals to catalyze the synthesis of organohalides has become a mature field in itself, and applying these technologies has allowed for a decrease in the production of waste, higher levels of regio- and stereoselectivity, and the ability to produce enantioenriched target compounds. Furthermore, transition metals offer the distinct advantage of possessing a diverse spectrum of mechanistic possibilities which translate to the capability to apply new substrate classes and afford novel and difficult-to-access structures. This Review provides comprehensive coverage of modern transition metal-catalyzed syntheses of organohalides via a diverse array of mechanisms. Attention is given to the seminal stoichiometric organometallic studies which led to the corresponding catalytic processes being realized. By breaking this field down into the synthesis of aryl, vinyl, and alkyl halides, it becomes clear which methods have surfaced as most favored for each individual class. In general, a pronounced shift toward the use of C-H bonds as key functional groups, in addition to methods which proceed by catalytic, radical-based mechanisms has occurred. Although always evolving, this field appears to be heading in the direction of using starting materials with a significantly lower degree of prefunctionalization in addition to less expensive and abundant metal catalysts. PMID:27341176

  16. Carbonaceous deposits in direct utilization hydrocarbon SOFC anode

    NASA Astrophysics Data System (ADS)

    He, Hongpeng; Vohs, John M.; Gorte, Raymond J.

    Carbonaceous deposits formed in Cu-based SOFC anode compartment by exposing porous YSZ anodes to n-butane at elevated temperatures were studied using a combination of V- I curves, impedance spectroscopy, SEM, and TPO measurements. While short-term exposure of a porous YSZ matrix to n-butane at 973 K resulted in the deposition of electronically conducting carbonaceous film and therefore to enhance the fuel cell performance, the power density decays quickly in n-butane at temperature 1073 K or higher for long-term operation. SEM results indicate that the carbonaceous deposits arising from gas phase reaction have different morphology, and a dense layer composed of poly-aromatic rings has been formed on the porous anode surface. The dense layer could block the penetration of fuels to the anode and ions transfer to the three-phase boundaries where electrochemical reactions occur, resulting in the drop of the power density. TPO measurements revealed that the amount of carbonaceous deposits increased and the type of deposits changed with exposure time to n-butane. The stability of deposits increased with extending the exposure time according to the increased oxidation temperature. Steam can remove the carbonaceous deposits from the porous YSZ anode, but the reaction temperature was severely elevated compared to that of oxygen. The carbonaceous deposits can also be removed at 973 K by steam but the deposition of carbon will be controlled by the speed of removal and formation from the gas phase reaction.

  17. Oxidative Difunctionalization of Alkenyl MIDA Boronates: A Versatile Platform for Halogenated and Trifluoromethylated α-Boryl Ketones.

    PubMed

    Lv, Wen-Xin; Zeng, Yao-Fu; Li, Qingjiang; Chen, Yunyun; Tan, Dong-Hang; Yang, Ling; Wang, Honggen

    2016-08-16

    The synthesis of halogenated and trifluoromethylated α-boryl ketones via a one-pot oxidative difunctionalization of alkenyl MIDA boronates is reported. These novel densely functionalized organoborons bearing synthetically and functionally valuable carbonyl, halogen/CF3 and boronate moieties within the same molecule are synthetically challenging for the chemist, but have great synthetic potential, as demonstrated by their applications in a straightforward synthesis of borylated furans. The generality of this reaction was extensively investigated. This reaction is attractive since the starting materials, alkenyl MIDA boronates, are easily accessible. PMID:27443890

  18. Degradation of halogenated aliphatic compounds by Xanthobacter autotrophicus GJ10.

    PubMed Central

    Janssen, D B; Scheper, A; Dijkhuizen, L; Witholt, B

    1985-01-01

    A bacterium that is able to utilize a number of halogenated short-chain hydrocarbons and halogenated carboxylic acids as sole carbon source for growth was identified as a strain of Xanthobacter autotrophicus. The organism constitutively produces two different dehalogenases. One enzyme is specific for halogenated alkanes, whereas the other, which is more heat stable and has a higher pH optimum, is specific for halogenated carboxylic acids. Haloalkanes were hydrolyzed in cell extracts to produce alcohols and halide ions, and a route for the metabolism of 1,2-dichlorethane is proposed. Both dehalogenases show a broad substrate specificity, allowing the degradation of bromine- and chlorine-substituted organic compounds. The results show that X. autotrophicus may play a role in the degradation of organochlorine compounds and that hydrolytic dehalogenases may be involved in the microbial metabolism of short-chain halogenated hydrocarbons in microorganisms. Images PMID:3994371

  19. Electrochemical activation of a tetrathiafulvalene halogen bond donor in solution.

    PubMed

    Oliveira, R; Groni, S; Fave, C; Branca, M; Mavré, F; Lorcy, D; Fourmigué, M; Schöllhorn, B

    2016-06-21

    The halogen bond donor properties of iodo-tetrathiafulvalene (I-TTF) can be electrochemically switched and controlled via reversible oxidation in the solution phase. Interestingly the activation of only one single halogen bond yielded already a strong and selective interaction, quantified by cyclic voltammetry. The standard potentials of the redox couples I-TTF(0/1+) and I-TTF(1+/2+) were observed to shift upon the addition of halides. These anions selectively stabilize the cationic I-TTF species through halogen bonding in polar liquid electrolytes. The thermodynamic affinity constants for chloride and bromide binding to the oxidized species have been determined. Competition in halide binding between I-TTF(1+) and other halogen bond donors allowed for comparing the relative donor strength of the respective electrophilic species. Furthermore it has been shown that halogen bonding can prevail over hydrogen bonding in the investigated system. PMID:27231819

  20. 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

  1. 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}.

  2. [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. PMID:22860296

  3. Study on the volatility of halogenated fluorenes.

    PubMed

    Oliveira, Juliana A S A; Oliveira, Tânia S M; Gaspar, Alexandra; Borges, Fernanda; Ribeiro da Silva, Maria D M C; Monte, Manuel J S

    2016-08-01

    This work reports the experimental determination of relevant thermophysical properties of five halogenated fluorenes. The vapor pressures of the compounds studied were measured at different temperatures using two different experimental techniques. The static method was used for studying 2-fluorofluorene (liquid and crystal vapor pressures between 321.04 K and 411.88 K), 2-iodofluorene (liquid and crystal vapor pressures between 362.63 K and 413.86 K), and 2,7-dichlorofluorene (crystal vapor pressures between 364.64 K and 394.22 K). The Knudsen effusion method was employed to determine the vapor pressures of 2,7-difluorofluorene (crystal vapor pressures between 299.17 K and 321.19 K), 2,7-diiodofluorene (crystal vapor pressures between 393.19 K and 415.14 K), and (again) 2-iodofluorene (crystal vapor pressures between 341.16 K and 361.12 K). The temperatures and the molar enthalpies of fusion of the five compounds were determined using differential scanning calorimetry. The application to halogenated fluorenes of recently developed methods for predicting vapor pressures and enthalpies of sublimation and vaporization of substituted benzenes is also discussed. PMID:27206270

  4. 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

  5. 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.

  6. Carbonaceous particles reduce marine microgel formation.

    PubMed

    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 Ca(2+) 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

  7. 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.

  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. 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.

  10. Microscale Distribution of Hydrogen Isotopes in Two Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Young, A. F.; Nittler, L. R.; Alexander, C. M. O'D

    2004-01-01

    Hydrogen isotopes are highly variable among primitive meteorites and interplanetary dust particles (IDPs) [1, 2]. In particular, many primitive objects exhibit D (and N-15) enrichments, relative to terrestrial values, thought to represent partial preservation of presolar material fractionated in molecular clouds. However, the diversity of D/H ratios among IDPs and chondrites indicates a complex history of processing in the solar nebula and on meteorite parent bodies. Deconvolving this record requires identification and characterization of the carriers of D enrichments in different objects. Isotopic imaging has proven to be a powerful method to quantitatively explore the distribution of D/H ratios on a one to several m scale in IDPs [2-4] and the CR chondrite Renazzo [5, 6]. In this study, we have used ion imaging to explore the microscale D/H distribution of two carbonaceous chondrites, Tagish Lake (unique) and Al Rais (CR2). Previous D/H measurements (on a tens of microns scale) of Tagish Lake matrix fragments by Messenger [7] and Engrand et al. [8] have found different results, most likely related to the analytical techniques used. Previous work has also shown a large range of D/H ratios in CR chondrites, including very large variations on a scale of a few microns [5, 6, 9].

  11. Powder X-Ray Diffraction of the Grain Components of Carbonaceous Chondrite Meteorites.

    NASA Astrophysics Data System (ADS)

    Furton, D. G.; Hurt, Kendra; Bos, Abram

    Carbonaceous chondrite meteorites are thought to bring to Earth samples of primordial interstellar material. Detailed chemical analysis of meteorites representative of this class (i.e., Allende, Murchison, and Orgueil) establish the primordial character of the material they include and, among other things, reveal that nanometer-sized diamond grains are present in the carbonaceous component of these meteorites at about the 1,000 ppm level (Lewis et al. 1987, Nature, 326, 160). The high abundance of nanodiamonds in these meteoritic samples contributes to the hypothesis that nanodiamonds are present in the interstellar medium at relatively high abundance, but direct observational support of this hypothesis is not so conclusive. (It may also be, according to Dai et al. (2002, Nature, 418, 157), that the nanodiamond grains were formed in situ). On the other hand, there is a growing body of observational evidence that indicates nanometer-sized silicon grains are present in the interstellar medium at relatively high abundance (e.g., Smith & Witt 2001, ApJ, 565, 304). But, silicon nanoparticles have yet to be discovered in a sample of carbonaceous chondrite meteorite. It is relevant in this context that the chemical process that has been used to extract nanodiamond grains from meteoritic samples involves dissolving in strong acid the silicate component of the meteorite. The process is ultimately destructive to any silicon grains that may be present and possibly even alters the nanodiamonds it is used to extract (Mutschke et al. 1995, ApJL, 454, L160). There does not appear to be a similar chemical process that could be used to extract silicon nanoparticles from meteoritic samples. We are in the process of establishing to what extent powder X-ray diffraction can be use as a non-destructive analytical tool to examine nanometer-sized grain components of carbonaceous chondrite meteorites. We present powder X-ray diffraction patterns obtained from samples of the Murchison and

  12. 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.

  13. Factors influencing dissolution of carbonaceous materials in liquid iron

    SciTech Connect

    Sun, H.P.

    2005-12-01

    Carbon dissolution into liquid iron was investigated by a kinetic model assuming the rate is limited by interfacial carbon dissociation and mass transfer in the liquid iron. The rate influencing factors and the inter-relations among them were discussed with the aid of the kinetic model.

  14. Impact of aging mechanism on model simulated carbonaceous aerosols

    NASA Astrophysics Data System (ADS)

    Huang, Y.; Wu, S.; Dubey, M. K.; French, N. H. F.

    2013-07-01

    Carbonaceous aerosols including organic carbon and black carbon have significant implications for both climate and air quality. In the current global climate or chemical transport models, a fixed hydrophobic-to-hydrophilic conversion lifetime for carbonaceous aerosol (τ) is generally assumed, which is usually around one day. We have implemented a new detailed aging scheme for carbonaceous aerosols in a chemical transport model (GEOS-Chem) to account for both the chemical oxidation and the physical condensation-coagulation effects, where τ is affected by local atmospheric environment including atmospheric concentrations of water vapor, ozone, hydroxyl radical and sulfuric acid. The updated τ exhibits large spatial and temporal variations with the global average (up to 11 km altitude) calculated to be 2.6 days. The chemical aging effects are found to be strongest over the tropical regions driven by the low ozone concentrations and high humidity there. The τ resulted from chemical aging generally decreases with altitude due to increases in ozone concentration and decreases in humidity. The condensation-coagulation effects are found to be most important for the high-latitude areas, in particular the polar regions, where the τ values are calculated to be up to 15 days. When both the chemical aging and condensation-coagulation effects are considered, the total atmospheric burdens and global average lifetimes of BC, black carbon, (OC, organic carbon) are calculated to increase by 9% (3%) compared to the control simulation, with considerable enhancements of BC and OC concentrations in the Southern Hemisphere. Model evaluations against data from multiple datasets show that the updated aging scheme improves model simulations of carbonaceous aerosols for some regions, especially for the remote areas in the Northern Hemisphere. The improvement helps explain the persistent low model bias for carbonaceous aerosols in the Northern Hemisphere reported in literature. Further

  15. 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.

  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. PMID:27343595

  18. Characterization of carbonaceous aerosols in urban air

    NASA Astrophysics Data System (ADS)

    Husain, Liaquat; Dutkiewicz, Vincent A.; Khan, A. J.; Ghauri, Badar M.

    Concentrations of black carbon, [BC], were determined with an Aethalometer every 5 min at Lahore, a city of about 10 million in Pakistan, from 22 November 2005 to 31 January 2006. [BC] were very high, ranging from about 5 to 110μgm-3, with a mean of 21.7μgm-3. A distinct diurnal variation was observed: concentrations were lowest from about 10 a.m. to 4 p.m. local time (LT), and highest around 5-9 p.m. No clear relationship was observed between surface wind directions and [BC], although some of the highest concentrations were observed when the airflow was from southwest to northwest. The daily variations in concentrations were strongly affected by the diurnal variations in the mixing height; BC concentrations were low during the day when the mixing heights were high, ˜1000m, and very high at night when the mixing heights were low <250m. Periods of light to dense fog occurred from 22 December through 4 January. [BC] were generally lower than average when fog occurred during the night and early morning, but they were not necessarily lower during daytime fogs. We also collected aerosols on quartz filters every 3, 6, or 12 h and determined the concentrations of elemental, [EC], and organic carbon, [OC], using the thermal-optical method. The [BC] were highly correlated with EC (r2=0.71), but on average 25% higher than [EC]. The [EC] and [OC] concentrations were moderately correlated (r2=0.65). The [OC]/[EC] ratios varied from 2.8 to 12, with a mean of 5.6. Although a large component of the carbonaceous aerosols in Lahore originated from fossil fuel combustion, a significant fraction was derived from biomass burning.

  19. 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

  20. 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

  1. Insights into enzymatic halogenation from computational studies

    NASA Astrophysics Data System (ADS)

    Senn, Hans

    2014-11-01

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

  2. Long term trend of selected halogenated hydrocarbons

    NASA Technical Reports Server (NTRS)

    Borchers, R.; Gunawardena, R.; Rasmussen, R. A.

    1994-01-01

    The so-called 'Library of Background Air' at the Oregon Graduate Institute was used to determine the trend in volume mixing ratios of selected halogenated hydrocarbons in the time period 1977-1989. This library consists of background air samples most of them taken at Cape Meares (Oregon). For storage stainless steel containers are used. Tests have shown the gases under consideration to be stable in these containers. Analyses using a GC/MS-system were performed for the CFCs 11, 12, 12B1 (HALON 1211, CBrClF2), 22, 113, 114 and CH3Cl, CH3Br, CH3CCl3, CCl4. The advantage of this unique investigation: different aged air samples are analyzed at the same time with the same instrument. No calibrations or intercalibrations are needed. All data are presented in normalized mixing ratios versus time. We discuss the results, derive rate constants and present a formula to describe the nonlinear increases.

  3. 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.

  4. 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

  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. Vibrational Spectroscopy of Halogen Substituted Benzene Derivatives

    NASA Astrophysics Data System (ADS)

    Dwivedi, Y.; Rai, S. B.

    2008-11-01

    The absorption spectra of halogen substituted benzenes have been studied in its pure form in the 400-20000 cm-1 region. Large number of bands involving fundamental, C-H overtones and combination bands has been observed. Vibrational frequencies, anharmonicity constants and dissociation energies, for the C-H stretch vibrations have been determined using local mode model. The frequencies obtained are compared with the frequencies obtained theoretically using B3LYP/6-311G* method. Effect of hydrogen atom substitution by chlorine and bromine atoms has been studied by measuring changes in the vibrational frequency and bond length of the C-H bond. Frequency changes have been well correlated with the change in charge density on the carbon as well as chlorine atoms.

  7. 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.

  8. 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.

  9. Genotoxic effects in bacteria of the light emitted by halogen tungsten lamps having treated quartz bulbs.

    PubMed

    Camoirano, A; Bennicelli, C; Bagnasco, M; De Flora, S

    1999-04-26

    Traditional halogen tungsten lamps, which are extensively used worldwide for the illumination of indoor environments, have a quartz bulb which transmits not only visible light but also ultraviolet (UV) light. Due to the output of far-UV wavelengths, halogen lamps were found in previous studies to be potently genotoxic in bacteria, clastogenic in cultured human cells, and carcinogenic in hairless mice. This discovery prompted the launching of new halogen lamps, known as UV-Stop, UV-Block, or similar trade names, which have the quartz glass treated in such a way to reduce its permeability to UV radiation. Surprisingly, these lamps are advertised for attenuating discolouration of UV-sensitive materials, such as fabrics, paintings, works of art and furniture, whereas protection of the human skin from potential carcinogenic risks is overlooked. We tested forty-seven 12 V-powered lamps with treated quartz bulb, which were made available by five producers as blind-coded samples. After exposure to either 1000 lx for 30 min or 2500 lx for 60 min, the 50 W lamps from two producers were borderline mutagenic in strains TA100 and TA104 of S. typhimurium, and induced an evident and dose-related DNA damage in the E. coli strain CM871 (uvrA- recA- lexA-), as compared to its isogenic, DNA repair-proficient counterpart WP2. The 50 W lamps supplied by the other three producers also induced a significant genotoxic damage, but only after exposure for 60 min at illuminance levels of 2500 lx or higher. In calibration experiments, one of these three lamp brands was found to induce in 60 min a genotoxic damage which was equivalent to the one induced in just 55 s by a traditional halogen lamp. Therefore, the new types of lamps with treated quartz bulbs provide an appreciable step forward in the safety of halogen lamps, but some output of genotoxic UV radiations does still occur. Moreover, the lamps manufactured by different producers are not equally effective to this respect. By comparison

  10. 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

  11. Reactive halogen chemistry in volcanic plumes

    NASA Astrophysics Data System (ADS)

    Bobrowski, N.; von Glasow, R.; Aiuppa, A.; Inguaggiato, S.; Louban, I.; Ibrahim, O. W.; Platt, U.

    2007-03-01

    Bromine monoxide (BrO) and sulphur dioxide (SO2) abundances as a function of the distance from the source were measured by ground-based scattered light Multiaxis Differential Optical Absorption Spectroscopy (MAX-DOAS) in the volcanic plumes of Mt. Etna on Sicily, Italy, in August-October 2004 and May 2005 and Villarica in Chile in November 2004. BrO and SO2 spatial distributions in a cross section of Mt. Etna's plume were also determined by Imaging DOAS. We observed an increase in the BrO/SO2 ratio in the plume from below the detection limit near the vent to about 4.5 × 10-4 at 19 km (Mt. Etna) and to about 1.3 × 10-4 at 3 km (Villarica) distance, respectively. Additional attempts were undertaken to evaluate the compositions of individual vents on Mt. Etna. Furthermore, we detected the halogen species ClO and OClO. This is the first time that OClO could be detected in a volcanic plume. Using calculated thermodynamic equilibrium compositions as input data for a one-dimensional photochemical model, we could reproduce the observed BrO and SO2 vertical columns in the plume and their ratio as function of distance from the volcano as well as vertical BrO and SO2 profiles across the plume with current knowledge of multiphase halogen chemistry, but only when we assumed the existence of an "effective source region," where volcanic volatiles and ambient air are mixed at about 600°C (in the proportions of 60% and 40%, respectively).

  12. 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. PMID:19226745

  13. 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.

  14. Sorption Properties of Halogen Containing Graphene Oxide Frameworks

    NASA Astrophysics Data System (ADS)

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

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

  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. Quenched carbonaceous composite - Fluorescence spectrum compared to the extended red emission observed in reflection nebulae

    NASA Technical Reports Server (NTRS)

    Sakata, Akira; Wada, Setsuko; Narisawa, Takatoshi; Asano, Yoichi; Iijima, Yutaka; Onaka, Takashi; Tokunaga, Alan T.

    1992-01-01

    The photoluminescence (fluorescence) of a film of the laboratory-synthesized quenched carbonaceous composite (filmy QCC) is shown to have a single broad emission feature with a peak wavelength that varies from 670 to 725 nm, and coincides with that of the extended red emission observed in reflection nebulae. The rapid decay of the filmy QCC red fluorescence in air and of the stable blue fluorescence of the filmy QCC dissolved in liquid Freon suggests that the red fluorescence originates from the interaction of active chemical species and aromatic components in the filmy QCC. A material similar in nature to that of the filmy QCC may be a major component of interstellar dust.

  17. 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.

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

    PubMed

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

    2013-01-01

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

  19. `Indicator' carbonaceous phyllite/graphitic schist in the Archean Kundarkocha gold deposit, Singhbhum orogenic belt, eastern India: Implications for gold mineralization vis-a-vis organic matter

    NASA Astrophysics Data System (ADS)

    Sahoo, P. R.; Venkatesh, A. S.

    2014-10-01

    Carbonaceous rocks in the form of graphitic schist and carbonaceous phyllite are the major host rocks of the gold mineralization in Kundarkocha gold deposit of the Precambrian Singhbhum orogenic belt in eastern India. The detection of organic carbon, essentially in the carbonaceous phyllite and graphitized schist within the Precambrian terrain, is noted from this deposit. A very close relationship exists between gold mineralization and ubiquitous carbonaceous rocks containing organic carbon that seems to play a vital role in the deposition of gold in a Precambrian terrain in India and important metallogenetic implications for such type of deposits elsewhere. However, the role played by organic matter in a Precambrian gold deposit is debatable and the mechanism of precipitation of gold and other metals by organic carbon has been reported elsewhere. Fourier transform infrared spectroscopy (FTIR) results and total organic carbon (TOC) values suggest that at least part of the organic material acted as a possible source for the reduction that played a significant role in the precipitation of gold. Lithological, electron probe analysis (EPMA), fluid inclusions associated with gold mineralization, Total Carbon (TC), TOC and FTIR results suggest that the gold mineralization is spatially and genetically associated with graphitic schist, carbonaceous phyllite/shale that are constituted of immature organic carbon or kerogen. Nano-scale gold inclusions along with free milling gold are associated with sulfide mineral phases present within the carbonaceous host rocks as well as in mineralized quartz-carbonate veins. Deposition of gold could have been facilitated due to the organic redox reactions and the graphitic schist and carbonaceous phyllite zone may be considered as the indicator zone.

  20. Organic free radicals and micropores in solid graphitic carbonaceous matter at the Oklo natural fission reactors, Gabon

    SciTech Connect

    Rigali, M.J.; Nagy, B.

    1997-01-01

    The presence, concentration, and distribution of organic free radicals as well as their association with specific surface areas and microporosities help characterize the evolution and behavior of the Oklo carbonaceous matter. Such information is necessary in order to evaluate uranium mineralization, liquid bitumen solidification, and radio nuclide containment at Oklo. In the Oklo ore deposits and natural fission reactors carbonaceous matter is often referred to as solid graphitic bitumen. The carbonaceous parts of the natural reactors may contain as much as 65.9% organic C by weight in heterogeneous distribution within the clay-rich matrix. The solid carbonaceous matter immobilized small uraninite crystals and some fission products enclosed in this uraninite and thereby facilitated radio nuclide containment in the reactors. Hence, the Oklo natural fission reactors are currently the subjects of detailed studies because they may be useful analogues to support performance assessment of radio nuclide containment at anthropogenic radioactive waste repository sites. Seven carbonaceous matter rich samples from the 1968 {+-} 50 Ma old natural fission reactors and the associated Oklo uranium ore deposit were studied by electron spin resonance (ESR) spectroscopy and by measurements of specific surface areas (BET method). Humic acid, fulvic acid, and fully crystalline graphite standards were also examined by ESR spectroscopy for comparison with the Oklo solid graphitic bitumens. With one exception, the ancient Oklo bitumens have higher organic free radical concentrations than the modem humic and fulvic acid samples. The presence of carbon free radicals in the graphite standard could not be determined due to the conductivity of this material. 72 refs., 7 figs., 1 tab.

  1. 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

  2. A naphthalimide-based fluorescent sensor for halogenated solvents.

    PubMed

    Dai, Li; Wu, Di; Qiao, Qinglong; Yin, Wenting; Yin, Jun; Xu, Zhaochao

    2016-02-01

    A fluorescent sensor for halogenated solvents termed AMN is reported. AMN shows strong fluorescence in most halogenated solvents (QE > 0.1) but weak fluorescence (QE<0.01) in most non-halogenated solvents. In chlorinated solvents, the fluorescence intensity decreased with the reduction of chlorine content. On the contrary, in brominated solvents the fluorescence intensity increased with the reduction of bromine content. It is worth mentioning that AMN displayed fluorescence emission centered at 520 nm in CCl4 with a quantum yield of 0.607, at 556 nm in CHCl3 with a quantum yield of 0.318, at 584 nm in CH2Cl2 with a quantum yield of 0.128, whereas in CHBr3 was centered at 441 nm with a quantum yield of 0.012. AMN was shown to have the ability to differentiate CCl4, CHCl3, CH2Cl2 and CHBr3 halogenated solvents. PMID:26691881

  3. CATALYTIC DEHYDROHALOGENATION: A CHEMICAL DESTRUCTION METHOD FOR HALOGENATED ORGANICS

    EPA Science Inventory

    Dehydrohalogenation shows potential as a means for converting certain halogenated organics in wastes to inorganic salts and gaseous aliphatic compounds. Dehydrohalogenation is a dehalogenation/elimination reaction that is initiated by a strong base. The resulting products are the...

  4. 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. PMID:27518595

  5. Hydrated interplanetary dust particle linked with carbonaceous chondrites?

    NASA Astrophysics Data System (ADS)

    Tomeoka, K.; Buseck, P. R.

    1985-03-01

    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.

  6. 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.

  7. Aqueous alteration in the Kaba CV3 carbonaceous chondrite

    NASA Technical Reports Server (NTRS)

    Keller, Lindsay P.; Buseck, Peter R.

    1990-01-01

    Results from TEM and SEM examinations of the Kaba CV3 carbonaceous chondrite are presented, showing that the chondrules and the matrix of Kaba have undergone pervasive low-temperature aqueous alteration, resulting in the formation of Fe-bearing saponite from glass and enstatite in chondrules, and from anhydrous silicates in matrix. The alteration products in Kaba were found to resemble those in other aqueously altered carbonaceous chondrites such as the Mokoia CV3 and in Orgueil CI chondrites and Y-82162 chondrites. However, Kaba lacks the abundant high-Al phyllosilicates, reported for CAIs from Mokoia, and the serpentine and ferrihydrite, found in Orgueil.

  8. 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.

  9. 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.

  10. 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. PMID:25769232

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Fluid/Melt Partition Coefficients Of Halogens In Basaltic Melt

    NASA Astrophysics Data System (ADS)

    Alletti, M.; Baker, D.; Scaillet, B.; Aiuppa, A.; Moretti, R.; Ottolini, L.

    2007-12-01

    Despite the importance of halogens (F, Cl) in volcanic degassing, solubility and fluid/melt partitioning of these elements have not been comprehensively studied in natural basaltic melts. Experimental determinations of halogen solubility in Mount Etna melts are lacking, despite this volcano being one of the most active and intensively monitored on Earth with an estimated output of thousands tonnes of halogens per day. In order to better understand halogen degassing, we present the results of a series of halogen partitioning experiments performed at different pressures (1-200 MPa), redox conditions (from Δ NNO = + 2 to Δ NNO = - 0.3) and fluid compositions. Experiments used a hawaiitic, glassy, alkaline basalt with Mg# = 0.59, sampled during the July 2001 eruption of Mount Etna. A series of experiments were conducted using H2O-NaCl or H2O-NaF solutions. The effect of CO2 in multi-component fluid H2O-CO2-NaCl or H2O-CO2-NaF was also investigated. The experimental run products were mostly glasses, but a few run products contained less than 10% crystals. The concentration of halogens in the fluid phase after the experiment was calculated from mass balance, and the partition coefficients for both Cl and F at the studied conditions determined. Using these measurements and thermodynamical models, the dependence of these partition coefficients on the fugacities of various gaseous species was investigated.

  17. 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

  18. 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. PMID:23246760

  19. Non-halogen Flame retardant High Impact Polystyrene Composites

    NASA Astrophysics Data System (ADS)

    Rafailovich, Miriam; Si, Mayu; Sokolov, Jonathan; Otaigbe, Joshia; Yudin, Vladimir E.

    2006-03-01

    In recent years, driven by the health issues and the incurred banning policy of bromine compounds, it is a great demand to find an alternate to replace brominated compounds in polymer flame retardant industry. High impact polystyrene (HIPS), a popular materials widely used for electrical appliances and electronic instruments, attracts extensive attention for its dominant flame retardant agent, decabromodiphenyl ether. Here we propose a novel idea to prepare non-halogen HIPS self-extinguishing composites based on the combination of phosphorus compounds and clay. The combustion behavior was thoroughly investigated by UL 94 V-0, LOI, and cone calorimeter measurements. The addition of Cloisite 20A dramatically decreases the value of LOI and the resulted HIPS composites could not pass UL 94 V-0. On the other hand, the introduction of thermal stable clay significantly increases the value of LOI and the corresponding HIPS composites can successfully self-extinguish. These results strongly demonstrate that the thermal stability of clay is the key factor to determine the final flame retardant performance. The synergy between the clay and phosphorus compounds is further studied.

  20. Fossils of Cyanobacteria in CI1 Carbonaceous Meteorites: Implications to Life on Comets, Europa and Enceladus

    NASA Astrophysics Data System (ADS)

    Hoover, Richard B.

    2011-10-01

    Environmental (ESEM) and Field Emission Scanning Electron Microscopy (FESEM) investigations of the internal surfaces of the CI1 Carbonaceous Meteorites have yielded images of large complex filaments. The filaments have been observed to be embedded in freshly fractured internal surfaces of the stones. They exhibit recognizable features (e.g., the size and size ranges of the internal cells and their location and arrangement within sheaths) that are diagnostic of known genera and species of filamentous trichomic cyanobacteria and other trichomic prokaryotes (such as filamentous sulfur bacteria). ESEM and FESEM studies of living and fossil cyanobacteria show features similar to the filaments found in the meteorites -- uniseriate and multiseriate, branched or unbranched, isodiametric or tapered, polarized or unpolarized filaments with trichomes encased within thin or thick external sheaths. Some of the filaments found in the CI1 meteorites also exhibit specialized cells and structures used by cyanobacteria for reproduction (baeocytes, akinetes and hormogonia), nitrogen fixation (basal, intercalary or apical heterocysts), attachment (pili or fimbriae) or indicative of oscillatoria type locomotion (escaped or coiling hormogonia and flattened and coiled empty sheaths). Energy dispersive X-ray Spectroscopy (EDS) studies indicate that the Orgueil meteorite filaments are typically carbon-rich sheaths infilled with magnesium sulfate and other minerals characteristic of the CI1 carbonaceous meteorites. However, the size, structure, detailed morphological characteristics and chemical compositions of the meteorite filaments are not consistent with known species of abiotic minerals. The nitrogen content of the meteorite filaments are almost always below the detection limit of the EDS detector. EDS analysis of living and dead biological materials (e.g., filamentous cyanobacteria; bacteria, mummy and mammoth hair and tissues, and fossils of cyanobacteria, trilobites and insects in