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Sample records for carbonaceous materials halogen

  1. The use of halogen carriers and buffers in the spectrographic determination of boron in carbonaceous materials and their combustion products

    International Nuclear Information System (INIS)

    For the determination of boron in carbonaceous materials (high purity graphite, coals and their processed products, such as ashes and slags from thermoelectric power plants) by atomic emission spectroscopy with direct current are excitation and photographic recording, the behaviour of the analyte in the presence of halide compounds or spectrochemical buffers has been studied. Among the halides, cupric fluoride at a low concentration (2%) becomes very suitable for the graphite analysis, and at a higher concentration (25 %) for coals, being necessary in this case to carry out a dilution of samples with graphite. Strontium carbonate as a spectrochemical buffer allows to analyse satisfactorily coals and their combustion products. (Author) 13 refs

  2. Terminology of carbonaceous materials

    Energy Technology Data Exchange (ETDEWEB)

    Bagrov, G.N.; Nagornyi, V.G.; Ostrovskii, V.S.

    1986-07-01

    The need is discussed to standardize definition of carbonaceous material. Terms related to carbonaceous materials and their products are selected and analyzed. Diagramatic representation is given of relationships between carbonaceous materials. Carbon has two forms of structure, cubic and hexagonal, characterized by sp/sup 3/-hybrid groups of atoms forming spatial system of tetrahedral bonds. Hexagonal form of carbon is represented by natural materials such as graphite, shungite, anthracite and a number of artificial materials obtained during thermal treatment of organic substances at temperatures above carbonization temperature. 4 references.

  3. Distilling solid carbonaceous materials

    Energy Technology Data Exchange (ETDEWEB)

    Ainscow, J.W.H.

    1928-11-19

    Carbonaceous materials such as coal or oil shale are distilled by being passed in a continuous stream through a retort heated externally and at temperatures increasing from the inlet to the outlet end, the distillates being taken off through openings in the retort wall.

  4. Distillation of carbonaceous material

    Energy Technology Data Exchange (ETDEWEB)

    Ainscow, J.W.H.

    1936-10-03

    To recover hydrocarbon products by distillation of carbonaceous material in a plurality of horizontal zones maintained at different temperatures, a retort has a plurality of superimposed (3) retort chambers, the uppermost being in communication at one end with a hopper and at the other end through coupled junction not shown with one end of the next lower chamber, whose opposite end communicates with lowermost chamber, the other end of which has a sealed discharge passage, tank, and conveyor not shown. Each retort chamber has stirring and conveying means consisting of helical blades (2) attached to radial arms on shaft mounted in water cooled bearings and driven through suitably mounted sprocket wheels and chains not shown. Each retort chamber has a gas dome, with pyrometer tube, and off-take connected to a common main opening into a dust eliminator which in turn connects with a plurality of vertical condensation towers of known construction, maintained at different temperatures by means of steam from a superheater not shown situated in one retort chamber. The retort heating gases pass from the furnace via zig-zag, (three) baffles under and around each retort chamber to a flue not shown.

  5. Carbonaceous Material in Extraterrestrial Matter

    Science.gov (United States)

    Martins, Zita

    2015-08-01

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

  6. Halogenated arsenenes as Dirac materials

    Science.gov (United States)

    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. The use of halogen carriers and buffers in the spectrographic determination of boron in carbonaceous materials and their combustion products; Empleo de agentes halogenantes y reguladores en la determinacion espectrografica de Boro en carbones y productos derivados

    Energy Technology Data Exchange (ETDEWEB)

    Rucandio, M. I.; Martin, M.; Roca, M.

    1992-07-01

    For the determination of boron in carbonaceous materials (high purity graphite, coals and their processed products, such as ashes and slags from thermoelectric power plants) by atomic emission spectroscopy with direct current are excitation and photographic recording, the behaviour of the analyte in the presence of halide compounds or spectrochemical buffers has been studied. Among the halides, cupric fluoride at a low concentration (2%) becomes very suitable for the graphite analysis, and at a higher concentration (25 %) for coals, being necessary in this case to carry out a dilution of samples with graphite. Strontium carbonate as a spectrochemical buffer allows to analyse satisfactorily coals and their combustion products. (Author) 13 refs.

  8. Photolytic process for gasification of carbonaceous material

    International Nuclear Information System (INIS)

    Process and apparatus are disclosed for converting carbon dioxide to carbon monoxide by subjecting the carbon dioxide to radiation in the presence of carbonaceous material such as coal to form carbon monoxide. The preferred form of radiation is solar energy, and the process is preferably carried out in an atmosphere essentially free of oxygen. The invention also includes subjecting carbon monoxide to radiation to form purified carbon and useful heat energy. The two procedures can be combined into a single process for converting solar or other energy into useful thermal energy with the production of useful products. The reactor apparatus is specifically designed to carry out the radiation-induced conversions. Coal can be desulfurized and its caking characteristics altered by solar radiation in the presence of suitable gases. 3 figures

  9. Detection of carbonaceous material in Naga Bhasma

    Directory of Open Access Journals (Sweden)

    S K Singh

    2012-01-01

    Full Text Available Traditional medicines have maintained their popularity in all regions of the developing world and are being adopted increasingly by people worldwide. Indian traditional system of medicine Ayurveda make use of unique metallic-herbal preparations (called Bhasma which involves different processing steps including repeated steps of calcination of metal in the presence of natural precursor (herbal juices, decoctions, and powders, etc. It has been recently established that Bhasma contains nano/sub-micron size particles and different nutrient elements. However, the role and the end product of the raw materials, especially the herbal parts, used during the synthesis of the drug (Bhasma is one of the important but unanswered problems in such medicinal preparations. Present work on Naga Bhasma is an attempt to understand the role of natural precursors in detail. Our results on infrared, Raman and X-ray photoelectron spectroscopy along with thermal measurements identify the presence of carbonaceous material (hydrogenated amorphous carbon in the drug along with other compounds. In addition, this work also suggests the science and mechanism behind such complex preparations which could help in standardization of such medicines.

  10. In situ remediation of contaminated sediments using carbonaceous materials

    NARCIS (Netherlands)

    Rakowska, M.I.; Kupryianchyk, D.; Harmsen, J.; Grotenhuis, J.T.C.; Koelmans, A.A.

    2012-01-01

    Carbonaceous materials (CM), such as activated carbons or biochars, have been shown to significantly reduce porewater concentrations and risks by binding hydrophobic organic compounds (HOCs) present in aquatic sediments. In the present study, the authors review the current state-of-the-art use of CM

  11. Immobilization of pentachlorophenol in soil using carbonaceous material amendments

    Energy Technology Data Exchange (ETDEWEB)

    Wen Bei [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Shuangqing Road, Haidian District, Beijing 100085 (China)], E-mail: bwen@rcees.ac.cn; Li Ruijuan; Zhang Shuzhen [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Shuangqing Road, Haidian District, Beijing 100085 (China); Shan Xiaoquan [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Shuangqing Road, Haidian District, Beijing 100085 (China)], E-mail: xiaoquan@rcees.ac.cn; Fang Jing; Xiao Ke [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Shuangqing Road, Haidian District, Beijing 100085 (China); Khan, Shahamat U. [Department of Chemistry and Biochemistry, MSN 3E2, George Mason University, 4400 University Drive, Fairfax, VA 22030-4444 (United States)

    2009-03-15

    In this study, three pentachlorophenol (PCP) laboratory-spiked and one field-contaminated soil were amended with 2.0% char, humic acid (HA) and peat, respectively. The amended soils were aged for either 7 or 250 days. After amendment, CaCl{sub 2} extractability of PCP was significantly decreased. Desorption kinetics indicated that the proposed amendment could lead to a strong binding and slow desorption of PCP in soils. Amendment with char reduced the bioaccumulation factor (BAF) of PCP most significantly for earthworms (Eisenia fetida) in all soils studied. The results of both physicochemical and biological tests suggested that amendment reduced PCP bioavailability quickly and enduringly, implying that carbonaceous material amendment, especially char amendment, was a potentially attractive in situ remediation method for sequestration of PCP in contaminated soil. - Carbonaceous material amendment was a potential in situ remediation method for pentachlorophenol contaminated soil.

  12. The kinetic parameters of carbonaceous materials activated with potassium hydroxide

    Energy Technology Data Exchange (ETDEWEB)

    Yong, Z.; Han, B.X.

    2000-07-01

    On the basis of microspore formation in carbonaceous materials, the activation energy for the potassium hydroxide activation of Chinese petroleum coke and coal has been deduced theoretically as dB(O)/dt = A exp(-E(a)) is an element of/RT), where is an element of is the formation energy for the metastable solid formed at the activation temperature. The kinetic parameters (frequency factor, A, and apparent activation energy, E(a) were calculated from this equation as being 5.319 mg/(g min), 36.51 kJ/mol and 6.64 mg/(g min), 49.46 kJ/mol, respectively, for the two carbonaceous materials studied.

  13. Active coke: Carbonaceous materials as catalysts for alkane dehydrogenation

    OpenAIRE

    McGregor, J.; Huang, Z; Parrott, E.; Zeitler, J.; Nguyen, K.; Rawson, J.; Carley, A; Hansen, T.; Tessonnier, J.; Su, D.; Teschner, D; Vass, E.; Knop-Gericke, A.; Schlögl, R.; Gladden, L.

    2010-01-01

    The catalytic dehydrogenation (DH) and oxidative dehydrogenation (ODH) of light alkanes are of significant industrial importance. In this work both carbonaceous materials deposited on VOx/Al2O3 catalysts during reaction and unsupported carbon nanofibres (CNFs) are shown to be active for the dehydrogenation of butane in the absence of gas-phase oxygen. Their activity in these reactions is shown to be dependent upon their structure, with different reaction temperatures yielding structurally dif...

  14. Biomass-derived carbonaceous materials as components in wood briquettes

    Energy Technology Data Exchange (ETDEWEB)

    Stengl, S.; Koch, C.; Stadlbauer, E.A.; Scheer, J. [Univ. of Applied Sciences, THM Campus Giessen, Giessen (Germany); Weber, B. [Instituto de Ingenieria de la Universidad Nacional Autonoma de Mexico (UNAM), Coyoacan (Mexico); Strohal, U.; Fey, J. [Strohal Anlagenbau, Staufenberg (Germany)

    2012-11-01

    The present paper describes a briquette composed of a substantial amount of wooden biomass and up to 35% of carbonaceous materials derived from biogenic residues. The cellulosic component may be a mixture of any wooden residue. Suitable substrates for the carbonaceous fraction are vegetation wastes from land management or agriculture. Depending on physical and chemical nature of the substrate, Hydrothermal Carbonisation (HTC) or Low Temperature Conversion (LTC) may be used to produce the carbonaceous part of the briquette. HTC turns wet biomass at temperatures around 200 deg C in an autoclave into lignite whereas LTC treatment at 400 deg C and atmospheric pressure produces black coal. This is manifested by a molar ratio of 0.1 {<=} H/C (LTC) {<=} 0.7; 0.05{<=} O/C (LTC) {<=} 0.4 and 0.7 < H/C (HTC) <1.5 ; 0.2< O/C (HTC) < 0.5. Solid state {sup 13}C-NMR confirms these findings showing a strong absorption band for sp{sup 2}-hybridized carbon atoms at chemical shifts of 100 ppm und 165 ppm for LTC biochar. Depending on the substrate, HTC gives rise to an increase in the specific calorific value (MJ/kg) by a factor of {Psi} {approx} 1.2 - 1.4; LTC by 1.5 - 1.8. In addition ash melting points are significantly increased; in case of wheat straw by about 200 deg C. Compacted products may have a cylindrical or rectangular profile.

  15. The structural evolution of carbonaceous material during metamorphism : a geothermometer

    Science.gov (United States)

    Beyssac, O.; Goffe, B.; Brunet, F.; Bollinger, L.; Avouac, J.; Rouzaud, J.

    2003-12-01

    With increasing metamorphic temperature, the organic matter present in sedimentary rocks is progressively transformed into graphite (graphitization). The degree of organization of this carbonaceous material (CM) as characterized by Raman spectroscopy (RSCM), can be used as a geothermometer which yields the maximum temperature reached during the metamorphic cycle (Beyssac et al., 2002). We used this RSCM geothermometer to map the maximum metamorphic temperatures through the Lesser Himalaya (LH) in Nepal. This study provides a large dataset (80 samples) to estimate uncertainty of this method and to ascertain its reliability by comparison with conventional petrological investigations. We show that the RSCM geothermometer might be used to detect inter-samples temperature variations as small as 10° C or so, but absolute temperatures are only loosely determined to +/- 50° C due to the uncertainty on the calibration. This successful application of the RSCM geothermometer confirms that, at the timescale of regional metamorphism (several My), the transformation of CM is mainly controlled by temperature. However, laboratory investigations suggest that, in addition to temperature, pressure should also play a role (Beyssac et al. 2003). As a matter of fact, high degree of organizations encountered in natural CM cannot be reproduced in laboratory without pressure, even at temperatures as high as 3000° C. In addition to the data acquired on natural CM, we will discuss laboratory experiments performed up to 8 GPa which show that (1) a few kbar of hydrostatic pressure are required to initiate microtextural and subsequent structural transformations within CM and (2) the overall effect of increasing pressure is to speed up graphitization process. Beyssac, O., Goffe, B., Chopin, C., and Rouzaud, J.N., 2002, Raman spectra of carbonaceous material in metasediments: a new geothermometer. Journal of Metamorphic Geology, 20, 859-871. Beyssac, O., Brunet, F., Petitet, J.P., Goffe, B

  16. Delivery of Dark Material to Vesta via Carbonaceous Chondritic Impacts

    CERN Document Server

    Reddy, Vishnu; O'Brien, David P; Nathues, Andreas; Cloutis, Edward A; Durda, Daniel D; Bottke, William F; Bhatt, Megha U; Nesvorny, David; Buczkowski, Debra; Scully, Jennifer E C; Palmer, Elizabeth M; Sierks, Holger; Mann, Paul J; Becker, Kris J; Beck, Andrew W; Mittlefehldt, David; Li, Jian-Yang; Gaskell, Robert; Russell, Christopher T; Gaffey, Michael J; McSween, Harry Y; McCord, Thomas B; Combe, Jean-Philippe; Blewett, David

    2012-01-01

    NASA's Dawn spacecraft observations of asteroid (4) Vesta reveal a surface with the highest albedo and color variation of any asteroid we have observed so far. Terrains rich in low albedo dark material (DM) have been identified using Dawn Framing Camera (FC) 0.75 {\\mu}m filter images in several geologic settings: associated with impact craters (in the ejecta blanket material and/or on the crater walls and rims); as flow-like deposits or rays commonly associated with topographic highs; and as dark spots (likely secondary impacts) nearby impact craters. This DM could be a relic of ancient volcanic activity or exogenic in origin. We report that the majority of the spectra of DM are similar to carbonaceous chondrite meteorites mixed with materials indigenous to Vesta. Using high-resolution seven color images we compared DM color properties (albedo, band depth) with laboratory measurements of possible analog materials. Band depth and albedo of DM are identical to those of carbonaceous chondrite xenolith-rich howar...

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

    Science.gov (United States)

    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

  18. Origins of interstellar and solar system: Carbonaceous materials

    Science.gov (United States)

    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.

  19. On thermodynamics of methane+carbonaceous materials adsorption

    KAUST Repository

    Rahman, Kazi Afzalur

    2012-01-01

    This study presents the theoretical frameworks for the thermodynamic quantities namely the heat of adsorption, specific heat capacity, entropy, and enthalpy for the adsorption of methane onto various carbonaceous materials. The proposed theoretical frameworks are developed from the rigor of thermodynamic property surfaces of a single component adsorbate-adsorbent system and by incorporating the micropore filling theory approach, where the effect of adsorbed phase volume is considered. The abovementioned thermodynamic properties are quantitatively evaluated from the experimental uptake data for methane adsorption onto activated carbons such as Maxsorb III at temperatures ranging from 120 to 350 K and pressures up to 25 bar. Employing the proposed thermodynamic approaches, this paper shows the thermodynamic maps of the charge and discharge processes of adsorbed natural gas (ANG) storage system for understanding the behaviors of natural gas in ANG vessel. © 2011 Elsevier Ltd. All rights reserved.

  20. Proton catalysis with active carbons and partially pyrolyzed carbonaceous materials

    Institute of Scientific and Technical Information of China (English)

    V. V. Strelko; S. S. Stavitskaya; Yu. I. Gorlov

    2014-01-01

    The development of environmentally friendly solid acid catalysts is a priority task. Highly oxidized activated carbon and their ion-substituted (saline) forms are effective proton transfer catalysts in esterification, hydrolysis, and dehydration, and thus are promising candidates as solid acid cata-lysts. Computations by the ab initio method indicated the cause for the enchanced acidity of the carboxylic groups attached to the surface of highly oxidized carbon. The synthesis of phosphorilated carbon was considered, and the proton transfer reactions catalyzed by them in recent studies were analyzed. The development of an amorphous carbon acid catalyst comprising polycyclic carbonaceous (graphene) sheets with-SO3H,-COOH and phenolic type OH-groups was carried out. These new catalysts were synthesized by partial pyrolysis and subsequent sulfonation of carbohydrates, polymers, and other organic compounds. Their high catalytic activities in proton transfere reactions including the processing of bio-based raw materials was demonsrated.

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

    Science.gov (United States)

    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.

  2. Functional Group Compositions of Carbonaceous Materials of Hayabusa-Returned Samples

    Science.gov (United States)

    Yabuta, H.; Uesugi, M.; Naraoka, H.; Ito, M.; Kilcoyne, D.; Sandford, S. A.; Kitajima, F.; Mita, H.; Takano, Y.; Yada, T.; Karouji, Y.; Ishibashi, Y.; Okada, T.; Abe, M.

    2014-09-01

    We have analyzed the functional group compositions of the carbonaceous materials of Hayabusa-returned samples by STXM-XANES, in order to identify whether the materials are terrestrial or extraterrestrial.

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

    Science.gov (United States)

    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

  4. Analyses and characterization of fossil carbonaceous materials for silicon production

    Energy Technology Data Exchange (ETDEWEB)

    Myrvaagnes, Viktor

    2008-01-15

    Production of high silicon alloys is carried out in submerged arc furnaces by reduction of silicon bearing oxides (typically quartz) with carbon materials. Carbonaceous materials like coal, coke, charcoal and woodchips are commonly used as reduction materials in the process. Primarily based on historical prices of charcoal compared to fossil reduction materials, the Norwegian Ferroalloy Industry has mostly been using coal and coke (char) as the source of carbon. From a process point of view, the most important role of the carbonaceous material is to react with SiO gas to produce SiC. The ability of the reduction materials to react with SiO gas can be measured and the value is recognized as the reactivity of the carbon source. Reactivity is one of the most important parameters in the smelting process and is commonly acknowledged to strongly affect both productivity and specific energy consumption. The main objectives of this work has been to establish methods to characterize the material properties of fossil carbonaceous reduction materials used in the silicon process and to evaluated how these properties affect the reactivity towards SiO gas. In order to accomplish these objectives, three run of mine (ROM) single seam coals which are particularly well suited for ferroalloy production were selected. Two Carboniferous coals from USA (Blue Gem) and Poland (Staszic) with similar rank, but significantly different composition as well as a Permian coal from Australia (Peak Downs) have been characterized by chemical- and petrographical methods. Blue Gem is a homogeneous coal, low in mineral inclusions and macerals of the inertinite group and determined to have a random vitrinite reflectance of 0.71 %. Staszic has a similar reflectance of vitrinite (0.72 %), but is determined to be a very inhomogeneous coal with both inertinite macerals and minerals embedded in the vitrinite matrix. Peak Downs has a random reflectance of vitrinite of 1.32 % and is hence the coal sample of

  5. Analyses and characterization of fossil carbonaceous materials for silicon production

    Energy Technology Data Exchange (ETDEWEB)

    Myrvaagnes, Viktor

    2008-01-15

    Production of high silicon alloys is carried out in submerged arc furnaces by reduction of silicon bearing oxides (typically quartz) with carbon materials. Carbonaceous materials like coal, coke, charcoal and woodchips are commonly used as reduction materials in the process. Primarily based on historical prices of charcoal compared to fossil reduction materials, the Norwegian Ferroalloy Industry has mostly been using coal and coke (char) as the source of carbon. From a process point of view, the most important role of the carbonaceous material is to react with SiO gas to produce SiC. The ability of the reduction materials to react with SiO gas can be measured and the value is recognized as the reactivity of the carbon source. Reactivity is one of the most important parameters in the smelting process and is commonly acknowledged to strongly affect both productivity and specific energy consumption. The main objectives of this work has been to establish methods to characterize the material properties of fossil carbonaceous reduction materials used in the silicon process and to evaluated how these properties affect the reactivity towards SiO gas. In order to accomplish these objectives, three run of mine (ROM) single seam coals which are particularly well suited for ferroalloy production were selected. Two Carboniferous coals from USA (Blue Gem) and Poland (Staszic) with similar rank, but significantly different composition as well as a Permian coal from Australia (Peak Downs) have been characterized by chemical- and petrographical methods. Blue Gem is a homogeneous coal, low in mineral inclusions and macerals of the inertinite group and determined to have a random vitrinite reflectance of 0.71 %. Staszic has a similar reflectance of vitrinite (0.72 %), but is determined to be a very inhomogeneous coal with both inertinite macerals and minerals embedded in the vitrinite matrix. Peak Downs has a random reflectance of vitrinite of 1.32 % and is hence the coal sample of

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

    Science.gov (United States)

    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. Preparation and characterization of a new carbonaceous material for electrochemical systems

    Directory of Open Access Journals (Sweden)

    ZI JI LIN

    2010-02-01

    Full Text Available A new carbonaceous material was successfully prepared by the py-rolysis of scrap tire rubber at 600 °C under a nitrogen atmosphere. The physical characteristics of the prepared carbonaceous material were studied by scanning electron microscopy (SEM, X-ray powder diffraction (XRD and X-ray photoelectron spectroscopy (XPS. It was proved that the carbonaceous material had a disordered structure and spherical morphology with an average particle size about 100 nm. The prepared carbonaceous material was also used as electrodes in electrochemical systems to examine its electrochemical performances. It was demonstrated that it delivered a lithium insertion capacity of 658 mA h g-1 during the first cycle with a coulombic efficiency of 68 %. Cyclic voltammograms test results showed that a redox reaction occurred during the cycles. The chemical diffusion coefficient based on the impedance diagram was about 10-10 cm2 s-1. The pyrolytic carbonaceous material derived from scrap tire rubber is therefore considered to be a potential anode material in lithium secondary batteries or capacitors. Furthermore, it is advantageous for environmental protection.

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

    Science.gov (United States)

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

    2010-07-19

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

  9. Liquefaction of solid carbonaceous material with catalyst recycle

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  11. Raman Spectroscopy of Carbonaceous Materials geothermometry: a reliable method to investigate thermal history of foreland basins.

    OpenAIRE

    Lahfid, Abdeltif; Lacroix, Brice; Hoareau, Guilhem; Delchini, Sylvain; Bourrat, Xavier

    2014-01-01

    To investigate the thermal evolu-tion of foreland basins, many classical methods includ-ing clay mineralogy, vitrinite reflectance, fluid inclu-sions and illite cristalinity are used. These methods are probably not perfectly reliable taken individually, but provides a robust estimate when they give a coherent results. Raman Spectroscopy of Carbonaceous Materials (RSCM) could be an alternative method to constrain paleotempeartures of rocks. This method has been calibrated firstly in the range ...

  12. Key parameters when developing carbonaceous materials for catalytic wet peroxide oxidation

    OpenAIRE

    Ribeiro, Rui; Silva, Adrián; Pastrana-Martínez, Luisa; Figueiredo, José; Faria, Joaquim; Gomes, Helder

    2014-01-01

    Catalytic wet peroxide oxidation (CWPO) is an advanced oxidation process, operated using simple equipment and mild operating conditians, in which highly oxidizing hydraxyl radicaIs (HO') are generated fram the catalytic decompasition af hydrogen peroxide (H,O,) [L 2). Sinee the report of Lüeking el ai. in 1998 [3], the develapment af suitab-Ie -carbonaceous materials (without any added metal phase) for CWPO has been intensively explored [4). lhe influenee of struetUfal and surr...

  13. Carbon Paste Electrodes Made from Different Carbonaceous Materials: Application in the Study of Antioxidants

    OpenAIRE

    Constantin Apetrei; Maria Luz Rodriguez-Mendez; Jose Antonio De Saja; Irina Mirela Apetrei

    2011-01-01

    This work describes the sensing properties of carbon paste electrodes (CPEs) prepared from three different types of carbonaceous materials: graphite, carbon microspheres and carbon nanotubes. The electrochemical responses towards antioxidants including vanillic acid, catechol, gallic acid, L-ascorbic acid and L-glutathione have been analyzed and compared. It has been demonstrated that the electrodes based on carbon microspheres show the best performances in terms of kinetics and stability, wh...

  14. Anomalous Lithium Adsorption Propensity of Monolayer Carbonaceous Materials: A Density Functional Study

    Indian Academy of Sciences (India)

    SWATI PANIGRAHI; DEIVASIGAMANI UMADEVI; G NARAHARI SASTRY

    2016-10-01

    Interaction between lithium and carbonaceous materials has gained a lot of importance in lithium battery industry as an important source of energy and storage. The size, dimension, curvature and chirality of the carbonaceous materials are found to be very important factors in controlling the sequential binding oflithium. The propensity of lithium binding to the monolayer carbonaceous materials has been studied using Density functional theory (DFT). Structural and energetical parameters of the complexes have been analyzed through interaction energy, sequential energy, Mulliken population analysis and spin density distribution. Spindensity of odd Li doped systems reveals the preferences for addition of further lithium atoms on the surface. Upon analyzing the interaction energy in armchair carbon nanotubes (A-CNTs) and zigzag carbon nanotubes (Z-CNTs), it has been observed that external and internal surfaces of CNTs have contrasting binding preferences for sequential addition of Li atoms. Internal surface is found to be more feasible site for lithium adsorption than the external surface. This current study provides fundamental understanding of the mechanism of lithium adsorption in lithium battery.

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

    Directory of Open Access Journals (Sweden)

    Mohamed E. Mahmoud

    2012-01-01

    Full Text Available 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.

  16. Low extraction recovery of fullerene from carbonaceous geological materials spiked with C{sub 60}

    Energy Technology Data Exchange (ETDEWEB)

    Jehlicka, J.; Frank, O.; Hamplova, V.; Pokorna, Z.; Juha, L.; Bohacek, Z.; Weishauptova, Z. [Charles University, Prague (Czech Republic). Inst. for Geochemical Mineral & Mineral Resources

    2005-08-01

    Soxhlet extraction, sonication, and ultracritical extraction were tested with respect to their capacity to extract fullerenes from natural carbonaceous materials. Toluene solutions with various contents of synthetic C{sub 60} were added to powdered graphite, shungite, bituminous coal, and quartz, with final C{sub 60} concentration 0.1-100 ppm. The C{sub 60}-doped materials were leached in three kinds of extraction apparatus. High-performance liquid chromatography (HPLC) was used to analyse the fullerene content in the obtained toluene extracts. Surprisingly low yields of the C{sub 60} extraction (most of them well below 5%) were determined for all the carbonaceous matrices and all the extraction techniques employed in the fullerene isolation. This finding has serious consequences for better understanding of the reported fullerene occurrence in the geological environment, because a greatly limited extraction yield can be responsible for some negative results of fullerene analyses in various geological samples. Both fullerene stability in solvents and fullerene interaction with the surfaces of geological carbonaceous matrices are discussed to explain the obtained results.

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

    Science.gov (United States)

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

    2010-04-01

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

  18. Halogenation of microcapsule walls

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  20. Removal of blue indigo and cadmium present in aqueous solutions using a modified zeolitic material and an activated carbonaceous material

    International Nuclear Information System (INIS)

    In the last years the use of water has been increased substantially, it has been also altered its quality as a result of human activities such as mining, industrial activities and others. Water pollution caused by dyes and heavy metals has adverse effects on the environment, since both pollutants are very persisten even after conventional treatments. Denim blue and cadmium are not biodegradable. There is a growing interest in finding new, efficient and low cost alternative materials to remove such pollutants from the aqueous medium. The purpose of this work was to evaluate a modified zeolitic tuff and an activated carbonaceous material obtained from the pyrolysis of sewage sludge for the removal of denim blue and cadmium. The zeolitic material was modified with Na+ and Fe3+ solutions to improve its sorption properties for the removal of cadmium and denim blue, respectively. Carbonaceous material was treated with 10% HCl solution to remove ashes. Both materials were characterized by scanning electron microscopy and elemental analysis (EDS), specific surface areas (Bet), thermogravimetric analysis, infrared spectroscopy and X-ray diffraction. Simultaneously, the denim blue dye was characterized by infrared spectroscopy and its pKa value was determined, these data allowed the determination of its chemical properties and its acid-base behavior in solution. In the content of this work the term indigo blue was changed by denim blue, as it corresponds to the commercial name of the dye. To assess the sorption capacity of sorbents, the sorption kinetics and sorption isotherms in batch system were determined; the results were fitted to mathematical models such as the pseudo-first order, pseudo second order and second order to describe the sorption kinetics and the Langmuir, Freundlich and Langmuir-Freundlich isotherms to describe sorption processes. The results show that the most efficient material to remove denim blue from aqueous solutions is the carbonaceous material, and

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

    Directory of Open Access Journals (Sweden)

    Magdalena Hofman

    2012-01-01

    Full Text Available 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.

  2. Sorption of indigo carmine by a Fe-zeolitic tuff and carbonaceous material from pyrolyzed sewage sludge

    International Nuclear Information System (INIS)

    Indigo carmine removal from aqueous solution has been evaluated using Fe-zeolitic tuff and carbonaceous material from pyrolyzed sewage sludge treated with HCl (CM). The adsorbents were characterized by scanning electron microscopy, BET surface area and X-ray diffraction. Sorption kinetics and isotherms were determined and the adsorption behaviors analyzed. Kinetic pseudo-second order and Langmuir-Freundlich models were successfully applied to the experimental results obtained with the Fe-zeolitic material, while kinetic first order and Langmuir-Freundlich models were applied to the results from the carbonaceous materials. This indicates mechanisms of chemisorption and physic sorption, respectively, on the heterogeneous materials. The results indicate that the carbonaceous material from the pyrolysis of sewage sludge (sorption capacity 92.83 mg/g) is a better adsorbent of indigo carmine than the zeolitic material (sorption capacity 32.83 mg/g).

  3. CO2 Separation and Capture Properties of Porous Carbonaceous Materials from Leather Residues

    Directory of Open Access Journals (Sweden)

    Ana Arenillas

    2013-10-01

    Full Text Available Carbonaceous porous materials derived from leather skin residues have been found to have excellent CO2 adsorption properties, with interestingly high gas selectivities for CO2 (α > 200 at a gas composition of 15% CO2/85% N2, 273K, 1 bar and capacities (>2 mmol·g−1 at 273 K. Both CO2 isotherms and the high heat of adsorption pointed to the presence of strong binding sites for CO2 which may be correlated with both: N content in the leather residues and ultrasmall pore sizes.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

  6. A new star(ch is born: Starbons as biomass-derived mesoporous carbonaceous materials

    Directory of Open Access Journals (Sweden)

    P.S. Shuttleworth

    2012-06-01

    Full Text Available Porous carbon materials are present in a wide rangeof technologically important applications, includingseparation science, heterogeneous catalyst supports,water purification filters, stationary phase materials,as well as the developing future areas of energygeneration and storage applications. Hard templateroutes to ordered mesoporous carbons are wellestablished, but whilst offering different mesoscopictextural phases, the surface of the material is difficultto chemically post-modify and processing is energy,resource and step intensive. The production of carbonmaterials from biomass (i.e. sugars orpolysaccharides is a relatively new but rapidlyexpanding research area. In this manuscript, wedescribe the preparation, properties and applicationsof a novel family of polysaccharide-derivedmesoporous carbonaceous materials derived fromrenewable resources (namely polysaccharidesdenoted as Starbons®.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  9. Kocite /sup R/ materials for electrocatalysts novel approach to carbonaceous supports

    International Nuclear Information System (INIS)

    Kocite materials are composite structures of a thin film semiconducting pyropolymer chemically bonded to the surface of a high-surface-area alumina support. For use in H3PO4 fuel cells, the alumina substrate is leached from the composite structure leaving a high-surface-area carbonaceous support, which is then impregnated with catalytically active materials. With process modification, alterations of the pore structure or pyropolymer structure of these supports can be achieved, producing different types of Kocite electrocatalysts. In this paper, the preparation, characterization and testing of such Kocite electrocatalysts will be reviewed, including results on support corrosion, catalytic metal agglomeration during electrocatalyst aging and the performance in model H3PO4 fuel cells

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

    Science.gov (United States)

    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.

  11. Method of treating oils derived by thermal treatment of solid carbonaceous materials

    Energy Technology Data Exchange (ETDEWEB)

    Culbertson, W.J.; Nevens, T.D.; Schnackenberg, W.D.

    1966-08-09

    A method for treating a heavy fraction separated under substantially non-cracking conditions from a crude oil derived by thermal treatment of solid carbonaceous material in order to produce a heavy fraction and a light fraction consists of heat treating the separated heavy fraction at a temperature above about 600$F. This temperature is below the point of incipient thermal decomposition of the heavy fraction. The heat treatment takes place for a period of time which is inversely proportional to the temperature to produce a product which, when combined with at least part of a light fraction, results in an oil having a pour point lower than that of the original crude oil. The heat treatment produces substantially no non-condensible hydrocarbons and substantially no elemental carbon. (21 claims)

  12. Predicting heating values of lignocellulosics and carbonaceous materials from proximate analysis

    Energy Technology Data Exchange (ETDEWEB)

    Cordero, T.; Marquez, F.; Rodriguez-Morasol, J.; Rodriguez, J.J. [University of Malaga, Malaga (Spain). Dept. of Chemical Engineering

    2001-09-21

    A simple equation based on proximate analysis (volatile matter and fixed carbon contents) is presented which allows calculation of the higher heating value of lignocellulosics as well as the charcoals resulting form their carbonization. The equation has been tested with different lignocellulosic wastes and chars obtained from carbonization at different temperatures. Deviations from the experimental heating values fall in most cases below 2%. A comparison is presented with some other equations from the literature based on proximate, ultimate and chemical analysis data. As a general conclusion the equation proposed in this paper leads to comparable and in many cases more accurate predictions of heating values and has the advantage of being applicable to a wide range of carbonaceous materials, requiring only a simple rapid and cheap proximate analysis of the samples. 14 refs., 5 tabs.

  13. Carbon Paste Electrodes Made from Different Carbonaceous Materials: Application in the Study of Antioxidants

    Directory of Open Access Journals (Sweden)

    Constantin Apetrei

    2011-01-01

    Full Text Available This work describes the sensing properties of carbon paste electrodes (CPEs prepared from three different types of carbonaceous materials: graphite, carbon microspheres and carbon nanotubes. The electrochemical responses towards antioxidants including vanillic acid, catechol, gallic acid, L-ascorbic acid and L-glutathione have been analyzed and compared. It has been demonstrated that the electrodes based on carbon microspheres show the best performances in terms of kinetics and stability, whereas G-CPEs presented the smallest detection limit for all the antioxidants analyzed. An array of electrodes has been constructed using the three types of electrodes. As demonstrated by means of Principal Component Analysis, the system is able to discriminate among antioxidants as a function of their chemical structure and reactivity.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Kaneki, Shunya; Hirono, Tetsuro

    2016-05-01

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

  16. Detection of serpentine in exogenic carbonaceous chondrite material on Vesta from Dawn FC data

    Science.gov (United States)

    Nathues, Andreas; Hoffmann, Martin; Cloutis, Edward A.; Schäfer, Michael; Reddy, Vishnu; Christensen, Ulrich; Sierks, Holger; Thangjam, Guneshwar Singh; Le Corre, Lucille; Mengel, Kurt; Vincent, Jean-Baptist; Russell, Christopher T.; Prettyman, Tom; Schmedemann, Nico; Kneissl, Thomas; Raymond, Carol; Gutierrez-Marques, Pablo; Hall, Ian; Büttner, Irene

    2014-09-01

    The Dawn mission’s Framing Camera (FC) observed Asteroid (4) Vesta in 2011 and 2012 using seven color filters and one clear filter from different orbits. In the present paper we analyze recalibrated HAMO color cubes (spatial resolution ∼60 m/pixel) with a focus on dark material (DM). We present a definition of highly concentrated DM based on spectral parameters, subsequently map the DM across the Vestan surface, geologically classify DM, study its spectral properties on global and local scales, and finally, compare the FC in-flight color data with laboratory spectra. We have discovered an absorption band centered at 0.72 μm in localities of DM that show the lowest albedo values by using FC data as well as spectral information from Dawn’s imaging spectrometer VIR. Such localities are contained within impact-exposed outcrops on inner crater walls and ejecta material. Comparisons between spectral FC in-flight data, and laboratory spectra of meteorites and mineral mixtures in the wavelength range 0.4-1.0 μm, revealed that the absorption band can be attributed to the mineral serpentine, which is typically present in CM chondrites. Dark material in its purest form is rare on Vesta’s surface and is distributed globally in a non-uniform manner. Our findings confirm the hypothesis of an exogenic origin of the DM by the infall of carbonaceous chondritic material, likely of CM type. It further confirms the hypothesis that most of the DM was deposited by the Veneneia impact.

  17. Electrospun carbon nanofibers from polyacrylonitrile blended with activated or graphitized carbonaceous materials for improving anodic bioelectrocatalysis.

    Science.gov (United States)

    Patil, Sunil A; Chigome, Samuel; Hägerhäll, Cecilia; Torto, Nelson; Gorton, Lo

    2013-03-01

    The electrospun carbon nanofibers obtained from polyacrylonitrile (PAN) and PAN blends with either activated carbon (PAN-AC) or graphite (PAN-GR) were tested as anodes using Shewanella oneidensis MR-1. Extensive physico-chemical and electrochemical characterization confirmed their formation, their fibrous and porous nature, and their suitability as electrodes. N2 adsorption measurements revealed high specific surface area (229.8, 415.8 and 485.2m(2) g(-1)) and porosity (0.142, 0.202 and 0.239cm(3)g(-1)) for PAN, PAN-AC and PAN-GR, respectively. The chronoamperometric measurements showed a considerable decrease in start-up time and more than a 10-fold increase in the generation of current with these electrodes (115, 139 and 155μAcm(-2) for PAN, PAN-AC and PAN-GR, respectively) compared to the graphite electrode (11.5μAcm(-2)). These results indicate that the bioelectrocatalysis benefits from the blending of PAN with activated or graphitized carbonaceous materials, presumably due to the increased specific surface area, total pore volume and modification of the carbon microstructure. PMID:23399497

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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. Mineral associations and character of isotopically anomalous organic material in the Tagish Lake carbonaceous chondrite

    Science.gov (United States)

    Zega, Thomas J.; Alexander, Conel M. O.'D.; Busemann, Henner; Nittler, Larry R.; Hoppe, Peter; Stroud, Rhonda M.; Young, Andrea F.

    2010-10-01

    We report a coordinated analytical study of matrix material in the Tagish Lake carbonaceous chondrite in which the same small (⩽20 μm) 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.g., serpentine

  1. Production of carbonaceous material from avocado peel for its application as alternative adsorbent for dyes removal

    Institute of Scientific and Technical Information of China (English)

    Carolyn Palma; Lucia Lloret; Antonio Puen; Maira Tobar; Elsa Contreras

    2016-01-01

    Adsorption processes have received special attention for contaminants removal thanks to their capability to gen-erate effluents with high quality as well as their simple design. In the current work, the agro-waste residue avo-cado peel is proposed to be used as alternative to conventional activated carbons whose use is sometimes restricted to high costs, upgraded by their exhausting after long term operations. The carbonization procedure was optimized and analyzed through factorial design and response surface methodology by evaluating temper-ature (400–900 °C) and time (30–90 min) effects:optimal conditions were found at 900 °C and 65 min, gener-ating an adsorbent with 87.52 m2·g−1 of BET surface area, a mesopore volume of 74%and a zero point charge at 8.6. The feasibility of the carbonaceous material was proved for the removal of a variety of dyes by investigating substrate (10–50 mg·L−1) and solid (0.5–20 g·L−1) concentration effects and statistical significance:complete removal of Naphthol Blue Black and Reactive Black 5 was reached under optimal conditions (10 mg·L−1 and 20 g·L−1 of dye and solid, respectively), while Basic Blue 41 was eliminated by using 13.4 g·L−1 of the adsorbent. Overal , dyes removal by adsorption on carbonized avocado peel is presented as a promising technology due to the low cost and easy availability of the precursor, as well as the straightforward generation, the satisfactory char-acteristics and the proved adsorption capacity of the adsorbent.

  2. Sorption/desorption reversibility of polycyclic aromatic hydrocarbons (PAHs) in soils and carbonaceous materials

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Guohui

    2008-07-01

    the determination of the sorption/desorption enthalpies which gives insight into the sorbent-sorbate interactions. In order to attain sorption/desorption equilibrium, all the samples were pulverized to shorten the laboratory experimental time. The sorbate losses were carefully monitored and considered in the isotherm calculation. Additionally, release of native phenanthrene was also investigated at different temperatures and compared with the freshly spiked samples to investigate the aging effect. The batch results show that for all individual temperature steps sorption and desorption isotherms coincide. Furthermore, the solubility-normalized sorption/desorption isotherms at different temperatures collapse to unique overall isotherms. Leaching of native phenanthrene occurred at much lower concentrations but was well predicted by extrapolation of the spiked equilibrium sorption isotherms. The absolute values of sorption/desorption isosteric heats ({delta}H) determined are in a range of 19 - 35 kJ mol{sup -1}, which is higher than the heat of aqueous solution of subcooled phenanthrene but much less than the heat of condensation of solid phenanthrene from water. No significant difference of the enthalpies between sorption and desorption was observed. Furthermore, the desorption enthalpy of the native phenanthrene was not significantly higher than expected from the sorption experiments with spiked samples. Sorption and desorption kinetics were monitored in on-line column experiments with stepwise increases of temperature. An intraparticle diffusion model was used to simulate the desorption profile in order to get the apparent diffusion coefficients of phenanthrene from the carbonaceous materials. Desorption activation energies were calculated by Arrhenius relationship based on the high-resolution measurement of concentration increases at each temperature step. The activation energies determined range from 58 - 71 kJ mol{sup -1}. No significant trend of increasing

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

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Carbonaceous materials were prepared from exhausted sludge materials. • High surface area and good physicochemical properties were achieved. • Utilization of waste sludge materials and mixed anaerobic cultures were used in a continuous anaerobic UPBR system (upflow packed bed biological reactor). • Effective treatment of dye contaminated wastewater in a cheapest and environmental friendly method was demonstrated. - Abstract: 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 202.0 m2/g of surface area. Biodecolorization levels of 76% were achieved for SBC600 and 86% for SBC800 at space time (τ) of 1.0 min, 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

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

    Science.gov (United States)

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

    2003-03-01

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

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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 (punderstanding of the environmental behaviors and risks of PBDEs. PMID:27037476

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

    Science.gov (United States)

    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

  8. Removal of blue indigo and cadmium present in aqueous solutions using a modified zeolitic material and an activated carbonaceous material; Remocion de azul indigo y cadmio presentes en soluciones acuosas empleando un material zeolitico modificado y un material carbonoso activado

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez S, E. E.

    2011-07-01

    In the last years the use of water has been increased substantially, it has been also altered its quality as a result of human activities such as mining, industrial activities and others. Water pollution caused by dyes and heavy metals has adverse effects on the environment, since both pollutants are very persisten even after conventional treatments. Denim blue and cadmium are not biodegradable. There is a growing interest in finding new, efficient and low cost alternative materials to remove such pollutants from the aqueous medium. The purpose of this work was to evaluate a modified zeolitic tuff and an activated carbonaceous material obtained from the pyrolysis of sewage sludge for the removal of denim blue and cadmium. The zeolitic material was modified with Na{sup +} and Fe{sup 3+} solutions to improve its sorption properties for the removal of cadmium and denim blue, respectively. Carbonaceous material was treated with 10% HCl solution to remove ashes. Both materials were characterized by scanning electron microscopy and elemental analysis (EDS), specific surface areas (Bet), thermogravimetric analysis, infrared spectroscopy and X-ray diffraction. Simultaneously, the denim blue dye was characterized by infrared spectroscopy and its pKa value was determined, these data allowed the determination of its chemical properties and its acid-base behavior in solution. In the content of this work the term indigo blue was changed by denim blue, as it corresponds to the commercial name of the dye. To assess the sorption capacity of sorbents, the sorption kinetics and sorption isotherms in batch system were determined; the results were fitted to mathematical models such as the pseudo-first order, pseudo second order and second order to describe the sorption kinetics and the Langmuir, Freundlich and Langmuir-Freundlich isotherms to describe sorption processes. The results show that the most efficient material to remove denim blue from aqueous solutions is the carbonaceous

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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

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

    International Nuclear Information System (INIS)

    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.

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

    Science.gov (United States)

    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.

  14. A new star(ch) is born: Starbons as biomass-derived mesoporous carbonaceous materials

    OpenAIRE

    Shuttleworth, P. S.; Clark, J H; V. Budarin; Luque, R.

    2012-01-01

    Porous carbon materials are present in a wide rangeof technologically important applications, includingseparation science, heterogeneous catalyst supports,water purification filters, stationary phase materials,as well as the developing future areas of energygeneration and storage applications. Hard templateroutes to ordered mesoporous carbons are wellestablished, but whilst offering different mesoscopictextural phases, the surface of the material is difficultto chemically post-modify and proc...

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    DEFF Research Database (Denmark)

    Van Kooten, Elishevah M M E; Wielandt, Daniel; Schiller, Martin;

    2016-01-01

    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...

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

    Directory of Open Access Journals (Sweden)

    Kristine M Garza

    2008-03-01

    Full Text Available Kristine M Garza1, Karla F Soto2, Lawrence E Murr31Department of Biological Sciences, The University of Texas at El Paso, El Paso, TX, USA; 2Lockheed Martin Aeronautics Company, Forth Worth, TX, USA; 3Department of Metallurgical and Materials Engineering, The University of Texas at El Paso, El Paso, TX, USAAbstract: 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.Keywords: cytotoxicity assessment, ROS assays, FESEM and TEM analysis, nanoparticulate aggregates

  19. 水热碳化法制备碳纳米材料%Fabricating Nanostructured Carbonaceous Materials via Hydrothermal Carbonization Process:A Review

    Institute of Scientific and Technical Information of China (English)

    李赛赛; 曹迎楠; 王军凯; 梁峰; 段红娟; 张海军

    2016-01-01

    形态可控的碳纳米材料由于独特的结构和性能而受到研究者的普遍关注,常见的制备方法有化学气相沉积法(CVD)、乳液法和水热碳化法等。水热碳化法是一种重要的碳纳米材料制备方法,具有成本低、反应条件温和、产物粒径均匀且形态可控等特点。综述了近年来以糖类及淀粉等有机物为原料,采用水热碳化法制备各种形态可控碳纳米材料的研究现状,重点介绍了水热碳化工艺条件对合成碳微球、空心碳微球、核壳结构碳复合材料显微形貌的影响,并提出了水热碳化法制备碳纳米材料研究中存在的问题和今后可能的发展方向。%The morphology-controlled carbonaceous nanostructured materials have attracted considerable atten-tion because of its special structures and properties.Chemical vapor deposition,emulsion process and hydrothermal carbonization method are widely used for the preparation of carbonaceous nanostructured materials.Hydrothermal car-bonization method is one of the most important methods to prepare carbonaceous nanostructured materials with the ad-vantages of low cost and mild conditions.In addition,the prepared carbonaceous nanostructured materials usually have controllable structure and uniform particle sizes.Recent development of the morphology-controlled carbonaceous nano-structured materials prepared via hydrothermal carbonization process with glucose and saccharides as the main raw ma-terials is summarized.The effects of preparation parameters on the properties of carbon spheres,carbon hollow spheres and core-shell structured composite materials synthesized by this method are reviewed.The advantages of the hydrothermal carbonization method are also introduced and the potential development directions are proposed.

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

    Science.gov (United States)

    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.

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

    OpenAIRE

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

    2015-01-01

    Using a scanning electron microscopy, elemental analysis, electron paramagnetic resonance, and Raman scattering methods, two types of the shungite materials (Sh-II from Zazhogino deposit and shungite from a commercial filter (ShF)), with different carbon content and porosity, are studied in this work. It was established by scanning electron microscopy data that the structure of the shungite samples is formed by a micron-size agglomeration of carbon and silicon dioxide clusters. It is found fr...

  2. Cytotoxicity of halogenated graphenes

    Science.gov (United States)

    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

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

    Science.gov (United States)

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

    2015-02-01

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

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

    Science.gov (United States)

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

    2016-04-01

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

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

    Science.gov (United States)

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

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

  6. Biological regeneration of carrier material for the adsorption of halogen hydrocarbons in plants for cleaning up contaminated groundwater. Final report

    International Nuclear Information System (INIS)

    Halogen hydrocarbons and above all chlorinated hydrocarbons are widespread harmful substances in soils and in groundwater. When cleaning up groundwater contamination, the contaminants are brought into the gas phase by strip processes. From the gas phase, the contaminants can be adsorbed on different carrier materials, mostly active carbon. One was searching for ways to regenerate this adsorption material. The mixed culture from a sea sediment most suitable for the decomposition of chlorinated hydrocarbons was optimized regarding its decomposition performance and was later used on the technical scale. In the decomposition experiments on the large technical scale, the cultures were lodged on filling bodies which has a much higher amount of gaps. In this case, an optimum supply of the micro-organisms with oxygen and methane is guaranteed, which is used as co-substrate. No intermediate product was found in a gas chromatography examination. The biologically occupied stage is situated between a desorption column and the active carbon filters, and reduces the load of harmful substances which can no longer be brought into the gas phase by stripping out. This has the advantage that it can be integrated in existing plants and can be adapted to any case of contamination by lodging adapted micro-organisms on it. The basis for each application must be separately researched. (orig.)

  7. 无卤阻燃电缆料的研究现状%Research Status of Halogen-free Flame Retardant Cable Material

    Institute of Scientific and Technical Information of China (English)

    关健; 虞鑫海

    2014-01-01

    主要从氢氧化物阻燃体系、磷系阻燃体系、膨胀型阻燃体系、有机硅阻燃体系、硼系阻燃体系和纳米阻燃体系等方面综述了无卤阻燃电缆料的研究与应用现状,并展望了电缆料无卤阻燃技术的发展方向。%The recent research and application status of halogen-free flame retardant cable material were reviewed from hydroxide flame retardant system, phosphorus flame retardant system, intumescent flame re-tardant system, silicone flame retardant system, boron flame retardant system and nano flame retardant system. The development direction of halogen-free flame retardant cable material was proposed.

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

    Science.gov (United States)

    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.

  9. Influence of halogen irradiance on short- and long-term wear resistance of resin-based composite materials.

    LENUS (Irish Health Repository)

    Bhamra, Gurcharn S

    2009-02-01

    The Oregon Health Science University (OHSU) four-chamber oral wear simulator was used to examine the impact of halogen irradiance on the short- and long-term wear behavior of four-methacrylate resin-based composites (RBCs). The hypothesis proposed was that exacerbated wear would occur following the long-term wear of RBCs irradiated under non-optimized irradiance conditions.

  10. Informative document halogenated hydrocarbon-containing waste

    NARCIS (Netherlands)

    Verhagen H

    1992-01-01

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

  11. Thermodynamic Property Surfaces for Adsorption of R507A, R134a, and n -Butane on Pitch-Based Carbonaceous Porous Materials

    KAUST Repository

    Chakraborty, Anutosh

    2010-10-01

    The thermodynamic property surfaces of R507A, R134a, and n-butane on pitch-based carbonaceous porous material (Maxsorb III) are developed from rigorous classical thermodynamics and experimentally measured adsorption isotherm data. These property fields enable us to compute the entropy, enthalpy, internal energy, and heat of adsorption as a function of pressure, temperature, and the amount of adsorbate. The entropy and enthalpy maps are necessary for the analysis of adsorption cooling cycle and gas storage. We have shown here that it is possible to plot an adsorption cooling cycle on the temperature-entropy (T-s) and enthalpy-uptake (h-x) maps. Copyright © Taylor and Francis Group, LLC 2010.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  14. Comparative study of adsorptive role of carbonaceous materials in removal of UV-active impurities of paclitaxel extracts

    Directory of Open Access Journals (Sweden)

    Jaber Nasiri

    2015-12-01

    Full Text Available Graphite oxide (GO and reduced graphene oxide (rGO nanosheets were synthesized with a low-cost manufacturing method. The morphology and structures of the synthesized samples were studied using X-ray diffraction (XRD, atomic force microscopy (AFM, Fourier-transform infrared (FTIR and Raman spectroscopy. The efficiencies of GO and rGO as novel candidate adsorbents in the pre-purification of paclitaxel were compared and contrasted with those of commercial graphite (Gt, graphene (G and multi-wall carbon nanotube (MWCNT. According to UV–vis and HPLC analyses, rGO was evaluated as the best absorbent for the removal of impurities in pre-purification of paclitaxel from plant cell cultures. In contrast, the GO had the poorest proficiency for paclitaxel pre-purification in comparison with the other carbonaceous adsorbents. This is attributed to the existence of many localized defects in the π-structure of GO that is related to weakness of π–π stacking interactions between crude extract impurities and GO.

  15. Comparative study of adsorptive role of carbonaceous materials in removal of UV-active impurities of paclitaxel extracts

    Institute of Scientific and Technical Information of China (English)

    Jaber Nasiri; Elaheh Motamedi; Mohammad Reza Naghavi

    2015-01-01

    Graphite oxide (GO) and reduced graphene oxide (rGO) nanosheets were synthesized with a low-cost manufacturing method. The morphology and structures of the synthesized samples were studied using X-ray diffraction (XRD), atomic force microscopy (AFM), Fourier-transform infrared (FTIR) and Raman spectroscopy. The efficiencies of GO and rGO as novel candidate adsorbents in the pre-purification of paclitaxel were compared and contrasted with those of commercial graphite (Gt), graphene (G) and multi-wall carbon nanotube (MWCNT). According to UV–vis and HPLC analyses, rGO was evaluated as the best absorbent for the removal of impurities in pre-purification of paclitaxel from plant cell cultures. In contrast, the GO had the poorest proficiency for paclitaxel pre-purification in comparison with the other carbonaceous adsorbents. This is attributed to the existence of many localized defects in the π-structure of GO that is related to weakness ofπ–πstacking interactions between crude extract impurities and GO.

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

    Science.gov (United States)

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

    2013-12-01

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

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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. Carbonaceous Chondrite Clasts in HED Achondrites

    Science.gov (United States)

    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).

  2. Contribution of carbonaceous material to cloud condensation nuclei concentrations in European background (Mt. Sonnblick) and urban (Vienna) aerosols

    Science.gov (United States)

    Hitzenberger, R.; Berner, A.; Giebl, H.; Kromp, R.; Larson, S. M.; Rouc, A.; Koch, A.; Marischka, S.; Puxbaum, H.

    During four intensive measurement campaigns (two on Mt. Sonnblick, European background aerosol, and two in Vienna, urban aerosol), cloud condensation nuclei (CCN) were measured at supersaturations of 0.5%. Impactor measurements of the mass size distribution in the size range 0.1-10 μm were performed and later analyzed for Cl -, NO -3, SO 2-4, Na +, NH +4, K +, Ca 2+ and Mg 2+ by ion chromatography, for total carbon (TC) using a combustion method, and for black carbon (BC) by an optical method (integrating sphere). Organic carbon (OC) was defined as the difference between TC (minus carbonate carbon) and BC. At all sites, the mass fraction of BC in the submicron aerosol was comparable (4-5%). CCN concentrations on Mt. Sonnblick were found to be 10-30% of those measured in Vienna, although high Mt. Sonnblick concentrations were comparable to low Vienna concentrations (around 800 cm -3). The contribution of organic material was estimated from the mass concentrations of the chemical species sampled on the impactor stage with the lowest cut point (0.1-0.215 μm aerodynamic equivalent diameter). On Mt. Sonnblick, TC material contributed 11% to the total mass in fall 1995, and 67% in summer 1996, while the OC fraction was 6 and 61%. The combined electrolytes and mineral material contributed 18 and 16% in fall and summer. During the Vienna spring campaign, the contributions of OC and electrolytes to the total mass concentration in this size range were 48 and 36%, respectively.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

    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

    Directory of Open Access Journals (Sweden)

    Daniela Lehr

    2015-11-01

    Full Text Available 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.

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

    International Nuclear Information System (INIS)

    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

  7. Marine mammal blubber reference and control materials for use in the determination of halogenated organic compounds and fatty acids

    Energy Technology Data Exchange (ETDEWEB)

    Kucklick, John R.; Pugh, Rebecca S.; Becker, Paul R. [Hollings Marine Laboratory, National Institute of Standards and Technology (NIST), Charleston, SC (United States); Schantz, Michele M.; Porter, Barbara J.; Poster, Dianne L.; Leigh, Stefan; Wise, Stephen A. [NIST, Analytical Chemistry Division, Gaithersburg, MD (United States); Rowles, Teri K. [National Marine Fisheries Service, National Oceanic and Atmospheric Administration, Silver Spring, MD (United States)

    2010-05-15

    The National Institute of Standards and Technology (NIST) has a diverse collection of control materials derived from marine mammal blubber, fat, and serum. Standard Reference Material (SRM) 1945 Organics in Whale Blubber was recertified for polychlorinated biphenyl (PCB) congeners, organochlorine pesticides, and polybrominated diphenyl ether (PBDE) congeners. SRM 1945 has also been assigned mass fraction values for compounds not frequently determined in marine samples including toxaphene congeners, coplanar PCBs, and methoxylated PBDE congeners which are natural products. NIST also has assigned mass fraction values, as a result of interlaboratory comparison exercises, for PCB congeners, organochlorine pesticides, PBDE congeners, and fatty acids in six homogenate materials produced from marine mammal blubber or serum. The materials are available from NIST upon request; however, the supply is very limited for some of the materials. The materials include those obtained from pilot whale blubber (Homogenates III and IV), Blainville's beaked whale blubber (Homogenate VII), polar bear fat (Homogenate VI), and California sea lion serum (Marine Mammal Control Material-1 Serum) and blubber (Homogenate V). (orig.)

  8. Halogenated fatty acids

    DEFF Research Database (Denmark)

    Mu, Huiling; Sundin, Peter; Wesén, Clas

    1997-01-01

    Halogenated fatty acids are the major contributors to organohalogen compounds in lipids of marine mammals, fish, and bivalves. For the initial characterization of these recently noticed compounds, a determination of the halogen concentration has usually been combined with some lipid isolation...... and separation method. This review covers separation by solid phase chromatography, gel permeation chromatography, and liquid-liquid extraction, followed by halogen determination. All studies performed according to this outline have indicated that the major organohalogen compounds are chlorinated fatty acids...... bound in different lipids. For the detection and identification of individual, halogenated fatty acid methyl esters (FAMEs) liberated from the lipids, gas chromatography (GC) has been employed together with detection methods such as electron capture detection, electrolytic conductivity detection (ELCD...

  9. Research and Application of Nano MgO and Nano MgO/halogen Adduct New Antibacterial Material%纳米氧化镁/卤素加合物新型抗菌材料研究与应用

    Institute of Scientific and Technical Information of China (English)

    崔洪梅; 武晓峰; 陈运法; 李东艳

    2012-01-01

    Nano MgO and nano MgO/halogen adduct have become a focal point in antibacterial materials because of their benefits such as broad-spectrum antibactria, high sterilization efficiency and changeless in color. In this paper, the development background of the MgO antibacterial materials, research progress, mechanism of the MgO adsorbed halogen, MgO/halogens adduct as antibacterial material and its antibacterial mechanism is summarized. Finally, the problems and needs further research directions are pointed out.%纳米MgO及纳米MgO/卤素加合物由于其广谱、高效、不变色的优点成为当前抗菌材料领域研究的热点.本文总结了纳米MgO抗菌材料的发展背景、研究进展及纳米MgO/卤素加合物在抗菌方面的研究进展,对MgO吸附卤素的机理研究进行了总结,并分析了其抗菌机理.最后指出所存在的问题和需要进一步研究的方向.

  10. Carbonaceous materials for adsorptive refrigerators

    Science.gov (United States)

    Buczek, B.; Wolak, E.

    2012-06-01

    Carbon monoliths prepared from hard coal precursors were obtained. The porous structure of the monoliths was evaluated on the basis of nitrogen adsorption — desorption equilibrium data. The investigated monoliths have a well-developed microporous structure with significant specific surface area (S BET ). Equilibrium studies of methanol vapour adsorption were used to characterize the methanol adsorptive capacity that was determined using a volumetric method. The heat of wetting by methanol was determined in order to estimate the energetic effects of the adsorption process. The results of the investigations show that all monoliths exhibit high adsorption capacity and high heat of wetting with methanol.

  11. Scientific conferences: A big hello to halogen bonding

    Science.gov (United States)

    Erdelyi, Mate

    2014-09-01

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

  12. Occurrence of halogenated alkaloids.

    Science.gov (United States)

    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

  13. 密度泛函方法研究甲烷与碳材料之间的相互作用%A DFT study of the interaction of methane with carbonaceous materials

    Institute of Scientific and Technical Information of China (English)

    孙文晶; 江成发; 薛英

    2011-01-01

    基于密度泛函方法,研究了甲烷在两种碳材料模型(Armchair和Tip)表面的物理吸附和化学解离过程。物理吸附过程考察了甲烷在两种模型上7种活性位的吸附能与结构参数,结果表明,甲烷在碳材料表面倾向于吸附在具有苯环结构的碳原子顶位;化学解离过程考察了甲烷在两种构型的活性位上的化学解离过程,结果表明,甲烷C—H键在Tip模型上比在Armchair模型更容易解离,解离路径倾向于沿着T2—T6—T5路径。%Based on the density functional theory(DFT) study,the physisorption and chemical dissociation of methane on the surface of carbonaceous materials(Armchair and Tip model) were investigated.The adsorption energy and structural parameters of methane on seven active sites of two carbonaceous materials were investigated.The results show that methane is infavor of physical adsorption on the top of carbon atom with the benzene ring structure.The processes of methane dissociated on the two carbonaceous materials were also investigated.The results show that the C—H bond is easier to be dissociated on the Tip model and the dissociation pathway following the T2—T6—T5 pathway.

  14. Biogeochemistry of Halogenated Hydrocarbons

    Science.gov (United States)

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

    2003-12-01

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

  15. Extraterrestrial Nucleobases in Carbonaceous Chondrites

    Science.gov (United States)

    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

  16. Halogens in CM Chondrites

    Science.gov (United States)

    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.

  17. f-element compound synthesis employing powerful halogenating agents

    International Nuclear Information System (INIS)

    This paper reports that conventional halogenation reactions involving f elements typically employ high-temperature conditions. Recent synthetic techniques use halogenation agents that are either inherently reactive or have been activated by physical methods such as photolysis. These techniques allow lower temperature syntheses. Consequently, they have significant advantages with respect to safety, material compatibility, and accountability, as well as providing routes to thermally unstable materials

  18. Halogen Chemistry on Catalytic Surfaces.

    Science.gov (United States)

    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

  19. Tropospheric Halogen Chemistry

    Science.gov (United States)

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

    2003-12-01

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

  20. 垃圾中含碳有机物厌氧降解过程的独立性探讨%Independence of Anaerobic Biodegradation of Carbonaceous Organic Materials

    Institute of Scientific and Technical Information of China (English)

    孙晓杰; 王敦球; 王洪涛; 陆文静; 张玲; 陆美菊; 吴安杰; 项振宇; 黄亮

    2011-01-01

    Independence of anaerobic biodegradation of carbonaceous organic material is of importance. It can provide theoretical basis for the simulation and prediction of the gasification characteristics and stabilization process. According to the research of the predecessor, this paper analyses the independence of anaerobic biodegradation of carbonaceous organic material. There might be catabolite repression in pure culture for bacteria, but not absolutely. During the landfill of the refuse, mutant resistant to the repressor may occur because micro-bial ecosystem is complex. The further study will go on for determining the independence of anaerobic biodegradation of carbonaceous organic material.%混合垃圾中单物质纤维素、淀粉、脂肪和蛋白质降解的独立性与否可为模拟和预测填埋场任意时刻的产气特性和稳定化进程提供依据.本文对单物质降解的独立性进行了探讨,已有的试验研究结果表明,在厌氧填埋环境下,单物质的厌氧产气量具有可叠加性,即各种单物质的降解是独立的.但是根据葡萄糖效应,在单一菌种纯培养试验中,会出现分解代谢物的阻遏作用,即难降解有机物的分解转化会受到易降解有机物的抑制.在垃圾填埋过程中,由于微生物生态系统复杂,可能会在具体环境中产生一些特殊的抗分解代谢物阻遏作用的微生物.如要从理论上确定填埋垃圾中有机物厌氧降解过程的独立性问题,需要设计专门的微生物学和酶学试验作进一步研究.

  1. Carbonaceous Chondrite Fragments in the Polymict Eucrite Yamato 791834

    Science.gov (United States)

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

    2003-01-01

    Buchanan et al. and Zolensky et al. described carbonaceous chondrite fragments in a variety of howardites and concluded that the majority are CM2 and CR2 materials. Gounelle et al. also described similar, but very small, fragments in these meteorites. These clasts are important because they represent materials that were in orbital proximity to the HED parent body (4 Vesta) and they may be similar to the primitive materials that originally accreted to form this body. The present study describes two carbonaceous chondrite clasts in the Yamato 791834 (Y791834) polymict eucrite.

  2. Microfossils in carbonaceous meteorites

    Science.gov (United States)

    Hoover, Richard B.

    2009-08-01

    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 bio-contaminants.

  3. Carbonaceous Survivability on Impact

    Science.gov (United States)

    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.

  4. Microfossils in Carbonaceous Meteorites

    Science.gov (United States)

    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.

  5. Carbonaceous particles in the atmosphere: A historical perspective to the Fifth International Conference on Carbonaceous Particles in the Atmosphere

    Science.gov (United States)

    Penner, Joyce E.; Novakov, T.

    1996-08-01

    Carbonaceous aerosol species together with sulfates, other water-soluble inorganic compounds, and mineral particles play an important role in a variety of environmental effects. Carbonaceous particles contribute to the extinction of visible light by both scattering and absorption, thus influencing visibility degradation and radiative transfer through the atmosphere. These particles may serve as sites for condensation of water vapor and organic compounds. Components of carbonaceous material may contribute to atmospheric chemical processes because of their chemical and catalytic properties. Many of the original results in this field of research were first presented at the International Conferences on Carbonaceous Particles in the Atmosphere held in Berkeley (1978 and 1987) and in Linz and Vienna, Austria (1983 and 1991, respectively). At the fifth conference, August 23-26, 1994, at Lawrence Berkeley Laboratory, 85 papers were presented. This volume contains papers accepted for publication after peer review. In this introduction we attempt to provide an overview of research on carbonaceous particles from the 1950s to mid-1970s, which provided the backdrop for the first conference. We follow this by outlining research accomplishments and evolution of emphasis (as evidenced by the material presented at these conferences) and by summarizing the present state of this field of research.

  6. Organic halogens in landfill leachates

    DEFF Research Database (Denmark)

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

    2000-01-01

    Using a group parameter, total organic halogens (TOX), high TOX concentrations were found in leachates and leachate contaminated groundwaters at two Danish mixed sanitary and hazardous waste sites. With commonly used screening procedures for organic contaminants, the individual halogenated organic...... compounds behind the high TOX could not be found. Conversely, part of the TOX could be attributed to halogenated humic substances that can not be analysed with conventional organic contaminant analyses. Even though TOX can still be considered an indicator of leachate contamination in the aquifers, attempts...

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

    Science.gov (United States)

    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.

  8. Fluid Inclusions in Carbonaceous Chondrites

    Science.gov (United States)

    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.

  9. The Halogen Occultation Experiment

    Science.gov (United States)

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

    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.

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

    Science.gov (United States)

    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

  11. Keto-acids in Carbonaceous Meteorites

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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. Synthesis and thermal properties of cured materials of halogen-free flame-retardant epoxy resin%无卤阻燃环氧树脂固化物及其结构与性能

    Institute of Scientific and Technical Information of China (English)

    闵玉勤; 华正江; 张兴宏

    2014-01-01

    环氧树脂固化物具有一系列性能优势,是重要的电子材料之一,但因其极易燃烧而存在火灾隐患。采用一类扭曲非对称结构的二氮杂萘酮型二胺和二酚型无卤阻燃固化剂,与双酚A型环氧树脂(E51)和含磷环氧树脂固化,所得固化物具有优异的热学和动态力学性能,T 可达157℃,热线胀系数低;与含磷树脂固化后所得g材料的阻燃性顺利通过UL94 V-0级测试。%The epoxy thermosets have a series of advantages,and are one of the most important electronic materials.However,the common epoxy materials are highly flammable.In this paper,two nitrogen-containing flame-retardant curing agents was synthesized by using phenolphthalein as the raw material.The bisphenol A epoxy resin E51 and the phosphorus-containing epoxy resin were cured with the diamine and diphenol halogen-free flame-retardant curing agents,which contain the phthalazinone moieties and have the twisty and unsymmetrical structural,and the cured exhibited excellent thermal and dynamic mechaincal properties,T of 157℃,and lower linear expansion coefficient.When curedg with the phosphorus-containing epoxy resin,it exhibited excellent flame retardant performance(UL 94 V-0).

  14. Hydrocarbon components in carbonaceous meteorites

    Science.gov (United States)

    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

  15. Halogen Bonding in Organic Synthesis and Organocatalysis.

    Science.gov (United States)

    Bulfield, David; Huber, Stefan M

    2016-10-01

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

  16. A study of carbonaceous char oxidation in air by semi-quantitative FTIR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Koch, A.; Krzton, A.; Finqueneisel, G.; Heintz, O.; Weber, J.-V.; Zimny, T. [IUT Saint-Avold (France). Departement Chimie

    1998-05-01

    The paper describes the methodology of semi-quantitative characterization of coal-derived carbonaceous material oxidized under mild thermal conditions. Infrared spectroscopic analysis was applied to the determination of chemical changes induced by oxidation. A curve fitting model has thus been developed to evidence the evolution of specific chemical groups during treatment. The possibility to follow mechanisms and kinetics of carbonaceous char oxidation through data obtained by this model has been demonstrated. 28 refs., 7 figs., 2 tabs.

  17. 含再生材料的PC/PET无卤阻燃合金加工稳定性%Processing Stability of Recycled Materials PC/PET Alloy Containing Halogen-Free Flame Retardant

    Institute of Scientific and Technical Information of China (English)

    高磊; 李强; 李文强; 罗明华

    2016-01-01

    通过对再生聚对苯二甲酸乙二酯(PET–R)的多次挤出,研究了扩链对PET–R稳定性的影响。同时,也通过多次挤出和多次注塑的Regrind实验,研究了丙烯腈–苯乙烯塑料接枝甲基丙烯酸缩水甘油酯(AS-g-GMA)加入后再生聚碳酸酯(PC)/PET体系的相容性和稳定性,以及熔体流动速率和冲击强度的变化。通过11个月内的生产数据反映出,经过扩链和稳定化处理后的含再生材料的PC/PET无卤阻燃合金具有很好的加工稳定性。%The influence of chain extending on the stability of recycled polyethylene terephthalate (PET–R) was studied by multi-extrusion experiment. Meanwhile the changes of compatibility, stability, melt flow rate and impact strength of recycled polycarbonate (PC–R)/PET–R alloy after adding acrylonitrile-styrene grafted glycidyl methacrylate (AS-g-GMA) was discussed through multi-extrusion and multi-injection Regrind experiments. The production data of eleven months indicates that after the process of chain extending and stabilizing, the halogen-free flame retardant PC/PET alloy containing recycled materials has better stabilization.

  18. Organic Chemistry of Carbonaceous Meteorites

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  1. Modeling Orbital Gamma-Ray Spectroscopy Experiments at Carbonaceous Asteroids

    CERN Document Server

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

    2016-01-01

    To evaluate the feasibility of measuring differences in bulk composition among carbonaceous meteorite parent bodies from an asteroid or comet orbiter, we present the results of a performance simulation of an orbital gamma-ray spectroscopy ("GRS") experiment in a Dawn-like orbit around spherical model asteroids with a range of carbonaceous compositions. The orbital altitude was held equal to the asteroid radius for 4.5 months. Both the asteroid gamma-ray spectrum and the spacecraft background flux were calculated using the MCNPX Monte-Carlo code. GRS is sensitive to depths below the optical surface (to ~20--50 cm depth depending on material density). This technique can therefore measure underlying compositions beneath a sulfur-depleted (e.g., Nittler et al. 2001) or desiccated surface layer. We find that 3\\sigma\\ uncertainties of under 1 wt% are achievable for H, C, O, Si, S, Fe, and Cl for five carbonaceous meteorite compositions using the heritage Mars Odyssey GRS design in a spacecraft- deck-mounted configu...

  2. Indigenous Carbonaceous Matter in the Nakhla Mars Meteorite

    Science.gov (United States)

    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.

  3. Determination of total organic halogens (TOX); Bias from a non-halogenated organic compound

    Energy Technology Data Exchange (ETDEWEB)

    Gron, C. [Technical Univ. of Denmark, Lyngby (Denmark); Dybdahl, H.P. [Water Quality Institute, Harsholm (Denmark)

    1996-08-01

    Determination of total organic halogens (TOX) has proven susceptible to bia high concentrations of a non-halogenated organic compound, N-butylbenzenesulfonamide (NBSA). High apparent TOX values occurred with more than 5-10 mg of NBSA applied to the carbon columns of the TOX procedure. Other non-halogenated organic compounds and inorganic sulfide may bias the method as well. When the TOX method is used as a measure of total organic halogens in environmental regulation and control, the risk of positive bias from non-halogenated compounds should always be emphasized. 16 refs., 3 figs.

  4. Carbonaceous aerosols in Norwegian urban areas

    Directory of Open Access Journals (Sweden)

    K. E. Yttri

    2009-03-01

    Full Text Available Little is known regarding levels and source strength of carbonaceous aerosols in Scandinavia. In the present study, ambient aerosol (PM10 and PM2.5 concentrations of elemental carbon (EC, organic carbon (OC, water-insoluble organic carbon (WINSOC, and water-soluble organic carbon (WSOC are reported for a curbside site, an urban background site, and a suburban site in Norway in order to investigate their spatial and seasonal variations. Aerosol filter samples were collected using tandem filter sampling to correct for the positive sampling artefact introduced by volatile and semivolatile OC. Analyses were performed using the thermal optical transmission (TOT instrument from Sunset Lab Inc., which corrects for charring during analysis. Finally, we estimated the relative contribution of OC from wood burning based on the samples content of levoglucosan.

    Levels of EC varied by more than one order of magnitude between sites, likely due to the higher impact of vehicular traffic at the curbside and the urban background sites. In winter, the level of particulate organic carbon (OCp at the suburban site was equal to (for PM10 or even higher (for PM2.5 than the levels observed at the curbside and the urban background sites. This finding was attributed to the impact of residential wood burning at the suburban site in winter, which was confirmed by a high mean concentration of levoglucosan (407 ng m−3. This finding indicates that exposure to primary combustion derived OCp could be equally high in residential areas as in a city center. It is demonstrated that OCp from wood burning (OCwood accounted for almost all OCp at the suburban site in winter, allowing a new estimate of the ratio TCp/levoglucosan for both PM10 and PM2.5. Particulate carbonaceous material (PCM

  5. Organic halogen compounds in the environment

    International Nuclear Information System (INIS)

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

  6. Natural halogenated compounds in forest soils

    DEFF Research Database (Denmark)

    Albers, Christian Nyrop

    føre til dannelsen af halogenerede stoffer i jord. Det understreges, at der bør skelnes skarpt mellem stoffer udskilt fra mikroorganismer med et specifikt formål og uspecifik halogenering induceret af enzymer, udskilt med andet formål. Denne uspecifikke halogenering, der kan sammenlignes med de...

  7. Halogen versus halide electronic structure

    Institute of Scientific and Technical Information of China (English)

    Willem-Jan; van; Zeist; F.Matthias; Bickelhaupt

    2010-01-01

    Halide anions X-are known to show a decreasing proton affinity(PA),as X descends in the periodic table along series F,Cl,Br and I.But it is also well-known that,along this series,the halogen atom X becomes less electronegative(or more electropositive).This corresponds to an increasing energy of the valence np atomic orbital(AO) which,somewhat contradictorily,suggests that the electron donor capability and thus the PA of the halides should increase along the series F,Cl,Br,I.To reconcile these contradictory observations,we have carried out a detailed theoretical analysis of the electronic structure and bonding capability of the halide anions X-as well as the halogen radicals X-,using the molecular orbital(MO) models contained in Kohn-Sham density functional theory(DFT,at SAOP/TZ2P as well as OLYP/TZ2P levels) and ab initio theory(at the HF/TZ2P level).We also resolve an apparent intrinsic contradiction in Hartree-Fock theory between orbital-energy and PA trends.The results of our analyses are of direct relevance for understanding elementary organic reactions such as nucleophilic substitution(SN2) and base-induced elimination(E2) reactions.

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

    Science.gov (United States)

    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

  9. The carbonaceous concrete based on sawdust

    Directory of Open Access Journals (Sweden)

    BELOUSOVA Elena Sergeevna

    2015-06-01

    Full Text Available Today there are many requirements for strength, ecology and economy of produced concretes. The authors of the paper study attenuation of electromagnetic radiation of carbonaceous powders in the concrete composition. Carbon black was selected as a carbon powder for addition in concrete composition. Carbon black is a nanomaterial with disoriented structure of particles (average size is about 50 nm. The composition of the carbon black contains at least 90 wt.% amorphous carbon, more than 5 wt. % chemisorbed oxygen and about 4 wt.% of impurities. Materials with the addition of carbon black have electrical conductivity due to the high content of carbon. These materials are able to absorb electromagnetic radiation. For cement composition with addition of carbon black (more than 30 wt. % and water transmission coefficient of electromagnetic radiation is about –10 dB, for cement composition with 20 wt. % of carbon black the reflection coefficient is –8 dB in the frequency range 8–12 GHz. The concretes with a saturated aqueous solution of calcium chloride and 10% of carbon black possess minimal reflection coefficient (–14... –8 dB. Electromagnetic radiation shielding of concrete with the addition of sawdust was investigated. The concrete with sawdust (40 wt. % impregnated with an aqueous solution with carbon black has the reflection coefficient less than –8 dB and transmission coefficient –40 dB in the frequency range 8–12 GHz. These concretes can be used for creation of a shielded room with the technical equipment for information processing to prevent data leakage through the compromising emanations and crosstalk.

  10. Carbonaceous Components in the Comet Halley Dust

    Science.gov (United States)

    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. Origin of Thorium/Uranium Variations in Carbonaceous Chondrites

    OpenAIRE

    Goreva, J. S.; Burnett, D. S.

    2000-01-01

    Thorium-, U-, and Pb-isotopic analyses of a wide variety of planetary materials show that Th/U ratio (by weight) varies from 3.5 to 4.2. It is generally believed that chondritic meteorites contain refractory lithophile elements in a relative proportions close to solar, i.e., CI chondrites [1]. Surprisingly, a number of analyses of different types of carbonaceous chondrites show a large (at least a factor of 3) scatter in Th/U measurements [2]. The widest spread in Th/U is observed in the most...

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

    Science.gov (United States)

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

    2005-07-01

    The carbonaceous Murchison chondrite is one of the most studied meteorites. It is considered to be an astrobiology standard for detection of extraterrestrial organic matter. Considerable work has been done to resolve the elemental composition of this meteorite. Raman spectroscopy is a very suitable technique for non-destructive rapid in situ analyses to establish the spatial distribution of carbonaceous matter. This report demonstrates that Raman cartography at a resolution of 1 μm 2 can be performed. Two-dimensional distribution of graphitised carbon, amorphous carbonaceous matter and minerals were obtained on 100 μm 2 maps. Maps of the surface of native stones and of a powdered sample are compared. Graphitic and amorphous carbonaceous domains are found to be highly overlapping in all tested areas at the surface of the meteorite and in its interior as well. Pyroxene, olivine and iron oxide grains are embedded into this mixed carbonaceous material. The results show that every mineral grain with a size of less than a few μm 2 is encased in a thin carbonaceous matrix, which accounts for only 2.5 wt.%. This interstitial matter sticks together isolated mineral crystallites or concretions, including only very few individualized graphitised grains. Grinding separates the mineral particles but most of them retain their carbonaceous coating. This Raman study complements recent findings deduced from other spatial analyses performed by microprobe laser-desorption laser-ionisation mass spectrometry (μL 2MS), transmission electron microscopy (TEM) and scanning transmission X-ray microscopy (STXM).

  13. Very Low Grade Metamorphic Temperatures of the Upper Paleozoic Strata in Northern Daxing’anling Area,NE China:Evidence from Raman Spectrum Studies of Carbonaceous Materials%大兴安岭北部上古生界极低级变质温度来自碳质物拉曼光谱的证据

    Institute of Scientific and Technical Information of China (English)

    胡大千; 王岩泉; 沙茜; 王春光; 陈旭; 马瑞

    2015-01-01

    Using the Renishaw System-1000 laser Raman spectrometer,authors have studied the laser Raman spectrum characteristics of the carbonaceous materials in pelitic rocks outcropped in northern Daxing ’anling area and its indication to the metamorphic temperature.The relationship between the various parameters of the Raman spectrum and the vitrinite reflectance (Ro) of the carbonaceous materials is also discussed.The study shows that the carbonaceous material of Upper Paleozoic pelitic rock has not the Raman spectrum absorption peak of graphite,revealing its metamorphic grade below the low-greenschist facies.Using Raman spectroscopy constructed and proposed by Barker et al.(1 986)and by Rahl et al.(2005),the metamorphic temperature of Upper Paleozoic pelitic rock in the studied area is estimated at 270℃ to 320℃,indicating the Paleozoic strata of the area have merely undergone very low grade metamorphism and metamorphic grade belongs to anchizone.Based on the relationship between the laser Raman spectrometer of carbonaceous materials and the vitrinite reflectance (Ro)proposed by Wang Y,et al.(2002),the Rovalues (maturity of organic materials)of pelitic rocks are estimated to be from 3.03% to 4.23%,consistent with the measured values,showing that the evolution of organic matter of the area is at the over-mature stage,and the pelitic rocks in the area are capable to be generate the hydrocarbon generation and part of the them may have the potential for oil and gas resources.%使用 Renishaw System 1000型激光拉曼光谱仪,研究了大兴安岭北部上古生界泥质岩石碳质物的拉曼光谱特征及其对形成温度的表征,探讨了拉曼光谱参数与镜质体反射率(Ro)的关系。研究表明:研究区上古生界泥质岩石碳质物不具有石墨的拉曼光谱谱带吸收峰,揭示了地层的变质程度未达到低绿片岩相。利用此次经过完善建立的拉曼光谱地质温度计,对大兴安岭北部上古生界泥质岩石变质

  14. Microporous carbonaceous adsorbents for CO2 separation via selective adsorption

    KAUST Repository

    Zhao, Yunfeng

    2015-01-01

    Selective adsorption of CO2 has important implications for many energy and environment-related processes, which require the separation of CO2 from other gases (e.g. N2 and CH4) with high uptakes and selectivity. The development of high-performance adsorbents is one of the most promising solutions to the success of these processes. The present review is focused on the state-of-the-art of carbon-based (carbonaceous) adsorbents, covering microporous inorganic carbons and microporous organic polymers, with emphasis on the correlation between their textural and compositional properties and their CO2 adsorption/separation performance. Special attention is given to the most recently developed materials that were not covered in previous reviews. We summarize various effective strategies (N-doping, surface functionalization, extra-framework ions, molecular design, and pore size engineering) for enhancing the CO2 adsorption capacity and selectivity of carbonaceous adsorbents. Our discussion focuses on CO2/N2 separation and CO2/CH4 separation, while including an introduction to the methods and criteria used for evaluating the performance of the adsorbents. Critical issues and challenges regarding the development of high-performance adsorbents as well as some overlooked facts and misconceptions are also discussed, with the aim of providing important insights into the design of novel carbonaceous porous materials for various selective adsorption based applications. This journal is © The Royal Society of Chemistry.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  17. Organic halogens in spruce forest throughfall

    DEFF Research Database (Denmark)

    Öberg, G.; Johansen, C.; Grøn, C.

    1998-01-01

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

  18. Noble Gases and Halogens in Icelandic Basalts

    OpenAIRE

    Weston, Bridget

    2013-01-01

    Noble gas and halogen data from a suite of Icelandic samples are presented. Iceland combines hotspot volcanism, a spreading ridge and abundant subglacially erupted samples. This combination allows for samples that erupted under high enough pressures to retain a measurable mantle volatile content, and also display signatures representing interaction between ocean island basalt (OIB) and mid-ocean ridge basalt (MORB) mantle sources.Erupted samples used to determine the mantle’s halogen and nobl...

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

    Science.gov (United States)

    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.

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

    International Nuclear Information System (INIS)

    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-1 (OC) and 0.120 to 0.160 mg/m-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-3 (OC) and 0.006--0.050 mg/m-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)

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

    Science.gov (United States)

    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).

  2. Functionalization of biomass carbonaceous aerogels: selective preparation of MnO2@CA composites for supercapacitors.

    Science.gov (United States)

    Ren, Yumei; Xu, Qun; Zhang, Jianmin; Yang, Hongxia; Wang, Bo; Yang, Daoyuan; Hu, Junhua; Liu, Zhimin

    2014-06-25

    Functionalized porous carbon materials with hierarchical structure and developed porosity coming from natural and renewable biomass have been attracting tremendous attention recently. In this work, we present a facile and scalable method to synthesize MnO2 loaded carbonaceous aerogel (MnO2@CA) composites via the hydrothermal carbonaceous (HTC) process. We employ two reaction systems of the mixed metal ion precursors to study the optimal selective adsorption and further reaction of MnO2 precursor on CA. Our experimental results show that the system containing KMnO4 and Na2S2O3·5H2O exhibits better electrochemical properties compared with the reaction system of MnSO4·H2O and (NH4)2S2O8. For the former, the obtained MnO2@CA displays the specific capacitance of 123.5 F·g(-1). The enhanced supercapacitance of MnO2@CA nanocomposites could be ascribed to both electrochemical contributions of the loaded MnO2 nanoparticles and the porous structure of three-dimensional carbonaceous aerogels. This study not only indicates that it is vital for the reaction systems to match with porous carbonaceous materials, but also offers a new fabrication strategy to prepare lightweight and high-performance materials that can be used in energy storage devices. PMID:24882146

  3. Treatment System for Removing Halogenated Compounds from Contaminated Sources

    Science.gov (United States)

    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.

  4. A QTAIM exploration of the competition between hydrogen and halogen bonding in halogenated 1-methyluracil: Water systems

    Science.gov (United States)

    Huan, Guo; Xu, Tianlv; Momen, Roya; Wang, Lingling; Ping, Yang; Kirk, Steven R.; Jenkins, Samantha; van Mourik, Tanja

    2016-10-01

    Using QTAIM we show that the hydrogen bonding complexes of 5-halogenated-1-methyluracil (XmU; X = F, Cl, Br, I or At) with a water molecule were always stronger than the corresponding halogen bonds. The strength of the hydrogen bond decreased with increasing halogen size. The hydrogen bonds displayed an admixture of covalent character but all the halogen bonds were purely electrostatic in nature. An F---O halogen bond was found and was facilitated by an intermediate F---H bonding interaction. The metallicity ξ(rb) of the C = O bonds neighboring the hydrogen bonds and of the C-X bonds contiguous with the halogen bonds was explored.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

  7. SYNTHESIS AND CHARACTERIZATION OF NEW HALOGENATED CURCUMINOIDS

    Directory of Open Access Journals (Sweden)

    Eugenio Torres

    2013-12-01

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

  8. HALOGEN LAMP BURST PHOTOKERATITIS: A MASS INCIDENCE

    Directory of Open Access Journals (Sweden)

    Snehal

    2014-04-01

    Full Text Available : Tungsten-halogen lamps, used in stage lighting and outdoor events pose a risk with their improper use or as a consequence of lamp rupture. Acute over-exposure to ultraviolet radiation produced by the lamps can lead to photokeratitis. We report an event of, blast of 15 halogen lamps involving 205 patients presenting with blephorospasm, photophobia and burning sensations. 167 had conjunctival congestion and 43 keratoconjunctivitis. Visual acuity between 6/12 and 6/60, was noted in 33 cases. One patient had iridocyclitis and one episcleritis. Ultraviolet irradiance overexposure in an acute setting due to halogen lamps is hitherto unreported and ophthalmologists need to be aware of the clinical spectrum of acute UV radiation keratitis when caring for patients in these uncommon situations.

  9. Evaluation of Halogenated Coumarins for Antimosquito Properties

    Directory of Open Access Journals (Sweden)

    Venugopala K. Narayanaswamy

    2014-01-01

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

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

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

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

  12. Volatile Halogenated Organic Compounds Released to Seawater from Temperate Marine Macroalgae

    Science.gov (United States)

    Gschwend, Philip M.; Macfarlane, John K.; Newman, Kathleen A.

    1985-03-01

    Volatile halogenated organic compounds synthesized by various industrial processes are troublesome pollutants because they are persistent in terrestrial ecosystems and because they may be present in sufficient quantities to alter the natural atmospheric cycles of the halogens. Certain of these compounds, including polybromomethanes and several previously unobserved alkyl monohalides and dihalides, appear to be natural products of the marine environment. A variety of temperate marine macroalgae (the brown algae Ascophyllum nodosum and Fucus vesiculosis, the green algae Enteromorpha linza and Ulva lacta, and the red alga Gigartina stellata) not only contain volatile halogenated organic compounds but also release them to seawater at rates of nanograms to micrograms of each compound per gram of dry algae per day. The macroalgae may be an important source of bromine-containing material released to the atmosphere.

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

    Science.gov (United States)

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

    KAUST Repository

    Ward, Jeremy W.

    2014-05-15

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

  15. Retention of Halogens in Waste Glass

    Energy Technology Data Exchange (ETDEWEB)

    Hrma, Pavel R.

    2010-05-01

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

  16. Halogen Bonding in (Z-2-Iodocinnamaldehyde

    Directory of Open Access Journals (Sweden)

    Miriam Rossi

    2013-07-01

    Full Text Available Based on the bulkiness of the iodine atom, a non-planar conformation was expected for the title compound. Instead, its molecular structure is planar, as experimentally determined using single crystal X-ray diffraction, and confirmed theoretically by DFT calculations on the single molecule and the halogen pair paired molecules, therefore ruling out crystal packing forces as a principal factor leading to planarity. Indeed, planarity is ascribed to the carbonyl double bond, as when this bond is saturated on forming the related alcohol derivative, the molecule loses planarity. The X-ray molecular structure shows an intermolecular separation between the iodine and the oxygen of the carbonyl shorter than the corresponding van der Waals distance suggesting a weak halogen bond interaction. DFT minimization of this 2-molecule arrangement shows the iodine--oxygen distance much shorter than that observed in the crystal interaction and confirming its stronger halogen bond nature. A trend between increasing I•••O(carbonyl separation and decreasing C-I•••O(carbonyl angle is demonstrated, further confirming the existence of a halogen bond.

  17. Natural halogenated compounds in forest soils

    DEFF Research Database (Denmark)

    Albers, Christian Nyrop

    miljøproblemer der har været relateret til visse af disse stoffer (f.eks. PCB´er, dioxiner, klorerede opløsningsmidler samt visse pesticider). Ikke alle halogenerede stoffer er dog giftige, og mange naturstoffer, giftige såvel som ikke giftige, indeholder halogener. Kloroform er et af disse stoffer, der udover...

  18. Chiral biomarkers and microfossils in carbonaceous meteorites

    Science.gov (United States)

    Hoover, Richard B.

    2010-09-01

    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.

  19. Microfossils in CI and CO Carbonaceous Meteorites

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Directory of Open Access Journals (Sweden)

    Toshio Miwa

    2013-05-01

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

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

    Science.gov (United States)

    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...

  3. Chemical analysis of organic molecules in carbonaceous meteorites

    NARCIS (Netherlands)

    Torrao Pinto Martins, Zita Carla

    2007-01-01

    Meteorites are extraterrestrial objects that survive the passage through the Earth’s atmosphere and impact the Earth's surface. They can be divided into several classes, the carbonaceous chondrites being one of them. Carbonaceous chondrites are the oldest and best preserved meteorites and contain a

  4. Evidence of Microfossils in Carbonaceous Chondrites

    Science.gov (United States)

    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.

  5. Multi-wavelength characterization of carbonaceous aerosol

    Science.gov (United States)

    Massabò, Dario; Caponi, Lorenzo; Chiara Bove, Maria; Piazzalunga, Andrea; Valli, Gianluigi; Vecchi, Roberta; Prati, Paolo

    2014-05-01

    Carbonaceous aerosol is a major component of the urban PM. It mainly consists of organic carbon (OC) and elemental carbon (EC) although a minor fraction of carbonate carbon could be also present. Elemental carbon is mainly found in the finer PM fractions (PM2.5 and PM1) and it is strongly light absorbing. When determined by optical methods, it is usually called black carbon (BC). The two quantities, EC and BC, even if both related to the refractory components of carbonaceous aerosols, do not exactly define the same PM component (Bond and Bergstrom, 2006; and references therein). Moreover, another fraction of light-absorbing carbon exists which is not black and it is generally called brown carbon (Andreae and Gelencsér, 2006). We introduce a simple, fully automatic, multi-wavelength and non-destructive optical system, actually a Multi-Wavelength Absorbance Analyzer, MWAA, to measure off-line the light absorption in Particulate Matter (PM) collected on filters and hence to derive the black and brown carbon content in the PM This gives the opportunity to measure in the same sample the concentration of total PM by gravimetric analysis, black and brown carbon, metals by, for instance, X Ray Fluorescence, and finally ions by Ion Chromatography. Up to 16 samples can be analyzed in sequence and in an automatic and controlled way within a few hours. The filter absorbance measured by MWAA was successfully validated both against a MAAP, Multi Angle Absorption Photometer (Petzold and Schönlinner, 2004), and the polar photometer of the University of Milan. The measurement of sample absorbance at three wavelengths gives the possibility to apportion different sources of carbonaceous PM, for instance fossil fuels and wood combustion. This can be done following the so called "aethalometer method" (Sandradewi et al., 2008;) but with some significant upgrades that will be discussed together the results of field campaigns in rural and urban sites. Andreae, M.O, and Gelencsér, A

  6. Acid/base bifunctional carbonaceous nanomaterial with large surface area: Preparation, characterization, and adsorption properties for cationic and anionic compounds

    International Nuclear Information System (INIS)

    Nanostructured carbonaceous materials are extremely important in the nano field, yet developing simple, mild, and “green” methods that can make such materials possess large surface area and rich functional groups on their surfaces still remains a considerable challenge. Herein, a one-pot and environment-friendly method, i.e., thermal treatment (180 °C; 18 h) of water mixed with glucose and chitosan (CTS), has been proposed. The resultant carbonaceous nanomaterials were characterized by field emitting scanning electron microscope, N2 adsorption/desorption, Fourier transform infrared spectroscope, X-ray photoelectron spectroscopy, and zeta-potential analysis. It was found that, in contrast to the conventional hydrothermally carbonized product from pure glucose, with low surface area (9.3 m2 g−1) and pore volume (0.016 cm3 g−1), the CTS-added carbonaceous products showed satisfactory textural parameters (surface area and pore volume up to 254 m2 g−1 and 0.701 cm3 g−1, respectively). Moreover, it was also interestingly found that these CTS-added carbonaceous products possessed both acidic (–COOH) and basic (–NH2) groups on their surfaces. Taking the advantages of large surface area and –COOH/–NH2 bifunctional surface, the carbonaceous nanomaterials exhibited excellent performance for adsorptions of cationic compound (i.e., methylene blue) at pH 10 and anionic compound (i.e., acid red 18) at pH 2, respectively. This work not only provides a simple and green route to prepare acid/base bifunctional carbonaceous nanomaterials with large surface area but also well demonstrates their potential for application in adsorption. - Highlights: • A simple and green method was proposed to prepare carbon nanomaterials. • The carbon product showed acid/base bifunctional surface with large surface area. • The carbon material could efficiently adsorb both cationic and anionic compounds

  7. Global cloud condensation nuclei influenced by carbonaceous combustion aerosol

    Science.gov (United States)

    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.

  8. Global cloud condensation nuclei influenced by carbonaceous combustion aerosol

    Directory of Open Access Journals (Sweden)

    D. V. Spracklen

    2011-09-01

    Full Text Available 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.

  9. Halogen bonding origin properties and applications

    International Nuclear Information System (INIS)

    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

  10. Halogen bonding origin properties and applications

    Energy Technology Data Exchange (ETDEWEB)

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

    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.

  11. Microfossils of Cyanobacteria in Carbonaceous Meteorites

    Science.gov (United States)

    Hoover, Richard B.

    2007-01-01

    During the past decade, Environmental and Field Emission Scanning Electron Microscopes have been used at the NASA/Marshall Space Flight Center to investigate freshly fractured interior surfaces of a large number of different types of meteorites. Large, complex, microfossils with clearly recognizable biological affinities have been found embedded in several carbonaceous meteorites. Similar forms were notably absent in all stony and nickel-iron meteorites investigated. The forms encountered are consistent in size and morphology with morphotypes of known genera of Cyanobacteria and microorganisms that are typically encountered in associated benthic prokaryotic mats. Even though many coccoidal and isodiametric filamentous cyanobacteria have a strong morphological convergence with some other spherical and filamentous bacteria and algae, many genera of heteropolar cyanobacteria have distinctive apical and basal regions and cellular differentiation that makes it possible to unambiguously recognize the forms based entirely upon cellular dimensions, filament size and distinctive morphological characteristics. For almost two centuries, these morphological characteristics have historically provided the basis for the systematics and taxonomy of cyanobacteria. This paper presents ESEM and FESEM images of embedded filaments and thick mats found in-situ in the Murchison CM2 and Orgueil cn carbonaceous meteorites. Comparative images are also provided for known genera and species of cyanobacteria and other microbial extremophiles. Energy Dispersive X-ray Spectroscopy (EDS) studies indicate that the meteorite filaments typically exhibit dramatic chemical differentiation with distinctive difference between the possible microfossil and the meteorite matrix in the immediate proximity. Chemical differentiation is also observed within these microstructures with many of the permineralized filaments enveloped within electron transparent carbonaceous sheaths. Elemental distributions of

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

    Science.gov (United States)

    Ford, Melissa Coates; Ho, P Shing

    2016-03-10

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

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

    International Nuclear Information System (INIS)

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

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

    Directory of Open Access Journals (Sweden)

    Tharaporn Permpool

    2013-01-01

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

  15. Metal-dusting resistance of uncoated and coated iron and nickel base materials against metal-dusting in heat treatment furnaces with carbonaceous atmospheres; Bestaendigkeit von unbeschichteten und beschichteten Eisen- und Nickelbasiswerkstoffen gegenueber Metal-Dusting in Aufkohlanlagen

    Energy Technology Data Exchange (ETDEWEB)

    Kleingries, Mirko; Ackermann, Helen; Lucka, Klaus [OWI Oel-Waerme-Institut GmbH, Aachen (Germany); Hoja, Timo; Mehner, Andeas; Zoch, Hans-Werner [IWT, Stiftung Institut fuer Werkstofftechnik, Bremen (Germany); Altena, Herwig [AICHELIN Ges.m.b.H, Moedling (Austria)

    2010-03-15

    Metal-Dusting is a well-known corrosion problem that occurs in carburizing atmospheres in industrial thermal processing plants. In literature almost no quantitative data on the metal dusting resistance of typical alloys employed in industrial furnaces are available. Therefore, a series of experiments with uncoated and sol gel ZrO{sub 2} coated high temperature materials was conducted in order to quantify their metal dusting behaviour under conditions close to those in case hardening furnaces. The experimental results show a strong influence of the surface conditions on the alloys resistance and a noticeable enhancement of the resistance by sol gel coatings. (orig.)

  16. Carbonaceous chondrites and the origin of life

    Science.gov (United States)

    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.

  17. Methods of ultimate carbonaceous BOD determination

    Science.gov (United States)

    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.

  18. Global cloud condensation nuclei influenced by carbonaceous combustion aerosol

    Directory of Open Access Journals (Sweden)

    D. V. Spracklen

    2011-03-01

    Full Text Available 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.

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

    Science.gov (United States)

    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.

  20. Adsorption and Desorption of Carbon Dioxide and Water Mixtures on Synthetic Hydrophobic Carbonaceous Adsorbents

    Science.gov (United States)

    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.

  1. 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.

    Science.gov (United States)

    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

  2. Generation of oil from coal and carbonaceous shale

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

    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

  4. Bacterial morphologies in carbonaceous meteorites and comet dust

    CERN Document Server

    Wickramasinghe, N Chandra; Gibson, Carl H; Wallis, Jamie; Al-Mufti, Shirwan; Miyake, Nori

    2010-01-01

    Three decades ago the first convincing evidence of microbial fossils in carbonaceous chondrites was discovered and reported by Hans Dieter Pflug and his collaborators. In addition to morphology, other data, notably laser mass spectroscopy, confirmed the identification of such structures as putative bacterial fossils. Balloon-borne cryosampling of the stratosphere enables recovery of fragile cometary dust aggregates with their structure and carbonaceous matter largely intact. Scanning electron microscope studies of texture and morphology of particles in the Cardiff collection, together with Energy Dispersive X-ray identifications, show two main types of putative bio-fossils - firstly organic-walled hollow spheres around 10 microns across, secondly siliceous diatom skeletons similar to those found in carbonaceous chondrites and terrestrial sedimentary rocks and termed "acritarchs". Since carbonaceous chondrites (particularly Type 1 chondrites) are thought to be extinct comets the data reviewed in this article p...

  5. TESTING OF CARBONACEOUS ADSORBENTS FOR REMOVAL OF POLLUTANTS FROM WATER

    Directory of Open Access Journals (Sweden)

    RAISA NASTAS

    2012-03-01

    Full Text Available Testing of carbonaceous adsorbents for removal of pollutants from water. Relevant direction for improving of quality of potable water is application of active carbons at various stages of water treatments. This work includes complex research dealing with testing of a broad spectrum of carbonaceous adsorbents for removal of hydrogen sulfide and nitrite ions from water. The role of the surface functional groups of carbonaceous adsorbents, their acid-basic properties, and the influence of the type of impregnated heteroatom (N, O, or metals (Fe, Cu, Ni, on removal of hydrogen sulfide species and nitrite ions have been researched. The efficiency of the catalyst obtained from peach stones by impregnation with Cu2+ ions of oxidized active carbon was established, being recommended for practical purposes to remove the hydrogen sulfide species from the sulfurous ground waters. Comparative analysis of carbonaceous adsorbents reveals the importance of surface chemistry for oxidation of nitrite ions.

  6. Mercury and halogens in coal: Chapter 2

    Science.gov (United States)

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

    2014-01-01

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

  7. Boiling Heat Transfer to Halogenated Hydrocarbon Refrigerants

    Science.gov (United States)

    Yoshida, Suguru; Fujita, Yasunobu

    The current state of knowledge on heat transfer to boiling refrigerants (halogenated hydrocarbons) in a pool and flowing inside a horizontal tube is reviewed with an emphasis on information relevant to the design of refrigerant evaporators, and some recommendations are made for future research. The review covers two-phase flow pattern, heat transfer characteristics, correlation of heat transfer coefficient, influence of oil, heat transfer augmentation, boiling from tube-bundle, influence of return bend, burnout heat flux, film boiling, dryout and post-dryout heat transfer.

  8. CARES: Carbonaceous Aerosol and Radiative Effects Study Science Plan

    Energy Technology Data Exchange (ETDEWEB)

    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.

  9. Recommendations for Estimating Carbonaceous Aerosol Inventories

    Science.gov (United States)

    Liousse, C.; Cachier, H.; Bond, T.; Penner, J.; Carmichael, G.; Reddy, M.; Gadi, R.; Michel, C.

    2002-12-01

    Increasing interest for carbonaceous aerosol studies is due to the recognized effect of such particles on regional and global radiative balance and climate. Recent calculations (Jacobson et al.,2002) have shown for example that reduction of black carbon (BC) and organic carbon (OC) particle emissions by fossil fuel combustions especially diesel combustions, may slow the global warming more efficiently that any reductions of carbon dioxide. Also, modeling studies of aerosol radiative forcing have pointed out its high sensitivity to the choice of BC source inventory, as BC is the main absorbing component of the aerosol phase. However, such studies rely on very different existing BC inventories (Penner et al., 1993, Cooke and Wilson, 1996, Liousse et al., 1996, Cooke et al., 1999, LavouZ˜ et al., 2000) while other developments for the global (Bond, Shulz or Chin works) and regional scales (Streets, Reddy, Michel, Liousse works) are currently underway. Actually, the budgets which are presented in the various inventories differ significantly. Yearly global BC emissions from Bond is roughly half of those given by Cooke et al., 1999. Let us note also that there is an important lack of knowledge for organic particulates. We created a working group on this topic and the first meeting took place in Toulouse last June. The aim is also to keep close connection with other initiatives and to conduct intercomparisons with the different inventories with a double focus, the global scale and zooms over some areas of particular interest for combustion aerosols (Asia and Africa). Our role is above all to obtain consistent inventories relying firstly in the definition of carbonaceous aerosol, secondly in the methods chosen for carbon measurements. Thus we will be able to propose clear recommendations for existing emission factor values for fossil fuel (especially for diesel and coal) and biomass burning (especially for domestic fires, savanna and forest fires) or future experiments

  10. Distinct Purine Distribution in Carbonaceous Chondrites

    Science.gov (United States)

    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

  11. 40 CFR 721.10015 - Halogenated benzimidazole (generic).

    Science.gov (United States)

    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...

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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

  14. Microscale Distribution of Hydrogen Isotopes in Two Carbonaceous Chondrites

    Science.gov (United States)

    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].

  15. Home-made carbonaceous adsorbents for the iodine filter

    International Nuclear Information System (INIS)

    Assuming, that at the moment, an activated charcoal is the most widely used adsorbent in off-gas cleaning systems for elemental iodine removal, it was analyzed how to improve the adsorption properties of this filter material for removing the organic iodine compounds, especially in the presence of high relative humidity. Three different indigenous activated charcoals were selected for studies: two kinds of charcoal, designated as type A and N, as well as the charcoals used for flue gas desulfurization, as the third type S. These charcoals were impregnated with tin iodide (SnI2), potassium iodide (KI) and triethylenediamine (TEDA). Considering the results of the laboratory tests of the efficiency methyl iodide retention by the impregnated charcoals, it was concluded, that the carbonaceous adsorbent containing 1+1.5% KI showed efficient retention of the methyl iodide (CH3I), compared with, for example, foreign activated charcoals, as, NORIT-CGI 1% KI (West Germany) and GA-1 0.5% KI (Czechoslovakia). (author)

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

    Science.gov (United States)

    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

  17. Investigation of nanocrystalline structure in selected carbonaceous materials

    Institute of Scientific and Technical Information of China (English)

    Manoj B

    2014-01-01

    The structural parameters of nine Indian coals were determined by X-ray diffraction (XRD) and Raman spectroscopy. The study revealed that the coals contain crystalline carbon of turbostratic structure with amorphous carbon. The stacking height (Lc) and interlayer spacing (d002) of the crystallite structure of the coals ranged from 1.986 to 2.373 nm and from 0.334 to 0.340 nm, respectively. The degree of graphitization was calculated to range from 42%to 99%, thereby confirming the ordering of the carbon layers with the increase in coal rank. An exponential correlation was observed among the aromaticity (fa), the lateral size (La), and the rank (I20/I26), suggesting that the coal crys-tallites are nanocrystalline in nature. A very strong correlation was observed between the structural parameters (fa, d002, Lc, the H/C ratio, and I20/I26), the volatile matter content, and the elemental carbon content, indicating the structures of coals are controlled by the degree of contact metamorphism. The Raman spectra exhibited two prominent bands:the graphitic band (G) and the first-order characteristic defect band (D). The deconvolution resulted in five peaks:G, D1, D2, D3, and D4. The intense D1 band, which appeared at~1350 cm-1, corresponds to a lat-tice vibration mode with A1g symmetry. The D2 mode, which appeared at~1610 cm-1, arises from the structural disorder as a shoulder on the G band.

  18. Determination of halogens and sulfur in high-purity polyimide by IC after digestion by MIC.

    Science.gov (United States)

    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

  19. Carbonaceous aerosols in PM10 and pollution gases in winter in Beijing

    Institute of Scientific and Technical Information of China (English)

    ZHANG Ren-Jian; CAO Jun-ji; LEE Shun-cheng; SHEN Zhen-xing; HO Kin-Fai

    2007-01-01

    An intensive observation of organic carbon (OC) and element carbon (EC) in PM10 and gaseous materials (SO2, CO, and O3,) was conducted continuously to assess the characteristics of wintertime carbonaceous aerosols in an urban area of Beijing, China. Results showed that the averaged total carbon (TC) and PM10 concentrations in observation period are 30.2±120.4 and 172.6±198.3 μ/m3, respectively. Average OC concentration in nighttime (24.9±19.6 μ/m3) was 40% higher than that in daytime (17.7±10.9 μ/m3). Average EC concentrations in daytime (8.8±15.2 μ/m3) was close to that in nighttime (8.9±15.1 μ/m3). The OC/EC ratios in nighttime ranging from 2.4 to 2.7 are higher than that in daytime ranging from 1.9 to 2.0. The concentrations of OC, EC, PM10 were low with strong winds and high with weak winds. The OC and EC were well correlated with PM10, CO and SO2, which implies they have similar sources. OC and EC were not well correlated with O3. By considering variation of OC/EC ratios in daytime and night time, correlations between OC and O3, and meteorological condition, we speculated that OC and EC in Beijing PM10 were emitted as the primary particulate form. Emission of motor vehicle with low OC/EC ratio and coal combustion sources with high OC/EC ratio are probably the dominant sources for carbonaceous aerosols in Beijing in winter. A simple method was used to estimate the relative contribution of sources to carbonaceous aerosols in Beijing PM10. Motor vehicle source accounts for 80% and 68%, while coal combustion accounts for 20% and 32% in daytime and nighttime, respectively in Beijing. Averagely, the motor vehicle and coal combustion accounted for 74% and 26%, respectively, for carbonaceous aerosols during the observation period. It points to the motor vehicle is dominant emission for carbonaceous aerosols in Beijing PM10 in winter period, which should be paid attention to control high level of PM10 in Beijing effectively.

  20. Physical and Chemical Characterization of Carbonaceous Aerosols in Korea

    Science.gov (United States)

    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.

  1. Insights into enzymatic halogenation from computational studies

    Science.gov (United States)

    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. Halogenated DOPA in a Marine Adhesive Protein.

    Science.gov (United States)

    Sun, Cheng Jun; Srivastava, Aasheesh; Reifert, Jack R; Waite, J Herbert

    2009-02-01

    The sandcastle worm Phragmatopoma californica, a marine polychaete, constructs a tube-like shelter by cementing together sand grains using a glue secreted from the building organ in its thorax. The glue is a mixture of post-translationally modified proteins, notably the cement proteins Pc-1 and Pc-2 with the amino acid, 3,4-dihydroxyphenyl-L-alanine (DOPA). Significant amounts of a halogenated derivative of DOPA were isolated from the worm cement following partial acid hydrolysis and capture of catecholic amino acids by phenylboronate affinity chromatography. Analysis by tandem mass spectrometry and (1)H NMR indicates the DOPA derivative to be 2-chloro-4, 5-dihydroxyphenyl-L-alanine. The potential roles of 2-chloro-DOPA in chemical defense and underwater adhesion are considered.

  3. Halogenated coumarin derivatives as novel seed protectants.

    Science.gov (United States)

    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

  4. Laboratory Studies Of Circumstellar Carbonaceous Grain Formation

    Science.gov (United States)

    Contreras, Cesar; Sciamma-O'Brien, Ella; Salama, Farid

    2014-06-01

    The study of the formation processes of dust is essential to understand the budget of extraterrestrial organic molecules. Although dust with all its components plays an important role in the evolution of interstellar (IS) chemistry and in the formation of organic molecules, little is known on the formation processes of carbonaceous dust. We report the progress that was recently achieved in this domain using NASA Ames’ COSmIC facility (Contreras & Salama 2013, ApJS, 208, 6). PAHs are important chemical building blocks of IS dust. They are detected in IDPs and in meteoritic samples. Additionally, observational, laboratory, and theoretical studies have shown that PAHs are an important, ubiquitous component of the ISM. The formation of PAHs from smaller molecules has not been extensively studied. Therefore, we have performed laboratory experiments to study the dynamic processes of carbon grain formation, starting from the smallest hydrocarbon molecules into the formation of larger PAH and further into nanograins. Studies of IS dust analogs formed from a variety of PAH and hydrocarbon precursors as well as species that include the atoms O, N, and S, have recently been performed in our laboratory using the COSmIC facility to provide conditions that simulate IS and circumstellar environments. The species formed in the COSmiC chamber through a pulsed discharge nozzle plasma source are detected and characterized with a cavity ringdown spectrometer coupled to a time-of-flight mass spectrometer, thus providing both spectroscopic and ion mass information in-situ. Analysis of solid soot particles was also conducted using scanning electron microscopy at the UCSC/NASA Ames’ MACS facility. The SEM analysis of the deposition of soot from methane and acetylene precursors seeded in argon plasmas provide examples on the types of nanoparticles and micrograins that are produced in these gas mixtures under our experimental conditions. From these measurements, we derive information on

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

    KAUST Repository

    Fu, Boyi

    2015-04-01

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

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

    Directory of Open Access Journals (Sweden)

    Alaghehmand H.

    2006-08-01

    Full Text Available Background and Aim: Sufficient polymerization is a critical factor to obtain optimum physical properties and clinical efficacy of resin restorations. The aim of this study was to evaluate wear rates of composite resins polymerized by two different systems Light Emitting Diodes (LED to and Halogen lamps. Materials and Methods: In this laboratory study, 20 specimens of A3 Tetric Ceram composite were placed in brass molds of 2*10*10 mm dimensions and cured for 40 seconds with 1 mm distance from surface. 10 specimens were cured with LED and the other 10 were cured with Halogen unit. A device with the ability to apply force was developed in order to test the wear of composites. After storage in distilled water for 10 days, the specimens were placed in the wear testing machine. A chrome cobalt stylus with 1.12 mm diameter was applied against the specimens surfaces with a load of 2 kg. The weight of each samples before and after 5000, 10000, 20000, 40000, 80000 and 120000 cycles was measured using an electronic balance with precision of 10-4 grams. Data were analyzed using t test and paired t test. P0.05. Conclusion: Based on the results of this study, LED and halogen light curing units resulted in a similar wear rate in composite resin restorations.

  7. Factors determining the structure of Au, Ag and Cr thin layers deposited on alkaline halogen substrates

    International Nuclear Information System (INIS)

    Metal thin layer deposited on dielectric substrates, in general, and on alkaline halogen substrates, in particular, have been thoroughly studied in order to make clear the phenomenology of the formation and development processes, to set out fundamental factors in determining their structure and to determine optimum conditions for the obtaining of monocrystal thin layers or metastable structured thin layers in view of their practical applications. Starting from a systematic programme of experimental investigations, an attempt has been made to investigate the influence of substrate composition, of defects within alkaline halogen substrates and of deposition conditions on the orientated formation and development of Au layer and on the formation of metastable Cr-delta structures in the case of thin Cr layers. A systematic study on the influence of deposition conditions and on alkaline halogen substrates with colloidal centres is carried out in view of elaborating a method for the development of monocrystal Au layers for ''channeling targets''. A correlation between characteristic parameters which define the atomic theory of nucleation including deposition conditions and material parameters, Au parameters for the case of epitaxial layers deposited on KBr, KCl and NaCl substrates has been attempted. (author)

  8. Halogen Bonding Promotes Higher Dye-Sensitized Solar Cell Photovoltages.

    Science.gov (United States)

    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.

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

    Data.gov (United States)

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

  10. Halogenated naphthyl methoxy piperidines for mapping serotonin transporter sites

    Science.gov (United States)

    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.

  11. Crystallography of Magnetite Plaquettes and their Significance as Asymmetric Catalysts for the Synthesis of Chiral Organics in Carbonaceous Chondrites

    Science.gov (United States)

    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.

  12. Acid/base bifunctional carbonaceous nanomaterial with large surface area: Preparation, characterization, and adsorption properties for cationic and anionic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Li, Kai; Ma, Chun–Fang; Ling, Yuan; Li, Meng [Department of Chemistry, Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan 430074 (China); Gao, Qiang, E-mail: gaoqiang@cug.edu.cn [Department of Chemistry, Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan 430074 (China); Engineering Research Center of Nano-Geo Materials of Ministry of Education, China University of Geosciences, Wuhan 430074 (China); Luo, Wen–Jun, E-mail: heartnohome@yahoo.com.cn [Department of Chemistry, Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan 430074 (China)

    2015-07-15

    Nanostructured carbonaceous materials are extremely important in the nano field, yet developing simple, mild, and “green” methods that can make such materials possess large surface area and rich functional groups on their surfaces still remains a considerable challenge. Herein, a one-pot and environment-friendly method, i.e., thermal treatment (180 °C; 18 h) of water mixed with glucose and chitosan (CTS), has been proposed. The resultant carbonaceous nanomaterials were characterized by field emitting scanning electron microscope, N{sub 2} adsorption/desorption, Fourier transform infrared spectroscope, X-ray photoelectron spectroscopy, and zeta-potential analysis. It was found that, in contrast to the conventional hydrothermally carbonized product from pure glucose, with low surface area (9.3 m{sup 2} g{sup −1}) and pore volume (0.016 cm{sup 3} g{sup −1}), the CTS-added carbonaceous products showed satisfactory textural parameters (surface area and pore volume up to 254 m{sup 2} g{sup −1} and 0.701 cm{sup 3} g{sup −1}, respectively). Moreover, it was also interestingly found that these CTS-added carbonaceous products possessed both acidic (–COOH) and basic (–NH{sub 2}) groups on their surfaces. Taking the advantages of large surface area and –COOH/–NH{sub 2} bifunctional surface, the carbonaceous nanomaterials exhibited excellent performance for adsorptions of cationic compound (i.e., methylene blue) at pH 10 and anionic compound (i.e., acid red 18) at pH 2, respectively. This work not only provides a simple and green route to prepare acid/base bifunctional carbonaceous nanomaterials with large surface area but also well demonstrates their potential for application in adsorption. - Highlights: • A simple and green method was proposed to prepare carbon nanomaterials. • The carbon product showed acid/base bifunctional surface with large surface area. • The carbon material could efficiently adsorb both cationic and anionic compounds.

  13. Halogen Bonding: An AIM Analysis of the Weak Interactions

    Institute of Scientific and Technical Information of China (English)

    ZOU, Jian-Wei; LU, Yun-Xiang; YU, Qing-Sen; ZHANG, Hua-Xin; JIANG, Yong-Jun

    2006-01-01

    A series of complexes formed between halogen-containing molecules and ammonia have been investigated by means of the atoms in molecules (AIM) approach to gain a deeper insight into halogen bonding. The existence of the halogen bond critical points (XBCP) and the values of the electron density (ρb) and Laplacian of electron density (▽2pb) at the XBCP reveal the closed-shell interactions in these complexes. Integrated atomic properties such as charge, energy, polarization moment, volume of the halogen bond donor atoms, and the corresponding changes (△) upon complexation have been calculated. The present calculations have demonstrated that the halogen bond represents different AIM properties as compared to the well-documented hydrogen bond. Both the electron density and the Laplacian of electron density at the XBCP have been shown to correlate well with the interaction energy, which indicates that the topological parameters at the XBCP can be treated as a good measure of the halogen bond strength.In addition, an excellent linear relationship between the interatomic distance d(X…N) and the logarithm of ρb has been established.

  14. A theoretical model on the formation mechanism and kinetics of highly toxic air pollutants from halogenated formaldehydes reacted with halogen atoms

    Directory of Open Access Journals (Sweden)

    Y. M. Ji

    2013-07-01

    Full Text Available The atmospheric reactions of halogenated formaldehydes with halogen atoms were investigated by high-accuracy molecular orbital calculation. Studies showed that halogen atoms could easily abstract hydrogen atom from halogenated formaldehydes to form halogenated formyl radical and hydrogen halide (HX. In specific areas with high concentration of halogen atoms, such as the marine boundary layer (MBL, halogenated formyl radical was easily to react with halogen atoms and finally transformed into HX and CO2 in the presence of water; otherwise, this radical was degraded to CO2, halogen gas, and halogenated oxide. By using the canonical variational transition state theory, the kinetics calculations were performed within a wide atmospheric temperature range of 200–368 K, and theoretical values agreed well with the available experimental data. Under atmospheric conditions, the rate constants decreased as altitude increased, and especially the rate constants of halogen atoms reaction with FCHO quickly reduced. Although the reactions of halogenated formaldehydes with F atoms were more easily occurred than did those with Cl and Br atoms, the two latter reactions were still important atmospheric degradation process, especially in the MBL. The modified Arrhenius formulas of rate constants within the atmospheric temperature range were fitted, which helped to understand the established atmospheric model and estimate the contribution of title reactions to atmospheric chemistry pollution.

  15. Aerosol-halogen interaction: Change of physico-chemical properties of SOA by naturally released halogen species

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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

  17. Estimation of Ba, Ag, Sn, Ti, Cu, Zn, Y and Zr in carbonaceous rocks using energy dispersive X-ray fluorescence spectrometer

    International Nuclear Information System (INIS)

    Carbonaceous rocks include carbon phyllites, carbonaceous shale, coal, variants of coaly sandstone, carbonaceous sandstone and graphite schist. Estimation of trace elements in these rocks by X-ray Fluorescence (XRF) method is generally done using coal ash samples. However, one advantage of analyzing whole coal is that volatile elements which are normally lost in ashing, can also be determined. XRF analysis is a rapid, nondestructive comparative method for which a number of matching geostandards/certified reference materials (CRM) is required. Estimation of Ag, Sn, Cu, Ba, Ti, Y and Zr in bromo heavies separated from whole coal samples has been attempted using EDXRFS by formulating procedures with pressed pellets of CRMs comprising of soil (SO-1, SO-2, SO-3, SO-4), shale (SCO-1, SGR-1, SDC-1, GXR-2, GXR-4, GXR-6) and schist rock (ASK-2)

  18. [Investigation of Carbonaceous Airborne Particles by Scanning Proton Microprobe].

    Science.gov (United States)

    Bao, Liang-man; Liu, Jiang-feng; Lei, Qian-tao; Li, Xiao-lin; Zhang, Gui-lin; Li, Yan

    2016-01-15

    Carbonaceous particles are an important component of the atmospheric aerosol particles and important for global climate change, air quality and human health. The PM₁₀ single particles from two environmental monitor locations and seven pollution emission sources were analyzed using scanning proton microprobe (SPM) techniques. The concentration of carbon in individual particles was quantitatively determined by proton non-Rutherford elastic backscattering spectrometry (EBS). The results of this investigation showed that carbonaceous particles were dominant in the pollution sources of coal and oil combustions, diesel busexhaust and automobile exhaust, while inorganic particles were dominant in the sources of steel industry, cement dust and soil dust. Carbonaceous matter was enriched in particles from the city center, while mineral matter was the main component of airborne particles in the industrial area. Elemental mapping of single aerosol particles yielded important information on the chemical reactions of aerosol particles. The micro-PIXE (particle induced X-ray emission) maps of S, Ca and Fe of individual carbonaceous particles showed that sulfuration reaction occurred between SO₂and mineral particles, which increased the sulfur content of particles. PMID:27078933

  19. The Chromium Isotopic Composition of the Ungrouped Carbonaceous Chondrite Tagish Lake

    Science.gov (United States)

    Petitat, M.; Birck, J.-L.; Luu, T. H.; Gounelle, M.

    2011-07-01

    Early solar materials bear a variety of isotopic anomalies that reflect compositional differences deriving from distinct stellar nucleosynthetic processes. As shown in previous studies, the stepwise dissolution with increasing acid strengths of bulk rock carbonaceous chondrites liberates Cr with both excesses and deficits in 53Cr and 54Cr relative to the terrestrial standard. The magnitude of the 54Cr variations within a meteorite decreases in the sequence CI1 > CR2 > CM2 > CV3 > CO3 > CK4 and correlates with the degree of metamorphism of each carbonaceous chondrite class. This study shows that the Tagish Lake meteorite presents the highest excesses in 54Cr ever measured in a bulk silicate phase. According to this study, the Tagish Lake meteorite is composed of the least re-equilibrated material known at this time. The magnitude of 54Cr variation decreases now in the following sequence: Tagish Lake (ungrouped CI2) > Orgueil (CI1) > Murchison (CM2) > Allende (CV2). Moreover, this study shows that excesses in 53Cr relative to Earth can be interpreted as representing the extent of aqueous alteration on meteorite parent bodies. Finally, the high 54Cr anomalies measured in this meteorite make Tagish Lake one of the major targets to decipher the host of these anomalies.

  20. Checking Contamination during Storage of Carbonaceous Chondrites for Micro FTIR Measurements

    Science.gov (United States)

    Zolensky, Michael E.

    2008-01-01

    We examined organic contamination by Fourier transform infrared micro spectroscopic (micro FTIR) measurements of carbonaceous chondrite samples. Carbonaceous chondrites, Tagish Lake (C2), Murchison (CM2) and Moss (CO3), and some mineral powder samples pressed on aluminum plates were measured by micro FTIR before and after storage in several containers with silicone rubber mat. During storage, samples did not touch directly anything except the holding aluminum plates. The carbonaceous chondrites containing hydrous minerals (Tagish Lake and Murchison) pressed on aluminum plates and measured by transmission-reflection micro FTIR measurements were found to be contaminated during storage after only one day, as revealed by an increase of approximately 2965 /cm and approximately 1260 /cm peaks. The Moss meteorite which contains no hydrous minerals, did not show an increase of these peaks, indicating no organic contamination. This difference is probably related to the differing mineralogy and physical properties (including porosity and permeability) of these chondrites. Hydrous minerals such as antigorite, muscovite, montmorillonite and silica gel showed organic contamination by the same infrared measurements, while anhydrous materials such as SiO2 and KBr showed no contamination. These results indicate importance of surface OH groups for the organic contamination. Organic contamination was found on silica gel samples pressed on aluminum plates when they were stored within containers including silicone rubber, silicone grease or adhesive tape. Long path gas cell FTIR measurements for silicone rubber indicated methylsiloxane oligomers were released from the silicone rubber. In-situ heating infrared measurements on the contaminated antigorite and Tagish Lake showed decrease of the 1262 /cm (Si-CH3) and 2963 /cm (CH3) peaks from room temperature to 200-300 C indicating desorption of volatile contaminants. These results indicate that careful preparation and storage are

  1. Synthesis and characterization of lead-free tin silver nanosolders and their application to halogen free nanosolder pastes

    Science.gov (United States)

    Wernicki, Evan

    Solder paste is a key material used in attaching electronic components to printed circuit boards (PCBs). Commonly used lead-based solders, such as eutectic Sn/37Pb, are currently being replaced by lead-free alloy materials due to health and environmental concerns associated with lead. Many solder pastes, both lead-containing and lead-free, contain halogens which act as activators to remove surface oxide and enhance surface wetting, posing further environmental concern from the halogen species. Difficulties in obtaining reliable joints can occur since lead-free solder material candidates have higher melting temperatures (30-50 °C) than that of lead-based solders. Differences in material properties between the numerous materials used in assembly and packaging processes can lead to component damage during manufacturing. Furthermore, designs that include more electrical interconnects in smaller areas give rise for the need for new materials to allow this trend to continue. A surfactant-assisted chemical reduction method was used to synthesize Sn/Ag alloy nanoparticles with a target composition range of 3.5-5 wt% Ag that served as the lead-free solder material within a nanosolder paste. Structure and size characterization via SEM and TEM showed Sn-Ag nanosolders size average approximately 19 nm. Differential scanning calorimetry (DSC) measurements of the nanosolder samples containing 4.5 wt% Ag showed an endothermic peak at 222.5 °C and an onset of 219.2 °C, indicating up to 17.5 °C melting temperature depression when compared to the bulk liquidus value of 240 °C. Composition of the nanosolder material was confirmed using energy dispersive x-ray spectroscopy (EDS) and structures formed were analyzed via x-ray diffraction (XRD). Both halogen-free and halogen-containing flux materials were combined with the nanosolder material, respectively, with varying preparation parameters to form a design of experiments (DoE) for nanosolder paste preparation. Solder pastes

  2. Catalytic mechanisms, basic roles, and biotechnological and environmental significance of halogenating enzymes

    Institute of Scientific and Technical Information of China (English)

    Xianping Chen; Karl-Heinz van Pée

    2008-01-01

    The understanding of enzymatic incorporation of halogen atoms into organic molecules has increased during the last few years. Two novel types of halogenating enzymes, flavindependent halogenases and α-ketoglutarate-dependent halogenases, are now known to play a significant role in enzyme-catalyzed halogenation. The recent advances on the halogenating enzymes RebH, SyrB2, and CytC3 have suggested some new mechanisms for enzymatic halogenations. This review concentrates on the occurrence, catalytic mechanisms, and biotechnological applications of the halogenating enzymes that are currently known.

  3. The contribution of hydrothermally altered ocean crust to the mantle halogen and noble gas cycles

    Science.gov (United States)

    Chavrit, Déborah; Burgess, Ray; Sumino, Hirochika; Teagle, Damon A. H.; Droop, Giles; Shimizu, Aya; Ballentine, Chris J.

    2016-06-01

    Recent studies suggest that seawater-derived noble gases and halogens are recycled into the deep mantle by the subduction of oceanic crust. To understand the processes controlling the availability of halogens and noble gases for subduction, we determined the noble gas elemental and isotopic ratios and halogen (Cl, Br, I) concentrations in 28 igneous samples from the altered oceanic crust (AOC) from 5 ODP sites in the Eastern and Western Pacific Ocean. Crushing followed by heating experiments enabled determination of noble gases and halogens in fluid inclusions and mineral phases respectively. Except for He and Ar, Ne, Kr and Xe isotopic ratios were all air-like suggesting that primary MORB signatures have been completely overprinted by air and/or seawater interaction. In contrast, 3He/4He ratios obtained by crushing indicate that a mantle helium component is still preserved, and 40Ar/36Ar values are affected by radiogenic decay in the mineral phases. The 130Xe/36Ar and 84Kr/36Ar ratios are respectively up to 15 times and 5 times higher than those of seawater and the highest ratios are found in samples affected by low temperature alteration (shallower than 800-900 m sub-basement). We consider three possible processes: (i) adsorption onto the clays present in the samples; (ii) fluid inclusions with a marine pore fluid composition; and (iii) fractionation of seawater through phase separation caused by boiling. Ninety percent of the Cl, Br and I were released during the heating experiments, showing that halogens are dominantly held in mineral phases prior to subduction. I/Cl ratios vary by 4 orders of magnitude, from 3 × 10-6 to 2 × 10-2. The mean Br/Cl ratio is 30% lower than in MORB and seawater. I/Cl ratios lower than MORB values are attributed to Cl-rich amphibole formation caused by hydrothermal alteration at depths greater than 800-900 m sub-basement together with different extents of I loss during low and high temperature alteration. At shallower depths, I

  4. Pyrolysis oil from carbonaceous solid wastes in Malaysia

    International Nuclear Information System (INIS)

    The agro-industrial sector of Malaysia produces a huge amount of oil palm and paddy rice. These generate a significant amount of renewable biomass solid wastes in the forms of oil palm shell and rice husk. Apart from this a huge quantity of scrap tyre is generated from the country's faster increasing usage of transportation vehicles like motorcycle, car, bus and lorries. These wastes are producing pollution and disposal problems affecting the environment. Besides energy is not recovered efficiently from these waste resources. From the elemental composition and thermogravimetric analysis (TGA) studies of the wastes, it appeared that the wastes could be used for pyrolysis liquid oil production. Pyrolysis at present is deemed to be a potential method for the conversion of carbonaceous solid wastes into upgraded liquid products which can either be tried for liquid fuel or value-added chemical. A fluidized bed bench scale fast pyrolysis system was employed for this thermochemical conversion process of solid wastes. Silica sand was used as fluidized bed material and nitrogen gas as the fluidising medium. The products obtained were liquid oil, solid char and gas. The liquid oil and solid char were collected separately while the gas was flared. The maximum liquid product yield was found to vary with feedstock material fluidized bed temperature. The maximum liquid product yield was found to be 58, 53 and 40 wt. % of biomass fed at fluidized bed temperature at 500, 525 and 4500C respectively for oil palm shell, scrap tyre and rice husk. The solid char yield was 25, 36 and 53 wt. % of biomass fed at the condition of maximum liquid product yield for oil palm shell, scrap tyre and rice husk respectively. The oil products were subjected to FTIR, GC and GC/MS analysis for their group composition and detailed chemical compositions. The pyrolysis oil from scrap tyre was found to contain highest percentage of pure hydrocarbons (25 wt. % of total feed) with esters and oxygenated

  5. Thermal history of type 3 chondrites from the Antarctic meteorite collection determined by Raman spectroscopy of their polyaromatic carbonaceous matter

    Science.gov (United States)

    Bonal, Lydie; Quirico, Eric; Flandinet, Laurène; Montagnac, Gilles

    2016-09-01

    This paper is focused on the characterization of the thermal history of 151 CV, CO and unequilibrated ordinary chondrites (UOCs) from the NASA Antarctic meteorite collection, using an approach based on the structure of the included polyaromatic carbonaceous matter determined by Raman spectroscopy. 114 out of these 151 chondrites provided Raman spectra of carbonaceous matter and allowing to assign a petrologic type, which mostly reflects the peak temperature experienced by the rock on the parent body. A thorough review of literature shows however that it is not possible to deduce a peak temperature because accurate calibration is not available. Twenty-three new weakly metamorphosed chondrites have been identified: MIL 07671 (CV3.1); DOM 08006 (CO3.0); DOM 03238, MIL 05024, MIL 05104, MIL 07193 (CO3.1); TIL 82408, LAR 06279 (LL3.05-3.1); EET 90628 (L3.0); GRO 06054, QUE 97008 (L3.05), ALHA 77176, EET 90066, LAR 04380, MET 96515, MIL 05050 (L3.1); ALHA 78133, EET 87735, EET 90909, LEW 87208, PRE 95401 (L3.05-3.1); MCY 05218 (H3.05-3.1) and MET 00506 (H3.1). This study confirms that the width of the D band (FWHMD) and the ratio of the peak intensity of the D and G bands (ID/IG) are the most adapted tracers of the extent of thermal metamorphism in type 3 chondrites. It also unambiguously shows, thanks to the large number of samples, that the width of the G band (FWHMG) does not correlate with the maturity of polyaromatic carbonaceous matter. This parameter is nevertheless very valuable because it shows that Raman spectra of CV chondrites preserve memory of either the metamorphic conditions (possibly oxidation controlled by aqueous alteration) or the nature of the organic precursor. Oxidation memory is our preferred interpretation, however an extensive petrologic characterization of this CV series is required to get firm conclusions. Pre-graphitic carbonaceous matter is reported in seven chondrites and is even the only carbonaceous material detected in the chondrites

  6. The mechanism of halogen liberation in the polar troposphere

    Directory of Open Access Journals (Sweden)

    E. Lehrer

    2004-06-01

    Full Text Available Sudden depletions of tropospheric ozone during spring were reported from the Arctic and also from Antarctic coastal sites. Field studies showed that those depletion events are caused by reactive halogen species, especially bromine compounds. However the source and seasonal variation of reactive halogen species is still not completely understood. There are several indications that the halogen mobilisation from the sea ice surface of the polar oceans may be the most important source for the necessary halogens. Here we present a 1-D model study aimed at determining the primary source of reactive halogens. The model includes gas phase and heterogeneous bromine and chlorine chemistry as well as vertical transport between the surface and the top of the boundary layer. The autocatalytic Br release by photochemical processes (bromine explosion and subsequent rapid bromine catalysed ozone depletion is well reproduced in the model and the major source of reactive bromine appears to be the sea ice surface. The sea salt aerosol alone is not sufficient to yield the high levels of reactive bromine in the gas phase necessary for fast ozone depletion. However, the aerosol efficiently 'recycles' less reactive bromine species (e.g. HBr and feeds them back into the ozone destruction cycle. Isolation of the boundary layer air from the free troposphere by a strong temperature inversion was found to be critical for boundary layer ozone depletion to happen. The combination of strong surface inversions and presence of sunlight occurs only during polar spring.

  7. Halogen chemistry in the marine boundary layer

    Science.gov (United States)

    Plane, J. M. C.; Gomez Martin, J. C.; Kumar, R.; Mahajan, A. S.; Oetjen, H.; Saunders, R. W.

    2009-04-01

    Important atmospheric sources of iodine include the air-sea exchange of biogenic iodocarbons, and the emission of I2 from macro-algae. The major source of bromine is the release of bromide ions from sea-salt aerosol. The subsequent atmospheric chemistry of these halogens (1), changes the oxidizing capacity of the marine boundary layer by destroying ozone and changing the hydroxyl radical concentration; (2), reacts efficiently with dimethyl sulphide and mercury (in the polar regions); and (3), leads to the formation of ultra-fine particles which may contribute to cloud condensation nuclei (CCN) and hence affect climate. This paper will report observations of IO, BrO, OIO and I2 made by the technique of differential optical absorption spectroscopy, in several contrasting marine environments: the equatorial mid-Atlantic (Cape Verde); mid-latitude clean coastal (Mace Head, Ireland); polluted coastal (Roscoff, France); and the polar marine boundary layer (Hudson Bay, Canada). Both IO and BrO are observed in all these locations at significant concentrations (> 1 pptv), and so have a major impact on (1) and (2) above. To complement the field campaigns we have also carried out wide-ranging laboratory investigation. A new study of OIO photochemistry shows that absorption in the visible bands between 490 and 630 nm leads to I atom production with a quantum yield of unity, which now means that iodine is a particularly powerful ozone-depleting agent. We have also studied the formation and growth kinetics of iodine oxide nano-particles, and their uptake of water, sulphuric acid and di-carboxylic organic acids, in order to model their growth to a size where they can act as CCN. Their ice-nucleating properties will also be reported.

  8. Young Pb-Isotopic Ages of Chondrules in CB Carbonaceous Chondrites

    Science.gov (United States)

    Amelin, Yuri; Krot, Alexander N.

    2005-01-01

    CB (Bencubbin-type) carbonaceous chondrites differ in many ways from more familiar CV and CO carbonaceous chondrites and from ordinary chondrites. CB chondrites are very rich in Fe-Ni metal (50-70 vol%) and contain magnesian silicates mainly as angular to sub-rounded clasts (or chondrules) with barred olivine (BO) or cryptocrystalline (CC) textures. Both metal and silicates appear to have formed by condensation. The sizes of silicate clasts vary greatly between the two subgroups of CB chondrites: large (up to one cm) in CB(sub a) chondrites, and typically to much much less than 1 mm in CB(sub b) chondrites. The compositional and mineralogical differences between these subgroups and between the CB(sub s) and other types of chondrites suggest different environment and possibly different timing of chondrule formation. In order to constrain the timing of chondrule forming processes in CB(sub s) and understand genetic relationship between their subgroups, we have determined Pb-isotopic ages of silicate material from the CB(sub a) chondrite Gujba and CB(sub b) chondrite Hammadah al Hamra 237 (HH237 hereafter).

  9. Carbonaceous thin film coating with Fe-N4 site for enhancement of dioxovanadium ion reduction

    Science.gov (United States)

    Maruyama, Jun; Hasegawa, Takahiro; Iwasaki, Satoshi; Fukuhara, Tomoko; Orikasa, Yuki; Uchimoto, Yoshiharu

    2016-08-01

    It has been found that carbonaceous materials containing a transition metal coordinated by 4 nitrogens in the square-planar configuration (metal-N4 site) on the surface possessed a catalytic activity for various electrochemical reactions related to energy conversion and storage; i.e., oxygen reduction, hydrogen evolution, and quite recently, the electrode reactions in vanadium redox flow batteries (VRFB). The catalyst for the VRFB positive electrode discharge reaction, i.e., the dioxovanadium ion reduction, was formed by coating the surface of cup-stack carbon nanotubes with a carbonaceous thin film with the Fe-N4 site generated by the sublimation, deposition, and pyrolysis of iron phthalocyanine. In this study, the influence of the physical properties of the catalyst on the electrochemical reactions was investigated to optimize the coating. With an increase in the coating, the specific surface area increased, whereas the pore size decreased. The surface Fe concentration was increased in spite of the Fe aggregation inside the carbon matrix. The catalytic activity enhancement was achieved due to the increase in the specific surface area and the surface Fe concentration, but was lowered due to the decrease in the pore size, which was disadvantageous for the penetration of the electrolyte and the mass transfer.

  10. Petrologic Locations of Nanodiamonds in Carbonaceous Chondrite Meteorites

    Science.gov (United States)

    Garvie, Laurence

    Nanodiamonds (NDs), with dimensions near two nanometers, are widespread accessory minerals in primitive meteorites. They have been studied extensively in concentrates made from acid-insoluble residues, but surprisingly little is known about their petrologic settings in the meteorites because they have not been studied in situ. Information about such settings is fundamental for determining how they formed and were incorporated into the meteorites. The primary goal of the planned research is to determine and compare the petrologic settings of NDs within matrix of different types of carbonaceous chondrites, with the long-term aim of providing new insights regarding the origin of NDs. This research will also provide new data on the structure and major and trace element compositions of individual NDs and regions within them. Transmission electron microscopes (TEMs) provide uniquely powerful information regarding chemical, bonding, and structural data on the scale needed to solve this problem, assuming the NDs can be located within the host matrix. We have developed methods of observing NDs in situ within the fine-grained matrix of primitive meteorites and will use various TEMs to accomplish that goal for several meteorites. High- resolution imaging and electron energy-loss spectroscopy (EELS) will permit determination of both structural and chemical information about the NDs and their adjacent minerals. By the middle of the proposed grant period, two state-of-the-art, aberration-corrected TEMs will have been installed at ASU and will be used to locate heavy elements such as Xe, Te, and Pd within the NDs. These TEMs permit the imaging of individual atoms of heavy elements with annular dark-field (ADF) imaging, and these atoms can be identified using EELS. The result of these new types of measurements will provide information about whether such elements, which have been used to determine whether NDs formed in supernovae, occur within the interiors or on the surfaces of

  11. Determination of halogens by flame emission of metal halogenides

    International Nuclear Information System (INIS)

    The A-B systems InF, InCl, InBr, and InI have been excited by laminar H2-N2 flames in order to dermine individual halogens or their mixtures qualitatively or quantitatively. In optimizing the fuel gas composition two different behavior patterns have been found for band intensities, which are correlated with binding energies of InX (X = halogen). The low temperature of the flame leads to complicated matrix effects which first of all result from effects on excitation and from competitive reactions. In general, cations cause a decreased intensity. Therefore, salts have to be converted into hydrohalide acids by ion exchange. Qualitative determinations of individual halogens are possible at a 500 to 50,000fold excess of the others, whereas quantitative determinations can be performed at a 100 to 5,000fold excess in 10-4 molar solutions with errors of 2 to 10 per cent. (author)

  12. Biodegradation of Trihalomethanes and Other Halogenated Aliphatic Compounds

    Science.gov (United States)

    Smith, G. B.

    1996-01-01

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

  13. Halogen radicals contribute to photooxidation in coastal and estuarine waters

    Science.gov (United States)

    Parker, Kimberly M.; Mitch, William A.

    2016-05-01

    Although halogen radicals are recognized to form as products of hydroxyl radical (•OH) scavenging by halides, their contribution to the phototransformation of marine organic compounds has received little attention. We demonstrate that, relative to freshwater conditions, seawater halides can increase photodegradation rates of domoic acid, a marine algal toxin, and dimethyl sulfide, a volatile precursor to cloud condensation nuclei, up to fivefold. Using synthetic seawater solutions, we show that the increased photodegradation is specific to dissolved organic matter (DOM) and halides, rather than other seawater salt constituents (e.g., carbonates) or photoactive species (e.g., iron and nitrate). Experiments in synthetic and natural coastal and estuarine water samples demonstrate that the halide-specific increase in photodegradation could be attributed to photochemically generated halogen radicals rather than other photoproduced reactive intermediates [e.g., excited-state triplet DOM (3DOM*), reactive oxygen species]. Computational kinetic modeling indicates that seawater halogen radical concentrations are two to three orders of magnitude greater than freshwater •OH concentrations and sufficient to account for the observed halide-specific increase in photodegradation. Dark •OH generation by gamma radiolysis demonstrates that halogen radical production via •OH scavenging by halides is insufficient to explain the observed effect. Using sensitizer models for DOM chromophores, we show that halogen radicals are formed predominantly by direct oxidation of Cl- and Br- by 3DOM*, an •OH-independent pathway. Our results indicate that halogen radicals significantly contribute to the phototransformation of algal products in coastal or estuarine surface waters.

  14. Halogen radicals contribute to photooxidation in coastal and estuarine waters.

    Science.gov (United States)

    Parker, Kimberly M; Mitch, William A

    2016-05-24

    Although halogen radicals are recognized to form as products of hydroxyl radical ((•)OH) scavenging by halides, their contribution to the phototransformation of marine organic compounds has received little attention. We demonstrate that, relative to freshwater conditions, seawater halides can increase photodegradation rates of domoic acid, a marine algal toxin, and dimethyl sulfide, a volatile precursor to cloud condensation nuclei, up to fivefold. Using synthetic seawater solutions, we show that the increased photodegradation is specific to dissolved organic matter (DOM) and halides, rather than other seawater salt constituents (e.g., carbonates) or photoactive species (e.g., iron and nitrate). Experiments in synthetic and natural coastal and estuarine water samples demonstrate that the halide-specific increase in photodegradation could be attributed to photochemically generated halogen radicals rather than other photoproduced reactive intermediates [e.g., excited-state triplet DOM ((3)DOM*), reactive oxygen species]. Computational kinetic modeling indicates that seawater halogen radical concentrations are two to three orders of magnitude greater than freshwater (•)OH concentrations and sufficient to account for the observed halide-specific increase in photodegradation. Dark (•)OH generation by gamma radiolysis demonstrates that halogen radical production via (•)OH scavenging by halides is insufficient to explain the observed effect. Using sensitizer models for DOM chromophores, we show that halogen radicals are formed predominantly by direct oxidation of Cl(-) and Br(-) by (3)DOM*, an (•)OH-independent pathway. Our results indicate that halogen radicals significantly contribute to the phototransformation of algal products in coastal or estuarine surface waters. PMID:27162335

  15. The role of halogen species in the troposphere.

    Science.gov (United States)

    Platt, U; Hönninger, G

    2003-07-01

    While the role of reactive halogen species (e.g. Cl, Br) in the destruction of the stratospheric ozone layer is well known, their role in the troposphere was investigated only since their destructive effect on boundary layer ozone after polar sunrise became obvious. During these 'Polar Tropospheric Ozone Hole' events O(3) is completely destroyed in the lowest approximately 1000 m of the atmosphere on areas of several million square kilometres. Up to now it was assumed that these events were confined to the polar regions during springtime. However, during the last few years significant amounts of BrO and Cl-atoms were also found outside the Arctic and Antarctic boundary layer. Recently even higher BrO mixing ratios (up to 176 ppt) were detected by optical absorption spectroscopy (DOAS) in the Dead Sea basin during summer. In addition, evidence is accumulating that BrO (at levels around 1-2 ppt) is also occurring in the free troposphere at all latitudes. In contrast to the stratosphere, where halogens are released from species, which are very long lived in the troposphere, likely sources of boundary layer Br and Cl are autocatalytic oxidation of sea salt halides (the 'Bromine Explosion'), while precursors of free tropospheric BrO and coastal IO probably are short-lived organo-halogen species. At the levels suggested by the available measurements reactive halogen species have a profound effect on tropospheric chemistry: In the polar boundary layer during 'halogen events' ozone is usually completely lost within hours or days. In the free troposphere the effective O(3)-losses due to halogens could be comparable to the known photochemical O(3) destruction. Further interesting consequences include the increase of OH levels and (at low NO(X)) the decrease of the HO(2)/OH ratio in the free troposphere. PMID:12738256

  16. The origin of carbonaceous matter in pre-3.0 Ga greenstone terrains: A review and new evidence from the 3.42 Ga Buck Reef Chert

    Science.gov (United States)

    Tice, Michael M.; Lowe, Donald R.

    2006-06-01

    The geological record of carbonaceous matter from at least 3.5 Ga to the end of the Precambrian is fundamentally continuous in terms of carbonaceous matter structure, composition, environments of deposition/preservation, and abundance in host rocks. No abiotic processes are currently known to be capable of producing continuity in all four of these properties. Although this broad view of the geological record does not prove that life had arisen by 3.5 Ga, the end of the early Archean, it suggests a working hypothesis: most if not all carbonaceous matter present in rocks older than 3.0 Ga was produced by living organisms. This hypothesis must be tested by studies of specific early geological units designed to explore the form, distribution, and origin of enclosed carbonaceous matter. The carbonaceous, environmentally diverse 3416 Ma Buck Reef Chert (BRC) of the Barberton greenstone belt, South Africa, provides an opportunity for such a study. Upward facies progressions in the BRC reflect deposition in environments ranging from shallow marine evaporitic brine ponds to a storm- and wave-active shelf to a deep, low-energy basinal setting below storm wave base. Abundances and ratios of Al 2O 3, Zr, TiO 2, and Cr track inputs of various types of volcaniclastic and terrigenous clastic materials. In particular, Zr/Al 2O 3 and Zr serve as proxies for concentration of windblown dust and, indirectly, as proxies for sedimentation rate. Cu, Zn, Ni, and FeO were concentrated in the most slowly deposited transitional and basinal sediments, inconsistent with a hydrothermal setting but consistent with a normal marine setting. The distribution of microfacies defined by associations and layering of clastic, ferruginous, and carbonaceous grains correlates with facies transitions. Fine carbonaceous laminations, which occur only in shallow platform settings, represent photosynthetic microbial mats. These were ripped up and the debris widely redistributed in shallow and deep water by

  17. Non-polar halogenated natural products bioaccumulated in marine samples. II. Brominated and mixed halogenated compounds.

    Science.gov (United States)

    Vetter, Walter; Jun, Wu

    2003-07-01

    Several identified and potential natural brominated bioaccumulative compounds were studied in this work. 4,6-dibromo-2-(2('),4(')-dibromo)phenoxyanisole (BC-2) previously detected in Australian marine mammals and isolated from sponges, was synthesized. Two byproducts (a tetrabromo isomer and a tribromo congener) were investigated as well. The byproducts of the synthesis were not identified in the environmental samples investigated. Previously described natural brominated compounds (BC-1, BC-2, BC-3, BC-10, BC-11, MHC-1) and anthropogenic brominated diphenyl ethers (BDE-47, BDE-99, BDE-100, BDE-154) were detected in a sample of human milk. The sample was from a woman from the Faeroe Islands who frequently consumed fish as well as whale blubber and meat. The most abundant compound originated from the natural tetrabromo phenoxyanisole BC-3 which may have a 3:1 distribution of bromine on the two phenyl units. This sample also accumulated a dibromochloroanisole, as well as a previously unknown mixed halogenated compound (MHC-X) and an unknown, most likely aromatic brominated compound. Co-elutions on a DB-5 column were found for BDE-99 and BC-11 as well as BDE-154 and the unknown brominated compound. This suggests that quantification of these two compounds has to be carried out carefully.Two samples of lower trophic level, namely Baltic cod liver and Mexican mussel tissue, were investigated as well. The cod liver samples contained BDE congeners but also abundant signals for the natural 2,3,3('),4,4('),5,5(')-heptachloro-1(')-methyl-1,2(')-bipyrrole Q1 and tribromoanisole (TBA). The mussel sample contained Q1, TBA, another halogenated anisole, BC-1, BC-2, and BC-3, as well as additional, potential natural brominated compounds in the elution range of tribromophenoxyanisoles. PMID:12738265

  18. Synthesis of Two-dimensional Microporous Carbonaceous Polymer Nanosheets and Their Application as High-performance CO2 Capture Sorbent.

    Science.gov (United States)

    Zhang, Miao; Liu, Lin; He, Teng; Wu, Guotao; Chen, Ping

    2016-06-21

    The synthesis of two-dimensional (2D) polymer nanosheets with a well-defined microporous structure remains challenging in materials science. Here, a new kind of 2D microporous carbonaceous polymer nanosheets was synthesized through polymerization of a very low concentration of 1,4-dicyanobenzene in molten zinc chloride at 400-500 °C. This type of nanosheets has a thickness in the range of 3-20 nm, well-defined microporosity, a high surface area (∼537 m(2)  g(-1) ), and a large micropore volume (∼0.45 cm(3)  g(-1) ). The microporous carbonaceous polymer nanosheets exhibit superior CO2 sorption capability (8.14 wt % at 298 K and 1 bar) and a relatively high CO2 selectivity toward N2 (25.6). Starting from different aromatic nitrile monomers, a variety of 2D carbonaceous polymer nanosheets can be obtained showing a certain universality of the ionothermal method reported herein.

  19. The thiocyanate anion as a polydentate halogen bond acceptor

    OpenAIRE

    Cauliez, Pascal; Polo, Victor; Roisnel, Thierry; Llhusar, Rosa; Fourmigué, Marc

    2010-01-01

    International audience Co-crystallisation of the Et4N+ or n-Bu4N+ salts of the thiocyanate anion with o-, m- and p-diodoperfluorobenzene or the sym-trifluorotriiodobenzene allowed for the isolation of six different salts which were structurally characterized by single crystal X-ray diffraction. Halogen bonding interactions are observed between the neutral iodinated molecules acting as halogen bond donors and the S or N ends of the thiocyanate anion, with a variety of bonding modes (termina...

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

    Energy Technology Data Exchange (ETDEWEB)

    Miura, Michiko; Wu, Haitao

    2013-05-21

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

  1. Reactive halogen species above salt lakes and salt pans

    OpenAIRE

    Holla, Robert

    2013-01-01

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

  2. Uranium band types in carbonaceous sediments with different diagenesis levels

    International Nuclear Information System (INIS)

    Uraniferous peats, lignites and coals were studied by chemical and geological methods in order to determine the influence of carbonaceous substances with different diagenesis levels on uranium enrichment in sediments. It was found that the main factor of deposit genesis is not the chemical bending of uranium to the organic substance but rather the reduction from mobile U(VI) to immobile U(IV) in the course of diagenesis to epigenesis. (orig./PW)

  3. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  4. Kirishites—high-carbonaceous hairlike fibers associated with volkhovites

    Science.gov (United States)

    Skublov, G. T.; Marin, Yu. B.; Skublov, S. G.; Vasil'Ev, E. V.; Gembitskaya, I. M.; Nechaeva, E. S.; Tarasenko, Yu. N.

    2009-12-01

    Kirishites are highly carbonaceous hairlike fibers 30-100 μm in thickness and 3-30 mm long, which jut out as bunches on the surface of cinder and shungite fragments associated with volkhovites (Holocene tectitelike glasses corresponding to the rocks of kimberlite-lamproite-carbonatite series in composition). Kirishite fibers are zonal. Their inner (axial) zone is composed of high-nitrogen proteinlike compounds, whereas the outer zone is essentially carbonaceous, with a high content of organoelemental complexes (Si, Fe) and numerous micrometer-sized anomalies of major, volatile, trace, and ore elements. Longitudinal zoning is established in aposhungite kirishites: the consecutive change of maximum concentrations—K, Na, Cl, C, Mn → C, S, V, Ni, Cu, Zn → S, N, Ba, Te, Pb, Bi, Nd—is traced from the roots of fibers to their ends. It is suggested that as volkhovites were forming, fragments of cinder and shungite underwent partial melting. The highly carbonaceous compounds released due decompression and explosion were squeezed out from fragments and solidified as fibers during fall of fragments on the Earth’s surface.

  5. Experimental simulation of organic matter alteration in carbonaceous chondrites under an in situ micro FTIR spectroscopy

    Science.gov (United States)

    Kebukawa, Y.; Nakashima, S.; Saiki, K.; Zolensky, M. E.

    2007-12-01

    Carbonaceous chondrites contain organic matter up to a few weight percents, most of which consists of kerogen- like macromolecular material. Chondritic organic matter preserves signatures of various evolutional steps from presolar materials, through aqueous alteration and thermal metamorphism in the parent asteroid up to delivery to the Earth. The organic-mineral interactions during these processes are little known. We report here on the experimental simulation of organic matter alteration on carbonaceous chondrite parent body under micro FTIR spectroscopy with a heating stage. Leonardite humic acid (IHSS standard humic acid) and synthetic saponite or natural antigorite were used as the macromolecular organic matter and the matrix mineral. These powdered samples were dispersed by MilliQ water then dropped on a CaF2 plate and dried. They were heated in the heating stage from room temperature to 600 °C with a heating rate of 10 °C/min in air, Ar gas, and H2+CO2 gas mixture (mixing ratio 1:1). H2+CO2 gas mixture enables controls of not only oxygen fugacity but also water vapor fugacity, and aqueous processing on chondrite parent bodies can be partly simulated. IR spectra were collected at every 20 °C under the micro FTIR spectroscopy. Aliphatic C-H increased from room temperature to approximately 250 °C then decreased. Aromatic C-H increased from room temperature to around 400-450 °C then decreased. These aliphatic C-H decrease and aromatic C-H increase are faster in air than in Ar or H2+CO2. These CH changes of leonardite humic acid are slower with the presence of saponite. These results indicate that organic matter transformation might be prevented by the clay mineral (saponite). Some carbonaceous chondrite samples mixed with the organic material (leonardite humic acid) will also be investigated by the same way. These results will elucidate interactions of chondritic macromolecular organic matter with matrix minerals during parent body processes.

  6. Solution phase synthesis of halogenated graphene and the electrocatalytic activity for oxygen reduction reaction

    Institute of Scientific and Technical Information of China (English)

    Kuang-Hsu Wu; Da-Wei Wang; Qingcong Zeng; Yang Li; Ian R. Gentle

    2014-01-01

    Metal-free carbon electrocatalyts for the oxygen reduction reaction (ORR) are attractive for their high activity and economic advantages. However, the origin of the activity has never been clearly elucidated in a systematic manner. Halogen group elements are good candidates for elucidating the effect, although it has been a difficult task due to safety issues. In this report, we demonstrate the synthesis of Cl-, Br-and I-doped reduced graphene oxide through two solution phase syntheses. We have evaluated the effectiveness of doping and performed electrochemical measurements of the ORR activity on these halogenated graphene materials. Our results suggest that the high electroneg-ativity of the dopant is not the key factor for high ORR activity;both Br-and I-doped graphene pro-moted ORR more efficiently than Cl-doped graphene. Furthermore, an unexpected sulfur-doping in acidic conditions suggests that a high level of sulfide can degrade the ORR activity of the graphene material.

  7. In situ observation of D-rich carbonaceous globules embedded in NWA 801 CR2 chondrite

    Science.gov (United States)

    Hashiguchi, Minako; Kobayashi, Sachio; Yurimoto, Hisayoshi

    2013-12-01

    Eighty-five D-rich carbonaceous particles were identified in the matrix of the NWA 801 CR2 chondrite using isotope microscopy. The occurrence of 67 D-rich carbonaceous particles was characterized using secondary electron microscopy combined with X-ray elemental mapping. The close association of H and C, and D-enrichment suggests that the D-rich carbonaceous particles correspond to organic matter. The D-rich organic particles were scattered ubiquitously throughout the matrix at a concentration of approximately 660 ppm. The morphology of the D-rich carbonaceous particles is globular up to about 1 μm in diameter and is classified into four types: ring globules, round globules, irregular-shaped globules, and globule aggregates. The ring globules are ring-shaped organic matter containing silicate and/or oxide, with or without a void in the center. This is the first report of silicate and oxide grains surrounded by D-rich organic matter. The globule aggregates are composed of several D-rich organic globules mixed with silicates. Morphology of ring globules is very similar to core-mantle grain produced in the molecular cloud or in the outer solar nebula inferring by astronomy, suggesting that the organic globules have formed by UV photolysis in the ice mantle. Silicates or oxides attached to D-rich organic globules are the first observation among chondrites so far and may be unique nature of CR2 chondrites. The hydrogen isotopic compositions of the ring globules, round globules, irregular-shaped globules, and globule aggregates are δD = 3000-4800, 2900-8100, 2700-11,000, and 2500-11,000‰, respectively. Variations of D/H ratio of these organic globules seemed to be attributed to variations of D/H ratio of the organic radicals or differences of content of the D-rich organic radicals. There are no significant differences in the hydrogen isotopic compositions among the four types of D-rich carbonaceous matter. The D-enrichments suggest that these organic globules have

  8. Halogen activation via interactions with environmental ice and snow

    Directory of Open Access Journals (Sweden)

    X. Yang

    2012-04-01

    Full Text Available The role of ice in the formation of chemically active halogens in the environment requires a full understanding because of its role in atmospheric chemistry, including controlling the oxidizing capacity of the atmosphere. In particular, ice and snow are important for facilitating multiphase oxidative chemistry and as media upon which marine algae live. This paper reviews the nature of environmental ice substrates that participate in halogen chemistry, describes the multiphase reactions that occur on such substrates, presents the field evidence for ice-mediated halogen activation, summarizes our best understanding of ice-halogen activation mechanisms, and describes the current state of modeling these processes at different scales. Given the rapid pace of developments in the field, this paper largely addresses advances made in the past five years, with emphasis given to the polar boundary layer. The integrative nature of this field is highlighted in the presentation of work from the molecular to the regional scale, with a focus on understanding fundamental processes. This is essential for developing realistic parameterizations and descriptions of these processes for inclusion in larger scale models that are used to determine their regional and global impacts.

  9. Influence of saponins on the biodegradation of halogenated phenols.

    Science.gov (United States)

    Kaczorek, Ewa; Smułek, Wojciech; Zdarta, Agata; Sawczuk, Agata; Zgoła-Grześkowiak, Agnieszka

    2016-09-01

    Biotransformation of aromatic compounds is a challenge due to their low aqueous solubility and sorptive losses. The main obstacle in this process is binding of organic pollutants to the microbial cell surface. To overcome these, we applied saponins from plant extract to the microbial culture, to increase pollutants solubility and enhance diffusive massive transfer. This study investigated the efficiency of Quillaja saponaria and Sapindus mukorossi saponins-rich extracts on biodegradation of halogenated phenols by Raoultella planticola WS2 and Pseudomonas sp. OS2, as an effect of cell surface modification of tested strains. Both strains display changes in inner membrane permeability and cell surface hydrophobicity in the presence of saponins during the process of halogenated phenols biotransformation. This allows them to more efficient pollutants removal from the environment. However, only in case of the Pseudomonas sp. OS2 the addition of surfactants to the culture improved effectiveness of bromo-, chloro- and fluorophenols biodegradation. Also introduction of surfactant allowed higher biodegradability of halogenated phenols and can shorten the process. Therefore this suggests that usage of plant saponins can indicate more successful halogenated phenols biodegradation for selected strains. PMID:27232205

  10. Airborne contamination of forest soils by carbonaceous particles from industrial coal processing

    OpenAIRE

    Schmidt, M. W. I.; Knicker, Heike; Hatcher, Patrick G.; Kögel-Knabner, I.

    2000-01-01

    In the German Ruhr-area industrial coal processing emitted large amounts of carbonaceous particles for a century until 1970. Our objectives were to detect the presence of airborne carbonaceous particles and assess their impact on the chemical structure of soil organic matter in two forest soils (Podzols) with potential sources of carbonaceous particles approximately 10 to 30 km away. Contamination was not visible macroscopicaily. Organic matter was characterized in bulk soils and in particle-...

  11. Ozone-biological activated carbon integrated treatment for removal of precursors of halogenated nitrogenous disinfection by-products.

    Science.gov (United States)

    Chu, Wenhai; Gao, Naiyun; Yin, Daqiang; Deng, Yang; Templeton, Michael R

    2012-03-01

    Pilot-scale tests were performed to reduce the formation of several nitrogenous and carbonaceous disinfection by-products (DBPs) with an integrated ozone and biological activated carbon (O(3)-BAC) treatment process following conventional water treatment processes (coagulation-sedimentation-filtration). Relative to the conventional processes alone, O(3)-BAC significantly improved the removal of turbidity, dissolved organic carbon, UV(254), NH(4)(+) and dissolved organic nitrogen from 98-99%, 58-72%, 31-53%, 16-93% and 35-74%, respectively, and enhanced the removal efficiency of the precursors for the measured DBPs. The conventional process was almost ineffective in removing the precursors of trichloronitromethane (TCNM) and dichloroacetamide (DCAcAm). Ozonation could not substantially reduce the formation of DCAcAm, and actually increased the formation potential of TCNM; it chemically altered the molecular structures of the precursors and increased the biodegradability of N-containing organic compounds. Consequently, the subsequent BAC filtration substantially reduced the formation of the both TCNM and DCAcAm, thus highlighting a synergistic effect of O(3) and BAC. Additionally, O(3)-BAC was effective at controlling the formation of the total organic halogen, which can be considered as an indicator of the formation of unidentified DBPs.

  12. Nanostructural Materials for Energy Storage Systems

    Directory of Open Access Journals (Sweden)

    Bronislaw Buczek

    2011-01-01

    Full Text Available The aim of this study was to assess of carbonaceous monoliths used for adsorption cooling systems. The carbonaceous monoliths prepared from coal precursors are obtained. The porous structure of monoliths was evaluated on the basis of nitrogen adsorption-desorption data. The investigated monoliths have significantly developed microporous structure. The large specific area of carbonaceous monoliths (about 2000 m2/g and volume of micropores are observed. Methanol adsorption isotherms and heat of wetting using methanol was determined. Results show that monoliths materials are high adsorption capacity of methanol and heat of wetting, which can improve of heat exchange and efficiency in processes of refrigeration and air conditioning.

  13. Radar-enabled recovery of the Sutter's Mill meteorite, a carbonaceous chondrite regolith breccia.

    Science.gov (United States)

    Jenniskens, Peter; Fries, Marc D; Yin, Qing-Zhu; Zolensky, Michael; Krot, Alexander N; Sandford, Scott A; Sears, Derek; Beauford, Robert; Ebel, Denton S; Friedrich, Jon M; Nagashima, Kazuhide; Wimpenny, Josh; Yamakawa, Akane; Nishiizumi, Kunihiko; Hamajima, Yasunori; Caffee, Marc W; Welten, Kees C; Laubenstein, Matthias; Davis, Andrew M; Simon, Steven B; Heck, Philipp R; Young, Edward D; Kohl, Issaku E; Thiemens, Mark H; Nunn, Morgan H; Mikouchi, Takashi; Hagiya, Kenji; Ohsumi, Kazumasa; Cahill, Thomas A; Lawton, Jonathan A; Barnes, David; Steele, Andrew; Rochette, Pierre; Verosub, Kenneth L; Gattacceca, Jérôme; Cooper, George; Glavin, Daniel P; Burton, Aaron S; Dworkin, Jason P; Elsila, Jamie E; Pizzarello, Sandra; Ogliore, Ryan; Schmitt-Kopplin, Phillipe; Harir, Mourad; Hertkorn, Norbert; Verchovsky, Alexander; Grady, Monica; Nagao, Keisuke; Okazaki, Ryuji; Takechi, Hiroyuki; Hiroi, Takahiro; Smith, Ken; Silber, Elizabeth A; Brown, Peter G; Albers, Jim; Klotz, Doug; Hankey, Mike; Matson, Robert; Fries, Jeffrey A; Walker, Richard J; Puchtel, Igor; Lee, Cin-Ty A; Erdman, Monica E; Eppich, Gary R; Roeske, Sarah; Gabelica, Zelimir; Lerche, Michael; Nuevo, Michel; Girten, Beverly; Worden, Simon P

    2012-12-21

    Doppler weather radar imaging enabled the rapid recovery of the Sutter's Mill meteorite after a rare 4-kiloton of TNT-equivalent asteroid impact over the foothills of the Sierra Nevada in northern California. The recovered meteorites survived a record high-speed entry of 28.6 kilometers per second from an orbit close to that of Jupiter-family comets (Tisserand's parameter = 2.8 ± 0.3). Sutter's Mill is a regolith breccia composed of CM (Mighei)-type carbonaceous chondrite and highly reduced xenolithic materials. It exhibits considerable diversity of mineralogy, petrography, and isotope and organic chemistry, resulting from a complex formation history of the parent body surface. That diversity is quickly masked by alteration once in the terrestrial environment but will need to be considered when samples returned by missions to C-class asteroids are interpreted. PMID:23258889

  14. Silicon carbide sintered body manufactured from silicon carbide powder containing boron, silicon and carbonaceous additive

    Science.gov (United States)

    Tanaka, Hidehiko

    1987-01-01

    A silicon carbide powder of a 5-micron grain size is mixed with 0.15 to 0.60 wt% mixture of a boron compound, i.e., boric acid, boron carbide (B4C), silicon boride (SiB4 or SiB6), aluminum boride, etc., and an aluminum compound, i.e., aluminum, aluminum oxide, aluminum hydroxide, aluminum carbide, etc., or aluminum boride (AlB2) alone, in such a proportion that the boron/aluminum atomic ratio in the sintered body becomes 0.05 to 0.25 wt% and 0.05 to 0.40 wt%, respectively, together with a carbonaceous additive to supply enough carbon to convert oxygen accompanying raw materials and additives into carbon monoxide.

  15. Did the Siberian Traps eruptions emit enough halogens to have an impact on ozone geochemistry?

    Science.gov (United States)

    Sibik, Svetlana; Edmonds, Marie; Villemant, Benoit; Thierry, Pauline; Polozov, Alexander

    2015-04-01

    The Siberian Traps Large Igneous Province is thought to have formed over 1 Ma at the end of the Permian, synchronous with the largest mass extinction in Earth's history. There remains much controversy as to the exact mechanism of the mass extinction, but all hypotheses revolve around the emission of volatiles in various forms. The research to date has tended to focus on sulfur and carbon rather than halogen degassing, despite this being probably critical in terms of environmental impact as they might have been played a crucial role in ozone layer depletion and therefore promote mass extinction. Current study aims to look at the behaviour of chlorine, bromine, iodine and fluorine to evaluate the halogen budget contribution from heterogeneous mantle source and from evaporates, which dominate in the south (Cambrian evaporites) and north (Devonian evaporites) of Siberian platform. For this study we use basaltic sills and lava flows emplaced in the area with no volatile-rich sediments south-east from Norilsk (Dyupkin lake and Lower Tunguska river regions) and a sill intruded into evaporates in Nepa location in the south of the platform, originally aimed at prospecting for potassium salts. Borehole samples of basalts intruded into evaporites might have been penetrated by salts and anhydrite. In order to eliminate this effect and ensure that we analyse halogen contents in pure basalts prior to any further analysis the samples were specifically treated so that penetrated material was removed as leachates. Whole rock fine powders of basalts were analysed for halogens, major and trace elements. The solutions obtained by basalt pyrohydrolysis extraction, leachates of basaltic powders and dissolved evaporites were analysed by ion chromatography for chlorine and fluorine and by ICP-MS for bromine and iodine. Basalts intruded into evaporites demonstrate predicted pronounced chlorine, bromine and iodine enrichments associated with salt assimilation. The results show that bromine

  16. Source apportionment of carbonaceous aerosol in southern Sweden

    Directory of Open Access Journals (Sweden)

    J. Genberg

    2011-05-01

    Full Text Available A one-year study was performed at the Vavihill background station in southern Sweden to estimate the anthropogenic contribution to the carbonaceous aerosol. Weekly samples of the particulate matter PM10 were collected on quartz filters, and the amounts of organic carbon, elemental carbon, radiocarbon (14C and levoglucosan were measured. This approach enabled source apportionment of the total carbon in the PM10 fraction using the concentration ratios of the sources. The sources considered in this study were emissions from the combustion of fossil fuels and biomass, as well as biogenic sources. During the summer, the carbonaceous aerosol mass was dominated by compounds of biogenic origin (82 %, which are associated with biogenic primary and secondary organic aerosols. During the winter months, biomass combustion (38 % and fossil fuel combustion (33 % were the main contributors to the carbonaceous aerosol. Elemental carbon concentrations in winter were about twice as large as during summer, and can be attributed to biomass combustion, probably from domestic wood burning. The contribution of fossil fuels to elemental carbon was stable throughout the year, although the fossil contribution to organic carbon increased during the winter. Thus, the organic aerosol originated mainly from natural sources during the summer and from anthropogenic sources during the winter. The result of this source apportionment was compared with results from the EMEP model. The model and measurements were generally consistent for total atmospheric organic carbon, however, the contribution of the sources varied substantially. E.g. the biomass burning contributions of OC were underestimated by the model by a factor of 8.2 compared to the measurements.

  17. Characteristics and sources of carbonaceous aerosols from Shanghai, China

    Science.gov (United States)

    Cao, J.-J.; Zhu, C.-S.; Tie, X.-X.; Geng, F.-H.; Xu, H.-M.; Ho, S. S. H.; Wang, G.-H.; Han, Y.-M.; Ho, K.-F.

    2013-01-01

    An intensive investigation of carbonaceous PM2.5 and TSP (total suspended particles) from Pudong (China) was conducted as part of the MIRAGE-Shanghai (Megacities Impact on Regional and Global Environment) experiment in 2009. Data for organic and elemental carbon (OC and EC), organic species, including C17 to C40 n-alkanes and 17 polycyclic aromatic hydrocarbons (PAHs), and stable carbon isotopes OC (δ13COC) and EC (δ13CEC) were used to evaluate the aerosols' temporal variations and identify presumptive sources. High OC/EC ratios indicated a large fraction of secondary organic aerosol (SOA); high char/soot ratios indicated stronger contributions to EC from motor vehicles and coal combustion than biomass burning. Diagnostic ratios of PAHs indicated that much of the SOA was produced via coal combustion. Isotope abundances (δ13COC = -24.5 ± 0.8‰ and δ13CEC = -25.1 ± 0.6‰) indicated that fossil fuels were the most important source for carbonaceous PM2.5 (particulate matter less than 2.5 micrometers in diameter), with lesser impacts from biomass burning and natural sources. An EC tracer system and isotope mass balance calculations showed that the relative contributions to total carbon from coal combustion, motor vehicle exhaust, and SOA were 41%, 21%, and 31%; other primary sources such as marine, soil and biogenic emissions contributed 7%. Combined analyses of OC and EC, n-alkanes and PAHs, and stable carbon isotopes provide a new way to apportion the sources of carbonaceous particles.

  18. Fluorescence spectroscopy for monitoring reduction of natural organic matter and halogenated furanone precursors by biofiltration.

    Science.gov (United States)

    Peleato, Nicolás M; McKie, Michael; Taylor-Edmonds, Lizbeth; Andrews, Susan A; Legge, Raymond L; Andrews, Robert C

    2016-06-01

    The application of fluorescence spectroscopy to monitor natural organic matter (NOM) reduction as a function of biofiltration performance was investigated. This study was conducted at pilot-scale where a conventional media filter was compared to six biofilters employing varying enhancement strategies. Overall reductions of NOM were identified by measuring dissolved organic carbon (DOC), and UV absorbance at 254 nm, as well as characterization of organic sub-fractions by liquid chromatography-organic carbon detection (LC-OCD) and parallel factors analysis (PARAFAC) of fluorescence excitation-emission matrices (FEEM). The biofilter using granular activated carbon media, with exhausted absorptive capacity, was found to provide the highest removal of all identified PARAFAC components. A microbial or processed humic-like component was found to be most amenable to biodegradation by biofilters and removal by conventional treatment. One refractory humic-like component, detectable only by FEEM-PARAFAC, was not well removed by biofiltration or conventional treatment. All biofilters removed protein-like material to a high degree relative to conventional treatment. The formation potential of two halogenated furanones, 3-chloro-4(dichloromethyl)-2(5H)-furanone (MX) and mucochloric acid (MCA), as well as overall treated water genotoxicity are also reported. Using the organic characterization results possible halogenated furanone and genotoxicity precursors are identified. Comparison of FEEM-PARAFAC and LC-OCD results revealed polysaccharides as potential MX/MCA precursors. PMID:27016810

  19. Comets, carbonaceous meteorites, and the origin of the biosphere

    Directory of Open Access Journals (Sweden)

    r. b. Hoover

    2006-01-01

    Full Text Available The Biosphere is considered to represent the Earth's crust, atmosphere, oceans, and ice caps and the living organisms that survive within this habitat. This paper considers the significance of comets and carbonaceous meteorites to the origin and evolution of the Biosphere and presents new Field Emission Scanning Electron Microscope (FESEM images of indigenous microfossils in the Orgueil and Murchison meteorites. The discovery of microbial extremophiles in deep crustal rocks, hydrothermal vents and ancient ice has established that the biosphere is far more extensive than previously recognized. Chemical and molecular biomarkers and microfossils in Archaean rocks indicate that life appeared very early on the primitive Earth and the origin of the biosphere is closely linked with the emergence of life. The role of comets, carbonaceous meteorites, interstellar dust and asteroids in the delivery of water, organics and prebiotic chemicals to Earth during the Hadean (4.5–3.8 Ga period of heavy bombardment has become more widely recognized. Spacecraft observations of the chemical compositions and characteristics of the nuclei of several comets (Halley, Borrelly, Wild 2, and Tempel 1 have established that comets contain complex organic chemicals; that water is the predominant volatile; and that high temperatures (~400 K can be reached on the black (albedo~0.03 nuclei when near perihelion. The microscopic dust particles in the Tempel 1 ejecta are similar in size to the particulates of the Orgueil meteorite and evidence is mounting that comets may represent the parent bodies of the CI meteorites. Impact craters and pinnacles on comet Wild 2 suggest a thick crust. Episodic outbursts and jets of Halley, Borrelly, Wild 2 and Tempel 1 near perihelion indicate that localized regimes of liquid water may periodically exist beneath the thick crust of many comets. This increases the possibility that microbial life might survive in comets and therefore the

  20. Organic matter in carbonaceous chondrites, planetary satellites, asteroids and comets

    Science.gov (United States)

    Cronin, John R.; Pizzarello, Sandra; Cruikshank, Dale P.

    1988-01-01

    A detailed review is given of the organic compounds found in carbonaceous chondrite meteorites, especially the Murchison meteorite, and detected spectroscopically in other solar-system objects. The chemical processes by which the organic compounds could have formed in the early solar system and the conditions required for these processes are discussed, taking into account the possible alteration of the compounds during the lifetime of the meteoroid. Also considered are the implications for prebiotic evolution and the origin of life. Diagrams, graphs, and tables of numerical data are provided.

  1. Application of Scanning-Imaging X-Ray Microscopy to Fluid Inclusion Candidates in Carbonates of Carbonaceous Chondrites

    Science.gov (United States)

    Tsuchiyama, Akira; Nakano, Tsukasa; Miyake, Akira; Akihisa, Takeuchi; Uesugi, Kentaro; Suzuki, Yoshio; Kitayama, Akira; Matsuno, Junya; Zolensky, Michael E.

    2016-01-01

    In order to search for such fluid inclusions in carbonaceous chondrites, a nondestructive technique using x-ray micro-absorption tomography combined with FIB sampling was developed and applied to a carbonaceous chondrite. They found fluid inclusion candidates in calcite grains, which were formed by aqueous alteration. However, they could not determine whether they are really aqueous fluids or merely voids. Phase and absorption contrast images can be simultaneously obtained in 3D by using scanning-imaging x-ray microscopy (SIXM). In refractive index, n=1-sigma+i(beta), in the real part, 1-sigma is the refractive index with decrement, sigma, which is nearly proportional to the density, and the imaginary part, beta, is the extinction coefficient, which is related to the liner attenuation coefficient, mu. Many phases, including water and organic materials as well as minerals, can be identified by SIXM, and this technique has potential availability for Hayabusa-2 sample analysis too. In this study, we examined quantitative performance of d and m values and the spatial resolution in SIXM by using standard materials, and applied this technique to carbonaceous chondrite samples. We used POM ([CH2O]n), silicon, quartz, forsterite, corundum, magnetite and nickel as standard materials for examining the sigma and mu values. A fluid inclusion in terrestrial quartz and bi-valve shell (Atrina vexillum), which are composed of calcite and organic layers with different thickness, were also used for examining the spatial resolution. The Ivuna (CI) and Sutter's Mill (CM) meteorites were used as carbonaceous chondrite samples. Rod- or cube-shaped samples 20-30 micron in size were extracted by using FIB from cross-sectional surfaces of the standard materials or polished thin sections of the chondrites, which was previously observed with SEM. Then, the sample was attached to a thin W-needle and imaged by SIXM system at beamline BL47XU, SPring-8, Japan. The slice thickness was 109.3 nm

  2. ‘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

    Indian Academy of Sciences (India)

    P R Sahoo; A S Venkatesh

    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.

  3. Structure of high-molecular carbonaceous compound in carbonaceous chondrites and formation of IR-spectroscopically similar compounds in the laboratory

    Science.gov (United States)

    Murae, T.

    1997-05-01

    Main components of carbonaceous matter in carbonaceous chondrites are high molecular organic matter. Examinations of the compounds using pyrolysis GC/MS and FT-IR indicated the structural resemblance of major part of the molecule for all of the compounds from different types of carbonaceous chondrites (8 Antarctic and 2 none-Antarctic meteorites). A carbonaceous matter derived from graphite on a shock experiment using a rail gun (1g projectile at 7 km/s) showed similar IR spectrum to those of the meteoritic high-molecular organic matter. C-60 fulleren also gave a similar compound (with minor differences in IR spectra) on a shock experiment under the same conditions. A shock experiment using coronene also examined.

  4. Synthesis of biodiesel from acidified soybean soapstock using a lignin-derived carbonaceous catalyst

    International Nuclear Information System (INIS)

    Graphical abstract: Lignin derived catalyst has hydrophilic and hydrophobic groups, such as hydroxyl group and polycyclic aromatic carbon. Therefore, methanol and oleic acid are easily absorbed on the surface of solid acid catalysts, which is benefit to the contact between reactants and active sites. The active sites of SO3H groups play the role of Bronsted acid as proton donor in the reaction. Highlights: ► Lignin-derived carbonaceous catalyst was firstly synthesized for biodiesel synthesis. ► Active sites are linked to amorphous structure by the form of C-O-SO3H. ► Acidified soybean soapstock (ASS) was used as oil material for biodiesel synthesis. ► A maximum biodiesel yield of 97.2% was achieved in esterification of ASS. ► The catalytic efficiency of solid acid was similar to that of 1.5 wt.% of H2SO4. -- Abstract: Biodiesel was produced from acidified soybean soapstocks by using lignin-derived carbonaceous catalyst (LCC). LCC was a solid acidic catalyst prepared by direct sulfonation of residual lignin from Xanthoceras sorbifolia Bunge hulls. The textural properties of the catalyst were characterized by 13C MAS NMR, X-ray diffraction, FT-IR, elemental analysis and BET surface area measurement. When 7 wt.% of LCC was used in the esterification, the maximum free fatty acids (FFAs) conversion (above 97%) could be achieved at a molar ratio of methanol/oil of 1:9 and a reaction temperature of 70 °C for 5 h. A comparison of catalytic activity between sulfuric acid and LCC revealed that LCC performed 3.5 times higher activity than sulfuric acid with the equivalent active group (-SO3H). Additionally, LCC could be reused at least three times with high FFAs conversion (>80%).

  5. Presolar diamond, silicon carbide, and graphite in carbonaceous chondrites: implications for thermal processing in the solar nebula

    Science.gov (United States)

    Huss, Gary R.; Meshik, Alex P.; Smith, Julie B.; Hohenberg, C. M.

    2003-12-01

    We have determined abundances of presolar diamond, silicon carbide, graphite, and Xe-P1 (Q-Xe) in eight carbonaceous chondrites by measuring the abundances of noble gas tracers in acid residues. The meteorites studied were Murchison (CM2), Murray (CM2), Renazzo (CR2), ALHA77307 (CO3.0), Colony (CO3.0), Mokoia (CV3 ox), Axtell (CV3 ox), and Acfer 214 (CH). These data and data obtained previously by Huss and Lewis (1995) provide the first reasonably comprehensive database of presolar-grain abundances in carbonaceous chondrites. Evidence is presented for a currently unrecognized Ne-E(H) carrier in CI and CM2 chondrites. After accounting for parent-body metamorphism, abundances and characteristics of presolar components still show large variations across the classes of carbonaceous chondrites. These variations correlate with the bulk compositions of the host meteorites and imply that the same thermal processing that was responsible for generating the compositional differences between the various chondrite groups also modified the initial presolar-grain assemblages. The CI chondrites and CM2 matrix have the least fractionated bulk compositions relative to the sun and the highest abundances of most types of presolar material, particularly the most fragile types, and thus are probably most representative of the material inherited from the sun's parent molecular cloud. The other classes can be understood as the products of various degrees of heating of bulk molecular cloud material in the solar nebula, removing the volatile elements and destroying the most fragile presolar components, followed by chondrule formation, metal-silicate fractionation in some cases, further nebula processing in some cases, accretion, and parent body processing. If the bulk compositions and the characteristics of the presolar-grain assemblages in various chondrite classes reflect the same processes, as seems likely, then differential condensation from a nebula of solar composition is ruled out as

  6. Enantiomeric and Isotopic Analysis of Sugar Derivatives in Carbonaceous Meteorites

    Science.gov (United States)

    Cooper, George; Asiyo, Cynthia; Turk, Kendra; DeVincenzi, Donald (Technical Monitor)

    2002-01-01

    Several classes of organic compounds are found in carbonaceous meteorites including amino acids, carboxylic acids, hydroxy acids, purines, and pyrimidines. Such compounds are thought to have been delivered to the early Earth in asteroids and comets and may have played a role in the origin of life. Likewise, sugar derivatives are critical to all known lifeforms. Recent analyses of the Murchison and Murray carbonaceous meteorites revealed a diverse suite of such derivatives, i.e., sugar alcohols, and sugar acids. This presentation will focus primarily on the analysis of individual sugar acids - their enantiomeric and isotopic composition. Analysis of these compounds may reveal the nature of past (or present) meteoritic sugars themselves. For example, if parent sugars decomposed (by well-known mechanisms) to give the present acids, were their enantiomeric ratios preserved? Combined with other evidence, the enantiomeric composition of such compounds as glyceric acid and (especially) rare acids may help to answer such questions. C-13 and D isotope analysis of meteoritic sugar alcohols (glycerol, threitol, ribitol, etc.) as a group revealed that they were indigenous to the meteorite. Preliminary C-13 analysis of glyceric acid shows that it is also extraterrestrial.

  7. A new extraction process of carbonaceous refractory gold concentrate

    Institute of Scientific and Technical Information of China (English)

    MENG Yu-qun

    2005-01-01

    A new hydrometallurgical process for a carbonaceous refractory gold concentrate at ambient temperature and pressure was presented, including grinding-leaching, intensified alkaline leaching(IAL), thiosulfate leaching and cementation by zinc powder. The experimental results show that the grinding-leaching and intensified alkaline leaching process result in the selective oxidation of arsenopyrite and pyrite. The oxidation ratio of As is 96.6%, and 46.7 % for S. The total consumption of NaOH in alkaline leaching is only 28 % of that theoretically calculated under the conditions of full oxidization for the same amount of arsenopyrite and pyrite transforming into arsenates and sulfates, and 83. 6 % of gold is synchro-dissoluted by thiosulfate self-generated during pretreatment. Since the carbonaceous matter in concentrate possesses a strong capability of preg robbing, the cyanidation process is not suitable for the extraction of gold after pretreatment. However, the gold leaching rate by thiosulfate leaching for 24 h is increased to 91.7% from 0 - 3.2% by ultra-fine grinding without the pretreatment. The recovery of gold by zinc cementation gets to 99.6 %. Due to the thiosulfate self-generated during alkaline leaching, the reagent addition in thiosulfate leaching afterwards is lower than the normal one.

  8. Carbonaceous aerosols from different tropical biomass burning sources

    Science.gov (United States)

    Cachier, Hélène; Brémond, Marie-Pierre; Buat-Ménard, Patrick

    1989-08-01

    FOLLOWING a repetitive pattern, biomass burning affects the intertropical belt on a continental scale during the dry season1. The importance of these anthropogenic activities with regard to carbonaceous-component emissions into the global atmosphere is now well recognized2-4. It has been suggested that large injections of black carbon aerosols from the Tropics are of potential importance for the radiative and chemical balance of the troposphere5-10. Studies on carbonaceous aerosols have indicated that, on an annual basis, the intensity of the emissions from tropical biomass burning could compare with that of emissions from fossil-fuel burning in industrial countries7,8. Also, results from combustion chamber experiments have determined the important range of the emission factor for both the organic and the black carbon components of the aerosol1-16. Following on from our earlier studies on total atmospheric particulate carbon (Ct) and isotopic composition (δ13C) (ref. 2), we now present new data on the black carbon content (Cb) of atmospheric particles sampled during the biomass-burning season in the wooden savannah of the Ivory Coast. The Cb/Ct ratio is generally lower than expected and highly variable. This variability indicates that there are drastic changes in source apportionment, which from our isotope studies may be ascribed to the variety of vegetation fuel and also to the mode of combustion. Therefore the Cb/Ct ratio can potentially discriminate biomass-burning emissions from different tropical ecosystems.

  9. Ethanol and other oxygenateds from low grade carbonaceous resources

    Energy Technology Data Exchange (ETDEWEB)

    Joo, O.S.; Jung, K.D.; Han, S.H. [Korea Institute of Science and Technology, Seoul (Korea, Democratic People`s Republic of)] [and others

    1995-12-31

    Anhydrous ethanol and other oxygenates of C2 up can be produced quite competitively from low grade carbonaceous resources in high yield via gasification, methanol synthesis, carbonylation of methanol an hydrogenation consecutively. Gas phase carbonylation of methanol to form methyl acetate is the key step for the whole process. Methyl acetate can be produced very selectively in one step gas phase reaction on a fixed bed column reactor with GHSV over 5,000. The consecutive hydrogenation of methyl or ethyl acetate produce anhydrous ethanol in high purity. It is also attempted to co-produce methanol and DME in IGCC, in which low grade carbonaceous resources are used as energy sources, and the surplus power and pre-power gas can be stored in liquid form of methanol and DME during base load time. Further integration of C2 up oxygenate production with IGCC can improve its economics. The attempt of above extensive technology integration can generate significant industrial profitability as well as reduce the environmental complication related with massive energy consumption.

  10. Comparisons of Halogenated β-Nitrostyrenes as Antimicrobial Agents

    Directory of Open Access Journals (Sweden)

    Hugh Cornell

    2014-08-01

    Full Text Available The influence of three types of halogen-substituted E-β-methyl-β-nitrostyrenes (such as Compounds B, D, H to overcome bacterial activity that is currently a significant health threat was studied. The evaluations of their bio-potency was measured and related to their structure and activity relationships for the purposes of serving to inhibit and overcoming resistant microorganisms. In particular, fluorine-containing β-nitrostyrenes were found to be highly active antimicrobial agents. The addition of the β-bromo group enhanced the antibacterial activity significantly. Our work has illustrated that halogen substituents at both the 4-position in the aromatic ring and also at the β-position on the alkene side chain of nitropropenyl arenes enhanced the antimicrobial activity of these compounds.

  11. Infrared multiphoton dissociation processes of some halogenated hydrocarbons

    International Nuclear Information System (INIS)

    We review our studies on mechanisms and dynamics of infrared multiphoton dissociation of CF3CHClF, C2HCl3, CBrF2CHClF, CBrF2CHBrF, CBrF2CBrClF, and c-C4F8 using a photofragmentation translational spectroscopy and ab initio MO calculations. In the case of CF3CHClF, three-centered HCl elimination and C-Cl bond rupture occurred competitively as primary dissociation processes. The center-of-mass translational energy distribution of the products produced by the HCl elimination indicates that an exit barrier of several kcal/mol exists in the potential energy surface of the reaction. In the case of C2HCl3, three- and four-centered eliminations of HCl occurred competitively. Halogenated ethanes containing bromine atoms dissociated through a C-Br bond rupture channel. The halogenated ethyl radicals produced by the C-Br bond ruptures subsequently dissociated through a C-halogen bond rupture channel. The translational energy distributions for the C-halogen bond ruptures observed are almost consistent with those calculated by RRKM theory. In the case of c-C4F8, dissociation of c-C4F8 to two C2F4 molecules was observed as a primary process. About 30% of the exit barrier for this reaction is converted to the translational energy of the products. This indicates that the dissociation proceeds through a loose transition state. This conclusion is supported by the transition state structure calculated by an ab initio MO method. (author)

  12. Abundance, degassing and chemistry of halogens at Kilauea Volcano

    Science.gov (United States)

    Edmonds, M.

    2007-12-01

    The source concentration of halogens in the mantle, as well as other volatiles, is heterogeneous and related to tectonic setting. Intra-plate magmas, which give rise to ocean island basalts and are derived from a mantle plume source, are typically enriched in halogens relative to mid-oceanic ridge basalts but depleted relative to arc magmas. Fourier Transform Infra Red (FTIR) spectroscopy measurements of volcanic gases were supplemented with electron microprobe analyses of glasses in erupted products from Kilauea Volcano, Hawaii, to provide the first detailed picture of the abundance, degassing and plume chemistry of halogens at this volcano. This study reveals that typical fluxes of both HCl and HF are 50-100 t/d; Cl/S ranges from 0.01 to 0.07 and F/S from 0.01 to 0.05. SiF4 and HBr are below detection. The abundance of halogens in melt inclusions and matrix glasses in the lavas allow formulation of their degassing path prior to eruption. Kilauea volcanic gases have lower Cl/S than volcanoes in arc settings, but are similar to those measured at other volcanoes in plume settings. F/S, on the other hand, is within range of that measured at Soufriere Hills, Masaya and Etna, indicating that there is a higher degree of homogeneity in the mantle distribution of F. The relative proportion of Cl, F and S in the volcanic plume varies considerably over time and space. This variability may be due to a number of factors: the depth of vapour-melt separation in the conduit; the degree of degassing of shallow, stagnant magma (S-rich gases exsolve first); interaction between vapour and a hydrothermal system; the relative rates of diffusion between the species; or processes occurring in the plume such as adsorption of or reaction between acidic gases and silicate particles.

  13. Halogen Bonding in Iodo-perfluoroalkane/Pyridine Mixtures

    Science.gov (United States)

    Fan, Haiyan; Eliason, Jeffrey K.; Moliva A., C. Diane; Olson, Jason L.; Flancher, Scott M.; Gealy, M. W.; Ulness, Darin J.

    2009-12-01

    Mole fraction and temperature studies of halogen bonding between 1-iodo-perfluorobutane, 1-iodo-perfluorohexane, or 2-iodo-perfluoropropane and pyridine were performed using noisy light-based coherent anti-Stokes Raman scattering (I(2) CARS) spectroscopy. The ring breathing mode of pyridine both is highly sensitive to halogen bonding and provides a strong I(2) CARS signal. As the lone pair electrons from the pyridinyl nitrogen interact with the σ-hole on the iodine from the iodo-perfluoroalkane, the ring breathing mode of pyridine blue-shifts proportionately with the strength of the interaction. The measured blue shift for halogen bonding of pyridine and all three iodo-perfluoroalkanes is comparable to that for hydrogen bonding between pyridine and water. 2-Iodo-perfluoropropane displays thermodynamic behavior that is different from that of the 1-iodo-perfluoroalkanes, which suggests a fundamental difference at the molecular level. A potential explanation of this difference is offered and discussed.

  14. Transepidermal water loss during halogen spotlight phototherapy in preterm infants.

    Science.gov (United States)

    Grünhagen, Dirk J; de Boer, Mark G J; de Beaufort, Arnout Jan; Walther, Frans J

    2002-03-01

    Among preterm infants there is a relationship between skin blood flow and transepidermal water loss (TEWL). The aim of this study was to assess whether halogen spotlight phototherapy without significant heat stress increases TEWL and affects maintenance fluid requirements in preterm infants. TEWL was measured noninvasively before the start and after 1 h of halogen spotlight phototherapy in a group of preterm infants, nursed in double-walled incubators with moderately high relative humidity. Relative humidity and ambient temperature in the incubator were tightly controlled. Mean +/- SD birth weight of the 18 infants was 1412 +/- 256 g, gestational age 30.6 +/- 1.6 wk, and age at measurement 5 +/- 3 d. Nine infants received ventilatory assistance. Relative humidity was 40-80% (mean 52%). Average TEWL increased from 13.6 to 16.5 g/m(2)/h during phototherapy. These data show that TEWL increases by approximately 20% during phototherapy despite constant skin temperature and relative humidity. Maintenance fluids of preterm infants should be increased by 0.35 mL/kg/h during exposure to halogen spotlight phototherapy.

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

    Science.gov (United States)

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

    1998-01-01

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

  16. Reactive Halogens in the Marine Boundary Layer (RHaMBLe: the tropical North Atlantic experiments

    Directory of Open Access Journals (Sweden)

    J. D. Lee

    2010-02-01

    these air mass classifications is observed in the time series of soluble gas and aerosol composition measurements, with additional identification of periods of slightly elevated dust concentrations consistent with the trajectories passing over the African continent. The CVAO is shown to be broadly representative of the wider North Atlantic marine boundary layer; measurements of NO, O3 and black carbon from the ship are consistent with a clean Northern Hemisphere marine background. Aerosol composition measurements do not indicate elevated organic material associated with clean marine air. Closer to the African coast, black carbon and NO levels start to increase, indicating greater anthropogenic influence. Lower ozone in this region is possibly associated with the increased levels of measured halocarbons, associated with the nutrient rich waters of the Mauritanian upwelling. Bromide and chloride deficits in coarse mode aerosol at both the CVAO and on D319 and the continuous abundance of inorganic gaseous halogen species at CVAO indicate significant reactive cycling of halogens.

    Aircraft measurements of O3 and CO show that surface measurements are representative of the entire boundary layer in the vicinity both in diurnal variability and absolute levels. Above the inversion layer similar diurnal behaviour in O3 and CO is observed at lower mixing ratios in the air that had originated from south of Cape Verde, possibly from within the ITCZ. ECMWF calculations on two days indicate very different boundary layer depths and aircraft flights over the ship replicate this, giving confidence in the calculated boundary layer depth.

  17. Reactive Halogens in the Marine Boundary Layer (RHaMBLe: the tropical North Atlantic experiments

    Directory of Open Access Journals (Sweden)

    J. D. Lee

    2009-10-01

    slightly elevated dust concentrations consistent with the trajectories passing over the African continent. The CVAO is shown to be broadly representative of the wider North Atlantic marine boundary layer; measurements of NO, O3 and black carbon from the ship are consistent with a clean Northern Hemisphere marine background. Aerosol composition measurements do not indicate elevated organic material associated with clean marine air. Closer to the African coast, black carbon and NO levels start to increase, indicating greater anthropogenic influence. Lower ozone in this region is possibly associated with the increased levels of measured halocarbons, associated with the nutrient rich waters of the Mauritanian upwelling. Bromide and chloride deficits in coarse mode aerosol at both the CVAO and on D319 and the continuous abundance of inorganic gaseous halogen species at CVAO indicate significant reactive cycling of halogens.

    Aircraft measurements of O3 and CO show that surface measurements are representative of the entire boundary layer in the vicinity both in diurnal variability and absolute levels. Above the inversion layer similar diurnal behaviour in O3 and CO is observed at lower mixing ratios in the air that had originated from south of Cape Verde, possibly from within the ITCZ. ECMWF calculations on two days indicate very different boundary layer depths and aircraft flights over the ship replicate this, giving confidence in the calculated boundary layer depth.

  18. Halogen content in Lesser Antilles arc volcanic rocks : exploring subduction recycling

    Science.gov (United States)

    Thierry, Pauline; Villemant, Benoit; Caron, Benoit

    2016-04-01

    Halogens (F, Cl, Br and I) are strongly reactive volatile elements which can be used as tracers of igneous processes, through mantle melting, magma differentiation and degassing or crustal material recycling into mantle at subduction zones. Cl, Br and I are higly incompatible during partial melting or fractional cristallization and strongly depleted in melts by H2O degassing, which means that no Cl-Br-I fractionation is expected through magmatic differenciation [current thesis]. Thus, Cl/Br/I ratios in lavas reflect the halogen content of their mantle sources. Whereas these ratios seemed quite constant (e.g. Cl/Br =300 as seawater), recent works suggest significant variations in arc volcanism [1,2]. In this work we provide high-precision halogen measurements in volcanic rocks from the recent activity of the Lesser Antilles arc (Montserrat, Martinique, Guadeloupe, Dominique). Halogen contents of powdered samples were determined through extraction in solution by pyrohydrolysis and analysed by Ion Chromatography for F and Cl and high performance ICP-MS (Agilent 8800 Tripe Quad) for Cl, Br and I [3,4]. We show that lavas - and mantle sources - display significant vraiations in Cl/Br/I ratios along the Lesser Antilles arc. These variations are compared with Pb, Nd and Sr isotopes and fluid-mobile elements (Ba, U, Sr, Pb etc.) compositions which vary along the arc from a nothern ordinary arc compositions to a southern 'crustal-like' composition [5,6]. These characteristics are attributed to subducted sediments recycling into the mantle wedge, whose contribution vary along the arc from north to south [7,8]. The proportion of added sediments is also related to the distance to the trench as sediment melting and slab dehydration may occur depending on the slab depth [9]. Further Cl-Br-I in situ measurements by LA-ICP-MS in Lesser Antilles arc lavas melt inclusions will be performed, in order to provide better constraints on the deep halogen recycling cycle from crust to

  19. Ultrasonication assisted preparation of carbonaceous nanoparticles modified polyurethane foam with good conductivity and high oil absorption properties

    Science.gov (United States)

    Shi, Hengchong; Shi, Dean; Yin, Ligang; Yang, Zhihua; Luan, Shifang; Gao, Jiefeng; Zha, Junwei; Yin, Jinghua; Li, Robert K. Y.

    2014-10-01

    In this work, we report a facile, low cost and time-saving method for the fabrication of compressible, electrically conductive, oil absorptive, cost-effective and flexible polyurethane (PU) foam through ultrasonication induced carbonaceous nanoparticles (CNP) onto flexible PU foam (CNP-PU foam). SEM images showed that the CNP could be firmly anchored onto the PU foam, and made the PU foam surface much rougher. Zero-dimensional carbonaceous nanoparticles were easier to anchor onto the PU foam surface than one-dimensional nanoparticles (e.g., carbon nanotube) or two-dimensional nanoparticles (e.g., graphene oxide). The CNP-PU foam exhibited excellent elasticity and high mechanical durability even when it was subjected to 500 cyclic compression. The CNP-PU foam had excellent absorption of organic solvents up to 121 times the weight of the initial PU foam. In addition, the electrical conductivity of PU foams was considerably increased with the anchoring of CNP onto the matrix. In addition, compression experiments confirmed that the electrical conductivity of CNP-PU foams changed with their compression ratios, thus exhibiting excellent pressure sensitivity. The as-prepared materials have significant potential as oil absorbents, elastic conductors, flexible electrodes, pressure sensors, etc.In this work, we report a facile, low cost and time-saving method for the fabrication of compressible, electrically conductive, oil absorptive, cost-effective and flexible polyurethane (PU) foam through ultrasonication induced carbonaceous nanoparticles (CNP) onto flexible PU foam (CNP-PU foam). SEM images showed that the CNP could be firmly anchored onto the PU foam, and made the PU foam surface much rougher. Zero-dimensional carbonaceous nanoparticles were easier to anchor onto the PU foam surface than one-dimensional nanoparticles (e.g., carbon nanotube) or two-dimensional nanoparticles (e.g., graphene oxide). The CNP-PU foam exhibited excellent elasticity and high mechanical

  20. Formation of halogen-induced secondary organic aerosol (XOA)

    Science.gov (United States)

    Kamilli, Katharina; Ofner, Johannes; Zetzsch, Cornelius; Held, Andreas

    2013-04-01

    Reactive halogen species (RHS) are very important due to their potential of stratospheric ozone depletion and surface ozone destruction. RHS seem to interact with precursors of secondary organic aerosol (SOA) similarly to common atmospheric oxidants like OH radicals and ozone. The potential interaction of RHS with preformed SOA has recently been studied (Ofner et al., 2012). Although aerosol formation from reaction of RHS with typical SOA precursors was previously studied (e.g. Cai et al., 2006), no data are available on bromine-induced aerosol formation from organic precursors yet. An aerosol smog-chamber was used to examine the halogen-induced secondary organic aerosol (XOA) formation under atmospheric conditions using simulated sunlight. With a concentration of 10 ppb for the organic precursor, 2 ppb for molecular chlorine, and 10 ppb for molecular bromine, the experimental setup is close to ambient conditions. By combined measurements of the aerosol size distribution, ozone and NOx mixing ratios, as well as the decay of the organic precursor, aerosol yields and aerosol growth rates were determined. The decay of the organic precursor was analyzed by capillary gas chromatography coupled with flame-ionization detection (GC-FID) and the aerosol size distribution was measured using a Scanning Mobility Particle Sizer (SMPS). Additionally, with the decay rate of the precursor and the calculated photolysis rates of molecular halogen species, based on the well-known spectrum of the solar simulator, mechanistic details on the XOA formation pathways can be determined. We observed XOA formation even at very low precursor and RHS concentrations with a diameter mode at 10-20 nm and a number concentration up to 1000000 particles cm-3. While the XOA formation from chlorine is very rapid, the interaction of bromine with the organic precursors is about five times slower. The aerosol yield reached maximum values of 0.01 for the reaction of chlorine with α-pinene and 0.0004 for

  1. Non-conventional gas phase remediation of volatile halogenated compounds by dehydrated bacteria

    OpenAIRE

    Erable, Benjamin; Goubet, Isabelle; Seltana, Amira; Maugard, Thierry

    2009-01-01

    Traditional biological removal processes are limited by the low solubility of halogenated compounds in aqueous media. A new technology appears very suitable for the remediation of these volatile organic compounds (VOCs). Solid/gas bio-catalysis applied in VOC remediation can transform halogenated compounds directly in the gas phase using dehydrated cells as a bio-catalyst. The hydrolysis of volatile halogenated substrates into the corresponding alcohol was studied in a solid/gas bio...

  2. The Eocene Rusayl Formation, Oman, carbonaceous rocks in calcareous shelf sediments: Environment of deposition, alteration and hydrocarbon potential

    Energy Technology Data Exchange (ETDEWEB)

    Dill, H.G.; Wehner, H.; Kus, J. [Federal Institute for Geosciences and Natural Resources, P.O. Box 510163, D-30631 Hannover (Germany); Botz, R. [University Kiel, Geological-Paleontological Department, Olshausenstrasse 40-60, D-24118 Kiel (Germany); Berner, Z.; Stueben, D. [Technical University Karlsruhe, Institute for Mineralogy and Geochemistry, Fritz-Haber-Weg 2, D-76131 Karlsruhe (Germany); Al-Sayigh, A. [Sultan Qaboos University, Geological Dept. PO Box 36, Al-Khod (Oman)

    2007-10-01

    incursions make up a greater deal of the sedimentary record than mangrove swamps. Terra rossa paleosols mark the end of accumulation of organic material (OM) and herald supratidal conditions at the passage of Rusayl Formation into the overlying Seeb Formation. In the subtidal-supratidal cycles of lithofacies unit VIII the terra rossa horizons are thining upwards and become gradually substituted for by deep-water middle ramp sediments of lithofacies unit IX. Framboidal pyrite, (ferroan) dolomite with very little siderite are indicative of an early diagenetic alteration stage I under rather moderate temperatures of formation. During a subsequent stage II, an increase in the temperature of alteration was partly induced by burial and a high heat flow from the underlying Semail Ophiolite. Type-III kerogen originating from higher plants and, in addition, some marine biota gave rise to the generation of small amounts of soluble organic matter during this stage of diagenesis. The average reflectance of humic particles marks the beginning of the oil window and the production index reveals the existence of free hydrocarbons. Further uplift of the Eocene strata and oxidation during stage IIII caused veins of satin spar to form from organic sulfur and pyrite in the carbonaceous material. Lowering of the pH value of the pore fluid led to the precipitation of jarosite and a set of hydrated aluminum sulfates dependant upon the cations present in the wall rocks. AMD minerals (= acid mine drainage) are not very widespread in this carbonaceous series intercalated among calcareous rocks owing to the buffering effect of carbonate minerals. These carbonate-hosted carbonaceous rocks are below an economic level as far as the mining of coal is concerned, but deserves particular attention as source rocks for hydrocarbons in the Middle East, provided a higher stage of maturity is reached. (author)

  3. Mineralized Remains of Morphotypes of Filamentous Cyanobacteria in Carbonaceous Meteorites

    Science.gov (United States)

    Hoover, Richard B.

    2005-01-01

    ) investigations of freshly fractured interior surfaces of carbonaceous meteorites, terrestrial rocks, and recent microbial extremophiles and filamentous cyanobacteria. These studies have resulted in the detection in a several carbonaceous meteorites of the mineralized remains of a wide variety of complex filamentous trichomic microorganisms. These embedded forms are consistent in size and microstructure with well-preserved morphotypes of mat- forming filamentous trichomic cyanobacteria and the degraded remains of microfibrils of cyanobacterial sheaths. We present the results of comparative imaging studies and EDAX elemental analyses of recent cyanobacteria (e.g. Calothrix, Oscillatoria, and Lyngbya) that are similar in size, morphology and microstructure to morphotypes found embedded in meteorites. EDAX elemental studies reveal that forms found in carbonaceous meteorites often have highly carbonized sheaths in close association with permineralized filaments, trichomes and microbial cells. Ratios of critical bioelements (C:O, C:N, C:P, and C:S) reveal dramatic differences between microfossils in Earth rocks and meteorites and in filaments, trichomes, hormogonia, and cells of recent cyanobacteria.

  4. The Effect of Aqueous Alteration in Antarctic Carbonaceous Chondrites from Comparative ICP-MS Bulk Chemistry

    Science.gov (United States)

    Alonso-Azcarate, J.; Trigo-Rodriguez, J. M.; Moyano-Cambero, C. E.; Zolensky, M.

    2014-01-01

    Terrestrial ages of Antarctic carbonaceous chondrites (CC) indicate that these meteorites have been preserved in or on ice for, at least, tens of thousands of years. Due to the porous structure of these chondrites formed by the aggregation of silicate-rich chondrules, refractory inclusions, metal grains, and fine-grained matrix materials, the effect of pervasive terrestrial water is relevant. Our community defends that pristine CC matrices are representing samples of scarcely processed protoplanetary disk materials as they contain stellar grains, but they might also trace parent body processes. It is important to study the effects of terrestrial aqueous alteration in promoting bulk chemistry changes, and creating distinctive alteration minerals. Particularly because it is thought that aqueous alteration has particularly played a key role in some CC groups in modifying primordial bulk chemistry, and homogenizing the isotopic content of fine-grained matrix materials. Fortunately, the mineralogy produced by parent-body and terrestrial aqueous alteration processes is distinctive. With the goal to learn more about terrestrial alteration in Antarctica we are obtaining reflectance spectra of CCs, but also performing ICP-MS bulk chemistry of the different CC groups. A direct comparison with the mean bulk elemental composition of recovered falls might inform us on the effects of terrestrial alteration in finds. With such a goal, in the current work we have analyzed some members representative of CO and CM chondrite groups.

  5. Ethanol adsorption onto carbonaceous and composite adsorbents for adsorptive cooling system

    International Nuclear Information System (INIS)

    The aim of the present paper is the experimental characterization of adsorbent materials suitable for practical applications in adsorption refrigeration systems, employing ethanol as refrigerant. Different commercial activated carbons as well as a properly synthesized porous composite, composed of LiBr inside a silica gel host matrix, have been tested. A complete thermo-physical characterization, comprising nitrogen physi-sorption, specific heat and thermo-gravimetric equilibrium curves of ethanol adsorption over the sorbents, has been carried out. The equilibrium data have been fitted by means of the Dubinin – Astakhov equation. On the basis of the experimental data, a thermodynamic evaluation of the achievable performance of each adsorbent pair has been estimated by calculating the maximum COP (Coefficient of Performance) under typical working boundary conditions for refrigeration and air conditioning applications. The innovative composite material shows the highest thermodynamic performances of 0.64–0.72 for both tested working conditions. Nevertheless, the best carbonaceous material reaches COP value comparable with the synthesized composite. The results have demonstrated the potential of the chosen adsorbents for utilization in adsorption cooling systems. - Highlights: • We studied ethanol adsorption for adsorption cooling systems. • Commercial activated carbons and composite sorbent, LiBr/SiO2, are tested by complete thermo-physical characterization. • A thermodynamic evaluation has been carried out on each working pairs to estimate the performance of a refrigeration cycle

  6. Non-PBDE halogenated flame retardants in Canadian indoor house dust: sampling, analysis, and occurrence.

    Science.gov (United States)

    Fan, Xinghua; Kubwabo, Cariton; Rasmussen, Pat E; Wu, Fang

    2016-04-01

    An analytical method was developed for the measurement of 18 novel halogenated flame retardants in house dust. Sample preparation was based on ultrasound-assisted solvent extraction and clean up with solid phase extraction (SPE). Sample extracts were analyzed by gas chromatography-mass spectrometry (GC/MS) operated in electron capture negative ion (ECNI) chemical ionization mode. Baseline data from 351 fresh (active) dust samples collected under the Canadian House Dust Study (CHDS) revealed that five out of 18 target chemicals were present with detection frequencies higher than 90 %. Median (range) concentrations for these five compounds were as follows: 104 (detection limits (MDLs). In addition, the method was also applied to the analysis of the targeted compounds in National Institute of Standards and Technology (NIST) standard reference material (SRM 2585, organic contaminants in house dust). Results from the current study could contribute to the potential certification of target chemicals in SRM 2585. PMID:26780041

  7. Metamorphosed CM and CI Carbonaceous Chondrites Could Be from the Breakup of the Same Earth-crossing Asteroid

    Science.gov (United States)

    Zolensky, Michael; Abell, Paul; Tonui, Eric

    2005-01-01

    Far from being the relatively unprocessed materials they were once believed to be, we now know that a significant number of carbonaceous chondrites were thermally metamorphosed on their parent asteroid(s). Numerous studies indicate that 7 "CM" and 2 "CI" chondrites have been naturally heated, variously, at from 400 to over 700 C on their parent asteroid(s). Petrographic textures reveal that this thermal metamorphism occurred after the dominant aqueous alteration phase, although some meteorites show evidence of a heating event between two aqueous alteration episodes, i.e. pro- and retrograde aqueous alteration. Aside from the issues of the identification of the transient heat source, timing of metamorphism, and the relation of these materials (if any) to conventional CM and CI chondrites, there is also a mystery related to their recovery. All of these meteorites have been recovered from the Antarctic; none are falls or finds from anyplace else. Indeed, the majority have been collected by the Japanese NIPR field parties in the Yamato Mountains. In fact, one estimate is that these meteorites account for approx. 64 wt% of the CM carbonaceous chondrites at the NIPR. The reasons for this are unclear and might be due in part to simple sampling bias. However we suggest that this recovery difference is related to the particular age of the Yamato Mountains meteorite recovery surfaces, and differences in meteoroid fluxes between the Yamato meteorites and recent falls and substantially older Antarctic meteorites. Additional information is included in the original extended abstract.

  8. Quartet excited halogen atoms produced in the electron pulse irradiation of rare gases containing halogenated compounds

    Science.gov (United States)

    Kuramasu, T.; Ohyama, H.; Yoshikawa, S.; Terazawa, N.; Ishikawa, Y.; Arai, S.

    1995-07-01

    Quartet excited halogen atoms F*(2p4 3s,4PJ), Cl*(3p4 4s,4PJ), Br*(4p4 5s,4PJ), and I*(5p4 6s,4PJ), where the J's are 5/2, 3/2, and 1/2, were found to be produced in the electron pulse irradiation of Ne or Ar containing one of SF6, CCl4, CClF3, CBrF3, CBr2F2, and CF3I. The population distribution ratios at the stage of production were 1.0(J=5/2):0.41(J=3/2):0.06(J=1/2) for F* in Ne containing SF6, 1.0(J=5/2):0.27(J=3/2):0.14(J=1/2) for Cl* in Ne containing CCl4, 1.0(J=5/2):0.29(J=3/2):0.2-0.3(J=1/2) for Br* in Ne containing CBr2F2, and 1.0(J=5/2):0.13(J=3/2):0.54(J=1/2) for I* in Ar containing CF3I. The observed ratios considerably differ from those calculated from the Boltzmann distribution law. F*(4P5/2), F*(4P3/2), and Cl*(4P5/2) are mainly produced by the reactions of lowest triplet excited diatomic molecules of neon with SF6 and CCl4. Cl*(4P3/2) and Cl*(4P1/2) are produced in a rapid process and deactivated into lower Cl*(4P5/2). Several reaction channels probably contribute to the formation of Br*(4PJ) and I*(4PJ). Rate constants for reactions of triplet excited diatomic molecules of neon or argon with these parent molecules were determined from observed absorption decay curves for Ne2* or Ar2* in the presence of parent molecules.

  9. Impact of nucleation of carbonaceous clusters on structural, electrical and optical properties of Cr+-implanted PMMA

    Science.gov (United States)

    Arif, Shafaq; Rafique, M. Shahid; Saleemi, Farhat; Naab, Fabian; Toader, Ovidiu; Mahmood, Arshad; Aziz, Uzma

    2016-09-01

    Specimens of polymethylmethacrylate (PMMA) have been implanted with 400 keV Cr+ ions at different ion fluences ranging from 5 × 1013 to 5 × 1015 ions/cm2. The possible chemical reactions involved in the nucleation of conjugated carbonaceous clusters in implanted PMMA are discussed. Furthermore, impact of formation of carbonaceous clusters on structural, optical, electrical and morphological properties of implanted PMMA has been examined. The structural modifications in implanted PMMA are observed by Raman spectroscopy. The variation in optical band gap and Urbach energy is measured using UV-visible spectroscopic analysis. The effects of Cr+ ion implantation on electrical and morphological properties are investigated by four-probe apparatus and atomic force microscopy, respectively. The Raman spectroscopic analysis confirmed the formation of carbonaceous clusters with the transformation of implanted layer of PMMA into amorphous carbon. Simultaneously, the optical band gap of implanted PMMA has reduced from 3.13 to 0.85 eV. The increase in Urbach energy favors the decline in band gap together with the structural modification in implanted PMMA. As a result of Cr+ ion implantation, the electrical conductivity of PMMA has improved from 2.14 ± 0.06 × 10-10 S/cm (pristine) to 7.20 ± 0.36 × 10-6 S/cm. The AFM images revealed a decrease in surface roughness with an increment in ion fluence up to 5 × 1014 ions/cm2. The modification in the electrical, optical and structural properties makes the PMMA a promising candidate for its future utilization, as a semiconducting and optically active material, in various fields like plastic electronics and optoelectronic devices.

  10. Comparing Amino Acid Abundances and Distributions Across Carbonaceous Chondrite Groups

    Science.gov (United States)

    Burton, Aaron S.; Callahan, Michael P.; Glavin, Daniel P.; Elsila, Jamie E.; Dworkin, Jason P.

    2012-01-01

    Meteorites are grouped according to bulk properties such as chemical composition and mineralogy. These parameters can vary significantly among the different carbonaceous chondrite groups (CI, CM, CO, CR, CH, CB, CV and CK). We have determined the amino acid abundances of more than 30 primary amino acids in meteorites from each of the eight groups, revealing several interesting trends. There are noticeable differences in the structural diversity and overall abundances of amino acids between meteorites from the different chondrite groups. Because meteorites may have been an important source of amino acids to the prebiotic Earth and these organic compounds are essential for life as we know it, the observed variations of these molecules may have been important for the origins of life.

  11. Petrogenesis of opaque assemblages in the Ningqiang carbonaceous chondrite

    Institute of Scientific and Technical Information of China (English)

    HSU; WeiBiao

    2007-01-01

    Numerous round to oblate opaque assemblages (OAs) are found in chondrules and matrix of the Ningqiang carbonaceous chondrite. They are mainly composed of Ni-rich metal,magnetite,Fe,Ni-sulfides,with minor amounts of phosphate,phosphoran-olivine,pyroxene and trace amounts of nano-sized platinum-group metal alloys. The mineralogy of Ningqiang OAs is very similar to that of OAs previously reported in Ca,Al-rich inclusions of CV chondrites. Being a rare mineral phase in nature,phosphoran-olivine is thought to form by nonequilibrium reactions between P-bearing molten metal and olivine crystals during rapid cooling. Its occurrence in Ningqiang OAs indicates that the precursor of OAs was locally produced during chondrule formation,rather than directly condensed from the solar nebula as previously thought. The petrographic and mineralogical characteristics of Ningqiang OAs reveal that OAs formed by low temperature alterations of pre-existing homogeneous alloys within chondrules on a planetary body.

  12. On the carbonaceous carriers of IR plateau and continuum emission

    CERN Document Server

    Papoular, Renaud

    2013-01-01

    This study explores the molecular origins of plateaus and continuum underlying IR and FIR bands emitted by compact nebulae, especially proto-planetary nebulae. Computational organic chemistry codes are used to deliver the vibrational integrated band intensities of various large, typical carbonaceous structures. These spectra are composed of a rather continuous distribution of weak modes from which emerge the fingerprints. The 6 to 18-mu region is interspersed with a great many weak lines, to which the plateaus are assigned. Similarly, the far IR spectrum is ascribed to the phonon (skeletal) spectrum which is readily identified beyond 18 mu. The absorptivities and absorption cross-sections per interstellar H atom deduced from these spectra are comparable with those of laboratory dust analogs and astronomical measurements, respectively. Moreover, the 5-35 mu spectra of two typical Proto-Planetary Nebula were reasonably well simulated with combinations of molecules containing functional groups which carry the 21...

  13. In situ growth of copper nanocrystals from carbonaceous microspheres with electrochemical glucose sensing properties

    International Nuclear Information System (INIS)

    Graphical abstract: In situ growth of copper nanoparticles from hydrothermal copper-containing carbonaceous microspheres was induced by annealing or electron beam irradiation. Obtained micro-nano carbon/copper composite microspheres show electrochemical glucose sensing properties. - Highlights: • We synthesized carbonaceous microspheres containing non-nanoparicle copper species through a hydrothermal route. • By annealing or electron beam irradiation, copper nanoparticles would form from the carbonaceous microspheres in situ. • By controlling the annealing temperature, particle size of copper could be controlled in the range of 50–500 nm. • The annealed carbon/copper hierarchical composite microspheres were used to fabricate an electrochemical glucose sensor. - Abstract: In situ growth of copper nanocrystals from carbon/copper microspheres was observed in a well-controlled annealing or an electron beam irradiation process. Carbonaceous microspheres containing copper species with a smooth appearance were yielded by a hydrothermal synthesis using copper nitrate and ascorbic acid as reactants. When annealing the carbonaceous microspheres under inert atmosphere, copper nanoparticles were formed on carbon microspheres and the copper particle sizes can be increased to a range of 50–500 nm by altering the heating temperature. Similarly, in situ formation of copper nanocrystals from these carbonaceous microspheres was observed on the hydrothermal product carbonaceous microspheres with electron beam irradiation in a vacuum transmission electron microscopy chamber. The carbon/copper composite microspheres obtained through annealing were used to modify a glassy carbon electrode and tested as an electrochemical glucose sensor

  14. Spatial Gradients in Halogen Oxides Across the North Slope of Alaska Indicate That Halogen Activated Airmasses are Spatially Large

    Science.gov (United States)

    Simpson, W. R.; Hoenninger, G. S.; Platt, U.

    2005-12-01

    Reactive halogens are important oxidizers in the polar atmosphere during springtime. They deplete tropospheric ozone, oxidize hydrocarbons, and oxidize gas-phase mercury, causing it to deposit to the snow pack. We want to understand the mechanism by which halides in on snow/ice crystals and/or in aerosol particles are converted to reactive halogen species. This understanding can assist in prediction of mercury deposition and how that deposition depends on environmental variables like sea-ice extent and temperature. This mechanistic knowledge is particularly important in the context of a changing Arctic system. To study halogen activation, we are working in the Studies of the Northern Alaskan Coastal System (SNACS) project and here show results from 2005 including the LEADX experiment. A number of studies have implicated leads (cracks in the sea ice) as a source of halogen activation, but it is unclear if halogens are directly activated on ice surfaces at the lead (e.g. frost flowers) or if the lead is less directly involved. To address the role of leads in halogen activation, we measured bromine monoxide (BrO) using Multiple Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) at Barrow and Atqasuk, Alaska over a four-month period. The locations of these sites, either on the coast near a recurring lead in the case of Barrow, or 100km inland in the case of Atqasuk provides an ability to measure spatial gradients on the 100km length scale. In addition, the Barrow instrument was the first implementation of fully automated two dimensional MAX-DOAS where both elevation and azimuth were scanned. Because the MAX-DOAS method typically detects path-averaged BrO amounts between the instrument and a range of approximately 10km, differences in BrO between viewing azimuths allows us to determine short-length scale BrO gradients. From the 2-D MAX-DOAS observations at Barrow, we find that there are very small if any spatial gradients on the 10km length scale. From the

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

    Science.gov (United States)

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

    2015-05-01

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

  16. Determination of halogens, with special reference to iodine, in geological and biological samples using pyrohydrolysis for preparation and inductively coupled plasma mass spectrometry and ion chromatography for measurement.

    Science.gov (United States)

    Schnetger, B; Muramatsu, Y

    1996-11-01

    A method for determining iodine, bromine, chlorine and fluorine in geological and biological materials is described. In a quartz tube, solid material was heated to 1100 degrees C under a wet oxygen flow (pyrohydrolysis). By this process the halogens (I, Br, Cl, F) were separated from the matrix and then collected in a receiver solution. The chemical yield of iodine was determined by a radioactive tracer. ICP-MS and ion chromatographic measurements were used for the determination of the halogens. The method was optimized by investigating different experimental conditions. All four halogens can be trapped in the receiver solution from one combustion procedure. Precision and accuracy were evaluated by the analysis of environmental standard reference materials (rock, soil, milk, leaves, marine tissue). The concentrations in the materials analysed were in the ranges 0.006-50 mg kg-1 for I, 0.06-1300 mg kg-1 for Br, 50-1100 mg kg-1 for F and 400-11000 mg kg-1 for Cl. The lower values represent the practical detection limit of this method. The results obtained by the proposed method and the certified values are in good agreement. PMID:8952450

  17. Pyrolysis of carbonaceous particles and properties of Carbonaceous-g-Poly (acrylic acid-co-acrylamide superabsorbent polymer for agricultural applications

    Directory of Open Access Journals (Sweden)

    Ghazali S.

    2016-01-01

    Full Text Available Utilisation of fertilizer and water are very important in determining the production of agriculture nowadays. The excessive use of fertilizer in plantation somehow could leads to environmental pollution. The present study reported a synthesis of controlled release water retention (CRWR fertilizer coating with superabsorbent polymer (SAPs. Superabsorbent polymer (SAPs are polymers that have ability to absorb and retain large amounts of water relative to their own mass. The presence of coating layer of SAPs on fertilizer granules was believed could reduce excessive used of fertilizer by controlling their dissolution rates and also reduce the environmental pollution. In this study, the effect on the addition of carbonaceous filler in SAPs on the water absorbency was also be compared with control SAPs (without carbonaceous particles. In this study, the carbonaceous filler were obtained from pyrolysis process of empty fruit bunch (EFB biomass. The synthesized of SAPs and carbonaceous-SAPs were carried out via solution polymerization technique by using monomer of poly(acrylic acid (AA, acrylamide (AM, cross linker, methylene bisacrylamide (MBA and initiator, ammonium peroxodisulfate (APS that partially neutralized with sodium hydroxide (NaOH. The CRWR fertilizer was later be prepared by coated the fertilizer granule with SAPs and carbonaceous-SAPs. The water absorbency, morphology and the bonding formation of both CRWR fertilizer were investigated by using tea-beg method, Scanning Electron Microscopy (SEM and Fourier Transform Infrared Spectrophotometer (FTIR, respectively. Moreover, the water retention studies was conducted in order to investigate the efficiency of CRWR coated with SAP and carbonaceous-SAP in retaining the water content in different soil (organic and top soil. Based on the results, the CRWR fertilizer that was coated with carbonaceous-SAP had higher water absorbency value than the CRWR fertilizer without carbonaceous-SAP. Meanwhile

  18. Revealing halogen bonding interactions with anomeric systems: an ab initio quantum chemical studies.

    Science.gov (United States)

    Lo, Rabindranath; Ganguly, Bishwajit

    2015-02-01

    A computational study has been performed using MP2 and CCSD(T) methods on a series of O⋯X (X=Br, Cl and I) halogen bonds to evaluate the strength and characteristic of such highly directional noncovalent interactions. The study has been carried out on a series of dimeric complexes formed between interhalogen compounds (such as BrF, BrCl and BrI) and oxygen containing electron donor molecule. The existence and consequences of the anomeric effect of the electron donor molecule has also been investigated through an exploration of halogen bonding interactions in this halogen bonded complexes. The ab initio quantum chemical calculations have been employed to study both the nature and directionality of the halogen molecules toward the sp(3) oxygen atom in anomeric systems. The presence of anomeric nO→σ*CN interaction involves a dominant role for the availability of the axial and equatorial lone pairs of donor O atom to participate with interhalogen compounds in the halogen-bonded complexes. The energy difference between the axial and equatorial conformers with interhalogen compounds reaches up to 4.60 kJ/mol, which however depends upon the interacting halogen atoms and its attaching atoms. The energy decomposition analysis further suggests that the total halogen bond interaction energies are mainly contributed by the attractive electrostatic and dispersion components. The role of substituents attached with the halogen atoms has also been evaluated in this study. With the increase of halogen atom size and the positive nature of σ-hole, the halogen atom interacted more with the electron donor atom and the electrostatic contribution to the total interaction energy enhances appreciably. Further, noncovalent interaction (NCI) studies have been carried out to locate the noncovalent halogen bonding interactions in real space. PMID:25522359

  19. Thermal analytical investigation of biopolymers and humic- and carbonaceous-based soil and sediment organic matter

    Energy Technology Data Exchange (ETDEWEB)

    Lu Zhang; Eugene J. LeBoeuf; Baoshan Xing [Vanderbilt University, Nashville, TN (United States). Department of Civil and Environmental Engineering

    2007-07-15

    Improved understanding of the physical, chemical, and thermodynamic properties of soil and sediment organic matter (SOM) is crucial in elucidating sorption mechanisms of hydrophobic organic compounds (HOCs) in soils and sediments. In this study, several thermoanalytical techniques, including thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), temperature-modulated differential scanning calorimetry (TMDSC), and thermal mechanical analysis (TMA) were applied to 13 different organic materials (three woods, two humic acids, three kerogens, and five black carbons) representing a spectrum of diagenetic and/or thermal histories. Samples included Pocahontas No. 3 bituminous coal. Second-order thermal transition temperatures (T{sub t}) were identified in most materials, where the highest observed T{sub t} values (typically characterized as glass transition temperatures (T{sub g})) were shown to closely relate to chemical characteristics of the organic samples as influenced by diagenetic or thermal alteration. Results further suggest a positive correlation between glass transition temperature and a defined diagenetic/thermal index, where humic-based SOM (e.g., humic and fulvic acids) possess lower transition temperatures than more 'mature' carbonaceous-based SOM (i.e., kerogens and black carbons). The observed higher thermal transition temperature of aliphatic-rich Green River shale kerogen (about 120{sup o}C) relative to that of aromatic-rich humic acids suggests that a sole correlation of aromaticity to thermal transition temperature may be inappropriate. 55 refs., 2 figs., 1 tab.

  20. Molecular dynamics of halogenated graphene - hexagonal boron nitride nanoribbons

    Science.gov (United States)

    Nemnes, G. A.; Visan, Camelia; Anghel, D. V.; Manolescu, A.

    2016-08-01

    The hybrid graphene - hexagonal boron nitride (G-hBN) systems offer new routes in the design of nanoscale electronic devices. Using ab initio density functional theory calculations we investigate the dynamics of zig-zag nanoribbons a few interatomic distances wide. Several structures are analyzed, namely pristine graphene, hBN and G-hBN systems. By passivating the nanoribbon edges with hydrogen and different halogen atoms, one may tune the electronic and mechanical properties, like the band gap energies and the natural frequencies of vibration.

  1. Preparation and Electrooxidative SO-Extrusion of Halogenated 7-Thiabicyclo[2.2.1]heptene 7-Oxides

    OpenAIRE

    Thiemann, Thies; Melo, M. Luísa Sá e; Neves, André S. Campos; Li, Yuanqiang; Mataka, Shuntaro; Tashiro, Masashi; Geißler, Uwe; Walton, David

    1998-01-01

    Halogenated thiophenes have been cycloadded oxidatively to maleimides to give halogenated thiabicyclo[2.2.1]heptene S-oxides which have been subjected to an electrochemical extrusion of SO to give various halogeno-substituted phthalimides.

  2. Assessment of the Halogen Content of Brazilian Inhalable Particulate Matter (PM10) Using High Resolution Molecular Absorption Spectrometry and Electrothermal Vaporization Inductively Coupled Plasma Mass Spectrometry, with Direct Solid Sample Analysis.

    Science.gov (United States)

    de Gois, Jefferson S; Almeida, Tarcisio S; Alves, Jeferson C; Araujo, Rennan G O; Borges, Daniel L G

    2016-03-15

    Halogens in the atmosphere play an important role in climate change and also represent a potential health hazard. However, quantification of halogens is not a trivial task, and methods that require minimum sample preparation are interesting alternatives. Hence, the aim of this work was to evaluate the feasibility of direct solid sample analysis using high-resolution continuum source molecular absorption spectrometry (HR-CS MAS) for F determination and electrothermal vaporization-inductively coupled plasma mass spectrometry (ETV-ICP-MS) for simultaneous Cl, Br, and I determination in airborne inhalable particulate matter (PM10) collected in the metropolitan area of Aracaju, Sergipe, Brazil. Analysis using HR-CS MAS was accomplished by monitoring the CaF molecule, which was generated at high temperatures in the graphite furnace after the addition of Ca. Analysis using ETV-ICP-MS was carried out using Ca as chemical modifier/aerosol carrier in order to avoid losses of Cl, Br, and I during the pyrolysis step, with concomitant use of Pd as a permanent modifier. The direct analysis approach resulted in LODs that were proven adequate for halogen determination in PM10, using either standard addition calibration or calibration against a certified reference material. The method allowed the quantification of the halogens in 14 PM10 samples collected in a northeastern coastal city in Brazil. The results demonstrated variations of halogen content according to meteorological conditions, particularly related to rainfall, humidity, and sunlight irradiation.

  3. Composition of carbonaceous smoke particles from prescribed burning of a Canadian boreal forest: 1. Organic aerosol characterization by gas chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Mazurek, M.A.; Laterza, C.; Newman, L.; Daum, P. [Brookhaven National Lab., Upton, NY (United States); Cofer, W.R. III; Levine, J.S. [National Aeronautics and Space Administration, Hampton, VA (United States). Langley Research Center; Winstead, E.L. [Science Applications International Corporation, Hampton, VA (United States)

    1995-06-01

    In this study we examine the molecular organic constituents (C8 to C40 lipid compounds) collected as smoke particles from a Canadian boreal forest prescribed burn. Of special interest are (1) the molecular identity of polar organic aerosols, and (2) the amount of polar organic matter relative to the total mass of aerosol particulate carbon. Organic extracts of smoke aerosol particles show complex distributions of the lipid compounds when analyzed by capillary gas chromatography/mass spectrometry. The molecular constituents present as smoke aerosol are grouped into non-polar (hydrocarbons) and polar {minus}2 oxygen atoms) subtractions. The dominant chemical species found in the boreal forest smoke aerosol are unaltered resin compounds (C20 terpenes) which are abundant in unburned conifer wood, plus thermally altered wood lignins and other polar aromatic hydrocarbons. Our results show that smoke aerosols contain molecular tracers which are related to the biofuel consumed. These smoke tracers can be related structurally back to the consumed softwood and hardwood vegetation. In addition, combustion of boreal forest materials produces smoke aerosol particles that are both oxygen-rich and chemically complex, yielding a carbonaceous aerosol matrix that is enriched in polar substances. As a consequence, emissions of carbonaceous smoke particles from large-scale combustion of boreal forest land may have a disproportionate effect on regional atmospheric chemistry and on cloud microphysical processes.

  4. Cost-effective new liquid halogen biocide with better performance and reduced corrosivity

    Energy Technology Data Exchange (ETDEWEB)

    Shim Sang-Hea [Justeq LLC, Northbrook, IL (United States)

    2009-12-15

    Halogen biocides, though widely used and largely effective, are corrosive and are unsatisfactory in controlling surface-attached microbes, such as slime. A newly patented product, composed of stabilized chlorine and unreacted bromide, controls surface-attached microbes, is much less corrosive and is much more cost-effective than other halogen biocides. (orig.)

  5. Toxicity of gaseous halogenated organic compounds. (Latest citations from the NTIS bibliographic database). Published Search

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-02-01

    The bibliography contains citations concerning the toxicology of halogenated hydrocarbons and their health effects. Topics cover halogenated gases used as industrial chemicals, fire extinguishers, anesthetics, solvents, pesticides, and aerosol propellants. (Contains 50-250 citations and includes a subject term index and title list.) (Copyright NERAC, Inc. 1995)

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

    DEFF Research Database (Denmark)

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

    2011-01-01

    The formation of halogen bonded complexes between toluene-d8 and the perfluoroiodopropanes 1-C3F7I and 2-C3F7I has been investigated using 19F NMR spectroscopy. For both Lewis acids, evidence was found for the formation of a C–I⋯π halogen bonded complex. The complex formed is a 1:1 type. Using...

  7. Halogen bonding-enhanced electrochemical halide anion sensing by redox-active ferrocene receptors.

    Science.gov (United States)

    Lim, Jason Y C; Cunningham, Matthew J; Davis, Jason J; Beer, Paul D

    2015-10-01

    The first examples of halogen bonding redox-active ferrocene receptors and their anion electrochemical sensing properties are reported. Halogen bonding was found to significantly amplify the magnitude of the receptor's metallocene redox-couple's voltammetric responses for halide sensing compared to their hydrogen bonding analogues in both acetonitrile and aqueous-acetonitrile solvent media. PMID:26289779

  8. Halogen free benzoxazine based curable compositions for high T.sub.g applications

    Energy Technology Data Exchange (ETDEWEB)

    Tietze, Roger; Nguyen, Yen-Loan

    2016-08-16

    A method for forming a halogen-free curable composition containing a benzoxazine monomer, at least one epoxy resin, a catalyst, a toughening agent and a solvent. The halogen-free curable composition is especially suited for use in automobile and aerospace applications since the composition, upon curing, produces a composite having a high glass transition temperature.

  9. Anaerobic microbial transformation of halogenated aromatics and fate prediction using electron density modeling.

    Science.gov (United States)

    Cooper, Myriel; Wagner, Anke; Wondrousch, Dominik; Sonntag, Frank; Sonnabend, Andrei; Brehm, Martin; Schüürmann, Gerrit; Adrian, Lorenz

    2015-05-19

    Halogenated homo- and heterocyclic aromatics including disinfectants, pesticides and pharmaceuticals raise concern as persistent and toxic contaminants with often unknown fate. Remediation strategies and natural attenuation in anaerobic environments often build on microbial reductive dehalogenation. Here we describe the transformation of halogenated anilines, benzonitriles, phenols, methoxylated, or hydroxylated benzoic acids, pyridines, thiophenes, furoic acids, and benzenes by Dehalococcoides mccartyi strain CBDB1 and environmental fate modeling of the dehalogenation pathways. The compounds were chosen based on structural considerations to investigate the influence of functional groups present in a multitude of commercially used halogenated aromatics. Experimentally obtained growth yields were 0.1 to 5 × 10(14) cells mol(-1) of halogen released (corresponding to 0.3-15.3 g protein mol(-1) halogen), and specific enzyme activities ranged from 4.5 to 87.4 nkat mg(-1) protein. Chlorinated electron-poor pyridines were not dechlorinated in contrast to electron-rich thiophenes. Three different partial charge models demonstrated that the regioselective removal of halogens is governed by the least negative partial charge of the halogen. Microbial reaction pathways combined with computational chemistry and pertinent literature findings on Co(I) chemistry suggest that halide expulsion during reductive dehalogenation is initiated through single electron transfer from B12Co(I) to the apical halogen site.

  10. Recycling of typical supercapacitor materials.

    Science.gov (United States)

    Vermisoglou, Eleni C; Giannouri, Maria; Todorova, Nadia; Giannakopoulou, Tatiana; Lekakou, Constantina; Trapalis, Christos

    2016-04-01

    A simple, facile and low-cost method for recycling of supercapacitor materials is proposed. This process aims to recover some fundamental components of a used supercapacitor, namely the electrolyte salt tetraethyl ammonium tetrafluoroborate (TEABF4) dissolved in an aprotic organic solvent such as acetonitrile (ACN), the carbonaceous material (activated charcoal, carbon nanotubes) purified, the current collector (aluminium foil) and the separator (paper) for further utilization. The method includes mechanical shredding of the supercapacitor in order to reduce its size, and separation of aluminium foil and paper from the carbonaceous resources containing TEABF4 by sieving. The extraction of TEABF4 from the carbonaceous material was based on its solubility in water and subsequent separation through filtering and distillation. A cyclic voltammetry curve of the recycled carbonaceous material revealed supercapacitor behaviour allowing a potential reutilization. Furthermore, as BF4(-) stemming from TEABF4 can be slowly hydrolysed in an aqueous environment, thus releasing F(-) anions, which are hazardous, we went on to their gradual trapping with calcium acetate and conversion to non-hazardous CaF2. PMID:26862148

  11. Proto-Planetary Disk Chemistry Recorded by D-Rich Organic Radicals in Carbonaceous Chondrites

    OpenAIRE

    Remusat, Laurent; Robert, François; Meibom, Anders; Mostefaoui, Smail; Delpoux, Olivier; Binet, Laurent; Gourier, Didier; Derenne, Sylvie

    2009-01-01

    Insoluble organic matter (IOM) in primitive carbonaceous meteorites has preserved its chemical composition and isotopic heterogeneity since the solar system formed ~4.567 billion years ago. We have identified the carrier moieties of isotopically anomalous hydrogen in IOM isolated from the Orgueil carbonaceous chondrite. Data from high spatial resolution, quantitative isotopic NanoSIMS mapping of Orgueil IOM combined with data from electron paramagnetic resonance spectroscopy reveals that orga...

  12. Autocatalytic halogen release from salt droplets and saltpans

    Science.gov (United States)

    Bleicher, S.; Buxmann, J.; Balzer, N.; Riedel, T.; Thornton, J.; Platt, U.; Zetzsch, C.

    2012-04-01

    Reactive bromine and chlorine species are known to have an impact on the ozone concentration, to change the chemical balance of nitrogen oxides and to have an influence on human health: through their reactions with hydrocarbons (HCs) among other trace gases and increased deposition of toxic compounds (like mercury). Especially the formation of higher halogen oxides (OIO, OBrO) and the role of chlorine in tropospheric chemistry are not clear yet. We present experiments on halogen activation from salt mixtures of NaCl/NaBr and salt droplet aerosols, simulating saltpans and sea spray in an illuminated Teflon chamber. The starting conditions influence the total amount of released halogens, so we varied the amounts of aerosol surface, NOx and HCs, monitoring the time profiles of the HCs by gas chromatography in order to determine the time profiles of OH and Cl. The chemical ionization mass spectrometer (CIMS) of the University of Washington was used to observe stable halogen species in a short campaign, and a multi-reflection cell (White-type) of the University of Heidelberg, coupled with Differential Optical Absorption Spectroscopy (DOAS), was employed to measure BrO, ClO and OClO. We observe a qualitative difference in Br2 release between the saltpan and the sea salt aerosol experiments: While BrO increases immediately to very high levels up to 6 ppb in the saltpan experiments (Buxmann et al., 2011), formation of BrO is delayed in the aerosol studies. This delay varies from about five to ten minutes after switching the solar simulator on, depending on HCs and NOxconcentrations. Furthermore, we observe a "chlorine explosion" with Cl2 mixing ratios of up to 12 ppb (by CIMS) as a function of the initial HC and NOx conditions. More than 3 ppb ClO, 3.5 ppb OClO and 650 ppt BrO were observed at initial levels of 150 ppb NO2 and of 770 ppb O3, leading to an ozone depletion rate of 0.6 ppb/s. The influence of NOx was tested on simulated sea spray alone. Due to the

  13. A comparative evaluation of the shear bond strength of five different orthodontic bonding agents polymerized using halogen and light-emitting diode curing lights: An in vitro investigation

    Directory of Open Access Journals (Sweden)

    Sujoy Banerjee

    2011-01-01

    Full Text Available Purpose: With the introduction of photosensitive (light-activated restorative materials in orthodontics, various methods have been suggested to enhance the polymerization of the materials used, including use of more powerful light curing devices. Bond strength is an important property and determines the amount of force delivered and the treatment duration. Many light-cured bonding materials have become popular but it is the need of the hour to determine the bonding agent that is the most efficient and has the desired bond strength. Aim: To evaluate and compare the shear bond strengths of five different orthodontic light cure bonding materials cured with traditional halogen light and low-intensity light-emitting diode (LED light curing unit. Materials and Methods: 100 human maxillary premolar teeth, extracted for orthodontic purpose, were used to prepare the samples. 100 maxillary stainless steel bicuspid brackets of 0.018 slot of Roth prescription, manufactured by D-tech Company, were bonded to the prepared tooth surfaces of the mounted samples using five different orthodontic bracket bonding light-cured materials, namely, Enlight, Fuji Ortho LC (resin-modified glass ionomer cement, Orthobond LC, Relybond, and Transbond XT. The bond strength was tested on an Instron Universal testing machine (model no. 5582. Results: In Group 1 (halogen group, Enlight showed the highest shear bond strength (16.4 MPa and Fuji Ortho LC showed the least bond strength (6.59 MPa (P value 0.000. In Group 2 (LED group, Transbond showed the highest mean shear bond strength (14.6 MPa and Orthobond LC showed the least mean shear bond strength (6.27 MPa (P value 0.000. There was no statistically significant difference in the shear bond strength values of all samples cured using either halogen (mean 11.49 MPa or LED (mean 11.20 MPa, as the P value was 0.713. Conclusion: Polymerization with both halogen and LED resulted in shear bond strength values which were above the

  14. A mechanistic examination of redox cycling activity in carbonaceous particulate matter

    Science.gov (United States)

    McWhinney, Robert David

    Mechanistic aspects of carbonaceous aerosol toxicity were examined with respect to the ability of particles to catalyse reactive oxygen species-generating redox cycling reactions. To investigate the role of secondary organic material, we examined two systems. In the first, two-stroke engine exhaust particles were found to increase their ability to catalyse redox cycling in the presence of a reducing agent, dithiothreitol (DTT), when the exhaust was exposed to ozone. This occurred through deposition of redox-active secondary organic aerosol (SOA) onto the particle that was ten times more redox active per microgram than the primary engine particle. In the second system, naphthalene SOA formed highly redox active particles. Activity was strongly correlated to the amount of the 1,4- and 1,2-naphthoquinone measured in the particle phase. However, these species and the newly quantified naphthalene oxidation product 5-hydroxy-1,4-naphthoquinone accounted for only 30% of the observed DTT decay from the particles. Gas-particle partitioning coefficients suggest 1,4- and 1,2- naphthoquinone are not strong contributors to ambient particle redox activity at 25 °C. However, a large number of redox active species are unidentified. Some of these may be highly oxidised products of sufficiently low vapour pressure to be atmospherically relevant. DTT activity of diesel particles was found to be high per unit mass. The activity was found to be associated with the insoluble fraction as filtration of the particles nearly eliminated DTT decay. Neither methanol nor dichloromethane extracts of diesel particles exhibited redox activity, indicating that the redox active species are associated with the black carbon portion of the particles. Examination of particle concentration techniques found that use of water condensation to grow and concentrate particles introduced a large organic artefact to the particles. Experiments with concentrated inorganic particles suggest that the source of this

  15. Multifunctional polymer composites containing inorganic nanoparticles and novel low-cost carbonaceous fillers

    Science.gov (United States)

    Wu, Hongchao

    Advanced polymer nanocomposites/composites containing inorganic nanoparticles and novel carbonaceous fillers were processed and evaluated for the multifunctional purposes. To prepare the high performance conformal coating materials for microelectronic industries, epoxy resin was incorporated with zirconium tungstate (ZrW 2O8) nanoparticles synthesized from hydrothermal reaction to alleviate the significant thermal expansion behavior. Three types of ZrW 2O8 at different loading levels were selected to study their effect of physical (morphology, particle size, surface area, etc.) and thermal (thermal expansivity) properties on the rheological, thermo-mechanical, dynamic-mechanical, and dielectric properties of epoxy resin. Epoxy resin incorporated by Type-1 ZrW2O8 exhibited the overall excellent performance. Hexagonal boron nitride (h-BN) nanoplatelets were non-covalently encapsulated by a versatile and mussel-adhesive protein polydopamine through the strong pi-pi* interaction. The high-temperature thermoset bisphenol E cyanate ester (BECy) reinforced with homogenously dispersed h-BN at different volume fractions and functionalities were processed to investigate their effect on thermo-mechanical, dynamic-mechanical, dielectric properties and thermal conductivity. Different theoretical and empirical models were also successfully applied for the prediction of CTE, thermal conductivity and dielectric constant of h-BN/BECy nanocomposites. On the basis of the improvement in dimensional stability, the enhancement in storage modulus in both glassy and rubbery regions, associated with the increment in thermal conductivity without deterioration of thermal stability, glassy transition temperature and dielectric properties, pristine h-BN/BECy nanocomposites exhibited the prospective application in microelectronic packaging industry. Polydopamine functionalized h-BN significantly increased the dielectric constant of cyanate ester at lower frequency region. Asphaltene, a

  16. The anthropogenic influence on carbonaceous aerosol in the European background

    Energy Technology Data Exchange (ETDEWEB)

    May, Barbara; Wagenbach, Dietmar; Hammer, Samuel (Institut fuer Umweltphysik, Univ. Heidelberg (Germany)). e-mail: barbara.may@iup.uni-heidelberg.de; Steier, Peter (VERA laboratory, Univ. of Vienna (Austria)); Puxbaum, Hans (Inst. for Chemical Technologies and Analytics, Vienna Univ. of Technology, Vienna (Austria)); Pio, Casimiro (CESAM and Dept. of Environment, Univ. of Aveiro (Portugal))

    2009-07-01

    To constrain the relatively uncertain anthropogenic impact on the organic aerosol load, radiocarbon analyses were performed on aerosol samples, collected year-round, at six non-urban sites including a maritime background and three remote mountain stations, lying on a west-east transect over Western Europe. From a crude three component model supported by TOC and levoglucosan filter data, the fossil fuel, biomass burning and biogenic TOC fraction are estimated, showing at all stations year-round, a relatively constant fossil fuel fraction of around (26 +- 6)%, a dominant biogenic contribution of on average (73 +- 7)% in summer and the continental as well as the maritime background TOC to be only about 50% biogenic. Assuming biomass burning as completely anthropogenic, the carbonaceous aerosol concentration at the mountain sites was found to have increased by a factor of up to (1.4 +- 0.2) in summer and up to (2.5 +- 1.0) in winter. This figure is significantly lower, however, than the respective TOC change since pre-industrial times seen in an Alpine ice core. Reconciling both observations would require an increase, since pre-industrial times, of the background biogenic aerosol load, which is estimated at a factor of 1.3-1.7.

  17. Carbonaceous species emitted from handheld two-stroke engines

    Science.gov (United States)

    Volckens, John; Olson, David A.; Hays, Michael D.

    Small, handheld two-stroke engines used for lawn and garden work (e.g., string trimmers, leaf blowers, etc.) can emit a variety of potentially toxic carbonaceous air pollutants. Yet, the emissions effluents from these machines go largely uncharacterized, constraining the proper development of human exposure estimates, emissions inventories, and climate and air quality models. This study samples and evaluates chemical pollutant emissions from the dynamometer testing of six small, handheld spark-ignition engines—model years 1998-2002. Four oil-gas blends were tested in each engine in duplicate. Emissions of carbon dioxide, carbon monoxide, and gas-phase hydrocarbons were predominant, and the PM emitted was organic matter primarily. An ANOVA model determined that engine type and control tier contributed significantly to emissions variations across all identified compound classes; whereas fuel blend was an insignificant variable accounting for engines were generally intermediate in magnitude compared with other gasoline-powered engines, numerous compounds traditionally viewed as motor vehicle markers are also present in small engine emissions in similar relative proportions. Given that small, handheld two-stroke engines used for lawn and garden work account for 5-10% of total US emissions of CO, CO 2, NO x, HC, and PM 2.5, source apportionment models and human exposure studies need to consider the effect of these small engines on ambient concentrations in air polluted environments.

  18. Measurement of carbonaceous aerosol with different sampling configurations and frequencies

    Directory of Open Access Journals (Sweden)

    Y. Cheng

    2015-03-01

    Full Text Available Carbonaceous aerosol in Beijing, China was measured with different sampling configurations (denuded vs. un-denuded and frequencies (24 vs. 48 h averaged. Our results suggest that the negative sampling artifact of a bare quartz filter could be remarkably enhanced due to the uptake of water vapor by the filter medium, indicating that the positive sampling artifact tends to be underestimated under high humidity conditions. It was also observed that the analytical artifact (i.e., the underestimation of elemental carbon by the operationally defined value of the thermal-optical method was more apparent for the low frequency samples such that their elemental carbon (EC concentrations were about 15% lower than the reference values measured by the high-frequency, denuded filters. Moreover, EC results of the low frequency samples were found to exhibit a stronger dependence on the charring correction method. In addition, optical attenuation (ATN of EC was retrieved from the carbon analyzer, and the low frequency samples were shown to be more significantly biased by the shadowing effect.

  19. CARES: Carbonaceous Aerosol and Radiative Effects Study Operations Plan

    Energy Technology Data Exchange (ETDEWEB)

    Zaveri, RA; Shaw, WJ; Cziczo, DJ

    2010-07-12

    The CARES field campaign is motivated by the scientific issues described in the CARES Science Plan. The primary objectives of this field campaign are to investigate the evolution and aging of carbonaceous aerosols and their climate-affecting properties in the urban plume of Sacramento, California, a mid-size, mid-latitude city that is located upwind of a biogenic volatile organic compound (VOC) emission region. Our basic observational strategy is to make comprehensive gas, aerosol, and meteorological measurements upwind, within, and downwind of the urban area with the DOE G-1 aircraft and at strategically located ground sites so as to study the evolution of urban aerosols as they age and mix with biogenic SOA precursors. The NASA B-200 aircraft, equipped with the High Spectral Resolution Lidar (HSRL), digital camera, and the Research Scanning Polarimeter (RSP), will be flown in coordination with the G-1 to characterize the vertical and horizontal distribution of aerosols and aerosol optical properties, and to provide the vertical context for the G-1 and ground in situ measurements.

  20. Preparation of carbonaceous electrodes and evaluation of their performance by electrochemical techniques

    International Nuclear Information System (INIS)

    Carbonaceous electrodes, from glassy carbon (GC), graphite rod or graphite powder, have been prepared for coulometric and voltammetric investigation. Beaker type graphite electrode of larger surface area was used as working electrode for the analysis of uranium and plutonium in solution by coulometry. Results have shown usefulness of the electrode for both uranium and plutonium analysis. Thus the graphite electrode can be used in place of mercury for uranium analysis and in place of platinum gauze for plutonium analysis. GC electrode ( from French and Indian material ), graphite or carbon paste electrode of smaller surface area prepared here have also been found to give satisfactory performance as could be observed from cyclic voltammetric (cv) patterns for standard K9Fe(CN)6/K4Fe(CN)6 redox system. Especially the GC electrode, (French) polished to 1μ finish with diamond paste gave very low values (1μ amp.) of background current in 1M KCl and the difference in cathodic and anodic peak potentials (δE values) was close to 60 mV from one electron transfer. Therefore the electrode can be used for various types of electrochemical studies relating to redox potentials, reaction mechanism, kinetic parameters etc. of different electrode processes. (author). 20 refs., 3 tabs., 10 figs., 8 photographs

  1. Progress In The Commercialization Of A Carbonaceous Solar Selective Absorber On A Glass Substrate

    Science.gov (United States)

    Garrison, John D.; Haiad, J. Carlos; Averett, Anthony J.

    1987-11-01

    A carbonaceous solar selective absorber is formed on a glass substrate by coating the glass with a silver infrared reflecting layer, electroplating a thin nickel catalyst coating on the silver using very special plating conditions, and then exposing the nickel coated, silvered glass substrate to acetylene at a temperature of about 400 - 500°C for about five minutes. A fairly large plater and conveyor oven have been constructed and operated for the formation of these solar selective absorbers in order to study the formation of this absorber by a process which might be used commercially. Samples of this selective absorber on a glass substrate have been formed using the plater and conveyor oven. The samples, which have the best optical properties, have an absorptance of about 0.9 and an emittance of about 0.03. Excessive decomposition of the acetylene by the walls of the oven at higher temperatures with certain wall materials and oven geometries can prevent the formation of good selective absorbers. Procedures for preventing excessive decomposition of the acetylene and the knowledge gained so far by these studies is discussed.

  2. A metagenomic-based survey of microbial (de)halogenation potential in a German forest soil

    Science.gov (United States)

    Weigold, Pascal; El-Hadidi, Mohamed; Ruecker, Alexander; Huson, Daniel H.; Scholten, Thomas; Jochmann, Maik; Kappler, Andreas; Behrens, Sebastian

    2016-01-01

    In soils halogens (fluorine, chlorine, bromine, iodine) are cycled through the transformation of inorganic halides into organohalogen compounds and vice versa. There is evidence that these reactions are microbially driven but the key enzymes and groups of microorganisms involved are largely unknown. Our aim was to uncover the diversity, abundance and distribution of genes encoding for halogenating and dehalogenating enzymes in a German forest soil by shotgun metagenomic sequencing. Metagenomic libraries of three soil horizons revealed the presence of genera known to be involved in halogenation and dehalogenation processes such as Bradyrhizobium or Pseudomonas. We detected a so far unknown diversity of genes encoding for (de)halogenating enzymes in the soil metagenome including specific and unspecific halogenases as well as metabolic and cometabolic dehalogenases. Genes for non-heme, no-metal chloroperoxidases and haloalkane dehalogenases were the most abundant halogenase and dehalogenase genes, respectively. The high diversity and abundance of (de)halogenating enzymes suggests a strong microbial contribution to natural halogen cycling. This was also confirmed in microcosm experiments in which we quantified the biotic formation of chloroform and bromoform. Knowledge on microorganisms and genes that catalyze (de)halogenation reactions is critical because they are highly relevant to industrial biotechnologies and bioremediation applications. PMID:27353292

  3. A metagenomic-based survey of microbial (de)halogenation potential in a German forest soil.

    Science.gov (United States)

    Weigold, Pascal; El-Hadidi, Mohamed; Ruecker, Alexander; Huson, Daniel H; Scholten, Thomas; Jochmann, Maik; Kappler, Andreas; Behrens, Sebastian

    2016-01-01

    In soils halogens (fluorine, chlorine, bromine, iodine) are cycled through the transformation of inorganic halides into organohalogen compounds and vice versa. There is evidence that these reactions are microbially driven but the key enzymes and groups of microorganisms involved are largely unknown. Our aim was to uncover the diversity, abundance and distribution of genes encoding for halogenating and dehalogenating enzymes in a German forest soil by shotgun metagenomic sequencing. Metagenomic libraries of three soil horizons revealed the presence of genera known to be involved in halogenation and dehalogenation processes such as Bradyrhizobium or Pseudomonas. We detected a so far unknown diversity of genes encoding for (de)halogenating enzymes in the soil metagenome including specific and unspecific halogenases as well as metabolic and cometabolic dehalogenases. Genes for non-heme, no-metal chloroperoxidases and haloalkane dehalogenases were the most abundant halogenase and dehalogenase genes, respectively. The high diversity and abundance of (de)halogenating enzymes suggests a strong microbial contribution to natural halogen cycling. This was also confirmed in microcosm experiments in which we quantified the biotic formation of chloroform and bromoform. Knowledge on microorganisms and genes that catalyze (de)halogenation reactions is critical because they are highly relevant to industrial biotechnologies and bioremediation applications. PMID:27353292

  4. [Source emission characteristics and impact factors of volatile halogenated organic compounds from wastewater treatment plant].

    Science.gov (United States)

    He, Jie; Wang, Bo-Guang; Liu, Shu-Le; Zhao, De-Jun; Tang, Xiao-Dong; Zou, Yu

    2011-12-01

    A low enrichment method of using Tenax as absorbent and liquid nitrogen as refrigerant has been established to sample the volatile halogenated organic compounds in Guangzhou Liede municipal wastewater treatment plant as well as its ambient air. The composition and concentration of target halogenated hydrocarbons were analyzed by combined thermal desorption/GC-MS to explore its sources profile and impact factors. The result showed that 19 halogenated organic compounds were detected, including 11 halogenated alkanets, 3 halogenated alkenes, 3 halogenated aromatic hydrocarbons and 2 haloesters, with their total concentrations ranged from 34.91 microg x m(-3) to 127.74 microg x m(-3) and mean concentrations ranged from n.d. to 33.39 microg x m(-3). Main pollutants of the studied plant were CH2Cl2, CHCl3, CFC-12, C2H4Cl2, CFC-11, C2HCl3 and C2Cl4, they came from the wastewater by volatilization. Among the six processing units, the dehydration room showed the highest level of halogenated organic compounds, followed by pumping station, while the sludge thickener was the lowest. The emissions from pumping station, aeration tank and biochemical pool were significantly affected by temperature and humidity of environment. PMID:22468521

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

    Directory of Open Access Journals (Sweden)

    W. R. Simpson

    2007-08-01

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

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

    Directory of Open Access Journals (Sweden)

    W. R. Simpson

    2007-03-01

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

  7. Synthetic ion transporters that work with anion-π interactions, halogen bonds, and anion-macrodipole interactions.

    Science.gov (United States)

    Vargas Jentzsch, Andreas; Hennig, Andreas; Mareda, Jiri; Matile, Stefan

    2013-12-17

    The transport of ions and molecules across lipid bilayer membranes connects cells and cellular compartments with their environment. This biological process is central to a host of functions including signal transduction in neurons and the olfactory and gustatory sensing systems, the translocation of biosynthetic intermediates and products, and the uptake of nutrients, drugs, and probes. Biological transport systems are highly regulated and selectively respond to a broad range of physical and chemical stimulation. A large percentage of today's drugs and many antimicrobial or antifungal agents take advantage of these systems. Other biological transport systems are highly toxic, such as the anthrax toxin or melittin from bee venom. For more than three decades, organic and supramolecular chemists have been interested in developing new transport systems. Over time, curiosity about the basic design has evolved toward developing of responsive systems with applications in materials sciences and medicine. Our early contributions to this field focused on the introduction of new structural motifs with emphasis on rigid-rod scaffolds, artificial β-barrels, or π-stacks. Using these scaffolds, we have constructed selective systems that respond to voltage, pH, ligands, inhibitors, or light (multifunctional photosystems). We have described sensing applications that cover the three primary principles of sensor development: immunosensors that use aptamers, biosensors (an "artificial" tongue), and differential sensors (an "artificial" nose). In this Account, we focus on our recent interest in applying synthetic transport systems as analytical tools to identify the functional relevance of less common noncovalent interactions, anion-π interactions, halogen bonds, and anion-macrodipole interactions. Anion-π interactions, the poorly explored counterpart of cation-π interactions, occur in aromatic systems with a positive quadrupole moment, such as TNT or hexafluorobenzene. To observe

  8. Evaluating the potential for halogen bonding in ketosteroid isomerase’s oxyanion hole using unnatural amino acid mutagenesis

    Science.gov (United States)

    Kraut, Daniel A; Churchil, Michael J; Dawson, Phillip E

    2009-01-01

    There has recently been an increasing interest in controlling macromolecular conformations and interactions through halogen bonding. Halogen bonds are favorable electrostatic interactions between polarized, electropositive chlorine, bromine or iodine atoms and electronegative atoms such as oxygen or nitrogen. These interactions have been likened to hydrogen bonds both in terms of their favored acceptor molecules, their geometries, and their energetics. We asked whether a halogen bond could replace a hydrogen bond in the oxyanion hole of ketosteroid isomerase, using semi-synthetic enzyme containing para-halogenated phenylalanine derivatives to replace the tyrosine hydrogen bond donor. Formation of a halogen bond to the oxyanion in the transition state would be expected to rescue the effects of mutation to phenylalanine, but all of the halogenated enzymes were comparable in activity to the phenylalanine mutant. We conclude that, at least in this active site, a halogen bond cannot functionally replace a hydrogen bond. PMID:19260691

  9. Petrologic study of the Belgica 7904 carbonaceous chondrite - Hydrous alteration, oxygen isotopes, and relationship to CM and CI chondrites

    Science.gov (United States)

    Ikeda, Y.; Prinz, M.

    1993-01-01

    The genetic relationships between the petrology, hydration reactions, and isotopic oxygen composition in the Belgica 7904 (B7904) carbonaceous chondrite, and the relationship between B7904 and the CM and CI chondrites were investigated by characterizing seven components separated from B7904. The seven specimens included two partially altered chondrules, two phylosilicate clasts, two olivine fragments, and one matrix sample. The results of the analyses and thermodynamic calculations suggest that CI chondrites may have been produced in a two-stage alteration process from materials similar to that of the B7904 matrix, by reactions with liquid water in their parent body. The common CM chondrites may have undergone aqueous alteration in the parent body, in addition to hydration in the nebula, resulting in two-stage alterations; the parent body may have been different from that of B7904.

  10. Volatile halogenated compounds and chlorophenols in the Skagerrak

    Science.gov (United States)

    Abrahamsson, Katarina; Ekdahl, Anja

    1996-02-01

    A total of 680 seawater samples were collected and analysed for volatile halogenated organic compounds, and 280 seawater samples were analysed for chlorinated phenols in the Skagerrak. The sampling was done along three transects along the Danish west coast on five occasions during the years 1991 to 1993. Pentachlorophenol (PCP) was the only chlorophenol detected on all occasions, which implies that it is transported as a dissolved species rather than particle bound. The results indicate that the origin of PCP in the Skagerrak is the Baltic and the coastal areas of Sweden and Norway. The biogenic volatile halocarbons constitute the largest fraction of the halocarbons in the area. The data support the findings that volatile chloroethenes are naturally produced. Therefore, the Skagerrak acts as a source for these compounds. The flux of the compounds investigated is directed from the sea to the atmosphere except for carbon tetrachloride.

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

    Directory of Open Access Journals (Sweden)

    Kazuo Yamagata

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

  12. Vertical ionization energies of halogen anions in solution

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Based on the constrained equilibrium state theory,the nonequilibrium solvation energy is derived in the framework of the continuum model.The formula for spectral shift and vertical ionization energy are deduced for a single sphere cavity with the point charge assumption.The new model is adopted to investigate the vertical ionization for halogen atomic and molecular anions X(X = Cl,Br,I,Cl2,Br2,I2) in aqueous solution.According to the calculation using the CCSD-t/aug-cc-pVQZ method in vacuum,our final estimated vertical ionization energies in solution are very close to the experimental observations,while the traditional nonequilibrium solvation theory overestimates these vertical ionization energies.

  13. Sun sensor boresight alignment testing for the Halogen Occultation Experiment

    Science.gov (United States)

    Moore, A. S.; Laney, V. S.; Mauldin, L. E., III

    1987-01-01

    The boresight alignment testing for the sun sensor assembly on the Halogen Occultation Experiment (HALOE) is described. The sun sensor assembly consists of three sensors that provide feedback signals for controlling dual axes gimbals. Two energy balancing silicon detectors are operated as wideband sensors in the azimuth and elevation axes. The third sensor is a silicon photodiode array operated as a narrow-band sensor in the elevation axis. These sensors are mounted on a common Invar structure which is mounted to the HALOE telescope. A blackbody was used as the stimulating source to perform the initial boresight alignment and this was checked with a heliostat solar look and a direct solar look. These tests are explained with a comparison between each source used.

  14. Iron Coordination and Halogen-Bonding Assisted Iodosylbenzene Activation

    DEFF Research Database (Denmark)

    Wegeberg, Christina

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

  15. Biosynthesis of the halogenated auxin, 4-chloroindole-3-acetic acid.

    Science.gov (United States)

    Tivendale, Nathan D; Davidson, Sandra E; Davies, Noel W; Smith, Jason A; Dalmais, Marion; Bendahmane, Abdelhafid I; Quittenden, Laura J; Sutton, Lily; Bala, Raj K; Le Signor, Christine; Thompson, Richard; Horne, James; Reid, James B; Ross, John J

    2012-07-01

    Seeds of several agriculturally important legumes are rich sources of the only halogenated plant hormone, 4-chloroindole-3-acetic acid. However, the biosynthesis of this auxin is poorly understood. Here, we show that in pea (Pisum sativum) seeds, 4-chloroindole-3-acetic acid is synthesized via the novel intermediate 4-chloroindole-3-pyruvic acid, which is produced from 4-chlorotryptophan by two aminotransferases, TRYPTOPHAN AMINOTRANSFERASE RELATED1 and TRYPTOPHAN AMINOTRANSFERASE RELATED2. We characterize a tar2 mutant, obtained by Targeting Induced Local Lesions in Genomes, the seeds of which contain dramatically reduced 4-chloroindole-3-acetic acid levels as they mature. We also show that the widespread auxin, indole-3-acetic acid, is synthesized by a parallel pathway in pea. PMID:22573801

  16. QSAR Study of Halogen Phenols Toxicity to Tetrahymena Pyriformis

    Institute of Scientific and Technical Information of China (English)

    PENY Yan-Fen; LIU Tian-Bao

    2009-01-01

    Structural parameters of 22 halogen phenols were computed at four levels using Hartree-Fock and DFT methods. Based on the experimental data of the acute toxicity to Tetrahymena pyriformis (-lgEC50), three-parameter (energy of the lowest unoccupied molecular orbital (ELUMO), the molecular volume (V), and the lowest negative charge (Qmin)) dependent equations were developed using structural parameters as theoretical descriptors. Especially, -lgEC50 dependent equation calculated at the B3LYP/6-31G** level is more advantageous than the others in view of their correlation and predictive abilities. This dependent equation was validated by variance inflation factors (VIF) and t-test methods. Upon comparison, the predictive abilities of our work are all more advantageous than those calculated from the semi-empirical PM3 method.

  17. Dating recent lake sediments using spheroidal carbonaceous particle (SCP)

    Institute of Scientific and Technical Information of China (English)

    WU Yanhong; WANG Sumin; XIA Weilan; LIU Jian

    2005-01-01

    Dating lake sediment using sedimentary event is the supplement and calibration to traditional dating by radionuclide such as 210Pb and 137Cs. Based on the change of spheroidal carbonaceous particle (SCP) concentration, the age sequence of lake sediments can be deduced. It is one of the dating methods using sedimentary event. SCP is formed from combustion of fossil fuel at high temperature up to 1750℃ and at a rate of heating of approaching 104 ℃/s. It can be dispersed to several hundred kilometers away from its source and deposited with precipitation or dryly deposited, and kept in sediments. Compared with Cs or Pb, there is no evidence for SCP that it decays in lake sediments and is un-removable once stored except by physical disturbance because it is mainly composed of element carbon. Handy method to extract, identify and calculate has been developed. Although fossil fuel has been used early in China, combustion at high temperature started later since emergence of electricity generation. The productivity of SCP is positively related with the generated thermal power, which is reflected as the SCP concentration in lake sediments increases with the increase of generated thermal power. Therefore, reliable sediment markers from the start of the SCP record and the remarkable variation can be used for dating purpose. In China, electricity industry started from the 1950s, and rapid increase of generated power took place since 1978. Based on these time markers, SCP time sequences of lake sediment cores LH and LL-4 from Longgan Lake, the middle reach of the Yangtze River, have been established, which is comparable with the results from 137Cs and 210Pb, and has eliminated the errors of dating using 137Cs and 210Pb.

  18. Impact of carbonaceous aerosol emissions on regional climate change

    Science.gov (United States)

    Roeckner, E.; Stier, P.; Feichter, J.; Kloster, S.; Esch, M.; Fischer-Bruns, I.

    2006-11-01

    The past and future evolution of atmospheric composition and climate has been simulated with a version of the Max Planck Institute Earth System Model (MPI-ESM). The system consists of the atmosphere, including a detailed representation of tropospheric aerosols, the land surface, and the ocean, including a model of the marine biogeochemistry which interacts with the atmosphere via the dust and sulfur cycles. In addition to the prescribed concentrations of carbon dioxide, ozone and other greenhouse gases, the model is driven by natural forcings (solar irradiance and volcanic aerosol), and by emissions of mineral dust, sea salt, sulfur, black carbon (BC) and particulate organic matter (POM). Transient climate simulations were performed for the twentieth century and extended into the twenty-first century, according to SRES scenario A1B, with two different assumptions on future emissions of carbonaceous aerosols (BC, POM). In the first experiment, BC and POM emissions decrease over Europe and China but increase at lower latitudes (central and South America, Africa, Middle East, India, Southeast Asia). In the second experiment, the BC and POM emissions are frozen at their levels of year 2000. According to these experiments the impact of projected changes in carbonaceaous aerosols on the global mean temperature is negligible, but significant changes are found at low latitudes. This includes a cooling of the surface, enhanced precipitation and runoff, and a wetter surface. These regional changes in surface climate are caused primarily by the atmospheric absorption of sunlight by increasing BC levels and, subsequently, by thermally driven circulations which favour the transport of moisture from the adjacent oceans. The vertical redistribution of solar energy is particularly large during the dry season in central Africa when the anomalous atmospheric heating of up to 60 W m-2 and a corresponding decrease in surface solar radiation leads to a marked surface cooling, reduced

  19. The Brenner Moor - A saline bog as a source for halogenated and non-halogenated volatile compounds

    Science.gov (United States)

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

    2012-04-01

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

  20. Cytotoxic Responses and Potential Respiratory Health Effects of Carbon and Carbonaceous Nanoparticulates in the Paso del Norte Airshed Environment

    Directory of Open Access Journals (Sweden)

    K. M. Garza

    2008-03-01

    Full Text Available We have utilized a range of manufactured or commercial nanoparticulate materials, including surrogate carbon nano-PM along with combustion-generated carbonaceous (soot nano-PM characteristic of environmental nano-PM (both indoor and outdoor to investigate and compare their cytotoxic response in vitro with an immortalized human epithelial (lung model cell line (A549. These have included nano-Ag, Al2O3, TiO2, Fe2O3, ZrO2, Si3N4, chrysotile asbestos, BC, 2 types of MWCNT-aggregate PM (MWCNT-R and MWCNT-N, and high-volume glass fiber collected soots: candle, wood, diesel (truck, tire, and 3-types of natural gas kitchen burner-generated soots: yellow (fuel-rich flame, low-flow blue flame, and normal flow blue flame soot PM. These carbonaceous nano-PM species can be found in either the indoor and outdoor environments or microenvironments. Two-day and two-week in-vitro cultures of A549 showed cell death (or decreased cell viability for all nanoparticulate materials, but especially significant for all but the TiO2 and candle, wood, and diesel PM. The natural gas kitchen burner combustion PM cell death response was characteristic of BC and MWCNT PM. There was no correlation with total PAH content of the soot PM. Cytokine release (IL-6, IL-8 was detected for the Ag, Fe2 O3, asbestos, BC and the MWCNT PM. Reactive oxygen species (ROS production was also detected for Ag, Fe2 O3, ZrO2, asbestos, BC, and the MWCNT aggregate PM, as well as the natural gas kitchen burner combustion PM. TEM, FESEM, and optical microscopy examination of these nanomaterials illustrate the wide range in PM morphologies and crystallinities as well as cell morphologies. Taken together, these results illustrate proinflammatory and related respiratory health issues in relation to environmental nanoparticulates.

  1. Efficacy of carbonaceous nanocomposites for sorbing ionizable antibiotic sulfamethazine from aqueous solution.

    Science.gov (United States)

    Zhang, Chen; Lai, Cui; Zeng, Guangming; Huang, Danlian; Yang, Chunping; Wang, Yang; Zhou, Yaoyu; Cheng, Min

    2016-05-15

    This paper investigated the key factors and mechanisms of sulfamethazine (SMT) sorption on a novel carbonaceous nanocomposite, and the effects of harsh aging on SMT sorption in the presence and absence of soil and before as well as after aging. The carbonaceous nanocomposites were synthesized by dip-coating straw biomass in carboxyl functionalized multi-walled carbon nanotubes solution and then pyrolyzed at 300 °C and 600 °C in the absence of air. The sorption performance of high temperature carbonaceous nanocomposite on SMT was excellent, as measured sorption distribution coefficient in the order of 10(3)-10(5.5) L kg(-1). Carbonaceous nanocomposites were aged either alone or mixed with soil via exposure to nutrients and soil extract (biological aging) or 80 °C for 100 d (chemical aging). No obvious effects of harsh aging on SMT sorption were observed in the presence of soil and/or biological and chemical aging. The primary mechanisms for SMT sorption included partition caused by Van der Waals forces and adsorption caused by hydrogen bonding and π-π electron-donor-acceptor interaction. Comprehensively considering the cost, renewability, and the application to real water samples, the carbonaceous nanocomposites have potential in removal of SMT and possibly other persistent organic pollutants from wastewater. PMID:26986499

  2. Characterization of Organic Materials in the Xenolithic Clasts in Sharps (H3.4) Meteorite Using Micro-Raman Spectroscopy

    Science.gov (United States)

    Chan, Q. H. S.; Zolensky, M. E.; Bodnar, R. J.; Kebukawa, Y.

    2015-01-01

    Graphitization of carbon is an irreversible process which alters the structure of graphitic materials in response to the increase in metamorphic grade (temperature and/or pressure). Carbonaceous materials offer a reliable geothermometer as their Raman spectra change systematically with increasing metamorphic grade. In this study, we identified carbonaceous materials in the xenolithic clasts in Sharps and interpreted their metamorphic history by revealing the structural organization (order) of the polyaromatic organic phases using micro-Raman spectroscopy.

  3. Characterization of Organic Materials in the Xenolithic Clasts in Sharps (H3.4) Meteorite Using Microraman Spectroscopy

    Science.gov (United States)

    Chan, Q. H. S.; Zolensky, M. E.; Bodnar, R. J.; Kebukawa, Y.

    2015-01-01

    Graphitization of carbon is an irreversible process which alters the structure of graphitic materials in response to the increase in metamorphic grade (temperature and/or pressure). Carbonaceous materials offer a reliable geothermometer as their Raman spectra change systematically with increasing metamorphic grade [1-3]. In this study, we identified carbonaceous materials in the xenolithic clasts in Sharps and interpreted their metamorphic history by revealing the structural organization (order) of the polyaromatic organic phases using µ-Raman spectroscopy.

  4. PATTERN RECOGNITION STUDIES OF HALOGENATED ORGANIC COMPOUNDS USING CONDUCTING POLYMER SENSOR ARRAYS. (R825323)

    Science.gov (United States)

    Direct measurement of volatile and semivolatile halogenated organic compounds of environmental interest was carried out using arrays of conducting polymer sensors. Mathematical expressions of the sensor arrays using microscopic polymer network model is described. A classical, non...

  5. Iodide Recognition and Sensing in Water by a Halogen-Bonding Ruthenium(II)-Based Rotaxane.

    Science.gov (United States)

    Langton, Matthew J; Marques, Igor; Robinson, Sean W; Félix, Vítor; Beer, Paul D

    2016-01-01

    The synthesis and anion-recognition properties of the first halogen-bonding rotaxane host to sense anions in water is described. The rotaxane features a halogen-bonding axle component, which is stoppered with water-solubilizing permethylated β-cyclodextrin motifs, and a luminescent tris(bipyridine)ruthenium(II)-based macrocycle component. (1) H NMR anion-binding titrations in D2 O reveal the halogen-bonding rotaxane to bind iodide with high affinity and with selectively over the smaller halide anions and sulfate. The binding affinity trend was explained through molecular dynamics simulations and free-energy calculations. Photo-physical investigations demonstrate the ability of the interlocked halogen-bonding host to sense iodide in water, through enhancement of the macrocycle component's Ru(II) metal-ligand charge transfer (MLCT) emission. PMID:26626866

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

    International Nuclear Information System (INIS)

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-02-15

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

  8. Development of Non-Halogen Flame Retardant Optical Fiber and Optical Fiber Cord

    Institute of Scientific and Technical Information of China (English)

    Kazunori; Tanaka; Kaoru; Okuno; Tomoyuki; Hattori; Kiyoaki; Moriuchi; Hiroshi; Hayami; Wataru; Katsurashima; Yoshikyo; Tamekuni

    2003-01-01

    A non-halogen highly flame-retardant 0.9mm optical fiber and 2.0mm simplex optical cord, which are harmonized with the ecosystem, have been developed. The characteristics of them are presented in this paper.

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

    Science.gov (United States)

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

    2016-09-01

    The synthesis of the first halogen bonding [3]rotaxane host system containing a bis-iodo triazolium-bis-naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions and chloride, and exhibits enhanced recognition of anions relative to a hydrogen bonding analogue. This elaborate interlocked anion receptor functions via a novel dynamic pincer mechanism where upon nitrate anion binding, both macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodo-triazolium station anion recognition sites to form a unique 1:1 stoichiometric nitrate anion-rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the (1) H NMR anion binding results. PMID:27436297

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

    CERN Document Server

    MacKinlay, Alistair F; Whillock, M J

    1989-01-01

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

  11. Halogens in porewater of peat bogs – the role of peat decomposition and dissolved organic matter

    Directory of Open Access Journals (Sweden)

    H. Biester

    2005-09-01

    Full Text Available Peatlands are one of the largest active terrestrial reservoirs of halogens. Formation of organo-halogens is a key process for the retention of halogens by organic matter and halogen enrichment in peat is strongly influenced by climatically controlled humification processes. However, little is known about release and transport of halogens in peat bogs. In this study we investigated the release of halogens from peat in three peat bogs located in the Magellanic Moorlands, southern Chile. Peat porewaters were collected using a sipping technique, which allows in situ sampling down to a depth of more than 6 m. Halogens and halogen species in porewater were determined by ion-chromatography (IC (chlorine and IC-ICP-MS (bromine and iodine. Results show that halogen concentrations in porewater are 15–30 times higher than in rainwater suggesting that their release from peat during diagenesis is the major source of halogens in porewater. Mean concentrations of chlorine, bromine and iodine in porewater were 7–15 mg l−1, 56–123μg l−1, and 10–20μg l−1, which correspond to mean proportions of 10–15%, 1–2.3% and 0.5–2.2% of total concentrations in peat, respectively. Organo-bromine and organoiodine were predominant in porewaters, whereas the release of organo-chlorine compounds from peat appears to be of minor importance. Results show that the release of bromine and iodine from peat depend on the degree of peat degradation, whereas this relationship is weak for chlorine. Relatively higher release of bromine and iodine was observed in less degraded peat sections, where the release of dissolved organic carbon (DOC was also the most intensive. Here, proportions of released iodine and bromine follow proportions of released dissolved organic matter (DOM indicating that the release of halogenated DOM is the predominant process of iodine and bromine release from peat.

  12. Influence of C-5 halogenation of uridines on hairpin versus duplex RNA folding

    OpenAIRE

    Ennifar, Eric; Bernacchi, Serena; Wolff, Philippe; Dumas, Philippe

    2007-01-01

    Halogenation of bases is a widespread method used for solving crystal structures of nucleic acids. However, this modification may have important consequences on RNA folding and thus on the success of crystallization. We have used a combination of UV thermal melting, steady-state fluorescence, X-ray crystallography, and gel electrophoresis techniques to study the influence of uridine halogenation (bromination or iodination) on the RNA folding. The HIV-1 Dimerization Initiation Site is an RNA h...

  13. Genesis and organic geochemical characteristics of the carbonaceous rock stratabound gold deposits, South China

    Institute of Scientific and Technical Information of China (English)

    胡凯; 翟建平; 刘英俊; 王鹤年; 张景荣; 贾蓉芬

    2000-01-01

    The organic matter of three different chronological major carbonaceous rock gold-bearing formations of South China (Middle Proterozoic Shangqiaoshan group of northeastern Jiangxi, Lower Cambrian Shuikou group of northern Guangxi and Devonian Shetianqiao group of eastern Hunan) and related carbonaceous stratabound gold deposits such as Jinshan, Longshui and Shixia deposits, respectively, has been characterized by organic geochemical techniques. These organic geochemical results show that the average total organic carbon (TOC) content of the three chronological carbonaceous rock gold-bearing formations of South China ranges from 0.15% to 1.56%. The thermal maturity of the organic matter of host rocks in the three gold-bearing formations is high. The micro-component of the organic matter of the host rocks consists primarily of solid bitumen and graphite. The organic carbon and gold of the host rocks appear to syndeposit in situ during the formation of the gold-bearing formations. The organic carbon played

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

    Science.gov (United States)

    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 (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 for evidence for biomolecules and life on the icy moons of Jupiter and Saturn, asteroids and comets.

  15. QSARS for Acute Toxicity of Halogenated Benzenes to Bacteria in Natural Waters

    Institute of Scientific and Technical Information of China (English)

    GUAN-GHUA LU; CHAO WANG; YU-MEI LI

    2006-01-01

    Objective To measure the acute toxicity of halogenated benzenes to bacteria in natural waters and to study quantitative relationships between the structure and activity of chemicals. Methods The concentration values causing 50% inhibition of bacteria growth (24h-IC50) were determined according to the bacterial growth inhibition test method. The energy of the lowest unoccupied molecular orbital and the net charge of carbon atom of 20 halogenated benzenes were calculated by the quantum chemical MOPAC program. Results The log1/IC50 values ranged from 4.79 for 2,4-dinitrochlorobenzene to 3.65 for chlorobenzene. A quantitative structure-activity relationship model was derived from the toxicity and structural parameters: log1/IC50 =-0.531(ELUMO)+1.693(Qc)+0.163(logP)+3.375. This equation was found to fit well (r2=0.860, s=0.106), and the average percentage error was only 1.98%. Conclusion Halogenated benzenes and alkyl halogenated benzenes are non-polar narcotics, and have hydrophobicity-dependent toxicity. The halogenated phenols and anilines exhibit a higher toxic potency than their hydrophobicity, whereas 2,4-dinitrochlorobenzene is electrophile with the halogen acting as the leaving group.

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

    International Nuclear Information System (INIS)

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

  17. Magnesium and 54Cr isotope compositions of carbonaceous chondrite chondrules – Insights into early disk processes

    Science.gov (United States)

    Olsen, Mia B.; Wielandt, Daniel; Schiller, Martin; Van Kooten, Elishevah M.M.E.; Bizzarro, Martin

    2016-01-01

    We report on the petrology, magnesium isotopes and mass-independent 54Cr/52Cr compositions (μ54Cr) of 42 chondrules from CV (Vigarano and NWA 3118) and CR (NWA 6043, NWA 801 and LAP 02342) chondrites. All sampled chondrules are classified as type IA or type IAB, have low 27Al/24Mg ratios (0.04–0.27) and display little or no evidence for secondary alteration processes. The CV and CR chondrules show variable 25Mg/24Mg and 26Mg/24Mg values corresponding to a range of mass-dependent fractionation of ~500 ppm (parts per million) per atomic mass unit. This mass-dependent Mg isotope fractionation is interpreted as reflecting Mg isotope heterogeneity of the chondrule precursors and not the result of secondary alteration or volatility-controlled processes during chondrule formation. The CV and CR chondrule populations studied here are characterized by systematic deficits in the mass-independent component of 26Mg (μ26Mg*) relative to the solar value defined by CI chondrites, which we interpret as reflecting formation from precursor material with a reduced initial abundance of 26Al compared to the canonical 26Al/27Al of ~5 × 10−5. Model initial 26Al/27Al values of CV and CR chondrules vary from (1.5 ± 4.0) × 10−6 to (2.2 ± 0.4) × 10−5. The CV chondrules display significant μ54Cr variability, defining a range of compositions that is comparable to that observed for inner Solar System primitive and differentiated meteorites. In contrast, CR chondrites are characterized by a narrower range of μ54Cr values restricted to compositions typically observed for bulk carbonaceous chondrites. Collectively, these observations suggest that the CV chondrules formed from precursors that originated in various regions of the protoplanetary disk and were then transported to the accretion region of the CV parent asteroid whereas CR chondrule predominantly formed from precursor with carbonaceous chondrite-like μ54Cr signatures. The observed μ54Cr variability in chondrules from

  18. Magnesium and 54Cr isotope compositions of carbonaceous chondrite chondrules - Insights into early disk processes

    Science.gov (United States)

    Olsen, Mia B.; Wielandt, Daniel; Schiller, Martin; Van Kooten, Elishevah M. M. E.; Bizzarro, Martin

    2016-10-01

    We report on the petrology, magnesium isotopes and mass-independent 54Cr/52Cr compositions (μ54Cr) of 42 chondrules from CV (Vigarano and NWA 3118) and CR (NWA 6043, NWA 801 and LAP 02342) chondrites. All sampled chondrules are classified as type IA or type IAB, have low 27Al/24Mg ratios (0.04-0.27) and display little or no evidence for secondary alteration processes. The CV and CR chondrules show variable 25Mg/24Mg and 26Mg/24Mg values corresponding to a range of mass-dependent fractionation of ∼500 ppm (parts per million) per atomic mass unit. This mass-dependent Mg isotope fractionation is interpreted as reflecting Mg isotope heterogeneity of the chondrule precursors and not the result of secondary alteration or volatility-controlled processes during chondrule formation. The CV and CR chondrule populations studied here are characterized by systematic deficits in the mass-independent component of 26Mg (μ26Mg∗) relative to the solar value defined by CI chondrites, which we interpret as reflecting formation from precursor material with a reduced initial abundance of 26Al compared to the canonical 26Al/27Al of ∼5 × 10-5. Model initial 26Al/27Al values of CV and CR chondrules vary from (1.5 ± 4.0) × 10-6 to (2.2 ± 0.4) × 10-5. The CV chondrules display significant μ54Cr variability, defining a range of compositions that is comparable to that observed for inner Solar System primitive and differentiated meteorites. In contrast, CR chondrites are characterized by a narrower range of μ54Cr values restricted to compositions typically observed for bulk carbonaceous chondrites. Collectively, these observations suggest that the CV chondrules formed from precursors that originated in various regions of the protoplanetary disk and were then transported to the accretion region of the CV parent asteroid whereas CR chondrule predominantly formed from precursor with carbonaceous chondrite-like μ54Cr signatures. The observed μ54Cr variability in chondrules from CV

  19. Halogen bonds in some dihalogenated phenols: applications to crystal engineering.

    Science.gov (United States)

    Mukherjee, Arijit; Desiraju, Gautam R

    2014-01-01

    3,4-Dichlorophenol (1) crystallizes in the tetragonal space group I41/a with a short axis of 3.7926 (9) Å. The structure is unique in that both type I and type II Cl⋯Cl interactions are present, these contact types being distinguished by the angle ranges of the respective C-Cl⋯Cl angles. The present study shows that these two types of contacts are utterly different. The crystal structures of 4-bromo-3-chlorophenol (2) and 3-bromo-4-chlorophenol (3) have been determined. The crystal structure of (2) is isomorphous to that of (1) with the Br atom in the 4-position participating in a type II interaction. However, the monoclinic P21/c packing of compound (3) is different; while the structure still has O-H⋯O hydrogen bonds, the tetramer O-H⋯O synthon seen in (1) and (2) is not seen. Rather than a type I Br⋯Br interaction which would have been mandated if (3) were isomorphous to (1) and (2), Br forms a Br⋯O contact wherein its electrophilic character is clearly evident. Crystal structures of the related compounds 4-chloro-3-iodophenol (4) and 3,5-dibromophenol (5) were also determined. A computational survey of the structural landscape was undertaken for (1), (2) and (3), using a crystal structure prediction protocol in space groups P21/c and I41/a with the COMPASS26 force field. While both tetragonal and monoclinic structures are energetically reasonable for all compounds, the fact that (3) takes the latter structure indicates that Br prefers type II over type I contacts. In order to differentiate further between type I and type II halogen contacts, which being chemically distinct are expected to have different distance fall-off properties, a variable-temperature crystallography study was performed on compounds (1), (2) and (4). Length variations with temperature are greater for type II contacts compared with type I. The type II Br⋯Br interaction in (2) is stronger than the corresponding type II Cl⋯Cl interaction in (1), leading to elastic bending

  20. Halogen bonds in some dihalogenated phenols: applications to crystal engineering

    Directory of Open Access Journals (Sweden)

    Arijit Mukherjee

    2014-01-01

    Full Text Available 3,4-Dichlorophenol (1 crystallizes in the tetragonal space group I41/a with a short axis of 3.7926 (9 Å. The structure is unique in that both type I and type II Cl...Cl interactions are present, these contact types being distinguished by the angle ranges of the respective C—Cl...Cl angles. The present study shows that these two types of contacts are utterly different. The crystal structures of 4-bromo-3-chlorophenol (2 and 3-bromo-4-chlorophenol (3 have been determined. The crystal structure of (2 is isomorphous to that of (1 with the Br atom in the 4-position participating in a type II interaction. However, the monoclinic P21/c packing of compound (3 is different; while the structure still has O—H...O hydrogen bonds, the tetramer O—H...O synthon seen in (1 and (2 is not seen. Rather than a type I Br...Br interaction which would have been mandated if (3 were isomorphous to (1 and (2, Br forms a Br...O contact wherein its electrophilic character is clearly evident. Crystal structures of the related compounds 4-chloro-3-iodophenol (4 and 3,5-dibromophenol (5 were also determined. A computational survey of the structural landscape was undertaken for (1, (2 and (3, using a crystal structure prediction protocol in space groups P21/c and I41/a with the COMPASS26 force field. While both tetragonal and monoclinic structures are energetically reasonable for all compounds, the fact that (3 takes the latter structure indicates that Br prefers type II over type I contacts. In order to differentiate further between type I and type II halogen contacts, which being chemically distinct are expected to have different distance fall-off properties, a variable-temperature crystallography study was performed on compounds (1, (2 and (4. Length variations with temperature are greater for type II contacts compared with type I. The type II Br...Br interaction in (2 is stronger than the corresponding type II Cl...Cl interaction in (1, leading to elastic

  1. Formation of halogenated acetones in the lower troposphere

    Science.gov (United States)

    Sattler, Tobias; Wittmer, Julian; Krause, Torsten; Schöler, Heinz Friedrich; Kamilli, Katharina; Held, Andreas; Zetzsch, Cornelius; Ofner, Johannes; Atlas, Elliot

    2015-04-01

    Western Australia is a semi-/arid region that is heavily influenced by climate change and agricultural land use. The area is known for its saline lakes with a wide range of hydrogeochemical parameters and consists of ephemeral saline and saline groundwater fed lakes with a pH range from 2.5 to 7.1. In 2012 a novel PTFE-chamber was setup directly on the lakes. The 1.5 m³ cubic chamber was made of UV transparent PTFE foil to permit photochemistry while preventing dilution of the air due to lateral wind transport. This experimental setup allows linking measured data directly to the chemistry of and above the salt lakes. Air samples were taken using stainless steel canisters and measured by GC-MS/ECD. Sediment, crust and water samples were taken for investigation of potential VOC and VOX emissions in the laboratory using GC-MS. Several lakes were investigated and canister samples were taken over the day to see diurnal variations. The first samples were collected at 6 a.m. and from this time every 2 hours a canister was filled with chamber air. Concentrations of chloroacetone up to 15 ppb and of bromoacetone up to 40 ppb in the air samples were detected. The concentrations vary over the day and display their highest values around noon. Soil and water samples showed a variety of highly volatile and semi-volatile VOC/VOX but no halogenated acetones. An abiotic formation of these VOC/VOX seems conclusive due to iron-catalysed reactions below the salt crust [1]. The salt crust is the interface through which VOC/VOX pass from soil/groundwater to the atmosphere where they were photochemically altered. This explains the finding of halo acetones only in the air samples and not in water and soil samples measured in the laboratory. The main forming pathway for these haloacetones is the direct halogenation due to atomic chlorine and bromine above the salt lakes [2]. A minor pathway is the atmospheric degradation of chloropropane and bromopropane [3]. These halopropanes were found

  2. Hydrothermal venting on carbonaceous chondritic elevations on 1 Ceres and 4 Vesta

    Science.gov (United States)

    Hoffmann, Martin; Nathues, Andreas; Platz, Thomas; Thangjam, Guneshwar

    2016-04-01

    Framing Camera images of the Dawn spacecraft [1] led to the discovery of recent geologic activity on Ceres, including deposition of salts, formation of near surface haze [2], and impact associated spectral diversity. More detailed analyses revealed widespread flow features, partly composed of granular material, but also indicating sites of fluidized areas of the surface and sub-surface. The unexpected discovery of deposits of carbonaceous chondritic material on Vesta associated with indications of considerable amounts of volatiles at large impact structures hint at similar processes [3, 4]. Near large crater walls on both proto-/dwarf-planets, montes and domes appear to be associated with uplift and even release of water-driven material including salts and clays [5, 6]. We report morphologic and color band spectroscopic characteristics of selected key features on 1 Ceres and 4 Vesta which demonstrate this context. A first analysis indicates compositional differences of the proportion of the content of salts and phyllosilicates, e. g. on the different elevations of the primary and secondary spots in Occator and some flow features. The distribution and diversity of these color features is further characterized by a comparison with more widespread properties on the whole surface. During this investigation, not only the link between salt deposits and different types of materials at the centers of activity could be described, but we also offer an intriguing new interpretation of one of the most prominent surface features of Vesta: Lucaria Tholus. Several analogies with similar features and properties of Mars [7] further support the view of a related origin. References: [1] Sierks, H. et al., Space Sci. Rev., 163, 263-327, 2011. [2] Nathues, A. et al., Nature 528, 237-240, 2015. [3] Reddy, V. et al. Icarus, 221, 544-559, 2012. [4] Scully, J. E. C. et al., EPSC Abstracts 8, 2013-242-2, 2013. [5] Platz, T. et al. LPSC 2016 [6] Ruesch, O. et al. LPSC 2016 [7] Platz, T. et

  3. Destruction of halogen-containing pesticides by means of detonation combustion.

    Science.gov (United States)

    Biegańska, Jolanta

    2013-02-01

    Pesticides that contain a halogen functional group have been destructed by means of detonative combustion. The following compounds were examined: (1) atrazine-2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine-herbicide; (2) bromophos-O,4-bromo-2,5-dichlorophenyl O,O-dimethyl phosphorothioate-insecticide; (3) chloridazon-5-amino-4-chloro-2-phenylopyridazin-3(2H)-one-herbicide; (4) linuron-3-(3,4-dichlorophenyl)-1-metoxy-1-methylurea-herbicide; (5) metoxychlor-1,1,1-trichloro-2,2-bis(4-metoxyphenyl)ethane-insecticide and acaricide; and (6) trichlorfon-dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate-insecticide. Explosive material has been produced on the basis of ammonium nitrate, which served as an oxidizer while the pesticides were used as fuels. Composition of the explosive was adjusted in such a way as to respect thermodynamic parameters. Detonative decomposition of the mixtures has been carried out in shot-holes pre-drilled in soil. Efficiency of the pesticide decomposition has been examined with gas chromatography in order to determine pesticides residues in the environment. It was found that for some, the amount of pesticides in some compounds in the analyzed samples after decomposition was below the determination threshold of the applied method. PMID:23128990

  4. Analytical methods for the determination of halogens in bioanalytical sciences: a review.

    Science.gov (United States)

    Mello, Paola A; Barin, Juliano S; Duarte, Fabio A; Bizzi, Cezar A; Diehl, Liange O; Muller, Edson I; Flores, Erico M M

    2013-09-01

    Fluorine, chlorine, bromine, and iodine have been studied in biological samples and other related matrices owing to the need to understand the biochemical effects in living organisms. In this review, the works published in last 20 years are covered, and the main topics related to sample preparation methods and analytical techniques commonly used for fluorine, chlorine, bromine, and iodine determination in biological samples, food, drugs, and plants used as food or with medical applications are discussed. The commonest sample preparation methods, as extraction and decomposition using combustion and pyrohydrolysis, are reviewed, as well as spectrometric and electroanalytical techniques, spectrophotometry, total reflection X-ray fluorescence, neutron activation analysis, and separation systems using chromatography and electrophoresis. On this aspect, the main analytical challenges and drawbacks are highlighted. A discussion related to the availability of certified reference materials for evaluation of accuracy is also included, as well as a discussion of the official methods used as references for the determination of halogens in the samples covered in this review. PMID:23780223

  5. Analytical methods for the determination of halogens in bioanalytical sciences: a review.

    Science.gov (United States)

    Mello, Paola A; Barin, Juliano S; Duarte, Fabio A; Bizzi, Cezar A; Diehl, Liange O; Muller, Edson I; Flores, Erico M M

    2013-09-01

    Fluorine, chlorine, bromine, and iodine have been studied in biological samples and other related matrices owing to the need to understand the biochemical effects in living organisms. In this review, the works published in last 20 years are covered, and the main topics related to sample preparation methods and analytical techniques commonly used for fluorine, chlorine, bromine, and iodine determination in biological samples, food, drugs, and plants used as food or with medical applications are discussed. The commonest sample preparation methods, as extraction and decomposition using combustion and pyrohydrolysis, are reviewed, as well as spectrometric and electroanalytical techniques, spectrophotometry, total reflection X-ray fluorescence, neutron activation analysis, and separation systems using chromatography and electrophoresis. On this aspect, the main analytical challenges and drawbacks are highlighted. A discussion related to the availability of certified reference materials for evaluation of accuracy is also included, as well as a discussion of the official methods used as references for the determination of halogens in the samples covered in this review.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-09-15

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

  7. Dynamic Characterization of Crystalline Supramolecular Rotors Assembled through Halogen Bonding.

    Science.gov (United States)

    Catalano, Luca; Pérez-Estrada, Salvador; Terraneo, Giancarlo; Pilati, Tullio; Resnati, Giuseppe; Metrangolo, Pierangelo; Garcia-Garibay, Miguel A

    2015-12-16

    A modular molecular kit for the preparation of crystalline molecular rotors was devised from a set of stators and rotators to gain simple access to a large number of structures with different dynamic performance and physical properties. In this work, we have accomplished this with crystalline molecular rotors self-assembled by halogen bonding of diazabicyclo[2.2.2]octane, acting as a rotator, and a set of five fluorine-substituted iodobenzenes that take the role of the stator. Using variable-temperature (1)H T1 spin-lattice relaxation measurements, we have shown that all structures display ultrafast Brownian rotation with activation energies of 2.4-4.9 kcal/mol and pre-exponential factors of the order of (1-9) × 10(12) s(-1). Line shape analysis of quadrupolar echo (2)H NMR measurements in selected examples indicated rotational trajectories consistent with the 3-fold or 6-fold symmetric potential of the rotator. PMID:26583701

  8. Gas chromatography mass spectrometry computer analysis of volatile halogenated hydrocarbons in man and his environment--A multimedia environmental study.

    Science.gov (United States)

    Barkley, J; Bunch, J; Bursey, J T; Castillo, N; Cooper, S D; Davis, J M; Erickson, M D; Harris, B S; Kirkpatrick, M; Michael, L C; Parks, S P; Pellizzari, E D; Ray, M; Smith, D; Tomer, K B; Wagner, R; Zweidinger, R A

    1980-04-01

    As part of a study to make a comparative analysis of selected halogenated compounds in man and the environmental media, a quantitative gas chromatography mass spectrometric analysis of the levels of the halogenated compounds found in the breath, blood and urine of an exposed population (Old Love Canal area, Niagara, New York) and their immediate environment (air and water) was undertaken. In addition, levels of halogenated hydrocarbons in air samples taken in the general Buffalo, Niagara Falls area were determined.

  9. Gas chromatography mass spectrometry computer analysis of volatile halogenated hydrocarbons in man and his environment--A multimedia environmental study.

    Science.gov (United States)

    Barkley, J; Bunch, J; Bursey, J T; Castillo, N; Cooper, S D; Davis, J M; Erickson, M D; Harris, B S; Kirkpatrick, M; Michael, L C; Parks, S P; Pellizzari, E D; Ray, M; Smith, D; Tomer, K B; Wagner, R; Zweidinger, R A

    1980-04-01

    As part of a study to make a comparative analysis of selected halogenated compounds in man and the environmental media, a quantitative gas chromatography mass spectrometric analysis of the levels of the halogenated compounds found in the breath, blood and urine of an exposed population (Old Love Canal area, Niagara, New York) and their immediate environment (air and water) was undertaken. In addition, levels of halogenated hydrocarbons in air samples taken in the general Buffalo, Niagara Falls area were determined. PMID:7448328

  10. Spectral reflectance properties of carbonaceous chondrites: 2. CM chondrites

    Science.gov (United States)

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

    2011-11-01

    We have examined the spectral reflectance properties and available modal mineralogies of 39 CM carbonaceous chondrites to determine their range of spectral variability and to diagnose their spectral features. We have also reviewed the published literature on CM mineralogy and subclassification, surveyed the published spectral literature and added new measurements of CM chondrites and relevant end members and mineral mixtures, and measured 11 parameters and searched pair-wise for correlations between all quantities. CM spectra are characterized by overall slopes that can range from modestly blue-sloped to red-sloped, with brighter spectra being generally more red-sloped. Spectral slopes, as measured by the 2.4:0.56 μm and 2.4 μm:visible region peak reflectance ratios, range from 0.90 to 2.32, and 0.81 to 2.24, respectively, with values tandem, suggesting a single cause, specifically serpentine-group phyllosilicates. The generally high Fe content, high phyllosilicate abundance relative to mafic silicates, and dual Fe valence state in CM phyllosilicates, all suggest that the phyllosilicates will exhibit strong absorption bands in the 0.7 μm region (due to Fe 3+-Fe 2+ charge transfers), and the 0.9-1.2 μm region (due to Fe 2+ crystal field transitions), and generally dominate over mafic silicates. CM petrologic subtypes exhibit a positive correlation between degree of aqueous alteration and depth of the 0.7 μm absorption band. This is consistent with the decrease in fine-grained opaques that accompanies aqueous alteration. There is no consistent relationship between degree of aqueous alteration and evidence for a 0.65 μm region saponite-group phyllosilicate absorption band. Spectra of different subsamples of a single CM can show large variations in absolute reflectance and overall slope. This is probably due to petrologic variations that likely exist within a single CM chondrite, as duplicate spectra for a single subsample show much less spectral variability

  11. Direct Carbon Fuel Cell System Utilizing Solid Carbonaceous Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Turgut Gur

    2010-04-30

    This 1-year project has achieved most of its objective and successfully demonstrated the viability of the fluidized bed direct carbon fuel cell (FB-DCFC) approach under development by Direct Carbon technologies, LLC, that utilizes solid carbonaceous fuels for power generation. This unique electrochemical technology offers high conversion efficiencies, produces proportionately less CO{sub 2} in capture-ready form, and does not consume or require water for gasification. FB-DCFC employs a specialized solid oxide fuel cell (SOFC) arrangement coupled to a Boudouard gasifier where the solid fuel particles are fluidized and reacted by the anode recycle gas CO{sub 2}. The resulting CO is electrochemically oxidized at the anode. Anode supported SOFC structures employed a porous Ni cermet anode layer, a dense yttria stabilized zirconia membrane, and a mixed conducting porous perovskite cathode film. Several kinds of untreated solid fuels (carbon and coal) were tested in bench scale FBDCFC prototypes for electrochemical performance and stability testing. Single cells of tubular geometry with active areas up to 24 cm{sup 2} were fabricated. The cells achieved high power densities up to 450 mW/cm{sup 2} at 850 C using a low sulfur Alaska coal char. This represents the highest power density reported in the open literature for coal based DCFC. Similarly, power densities up to 175 mW/cm{sup 2} at 850 C were demonstrated with carbon. Electrical conversion efficiencies for coal char were experimentally determined to be 48%. Long-term stability of cell performance was measured under galvanostatic conditions for 375 hours in CO with no degradation whatsoever, indicating that carbon deposition (or coking) does not pose any problems. Similar cell stability results were obtained in coal char tested for 24 hours under galvanostatic conditions with no sign of sulfur poisoning. Moreover, a 50-cell planar stack targeted for 1 kW output was fabricated and tested in 95% CO (balance CO{sub 2

  12. Laboratory Experiments and Instrument Intercomparison Studies of Carbonaceous Aerosol Particles

    Energy Technology Data Exchange (ETDEWEB)

    Davidovits, Paul [Boston College, Chestnut Hill, MA (United States)

    2015-10-20

    Aerosols containing black carbon (and some specific types of organic particulate matter) directly absorb incoming light, heating the atmosphere. In addition, all aerosol particles backscatter solar light, leading to a net-cooling effect. Indirect effects involve hydrophilic aerosols, which serve as cloud condensation nuclei (CCN) that affect cloud cover and cloud stability, impacting both atmospheric radiation balance and precipitation patterns. At night, all clouds produce local warming, but overall clouds exert a net-cooling effect on the Earth. The effect of aerosol radiative forcing on climate may be as large as that of the greenhouse gases, but predominantly opposite in sign and much more uncertain. The uncertainties in the representation of aerosol interactions in climate models makes it problematic to use model projections to guide energy policy. The objective of our program is to reduce the uncertainties in the aerosol radiative forcing in the two areas highlighted in the ASR Science and Program Plan. That is, (1) addressing the direct effect by correlating particle chemistry and morphology with particle optical properties (i.e. absorption, scattering, extinction), and (2) addressing the indirect effect by correlating particle hygroscopicity and CCN activity with particle size, chemistry, and morphology. In this connection we are systematically studying particle formation, oxidation, and the effects of particle coating. The work is specifically focused on carbonaceous particles where the uncertainties in the climate relevant properties are the highest. The ongoing work consists of laboratory experiments and related instrument inter-comparison studies both coordinated with field and modeling studies, with the aim of providing reliable data to represent aerosol processes in climate models. The work is performed in the aerosol laboratory at Boston College. At the center of our laboratory setup are two main sources for the production of aerosol particles: (a

  13. Investigating the Early Carbon Cycle Using Carbonaceous Inclusions and Dissolved Carbon in Detrital Zircon

    Science.gov (United States)

    Bell, E. A.; Boehnke, P.; Harrison, M.; Mao, W. L.

    2015-12-01

    Because the terrestrial rock record extends only to ~4 Ga and older materials thus far identified are limited to detrital zircons, information about volatile abundances and cycles on early Earth is limited. Carbon, for instance, plays an important role not only in the modern biosphere but also in deep recycling of materials between the crust and mantle. We are investigating the record of carbon abundance and origin in Hadean zircons from Jack Hills (W. Australia) using two main approaches. First, carbon may partition into the zircon structure at trace levels during crystallization from a magma, and better understanding of this partitioning behavior will allow for zircon's use as a monitor of magmatic carbon contents. We have measured carbon abundances in zircon from a variety of igneous rocks (gabbro; I-, A-, and S-type granitoids) via SIMS and found that although abundances are typically low (average raw 12C/30Si ~ 1x10-6), S-type granite zircons can reach a factor of 1000 over this background. Around 10% of Hadean zircons investigated show similar enrichments, consistent with other evidence for the derivation of many Jack Hills zircons from S-type granitoids and with the establishment of modern-level carbon abundances in the crust by ca. 4.2 Ga. Diamond and graphite inclusions reported in the Jack Hills zircons by previous studies proved to be contamination by polishing debris, leaving the true abundance of these materials in the population uncertain. On a second front, we have identified and investigated primary carbonaceous inclusions in these zircons. From a population of over 10,000 Jack Hills zircons, we identified one concordant 4.10±0.01 Ga zircon that contains primary graphite inclusions (so interpreted due to their enclosure in a crack-free zircon host as shown by transmission X-ray microscopy and their crystal habit). Their δ13CPDB of -24±5‰ is consistent with a biogenic origin and, in the absence of a likely inorganic mechanism to produce such a

  14. Source apportionment of carbonaceous aerosol in Sao Paulo using 13C and 14C measurements

    Science.gov (United States)

    Oyama, Beatriz; Andrade, Maria de Fatima; Holzinger, Rupert; Röckmann, Thomas; Meijer, Harro A. J.; Dusek, Ulrike

    2016-04-01

    The Metropolitan Area of Sao Paulo is affected by high aerosol concentrations, which contain a large fraction of organic material. Up to date, not much is known about the composition and origin of the organic aerosol in this city. We present the first source apportionment of the carbonaceous aerosol fraction in Sao Paulo, using stable (13C) and radioactive carbon isotopes (14C). 14C provides a clear-cut distinction between fossil sources, which contain no 14C, and contemporary sources such as biofuels, biomass burning, or biogenic sources, which contain a typical contemporary 14C/12C ratio. 13C can be used to distinguish C3 plants, such as maize and sugarcane, from C4 plants. This can help to identify a possible impact of sugarcane field burning in the rural areas of Sao Paulo State on the aerosol carbon in the city. In the first part of the study, we compare two tunnel studies: Tunnel 1 is frequented only by light duty vehicles, which run mainly on mixtures of gasoline with ethanol (gasohol, 25% ethanol and 85% gasoline) or hydrated ethanol (5% water and 95% ethanol). Tunnel 2 contains a significant fraction of heavy-duty diesel vehicles, and therefore the fraction of biofuels in the average fleet is lower. Comparison of 14C in organic and elemental carbon (OC and EC) shows that in both tunnels there is no significant contribution of biofuels to EC. Combusting ethanol-gasoline fuels in a vehicle engine does apparently not result in significant EC formation from ethanol. Biofuels contribute around 45% to OC in Tunnel 1 an only 20% in Tunnel 2, reflecting a strong impact of diesel vehicles in Tunnel 2. In the second part of the study we conduct a source apportionment of ambient aerosol carbon collected in a field study during winter (July-August) 2012. Ambient EC has two main sources, vehicular emissions and biomass burning. We estimate a contribution of vehicular sources to EC of roughly 90% during weekdays and 80% during weekends, using the 14C values measured in

  15. Halogenated volatile organic compounds from the use of chlorine-bleach-containing household products.

    Science.gov (United States)

    Odabasi, Mustafa

    2008-03-01

    Sodium hypochlorite (NaOCl) and many organic chemicals contained in household cleaning products may react to generate halogenated volatile organic compounds (VOCs). Halogenated VOC emissions from eight different chlorine bleach containing household products (pure and diluted) were investigated by headspace experiments. Chloroform and carbon tetrachloride were the leading compounds along with several halogenated compounds in the headspace of chlorine bleach products. One of the most surprising results was the presence of carbon tetrachloride (a probable human carcinogen and a powerful greenhouse gas that was banned for household use by the U.S. Food and Drug Administration) in very high concentrations (up to 101 mg m(-3)). By mixing surfactants or soap with NaOCl, it was shown that the formation of carbon tetrachloride and several other halogenated VOCs is possible. In addition to quantitatively determined halogenated VOCs (n = 15), several nitrogen-containing (n = 4), chlorinated (n = 10), oxygenated compounds (n = 22), and hydrocarbons (n = 14) were identified in the headspace of bleach products. Among these, 1,1-dichlorobutane and 2-chloro-2-nitropropane were the most abundant chlorinated VOCs, whereas trichloronitromethane and hexachloroethane were the most frequently detected ones. Indoor air halogenated VOC concentrations resulting from the use of four selected household products were also measured before, during, and 30 min after bathroom, kitchen, and floor cleaning applications. Chloroform (2.9-24.6 microg m(-3)) and carbon tetrachloride (0.25-459 microg m(-3)) concentrations significantly increased during the use of bleach containing products. During/ before concentration ratios ranged between 8 and 52 (25 +/- 14, average +/- SD) for chloroform and 1-1170 (146 +/- 367, average +/- SD) for carbon tetrachloride, respectively. These results indicated that the bleach use can be important in terms of inhalation exposure to carbon tetrachloride, chloroform and

  16. R Raman Spectroscopy and Petrology of Antarctic CR Chondrites: Comparison with Other Carbonaceous Chondrites

    Science.gov (United States)

    Komatsu, M.; Fagan, T. J.; Yamaguchi, A.; Mikouchi, T.; Zolensky, M. E.; Yasutake, M.

    2015-01-01

    In Renazzo-like carbonaceous (CR) chondrites, abundant original Fe,Ni-metal is preserved in chrondules, but the matrix is characterized by fine-grained magnetite with phyllosilicate. This combination of reduced Fe in chrodrules with oxidized Fe and phyllosilicate in the matrix has been attributed to aqueous alteration of matrix at relatively low temperatures.

  17. Genesis and organic geochemical characteristics of the carbonaceous rock stratabound gold deposits, South China

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The organic matter of three different chronological major carbonaceous rock gold-bearing formations of South China (Middle Proterozoic Shangqiaoshan group of northeastern Jiangxi, Lower Cambrian Shuikou group of northern Guangxi and Devonian Shetianqiao group of eastern Hunan) and related carbonaceous stratabound gold deposits such as Jinshan, Longshui and Shixia deposits, respectively, has been characterized by organic geochemical techniques. These organic geochemical results show that the average total organic carbon (TOC) content of the three chronological carbonaceous rock gold-bearing formations of South China ranges from 0.15% to 1.56%. The thermal maturity of the organic matter of host rocks in the three gold-bearing formations is high. The micro-component of the organic matter of the host rocks consists primarily of solid bitumen and graphite. The organic carbon and gold of the host rocks appear to syndeposit in situ during the formation of the gold-bearing formations. The organic carbon played a certain role in controlling the geochemical environment of the gold-bearing formations. The metallogenetic mechanism of the carbonaceous rock stratabound gold deposits of South China is closely associated in genesis with the sedimentation, diagenesis and thermal evolution history of the organic matter of host rocks in the gold-bearing formations.

  18. Carbonaceous Aerosols Emitted from Light-Duty Vehicles Operating on Gasoline and Ethanol Fuel Blends

    Science.gov (United States)

    This study examines the chemical properties of carbonaceous aerosols emitted from three light-duty gasoline vehicles (LDVs) operating on gasoline (e0) and ethanol-gasoline fuel blends (e10 and e85). Vehicle road load simulations were performed on a chassis dynamometer using the t...

  19. Development of a carbonaceous selective absorber for solar thermal energy collection and process for its formation

    Science.gov (United States)

    Garrison, John D.

    1989-02-01

    The main goal of the US Department of Energy supported part of this project is to develop information about controlling the complicated chemical processes involved in the formation of a carbonaceous selective absorber and learn what equipment will allow production of this absorber commercially. The work necessary to accomplish this goal is not yet complete. Formation of the carbonaceous selective absorber in the conveyor oven tried so far has been unsatisfactory, because the proper conditions for applying the carbonaceous coating in each conveyor oven fabricated, either have been difficult to obtain, or have been difficult to maintain over an extended period of time. A new conveyor oven is nearing completion which is expected to allow formation of the carbonaceous selective absorber on absorber tubes in a continuous operation over many days without the necessity of cleaning the conveyor oven or changing the thickness of the electroplated nickel catalyst to compensate for changes in the coating environment in the oven. Work under this project concerned with forming and sealing glass panels to test ideas on evacuated glass solar collector designs and production have been generally quite satisfactory. Delays in completion of the selective absorber work, has caused postponement of the fabrication of a small prototype evacuated glass solar collector panel. Preliminary cost estimates of the selective absorber and solar collector panel indicate that this collector system should be lower in cost than evacuated solar collectors now on the market.

  20. Impact of anthropogenic emissions and open biomass burning on regional carbonaceous aerosols in South China

    International Nuclear Information System (INIS)

    Carbonaceous aerosols were studied at three background sites in south and southwest China. Hok Tsui in Hong Kong had the highest concentrations of carbonaceous aerosols (OC = 8.7 ± 4.5 μg/m3, EC = 2.5 ± 1.9 μg/m3) among the three sites, and Jianfeng Mountains in Hainan Island (OC = 5.8 ± 2.6 μg/m3, EC = 0.8 ± 0.4 μg/m3) and Tengchong mountain over the east edge of the Tibetan Plateau (OC = 4.8 ± 4.0 μg/m3, EC = 0.5 ± 0.4 μg/m3) showed similar concentration levels. Distinct seasonal patterns with higher concentrations during the winter, and lower concentrations during the summertime were observed, which may be caused by the changes of the regional emissions, and monsoon effects. The industrial and vehicular emissions in East, Southeast and South China, and the regional open biomass burning in the Indo-Myanmar region of Asia were probably the two major potential sources for carbonaceous matters in this region. - Anthropogenic emissions in China and open biomass burning in the Indo-Myanmar region were the two major potential sources for carbonaceous matters in South China region.

  1. Impact of anthropogenic emissions and open biomass burning on regional carbonaceous aerosols in South China

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Gan, E-mail: zhanggan@gig.ac.c [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Li Jun [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Li Xiangdong [Department of Civil and Structural Engineering, Hong Kong Polytechnic University, Hung Hom, Kowloon (Hong Kong); Xu Yue; Guo Lingli [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Tang Jianhui [Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); Lee, Celine S.L. [Department of Civil and Structural Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon (Hong Kong); Liu Xiang [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Chen Yingjun [Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China)

    2010-11-15

    Carbonaceous aerosols were studied at three background sites in south and southwest China. Hok Tsui in Hong Kong had the highest concentrations of carbonaceous aerosols (OC = 8.7 {+-} 4.5 {mu}g/m{sup 3}, EC = 2.5 {+-} 1.9 {mu}g/m{sup 3}) among the three sites, and Jianfeng Mountains in Hainan Island (OC = 5.8 {+-} 2.6 {mu}g/m{sup 3}, EC = 0.8 {+-} 0.4 {mu}g/m{sup 3}) and Tengchong mountain over the east edge of the Tibetan Plateau (OC = 4.8 {+-} 4.0 {mu}g/m{sup 3}, EC = 0.5 {+-} 0.4 {mu}g/m{sup 3}) showed similar concentration levels. Distinct seasonal patterns with higher concentrations during the winter, and lower concentrations during the summertime were observed, which may be caused by the changes of the regional emissions, and monsoon effects. The industrial and vehicular emissions in East, Southeast and South China, and the regional open biomass burning in the Indo-Myanmar region of Asia were probably the two major potential sources for carbonaceous matters in this region. - Anthropogenic emissions in China and open biomass burning in the Indo-Myanmar region were the two major potential sources for carbonaceous matters in South China region.

  2. Isotropic and high density carbon made from carbonaceous powder prepared by distillation under reduced pressure

    International Nuclear Information System (INIS)

    It is attempted to produce high density, high strength and isotropic carbon made from carbonaceous powder. The carbonaceous powder was prepared by carbonization of coal-tar pitch at a temperature of 440 - 5000C and subsequent distillation under reduced pressure. The distillation was performed at a temperature of 300 - 5000C below the carbonization temperature. In some cases additional quinoline extraction was carried out on the powder. Green carbon body was formed without binder pitch under isostatic pressure at room temperature. The body was heat-treated at a temperature of 1100 - 28000C. Bulk density, weight loss, shrinkage, strength, lattice parameter, crystallite size and BAF of the obtained carbon body were measured. It is confirmed that high density, high strength and isotropic carbon made from the carbonaceous powder and the following results were obtained. 1) BS (benzene soluble) fraction, β-resin (benzene insoluble and quinoline soluble) fraction and QI (quinoline insoluble) fraction were able to fractionate by distillation under reduced pressure. Concentration gradient of each fraction seems to exist in the carbonaceous powder. 2) Using the powder prepared by a lower temperature of the carbonization and/or the distillation, the carbon body had higher bulk density and higher strength. 3) The β-resin fraction had the effects of increasing the green density and enhancing the shrinkage of carbon body during the heat treatment. (author)

  3. The Effects of Parent Body Processes on Amino Acids in Carbonaceous Chondrites

    Science.gov (United States)

    Glavin, Daniel P.; Callahan, Michael P.; Dworkin, Jason P.; Elsila, Jamie E.

    2010-01-01

    To investigate the effect of parent body processes on the abundance, distribution, and enantiomeric composition of amino acids in carbonaceous chondrites, the water extracts from nine different powdered Cl, CM, and CR carbonaceous chondrites were analyzed for amino acids by ultrahigh performance liquid chromatography-fluorescence detection and time-of-flight mass spectrometry (UPLC-FD/ToF-MS). Four aqueously altered type 1 carbonaceous chondrites including Orgueil (C11), Meteorite Hills (MET) 01070 (CM1), Scott Glacier (SCO) 06043 (CM1), and Grosvenor Mountains (GRO) 95577 (CR1) were analyzed using this technique for the first time. Analyses of these meteorites revealed low levels of two- to five-carbon acyclic amino alkanoic acids with concentrations ranging from -1 to 2,700 parts-per-billion (ppb). The type 1 carbonaceous chondrites have a distinct distribution of the five-carbon (C5) amino acids with much higher relative abundances of the gamma- and delta-amino acids compared to the type 2 and type 3 carbonaceous chondrites, which are dominated by a-amino acids. Much higher amino acid abundances were found in the CM2 chondrites Murchison, Lonewolf Nunataks (LON) 94102, and Lewis Cliffs (LEW) 90500, the CR2 Elephant Moraine (EET) 92042, and the CR3 Queen Alexandra Range (QUE) 99177. For example, a-aminoisobutyric acid ((alpha-AIB) and isovaline were approximately 100 to 1000 times more abundant in the type 2 and 3 chondrites compared to the more aqueously altered type 1 chondrites. Most of the chiral amino acids identified in these meteorites were racemic, indicating an extraterrestrial abiotic origin. However, non-racemic isovaline was observed in the aqueously altered carbonaceous chondrites Murchison, Orgueil, SCO 06043, and GRO 95577 with L-isovaline excesses ranging from approximately 11 to 19%, whereas the most pristine, unaltered carbonaceous chondrites analyzed in this study had no detectable L-isovaline excesses. These results are consistent with the

  4. Paleontological analysis of a lacustrine carbonaceous uranium deposit at the Anderson mine, Date Creek basin, west-central Arizona (U.S.A.)

    Science.gov (United States)

    Otton, J.K.; Bradbury, J.P.; Forester, R.M.; Hanley, J.H.

    1990-01-01

    The Tertiary sedimentary sequence of the Date Creek basin area of Arizona is composed principally of intertonguing alluvial-fan and lacustrine deposits. The lacustrine rocks contain large intermediate- to, locally, high-grade uranium deposits that form one of the largest uranium resources in the United States (an estimated 670,000 tons of U3O8 at an average grade of 0.023% is indicated by drilling to date). At the Anderson mine, about 50,000 tons of U3O8 occurs in lacustrine carbonaceous siltstones and mudstones (using a cutoff grade of 0.01%). The Anderson mine constitutes a new class of ore deposit, a lacustrine carbonaceous uranium deposit. Floral and faunal remains at the Anderson mine played a critical role in creating and documenting conditions necessary for uranium mineralization. Organic-rich, uraniferous rocks at the Anderson mine contain plant remains and ostracodes having remarkably detailed preservation of internal features because of infilling by opaline silica. This preservation suggests that the alkaline lake waters in the mine area contained high concentrations of dissolved silica and that silicification occurred rapidly, before compaction or cementation of the enclosing sediment. Uranium coprecipitated with the silica. Thinly laminated, dark-colored, siliceous beds contain centric diatoms preserved with carbonaceous material suggesting that lake waters at the mine were locally deep and anoxic. These alkaline, silica-charged waters and a stagnant, anoxic environment in parts of the lake were necessary conditions for the precipitation of large amounts of uranium in the lake-bottom sediments. Sediments at the Anderson mine contain plant remains and pollen that were derived from diverse vegetative zones suggesting about 1500 m of relief in the area at the time of deposition. The pollen suggests that the valley floor was semiarid and subtropical, whereas nearby mountains supported temperate deciduous forests. ?? 1990.

  5. Spectro-microscopic measurements of carbonaceous aerosol aging in Central California

    Directory of Open Access Journals (Sweden)

    R. C. Moffet

    2013-04-01

    Full Text Available Carbonaceous aerosols are responsible for large uncertainties in climate models, degraded visibility, and adverse health effects. The Carbonaceous Aerosols and Radiative Effects Study (CARES was designed to study carbonaceous aerosols in the natural environment of Central Valley, California, and learn more about their atmospheric formation and aging. This paper presents results from spectro-microscopic measurements of carbonaceous particles collected during CARES at the time of pollution accumulation event (27–29 June 2010, when in situ measurements indicated an increase in the organic carbon content of aerosols as the Sacramento urban plume aged. Computer controlled scanning electron microscopy coupled with an energy dispersive X-ray detector (CCSEM/EDX and scanning transmission X-ray microscopy coupled with near edge X-ray absorption spectroscopy (STXM/NEXAFS were used to probe the chemical composition and morphology of individual particles. It was found that the mass of organic carbon on individual particles increased through condensation of secondary organic aerosol. STXM/NEXAFS indicated that the number fraction of homogenous organic particles lacking inorganic inclusions (greater than ~50 nm diameter increased with plume age as did the organic mass per particle. Comparison of the CARES spectro-microscopic data set with a similar dataset obtained in Mexico City during the MILAGRO campaign showed that individual particles in Mexico City contained twice as much carbon as those sampled during CARES. The number fraction of soot particles at the Mexico City urban site (30% was larger than at the CARES urban site (10% and the most aged samples from CARES contained less carbon-carbon double bonds. Differences between carbonaceous particles in Mexico City and California result from different sources, photochemical conditions, gas phase reactants, and secondary organic aerosol precursors. The detailed results provided by these spectro

  6. Spectro-Microscopic Measurements of Carbonaceous Aerosol Aging in Central California

    Energy Technology Data Exchange (ETDEWEB)

    Moffet, Ryan C.; Rodel, Tobias; Kelly, Stephen T.; Yu, Xiao-Ying; Carroll, Gregory; Fast, Jerome D.; Zaveri, Rahul A.; Laskin, Alexander; Gilles, Mary K.

    2013-10-29

    Carbonaceous aerosols are responsible for large uncertainties in climate models, degraded visibility, and adverse health effects. The Carbonaceous Aerosols and Radiative Effects Study (CARES) was designed to study carbonaceous aerosols in the natural environment of Central Valley, California, and learn more about their atmospheric formation and aging. This paper presents results from spectro-microscopic measurements of carbonaceous particles collected during CARES at the time of pollution accumulation event (June 27-29, 2010), when in situ measurements indicated an increase in the organic carbon content of aerosols as the Sacramento urban plume aged. Computer controlled scanning electron microscopy coupled with an energy dispersive X-ray detector (CCSEM/EDX) and scanning transmission X-ray microscopy coupled with near edge X-ray absorption spectroscopy (STXM/NEXAFS) were used to probe the chemical composition and morphology of individual particles. It was found that the mass of organic carbon on individual particles increased through condensation of secondary organic aerosol. STXM/NEXAFS indicated that the number fraction of homogenous organic particles lacking inorganic inclusions (greater than ~50 nm diameter) increased with plume age as did the organic mass per particle. Comparison of the CARES spectro-microscopic data set with a similar dataset obtained in Mexico City during the MILAGRO campaign showed that individual particles in Mexico City contained twice as much carbon as those sampled during CARES. The number fraction of soot particles at the Mexico City urban site (30%) was larger than at the CARES urban site (10%) and the most aged samples from CARES contained less carbon-carbon double bonds. Differences between carbonaceous particles in Mexico City and California result from different sources, photochemical conditions, gas phase reactants, and secondary organic aerosol precursors. The detailed results provided by these spectro-microscopic measurements

  7. Spectro-microscopic measurements of carbonaceous aerosol aging in Central California

    Science.gov (United States)

    Moffet, R. C.; Rödel, T. C.; Kelly, S. T.; Yu, X. Y.; Carroll, G. T.; Fast, J.; Zaveri, R. A.; Laskin, A.; Gilles, M. K.

    2013-10-01

    Carbonaceous aerosols are responsible for large uncertainties in climate models, degraded visibility, and adverse health effects. The Carbonaceous Aerosols and Radiative Effects Study (CARES) was designed to study carbonaceous aerosols in the natural environment of the Central Valley, California, and learn more about their atmospheric formation and aging. This paper presents results from spectro-microscopic measurements of carbonaceous particles collected during CARES at the time of a pollution accumulation event (27-29 June 2010), when in situ measurements indicated an increase in the organic carbon content of aerosols as the Sacramento urban plume aged. Computer-controlled scanning electron microscopy coupled with an energy dispersive X-ray detector (CCSEM/EDX) and scanning transmission X-ray microscopy coupled with near-edge X-ray absorption spectroscopy (STXM/NEXAFS) were used to probe the chemical composition and morphology of individual particles. It was found that the mass of organic carbon on individual particles increased through condensation of secondary organic aerosol. STXM/NEXAFS indicated that the number fraction of homogenous organic particles lacking inorganic inclusions (greater than ~50 nm equivalent circular diameter) increased with plume age, as did the organic mass per particle. Comparison of the CARES spectro-microscopic dataset with a similar dataset obtained in Mexico City during the MILAGRO campaign showed that fresh particles in Mexico City contained three times as much carbon as those sampled during CARES. The number fraction of soot particles at the Mexico City urban site (ranging from 16.6 to 47.3%) was larger than at the CARES urban site (13.4-15.7%), and the most aged samples from CARES contained fewer carbon-carbon double bonds. Differences between carbonaceous particles in Mexico City and California result from different sources, photochemical conditions, gas phase reactants, and secondary organic aerosol precursors. The detailed

  8. Analysis of Halogen-Mercury Reactions in Flue Gas

    Energy Technology Data Exchange (ETDEWEB)

    Paula Buitrago; Geoffrey Silcox; Constance Senior; Brydger Van Otten

    2010-01-01

    Oxidized mercury species may be formed in combustion systems through gas-phase reactions between elemental mercury and halogens, such as chorine or bromine. This study examines how bromine species affect mercury oxidation in the gas phase and examines the effects of mixtures of bromine and chlorine on extents of oxidation. Experiments were conducted in a bench-scale, laminar flow, methane-fired (300 W), quartz-lined reactor in which gas composition (HCl, HBr, NO{sub x}, SO{sub 2}) and temperature profile were varied. In the experiments, the post-combustion gases were quenched from flame temperatures to about 350 C, and then speciated mercury was measured using a wet conditioning system and continuous emissions monitor (CEM). Supporting kinetic calculations were performed and compared with measured levels of oxidation. A significant portion of this report is devoted to sample conditioning as part of the mercury analysis system. In combustion systems with significant amounts of Br{sub 2} in the flue gas, the impinger solutions used to speciate mercury may be biased and care must be taken in interpreting mercury oxidation results. The stannous chloride solution used in the CEM conditioning system to convert all mercury to total mercury did not provide complete conversion of oxidized mercury to elemental, when bromine was added to the combustion system, resulting in a low bias for the total mercury measurement. The use of a hydroxylamine hydrochloride and sodium hydroxide solution instead of stannous chloride showed a significant improvement in the measurement of total mercury. Bromine was shown to be much more effective in the post-flame, homogeneous oxidation of mercury than chlorine, on an equivalent molar basis. Addition of NO to the flame (up to 400 ppmv) had no impact on mercury oxidation by chlorine or bromine. Addition of SO{sub 2} had no effect on mercury oxidation by chlorine at SO{sub 2} concentrations below about 400 ppmv; some increase in mercury oxidation

  9. A QSRR Study on the Relative Retention Time of Halogenated Methyl-phenyl Ethers

    Institute of Scientific and Technical Information of China (English)

    XU Hui-Ying; YU Qing-Sen; ZOU Jian-Wei; WANG Yan-Hua; WANG Hong-Qing; CHEN Xue-Song

    2006-01-01

    Halogenated methyl-phenyl ethers (anisoles) are ubiquitous organic compounds in the environment. In the present study, geometrical optimization and electrostatic potential calculations have been performed for 42 halogenated anisoles at the HF/6-31 G* level. A number of statistically based parameters have been obtained. By multiple regression method, linear relationships between the gas-chromatographic relative retention time (RRT) and structural descriptors have been established for the training set of 32 halogenated anisoles. The result showed that the parameters derived from electrostatic potentials (ESPs) together with the molecular volume (Vmc) could be well used to express the quantitative structure-RRT relationships of halogenated anisoles. The best two-variable regression model gives a correlation coefficient of 0.980 and a standard deviation of 0.07, and the leave-one-out cross-validated correlation coefficient is 0.975. The goodness of the model has been further validated through exploring the predictive power for the testing set of 10 halogenated anisoles.

  10. Non-conventional gas phase remediation of volatile halogenated compounds by dehydrated bacteria.

    Science.gov (United States)

    Erable, Benjamin; Goubet, Isabelle; Seltana, Amira; Maugard, Thierry

    2009-06-01

    Traditional biological removal processes are limited by the low solubility of halogenated compounds in aqueous media. A new technology appears very suitable for the remediation of these volatile organic compounds (VOCs). Solid/gas bio-catalysis applied in VOC remediation can transform halogenated compounds directly in the gas phase using dehydrated cells as a bio-catalyst. The hydrolysis of volatile halogenated substrates into the corresponding alcohol was studied in a solid/gas biofilter where lyophilised bacterial cultures were used as the catalyst. Four strains containing dehalogenase enzymes were tested for the hydrolysis of 1-chlorobutane. The highest removal yield was obtained using the dhaA-containing strains, the maximal reaction rate of 0.8 micromol min(-1)g(-1) being observed with Escherichia coli BL21(DE3)(dhaA). Various treatments such as cell disruption by lysozyme or alkaline gas addition in the bio-filter could stabilise the dehalogenase activity of the bacteria. A pre-treatment of the dehydrated bacterial cells by ammonia vapour improved the stability of the catalyst and a removal activity of 0.9 micromol min(-1)g(-1) was then obtained for 60h. Finally, the process was extended to a range of halogenated substrates including bromo- and chloro-substrates. It was shown that the removal capacity for long halogenated compounds (C(5)-C(6)) was greatly increased relative to traditional biological processes.

  11. [Concentration and emission fluxes of halogenated flame retardants in sewage from sewage outlet in Dongjiang River].

    Science.gov (United States)

    Zeng, Yan-Hong; Luo, Xiao-Jun; Sun, Yu-Xin; Yu, Le-Huan; Chen, She-Jun; Mai, Bi-Xian

    2011-10-01

    Fourteen sewage samples from sewage outlets in Dongjiang River were collected. Halogented flame retardants were extracted and purified using dichloromethane and alumina/silica-gel column, respectively. The concentrations of halogenated flame retardants were measured utilizing GC/MS, and the emission fluxes were estimated. Decabromodiphenyl ethane (DBDPE) was the predominant halogenated pollutant (accounting for 64%) in sewage with the concentration ranging from 9.1 ng/L to 990 ng/L. The concentrations of polybrominated biphenyl ether (PBDEs), dominated by BDE209, in the sewage ranged from 6.9 ng/L to 470 ng/L, accounting for 30% of total halogenated flame retardants. The concentrations of other flame retardants, such as dechlorane plus (DP), 1, 2-bis(2, 4, 6-tribromophenoxy) ethane (BTBPE), hexabromobenzene (HBB), and pentabromotoluene (PBT), were ranged within 0.17-23.6, nd-26.3, nd-1.45 and nd-0.45 ng/L, respectively. The concentrations of PBDEs in sewage of Dongjiang River were comparable to those in influent wastewater of sewage treatment plants of Guangzhou, suggesting that the wastewater was discharged directly into Dongjiang River without any treatment. The emission flux of halogenated flame retardants from sewage was 191 kg. Emission from industrial wastewater, contributed to 48%-91% of total emission, was the main source of halogenated flame retardants. PMID:22279897

  12. Seaonal Sea Ice as a source of organo-halogens during Polar night

    Science.gov (United States)

    Abrahamsson, Katarina; Granfors, Anna; Ahnoff, Martin

    2016-04-01

    The release of bromine from snow and sea ice surfaces has mainly been attributed to the reaction of hypobromous acid with bromide at acidic conditions to form Br2. Little attention has been given to the role of volatile halogenated organic compounds (organo-halogens) in the formation of reactive halogen species in the atmosphere during bromine explosion events. The load of organo-halogens was studied during a winter expedition to the Weddell Sea in June to August 2013. These compounds are emitted from the different compartments of the cryosphere to the atmosphere where they are photolysed to BrO and IO, which are involved in the degradation of ozone. We will present results that show the importance of organo-halogens formed during polar winter. In newly formed ice, in contrast to summer sea ice, the concentration of organo-bromine was found at levels as high as nM. These high concentrations were reflected both in frost flowers and in the sea-snow interface. Moreover, air measurements revealed high loads of organo-bromine over the sea ice. The situation was similar for iodinated compounds. Interestingly, the precursers of IO, mainly diiodomethane, could be measured in sea ice and snow, most probably due to the low light levels.

  13. Halogens, OVOC and H2O Distributions over the Eastern Pacific Ocean during TORERO

    Science.gov (United States)

    Dix, B. K.; Apel, E. C.; Baidar, S.; Zondlo, M. A.; Volkamer, R.

    2013-12-01

    As part of the Tropical Ocean tRoposphere Exchange of Reactive halogen species and Oxygenated VOC (TORERO) field project 17 research flights were conducted with the NSF/NCAR GV aircraft over the Eastern Tropical Pacific Ocean (42S to 14N Lat.; 70W to 105W Long). Equipped with a combination of chemical in-situ sensors and remote sensing instruments, a broad spectrum of reactive halogen species, oxygenated hydrocarbons, and aerosols were measured over different ocean environments. Using optical remote sensing (airborne Multi Axis DOAS), we measured iodine monoxide (IO), bromine monoxide (BrO), glyoxal (CHOCHO) and water vapor among others. A newly developed parameterization method allowed us to directly convert the measured slant column densities into mixing ratios along the whole flight track. Atmospheric reactive halogen species and organic carbon are important, because they modify HOx radical abundances, influence the reactive chemistry and lifetime of climate active gases (e.g., ozone, methane, dimethyl sulfide), modify aerosol-cloud interactions and halogen radicals can also oxidize atmospheric mercury. Here we summarize and evaluate the spatial distribution of IO, BrO and glyoxal over the TORERO study area. For select case studies we present comparisons to halogen precursors and OVOCs measured in-situ by on-line mass spectrometry (trace organic gas analyzer). The correlation of remotely observed water vapor to in-situ measurements further allows us to conclude on the homogeneity of spatial scales covered by both remote and in-situ sensors.

  14. A DFT study of halogen atoms adsorbed on graphene layers

    Energy Technology Data Exchange (ETDEWEB)

    Medeiros, Paulo V C; De Brito Mota, F; De Castilho, Caio M C [Grupo de Fisica de Superfcies e Materiais, Instituto de Fisica, Universidade Federal da Bahia, Campus Universitario da Federacao/Ondina, 40170-115 Salvador, Bahia (Brazil); Mascarenhas, Artur J S, E-mail: caio@ufba.br [Instituto Nacional de Ciencia e Tecnologia em Energia e Ambiente-INCT-E and A, Universidade Federal da Bahia, 40170-280 Salvador, Bahia (Brazil)

    2010-12-03

    In this work, ab initio density functional theory calculations were performed in order to study the structural and electronic properties of halogens (X = fluorine, chlorine, bromine or iodine) that were deposited on both sides of graphene single layers (X-graphene). The adsorption of these atoms on only one side of the layer with hydrogen atoms adsorbed on the other was also considered (H,X-graphene). The results indicate that the F-C bond in the F-graphene system causes an sp{sup 2} to sp{sup 3} transition of the carbon orbitals, and similar effects seem to occur in the H,X-graphene systems. For the other cases, two configurations are found: bonded (B) and non-bonded (NB). For the B configuration, the structural arrangement of the atoms was similar to F-graphene and H-graphene (graphane), although the electronic structures present some differences. In the NB configuration, the interaction between the adsorbed atoms and the graphene layer seems to be essentially of the van der Waals type. In these cases, the original shape of the graphene layer presents only small deviations from the pristine form and the adsorbed atoms reach equilibrium far from the sheet. The F-graphene structure has a direct bandgap of approximately 3.16 eV at the {Gamma} point, which is a value that is close to the value of 3.50 eV that was found for graphane. The Cl-graphene (B configuration), H,F-graphene and H,Cl-graphene systems have smaller bandgap values. All of the other systems present metallic behaviours. Energy calculations indicate the possible stability of these X-graphene layers, although some considerations about the possibility of spontaneous formation have to be taken into account.

  15. Environmental Factors Influencing Arctic Halogen Chemistry During Late Spring

    Science.gov (United States)

    Burd, J.; Nghiem, S. V.; Simpson, W. R.

    2015-12-01

    Reactive halogen radicals (e.g. Br, Cl atoms and their oxides, BrO, ClO) are important oxidizers in the troposphere that decrease atmospheric pollutants and deplete tropospheric ozone, affecting the abundance of other oxidizers such as the hydroxyl radical. During Arctic springtime, the heterogeneous chemical cycles (often called the "bromine explosion") produce high levels of bromine monoxide (BrO), through reactions on saline snow, ice, and/or aerosol surfaces. Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) measured BrO at Barrow, AK, from 2008-2009 and 2012-2015, as well at various locations above the frozen Arctic Ocean with O-Buoys in 2008 and 2011-2015. Observed BrO levels drop suddenly during late spring (May-June) and generally do not recover, which indicates the bromine explosion cycle can no longer produce significant amounts of BrO. We have established, through an objective algorithm, the local day of year of this drop in BrO as the "seasonal end." Additionally, in about half of the years, "recurrence" events were observed where BrO levels recover for at least a day. This study investigates the environmental factors influencing seasonal end and recurrence events including: temperature, relative humidity, precipitation and snowmelt. Analysis of BrO and air temperature revealed the temperature reaches 0°C within five days of the seasonal end event; however, temperatures drop below freezing during a recurrence event. In addition, there are periods where the temperature remains below freezing, but no recurrence event is observed. This BrO and temperature analysis indicates above-freezing air temperature prevents reactive bromine release; however, it is not the only environmental factor influencing this heterogeneous recycling. Further analysis of additional environmental influences on the bromine explosion cycle could help to better understand and model bromine chemistry in the Arctic.

  16. Physiochemical properties of carbonaceous aerosol from agricultural residue burning: Density, volatility, and hygroscopicity

    Science.gov (United States)

    Li, Chunlin; Hu, Yunjie; Chen, Jianmin; Ma, Zhen; Ye, Xingnan; Yang, Xin; Wang, Lin; Wang, Xinming; Mellouki, Abdelwahid

    2016-09-01

    Size-resolved effective density, mixing state, and hygroscopicity of smoke particles from five kinds of agricultural residues burning were characterized using an aerosol chamber system, including a volatility/hygroscopic tandem differential mobility analyzer (V/H-TDMA) combined with an aerosol particle mass analyzer (APM). To profile relationship between the thermodynamic properties and chemical compositions, smoke PM1.0 and PM2.5 were also measured for the water soluble inorganics, mineral elements, and carbonaceous materials like organic carbon (OC) and elemental carbon (EC). Smoke particle has a density of 1.1-1.4 g cm-3, and hygroscopicity parameter (κ) derived from hygroscopic growth factor (GF) of the particles ranges from 0.20 to 0.35. Size- and fuel type-dependence of density and κ are obvious. The integrated effective densities (ρ) and hygroscopicity parameters (κ) both scale with alkali species, which could be parameterized as a function of organic and inorganic mass fraction (forg &finorg) in smoke PM1.0 and PM2.5: ρ-1 =finorg ·ρinorg-1 +forg · ρorg-1 and κ =finorg ·κinorg +forg ·κorg . The extrapolated values of ρinorg and ρorg are 2.13 and 1.14 g cm-3 in smoke PM1.0, while the characteristic κ values of organic and inorganic components are about 0.087 and 0.734, which are similar to the bulk density and κ calculated from predefined chemical species and also consistent with those values observed in ambient air. Volatility of smoke particle was quantified as volume fraction remaining (VFR) and mass fraction remaining (MFR). The gradient temperature of V-TDMA was set to be consistent with the splitting temperature in the OC-EC measurement (OC1 and OC2 separated at 150 and 250 °C). Combing the thermogram data and chemical composition of smoke PM1.0, the densities of organic matter (OM1 and OM2 correspond to OC1 and OC2) are estimated as 0.61-0.90 and 0.86-1.13 g cm-3, and the ratios of OM1/OC1 and OM2/OC2 are 1.07 and 1.29 on average

  17. Physiochemical properties of carbonaceous aerosol from agricultural residue burning: Density, volatility, and hygroscopicity

    Science.gov (United States)

    Li, Chunlin; Hu, Yunjie; Chen, Jianmin; Ma, Zhen; Ye, Xingnan; Yang, Xin; Wang, Lin; Wang, Xinming; Mellouki, Abdelwahid

    2016-09-01

    Size-resolved effective density, mixing state, and hygroscopicity of smoke particles from five kinds of agricultural residues burning were characterized using an aerosol chamber system, including a volatility/hygroscopic tandem differential mobility analyzer (V/H-TDMA) combined with an aerosol particle mass analyzer (APM). To profile relationship between the thermodynamic properties and chemical compositions, smoke PM1.0 and PM2.5 were also measured for the water soluble inorganics, mineral elements, and carbonaceous materials like organic carbon (OC) and elemental carbon (EC). Smoke particle has a density of 1.1-1.4 g cm-3, and hygroscopicity parameter (κ) derived from hygroscopic growth factor (GF) of the particles ranges from 0.20 to 0.35. Size- and fuel type-dependence of density and κ are obvious. The integrated effective densities (ρ) and hygroscopicity parameters (κ) both scale with alkali species, which could be parameterized as a function of organic and inorganic mass fraction (forg &finorg) in smoke PM1.0 and PM2.5: ρ-1 =finorg · ρinorg-1 +forg · ρorg-1 and κ =finorg ·κinorg +forg ·κorg . The extrapolated values of ρinorg and ρorg are 2.13 and 1.14 g cm-3 in smoke PM1.0, while the characteristic κ values of organic and inorganic components are about 0.087 and 0.734, which are similar to the bulk density and κ calculated from predefined chemical species and also consistent with those values observed in ambient air. Volatility of smoke particle was quantified as volume fraction remaining (VFR) and mass fraction remaining (MFR). The gradient temperature of V-TDMA was set to be consistent with the splitting temperature in the OC-EC measurement (OC1 and OC2 separated at 150 and 250 °C). Combing the thermogram data and chemical composition of smoke PM1.0, the densities of organic matter (OM1 and OM2 correspond to OC1 and OC2) are estimated as 0.61-0.90 and 0.86-1.13 g cm-3, and the ratios of OM1/OC1 and OM2/OC2 are 1.07 and 1.29 on average

  18. The Effect of Liquid Aluminium on the Corrosion of Carbonaceous Materials

    Directory of Open Access Journals (Sweden)

    Pietrzyk S.

    2014-06-01

    Full Text Available Podczas wielu procesów wytapiania aluminium występują bezpośrednie kontakty ciekłego metalu i materiałów węglowych stanowiących wyłożenia wanien, pieców, tygli i kadzi itp. W rezultacie zachodzą procesy tworzenia węglika glinu na powierzchni między fazowej a następnie jego roztwarzania, które są uznawane jest za jeden z najważniejszych mechanizmów powodujących zużycie powierzchni i obniżenia żywotności urządzeń, zwłaszcza w procesie elektrolizy aluminium. Niniejsza praca miała na celu bliższe poznanie początkowych etapów tworzenia AI4C3 na powierzchni granicznej aluminium/węgiel. Zbadano trzy rodzaje materiałów węglowych: amorficzne, semigrafitowe i grafitowe, w obecności oraz przy braku stopionego kriolitu. Ponieważ jest bardzo trudno zbadać warstwę AI4C3 bezpośrednio (in situ, zastosowano dwie pośrednie techniki eksperymentalne: pomiar potencjału i rezystancji elektryczjnej. Stwierdzono, iż proces powstawania węglika glinu będzie zależeć od wielu zjawisk związanych z obecnością elektrolitu (interkalacja, penetracja i rozpuszczanie, jak również od struktury materiału węglowego a zwłaszcza od obecności fazy nieuporządkowanej.

  19. The Influence of Carbonaceous Matrices and Electrocatalytic MnO2 Nanopowders on Lithium-Air Battery Performances

    Directory of Open Access Journals (Sweden)

    Alessandro Minguzzi

    2016-01-01

    Full Text Available Here, we report new gas diffusion electrodes (GDEs prepared by mixing two different pore size carbonaceous matrices and pure and silver-doped manganese dioxide nanopowders, used as electrode supports and electrocatalytic materials, respectively. MnO2 nanoparticles are finely characterized in terms of structural (X-ray powder diffraction (XRPD, energy dispersive X-ray (EDX, morphological (SEM, high-angle annular dark field (HAADF-scanning transmission electron microscopy (STEM/TEM, surface (Brunauer Emmet Teller (BET-Barrett Joyner Halenda (BJH method and electrochemical properties. Two mesoporous carbons, showing diverse surface areas and pore volume distributions, have been employed. The GDE performances are evaluated by chronopotentiometric measurements to highlight the effects induced by the adopted materials. The best combination, hollow core mesoporous shell carbon (HCMSC with 1.0% Ag-doped hydrothermal MnO2 (M_hydro_1.0%Ag allows reaching very high specific capacity close to  1400 mAh·g−1. Considerably high charge retention through cycles is also observed, due to the presence of silver as a dopant for the electrocatalytic MnO2 nanoparticles.

  20. Hydrogen isotope ratios of aliphatic and diterpenoid hydrocarbons in coals and carbonaceous mudstones from the Liaohe Basin, China

    Energy Technology Data Exchange (ETDEWEB)

    Tuo, J.C.; Zhang, M.F.; Wang, X.B.; Zhang, C.L. [Chinese Academy of Sciences, Lanzhou (China). Institute of Geology & Geophysics

    2006-02-15

    Hydrogen-isotope compositions of the aliphatic and diterpenoid hydrocarbons were determined for five coal and carbonaceous mudstone samples collected from drilling cores (1531-1767 m depths) in the Liaohe Basin, China. The bulk organic materials were mainly derived from terrestrial higher plants. {delta}D values for most of the n-alkanes varied from -150 parts per thousand to -220 parts per thousand, and were not significantly different among the samples. Pristane was 34-69 parts per thousand depleted in D relative to phytane; both pristane and phytane, however, had the same trend of variation in {delta}D from sample to sample.Diterpenoids were on average 49-81 parts per thousand depleted in D relative to the n-alkanes. Variations in {delta}D also occurred between different diterpenoids, indicating a different source for these compounds. An enrichment process for the heavy hydrogen isotope was observed as expected when a compound was progressively altered through diagenesis (especially the dehydrogenation process). Overall, {delta}D and {delta}-{sup 13}C showed distinct patterns between structurally different lipid classes, although possible hydrogen exchange cannot be completely excluded during maturation. Our results further support the notion that hydrogen isotopes of lipid biomarkers from ancient sediments can be used to assess the origin of the organic matter, to determine oil-source rock correlation, and perhaps to reconstruct the paleoenvironment under which the organic material was deposited.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-09-01

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

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

    Science.gov (United States)

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

    2015-10-01

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

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

    Institute of Scientific and Technical Information of China (English)

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

    2007-01-01

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

  4. Influence of C-5 halogenation of uridines on hairpin versus duplex RNA folding.

    Science.gov (United States)

    Ennifar, Eric; Bernacchi, Serena; Wolff, Philippe; Dumas, Philippe

    2007-09-01

    Halogenation of bases is a widespread method used for solving crystal structures of nucleic acids. However, this modification may have important consequences on RNA folding and thus on the success of crystallization. We have used a combination of UV thermal melting, steady-state fluorescence, X-ray crystallography, and gel electrophoresis techniques to study the influence of uridine halogenation (bromination or iodination) on the RNA folding. The HIV-1 Dimerization Initiation Site is an RNA hairpin that can adopt an alternative duplex conformation and was used as a model. We have shown that, unexpectedly, the RNA hairpin/duplex ratio is strongly dependent not only on the presence but also on the position of halogenation. PMID:17630326

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

    International Nuclear Information System (INIS)

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

  6. Effect of superalkali substituents on the strengths and properties of hydrogen and halogen bonds.

    Science.gov (United States)

    Tian, Wenkai; Huang, Xin; Li, Qingzhong; Li, Wenzuo; Cheng, Jianbo; Gong, Baoan

    2013-03-01

    Quantum chemical calculations have been performed for the complexes Li(3)OCCX-Y (X = Cl, Br, H; Y = NH(3), H(2)O, H(2)S) and Li(3)OCN-X'Y' (X'Y' = ClF, BrCl, BrF, HF) to study the role of superalkalis in hydrogen and halogen bonds. The results show that the presence of an Li(3)O cluster in a Lewis acid weakens its acidity, while its presence in a Lewis base enhances its basicity. Furthermore, the latter effect is more prominent than the former one, and the presence of an Na(3)O cluster causes an even greater effect than Li(3)O. The strengths of hydrogen and halogen bonds were analyzed using molecular electrostatic potentials. The contributions of superalkalis to the strength of hydrogen and halogen bonds were elucidated by analyzing differences in electron density. PMID:23179773

  7. Dissolved organic matter in Arizona reservoirs: assessment of carbonaceous sources

    Energy Technology Data Exchange (ETDEWEB)

    Mash, H.; Westerhoff, P.K. [Arizona State Univ., Tempe, AZ (United States). Dept. of Civil and Environmental Engineering; Baker, L.A. [University of Minnesota, St. Paul, MN (United States). Water Resources Center; Nieman, R.A. [Arizona State Univ., Tempe, AZ (United States). Dept. of Chemistry and Biochemistry; Nguyen, M.L. [AWWA Research Foundation, Denver, CO (United States)

    2004-07-01

    Most studies of freshwater dissolved organic matter (DOM) have been conducted in temperate climates where allochthonous organic material is abundant. Because climatic conditions of the Southwestern USA are different than temperate environments, DOM from three freshwater reservoirs (Saguaro Lake, Bartlett Lake and Lake Pleasant) was investigated to determine the importance of allochthonous and autochthonous organic material. Results from the study show hydrophobic acids constitute a small percentage of the DOM, while the neutral and hydrophilic fractions are more prevalent. C/N ratios are comparatively low relative to other freshwater systems, ranging between 28 and 35 for the hydrophobic acid fractions, while DOC/DON ratios are seasonally influenced by epilimnionic algal growth. The isolated organic fractions were low in aromatic content measured by solid-state {sup 13}C NMR resulting in low aromatic to aliphatic carbon ratios. Organic material recovered from Saguaro Lake and Lake Pleasant display traits that suggest most allochthonous contributions are highly attenuated favoring organic material from autochthonous sources (low C/N and aromatic/aliphatic carbon ratios), whereas organic material from Bartlett Lake demonstrated a greater seasonal perturbation in source influence. (author)

  8. Effects of halogen doping on nanocarbon catalysts synthesized by a solution plasma process for the oxygen reduction reaction.

    Science.gov (United States)

    Ishizaki, Takahiro; Wada, Yuta; Chiba, Satoshi; Kumagai, Sou; Lee, Hoonseung; Serizawa, Ai; Li, Oi Lun; Panomsuwan, Gasidit

    2016-08-01

    Halogen-doped carbon nanoparticles (CNPs) were synthesized by a simple one-step solution plasma process at room temperature using a mixture of benzene (C6H6) and organics containing halogen atoms as the precursors (i.e., hexafluorobenzene (C6F6), hexachlorobenzene (C6Cl6), and hexabromobenzene (C6Br6)). The experimental results demonstrated that halogen doping, especially F and Cl, could lead to more efficient removal of residual hydrogen compared to carbon synthesized with pure benzene. This phenomenon was related to the different binding energies between hydrogen and halogens to form hydrogen halides. Their crystallinity and morphology did not change and remained the same as non-doped carbon. The electrochemical evaluation of oxygen reduction reaction (ORR) activity in an alkaline solution revealed that halogen doping did not play a significant role in shifting the onset potential for the ORR, while a slight enhancement in diffusion limited current density was observed at high overpotentials. Moreover, the electron transfer number involved in the ORR process determined from the Koutecky-Levich plot at -0.6 V was found to increase for halogen-doped carbons in the following order: F-CNPs > Br-CNPs > Cl-CNPs > CNPs. The improved ORR performance of F-CNPs could reasonably be attributed to the synergistic effects of specific bonding states between the halogen and carbon, structural defects and surface functional groups. Our results confirmed the validity of using halogen doping to improve the ORR catalytic activity of CNPs. PMID:27435811

  9. 40 CFR Appendix III to Part 268 - List of Halogenated Organic Compounds Regulated Under § 268.32

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 26 2010-07-01 2010-07-01 false List of Halogenated Organic Compounds Regulated Under § 268.32 III Appendix III to Part 268 Protection of Environment ENVIRONMENTAL PROTECTION... Part 268—List of Halogenated Organic Compounds Regulated Under § 268.32 In determining...

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

    Science.gov (United States)

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

    2015-10-01

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

  11. Reconciliation of halogen-induced ozone loss with the total-column ozone record

    Science.gov (United States)

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

    2014-06-01

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

  12. Sorption characteristics and mechanisms of organic contaminant to carbonaceous biosorbents in aqueous solution

    Institute of Scientific and Technical Information of China (English)

    CHEN BaoLiang; ZHOU DanDan; ZHU LiZhong; SHEN XueYou

    2008-01-01

    A series of carbonaceous biosorbents was prepared by pyrolyzing pine needles, a model biomass, at various temperatures (100-700℃) under an oxygen-limited condition for 6 h. The elemental composi-tions and the specific surface areas (BET-N2) of the biosorbents were analyzed. Sorption properties of 4-nitrotoluene to the biosorbents and their mechanisms were investigated, and then correlated with the structures of the biosorbents. The result shows that with the increase of the pyrolytic temperature, the sromaticity of the carbonaceous biosorbents increases dramatically and the polarity (the (N+O)/C atomic ratio) decreases sharply. Correspondingly, conformations of the organic matter in the biosor-bents transform gradually from a "soft-state" to a "hard-state" and the specific surface areas of the resultant biosorbents extend rapidly. The sorption isotherms fit well with the Freundlich equation. The regression parameters (I.e., N and IgKf) are linearly related to the aromaticity indices (the H/C atomic ratio). Contributions of adsorption and partition to total sorption of the carbonaceous biosorbents are quantified. The adsorption of the carbonaceous biosorbents increases quickly with the increase of the pyrolytic temperature. The saturated adsorption amounts (Qmax) increase linearly with the increase of the specific surface areas (SA) of the biosorbents. For the carbonaceous biosorbents with hard-state carbon, the calculated normalized-Qmax values by SA are comparable to the theoretical estimation (2.45 μmol/m2). In comparison, for the carbonaceous sorbents with soft-state carbon, the calculated nor-malized-Qmax values by SA are much higher than the theoretical estimation. The partition coefficients (Kom) increase with the decrease of the polarity of the biosorbents, reaching a maximum, and then de-crease sharply with further decreasing the polarity, suggesting that partition mechanism be dominated by the compatibility and accessibility of the sorbent medium with

  13. Sorption characteristics and mechanisms of organic contaminant to carbonaceous biosorbents in aqueous solution

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A series of carbonaceous biosorbents was prepared by pyrolyzing pine needles,a model biomass,at various temperatures (100-700℃) under an oxygen-limited condition for 6h. The elemental composi-tions and the specific surface areas (BET-N2) of the biosorbents were analyzed. Sorption properties of 4-nitrotoluene to the biosorbents and their mechanisms were investigated,and then correlated with the structures of the biosorbents. The result shows that with the increase of the pyrolytic temperature,the aromaticity of the carbonaceous biosorbents increases dramatically and the polarity (the (N+O)/C atomic ratio) decreases sharply. Correspondingly,conformations of the organic matter in the biosor-bents transform gradually from a "soft-state" to a "hard-state" and the specific surface areas of the resultant biosorbents extend rapidly. The sorption isotherms fit well with the Freundlich equation. The regression parameters (i.e.,N and lgKf) are linearly related to the aromaticity indices (the H/C atomic ratio). Contributions of adsorption and partition to total sorption of the carbonaceous biosorbents are quantified. The adsorption of the carbonaceous biosorbents increases quickly with the increase of the pyrolytic temperature. The saturated adsorption amounts (Qmax) increase linearly with the increase of the specific surface areas (SA) of the biosorbents. For the carbonaceous biosorbents with hard-state carbon,the calculated normalized-Qmax values by SA are comparable to the theoretical estimation (2.45 μmol/m2). In comparison,for the carbonaceous sorbents with soft-state carbon,the calculated nor-malized-Qmax values by SA are much higher than the theoretical estimation. The partition coefficients (Kom) increase with the decrease of the polarity of the biosorbents,reaching a maximum,and then de-crease sharply with further decreasing the polarity,suggesting that partition mechanism be dominated by the compatibility and accessibility of the sorbent medium with organic

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-03-01

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

  15. Oxygen- and magnesium-isotope compositions of calcium-aluminum-rich inclusions from CR2 carbonaceous chondrites

    Science.gov (United States)

    Makide, Kentaro; Nagashima, Kazuhide; Krot, Alexander N.; Huss, Gary R.; Hutcheon, Ian D.; Bischoff, Addi

    2009-09-01

    We report both oxygen- and magnesium-isotope compositions measured in situ using a Cameca ims-1280 ion microprobe in 20 of 166 CAIs identified in 47 polished sections of 15 CR2 (Renazzo-type) carbonaceous chondrites. Two additional CAIs were measured for oxygen isotopes only. Most CR2 CAIs are mineralogically pristine; only few contain secondary phyllosilicates, sodalite, and carbonates - most likely products of aqueous alteration on the CR2 chondrite parent asteroid. Spinel, hibonite, grossite, anorthite, and melilite in 18 CAIs have 16O-rich (Δ 17O = -23.3 ± 1.9‰, 2 σ error) compositions and show no evidence for postcrystallization isotopic exchange commonly observed in CAIs from metamorphosed CV carbonaceous chondrites. The inferred initial 26Al/ 27Al ratios, ( 26Al/ 27Al) 0, in 15 of 16 16O-rich CAIs measured are consistent with the canonical value of (4.5-5) × 10 -5 and a short duration (oxygen- and magnesium-isotope compositions (˜11 and 23‰/amu, respectively), a deficit of 26Mg, and a relatively low ( 26Al/ 27Al) 0 = (2.0 ± 1.7) × 10 -5. This could be the first FUN ( Fractionation and Unidentified Nuclear effects) CAI found in CR2 chondrites. Because this inclusion is slightly 16O-depleted compared to most CR2 CAIs and has lower than the canonical ( 26Al/ 27Al) 0, it may have experienced multistage formation from precursors with nonsolar magnesium-isotope composition and recorded evolution of oxygen-isotope composition in the early solar nebula over 0.9+2.2-0.7 My. Eight of the 166 CR2 CAIs identified are associated with chondrule materials, indicating that they experienced late-stage, incomplete melting during chondrule formation. Three of these CAIs show large variations in oxygen-isotope compositions (Δ 17O ranges from -23.5‰ to -1.7‰), suggesting dilution by 16O-depleted chondrule material and possibly exchange with an 16O-poor (Δ 17O > -5‰) nebular gas. The low inferred ( 26Al/ 27Al) 0 ratios of these CAIs (2 My after crystallization

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-09-15

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-03-15

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

  18. Field Emission Electron Microprobe Analysis of Halogens in Apatite

    Science.gov (United States)

    Tacker, R. C.

    2011-12-01

    counts increase as expected from 10 to 20 kV, but the loss of chlorine is more strongly controlled by crystal orientation. With electron beam parallel to the c-axis, chlorine counts are very low, pointing to the chlorine loss during analysis. Hence fluorine and chlorine are fractionated during analysis as a complicated function of beam energies and crystal orientation. Routine analyses of halogens in apatite are unlikely to yield a quantitative analysis, and OH calculated by the difference in a normalized analysis is less likely to be meaningful. Further, the use of 15-20 kV secondary electron or backscatter electron imaging prior to analysis should be reconsidered. Stormer et al., 1993, Am. Min., 78, 641. Fialin and Chopin, 2006, Am. Min. 91, 503.

  19. Halogenated organic species over the tropical South American rainforest

    Directory of Open Access Journals (Sweden)

    S. Gebhardt

    2008-06-01

    Full Text Available Airborne measurements of the halogenated trace gases methyl chloride, methyl bromide and chloroform were conducted over the Atlantic Ocean and about 1000 km of pristine tropical rainforest in Suriname and French Guyana (3–6° N, 51–59° W in October 2005. In the boundary layer (0–1.4 km, maritime air masses, advected over the forest by southeasterly trade winds, were measured at various distances from the coast. Since the organohalogens presented here have relatively long atmospheric lifetimes (0.4–1.0 years in comparison to the advection times from the coast (1–2 days, emissions will accumulate in air traversing the rainforest. The distributions of methyl chloride, methyl bromide and chloroform were analyzed as a function of time the air spent over land and the respective relationship used to determine net fluxes from the rainforest for one week within the long dry season.

    Net fluxes from the rainforest ecosystem have been calculated for methyl chloride and chloroform as 9.5 (±3.8 2σ and 0.35 (±0.15 2σμg m-2 h−1, respectively. No significant flux was observed for methyl bromide within the limits of these measurements.

    The global budget of methyl chloride contains large uncertainties, in particular with regard to a possible source from tropical vegetation. Our measurements are used in a large-scale approach to determine the net flux from a tropical ecosystem to the planetary boundary layer. The obtained global net flux of 1.5 (±0.6 2σ Tg yr-1 for methyl chloride is at the lower end of current estimates for tropical vegetation sources, which helps to constrain the range of tropical sources and sinks (0.82 to 8.2 Tg yr-1 from tropical plants, 0.03 to 2.5 Tg yr-1 from senescent/dead leaves and a sink of 0.1 to 1.6 Tg yr-1 by soil uptake. Nevertheless, these results show that the contribution of the rainforest ecosystem is the major source in the

  20. Magnetite as Possible Template for the Synthesis of Chiral Organics in Carbonaceous Chondrites

    Science.gov (United States)

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

    2014-01-01

    The main goal of the Japanese Aerospace Ex-ploration Agency (JAXA) Hayabusa-2 mission is to visit and return to Earth samples of a C-type asteroid (162173) 1999 JU3 in order to understand the origin and nature of organic materials in the Solar System. Life on Earth shows preference towards the set of organics with particular spatial arrangements, this 'selectivity' is a crucial criterion for life. With only rare exceptions, life 'determines' to use the left- (L-) form over the right- (D-) form of amino acids, resulting in a L-enantiomeric excess (ee). Recent studies have shown that L-ee is found within the alpha-methyl amino acids in meteorites [1, 2], which are amino acids with rare terrestrial occurrence, and thus point towards a plausible abiotic origin for ee. One of the proposed origins of chiral asymmetry of amino acids in meteorites is their formation with the presence of asymmetric catalysts [3]. The catalytic mineral grains acted as a surface at which nebular gases (CO, H2 and NH3) were allowed to condense and react through Fisher Tropsch type (FTT) syntheses to form the organics observed in meteorites [4]. Magnetite is shown to be an effective catalyst of the synthesis of amino acids that are commonly found in meteorites [5]. It has also taken the form as spiral magnetites (a.k.a. 'plaquettes'), which were found in various carbonaceous chondrites (CCs), including C2s Tagish Lake and Esseibi, CI Orgueil, and CR chondrites [e.g., 6, 7, 8]. In addition, L-ee for amino acids are common in the aqueously altered CCs, as opposed to the unaltered CCs [1]. It seems possible that the synthesis of amino acids with chiral preferences is correlated to the alteration process experienced by the asteroid parent body, and related to the configuration of spiral magnetite catalysts. Since C-type asteroids are considered to be enriched in organic matter, and the spectral data of 1999 JU3 indicates a certain de-gree of aqueous alteration [9], the Hayabusa-2 mission serves as

  1. The formation and alteration of the Renazzo-like carbonaceous chondrites

    Science.gov (United States)

    Schrader, Devin Lee

    This study investigates the pre-accretionary formation conditions of individual minerals within chondrules and whole-rock parent asteroid processes from the Renazzo-like carbonaceous (CR) chondrites. It presents a comprehensive work on the whole-rock O-isotope composition, sulfide-bearing opaque minerals, and type-II chondrules within the CR chondrites. Whole-rock O-isotope composition and minerals present in type-II chondrules are found to be related to the degree of parent asteroid aqueous alteration. Primary minerals within chondrules, formed prior to accretion of the CR chondrite parent asteroid, are used to constrain both the environment and the conditions present during chondrule formation. Chondrule formation, as recorded by chondrules in the CR chondrites, took place under dust- and ice-rich conditions relative to solar values. Type-II (FeO-rich) chondrules contain FeO-poor fragments compositionally similar to type-I (FeO-poor) chondrules; the formation of type-II chondrules may have occurred after the formation of type-I chondrules. The dust and ice abundances present during type-II chondrule formation were higher than those of type-I chondrules, although both populations probably exchanged with the same 16O-poor gas reservoir. Both the oxygen fugacity (fo 2) and sulfur fugacity (fs2) appear to have increased from type-I to type-II chondrule formation, and between individual type-II chondrules. The increase in fo2 and fs2 may be due to the dissipation of H2 in the early Solar System. Gas-solid oxidation/sulfidation of Fe,Ni metal is recorded in both type-I and type-II chondrules. This corrosion occurred either during chondrule cooling after formation, or during chondrule reheating events, and suggests that S was present in the gas phase. After chondrule formation the CR chondrite parent asteroid accreted 16O-poor ice and experienced variable degrees of aqueous alteration, possibly due to heterogeneity in accreted ice or ammonia abundances and/or differing

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

    Directory of Open Access Journals (Sweden)

    H. Biester

    2006-01-01

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

  3. Two-step flotation recovery of iron concentrate from Donganshan carbonaceous iron ore

    Institute of Scientific and Technical Information of China (English)

    YIN Wan-zhong; HAN Yue-xin; XIE Feng

    2010-01-01

    The flotation of pure and natural carbonaceous iron ore samples in the oleate flotation system was investigated.Starch can depress hematite effectively in a wide pH range,but cannot depress siderite efficiently in neutral conditions.The flotation recovery of pure hematite,siderite,and quartz in the oleate-starch-CaCl2 system is significantly different when the slurry pH varies from 4 to 12.A novel two-step flotation process was developed for the separation of iron concentrate from Donganshan carbonaceous iron ore through which the siderite concentrate is first recovered and the high quality hematite concentrates with relative high iron recovery can be obtained in the second step flotation.The siderite concentrate may be utilized directly or undergo further concentration steps to increase iron grade.

  4. Formation of PAHs and Carbonaceous Solids in Gas-Phase Condensation Experiments

    CERN Document Server

    Jäger, C; Jansa, I Llamas; Henning, T; Huisken, F

    2009-01-01

    Carbonaceous grains represent a major component of cosmic dust. In order to understand their formation pathways, they have been prepared in the laboratory by gas-phase condensation reactions such as laser pyrolysis and laser ablation. Our studies demonstrate that the temperature in the condensation zone determines the formation pathway of carbonaceous particles. At temperatures lower than 1700 K, the condensation by-products are mainly polycyclic aromatic hydrocarbons (PAHs), that are also the precursors or building blocks for the condensing soot grains. The low-temperature condensates contain PAH mixtures that are mainly composed of volatile 3-5 ring systems. At condensation temperatures higher than 3500 K, fullerene-like carbon grains and fullerene compounds are formed. Fullerene fragments or complete fullerenes equip the nucleating particles. Fullerenes can be identified as soluble components. Consequently, condensation products in cool and hot astrophysical environments such as cool and hot AGB stars or W...

  5. Petrology of Amoeboid Olivine Aggregates in Antarctic CR Chondrites: Comparison With Other Carbonaceous Chondrites

    Science.gov (United States)

    Komatsu, M.; Fagan, T. J.; Yamaguchi, A.; Mikouchi, T.; Zolensky, M. E.; Yasutake, M.

    2016-01-01

    Amoeboid olivine aggregates (AOAs) are important refractory components of carbonaceous chondrites and have been interpreted to represent solar nebular condensates that experienced high-temperature annealing, but largely escaped melting. In addition, because AOAs in primitive chondrites are composed of fine-grained minerals (forsterite, anorthite, spinel) that are easily modified during post crystallization alteration, the mineralogy of AOAs can be used as a sensitive indicator of metamorphic or alteration processes. AOAs in CR chondrites are particularly important because they show little evidence for secondary alteration. In addition, some CR AOAs contain Mn-enriched forsterite (aka low-iron, Mn-enriched or LIME olivine), which is an indicator of nebular formation conditions. Here we report preliminary results of the mineralogy and petrology of AOAs in Antarctic CR chondrites, and compare them to those in other carbonaceous chondrites.

  6. Ion irradiation of carbonaceous chondrites as a simulation of space weathering on C-complex asteroids

    Science.gov (United States)

    Lantz, C.; Brunetto, R.; Barucci, M. A.; Bachelet, C.; Baklouti, D.; Bourçois, J.; Dartois, E.; Duprat, J.; Duret, P.; Engrand, C.; Godard, M.; Ledu, D.; Mivumbi, O.; Fornasier, S.

    2015-10-01

    We are investigating the effects of space weathering on primitive asteroids using ion irradiation on their meteoritic analogs. To do so, we exposed several carbonaceous chondrites (CV Allende, COs Lancé and Frontier Mountain 95002, CM Mighei, CI Alais, and ungrouped Tagish Lake) to 40 keV He+ ions as a simulation of solar wind irradiation using fluences up to 6.1016 ions/cm2 (implantation platform IRMA at CSNSM Orsay). As a test for our new experimental setup, we also studied samples of olivine and diopside. We confirm the reddening and darkening trends on S-type objects, but carbonaceous chondrites present a continuum of behaviors after ion irradiation as a function of the initial albedo and carbon content: from red to blue and from dark to bright.

  7. Review of Rate Constants and Exploration of Correlations of the Halogen Transfer Reaction of Tri-substituted Carbon-centered Radicals with Molecular Halogens

    Energy Technology Data Exchange (ETDEWEB)

    Poutsma, Marvin L [ORNL

    2012-01-01

    Rate constants for the reaction (R 3C + X2 R 3CX + X ; X = F, Cl, Br, and I) are reviewed. Because of curved Arrhenius plots and negative EX values, empirical structure-reactivity correlations are sought for log kX,298 rather than EX. The well-known poor correlation with measures of reaction enthalpy is demonstrated. The best quantitative predictor for R 3C is p, the sum of the Hammett p constants for the three substituents, R . Electronegative substituents with lone pairs, such as halogen or oxygen, thus appear to destabilize the formation of a polarized pre-reaction complex and/or TS ( +R---X---X -) by -inductive/field electron withdrawal while simultaneously stabilizing them by -resonance electron donation. The best quantitative predictor of the reactivity order of the halogens, I2 > Br2 >> Cl2 F2, is the polarizability of the halogen, (X-X). For the data set of 60 rate constants which span 6.5 orders of magnitude, a modestly successful correlation of log kX,298 is achieved with only two parameters, p and (X-X), with a mean unsigned deviation of 0.59 log units. How much of this residual variance is the result of inaccuracies in the data compared with over-simplification of the correlation approach remains to be seen.

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

    OpenAIRE

    Bourbin, Mathilde; Gourier, Didier; Binet, Laurent; Le Du, Yann; Derenne, Sylvie; Westall, Francès; Kremer, Barbara; Gautret, Pascale

    2013-01-01

    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 gre...

  9. Titanium-rich oxide-bearing plagioclase-olivine inclusions in the unusual Ningqiang carbonaceous chondrite

    OpenAIRE

    Lin,Yangting /Kimura,Makoto

    1997-01-01

    Two plagioclase-olivine inclusions (POIs) from the unusual Ningqiang carbonaceous chondrite were studied to understand their mineralogy and crystallization history. In addition to the major phases plagioclase, spinel, olivine and pyroxene, Ningqiang POIs are characterized by interstitial assemblages composed of Ca-rich and Ca-poor pyroxenes, Ti-rich oxides and the other phases. The Ti-rich oxides include an unidentified titanium mineral series referred to as phase T, Ca-rich and Mg, Fe-rich a...

  10. In Situ Mapping of the Organic Matter in Carbonaceous Chondrites and Mineral Relationships

    Science.gov (United States)

    Clemett, Simon J.; Messenger, S.; Thomas-Keprta, K. L.; Ross, D. K.

    2012-01-01

    Carbonaceous chondrite organic matter represents a fossil record of reactions that occurred in a range of physically, spatially and temporally distinct environments, from the interstellar medium to asteroid parent bodies. While bulk chemical analysis has provided a detailed view of the nature and diversity of this organic matter, almost nothing is known about its spatial distribution and mineralogical relationships. Such information is nevertheless critical to deciphering its formation processes and evolutionary history.

  11. Natural Radionuclides and Isotopic Signatures for Determining Carbonaceous Aerosol Sources, Aerosol Lifetimes, and Washout Processes

    International Nuclear Information System (INIS)

    This is the final technical report. The project description is as follows: to determine the role of aerosol radiative forcing on climate, the processes that control their atmospheric concentrations must be understood, and aerosol sources need to be determined for mitigation. Measurements of naturally occurring radionuclides and stable isotopic signatures allow the sources, removal and transport processes, as well as atmospheric lifetimes of fine carbonaceous aerosols, to be evaluated.

  12. Origin of fine carbonaceous particulate matter in the Western Mediterranean Basin: fossil versus modern sources

    Science.gov (United States)

    Cruz Minguillón, María.; Perron, Nolwenn; Querol, Xavier; Szidat, Sönke; Fahrni, Simon; Wacker, Lukas; Reche, Cristina; Cusack, Michael; Baltensperger, Urs; Prévôt, André S. H.

    2010-05-01

    The present work was carried out in the frame of the international field campaign DAURE (Determination of the sources of atmospheric Aerosols in Urban and Rural Environments in the western Mediterranean). The objective of this campaign is to study the aerosol pollution episodes occurring at regional scale during winter and summer in the Western Mediterranean Basin. As part of this campaign, this work focuses on identifying the origin of fine carbonaceous aerosols. To this end, fine particulate matter (PM1) samples were collected during two different seasons (February-March and July 2009) at two sites: an urban site (Barcelona, NE Spain) and a rural European Supersite for Atmospheric Aerosol Research (Montseny, NE Spain). Subsequently, 14C analyses were carried out on these samples, both in the elemental carbon (EC) fraction and the organic carbon (OC) fraction, in order to distinguish between modern carbonaceous sources (biogenic emissions and biomass burning emissions) and fossil carbonaceous sources (mainly road traffic). Preliminary results from the winter period show that 40% of the OC at Barcelona has a fossil origin whereas at Montseny this percentage is 30%. These values can be considered as unexpected given the nature of the sites. Nevertheless, the absolute concentrations of fossil OC at Barcelona and Montseny differ by a factor of 2 (the first being higher), since the total OC at Montseny is lower than at Barcelona. Further evaluation of results and comparison with other measurements carried out during the campaign are required to better evaluate the origin of the fine carbonaceous matter in the Western Mediterranean Basin. Acknowledgements: Spanish Ministry of Education and Science, for a Postdoctoral Grant awarded to M.C. Minguillón in the frame of Programa Nacional de Movilidad de Recursos Humanos del Plan nacional de I-D+I 2008-2011. Spanish Ministry of Education and Science, for the Acción Complementaria DAURE CGL2007-30502-E/CLI.

  13. Implementing a new EPR lineshape parameter for organic radicals in carbonaceous matter

    OpenAIRE

    Bourbin, Mathilde; Du, Yann Le; Binet, Laurent; Gourier, Didier

    2013-01-01

    Background Electron Paramagnetic Resonance (EPR) is a non-destructive, non-invasive technique useful for the characterization of organic moieties in primitive carbonaceous matter related to the origin of life. The classical EPR parameters are the peak-to-peak amplitude, the linewidth and the g factor; however, such parameters turn out not to suffice to fully determine a single EPR line. Results In this paper, we give the definition and practical implementation of a new EPR parameter based on ...

  14. Annual variations of carbonaceous PM2.5 in Malaysia: Influence by Indonesian peatland fires

    OpenAIRE

    Fujii, Y.; S. Tohno; Amil, N.; M. T. Latif; Oda, M.; Matsumoto, J.; A. Mizohata

    2015-01-01

    In this study, we quantified carbonaceous PM2.5 in Malaysia through annual observations of PM2.5, focusing on organic compounds derived from biomass burning. We determined organic carbon (OC), elemental carbon and concentrations of solvent-extractable organic compounds (biomarkers derived from biomass burning sources and n-alkanes). We observed seasonal variations in the concentrations of pyrolyzed OC (OP), levoglucosan (LG), mannosan (MN), galactosan, syringaldehyde, vanillic acid (VA) and c...

  15. Spheroidal carbonaceous particles are a defining stratigraphic marker for the Anthropocene

    OpenAIRE

    Swindles, GT; Watson, E.; Turner, TE; Galloway, JM; Hadlari, T; Wheeler, J; Bacon, KL

    2015-01-01

    There has been recent debate over stratigraphic markers used to demarcate the Anthropocene from the Holocene Epoch. However, many of the proposed markers are found only in limited areas of the world or do not reflect human impacts on the environment. Here we show that spheroidal carbonaceous particles (SCPs), a distinct form of black carbon produced from burning fossil fuels in energy production and heavy industry, provide unambiguous stratigraphic markers of the human activities that have ra...

  16. Natural Radionuclides and Isotopic Signatures for Determining Carbonaceous Aerosol Sources, Aerosol Lifetimes, and Washout Processes

    Energy Technology Data Exchange (ETDEWEB)

    Gaffney, Jeffrey [Univ. of Arkansas, Little Rock, AR (United States)

    2012-12-12

    This is the final technical report. The project description is as follows: to determine the role of aerosol radiative forcing on climate, the processes that control their atmospheric concentrations must be understood, and aerosol sources need to be determined for mitigation. Measurements of naturally occurring radionuclides and stable isotopic signatures allow the sources, removal and transport processes, as well as atmospheric lifetimes of fine carbonaceous aerosols, to be evaluated.

  17. Fermentation, gasification and pyrolysis of carbonaceous residues towards usage in fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Sequeira, C.A.C.; Santos, D.M.F. [Instituto Superior Tecnico, Av. Rovisco Pais 1, 1049-001, Lisboa (Portugal); Brito, P.S.D.; Mota, A.F.; Carvalho, J.L.; Rodrigues, L.F.F.T.T.G. [Escola Superior de Tecnologia e Gestao de Portalegre, Apartado 148, 7300-901 Portalegre (Portugal); Barrio, D.B.; Justo, D.M. [Facultad de Ciencias, Universidad de Valladolid, c/Real de Burgos sin, 47011 Valladolid (Spain)

    2007-07-15

    In this paper, the technologies of fermentation, gasification and pyrolysis of carbonaceous residues for the production of biohydrogen and other gaseous, liquid or solid fuels, are analysed. The energetic, economic and environmental advantages of linking these energy areas with the fuel cell engines are stressed. In addition, the current status of fuel cell technologies, namely their historic trends, basic electrode mechanisms, cell types, market drivers and leading issues, are reviewed. (author)

  18. Carbonaceous matter deposition in the high glacial regions of the Tibetan Plateau

    Science.gov (United States)

    Li, Chaoliu; Chen, Pengfei; Kang, Shichang; Yan, Fangping; Li, Xiaofei; Qu, Bin; Sillanpää, Mika

    2016-09-01

    Carbonaceous matter at glacial region plays important role in river ecosystems fed by glacier and albedo reduction of glacier surface. However, currently, limited knowledge are available on the carbonaceous matter within the glacial region of the Tibetan Plateau (TP). In this study, the data from six snowpits in the glacial region across the TP were reported. The results showed that dissolved organic carbon (DOC) concentrations of snowpit samples of the TP were comparable to those of European Alps and the Arctic. The ratio of DOC to carbonaceous matter (40.25 ± 8.98%) was lower than that of Alpine glaciers, thus indicating greater particulate carbon content in the TP glacial region. In addition, the DOC was significantly correlated with insoluble particulate carbon (IPC), indicating that IPC and DOC likely came from the same sources. Spatially, the DOC concentration decreased from the north (0.42 ± 0.29 mg-C L-1) to the south TP (0.15 ± 0.06 mg-C L-1), which was consistent with variations in the distribution of dust storm on the TP. Principal component analysis of major ions and DOC showed that mineral dust contributed the major part of DOC, followed by biogenic sources such as agriculture and livestock. Finally, based on DOC concentrations and precipitation amounts at different periods, the mean annul flux of DOC in the glacial region of the TP was calculated to be 0.11 ± 0.05 g-C m-2 yr-1.

  19. Garnet-filled trails associated with carbonaceous matter mimicking microbial filaments in Archean basalt.

    Science.gov (United States)

    Lepot, K; Philippot, P; Benzerara, K; Wang, G-Y

    2009-09-01

    The study of the earliest traces of life on Earth can be complicated by abiotically formed biomorphs. We report here the finding of clustered micrometer-sized filaments of iron- and calcium-rich garnets associated with carbonaceous matter in an agate amygdale from a 2.7-billion-year-old basalt of the Maddina Formation, Western Australia. The distribution of carbonaceous matter and the mineral phases composing the filaments were analyzed using a combination of confocal laser scanning microscopy, laser-Raman micro-spectroscopy, focused ion beam sectioning and transmission electron microscopy. The results allow consideration of possible biogenic and abiotic processes that produced the filamentous structures. The filaments have a range of sizes, morphologies and distributions similar to those of certain modern iron-mineralized filamentous bacteria and some ancient filamentous structures interpreted as microfossils. They also share a high morphological similarity with tubular structures produced by microbial boring activity. However, the microstructures and the distribution of carbonaceous matter are more suggestive of an abiotic origin for the filaments. They are characteristic features of trails produced by the displacement of inclusions associated with local dissolution of their silica matrix. Organic compounds found in kerogen or bitumen inclusions may have contributed significantly to the dissolution of the quartz (or silica gel) matrix driving filamentous growth. Discriminating the products of such abiotic organic-mediated processes from filamentous microfossils or microbial borings is important to the interpretation of the scarce Precambrian fossil record and requires investigation down to the nanoscale.

  20. A Carbonaceous Membrane based on a Polymer of Intrinsic Microporosity (PIM-1) for Water Treatment

    Science.gov (United States)

    Kim, Hee Joong; Kim, Dong-Gyun; Lee, Kyuchul; Baek, Youngbin; Yoo, Youngjae; Kim, Yong Seok; Kim, Byoung Gak; Lee, Jong-Chan

    2016-01-01

    As insufficient access to clean water is expected to become worse in the near future, water purification is becoming increasingly important. Membrane filtration is the most promising technologies to produce clean water from contaminated water. Although there have been many studies to prepare highly water-permeable carbon-based membranes by utilizing frictionless water flow inside the carbonaceous pores, the carbon-based membranes still suffer from several issues, such as high cost and complicated fabrication as well as relatively low salt rejection. Here, we report for the first time the use of microporous carbonaceous membranes via controlled carbonization of polymer membranes with uniform microporosity for high-flux nanofiltration. Further enhancement of membrane performance is observed by O2 plasma treatment. The optimized membrane exhibits high water flux (13.30 LMH Bar−1) and good MgSO4 rejection (77.38%) as well as antifouling properties. This study provides insight into the design of microporous carbonaceous membranes for water purification. PMID:27782212

  1. The Spatial Distribution of Organic Matter and Mineralogical Relationships in Carbonaceous Chondrites

    Science.gov (United States)

    Clemett, S. J.; Messenger, S.; Thomas-Keprta, K. L.; Nakamura-Messenger, K.

    2012-01-01

    Organic matter present within primitive carbonaceous meteorites represents the complex conglomeration of species formed in a variety of physically and temporally distinct environments including circumstellar space, the interstellar medium, the Solar Nebula & Jovian sub-nebulae and asteroids. In each case, multiple chemical pathways would have been available for the synthesis of organic molecules. Consequently these meteorites constitute a unique record of organic chemical evolution in the Universe and one of the biggest challenges in organic cosmochemistry has been in deciphering this record. While bulk chemical analysis has provided a detailed description of the range and diversity of organic species present in carbonaceous chondrites, there is virtually no hard experimental data as to how these species are spatially distributed and their relationship to the host mineral matrix, (with one exception). The distribution of organic phases is nevertheless critical to understanding parent body processes. The CM and CI chondrites all display evidence of low temperature (organics and synthesis of new organics coupled to aqueous mineral alteration. To address such issues we have applied the technique of microprobe two-step laser desorption / photoionization mass spectrometry (L2MS) to map in situ the spatial distribution of a broad range of organic species at the micron scale in the freshly exposed matrices of the Bells, Tagish Lake and Murchison (CM2) carbonaceous chondrites.

  2. Comets: Cosmic connections with carbonaceous meteorites, interstellar molecules and the origin of life

    Science.gov (United States)

    Chang, S.

    1979-01-01

    The ions, radicals, and molecules observed in comets may be derived intact or by partial decomposition from parent compounds of the sort found either in the interstellar medium or in carbonaceous meteorites. The early loss of highly reducing primitive atmosphere and its replacement by a secondary atmosphere dominated by H2O, CO2, and N2, as depicted in current models of the earth's evolution, pose a dilemma for the origin of life: the synthesis of organic compounds necessary for life from components of the secondary atmosphere appears to be difficult, and plausible mechanisms have not been evaluated. Both comets and carbonaceous meteorites are implicated as sources for the earth's atmophilic and organogenic elements. A mass balance argument involving the estimated ratios of hydrogen to carbon in carbonaceous meteorites, comets, and the crust and upper mantle suggests that comets supplied the earth with a large fraction of its volatiles. The probability that comets contributed significantly to the earth's volatile inventory suggests a chemical evolutionary link between comets, prebiotic organic synthesis, and the origin of life.

  3. Atmospheric carbonaceous aerosols from Indo-Gangetic Plain and Central Himalaya: impact of anthropogenic sources.

    Science.gov (United States)

    Ram, Kirpa; Sarin, M M

    2015-01-15

    In the present-day scenario of growing anthropogenic activities, carbonaceous aerosols contribute significantly (∼20-70%) to the total atmospheric particulate matter mass and, thus, have immense potential to influence the Earth's radiation budget and climate on a regional to global scale. In addition, formation of secondary organic aerosols is being increasingly recognized as an important process in contributing to the air-pollution and poor visibility over urban regions. It is, thus, essential to study atmospheric concentrations of carbonaceous species (EC, OC and WSOC), their mixing state and absorption properties on a regional scale. This paper presents the comprehensive data on emission sources, chemical characteristics and optical properties of carbonaceous aerosols from selected urban sites in the Indo-Gangetic Plain (IGP) and from a high-altitude location in the central Himalaya. The mass concentrations of OC, EC and WSOC exhibit large spatio-temporal variability in the IGP. This is attributed to seasonally varying emissions from post-harvest agricultural-waste burning, their source strength, boundary layer dynamics and secondary aerosol formation. The high concentrations of OC and SO4(2-), and their characteristic high mass scattering efficiency, contribute significantly to the aerosol optical depth and scattering coefficient. This has implications to the assessment of single scattering albedo and aerosol radiative forcing on a regional scale. PMID:25199599

  4. Anticorrosion properties of tin oxide coatings for carbonaceous bipolar plates of proton exchange membrane fuel cells

    Science.gov (United States)

    Kinumoto, Taro; Nagano, Keita; Yamamoto, Yuji; Tsumura, Tomoki; Toyoda, Masahiro

    2014-03-01

    An anticorrosive surface treatment of a carbonaceous bipolar plate used in proton exchange membrane fuel cells (PEMFCs) was demonstrated by addition of a tin oxide surface coating by liquid phase deposition (LPD), and its effectiveness toward corrosion prevention was determined. The tin oxide coating was deposited by immersion in tin fluoride and boric acid solutions, without any observable decrease in the bipolar plate electrical conductivity. Anticorrosion properties of a flat carbonaceous bipolar plate were investigated in an aqueous HClO4 electrolyte solution (10 μmol dm-3) at 80 °C. CO2 release due to corrosion was significant for the bare specimen above 1.3 V, whereas no CO2 release was noted for the tin-oxide-coated specimen, even approaching 1.5 V. Moreover, minimal changes in contact angle against a water droplet before and after treatment indicated suppressed corrosion of the surface-coated specimen. Anticorrosion properties were also confirmed for a model bipolar plate having four gas flow channels. The tin oxide layer remained on the channel surfaces (inner walls, corners and intersections) after durability tests. Based on these results, tin-oxide-based surface coatings fabricated by LPD show promise as an anticorrosion technique for carbonaceous bipolar plates for PEMFCs.

  5. Bulk Chemical Composition of the Ningqiang Carbonaceous Chondrite:An Issue of Classification

    Institute of Scientific and Technical Information of China (English)

    WANG Guiqin; LIN Yangting

    2007-01-01

    The Ningqiang meteorite is a fall carbonaceous chondrite, containing various Ca-, Al-rich inclusions that usually escaped from secondary events such as high-temperature heating and lowtemperature alteration. However, it has not yet been classified into any known chemical group. In order to address this issue, 41 elements of the bulk Ningqiang meteorite were analyzed using inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma atom emission spectrometry (ICP-AES) in this study. The Allende (CV3) carbonaceous chondrite and the Jilin (H5)ordinary chondrite were also measured as references, and our analyses are consistent with the previous results. Rare earth and other refractory lithophile elements are depleted in Ningqiang relative to both Allende and mean CK chondrites. In addition, the REE pattern of Ningqiang is nearly flat, while that of Allende shows slight enrichment of LREE relative to HREE. Siderophile elements of Ningqiang are close to those of mean CK chondrites, but lower than those of Allende. Our new analyses indicate that Ningqiang cannot be classified into any known group of carbonaceous chondrites, consistent with previous reports.

  6. Preparation of carbonaceous adsorbents from sewage sludge by chemical activation process - application to air and water treatments

    Energy Technology Data Exchange (ETDEWEB)

    Rio, S.; Le Coq, L.; Faur-Brasquet, C.; Le Cloirec, P. [Ecole des Mines de Nantes (UMR CNRS 6144 GEPEA), 44 - Nantes (France)

    2004-07-01

    Wastewater treatment plants produce considerable amounts of liquid waste material called sewage sludge. In France, sewage sludge production is about 950,000 tons of dried matter per year. The traditional ways of sludge valorization include farmland application, landfill and incineration. But, with some traditional disposal ways coming under pressure like farmland applications and others being phased out like landfill, it is necessary to seek cost - effective and innovative solutions to sewage sludge disposal problem. Today, one promising approach for production of cheap and efficient carbonaceous sorbent is the use of sewage sludge. This study aims to investigate the effect of sulfuric acid activation conditions on physico-chemical and adsorptive properties of the carbonaceous sorbents made from viscous liquid sludge collected at municipal wastewater treatment plant of Nantes, in France. Chemical activation by sulfuric acid is carried out using an impregnation method. Dried viscous liquid sludge is mixed with H{sub 2}SO{sub 4} solutions for 6 h. The resulting mixture is filtered and dried at 105 C. Then, impregnated sludge is activated in a horizontal furnace under nitrogen atmosphere. The effects of impregnation ratio (0.5 - 1.5 gH{sub 2}SO{sub 4}g{sup -1} sludge), temperature (600-800 C) and time (60-180 minutes) are studied using experimental design methodology. The physico-chemical properties of the resulting sorbents are determined using various characterization techniques: - Elemental analysis, determination of surface functional groups by the Boehm method, surface pH measurement and Point of Zero Charge (pH{sub pzc}) enable a complete characterization of the surface chemistry, - BET analyzer allows specific surface area and the meso-porosity and micro-porosity to be determined. Finally, Adsorption properties are determined during copper ion, dyes (Acid Red 18 and Basic Violet 4) and phenol removal experiments in aqueous solution as well as VOC in gas phase

  7. Performance of Halogen-Free Flame Retardant Cable and Extrusion Process%试析无卤低烟阻燃电缆性能与挤出工艺

    Institute of Scientific and Technical Information of China (English)

    王冬梅

    2013-01-01

    近年来,我国经济发展迅猛,电缆材料的阻燃技术也随之提高,无卤低烟阻燃将成为电缆行业主要的发展趋势。本文分析了无卤低烟阻燃电缆的结构与性能,阐述了这种电缆在生产过程中使用的挤制工艺。%In recent years, China's economy is rapidly developing, and the flame retardant technology of cable material is also increased. Halogen-free flame retardant will become the major trends in the cable industry. This paper analyzes the structure and property of the halogen-free flame retardant cable, and elaborates the extrusion process of the cable in the production process.

  8. Effects of halide ions on photodegradation of sulfonamide antibiotics: Formation of halogenated intermediates.

    Science.gov (United States)

    Li, Yingjie; Qiao, Xianliang; Zhang, Ya-Nan; Zhou, Chengzhi; Xie, Huaijun; Chen, Jingwen

    2016-10-01

    The occurrence of sulfonamide antibiotics (SAs) in estuarine waters urges insights into their environmental fate for ecological risk assessment. Although many studies focused on the photochemical behavior of SAs, yet the effects of halide ions relevant to estuarine and marine environments on their photodegradation have been poorly understood. Here, we investigated the effects of halide ions on the photodegradation of SAs with sulfapyridine, sulfamethazine, and sulfamethoxazole as representative compounds. Results showed that halide ions did not significantly impact the photodegradation of sulfapyridine and sulfamethoxazole, while they significantly promoted the photodegradation of sulfamethazine. Further experiments found that ionic strength applied with NaClO4 significantly enhanced the photodegradation of the SAs, which was attributed to the decreased quenching rate constant of the triplet-excited SAs ((3)SA(∗)). Compared with ionic strength, specific Cl(-) effects retarded the photodegradation of the SAs. Our study found that triplet-excited sulfamethazine can oxidize halide ions to produce halogen radicals, subsequently leading to the halogenation of sulfamethazine, which was confirmed by the identification of both chlorinated and brominated intermediates. These results indicate that halide ions play an important role in the photochemical behavior of some SAs in estuarine waters and seawater. The occurrence of halogenation for certain organic pollutants can be predicted by comparing the oxidation potentials of triplet-excited contaminants with those of halogen radicals. Our findings are helpful in understanding the photochemical behavior and assessing the ecological risks of SAs and other organic pollutants in estuarine and marine environment. PMID:27393965

  9. Modified Toepler pump for small-scale halogen-deuterium exchange reactions

    Energy Technology Data Exchange (ETDEWEB)

    Bindal, R.D.

    1987-04-06

    A modified version of the Toepler pump/microhydrogenator apparatus for the preparation of tritium labelled oestrogenic compounds using deuterium gas for halogen-tritium exchange, is described. The modifications allow the transferred gas to maintain atmospheric pressure during the course of the reaction and it allows small volumes of gas uptake to be followed. (U.K.).

  10. Synthesis of 4-Halogenated 3-Fluoro-6-methoxyquinolines: Key Building Blocks for the Synthesis of Antibiotics

    DEFF Research Database (Denmark)

    Flagstad, Thomas; Petersen, Mette Terp; Hinnerfeldt, Daniel Michael;

    2014-01-01

    A practical and scalable 4-step route is presented for the synthesis of 4-bromo-3-fluoro-6-methoxyoquinoline and 3-fluoro-4-iodo-6-methoxyoquinoline from readily available 2,4-dichloro-3-fluoroquinoline with an overall yield of 81-85%. Halogenated quinoline building blocks have found much use in ...

  11. 21 CFR 700.15 - Use of certain halogenated salicylanilides as ingredients in cosmetic products.

    Science.gov (United States)

    2010-04-01

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

  12. Electronic structures of halogen-doped Cu2O based on DFT calculations

    Science.gov (United States)

    Zhao, Zong-Yan; Yi, Juan; Zhou, Da-Cheng

    2014-01-01

    In order to construct p—n homojunction of Cu2O-based thin film solar cells that may increase its conversion efficiency, to synthesize n-type Cu2O with high conductivity is extremely crucial, and considered as a challenge in the near future. The doping effects of halogen on electronic structure of Cu2O have been investigated by density function theory calculations in the present work. Halogen dopants form donor levels below the bottom of conduction band through gaining or losing electrons, suggesting that halogen doping could make Cu2O have n-type conductivity. The lattice distortion, the impurity formation energy, the position, and the band width of donor level of Cu2O1-xHx (H = F, Cl, Br, I) increase with the halogen atomic number. Based on the calculated results, chlorine doping is an effective n-type dopant for Cu2O, owing to the lower impurity formation energy and suitable donor level.

  13. Free Radical Halogenation, Selectivity, and Thermodynamics: The Polanyi Principle and Hammond's Postulate

    Science.gov (United States)

    Scala, Alfred A.

    2004-01-01

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

  14. Vertical Structure and Vertical Evolution of Halogen Activation Events Observed by Autonomous Buoys

    Science.gov (United States)

    Simpson, W. R.; Peterson, P.; Burd, J.

    2015-12-01

    Heterogeneous reactions on saline surfaces release reactive halogen species in the Arctic during late winter / spring (Feb--May). These reactive halogens drastically alter the photooxidative environment, removing ozone and oxidizing mercury and hydrocarbons. Both the snowpack and suspended particles / blowing snow possess surfaces that can sustain this chemistry, leading to variations in reactive halogen vertical profiles and temporal evolution of those profiles. This chemistry also occurs in a typically stable (inverted) atmospheric structure that hinders vertical mixing, limiting the vertical extent of snowpack influence. In this presentation, Multiple-AXis Differential Optical Absorption Spectroscopy (MAXDOAS) of bromine monoxide (BrO) along with optimal estimation inversions are used to measure the vertical structure of BrO. The effective mixing height of the BrO layer varies with atmospheric stability, and an event is shown where a shallow but highly concentrated layer of surface BrO encounters sea-ice-lead-induced convection that vertically mixes the BrO higher, initially diluting the surface concentration. Over time, the surface concentration recovers and the now thicker layer grows to a higher column density of BrO. Understanding of the relationship between BrO event intensity and meteorological situations can help to understand BrO chemistry and remote sensing and assist in prediction of how reactive halogens may respond to a changing Arctic climate.

  15. Actinic-radiation curable polymers prepared from a reactive polymer, halogenated cyclic anhydride and glycidyl ester

    International Nuclear Information System (INIS)

    A novel class of photosensitive polymers are disclosed which are prepared by the reaction, preferably in the presence of a catalyst, of a reactive polymer, a halogenated cyclic anhydride and glycidyl ester of an alpha, beta-unsaturated carboxylic acid. These polymers are capable of undergoing vinyl-type polymerization when exposed to actinic radiation

  16. Stability, defect and electronic properties of graphane-like carbon-halogen compounds

    Institute of Scientific and Technical Information of China (English)

    Lu Di; Yang Yu-Rong; Xiao Yang; Zhang Xiao-Yu

    2011-01-01

    We perform first-principles total energy calculations to investigate the stabilities and the electronic structures of graphane-like structures of carbon-halogen compounds,where the hydrogen atoms in the graphane are substituted by halogen atoms.Three halogen elements,fluorine (F),chlorine (Cl) and bromine (Br),are considered,and the graphanelike structures are named as CF,CCl and CBr,respectively.It is found that for the single-atom adsorption,only the F adatom can be chemically adsorbed on the graphene.However,the stable graphane-like structures of CF,CCl and CBr can form due to the interaction between the halogen atoms.The carbon atoms in the stable CF,CCl and CBr compounds are in the sp3 hybridization,forming a hexagonal network similar to the graphane.The electronic band calculations show that CF and CCl are semiconductors with band gaps of 3.28 eV and 1.66 eV,respectively,while CBr is a metal.Moreover,the molecular dynamics simulation is employed to clarify the stabilities of CF and CCl.Those two compounds are stable at room temperature.A high temperature (≥ 1200 K) is needed to damage CF,while CCl is destroyed at 700 K.Furthermore,the effects of a vacancy on the structure and the electronic property of CF are discussed.

  17. Sources of Halogen Oxides Along the Coastline of New Zealand: A Field Measurement Study

    Science.gov (United States)

    Martínez-Avilés, Mónica; Kreher, Karin; Johnston, Paul; Thomas, Alan; Hay, Tim; Schofield, Robyn; Kenntner, Mareike

    2010-05-01

    The 2006 WMO/UNEP Scientific Assessment of Ozone Depletion identified halogenated very short-lived substances (VSLS) as contributors to the atmospheric budget of halogens. As well, it raised a question regarding the extent of the contribution of halogenated VSLS to atmospheric Bry and Iy. Traditionally, scientists have been more concerned in determining the anthropogenic budget of halogenated compounds while nature is the major producer of such species. In order to have a complete atmospheric budget of halogenated VSLS, it is important to have a better understanding of what species are biogenically produced as well as their respective degradation pathways. Oceanic emissions of halocarbons may be a new link between climate change and the composition of the global atmosphere. The rates of halocarbon emissions are sensitive to sea-surface temperatures (SSTs), nutrient supply and upwelling; all of which are to be affected by climate change. Therefore, increases in SSTs will increase emission rates. On the one hand, seaweed has been identified as a major producer of biogenic polyhalogenated VSLS. Marine macroalgae (kelp) and phytoplankton emit halogen containing gases into the marine boundary layer, constituting 90 to 95% of the total global flux of volatile halocarbons to the atmosphere. On the other hand, the possibility of industrial scale marine kelp farming as a means of carbon sequestration (i.e. marine analogy of the Kyoto Protocol forest) is being pondered by countries with long coastlines and little land suitable for forestation. Would a Kyoto Protocol forest analog be the right strategy for climate change mitigation? With the use of a portable Multi Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) spectrometer, studies have been performed in the coast of New Zealand in order to determine the presence of BrO and IO during the spring and summer months of the Southern Hemisphere. MAX-DOAS uses scattered sunlight received from multiple viewing

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

    Science.gov (United States)

    Ofner, Johannes; Zetzsch, Cornelius

    2013-04-01

    Reactive halogen species (RHS) are released to the atmosphere from various sources like photo-activated sea-salt aerosol and salt lakes. Recent studies (Cai et al., 2006 and 2008, Ofner et al., 2012) indicate that RHS are able to interact with SOA precursors similarly to common atmospheric oxidizing gases like OH radicals and ozone. The reaction of RHS with SOA precursors like terpenes forms so-called halogen-induced organic aerosol (XOA). On the other hand, RHS are also able to change the composition of functional groups, e.g. to initiate the decarboxylation of carboxylic acids (Ofner et al., 2012). The present study uses a 50 cm aerosol flow-reactor, equipped with a solar simulator to investigate the time-resolved evolution and transformation of vibrational features in the mid-infrared region. The aerosol flow-reactor is coupled to a home-made multi-reflection cell (Ofner et al., 2010), integrated into a Bruker IFS 113v FTIR spectrometer. The reactor is operated with an inlet feed (organic compound) and a surrounding feed (reactive halogen species). The moveable inlet of the flow reactor allows us to vary reaction times between a few seconds and up to about 3 minutes. Saturated vapours of different SOA precursors and carboxylic acids were fed into the flow reactor using the moveable inlet. The surrounding feed inside the flow reactor was a mixture of zero air with molecular chlorine as the precursor for the formation of reactive halogen species. Using this setup, the formation of halogen-induced organic aerosol could be monitored with a high time resolution using FTIR spectroscopy. XOA formation is characterized by hydrogen-atom abstraction, carbon-chlorine bond formation and later, even formation of carboxylic acids. Several changes of the entire structure of the organic precursor, caused by the reaction of RHS, are visible. While XOA formation is a very fast process, the decarboxylation of carboxylic acids, induced by RHS is rather slow. However, XOA formation

  19. Comets as Parent Bodies of CI1 Carbonaceous Meteorites and Possible Habitats of Ice-Microbiota

    Science.gov (United States)

    Wickramasinghe, N. Chandra; Wallis, Daryl H.; Rozanov, Alexei Yu.; Hoover, Richard B.

    2011-01-01

    Recent studies of comets and cometary dust have confirmed the presence of biologically relevant organic molecules along with clay minerals and water ice. It is also now well established by deuterium/hydrogen ratios that the CI1 carbonaceous meteorites contain indigenous extraterrestrial water. The evidence of extensive aqueous alteration of the minerals in these meteorites led to the hypothesis that water-bearing asteroids or comets represent the parent bodies of the CI1 (and perhaps CM2) carbonaceous meteorites. These meteorites have also been shown to possess a diverse array of complex organics and chiral and morphological biomarkers. Stable isotope studies by numerous independent investigators have conclusively established that the complex organics found in these meteorites are both indigenous and extraterrestrial in nature. Although the origin of these organics is still unknown, some researchers have suggested that they originated by unknown abiotic mechanisms and may have played a role in the delivery of chiral biomolecules and the origin of life on Early Earth. In this paper we review these results and investigate the thermal history of comets. We show that permanent as well as transient domains of liquid water can be maintained on a comet under a plausible set of assumptions. With each perihelion passage of a comet volatiles are preferentially released, and during millions of such passages the comet could shed crustal debris that may survive transit through the Earth s atmosphere as a carbonaceous meteorite. We review the current state of knowledge of comets and carbonaceous meteorites. We also present the results of recent studies on the long-term viability of terrestrial ice-microbiota encased in ancient glacial ice and permafrost. We suggest that the conditions which have been observed to prevail on many comets do not preclude either survivability (or even the active metabolism and growth) of many types of eukaryotic and prokaryotic microbial

  20. Spectro-microscopic measurements of carbonaceous aerosol aging in Central California

    Directory of Open Access Journals (Sweden)

    R. C. Moffet

    2013-10-01

    Full Text Available Carbonaceous aerosols are responsible for large uncertainties in climate models, degraded visibility, and adverse health effects. The Carbonaceous Aerosols and Radiative Effects Study (CARES was designed to study carbonaceous aerosols in the natural environment of the Central Valley, California, and learn more about their atmospheric formation and aging. This paper presents results from spectro-microscopic measurements of carbonaceous particles collected during CARES at the time of a pollution accumulation event (27–29 June 2010, when in situ measurements indicated an increase in the organic carbon content of aerosols as the Sacramento urban plume aged. Computer-controlled scanning electron microscopy coupled with an energy dispersive X-ray detector (CCSEM/EDX and scanning transmission X-ray microscopy coupled with near-edge X-ray absorption spectroscopy (STXM/NEXAFS were used to probe the chemical composition and morphology of individual particles. It was found that the mass of organic carbon on individual particles increased through condensation of secondary organic aerosol. STXM/NEXAFS indicated that the number fraction of homogenous organic particles lacking inorganic inclusions (greater than ~50 nm equivalent circular diameter increased with plume age, as did the organic mass per particle. Comparison of the CARES spectro-microscopic dataset with a similar dataset obtained in Mexico City during the MILAGRO campaign showed that fresh particles in Mexico City contained three times as much carbon as those sampled during CARES. The number fraction of soot particles at the Mexico City urban site (ranging from 16.6 to 47.3% was larger than at the CARES urban site (13.4–15.7%, and the most aged samples from CARES contained fewer carbon–carbon double bonds. Differences between carbonaceous particles in Mexico City and California result from different sources, photochemical conditions, gas phase reactants, and secondary organic aerosol

  1. Controllable Orientation of Ester-Group-Induced Intermolecular Halogen Bonding in a 2D Self-Assembly.

    Science.gov (United States)

    Zha, Bao; Dong, Meiqiu; Miao, Xinrui; Miao, Kai; Hu, Yi; Wu, Yican; Xu, Li; Deng, Wenli

    2016-08-18

    Halogen bonding with high specificity and directionality in the geometry has proven to be an important type of noncovalent interaction to fabricate and control 2D molecular architectures on surfaces. Herein, we first report how the orientation of the ester substituent for thienophenanthrene derivatives (5,10-DBTD and 5,10-DITD) affects positive charge distribution of halogens by density functional theory, thus determining the formation of an intermolecular halogen bond and different self-assembled patterns by scanning tunneling microscopy. The system presented here mainly includes heterohalogen X···O═C and X···S halogen bonds, H···Br and H···O hydrogen bonds, and I···I interaction, where the directionality and strength of such weak bonds determine the molecular arrangement by varying the halogen substituent. This study provides a detailed understanding of the role of ester orientation, concentration, and solvent effects on the formation of halogen bonds and proves relevant for identification of multiple halogen bonding in supramolecular chemistry. PMID:27482936

  2. Carbonaceous residues from biomass gasification as catalysts for biodiesel production

    Institute of Scientific and Technical Information of China (English)

    Rafael Luque; Antonio Pineda; Juan C. Colmenares; Juan M. Campelo; Antonio A. Romero; Juan Carlos Serrano-Ruiz; Luisa F. Cabeza; Jaime Cot-Gores

    2012-01-01

    Tars and alkali ashes from biomass gasification processes currently constitute one of the major problems in biomass valorisation,generating clogging of filters and issues related with the purity of syngas production.To date,these waste residues find no useful applications and they are generally disposed upon generation in the gasification process.A detailed analysis of these residues pointed out the presence of high quantities of Ca (>30 wt%).TG experiments indicated that a treatment under air at moderate temperatures (400-800 ℃) decomposed the majority of carbon species,while XRD indicated the presence of a crystalline CaO phase.CaO enriched valorized materials turned out to be good heterogeneous catalysts for biodiesel production from vegetable oils,providing moderate to good activities (50%-70% after 12 h) to fatty acid methyl esters in the transesterification of sunflower oil with methanol.

  3. Predictive Models for Halogen-bond Basicity of Binding Sites of Polyfunctional Molecules.

    Science.gov (United States)

    Glavatskikh, Marta; Madzhidov, Timur; Solov'ev, Vitaly; Marcou, Gilles; Horvath, Dragos; Graton, Jérôme; Le Questel, Jean-Yves; Varnek, Alexandre

    2016-02-01

    Halogen bonding (XB) strength assesses the ability of an electron-enriched group to be involved in complexes with polarizable electrophilic halogenated or diatomic halogen molecules. Here, we report QSPR models of XB of particular relevance for an efficient screening of large sets of compounds. The basicity is described by pKBI2 , the decimal logarithm of the experimental 1 : 1 (B : I2 ) complexation constant K of organic compounds (B) with diiodine (I2 ) as a reference halogen-bond donor in alkanes at 298 K. Modeling involved ISIDA fragment descriptors, using SVM and MLR methods on a set of 598 organic compounds. Developed models were then challenged to make predictions for an external test set of 11 polyfunctional compounds for which unambiguous assignment of the measured effective complexation constant to specific groups out of the putative acceptor sites is not granted. At this stage, developed models were used to predict pKBI2 of all putative acceptor sites, followed by an estimation of the predicted effective complexation constant using the ChemEqui program. The best consensus models perform well both in cross-validation (root mean squared error RMSE=0.39-0.47 logKBI2 units) and external predictions (RMSE=0.49). The SVM models are implemented on our website (http://infochim.u-strasbg.fr/webserv/VSEngine.html) together with the estimation of their applicability domain and an automatic detection of potential halogen-bond acceptor atoms. PMID:27491792

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

    Directory of Open Access Journals (Sweden)

    R. A. Salmon

    2010-11-01

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

  5. Computational insights into the photocyclization of diclofenac in solution: effects of halogen and hydrogen bonding.

    Science.gov (United States)

    Bani-Yaseen, Abdulilah Dawoud

    2016-08-21

    The effects of noncovalent interactions, namely halogen and hydrogen bonding, on the photochemical conversion of the photosensitizing drug diclofenac (DCF) in solution were investigated computationally. Both explicit and implicit solvent effects were qualitatively and quantitatively assessed employing the DFT/6-31+G(d) and SQM(PM7) levels of theory. Full geometry optimizations were performed in solution for the reactant DCF, hypothesized radical-based intermediates, and the main product at both levels of theories. Notably, in good agreement with previous experimental results concerning the intermolecular halogen bonding of DCF, the SQM(PM7) method revealed different values for d(ClO, Å) and ∠(C-ClO, °) for the two chlorine-substituents of DCF, with values of 2.63 Å/162° and 3.13 Å/142° for the trans and cis orientations, respectively. Employing the DFT/6-31+G(d) method with implicit solvent effects was not conclusive; however, explicit solvent effects confirmed the key contribution of hydrogen and halogen bonding in stabilizing/destabilizing the reactant and hypothesized intermediates. Interestingly, the obtained results revealed that a protic solvent such as water can increase the rate of photocyclization of DCF not only through hydrogen bonding effects, but also through halogen bonding. Furthermore, the atomic charges of atoms majorly involved in the photocyclization of DCF were calculated using different methods, namely Mulliken, Hirshfeld, and natural bond orbital (NBO). The obtained results revealed that in all cases there is a notable nonequivalency in the noncovalent intermolecular interactions of the two chlorine substituents of DCF and the radical intermediates with the solvent, which in turn may account for the discrepancy of their reactivity in different media. These computational results provide insight into the importance of halogen and hydrogen bonding throughout the progression of the photochemical conversion of DCF in solution. PMID:27424600

  6. Characteristics of a σ-Hole and the Nature of a Halogen Bond.

    Science.gov (United States)

    Kolář, Michal H; Deepa, Palanisamy; Ajani, Haresh; Pecina, Adam; Hobza, Pavel

    2015-01-01

    The nature of halogen bonding in 128 complexes was investigated using advanced quantum mechanical calculations. First, isolated halogen donors were studied and their σ-holes were described in terms of size and magnitude. Later, both partners in the complex were considered and their interaction was described in terms of DFT-SAPT decomposition. The whole set of complexes under study was split into two categories on the basis of their stabilisation energy. The first subset with 38 complexes possesses stabilisation energies in the range 7-32 kcal/mol, while the second subset with 90 complexes has stabilisation energies smaller than 7 kcal/mol. The first subset is characterised by small intermolecular distances (less than 2.5 Å) and a significant contraction of van der Waals (vdW) distance (sum of vdW radii). Here the polarisation/electrostatic energy is dominant, mostly followed by induction and dispersion energies. The importance of induction energy reflects the charge-transfer character of the respective halogen bonds. Intermolecular distances in the second subset are large and the respective contraction of vdW distance upon the formation of a halogen bond is much smaller. Here the dispersion energy is mostly dominant, followed by polarisation and induction energies. Considering the whole set of complexes, we conclude that the characteristic features of their halogen bonds arise from the concerted action of polarisation and dispersion energies and neither of these energies can be considered as dominant. Finally, the magnitude of the σ-hole and DFT-SAPT stabilisation energy correlates only weakly within the whole set of complexes. PMID:25791483

  7. Theoretical study on O$\\cdots$Br and O$\\cdots$Cl halogen bonds in some small model molecular systems

    Indian Academy of Sciences (India)

    Damanjit Kaur; Rajinder Kaur

    2014-11-01

    Halogen bonding interactions of type X$\\cdots$O=C are important in various fields including biological systems. In this work, theoretical calculations were carried out using B3LYP/6-31++G∗∗, MP2/6-31++G∗∗ and MP2/aug-cc-pVDZ methods on a series of O$\\cdots$X halogen bonds between CH2O andCH3CHO as halogen bond acceptor with X-Y (X = Cl, Br; Y = CF3, CF2 H, CFH2, CN, CCH, CCCN) as halogen bond donors. The strength of interaction energy for O$\\cdots$Br halogen-bonded complexes varies from −2.16 to −5.26 kcal/mol while for O$\\cdots$Cl complexes, it is between −1.65 to −3.67 kcal/mol, which indicate the O$\\cdots$Br bond to be stronger in comparison to O$\\cdots$Cl bond. SAPT analysis suggests that the strength of halogen bonding arises from the electrostatic and induction forces while dispersion is playing a comparatively smaller role. The halogen-bonded interaction energies were found to correlate well with positive electrostatic potential VS,max, halogen bonded distances, and the change in s-character of C-X bond. The halogen-bonded interaction energies were also evaluated for O$\\cdots$I bonded complexes and thus these complexes were found to be stronger than O$\\cdots$Br and O$\\cdots$Cl bonded complexes.

  8. The appearance of Carbonaceous Chondrites on (1) Ceres from observations by the Dawn Framing Camera

    Science.gov (United States)

    Schäfer, Tanja; Schäfer, Michael; Mengel, Kurt; Cloutis, Edward A.; Izawa, Matthew R. M.; Thangjam, Guneshwar; Hoffmann, Martin; Platz, Thomas; Nathues, Andreas; Kallisch, Jan; Ripken, Joachim; Russel, Christopher T.

    2016-04-01

    NASA's Dawn spacecraft reached dwarf planet Ceres in March 2015 and started data acquisition using three different instruments. These are the Framing Camera (FC; [1]), the Visible & Infrared Spectrometer (VIR; [2]), and the Gamma Ray and Neutron Detector (GRaND; [3]). In our work we focus on the potential appearance of carbonaceous chondritic (CC) material on the cerean surface using Dawn FC color mosaics covering the VIS/NIR wavelength region. In preparation of the Dawn arrival at Ceres, a discrimination scheme for CC groups using FC color ratios was developed by [4] and is based on 121 CC laboratory spectra compiled from RELAB. As the cerean surface material mainly differs by its spectral slope over the whole FC wavelength range (0.44-0.97 μm), we classified the color mosaics by this parameter. We applied the CC discrimination scheme only to those regions on the cerean surface (more than 90 %) which exhibit spectral slopes ≥ -1 % reflectance per μm to exclude the strongly negative sloped regions of large young craters such as Occator, Haulani, and Oxo. These are not likely to be similar to pure CC material as can be seen by their brightness and their bluish spectral slope [5]. We found that the surface material of Ceres is, among the suite of CCs, most similar to Ivuna samples artificially heated to 200 and 300°C [6] and unusual CCs, which naturally experienced heating. The latter ones comprise Dhofar 225, Y-86789 and Y-82162, which have been determined to have undergone aqueous alteration and subsequent thermal metamorphism (e.g. [7,8]).Our comparison with VIR data shows, that the spectra of Ivuna heated to 200°C and 300°C match well the OH-absorption at 2.7 μm but do not show the smaller 3.05-3.1 μm absorption observed on Ceres [9,10,11]. Nevertheless, the remarkably flat UV drop-off detected on the cerean surface may, at least spectrally, correspond to highly aqueously altered and subsequently thermally metamorphosed CC material. Further alteration of

  9. Halogen effect on structure and 13C NMR chemical shift of 3,6-disubstituted-N-alkyl carbazoles

    DEFF Research Database (Denmark)

    Radula-Janik, Klaudia; Kupka, Teobald; Ejsmont, Krzysztof;

    2013-01-01

    ). The decreasing electronegativity of the halogen substituent (F, Cl, Br and I) was reflected in both nonrelativistic and relativistic NMR results as decreased values of chemical shifts of carbon atoms attached to halogen (C3 and C6) leading to a strong sensitivity to halogen atom type at 3 and 6 positions....... The relativistic effect of Br and I atoms on nuclear shieldings was modeled using the spin-orbit ZORA method. Significant heavy atom shielding effects for the carbon atom directly bonded with bromine and iodine were observed (~ -10 and ~ -30 ppm while the other carbon shifts were practically unaffected...

  10. Light scattering by clouds of cosmic dust analogues with carbonaceous compounds (PROGRA2 experiment)

    Science.gov (United States)

    Hadamcik, Edith; Renard, Jean-Baptiste; Levasseur-Regourd, Anny-Chantal; Lasue, Jeremie

    Carbonaceous compounds are found in numerous clouds of solid particles in the Solar System (e.g. Cometary comae, Interplanetary dust, Titan's aerosols). Fluffy aggregates of submicron sized grains and more compact particles up to some tens of micrometers were present in the particles captured by the Stardust mission in the coma of comet 81P/Wild 2 [1]. Complex organic refractories were found in the particles together with silicates [2,3], while CHON particles were detected by mass spectrometer, as previously by Vega 1 and Giotto at 1P/Halley [4,5]. Titan's aerosols are complex organics (CxNyHz) and their light scattering properties can only be interpreted if they present a fluffy aggregates structure [6]. The light scattered by the dust particles is partially linearly polarized with a polarization degree depending on the physical properties of the dust and on the geometry (phase angle) and wavelength of observations [7]. Laboratory scattering measurements with the PROGRA2 experiment [8] (in A300- CNES and ESA dedicated microgravity flights or on ground for low density particles) offer an alternative to simulate the scattering properties of real particles particularly for structures too large or too complex to be handled easily by numerical simulations. Experimental simulations have been performed on numerous samples underlying the characteristics of the polarimetric phase curves such as maximum and minimum polarization as a function of the properties of the particles (grains and particles size, structure, refractive index) [9,10]. These results were used to interpret variations in polarization in cometary comae [11,12] or in the Titan's atmosphere [13]. In this presentation we emphasize the optical properties due to the presence of organics and C-bearing materials and compare them to the optical properties of more transparent materials included or not in organics. Finally we give some examples of application to the interpretation of Solar System dust observations

  11. EC Transmission Line Materials

    International Nuclear Information System (INIS)

    The purpose of this document is to identify materials acceptable for use in the US ITER Project Office (USIPO)-supplied components for the ITER Electron cyclotron Heating and Current Drive (ECH and CD) transmission lines (TL), PBS-52. The source of material property information for design analysis shall be either the applicable structural code or the ITER Material Properties Handbook. In the case of conflict, the ITER Material Properties Handbook shall take precedence. Materials selection, and use, shall follow the guidelines established in the Materials Assessment Report (MAR). Materials exposed to vacuum shall conform to the ITER Vacuum Handbook. (Ref. 2) Commercial materials shall conform to the applicable standard (e.g., ASTM, JIS, DIN) for the definition of their grade, physical, chemical and electrical properties and related testing. All materials for which a suitable certification from the supplier is not available shall be tested to determine the relevant properties, as part of the procurement. A complete traceability of all the materials including welding materials shall be provided. Halogenated materials (example: insulating materials) shall be forbidden in areas served by the detritiation systems. Exceptions must be approved by the Tritium System and Safety Section Responsible Officers.

  12. EC Transmission Line Materials

    Energy Technology Data Exchange (ETDEWEB)

    Bigelow, Tim S [ORNL

    2012-05-01

    The purpose of this document is to identify materials acceptable for use in the US ITER Project Office (USIPO)-supplied components for the ITER Electron cyclotron Heating and Current Drive (ECH&CD) transmission lines (TL), PBS-52. The source of material property information for design analysis shall be either the applicable structural code or the ITER Material Properties Handbook. In the case of conflict, the ITER Material Properties Handbook shall take precedence. Materials selection, and use, shall follow the guidelines established in the Materials Assessment Report (MAR). Materials exposed to vacuum shall conform to the ITER Vacuum Handbook. [Ref. 2] Commercial materials shall conform to the applicable standard (e.g., ASTM, JIS, DIN) for the definition of their grade, physical, chemical and electrical properties and related testing. All materials for which a suitable certification from the supplier is not available shall be tested to determine the relevant properties, as part of the procurement. A complete traceability of all the materials including welding materials shall be provided. Halogenated materials (example: insulating materials) shall be forbidden in areas served by the detritiation systems. Exceptions must be approved by the Tritium System and Safety Section Responsible Officers.

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

    NARCIS (Netherlands)

    S.L. Waaijers; D Kong; H.S. Hendriks; C.A. de Wit; I.T. Cousins; R.H.S. Westerink; P.E.G. Leonards; M.H.S. Kraak; W. Admiraal; P. de Voogt; J.R. Parsons

    2012-01-01

    Polymers are synthetic organic materials that have a high carbon and hydrogen content, which renders them readily combustible. When used in buildings, electrical appliances, furniture, textiles, transportation, mining, and in many other applications, polymers have to fulfill flame retardancy regulat

  14. High capacity disordered carbons obtained from coconut shells as anode materials for lithium batteries

    International Nuclear Information System (INIS)

    Carbonaceous materials have been obtained by the pyrolysis of coconut shells at 800 and 900 deg. C with pore forming substances such as KOH and ZnCl2. The prepared carbons were subjected to XRD, SEM, BET-surface area and charge-discharge studies. The structure and morphology were greatly changed by porogens, which in turn influence the electrochemical properties of the carbonaceous materials. Nanocrystalline tin (Sn) particles were prepared by chemical reduction method. The cycling tests showed that the addition of nanotin with the active material offers a stable cycling behavior. The electrochemical impedance spectra for the Li/C cells have been made and the results are discussed

  15. Delivery of Organic Material and Water through Asteroid Impacts

    NARCIS (Netherlands)

    Mueller, Michael; Frantseva, Kateryna; van der Tak, Floris; Helmich, Frank P.

    2014-01-01

    Meteorites, specifically carbonaceous chondrites, are frequently invoked as the primary source of Earth's water and organic materials, crucial ingredients for the formation of life. We have started developing a dynamical model of the delivery of their parent bodies, primitive low-albedo asteroids, f

  16. Carbon offers advantages as implant material in human body

    Science.gov (United States)

    Benson, J.

    1969-01-01

    Because of such characteristics as high strength and long-term biocompatability, aerospace carbonaceous materials may be used as surgical implants to correct pathological conditions in the body resulting from disease or injury. Examples of possible medical uses include bone replacement, implantation splints and circulatory bypass implants.

  17. Se···N chalcogen bond and Se···X halogen bond involving F2C═Se: influence of hybridization, substitution, and cooperativity.

    Science.gov (United States)

    Guo, Xin; An, Xiulin; Li, Qingzhong

    2015-04-01

    Quantum-chemical calculations have been performed for the chalcogen- and halogen-bonded complexes of F2CSe with a series of nitrogen bases (N2, NCH, NH3, NHCH2, NCLi, and NMe3) and dihalogen molecules (BrCl, ClF, and BrF), respectively. Both types of interactions are mainly driven by the electrostatic and orbital interactions. The chalcogen bond becomes stronger in the order of NCH (sp) < NH3 (sp(3)) < NHCH2 (sp(2)), showing some inconsistence with the electronegativity of the hybridized N atom. The Li and methyl groups have an enhancing effect on the strength of chalcogen bond; however, the former is jointly achieved through the electrostatic and orbital interactions, whereas the orbital interaction has dominant contribution to the latter enhancement. The halogen bond with F2CX (X = O, S, Se) as the electron donor is stronger for the heavier chalcogen atom, exhibiting a reverse dependence on the chalcogen atom with that in hydrogen bonds. The halogen bond is further strengthened by the presence of chalcogen bond in the ternary complexes. In addition, CSD research confirms the abundance of Se···N interaction in crystal materials. PMID:25797149

  18. Results of core drilling for uranium-bearing carbonaceous shale and lignite in the Goose Creek district, Cassia County, Idaho

    Science.gov (United States)

    Mapel, William J.; Hail, William J.

    1954-01-01

    Thirteen core holes, totaling 2,023 feet, were drilled during the fall of 1953 to explore the grade and extent of uranium-bearing beds of carbonaceous shale and lignite in the east-central part of the Goose Creek district, Cassia County, Idaho. The beds tested are interbedded with volcanic ash, bentonite, greenish-gray shale, sandstone, and conglomerate in two fairly well defined zones in the lower part of the Salt Lake formation of lower Pliocene age. Nine holes penetrated carbonaceous shale beds in the Barrett zone, and one hole penetrated carbonaceous shale and lignite beds in zone B, 160 feet stratigraphically below the Barrett zone. The highest concentration of uranium found by drilling is 0.10 percent in the upper part of a 4-foot bed of carbonaceous shale and lignite in zone B. The grade of carbonaceous shale beds in the Barrett zone ranges from 0.044 percent to less than 0.003 percent uranium. Inferred reserves in the district are estimated to be 790,000 tons in beds 1 foot or more thick containing an average of 0.014 percent or 120 tons of uranium.

  19. A Modeling Study of the Effects of Direct Radiative Forcing Due to Carbonaceous Aerosol on the Climate in East Asia

    Institute of Scientific and Technical Information of China (English)

    ZHANG Hua; WANG Zhili; GUO Pinwen; WANG Zaizhi

    2009-01-01

    The study investigated the effects of global direct radiative forcing due to carbonaceous aerosol on the climate in East Asia, using the CAM3 developed by NCAR. The results showed that carbonaceous aerosols cause negative forcing at the top of the atmosphere (TOA) and surface under clear sky conditions, but positive forcing at the TOA and weak negative forcing at the surface under all sky conditions. Hence, clouds could change the sign of the direct radiative forcing at the TOA, and weaken the forcing at the surface. Carbonaceous aerosols have distinct effects on the summer climate in East Asia. In southern China and India, it caused the surface temperature to increase, but the total cloud cover and precipitation to decrease. However, the opposite effects are caused for most of northern China and Bangladesh. Given the changes in temperature, vertical velocity, and surface streamflow caused by carbonaceous aerosol in this simulation, carbonaceous aerosol could also induce summer precipitation to decrease in southern China but increase in northern China.

  20. Organic halogenated contaminants in mother-fetus pairs of harbor seals (Phoca vitulina richardii) from Alaska, 2000-2002

    Science.gov (United States)

    Environmental stressors may interfere with foraging, survival and reproduction of marine mammals resulting in marine mammal population decline. In this study, organic halogenated pollutants [OHs, including organochlorine pesticides, polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCN...