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Sample records for alkane carbon number

  1. Distributions of C22 C30 even-carbon-number n-alkanes in Ocean Anoxic Event 1 samples from the Basque-Cantabrian Basin

    NASA Astrophysics Data System (ADS)

    Chaler, R.; Dorronsoro, C.; Grimalt, J. O.; Agirrezabala, L. M.; Fernández-Mendiola, P. A.; García-Mondejar, J.; Gómez-Pérez, I.; López-Horgue, M.

    2005-05-01

    The Ocean Anoxic Event 1 (OAE-1) in central sites of the Basque-Cantabrian Basin exhibits very reducing depositional conditions of sedimentation. These sedimentation events have left a distinct mixture of hydrocarbons that are represented by C22 C30 n-alkanes with a predominance of the even-carbon-number homologues, high relative proportions of squalane and C16 C24 n-alkylcyclopentanes predominated by n-undecyl-, n-tridecyl- and n-pentadecylcyclopentane. Other minor compounds encompass a series of C18 C21 n-alkylcyclohexanes and C18 C24 dimethyl n-alkylcyclohexanes maximized by the even-carbon-number homologues as well as iso- and anteiso-alkanes. This unusual distribution of n-alkanes in this environment provides a new case for comparison with previously reported hypersaline and phosphorite sedimentary deposits where the occurrence of similar n-alkane distributions was reported. In the present case, these major n-alkanes and squalane are indicative of transformation under strong reducing conditions. In contrast, the occurrence of the alkylcyclopentanes, irrespective of the presence of even-carbon-number n-alkanes or squalane, suggests that reductive cyclization of fatty acids is less dependent on strong reducing conditions.

  2. A molecular dynamics study of the effect of thermal boundary conductance on thermal transport of ideal crystal of n-alkanes with different number of carbon atoms

    NASA Astrophysics Data System (ADS)

    Rastgarkafshgarkolaei, Rouzbeh; Zeng, Yi; Khodadadi, J. M.

    2016-05-01

    Phase change materials such as n-alkanes that exhibit desirable characteristics such as high latent heat, chemical stability, and negligible supercooling are widely used in thermal energy storage applications. However, n-alkanes have the drawback of low thermal conductivity values. The low thermal conductivity of n-alkanes is linked to formation of randomly oriented nano-domains of molecules in their solid structure that is responsible for excessive phonon scattering at the grain boundaries. Thus, understanding the thermal boundary conductance at the grain boundaries can be crucial for improving the effectiveness of thermal storage systems. The concept of the ideal crystal is proposed in this paper, which describes a simplified model such that all the nano-domains of long-chain n-alkanes are artificially aligned perfectly in one direction. In order to study thermal transport of the ideal crystal of long-chain n-alkanes, four (4) systems (C20H42, C24H50, C26H54, and C30H62) are investigated by the molecular dynamics simulations. Thermal boundary conductance between the layers of ideal crystals is determined using both non-equilibrium molecular dynamics (NEMD) and equilibrium molecular dynamics (EMD) simulations. Both NEMD and EMD simulations exhibit no significant change in thermal conductance with the molecular length. However, the values obtained from the EMD simulations are less than the values from NEMD simulations with the ratio being nearly three (3) in most cases. This difference is due to the nature of EMD simulations where all the phonons are assumed to be in equilibrium at the interface. Thermal conductivity of the n-alkanes in three structures including liquid, solid, and ideal crystal is investigated utilizing NEMD simulations. Our results exhibit a very slight rise in thermal conductivity values as the number of carbon atoms of the chain increases. The key understanding is that thermal transport can be significantly altered by how the molecules and the

  3. The Number of High-Energy Bands in the Photoelectron Spectrum of Alkanes

    NASA Astrophysics Data System (ADS)

    Merris, Russell; Gutman, Ivan

    2000-12-01

    It was observed that within the Bieri-Dill-Heilbronner-Schmelzer model for the calculation of the ion-ization energies of alkanes CnH2n+2, there are exactly n C2s -electron energy levels lying below the degenerate α-ß manifold. We now show that, indeed, this regularity is obeyed by practically all alkane species. Exceptions do exist, but they must possess a (chemically infeasible) group of more than six mutually connected quaternary carbon atoms.

  4. Comparison of bulk and n-alkane PETM carbon isotope trends from the Bighorn Basin, Wyoming

    NASA Astrophysics Data System (ADS)

    Baczynski, A. A.; McInerney, F. A.; Kraus, M. J.; Wing, S.

    2010-12-01

    al. suggest a prolonged and sustained core of the CIE (113 ka) followed by a more rapid initial recovery (33 ka) to near pre-PETM δ13C values. Improving the PETM age model and refining the allocation of time within the event has important implications for understanding the carbon cycle. Carbon isotope values of individual odd-carbon-numbered, long-chain (n-C21-n-C35) n-alkanes extracted from PETM sediments tend to become more negative with increasing chain length within a particular sample. In addition, the magnitude of the negative CIE also tends to increase with increasing n-alkane chain length. Using the empirical observation that δ13C values tend to increase with increasing chain length in conifers while δ13C values decrease with increasing chain length in angiosperms, Smith et al. (2007) has suggested that plant community composition shifted from 50% conifer to an exclusively angiosperm flora at the PETM. The additional n-alkane carbon isotope data presented here is similar to previously published data and supports the plant community change hypothesis suggested by Smith et al. (2007).

  5. Stable hydrogen and carbon isotopic compositions of long-chain (C21-C33) n-alkanes and n-alkenes in insects

    NASA Astrophysics Data System (ADS)

    Chikaraishi, Yoshito; Kaneko, Masanori; Ohkouchi, Naohiko

    2012-10-01

    We report the molecular and stable isotopic (δD and δ13C) compositions of long-chain n-alkanes in common insects including the cabbage butterfly, swallowtail, wasp, hornet, grasshopper, and ladybug. Insect n-alkanes are potential candidates of the contamination of soil and sedimentary n-alkanes that are believed to be derived from vascular plant waxes. Long-chain n-alkanes (range C21-33; maximum C23-C29) are found to be abundant in the insects (31-781 μg/dry g), with a carbon preference index (CPI) of 5.1-31.5 and an average chain length (ACL) of 24.9-29.3. The isotopic compositions (mean ± 1σ, n = 33) of the n-alkanes are -195 ± 16‰ for hydrogen and -30.6 ± 2.4‰ for carbon. The insect n-alkanes are depleted in D by approximately 30-40‰ compared with wax n-alkanes from C3 (-155 ± 25‰) and C4 vascular plants (-167 ± 13‰), whereas their δ13C values fall between those of C3 (-36.2 ± 2.4‰) and C4 plants (-20.3 ± 2.4‰). Thus, the contribution of insect-derived n-alkanes to soil and sediment could potentially shift δD records of n-alkanes toward more negative values and potentially muddle the assumed original C3/C4 balance in the δ13C records of the soil and sedimentary n-alkanes. n-Alkenes are also found in three insects (swallowtail, wasp and hornet). They are more depleted in D relative to the same carbon numbered n-alkanes (δDn-alkene - δDn-alkane = -17 ± 16‰), but the δ13C values are almost identical to those of the n-alkanes (δ13Cn-alkene - δ13Cn-alkane = 0.1 ± 0.2‰). These results suggest that these n-alkenes are desaturated products of the same carbon numbered n-alkanes.

  6. Reprint of "Stable hydrogen and carbon isotopic compositions of long-chain (C21-C33) n-alkanes and n-alkenes in insects"

    NASA Astrophysics Data System (ADS)

    Chikaraishi, Yoshito; Kaneko, Masanori; Ohkouchi, Naohiko

    2013-06-01

    We report the molecular and stable isotopic (δD and δ13C) compositions of long-chain n-alkanes in common insects including the cabbage butterfly, swallowtail, wasp, hornet, grasshopper, and ladybug. Insect n-alkanes are potential candidates of the contamination of soil and sedimentary n-alkanes that are believed to be derived from vascular plant waxes. Long-chain n-alkanes (range C21-33; maximum C23-C29) are found to be abundant in the insects (31-781 μg/dry g), with a carbon preference index (CPI) of 5.1-31.5 and an average chain length (ACL) of 24.9-29.3. The isotopic compositions (mean ± 1σ, n = 33) of the n-alkanes are -195 ± 16‰ for hydrogen and -30.6 ± 2.4‰ for carbon. The insect n-alkanes are depleted in D by approximately 30-40‰ compared with wax n-alkanes from C3 (-155 ± 25‰) and C4 vascular plants (-167 ± 13‰), whereas their δ13C values fall between those of C3 (-36.2 ± 2.4‰) and C4 plants (-20.3 ± 2.4‰). Thus, the contribution of insect-derived n-alkanes to soil and sediment could potentially shift δD records of n-alkanes toward more negative values and potentially muddle the assumed original C3/C4 balance in the δ13C records of the soil and sedimentary n-alkanes. n-Alkenes are also found in three insects (swallowtail, wasp and hornet). They are more depleted in D relative to the same carbon numbered n-alkanes (δDn-alkene - δDn-alkane = -17 ± 16‰), but the δ13C values are almost identical to those of the n-alkanes (δ13Cn-alkene - δ13Cn-alkane = 0.1 ± 0.2‰). These results suggest that these n-alkenes are desaturated products of the same carbon numbered n-alkanes.

  7. Allochthonous carbon hypothesis for bulk OM and n-alkane PETM carbon isotope discrepancies

    NASA Astrophysics Data System (ADS)

    Baczynski, A. A.; McInerney, F. A.; Wing, S. L.; Kraus, M. J.; Fricke, H. C.

    2011-12-01

    The Paleocene-Eocene Thermal Maximum (PETM), a period of abrupt, transient, and large-scale global warming fueled by a large release of isotopically light carbon, is a relevant analogue for episodes of rapid global warming and recovery. The PETM is recorded in pedogenic carbonate, bulk organic matter, and n-alkanes as a prominent negative carbon isotope excursion (CIE) in paleosols exposed in the Bighorn Basin, WY. Here we present a composite stable carbon isotope record from n-alkanes and dispersed soil organic δ13C records from five individual sections that span the PETM in the southeastern Bighorn Basin. Four sections are from a 10km transect in the Cabin Fork area and one section was collected at Sand Creek Divide. These five new dispersed organic carbon (DOC) isotope records are compared to the previously published Polecat Bench (Magioncalda et al. 2004) and Honeycombs (Yans et al. 2006) isotope records. The high-resolution n-alkane curve shows an abrupt, negative shift in δ13C values, an extended CIE body, and a rapid recovery to more positive δ13C values. Although the five DOC records show similarly abrupt negative shifts in δ13C values, the DOC CIEs are compressed, smaller in magnitude, and return to more positive δ13C values more gradually relative to the n-alkane record. Moreover, the stratigraphic thickness of the body of the excursion and the pattern of the recovery phase are not consistent among the five DOC records. We modeled predicted DOC δ13C values from the n-alkane record by applying enrichment factors based on modern plants to the n-alkane δ13C values. The anomaly, difference between the expected and observed DOC δ13C values, was calculated for the PETM records and compared to weight percent carbon and grain size. There is no correlation between pre- and post-PETM anomaly values and grain size or weight percent carbon. PETM anomaly values, however, do trend with both grain size and weight percent carbon. The largest PETM anomaly values

  8. Branched aliphatic alkanes with quaternary substituted carbon atoms in modern and ancient geologic samples

    PubMed Central

    Kenig, Fabien; Simons, Dirk-Jan H.; Crich, David; Cowen, James P.; Ventura, Gregory T.; Rehbein-Khalily, Tatiana; Brown, Todd C.; Anderson, Ken B.

    2003-01-01

    A pseudohomologous series of branched aliphatic alkanes with a quaternary substituted carbon atom (BAQCs, specifically 2,2-dimethylalkanes and 3,3- and 5,5-diethylalkanes) were identified in warm (65°C) deep-sea hydrothermal waters and Late Cretaceous black shales. 5,5-Diethylalkanes were also observed in modern and Holocene marine shelf sediments and in shales spanning the last 800 million years of the geological record. The carbon number distribution of BAQCs indicates a biological origin. These compounds were observed but not identified in previous studies of 2.0 billion- to 2.2 billion-year-old metasediments and were commonly misidentified in other sediment samples, indicating that BAQCs are widespread in the geological record. The source organisms of BAQCs are unknown, but their paleobiogeographic distribution suggests that they have an affinity for sulfides and might be nonphotosynthetic sulfide oxidizers. PMID:14551322

  9. Branched aliphatic alkanes with quaternary substituted carbon atoms in modern and ancient geologic samples.

    PubMed

    Kenig, Fabien; Simons, Dirk-Jan H; Crich, David; Cowen, James P; Ventura, Gregory T; Rehbein-Khalily, Tatiana; Brown, Todd C; Anderson, Ken B

    2003-10-28

    A pseudohomologous series of branched aliphatic alkanes with a quaternary substituted carbon atom (BAQCs, specifically 2,2-dimethylalkanes and 3,3- and 5,5-diethylalkanes) were identified in warm (65 degrees C) deep-sea hydrothermal waters and Late Cretaceous black shales. 5,5-Diethylalkanes were also observed in modern and Holocene marine shelf sediments and in shales spanning the last 800 million years of the geological record. The carbon number distribution of BAQCs indicates a biological origin. These compounds were observed but not identified in previous studies of 2.0 billion- to 2.2 billion-year-old metasediments and were commonly misidentified in other sediment samples, indicating that BAQCs are widespread in the geological record. The source organisms of BAQCs are unknown, but their paleobiogeographic distribution suggests that they have an affinity for sulfides and might be nonphotosynthetic sulfide oxidizers. PMID:14551322

  10. Branched aliphatic alkanes with quaternary substituted carbon atoms in modern and ancient geologic samples.

    SciTech Connect

    Kenig, F.; Simons, D.-J. H.; Crich, D.; Cowen, J. P.; Ventura, G. T.; Rehbein-Khalily, T.; Brown, T. C.; Anderson, K. B.; Chemistry; Univ. of Illinois at Chicago; Univ. of Hawaii

    2003-01-01

    A pseudohomologous series of branched aliphatic alkanes with a quaternary substituted carbon atom (BAQCs, specifically 2,2-di-methylalkanes and 3,3- and 5,5-diethylalkanes) were identified in warm (65{sup o}C) deep-sea hydrothermal waters and Late Cretaceous black shales. 5,5-Diethylalkanes were also observed in modern and Holocene marine shelf sediments and in shales spanning the last 800 million years of the geological record. The carbon number distribution of BAQCs indicates a biological origin. These compounds were observed but not identified in previous studies of 2.0 billion- to 2.2 billion-year-old metasediments and were commonly misidentified in other sediment samples, indicating that BAQCs are widespread in the geological record. The source organisms of BAQCs are unknown, but their paleobiogeographic distribution suggests that they have an affinity for sulfides and might be nonphotosynthetic sulfide oxidizers.

  11. Mass transfer and adsorption equilibrium for low volatility alkanes in BPL activated carbon.

    PubMed

    Wang, Yu; Mahle, John J; Furtado, Amanda M B; Glover, T Grant; Buchanan, James H; Peterson, Gregory W; LeVan, M Douglas

    2013-03-01

    The structure of a molecule and its concentration can strongly influence diffusional properties for transport in nanoporous materials. We study mass transfer of alkanes in BPL activated carbon using the concentration-swing frequency response method, which can easily discriminate among mass transfer mechanisms. We measure concentration-dependent diffusion rates for n-hexane, n-octane, n-decane, 2,7-dimethyloctane, and cyclodecane, which have different carbon numbers and geometries: straight chain, branched chain, and cyclic. Micropore diffusion is determined to be the controlling mass transfer resistance except at low relative saturation for n-decane, where an external mass transfer resistance also becomes important, showing that the controlling mass transfer mechanism can change with system concentration. Micropore diffusion coefficients are found to be strongly concentration dependent. Adsorption isotherm slopes obtained from measured isotherms, the concentration-swing frequency response method, and a predictive method show reasonably good agreement.

  12. Structural transformations of even-numbered n-alkanes confined in mesopores

    SciTech Connect

    Huber, P.; Soprunyuk, V. P.; Knorr, K.

    2006-09-15

    The n-alkanes C{sub 12}H{sub 26}, C{sub 14}H{sub 30}, and C{sub 16}H{sub 34} have been imbibed and solidified in mesoporous Vycor glass with a mean pore diameter of 10 nm. The samples have been investigated by x-ray diffractometry and calorimetric measurements. The structures and phase sequences have been determined. Apart from a reduction and the hysteresis of the melting-freezing transition, pore-confined C12 reproduces the liquid-triclinic phase sequence of the bulk material, but for C16 an orthorhombic rotator mesophase appears that in the bulk state is absent for C16 but well known from odd-numbered alkanes of similar length. In pore-confined C14 this phase shows up on cooling but not on heating.

  13. Molecular dynamics simulation of diffusion and structure of some n-alkanes in near critical and supercritical carbon dioxide at infinite dilution.

    PubMed

    Feng, Huajie; Gao, Wei; Sun, Zhenfan; Lei, Bingxin; Li, Gaonan; Chen, Liuping

    2013-10-17

    The diffusion coefficients of n-alkanes (from CH4 to C14H30) in near critical and supercritical carbon dioxide at infinite dilution have been studied by molecular dynamics simulation. The simulation results agree well with experiment, which suggests that the simulation method is a powerful tool to obtain diffusion coefficients of solutes in fluids at high pressures. The local structures of such fluids are further investigated by calculating radial distribution functions and coordination numbers. Meanwhile, the dihedral, end-to-end distance and radius of gyration, which are calculated to characterize the flexibility of n-alkanes, are used to reasonably explain the abnormal trends on radial distribution functions and coordination numbers. Moreover, it is found that the flexibility effects on diffusion in pure n-alkanes and infinitely dilute n-alkane/CO2 system are different. The differences in MD simulation results of molecular diffusion in such systems could be qualitatively explained by the flexibility.

  14. Photocatalytic acceptorless alkane dehydrogenation: scope, mechanism, and conquering deactivation with carbon dioxide.

    PubMed

    Chowdhury, Abhishek Dutta; Julis, Jennifer; Grabow, Kathleen; Hannebauer, Bernd; Bentrup, Ursula; Adam, Martin; Franke, Robert; Jackstell, Ralf; Beller, Matthias

    2015-01-01

    Alkane dehydrogenation is of special interest for basic science but also offers interesting opportunities for industry. The existing dehydrogenation methodologies make use of heterogeneous catalysts, which suffer from harsh reaction conditions and a lack of selectivity, whereas homogeneous methodologies rely mostly on unsolicited waste generation from hydrogen acceptors. Conversely, acceptorless photochemical alkane dehydrogenation in the presence of trans-Rh(PMe3 )2 (CO)Cl can be regarded as a more benign and atom efficient alternative. However, this methodology suffers from catalyst deactivation over time. Herein, we provide a detailed investigation of the trans-Rh(PMe3 )2 (CO)Cl-photocatalyzed alkane dehydrogenation using spectroscopic and theoretical investigations. These studies inspired us to utilize CO2 to prevent catalyst deactivation, which leads eventually to improved catalyst turnover numbers in the dehydrogenation of alkanes that include liquid organic hydrogen carriers. PMID:25346450

  15. Vapor-liquid phase coexistence of alkane-carbon dioxide and perfluoroalkane-carbon dioxide mixtures

    SciTech Connect

    Cui, S.T.; Cochran, H.D.; Cummings, P.T. |

    1999-05-27

    Both government and industry are seeking benign substitutes for the many organic solvents used in industry. Solvents are used as media for cleaning, for chemical reactions, and for chemical separation, and most of the solvents used are hazardous to health, safety, and the environment. Supercritical carbon dioxide (SC-CO{sub 2}) is often considered as an ideal solvent substitute, but several important classes of substances -- water and hydrophilic substances; proteins, nucleic acids, and many other biomolecules; and most man-made high polymers, for example -- exhibit very low solubility in SC-CO{sub 2}. The authors carried out a molecular simulation study of the vapor-liquid equilibria of alkane-CO{sub 2} and perfluoroalkane-CO{sub 2} binary mixtures using the Gibbs ensemble Monte Carlo method. They used simple interaction site models and the conventional Lorentz-Berthelot combining rules for the cross interaction between the solute and solvent species with no adjustable parameters to predict the vapor-liquid phase equilibrium of the hexane-CO{sub 2} and perfluorohexane-CO{sub 2} mixtures. The predicted CO{sub 2} mole fraction on the liquid branch is higher than the experimental results by about 10--13%. The gas-phase solubility of hexane and perfluorohexane in CO{sub 2} is generally smaller than the experimental results. The model predicts a higher solubility for the perfluoroalkanes in CO{sub 2} in comparison with alkanes in CO{sub 2}, consistent with experiment. The simulation results suggest that the dispersion interaction and the geometric packing may have a predominant role in accounting for the solubility difference between alkane and pefluoroalkane in CO{sub 2}.

  16. Assessing biomarker syngeneity using branched alkanes with quaternary carbon (BAQCs) and other plastic contaminants

    NASA Astrophysics Data System (ADS)

    Brocks, Jochen J.; Grosjean, Emmanuelle; Logan, Graham A.

    2008-02-01

    Biomarker molecules are valuable for the elucidation of ancient microbial ecosystems and the characterization of petroleum source rocks. For such studies, acquisition of reliable hydrocarbon data and proof of their syngeneity are essential. However, contamination of geological samples with anthropogenic petroleum products during drilling, storage and sampling can be particularly problematic because these hydrocarbons may over-print an original indigenous biomarker profile. To evaluate the extent of contamination of drill core and outcrop material, we studied the distribution of hydrocarbons in 26 rocks from different locations in the world. All rocks had petroleum products on their exterior surfaces. Twenty-two samples also contained surficial hydrocarbons derived from polyethylene plastic, including branched alkanes with quaternary carbon centers (BAQCs) and alkylcyclopentanes with pronounced even-over-odd carbon number preference. Using three examples from the Paleoproterozoic Tawallah and McArthur Groups in northern Australia, we show how indigenous biomarkers can be recognized by comparing hydrocarbon distributions between exterior rock surfaces and the rock interior, and how infiltration of allochthonous hydrocarbons can be assessed through the spatial distribution of characteristic polyethylene derived hydrocarbons in the rock. The methods outlined in this paper give confidence in the interpretation of biomarkers in particularly sensitive applications such as the first occurrences of certain organisms in the geological record and the provenance of organic matter in meteorites.

  17. Characterization of n-alkanes and their carbon isotopic composition in sediments from a small catchment of the Dianchi watershed.

    PubMed

    Wang, Yanhua; Yang, Hao; Zhang, Jixiang; Gao, Wenjing; Huang, Changchun; Xie, Biao

    2015-01-01

    The biomarker composition and stable carbon isotope values of organic matter (OM) in sediment cores from Shuanglong catchment of the Dianchi watershed show an unimodal n-alkane distribution ranging from C15-C33 with a strong predominance of odd-numbered n-alkanes, maximizing at n-C27, n-C29 and n-C31. Organic carbon to nitrogen (OC/N) ratio indicates a strong terrestrial influence on the OM. The values of δ(13)C27, δ(13)C29 and δ(13)C31 of n-alkanes range from -36.1‰ to -26.1‰, -34.1‰ to -30.1‰ and -33.8‰ to -28.7‰, respectively, suggesting a mainly C3 land plants origin. The carbon preference index (CPI25-31), odd-even preference (OEP27-31), average chain length (ACL25-33), pristine/phytane (pr/ph), Paq, (C27+C29)/2C31, nC16-23/nC24-33 and 3C17/(C21+C23+C25) values are also consistent with the predominance of C3 land plant-derived OM. Different sources of OM are reflected by the peak of n-C15, ascribed to a contribution by aquatic algae and photosynthetic bacteria. Eutrophication seems to be enhanced by both autochthonous (weak) and allochthonous (strong) contributions of OM. A major factor affecting the OM accumulation in the catchment and OM transportation to the Dianchi Lake may be increased by human activities from 1871 to 2011. PMID:24630457

  18. Characterization of n-alkanes and their carbon isotopic composition in sediments from a small catchment of the Dianchi watershed.

    PubMed

    Wang, Yanhua; Yang, Hao; Zhang, Jixiang; Gao, Wenjing; Huang, Changchun; Xie, Biao

    2015-01-01

    The biomarker composition and stable carbon isotope values of organic matter (OM) in sediment cores from Shuanglong catchment of the Dianchi watershed show an unimodal n-alkane distribution ranging from C15-C33 with a strong predominance of odd-numbered n-alkanes, maximizing at n-C27, n-C29 and n-C31. Organic carbon to nitrogen (OC/N) ratio indicates a strong terrestrial influence on the OM. The values of δ(13)C27, δ(13)C29 and δ(13)C31 of n-alkanes range from -36.1‰ to -26.1‰, -34.1‰ to -30.1‰ and -33.8‰ to -28.7‰, respectively, suggesting a mainly C3 land plants origin. The carbon preference index (CPI25-31), odd-even preference (OEP27-31), average chain length (ACL25-33), pristine/phytane (pr/ph), Paq, (C27+C29)/2C31, nC16-23/nC24-33 and 3C17/(C21+C23+C25) values are also consistent with the predominance of C3 land plant-derived OM. Different sources of OM are reflected by the peak of n-C15, ascribed to a contribution by aquatic algae and photosynthetic bacteria. Eutrophication seems to be enhanced by both autochthonous (weak) and allochthonous (strong) contributions of OM. A major factor affecting the OM accumulation in the catchment and OM transportation to the Dianchi Lake may be increased by human activities from 1871 to 2011.

  19. Carbon and hydrogen isotopic composition of methane and C2+ alkanes in electrical spark discharge: implications for identifying sources of hydrocarbons in terrestrial and extraterrestrial settings.

    PubMed

    Telling, Jon; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

    2013-05-01

    The low-molecular-weight alkanes--methane, ethane, propane, and butane--are found in a wide range of terrestrial and extraterrestrial settings. The development of robust criteria for distinguishing abiogenic from biogenic alkanes is essential for current investigations of Mars' atmosphere and for future exobiology missions to other planets and moons. Here, we show that alkanes synthesized during gas-phase radical recombination reactions in electrical discharge experiments have values of δ(2)H(methane)>δ(2)H(ethane)>δ(2)H(propane), similar to those of the carbon isotopes. The distribution of hydrogen isotopes in gas-phase radical reactions is likely due to kinetic fractionations either (i) from the preferential incorporation of (1)H into longer-chain alkanes due to the more rapid rate of collisions of the smaller (1)H-containing molecules or (ii) by secondary ion effects. Similar δ(13)C(C1-C2+) and δ(2)H(C1-C2+) patterns may be expected in a range of extraterrestrial environments where gas-phase radical reactions dominate, including interstellar space, the atmosphere and liquid hydrocarbon lakes of Saturn's moon Titan, and the outer atmospheres of Jupiter, Saturn, Neptune, and Uranus. Radical recombination reactions at high temperatures and pressures may provide an explanation for the combined reversed δ(13)C(C1-C2+) and δ(2)H(C1-C2+) patterns of terrestrial alkanes documented at a number of high-temperature/pressure crustal sites.

  20. Carbon and hydrogen isotopic composition of methane and C2+ alkanes in electrical spark discharge: implications for identifying sources of hydrocarbons in terrestrial and extraterrestrial settings.

    PubMed

    Telling, Jon; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

    2013-05-01

    The low-molecular-weight alkanes--methane, ethane, propane, and butane--are found in a wide range of terrestrial and extraterrestrial settings. The development of robust criteria for distinguishing abiogenic from biogenic alkanes is essential for current investigations of Mars' atmosphere and for future exobiology missions to other planets and moons. Here, we show that alkanes synthesized during gas-phase radical recombination reactions in electrical discharge experiments have values of δ(2)H(methane)>δ(2)H(ethane)>δ(2)H(propane), similar to those of the carbon isotopes. The distribution of hydrogen isotopes in gas-phase radical reactions is likely due to kinetic fractionations either (i) from the preferential incorporation of (1)H into longer-chain alkanes due to the more rapid rate of collisions of the smaller (1)H-containing molecules or (ii) by secondary ion effects. Similar δ(13)C(C1-C2+) and δ(2)H(C1-C2+) patterns may be expected in a range of extraterrestrial environments where gas-phase radical reactions dominate, including interstellar space, the atmosphere and liquid hydrocarbon lakes of Saturn's moon Titan, and the outer atmospheres of Jupiter, Saturn, Neptune, and Uranus. Radical recombination reactions at high temperatures and pressures may provide an explanation for the combined reversed δ(13)C(C1-C2+) and δ(2)H(C1-C2+) patterns of terrestrial alkanes documented at a number of high-temperature/pressure crustal sites. PMID:23683048

  1. Alkane distribution and carbon isotope composition in fossil leaves: An interpretation of plant physiology in the geologic past

    NASA Astrophysics Data System (ADS)

    Graham, H. V.; Freeman, K. H.

    2014-12-01

    The relative chain-length distribution and carbon-isotope composition of n-alkanes extracted from sedimentary rocks are important geochemical tools for investigating past terrestrial ecosystems. Alkanes preserved in ancient sediments are assumed to be contemporaneous, derived from the same ecosystem, and integrated from the biomass present on the landscape at the time of deposition. Further, there is an underlying assumption that ancient plants exhibited the same metabolic and physiological responses to climate conditions that are observed for modern plants. Interpretations of alkane abundances and isotopic signatures are complicated by the strong influence of phylogenetic affiliation and ecological factors, such as canopy structure. A better understanding of how ecosystem and taxa influence alkane properties, including homologue abundance patterns and leaf-lipid carbon isotope fractionation would help strengthen paleoecological interpretations based on these widely employed plant biomarkers. In this study, we analyze the alkane chain-length distribution and carbon-isotope composition of phytoleim and alkanes (d13Cleaf and d13Clipid) extracted from a selection of Cretaceous and Paleocene fossil leaves from the Guaduas and Cerrejon Formations of Colombia. These data were compared with data for the same families in a modern analogue biome. Photosynthetic and biosynthetic fractionation (∆leaf and elipid) values determined from the fossil material indicate carbon metabolism patterns were similar to modern plants. Fossil data were incorporated in a biomass-weighted mixing model to represent the expected lipid complement of sediment arising from this ecosystem and compared with alkane measurements from the rock matrix. Modeled and observed isotopic and abundance patterns match well for alkane homologs most abundant in plants (i.e., n-C27 to n-C33). The model illustrates the importance of understanding biases in litter flux and taphonomic pressures inherent in the

  2. Binary and ternary adsorption of n-alkane mixtures on activated carbon

    SciTech Connect

    Kalies, G.; Braeuer, P.; Messow, U.

    1999-06-15

    The adsorption isotherms of the binary n-alkane mixtures n-hexane/n-octane, n-octane/n-tetradecane, and n-hexane/n-tetradecane on the activated carbon TA 95 are measured at 298 K and described with mathematical functions. About 40 experimental values of the adsorption excess of the ternary mixture n-hexane/n-octane/n-tetradecane on activated carbon TA 95 at 298 K are gas chromatographically measured inside the ternary triangle. The ternary data are represented in the three-dimensional space with the help of transformation of coordinates and by utilization of the conception of the quasi-two-component representation of the mole fractions. A consistency test for the specific wetting Gibbs energies calculated from the binary data is carried out. The possibilities for a mathematical prediction of ternary data from adsorption data for the constituent binary mixtures are proved.

  3. Molecular dynamics insight to phase transition in n-alkanes with carbon nanofillers

    SciTech Connect

    Rastogi, Monisha; Vaish, Rahul

    2015-05-15

    The present work aims to investigate the phase transition, dispersion and diffusion behavior of nanocomposites of carbon nanotube (CNT) and straight chain alkanes. These materials are potential candidates for organic phase change materials(PCMs) and have attracted flurry of research recently. Accurate experimental evaluation of the mass, thermal and transport properties of such composites is both difficult as well as economically taxing. Additionally it is crucial to understand the factors that results in modification or enhancement of their characteristic at atomic or molecular level. Classical molecular dynamics approach has been extended to elucidate the same. Bulk atomistic models have been generated and subjected to rigorous multistage equilibration. To reaffirm the approach, both canonical and constant-temperature, constant- pressure ensembles were employed to simulate the models under consideration. Explicit determination of kinetic, potential, non-bond and total energy assisted in understanding the enhanced thermal and transport property of the nanocomposites from molecular point of view. Crucial parameters including mean square displacement and simulated self diffusion coefficient precisely define the balance of the thermodynamic and hydrodynamic interactions. Radial distribution function also reflected the density variation, strength and mobility of the nanocomposites. It is expected that CNT functionalization could improve the dispersion within n-alkane matrix. This would further ameliorate the mass and thermal properties of the composite. Additionally, the determined density was in good agreement with experimental data. Thus, molecular dynamics can be utilized as a high throughput technique for theoretical investigation of nanocomposites PCMs.

  4. Molecular dynamics insight to phase transition in n-alkanes with carbon nanofillers

    NASA Astrophysics Data System (ADS)

    Rastogi, Monisha; Vaish, Rahul

    2015-05-01

    The present work aims to investigate the phase transition, dispersion and diffusion behavior of nanocomposites of carbon nanotube (CNT) and straight chain alkanes. These materials are potential candidates for organic phase change materials(PCMs) and have attracted flurry of research recently. Accurate experimental evaluation of the mass, thermal and transport properties of such composites is both difficult as well as economically taxing. Additionally it is crucial to understand the factors that results in modification or enhancement of their characteristic at atomic or molecular level. Classical molecular dynamics approach has been extended to elucidate the same. Bulk atomistic models have been generated and subjected to rigorous multistage equilibration. To reaffirm the approach, both canonical and constant-temperature, constant- pressure ensembles were employed to simulate the models under consideration. Explicit determination of kinetic, potential, non-bond and total energy assisted in understanding the enhanced thermal and transport property of the nanocomposites from molecular point of view. Crucial parameters including mean square displacement and simulated self diffusion coefficient precisely define the balance of the thermodynamic and hydrodynamic interactions. Radial distribution function also reflected the density variation, strength and mobility of the nanocomposites. It is expected that CNT functionalization could improve the dispersion within n-alkane matrix. This would further ameliorate the mass and thermal properties of the composite. Additionally, the determined density was in good agreement with experimental data. Thus, molecular dynamics can be utilized as a high throughput technique for theoretical investigation of nanocomposites PCMs.

  5. Environmental and biosynthetic influences on carbon and hydrogen isotope ratios of leaf wax n-alkanes

    NASA Astrophysics Data System (ADS)

    McInerney, F. A.; Freeman, K. H.; Polissar, P. J.; Feakins, S. J.

    2013-12-01

    Both carbon and hydrogen isotope ratios of leaf-wax n-alkanes are influenced by the availability of water in a plant's growth environment. Carbon isotope ratios of bulk tissues in C3 plants demonstrate a strong inverse relationship with measures of available moisture (e.g. mean annual precipitation and precipitation/evaporation). Similarly, hydrogen isotope ratios of leaf wax n-alkanes (δDl) can be enriched relative to precipitation (δDw) by transpiration, which is related to relative humidity and the leaf-to-air vapor pressure deficit. Thus, D-enrichment of leaf-wax n-alkanes relative to precipitation, termed the apparent fractionation (2ɛl/w), becomes more positive with increasing aridity. In theory, more positive values of leaf-wax δ13C (δ13Cl) and 2ɛl/w of leaf-wax n-alkanes should both correspond to more arid conditions in C3 plants. Here we review published and unpublished data on over 100 plants to examine this relationship. Contrary to expectations, C3 dicots show no clear relationship between δ13Cl and 2ɛl/w. This global lack of correlation is surprising given our understanding of aridity related isotopic effects in C3 plants. One possibility is that the implicit assumption of constant fractionation between lipid and bulk tissue is flawed due to the effects of different biosynthetic carriers and reaction pathways. We explore this possibility by examining the offset of leaf-wax carbon isotopes from the bulk leaf tissue (13ɛl/bulk). Different offsets would indicate additional biosynthetic processes are affecting δ13Cl in addition to any direct effects from aridity. We find that 13ɛl/bulk is highly variable, ranging from -1 to -16‰, which could explain the lack of correlation between δ13Cl and 2ɛl/w. In addition, 13ɛl/bulk values for C3 and C4 monocots (averages of -10.6 and -11.4‰ respectively) represent significantly greater offset between leaf wax and bulk tissue than in C3 dicots (average of -4.3‰), which is consistent with previous

  6. Growth factor controls on the distribution and carbon isotope composition of n-alkanes in leaf wax

    NASA Astrophysics Data System (ADS)

    Jia, C.; Xie, S.; Huang, X.

    2012-12-01

    Cuticular wax plays pivotal physiological and ecological roles in the interactions between plants and the environments in which they grow. Plant-derived long-chain alkanes are more resistant to decay than other biochemical polymers. n-Alkane distributions (Carbon Preference Index (CPI) values and Average Chain Length (ACL) values) and carbon isotopic values are used widely in palaeoenvironmental reconstruction. However, there is little information available on how growth stages of the plant might influence the abundance of n-alkanes in the natural environment. In this study, we analyzed n-alkane distributions and carbon isotope data from two tree species (Cinnamomum camphora (L.) Presl. and Liquidambar formosana Hance) collected monthly from 2009 to 2011 in Nanwang Shan, Wuhan, Hubei Province. CPI values for n-alkanes from C. camphora remained stable in autumn and winter but fluctuated dramatically during spring and autumn each year. Positive correlations between CPI values and the relative content of (C27+C29) were observed in both sun and shade leaves of C. camphora from April to July. In L. formosana, CPI values decreased gradually from April to December. A similar trend was observed in all three years suggesting that growth stages rather than temperature or relative humidity affected the CPI values on a seasonal timescale. In the samples of L. formosana ACL values were negatively correlated with CPI values in the growing season (from April to July) and positively correlated with CPI values in the other seasons. The δ13C values of C29 and C31 n-alkanes displayed more negative carbon isotopic values in autumn and winter compared with leaves sampled at the start of the growing season from both trees. The δ13C values of C29 and C31 n-alkanes of L. formosana decreased from April to December. These results demonstrate the importance of elucidating the growing factors that influence the distribution and δ13C values of alkanes in modern leaves prior to using CPI

  7. Compound-specific carbon isotope analyses of individual long-chain alkanes and alkanoic acids in Harmattan aerosols

    NASA Astrophysics Data System (ADS)

    Simoneit, Bernd R. T.

    The higher molecular weight n-alkane, n-alkanol and n-alkanoic acid series from higher plant wax are ubiquitous components of aerosol particles in remote areas. The carbon isotopic compositions of individual n-alkanes and n-alkanoic acids have been determined in samples of Harmattan aerosol and composited vegetation wax from Nigeria. The data confirm the terrestrial origin of these compounds and support the distinction among the vegetation sources of C 4 plants (savannah) from C 3 and CAM plants (wet climate, mixed vegetation). The superimposed petroleum components from vehicular emissions in urban areas could not be differentiated from C 3 vegetation by compound-specific isotope analysis.

  8. Inhibitory Potency of 4-Carbon Alkanes and Alkenes toward CYP2E1 Activity

    PubMed Central

    Hartman, Jessica H.; Miller, Grover P.; Boysen, Gunnar

    2016-01-01

    CYP2E1 has been implicated in the bioactivation of many small molecules into reactive metabolites which form adducts with proteins and DNA, and thus a better understanding of the molecular determinants of its selectivity are critical for accurate toxicological predictions. In this study, we determined the potency of inhibition of human CYP2E1 for various 4-carbon alkanes, alkenes and alcohols. In addition, known CYP2E1 substrates and inhibitors including 4-methylpyrazole, aniline, and dimethylnitrosamine were included to determine their relative potencies. Of the 1,3-butadiene-derived metabolites studied, 3,4-epoxy-1-butene was the strongest inhibitor with an IC50 of 110 μM compared to 1700 μM and 6600 μM for 1,2-butenediol and 1,2:3,4-diepoxybutane, respectively. Compared to known inhibitors, inhibitory potency of 3,4-epoxy-1-butene is between 4-methylpyrazole (IC50 = 1.8 μM) and dimethylnitrosamine (IC50 = 230 μM). All three butadiene metabolites inhibit CYP2E1 activity through a simple competitive mechanism. Among the 4-carbon compounds studied, the presence and location of polar groups seems to influence inhibitory potency. To further examine this notion, the investigation was extended to include structurally and chemically similar analogs, including propylene oxide and various butane alcohols. Those results demonstrated preferential recognition of CYP2E1 toward the type and location of polar and hydrophobic structural elements. Taken together, CYP2E1 metabolism may be modified in vivo by exposure to 4-carbon compounds, such as drugs, and nutritional constituents, a finding that highlights the complexity of exposure to mixtures. PMID:24561005

  9. A Neogene Higher Plant N-Alkane Carbon and Hydrogen Isotope Record From the Gulf of Mexico

    NASA Astrophysics Data System (ADS)

    Tipple, B. J.; Pagani, M.

    2006-12-01

    Water availability and a plant's capacity to cope with water stress are expressed in carbon and hydrogen isotopic compositions of leaf waxes. Therefore, coupled sedimentary n-alkane δ13C and δD isotope records provide unique continental-scale information about the paleo-hydrological cycle and its influence on biology over long time scales. In this study, we assess the relationship between Neogene North American climate and floral change, particularly C4 grass expansion, by establishing δ13C and δD records of higher-plant leaf wax n-alkanes from Gulf of Mexico sediments (DSDP site 94). Changes in the hydrogen isotope composition of leaf water can be driven by changes in evaporation/evapotranspiration or changes in the evaporative source from which precipitation derives. However, for this study changes in moisture source are unlikely because these sediments located in Gulf of Mexico likely received the majority of precipitation from the Gulf of Mexico itself over the time interval studied. In general, δ13C and δD values shift in concert, with the most positive δ13C and δD values occurring near the Epoch boundaries. N-alkane δ13C values reflect factors other than water stress alone, including the isotopic composition of atmospheric CO2, plant community, and atmospheric pCO2. Notably, 13C enrichment occurring near the Oligocene/Miocene boundary potentially reflects the rapid decrease in pCO2 at this time. In addition, between 4.5 and 5.5 Ma, n-alkane δ13C values trend more negative as δD becomes increasingly D-enriched, indicative of increased evaporation. Given that contemporaneous North American terrestrial isotope (Passey et al., 2002) and equatorial Atlantic marine (Wagner, 2002) records show similar trends, it appears that major changes in the hydrological cycle took place at this time.

  10. Carbon Isotopic Fractionation Associated with Cyanobacterial Biomarkers: 2-Methylhopanoids and Methyl-Branched Alkanes

    NASA Technical Reports Server (NTRS)

    Jahnke, L. L.; Summons, R. E.; Hope, J. M.; Cullings, K. W.

    2001-01-01

    This paper reports the carbon isotopic fractionations associated with the biosynthesis of biomarker lipids in a number of cyanobacteria obtained from culture collections and isolated from the coniform mats of Yellowstone National Park. Additional information is contained in the original extended abstract.

  11. Alkanes-filled photonic crystal fibers as sensor transducers

    NASA Astrophysics Data System (ADS)

    Marć, P.; Przybysz, N.; Stasiewicz, K.; Jaroszewicz, L. R.

    2015-09-01

    In this paper we propose alkanes-filled PCFs as the new class of transducers for optical fiber sensors. We investigated experimentally thermo-optic properties of a commercially available LMA8 partially filled with different alkanes with a higher number of carbon atoms. A partially filled PCF spliced with standard SMFs constitutes one of the newest type transducer. We have selected a group of eight alkanes which have melting points in different temperatures. An analysis of temperature spectral characteristics of these samples will allow to design an optical fiber sensor with different temperature thresholds at specific wavelengths.

  12. Carbon Isotopes of Alkanes in Hydrothermal Abiotic Organic Synthesis Processes at High Temperatures and Pressures: An Experimental Study

    NASA Technical Reports Server (NTRS)

    Fu, Qi; Socki, Richard A.; Niles, Paul B.

    2010-01-01

    Observation of methane in the Martian atmosphere has been reported by different detection techniques [1-4]. With more evidence showing extensive water-rock interaction in Martian history [5-7], abiotic formation by Fischer-Tropsch Type (FTT) synthesis during serpentization reactions may be one possible process responsible for methane generation on Mars [8, 9]. While the experimental studies performed to date leave little doubt that chemical reactions exist for the abiotic synthesis of organic compounds by mineral surface-catalyzed reactions [10-12], little is known about the reaction pathways by which CO2 and/or CO are reduced under hydrothermal conditions. Carbon and hydrogen isotope measurements of alkanes have been used as an effective tool to constrain the origin and reaction pathways of hydrocarbon formation. Alkanes generated by thermal breakdown of high molecular weight organic compounds have carbon and hydrogen isotopic signatures completely distinct from those formed abiotically [13-15]. Recent experimental studies, however, showed that different abiogenic hydrocarbon formation processes (e.g., polymerization vs. depolymerization) may have different carbon and hydrogen isotopic patterns [16]. Results from previous experiments studying decomposition of higher molecular weight organic compounds (lignite) also suggested that pressure could be a crucial factor affecting fractionation of carbon isotopes [17]. Under high pressure conditions, no experimental data are available describing fractionation of carbon isotope during mineral catalyzed FTT synthesis. Thus, hydrothermal experiments present an excellent opportunity to provide the requisite carbon isotope data. Such data can also be used to identify reaction pathways of abiotic organic synthesis under experimental conditions.

  13. Towards a practical development of light-driven acceptorless alkane dehydrogenation.

    PubMed

    Chowdhury, Abhishek Dutta; Weding, Nico; Julis, Jennifer; Franke, Robert; Jackstell, Ralf; Beller, Matthias

    2014-06-16

    The efficient catalytic dehydrogenation of alkanes to olefins is one of the most investigated reactions in organic synthesis. In the coming years, an increased supply of shorter-chain alkanes from natural and shale gas will offer new opportunities for inexpensive carbon feedstock through such dehydrogenation processes. Existing methods for alkane dehydrogenation using heterogeneous catalysts require harsh reaction conditions and have a lack of selectivity, whereas homogeneous catalysis methods result in significant waste generation. A strong need exists for atom-efficient alkane dehydrogenations on a useful scale. Herein, we have developed improved acceptorless catalytic systems under optimal light transmittance conditions using trans-[Rh(PMe3)2(CO)Cl] as the catalyst with different additives. Unprecedented catalyst turnover numbers are obtained for the dehydrogenation of cyclic and linear (from C4) alkanes and liquid organic hydrogen carriers. These reactions proceed with unique conversion, thereby providing a basis for practical alkane dehydrogenations. PMID:24829085

  14. Biomarkers and compound-specific stable carbon isotope of n-alkanes in crude oils from Eastern Llanos Basin, Colombia

    NASA Astrophysics Data System (ADS)

    Cortes, Jorge E.; Rincon, Jose M.; Jaramillo, Jose M.; Philp, R. Paul; Allen, Jon

    2010-03-01

    Representative samples of crude oils from Cusiana, Cupiagua, Apiay, Castilla and Chichimene fields in the Eastern Llanos Basin of Colombia were analyzed to determine its compound-specific stable carbon isotope composition (CSIA) using gas chromatography-isotopic ratio-mass spectrometry (GC-IRMS). GC-IRMS analyses of n-alkanes allowed differentiating between Cretaceous and Cretaceous/Tertiary oil samples. Cretaceous sourced samples have δ13C-enriched values than Cretaceous/Tertiary sourced samples; the heavier isotope composition of these samples is due to their major terrigenous organic matter input. Their isotope distribution patterns suggest significant algal and/or bacterial contribution (marine origin). The analysis of the n-alkane fractions by GC-IRMS confirms that the organic matter has marine origin in those samples from Cusiana, Cupiagua and Apiay while Castilla and Chichimene have marine origin with terrestrial inputs. The results were confirmed by gas chromatography/FID and gas chromatography/mass spectrometry (GC/MS). Basic geochemical composition show that samples from Cupiagua/Cusiana fields and Apiay/Castilla/Chichimene fields in the Llanos basin, Colombia present different characteristics reflecting a specific for each depositional environment.

  15. Evaluating Carbon Isotope Signature of Bulk Organic Matter and Plant Wax Derived n-alkanes from Lacustrine Sediments as Climate Proxies along the Western Side of the Andes

    NASA Astrophysics Data System (ADS)

    Contreras, S.; Werne, J. P.; Araneda, A.; Conejero, C. A.

    2015-12-01

    Sedimentary carbon isotope values (δ13C) of bulk organic matter and long chain (C25 to C35) n-alkanes are among the most long-lived and widely utilized proxies of organic matter and vegetation source. The carbon distribution (e.g. average carbon chain length, ACL) and isotope signature from long chain n-alkanes had been intensively used on paleoclimate studies because they are less influenced by diagenesis, differential preservation of compound classes, and changes in the sources of organic matter than bulk δ13C values. Recently, studies of modern plant n-alkanes have challenged the use of carbon distribution and carbon isotope signature from sedimentary n-alkanes as reliable indicators of vegetation and climate change. The climate in central-south western South America (SA) is projected to become significantly warmer and drier over the next several decades to centuries in response to anthropogenically driven warming. Paleolimnological studies along western SA are critical to obtain more realistic and reliable regional reconstructions of past climate and environments, including vegetation and water budget variability. Here we discuss bulk δ13C, distribution and δ13C in long chain n-alkanes from a suite of ~40 lake surface sediment (core-top) samples spanning the transition from a Mediterranean climate with a patchwork of cultivated vegetation, pastureland, conifers in central Chile to a rainy temperate climate dominated by broadleaf deciduous and evergreen forest. Data are compared to the latitudinal and orographic climatic trends of the Andes based on the climatology (e.g. precipitation and temperature) of the locations of all lakes involved in this study, using monthly gridded reanalysis products of the Climate Forecast System Reanalysis (CFSR), based on the NCEP global forecast model and meteorological stations available in the region, from January 1979 to December 2010 with a 0.5° horizontal resolution.

  16. Separation of alkanes and aromatic compounds by packed column gas chromatography using functionalized multi-walled carbon nanotubes as stationary phases.

    PubMed

    Speltini, Andrea; Merli, Daniele; Quartarone, Eliana; Profumo, Antonella

    2010-04-23

    In the present work, we show a novel application of pristine and functionalized Multi-Walled Carbon Nanotubes (MWCNTs) as stationary phase in low-cost packed columns for the gas chromatographic separation of alkanes and aromatic hydrocarbons. The MWCNTs were deeply investigated by means of physical and chemical methods, like thermal analysis, IR and atomic force microscopy, and Inverse Gas Chromatography (IGC) in order to correlate the adsorption process and surface properties with the material purity level and functionalization degree. The derivatization process of the pristine nanotubes was a key factor to achieve a successful separation of both the light n-alkanes (C3-C5) and the related isomers (C4-C5 branched alkanes). Satisfactory results were similarly obtained in the case of separation of aromatic hydrocarbons (BTX).

  17. Implications of carbon isotope ratios of C27-C33 alkanes and C37 alkenes for the sources of organic matter in the southern ocean surface sediments

    NASA Astrophysics Data System (ADS)

    Ohkouchi, N.; Kawamura, K.; Takemoto, N.; Ikehara, M.; Nakatsuka, T.

    2000-01-01

    Carbon isotopic ratios (δ13C) of C27-C33 n-alkanes and C37 alkenes were measured in the surface sediments from Australian sector of Southern Ocean (47.6°-65.5°S). The δ13C of C31 n-alkane derived from higher plant wax shows little change along the latitude (-28.7±0.6 ‰), whereas δ13C of C37 alkenes derived from haptophyte algae decreases from -24.6±0.7 ‰ at 47.6°S to -32.1±1.2 ‰ at 63.9°S. Relatively heavy δ13C values of C31 n-alkane suggest significant contribution of C4 plant waxes or conifer resin whose δ13C of n-alkanes are significantly heavier than those of C3 plants. The δ13C of total organic carbon exhibits a latitudinal pattern similar to that of C37 alkenes, suggesting that organic carbon in the sediments is primarily of marine origin.

  18. Source characterization of sedimentary organic matter using molecular and stable carbon isotopic composition of n-alkanes and fatty acids in sediment core from Lake Dianchi, China.

    PubMed

    Fang, Jidun; Wu, Fengchang; Xiong, Yongqiang; Li, Fasheng; Du, Xiaoming; An, Da; Wang, Lifang

    2014-03-01

    The distribution and compound-specific carbon isotope ratios of n-alkanes and fatty acids in a sediment core (63 cm) collected from Lake Dianchi were examined to investigate organic matter sources in the eutrophic lake. Fatty acids included free and bound fatty acids. The carbon isotope compositions of individual n-alkanes and fatty acids from Lake Dianchi sediments were determined using gas chromatography/isotope ratio mass spectrometry (GC-IRMS). The δ(13)C values of individual n-alkanes (C16-C31) varied between -24.1‰ and -35.6‰, suggesting a dominance of (13)C-depleted n-alkanes that originated from C3 plants and lacustrine algae. Fatty acids from the sediment extracts were analyzed for their abundances and carbon isotopic compositions. Molecular and isotopic evidence indicates that most of the short-chain fatty acids from Lake Dianchi sediment extracts are sourced from intense microbial recycling and resynthesis of organic matter. Long-chain free fatty acids are mainly derived from terrestrial sources. However, long-chain bound fatty acids are sourced from a combination of terrestrial organic matter, bacteria and algae, with the contribution from algal sources higher in the hypereutrophic stage.

  19. Vapor-liquid and vapor-liquid-liquid equilibria of carbon dioxide/n-perfluoroalkane/n-alkane ternary mixtures.

    PubMed

    Colina, Coray M; Gubbins, Keith E

    2005-02-24

    Perfluoroalkanes have numerous applications (e.g., in the medical field and the chemical industry), and their high affinity for carbon dioxide makes them attractive as surfactants and cosolvents. Although research in this area has grown in the past few years, very little phase-equilibrium data is available in the open literature for these systems. In this work, we present, for the first time, predictions of vapor-liquid and vapor-liquid-liquid equilibria of binary and ternary systems of carbon dioxide/n-perfluoroalkane/n-alkane. Our results are based on the SAFT-VR EOS (statistical associating fluid theory of variable range, equation of state), and we study the influence of temperature, pressure, composition, and chain length on the phase diagram. The predicted phase diagrams are based on temperature-independent binary interaction parameters, and no ternary parameters are introduced. Comparisons to the available experimental and molecular simulation data show that the predicted diagrams should provide a good representation of the phase equilibria.

  20. Room temperature dehydrogenation of ethane, propane, linear alkanes C4-C8, and some cyclic alkanes by titanium-carbon multiple bonds.

    PubMed

    Crestani, Marco G; Hickey, Anne K; Gao, Xinfeng; Pinter, Balazs; Cavaliere, Vincent N; Ito, Jun-Ichi; Chen, Chun-Hsing; Mindiola, Daniel J

    2013-10-01

    The transient titanium neopentylidyne, [(PNP)Ti≡C(t)Bu] (A; PNP(-)≡N[2-P(i)Pr2-4-methylphenyl]2(-)), dehydrogenates ethane to ethylene at room temperature over 24 h, by sequential 1,2-CH bond addition and β-hydrogen abstraction to afford [(PNP)Ti(η(2)-H2C═CH2)(CH2(t)Bu)] (1). Intermediate A can also dehydrogenate propane to propene, albeit not cleanly, as well as linear and volatile alkanes C4-C6 to form isolable α-olefin complexes of the type, [(PNP)Ti(η(2)-H2C═CHR)(CH2(t)Bu)] (R = CH3 (2), CH2CH3 (3), (n)Pr (4), and (n)Bu (5)). Complexes 1-5 can be independently prepared from [(PNP)Ti═CH(t)Bu(OTf)] and the corresponding alkylating reagents, LiCH2CHR (R = H, CH3(unstable), CH2CH3, (n)Pr, and (n)Bu). Olefin complexes 1 and 3-5 have all been characterized by a diverse array of multinuclear NMR spectroscopic experiments including (1)H-(31)P HOESY, and in the case of the α-olefin adducts 2-5, formation of mixtures of two diastereomers (each with their corresponding pair of enantiomers) has been unequivocally established. The latter has been spectroscopically elucidated by NMR via C-H coupled and decoupled (1)H-(13)C multiplicity edited gHSQC, (1)H-(31)P HMBC, and dqfCOSY experiments. Heavier linear alkanes (C7 and C8) are also dehydrogenated by A to form [(PNP)Ti(η(2)-H2C═CH(n)Pentyl)(CH2(t)Bu)] (6) and [(PNP)Ti(η(2)-H2C═CH(n)Hexyl)(CH2(t)Bu)] (7), respectively, but these species are unstable but can exchange with ethylene (1 atm) to form 1 and the free α-olefin. Complex 1 exchanges with D2C═CD2 with concomitant release of H2C═CH2. In addition, deuterium incorporation is observed in the neopentyl ligand as a result of this process. Cyclohexane and methylcyclohexane can be also dehydrogenated by transient A, and in the case of cyclohexane, ethylene (1 atm) can trap the [(PNP)Ti(CH2(t)Bu)] fragment to form 1. Dehydrogenation of the alkane is not rate-determining since pentane and pentane-d12 can be dehydrogenated to 4 and 4-d12 with comparable

  1. Surface freezing in binary alkane-alcohol mixtures

    SciTech Connect

    Ofer, E.; Sloutskin, E.; Tamam, L.; Deutsch, M.; Ocko, B. M.

    2006-08-15

    Surface freezing was detected and studied in mixtures of alcohol and alkane molecules, using surface tensiometry and surface-specific x-ray scattering methods. Considering that surface freezing in pure alkanes forms an ordered monolayer and in alcohols it forms an ordered bilayer, the length mismatch repulsion was minimized by varying the carbon number of the alkane component around 2n, where n is the carbon number of the alcohol molecule. A solutionlike behavior was found for all mixtures, where the ideal liquid mixture phase-separates upon freezing both in the bulk and the surface. The solid exhibits a herringbone crystalline phase below an alkane mole fraction {phi}{sub t}{approx_equal}0.8 and a rotator phase above it. The surface frozen film below {phi}{sub t} is an alkane monolayer exhibiting a next-nearest neighbor molecular tilt of a composition-dependent magnitude. Above {phi}{sub t}, no diffraction peaks were observed. This could be explained by the intrinsically shorter-range order of the rotator phase and a possible proliferation of defects.

  2. Alkane metathesis by tandem alkane-dehydrogenation-olefin-metathesis catalysis and related chemistry.

    PubMed

    Haibach, Michael C; Kundu, Sabuj; Brookhart, Maurice; Goldman, Alan S

    2012-06-19

    Methods for the conversion of both renewable and non-petroleum fossil carbon sources to transportation fuels that are both efficient and economically viable could greatly enhance global security and prosperity. Currently, the major route to convert natural gas and coal to liquids is Fischer-Tropsch catalysis, which is potentially applicable to any source of synthesis gas including biomass and nonconventional fossil carbon sources. The major desired products of Fischer-Tropsch catalysis are n-alkanes that contain 9-19 carbons; they comprise a clean-burning and high combustion quality diesel, jet, and marine fuel. However, Fischer-Tropsch catalysis also results in significant yields of the much less valuable C(3) to C(8)n-alkanes; these are also present in large quantities in oil and gas reserves (natural gas liquids) and can be produced from the direct reduction of carbohydrates. Therefore, methods that could disproportionate medium-weight (C(3)-C(8)) n-alkanes into heavy and light n-alkanes offer great potential value as global demand for fuel increases and petroleum reserves decrease. This Account describes systems that we have developed for alkane metathesis based on the tandem operation of catalysts for alkane dehydrogenation and olefin metathesis. As dehydrogenation catalysts, we used pincer-ligated iridium complexes, and we initially investigated Schrock-type Mo or W alkylidene complexes as olefin metathesis catalysts. The interoperability of the catalysts typically represents a major challenge in tandem catalysis. In our systems, the rate of alkane dehydrogenation generally limits the overall reaction rate, whereas the lifetime of the alkylidene complexes at the relatively high temperatures required to obtain practical dehydrogenation rates (ca. 125 -200 °C) limits the total turnover numbers. Accordingly, we have focused on the development and use of more active dehydrogenation catalysts and more stable olefin-metathesis catalysts. We have used thermally

  3. Microsomal preparation from an animal tissue catalyzes release of carbon monoxide from a fatty aldehyde to generate an alkane.

    PubMed

    Cheesbrough, T M; Kolattukudy, P E

    1988-02-25

    Alkanes are widely distributed in nature and impaired alkane synthesis was implicated in certain neurological disorders. However, the mechanism of synthesis of alkanes in animals is unknown. Our search to find a convenient animal tissue to study alkane biosynthesis resulted in the finding that the uropygial gland (a modified sebaceous gland) of the eared grebe (Podiceps nigricollis) produces large amounts of alkanes. These alkanes, which constitute 35-41% of the total lipid produced, are mainly C21, C23, C25, and C27 n-alkanes. Cell free homogenates of this tissue synthesized alkanes from both fatty acid and aldehyde in the absence of O2. Differential centrifugation of the homogenates indicated that this activity was located in the microsomal fraction. With isolated microsomes conversion of fatty acid to alkane required CoA, ATP, and NADH whereas conversion of an aldehyde to alkane did not require the addition of cofactors. That the final step in alkane synthesis is a decarbonylation was shown by the stoichiometric production of heptadecane and CO from octadecanal. CO was identified by adsorption to RhCl [(C6H6)3P]3 and oxidation of the trapped CO to CO2 by watergas shift reaction. The enzyme preparation also catalyzed incorporation of 14C from 14CO into octadecanal showing the reversible nature of the decarbonylase. This decarbonylase had a sharp pH optimum at 7.0, a Kapp of 180 microM and a V1/2 of 90 rho mol/min/mg protein for octadecanal. The enzyme was inhibited by the metal chelators EDTA, O-phenanthroline, and 8-hydroxyquinoline, but not by KCN. It was stimulated nearly 3-fold by 5 microM 2-mercaptoethanol and inhibited by the presence of O2. During the conversion of [1-3H]octadecanal to heptadecane, 3H was lost to water and 3H from 3H2O was incorporated into the alkane generated from unlabeled octadecanal. The mechanism of the decarbonylation and the nature of the enzyme remain to be elucidated.

  4. Organic Reference Materials for Hydrogen, Carbon, and Nitrogen Stable Isotope-Ratio Measurements: Caffeines, n-Alkanes, Fatty Acid Methyl Esters, Glycines, L-Valines, Polyethylenes, and Oils.

    PubMed

    Schimmelmann, Arndt; Qi, Haiping; Coplen, Tyler B; Brand, Willi A; Fong, Jon; Meier-Augenstein, Wolfram; Kemp, Helen F; Toman, Blaza; Ackermann, Annika; Assonov, Sergey; Aerts-Bijma, Anita T; Brejcha, Ramona; Chikaraishi, Yoshito; Darwish, Tamim; Elsner, Martin; Gehre, Matthias; Geilmann, Heike; Gröning, Manfred; Hélie, Jean-François; Herrero-Martín, Sara; Meijer, Harro A J; Sauer, Peter E; Sessions, Alex L; Werner, Roland A

    2016-04-19

    An international project developed, quality-tested, and determined isotope-δ values of 19 new organic reference materials (RMs) for hydrogen, carbon, and nitrogen stable isotope-ratio measurements, in addition to analyzing pre-existing RMs NBS 22 (oil), IAEA-CH-7 (polyethylene foil), and IAEA-600 (caffeine). These new RMs enable users to normalize measurements of samples to isotope-δ scales. The RMs span a range of δ(2)H(VSMOW-SLAP) values from -210.8 to +397.0 mUr or ‰, for δ(13)C(VPDB-LSVEC) from -40.81 to +0.49 mUr and for δ(15)N(Air) from -5.21 to +61.53 mUr. Many of the new RMs are amenable to gas and liquid chromatography. The RMs include triads of isotopically contrasting caffeines, C16 n-alkanes, n-C20-fatty acid methyl esters (FAMEs), glycines, and l-valines, together with polyethylene powder and string, one n-C17-FAME, a vacuum oil (NBS 22a) to replace NBS 22 oil, and a (2)H-enriched vacuum oil. A total of 11 laboratories from 7 countries used multiple analytical approaches and instrumentation for 2-point isotopic normalization against international primary measurement standards. The use of reference waters in silver tubes allowed direct normalization of δ(2)H values of organic materials against isotopic reference waters following the principle of identical treatment. Bayesian statistical analysis yielded the mean values reported here. New RMs are numbered from USGS61 through USGS78, in addition to NBS 22a. Because of exchangeable hydrogen, amino acid RMs currently are recommended only for carbon- and nitrogen-isotope measurements. Some amino acids contain (13)C and carbon-bound organic (2)H-enrichments at different molecular sites to provide RMs for potential site-specific isotopic analysis in future studies. PMID:26974360

  5. Reconstructing C3 and C4 vegetation cover using n-alkane carbon isotope ratios in recent lake sediments from Cameroon, Western Central Africa

    NASA Astrophysics Data System (ADS)

    Garcin, Yannick; Schefuß, Enno; Schwab, Valérie F.; Garreta, Vincent; Gleixner, Gerd; Vincens, Annie; Todou, Gilbert; Séné, Olivier; Onana, Jean-Michel; Achoundong, Gaston; Sachse, Dirk

    2014-10-01

    Trees and shrubs in tropical Africa use the C3 cycle as a carbon fixation pathway during photosynthesis, while grasses and sedges mostly use the C4 cycle. Leaf-wax lipids from sedimentary archives such as the long-chain n-alkanes (e.g., n-C27 to n-C33) inherit carbon isotope ratios that are representative of the carbon fixation pathway. Therefore, n-alkane δ13C values are often used to reconstruct past C3/C4 composition of vegetation, assuming that the relative proportions of C3 and C4 leaf waxes reflect the relative proportions of C3 and C4 plants. We have compared the δ13C values of n-alkanes from modern C3 and C4 plants with previously published values from recent lake sediments and provide a framework for estimating the fractional contribution (areal-based) of C3 vegetation cover (fC3) represented by these sedimentary archives. Samples were collected in Cameroon, across a latitudinal transect that accommodates a wide range of climate zones and vegetation types, as reflected in the progressive northward replacement of C3-dominated rain forest by C4-dominated savanna. The C3 plants analysed were characterised by substantially higher abundances of n-C29 alkanes and by substantially lower abundances of n-C33 alkanes than the C4 plants. Furthermore, the sedimentary δ13C values of n-C29 and n-C31 alkanes from recent lake sediments in Cameroon (-37.4‰ to -26.5‰) were generally within the range of δ13C values for C3 plants, even when from sites where C4 plants dominated the catchment vegetation. In such cases simple linear mixing models fail to accurately reconstruct the relative proportions of C3 and C4 vegetation cover when using the δ13C values of sedimentary n-alkanes, overestimating the proportion of C3 vegetation, likely as a consequence of the differences in plant wax production, preservation, transport, and/or deposition between C3 and C4 plants. We therefore tested a set of non-linear binary mixing models using δ13C values from both C3 and C4

  6. Carbon and Hydrogen Isotopic Composition of Plant Wax n-Alkanes: A Tool for Characterizing Soil Provenance in Forensic Science

    NASA Astrophysics Data System (ADS)

    Pedentchouk, N.; Wagner, T.; Jones, M.

    2009-04-01

    Forensic science is an integrative discipline that requires material evidence from diverse sources. Geochemical evidence derived from inorganic and organic substances is becoming increasingly popular among law enforcement agencies in industrialized countries. Previous investigations indicate that the relative distributions of individual plant-derived biomarkers found in soils are linked to the biomarker patterns found in the overlying vegetation. However, identification of soil provenance based on the distribution of plant-derived biomarkers for forensic purposes is inhibited by the fact that a significant number of terrestrial plant species have overlapping biomarker distributions. In order to enhance the resolving power of plant-derived biomarker signal, we propose to enhance the molecular approach by adding a stable isotope component, i.e. the delta13C/deltaD values of individual biomarkers. The first objective of this project is to determine the delta13C/deltaD signatures of n-alkanes derived from various higher plant types commonly growing in the UK. The second objective is to investigate whether the same species/plant types differ isotopically between two locations affected by different weather patterns in the UK: a relatively warmer and drier Norwich, Norfolk and a cooler and wetter Newcastle-upon-Tyne in NE England. The n-C29 alkane data from 14 tree species sampled during July 2007 and August 2008 in Newcastle show a clear negative trend between delta13C and deltaD values. When these data are plotted against each other, the six deciduous angiosperms (delta13C: c. -39 to -35 per mil; deltaD: c. -155 to -130 per mil) are completely separated from four evergreen angiosperms (delta13C: c. -33 to -28 per mil; deltaD: c. -195 to -165 per mil). The four gymnosperm species data plot between those of the deciduous and evergreen angiosperms. Because all 14 species in Newcastle experience the same environmental conditions, we suggest that the observed isotopic

  7. Catalytic functionalization of methane and light alkanes in supercritical carbon dioxide.

    PubMed

    Fuentes, M Ángeles; Olmos, Andrea; Muñoz, Bianca K; Jacob, Kane; González-Núñez, M Elena; Mello, Rossella; Asensio, Gregorio; Caballero, Ana; Etienne, Michel; Pérez, Pedro J

    2014-08-25

    The development of catalytic methods for the effective functionalization of methane yet remains a challenge. The best system known to date is the so-called Catalytica Process based on the use of platinum catalysts to convert methane into methyl bisulfate with a TOF rate of 10(-3) s. In this contribution, we report a series of silver complexes containing perfluorinated tris(indazolyl)borate ligands that catalyze the functionalization of methane into ethyl propionate upon reaction with ethyl diazoacetate (EDA) by using supercritical carbon dioxide (scCO2) as the reaction medium. The employment of this reaction medium has also allowed the functionalization of ethane, propane, butane, and isobutane.

  8. Catalytic functionalization of methane and light alkanes in supercritical carbon dioxide.

    PubMed

    Fuentes, M Ángeles; Olmos, Andrea; Muñoz, Bianca K; Jacob, Kane; González-Núñez, M Elena; Mello, Rossella; Asensio, Gregorio; Caballero, Ana; Etienne, Michel; Pérez, Pedro J

    2014-08-25

    The development of catalytic methods for the effective functionalization of methane yet remains a challenge. The best system known to date is the so-called Catalytica Process based on the use of platinum catalysts to convert methane into methyl bisulfate with a TOF rate of 10(-3) s. In this contribution, we report a series of silver complexes containing perfluorinated tris(indazolyl)borate ligands that catalyze the functionalization of methane into ethyl propionate upon reaction with ethyl diazoacetate (EDA) by using supercritical carbon dioxide (scCO2) as the reaction medium. The employment of this reaction medium has also allowed the functionalization of ethane, propane, butane, and isobutane. PMID:25065490

  9. n-Alkanes in surficial sediments of Visakhapatnam harbour, east coast of India

    NASA Astrophysics Data System (ADS)

    Punyu, V. R.; Harji, R. R.; Bhosle, N. B.; Sawant, S. S.; Venkat, K.

    2013-04-01

    Surface sediments collected from 19 stations along Visakhapatnam harbour were analysed for organic carbon (OC), δ 13Coc, total lipids (TL), total hydrocarbon (THC), n-alkane concentration and composition. OC, δ 13Coc, TL and THC ranged from 0.6% to 7.6%, -29.3 to -23.8‰, 300 to 14,948 \\upmu g g - 1 dw, and 0.2 to 2,277 \\upmu g g - 1 dw, respectively. Predominance of even carbon numbers n-alkanes C12-C21 with carbon preference index (CPI) of <1 suggests major microbial influence. Fair abundance of odd carbon number n-alkanes in the range of C15-C22 and C23-C33 indicates some input from phytoplankton and terrestrial sources, respectively. Petrogenic input was evident from the presence of hopanes and steranes. The data suggest that organic matter (OM) sources varied spatially and were mostly derived from mixed source.

  10. Adiabatic Coupling Constant of Nitrobenzene- n-Alkane Critical Mixtures. Evidence from Ultrasonic Spectra and Thermodynamic Data

    NASA Astrophysics Data System (ADS)

    Mirzaev, Sirojiddin Z.; Kaatze, Udo

    2016-09-01

    Ultrasonic spectra of mixtures of nitrobenzene with n-alkanes, from n-hexane to n-nonane, are analyzed. They feature up to two Debye-type relaxation terms with discrete relaxation times and, near the critical point, an additional relaxation term due to the fluctuations in the local concentration. The latter can be well represented by the dynamic scaling theory. Its amplitude parameter reveals the adiabatic coupling constant of the mixtures of critical composition. The dependence of this thermodynamic parameter upon the length of the n-alkanes corresponds to that of the slope in the pressure dependence of the critical temperature and is thus taken another confirmation of the dynamic scaling model. The change in the variation of the coupling constant and of several other mixture parameters with alkane length probably reflects a structural change in the nitrobenzene- n-alkane mixtures when the number of carbon atoms per alkane exceeds eight.

  11. Molecular mobility depending on chain length and thermally induced molecular motion of n-alkane/urea inclusion compounds

    NASA Astrophysics Data System (ADS)

    Nakaoki, Takahiko; Nagano, Hiromasa; Yanagida, Toshinori

    2004-08-01

    Solid-state high resolution 13C NMR was used to analyze the end group conformation and molecular mobility of n-alkanes in a urea host as a function of the carbon number of the n-alkane. It was shown that the chemical shift of the inner methylenes could be interpreted by the γ- gauche effect. Of further interest is our finding that the chemical shift of 3-methylene is independent of both chain length and temperature, a result indicating that the torsional rotation of the bond ω 3 between the 4-methylene and 5-methylene carbons is so inhibited that there is little gauche conformation. The chemical shift of the inner methylenes indicated a different tendency between the even- and the odd-numbered n-alkanes. The fact that the signals of the even-numbered n-alkanes were observed at a comparatively more upfield location than those of the odd-numbered ones indicated that the even-numbered n-alkane had a higher molecular mobility and tended to adopt a more gauche conformation. The decomposition temperature obtained by thermal analysis also suggested a difference between the even- and odd-numbered n-alkanes. The decomposition temperature of the even-numbered n-alkane/urea inclusion compounds was a little lower than that of the odd-numbered ones, a disparity corresponding to the higher molecular mobility of the n-alkane in the urea host. The spin-lattice relaxation time ( T1C) increased with increasing chain length for chains with less than the 14 carbon atoms but reached a constant value for all longer chains. This result is completely different from that for the n-alkane crystal, which gave a longer T1C depending on the chain length, and can be explained by a reduced intermolecular interaction between the n-alkane and the urea host. Clearly, T1C measurements can be applied to confirm the formation of inclusion compounds. However, the different T1C values between the methyl, 2-, 3-, and inner methylene carbons indicates that the n-alkane molecule does not rotate so fast

  12. Thermal decomposition of alkane hydrocarbons inside a porous Ni anode for fuel supply of direct carbon fuel cell: Effects of morphology and crystallinity of carbon

    NASA Astrophysics Data System (ADS)

    Li, Chengguo; Yi, Hakgyu; Jalalabadi, Tahereh; Lee, Donggeun

    2015-10-01

    This study improved the physical contact between anode and fuel in a direct carbon fuel cell (DCFC) by directly generating carbon in a porous Ni anode through thermal decomposition of three kinds of hydrocarbons (CH4, C2H6, C3H8). From electron microscope observations of the carbon particles generated from each hydrocarbon, carbon spheres (CS), carbon nanotubes (CNT) and carbon nanofibers (CNF) were identified with increasing carbon number. Raman scattering analysis was performed to determine the crystallinity of the carbon samples. As a result, the carbon samples (CS, CNT, and CNF) produced from CH4, C2H6 and C3H8 were found to be less crystalline and more flexible with increasing the carbon number. DCFC performance was measured at 700 °C for the anode fueled with the same mass of the carbon sample. It was found that the 1-dimensional CNT and CNF were more active to produce 148% and 210% times higher power density than the CS. The difference was partly attributed to the finding that the less-crystalline CNT and CNF had much lower charge transfer resistances than the CS. A lifetime test found that the CNT and CNF, which are capable of transporting electrons for much longer periods, maintained the power density much longer, as compared to the CS which can lose their point contacts between the particles shortly at high current density.

  13. Surface crystallization and thin film melting in normal alkanes

    SciTech Connect

    Wu, X.Z. |; Shao, H.H. |; Ocko, B.M.; Deutsch, M.; Sinha, S.K.; Kim, M.W.; King, H.E. Jr.; Sirota, E.B.

    1994-12-31

    Normal alkanes of carbon number n > 14 exhibit surface crystallization at their liquid-vapor interface. This has been investigated with x-ray reflectivity, grazing incidence scattering and surface tension measurements. The structure and thermodynamics of the surface layer is consistent with a monolayer of the bulk rotator phase occurring at the surface above the bulk melting temperature. On the other hand, thin films of alkanes on SiO{sub 2}, exhibit a reduction of the melting temperature. The surface crystalline phase is observed for carbon number n > 14. The vanishing of surface phase for small n may be due to a transition from surface freezing to surface melting behavior. These measurements can yield the relative surface energies of the various phases. 41 refs.

  14. Achlorophyllous alga Prototheca zopfii oxidizes n-alkanes with different carbon-chain lengths through a unique subterminal oxidation pathway.

    PubMed

    Takimura, Yasushi; Sakuradani, Eiji; Natsume, Yusuke; Miyake, Takashi; Ogawa, Jun; Shimizu, Sakayu

    2014-03-01

    Some Prototheca spp. were previously reported to convert n-hexadecane to 5-hexadecanol and then to 5-hexadecanone through a unique subterminal oxidation pathway. Further analysis of derivatives derived from n-hexadecane indicated that Prototheca zopfii oxidized n-alkanes with C11 to C17 chain lengths at not only the 5th but also the 4th, 3rd and 2nd positions. PMID:24099955

  15. Determination of n-alkanes contamination in soil samples by micro gas chromatography functionalized by multi-walled carbon nanotubes.

    PubMed

    Li, Yubo; Zhang, Runzhou; Wang, Tao; Wang, Yonghuan; Xu, Tianbai; Li, Lingfeng; Zhao, Weijun; Dong, Shurong; Wang, Xiaozhi; Luo, Jikui

    2016-09-01

    A new method for separation of 11 n-alkanes: octane, o-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentdecne, n-hexadecath, heptadecane, n-octadecane in soil samples was developed. Kuderna-Danish (K.D.) concentrator enrichment prior to ultrasonic extraction and the silicone chromatography column purification and with gas chromatography flame ionization detection (GC-FID) could be used for n-alkanes determination. The micro channels of open tubular column were fabricated onto a silicon wafer to replace the quartz capillary chromatographic column. The column structure and analysis parameters that affected the column separation were investigated and optimized. Under optimal conditions, the extract reagent was centrifuged and collected. A silicone chromatography column and a K.D. concentrator were used for further clean-up and enrichment. Using this method, the limits of detection (LOD) and limits of quantification (LOQ) were obtained in the range of 0.03-0.15 and 0.1-0.5 mg kg(-1) in soil samples, respectively. The relative standard deviation (RSD) was under 12%. The optimized procedure that presented good analytical performance (with recoveries ranging from 56.5% to 89.2%), was successfully applied to determine n-alkane content in farmland soil samples adjacent to a highway. The results showed that the MWCNTs-functionalized column is capable of separating the alkane contaminations with high resolution in about 3 min, which is much shorter than that of GC-MS and other conventional analytical methods, demonstrating its great potential for rapid analysis.

  16. Determination of n-alkanes contamination in soil samples by micro gas chromatography functionalized by multi-walled carbon nanotubes.

    PubMed

    Li, Yubo; Zhang, Runzhou; Wang, Tao; Wang, Yonghuan; Xu, Tianbai; Li, Lingfeng; Zhao, Weijun; Dong, Shurong; Wang, Xiaozhi; Luo, Jikui

    2016-09-01

    A new method for separation of 11 n-alkanes: octane, o-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentdecne, n-hexadecath, heptadecane, n-octadecane in soil samples was developed. Kuderna-Danish (K.D.) concentrator enrichment prior to ultrasonic extraction and the silicone chromatography column purification and with gas chromatography flame ionization detection (GC-FID) could be used for n-alkanes determination. The micro channels of open tubular column were fabricated onto a silicon wafer to replace the quartz capillary chromatographic column. The column structure and analysis parameters that affected the column separation were investigated and optimized. Under optimal conditions, the extract reagent was centrifuged and collected. A silicone chromatography column and a K.D. concentrator were used for further clean-up and enrichment. Using this method, the limits of detection (LOD) and limits of quantification (LOQ) were obtained in the range of 0.03-0.15 and 0.1-0.5 mg kg(-1) in soil samples, respectively. The relative standard deviation (RSD) was under 12%. The optimized procedure that presented good analytical performance (with recoveries ranging from 56.5% to 89.2%), was successfully applied to determine n-alkane content in farmland soil samples adjacent to a highway. The results showed that the MWCNTs-functionalized column is capable of separating the alkane contaminations with high resolution in about 3 min, which is much shorter than that of GC-MS and other conventional analytical methods, demonstrating its great potential for rapid analysis. PMID:27262105

  17. Enzymes and genes involved in aerobic alkane degradation

    PubMed Central

    Wang, Wanpeng; Shao, Zongze

    2013-01-01

    Alkanes are major constituents of crude oil. They are also present at low concentrations in diverse non-contaminated because many living organisms produce them as chemo-attractants or as protecting agents against water loss. Alkane degradation is a widespread phenomenon in nature. The numerous microorganisms, both prokaryotic and eukaryotic, capable of utilizing alkanes as a carbon and energy source, have been isolated and characterized. This review summarizes the current knowledge of how bacteria metabolize alkanes aerobically, with a particular emphasis on the oxidation of long-chain alkanes, including factors that are responsible for chemotaxis to alkanes, transport across cell membrane of alkanes, the regulation of alkane degradation gene and initial oxidation. PMID:23755043

  18. Latitudinal distribution of terrestrial lipid biomarkers and n-alkane compound-specific stable carbon isotope ratios in the atmosphere over the western Pacific and Southern Ocean

    NASA Astrophysics Data System (ADS)

    Bendle, James; Kawamura, Kimitaka; Yamazaki, Koji; Niwai, Takeji

    2007-12-01

    We investigated the latitudinal changes in atmospheric transport of organic matter to the western Pacific and Southern Ocean (27.58°N-64.70°S). Molecular distributions of lipid compound classes (homologous series of C 15 to C 35n-alkanes, C 8 to C 34n-alkanoic acids, C 12 to C 30n-alkanols) and compound-specific stable isotopes (δ 13C of C 29 and C 31n-alkanes) were measured in marine aerosol filter samples collected during a cruise by the R/V Hakuho Maru. The geographical source areas for each sample were estimated from air-mass back-trajectory computations. Concentrations of TC and lipid compound classes were several orders of magnitude lower than observations from urban sites in Asia. A stronger signature of terrestrial higher plant inputs was apparent in three samples collected under conditions of strong terrestrial winds. Unresolved complex mixtures (UCM) showed increasing values in the North Pacific, highlighting the influence of the plume of polluted air exported from East Asia. n-Alkane average chain length (ACL) distribution had two clusters, with samples showing a relation to latitude between 28°N and 47°S (highest ACL values in the tropics), whilst a subset of southern samples had anomalously high ACL values. Compound-specific carbon isotopic analysis of the C 29 (-25.6‰ to -34.5‰) and C 31n-alkanes (-28.3‰ to -37‰) revealed heavier δ 13C values in the northern latitudes with a transition to lighter values in the Southern Ocean. By comparing the isotopic measurements with back-trajectory analysis it was generally possible to discriminate between different source areas. The terrestrial vegetation source for a subset of the southernmost Southern Ocean is enigmatic; the back-trajectories indicate eastern Antarctica as the only intercepted terrestrial source area. These samples may represent a southern hemisphere background of well mixed and very long range transported higher plant organic material.

  19. Solar photothermochemical alkane reverse combustion

    PubMed Central

    Chanmanee, Wilaiwan; Islam, Mohammad Fakrul; Dennis, Brian H.; MacDonnell, Frederick M.

    2016-01-01

    A one-step, gas-phase photothermocatalytic process for the synthesis of hydrocarbons, including liquid alkanes, aromatics, and oxygenates, with carbon numbers (Cn) up to C13, from CO2 and water is demonstrated in a flow photoreactor operating at elevated temperatures (180–200 °C) and pressures (1–6 bar) using a 5% cobalt on TiO2 catalyst and under UV irradiation. A parametric study of temperature, pressure, and partial pressure ratio revealed that temperatures in excess of 160 °C are needed to obtain the higher Cn products in quantity and that the product distribution shifts toward higher Cn products with increasing pressure. In the best run so far, over 13% by mass of the products were C5+ hydrocarbons and some of these, i.e., octane, are drop-in replacements for existing liquid hydrocarbons fuels. Dioxygen was detected in yields ranging between 64% and 150%. In principle, this tandem photochemical–thermochemical process, fitted with a photocatalyst better matched to the solar spectrum, could provide a cheap and direct method to produce liquid hydrocarbons from CO2 and water via a solar process which uses concentrated sunlight for both photochemical excitation to generate high-energy intermediates and heat to drive important thermochemical carbon-chain-forming reactions. PMID:26903631

  20. Solar photothermochemical alkane reverse combustion.

    PubMed

    Chanmanee, Wilaiwan; Islam, Mohammad Fakrul; Dennis, Brian H; MacDonnell, Frederick M

    2016-03-01

    A one-step, gas-phase photothermocatalytic process for the synthesis of hydrocarbons, including liquid alkanes, aromatics, and oxygenates, with carbon numbers (Cn) up to C13, from CO2 and water is demonstrated in a flow photoreactor operating at elevated temperatures (180-200 °C) and pressures (1-6 bar) using a 5% cobalt on TiO2 catalyst and under UV irradiation. A parametric study of temperature, pressure, and partial pressure ratio revealed that temperatures in excess of 160 °C are needed to obtain the higher Cn products in quantity and that the product distribution shifts toward higher Cn products with increasing pressure. In the best run so far, over 13% by mass of the products were C5+ hydrocarbons and some of these, i.e., octane, are drop-in replacements for existing liquid hydrocarbons fuels. Dioxygen was detected in yields ranging between 64% and 150%. In principle, this tandem photochemical-thermochemical process, fitted with a photocatalyst better matched to the solar spectrum, could provide a cheap and direct method to produce liquid hydrocarbons from CO2 and water via a solar process which uses concentrated sunlight for both photochemical excitation to generate high-energy intermediates and heat to drive important thermochemical carbon-chain-forming reactions.

  1. Development of solid-phase microextraction fibers based on multi-walled carbon nanotubes for pre-concentration and analysis of alkanes in human breath.

    PubMed

    Tang, Zhentao; Liu, Yong; Duan, Yixiang

    2015-12-18

    In this work, a laboratory preparation method based on sol-gel technology was proposed to develop a new kind of SPME (solid phase microextraction) fibers. Multi-walled carbon nanotubes (MWCNT) were selected as sol-gel active organic component. Stainless steel wires were used as the substrate of the fibers. Instead of traditional modification methods, microwave induced plasma was used to modify the stainless steel wire surface, resulting in a significant improvement in chemical adhesion of the fiber substrate and coating. The MWCNT coating exhibited several good properties. Acceptable fiber-to-fiber reproducibility (RSD≤13%) and repeatability (RSD<7%) were obtained. End-tidal breath of 10 normal humans were collected by Bio-VOC(®) sampler and assayed by the optimized SPME-GC-MS method. The calibration curves were all linear (R(2)≥0.994) in the range from 0.03 to 403.3ppbv for five alkanes. Detection limits (down to 0.001ppbv) were about one order of magnitude better than those of commercial PDMS fibers. The recovery of the spiked alkanes in real breath sample at 1ppbv ranged from 89.71 to 101.08% and the relative standard deviations were less than 8%. These results demonstrated the feasibility and practicality of the proposed preparation procedure. Applications of the in-house fabricated fibers for human breath analysis were successfully verified. PMID:26614173

  2. Development of solid-phase microextraction fibers based on multi-walled carbon nanotubes for pre-concentration and analysis of alkanes in human breath.

    PubMed

    Tang, Zhentao; Liu, Yong; Duan, Yixiang

    2015-12-18

    In this work, a laboratory preparation method based on sol-gel technology was proposed to develop a new kind of SPME (solid phase microextraction) fibers. Multi-walled carbon nanotubes (MWCNT) were selected as sol-gel active organic component. Stainless steel wires were used as the substrate of the fibers. Instead of traditional modification methods, microwave induced plasma was used to modify the stainless steel wire surface, resulting in a significant improvement in chemical adhesion of the fiber substrate and coating. The MWCNT coating exhibited several good properties. Acceptable fiber-to-fiber reproducibility (RSD≤13%) and repeatability (RSD<7%) were obtained. End-tidal breath of 10 normal humans were collected by Bio-VOC(®) sampler and assayed by the optimized SPME-GC-MS method. The calibration curves were all linear (R(2)≥0.994) in the range from 0.03 to 403.3ppbv for five alkanes. Detection limits (down to 0.001ppbv) were about one order of magnitude better than those of commercial PDMS fibers. The recovery of the spiked alkanes in real breath sample at 1ppbv ranged from 89.71 to 101.08% and the relative standard deviations were less than 8%. These results demonstrated the feasibility and practicality of the proposed preparation procedure. Applications of the in-house fabricated fibers for human breath analysis were successfully verified.

  3. Liquid-liquid interfaces of semifluorinated alkane diblock copolymers with water, alkanes, and perfluorinated alkanes.

    SciTech Connect

    Perahia, Dvora, Dr.; Pierce, Flint; Tsige, Mesfin; Grest, Gary Stephen, Dr.

    2008-08-01

    The liquid-liquid interface between semifluorinated alkane diblock copolymers of the form F3C(CF2)n-1-(CH2)m-1CH3 and water, protonated alkanes, and perfluorinated alkanes are studied by fully atomistic molecular dynamics simulations. A modified version of the OPLS-AA (Optimized Parameter for Liquid Simulation All-Atom) force field of Jorgensen et al. has been used to study the interfacial behavior of semifluorinated diblocks. Aqueous interfaces are found to be sharp, with correspondingly large values of the interfacial tension. Due to the reduced hydrophobicity of the protonated block compared to the fluorinated block, hydrogen enhancement is observed at the interface. Water dipoles in the interfacial region are found to be oriented nearly parallel to the liquid-liquid interface. A number of protonated alkanes and perfluorinated alkanes are found to be mutually miscible with the semifluorinated diblocks. For these liquids, interdiffusion follows the expected Fickian behavior, and concentration-dependent diffusivities are determined.

  4. The origin of alkanes found in human skin surface lipids

    SciTech Connect

    Bortz, J.T.; Wertz, P.W.; Downing, D.T. )

    1989-12-01

    Lipids extracted from human skin contain variable amounts of paraffin hydrocarbons. Although the composition of these alkanes strongly resembles petroleum waxes, it has been proposed that they are biosynthetic products of human skin. To investigate this question, skin surface lipids from 15 normal subjects were analyzed for the amount and composition of alkanes, using quantitative thin-layer chromatography and quartz capillary gas chromatography. The alkanes were found to constitute 0.5% to 1.7% of the skin lipids. Subjects differed greatly in the chain length distribution of their alkanes between 15 and 35 carbon atoms, and in the relative amounts of normal alkanes (like those in petroleum waxes) and branched chain alkanes (like those in petroleum lubricating oils). In 6 subjects, the alkane content of cerumen from each ear was examined to investigate whether alkanes arrive at the skin surface by a systemic route or by direct contact with environmental surfaces. No trace of alkanes was found in 11 of the 12 cerumen samples. Using a tandem accelerator mass spectrometer for carbon-14 dating, a combined sample of the skin surface alkanes was found to have a theoretical age of 30,950 years, similar to that of a sample of petrolatum. These analyses indicate that the alkanes found on the surface of human skin are mixtures of a variety of petroleum distillation fractions that are acquired by direct contamination from the environment.

  5. Diffusion Coefficients of n-Alkanes and Polyethylenes Filled with Zinc Oxide Nanoparticles

    NASA Astrophysics Data System (ADS)

    Ozisik, Rahmi; Mattice, Wayne L.; von Meerwall, Ernst

    2003-03-01

    The diffusion coefficients of various n-alkane and polyethylene samples filled with zinc oxide nanoparticles were measured with pulsed-gradient spin-echo (PGSE) NMR technique. The n-alkanes used in this study had carbon numbers ranging between 12 and 60. The number average molecular weights of the two polyethylene samples were 6200 and 13900 g/mol. The different size of zinc oxide used with spherical geometry. The experiments were performed with three different zinc oxide nanoparticles that had differing sizes. This study investigates the effects of the nanoparticle size and the molecular weight on the diffusion coefficient of the polymer chains. The results account for the restriction to diffusion due to detour and tortuosity effects, which differ for n-alkanes and polyethylene. Because the effective diffusion distance in the PGSE NMR experiments is larger than the size of the nanoparticles, the observed diffusivities represent asymptotic averages over multiple encounters between the diffusing molecules and the nanoparticles.

  6. Particle size distribution of n-alkanes nda Pb-210 in aerosols off the coast of Peru

    NASA Astrophysics Data System (ADS)

    Schneider, J. K.; Gagosian, R. B.; Cochran, J. K.; Trull, T. W.

    1983-08-01

    The results of particle size distributions measurements of aliphatic hydrocarbons and Pb-210 in aerosols in the upwelling zone off the Peruvian coast are reported. The data were taken as part of the Sea/Air Exchange Program (Searex) using cascade impactor samples on ships cruising 10-100 km off the coast. The samplers were situated on masts on the bow of the ship, which was steered into the wind, with samples taken only when the wind speeds exceeded 5 m/sec. The dominant aliphatic hydrocarbon fraction was n-alkanes above C20, and n-alkane concentrations were calculated as a function of the carbon number. Increasing Pb-210 concentrations were observed with decreasing particle size, a similar situation to that of the n-alkanes. It is suggested that the particle size distribution characteristics are due to fossil fuel combustion and gas-particle partitioning of the n-alkanes.

  7. Thermal conductivity of liquid n-alkanes

    SciTech Connect

    Calado, J.C.G.; Fareleira, J.M.N.A.; Mardolcar, U.V.; Nieto de Castro, C.A.

    1988-05-01

    The thermal conductivity of liquids has been shown in the past to be difficult to predict with a reasonable accuracy, due to the lack of accurate experimental data and reliable prediction schemes. However, data of a high accuracy, and covering wide density ranges, obtained recently in laboratories in Boulder, Lisbon, and London with the transient hot-wire technique, can be used to revise an existing correlation scheme and to develop a new universal predictive technique for the thermal conductivity of liquid normal alkanes. The proposed correlation scheme is constructed on a theoretically based treatment of the van der Waals model of a liquid, which permits the prediction of the density dependence and the thermal conductivity of liquid n-alkanes, methane to tridecane, for temperatures between 110 and 370 K and pressures up to 0.6 MPa, i.e., for 0.3 less than or equal to T/T/sub c/ less than or equal to 0.7 and 2.4 less than or equal to rho/rho/sub c/ less than or equal to 3.7, with an accuracy of +/-1%, given a known value of the thermal conductivity of the fluid at the desired temperature. A generalization of the hard-core volumes obtained, as a function of the number of carbon atoms, showed that it was possible to predict the thermal conductivity of pentane to tetradecane +/- 2%, without the necessity of available experimental measurements.

  8. n-Alkanes and stable C, N isotopic compositions as identifiers of organic matter sources in Posidonia oceanica meadows of Alexandroupolis Gulf, NE Greece.

    PubMed

    Apostolopoulou, Maria-Venetia; Monteyne, Els; Krikonis, Konstantinos; Pavlopoulos, Kosmas; Roose, Patrick; Dehairs, Frank

    2015-10-15

    We analyzed n-alkane contents and their stable carbon isotope composition, as well as the carbon and nitrogen isotope composition (δ(13)C, δ(15)N) of sediment organic matter and different tissues of Posidonia oceanica seagrass sampled in Alexandroupolis Gulf (A.G.), north-eastern Greece, during 2007-2011. n-Alkane contents in P. oceanica and in sediments showed similar temporal trends, but relative to bulk organic carbon content, n-alkanes were much more enriched in sediments compared to seagrass tissue. Individual n-alkanes in sediments had similar values than seagrass roots and rhizomes and were more depleted in (13)C compared to seagrass leaves and sheaths, with δ(13)C values ranging from -35‰ to -28‰ and from -25‰ to -20‰, respectively. n-Alkane indexes such as the Carbon Preference Index, carbon number maximum, and n-alkane proxy 1 (C23+C25/C23+C25+C29+C31) indicate strong inputs of terrestrial organic matter, while the presence of unresolved complex mixtures suggests potential oil pollution in some sampled areas. PMID:26194407

  9. The hydrodeoxygenation of bioderived furans into alkanes

    NASA Astrophysics Data System (ADS)

    Sutton, Andrew D.; Waldie, Fraser D.; Wu, Ruilian; Schlaf, Marcel; ‘Pete' Silks, Louis A.; Gordon, John C.

    2013-05-01

    The conversion of biomass into fuels and chemical feedstocks is one part of a drive to reduce the world's dependence on crude oil. For transportation fuels in particular, wholesale replacement of a fuel is logistically problematic, not least because of the infrastructure that is already in place. Here, we describe the catalytic defunctionalization of a series of biomass-derived molecules to provide linear alkanes suitable for use as transportation fuels. These biomass-derived molecules contain a variety of functional groups, including olefins, furan rings and carbonyl groups. We describe the removal of these in either a stepwise process or a one-pot process using common reagents and catalysts under mild reaction conditions to provide n-alkanes in good yields and with high selectivities. Our general synthetic approach is applicable to a range of precursors with different carbon content (chain length). This allows the selective generation of linear alkanes with carbon chain lengths between eight and sixteen carbons.

  10. The hydrodeoxygenation of bioderived furans into alkanes.

    PubMed

    Sutton, Andrew D; Waldie, Fraser D; Wu, Ruilian; Schlaf, Marcel; Silks, Louis A Pete; Gordon, John C

    2013-05-01

    The conversion of biomass into fuels and chemical feedstocks is one part of a drive to reduce the world's dependence on crude oil. For transportation fuels in particular, wholesale replacement of a fuel is logistically problematic, not least because of the infrastructure that is already in place. Here, we describe the catalytic defunctionalization of a series of biomass-derived molecules to provide linear alkanes suitable for use as transportation fuels. These biomass-derived molecules contain a variety of functional groups, including olefins, furan rings and carbonyl groups. We describe the removal of these in either a stepwise process or a one-pot process using common reagents and catalysts under mild reaction conditions to provide n-alkanes in good yields and with high selectivities. Our general synthetic approach is applicable to a range of precursors with different carbon content (chain length). This allows the selective generation of linear alkanes with carbon chain lengths between eight and sixteen carbons. PMID:23609095

  11. Alkane production from biomass: chemo-, bio- and integrated catalytic approaches.

    PubMed

    Deneyer, Aron; Renders, Tom; Van Aelst, Joost; Van den Bosch, Sander; Gabriëls, Dries; Sels, Bert F

    2015-12-01

    Linear, branched and cyclic alkanes are important intermediates and end products of the chemical industry and are nowadays mainly obtained from fossil resources. In search for alternatives, biomass feedstocks are often presented as a renewable carbon source for the production of fuels, chemicals and materials. However, providing a complete market for all these applications seems unrealistic due to both financial and logistic issues. Despite the very large scale of current alkane-based fuel applications, biomass definitely has the potential to offer a partial solution to the fuel business. For the smaller market of chemicals and materials, a transition to biomass as main carbon source is more realistic and even probably unavoidable in the long term. The appropriate use and further development of integrated chemo- and biotechnological (catalytic) process strategies will be crucial to successfully accomplish this petro-to-bio feedstock transition. Furthermore, a selection of the most promising technologies from the available chemo- and biocatalytic tool box is presented. New opportunities will certainly arise when multidisciplinary approaches are further explored in the future. In an attempt to select the most appropriate biomass sources for each specific alkane-based application, a diagram inspired by van Krevelen is applied, taking into account both the C-number and the relative functionality of the product molecules.

  12. Alkane production from biomass: chemo-, bio- and integrated catalytic approaches.

    PubMed

    Deneyer, Aron; Renders, Tom; Van Aelst, Joost; Van den Bosch, Sander; Gabriëls, Dries; Sels, Bert F

    2015-12-01

    Linear, branched and cyclic alkanes are important intermediates and end products of the chemical industry and are nowadays mainly obtained from fossil resources. In search for alternatives, biomass feedstocks are often presented as a renewable carbon source for the production of fuels, chemicals and materials. However, providing a complete market for all these applications seems unrealistic due to both financial and logistic issues. Despite the very large scale of current alkane-based fuel applications, biomass definitely has the potential to offer a partial solution to the fuel business. For the smaller market of chemicals and materials, a transition to biomass as main carbon source is more realistic and even probably unavoidable in the long term. The appropriate use and further development of integrated chemo- and biotechnological (catalytic) process strategies will be crucial to successfully accomplish this petro-to-bio feedstock transition. Furthermore, a selection of the most promising technologies from the available chemo- and biocatalytic tool box is presented. New opportunities will certainly arise when multidisciplinary approaches are further explored in the future. In an attempt to select the most appropriate biomass sources for each specific alkane-based application, a diagram inspired by van Krevelen is applied, taking into account both the C-number and the relative functionality of the product molecules. PMID:26360875

  13. Determination of the n-alkane profile of epicuticular wax extracted from mature leaves of Cestrum nocturnum (Solanaceae: Solanales).

    PubMed

    Chowdhury, Nandita; Ghosh, Anupam; Bhattacharjee, Indranil; Laskar, Subrata; Chandra, Goutam

    2010-09-01

    An n-hexane extract of fresh, mature leaves of Cestrum nocturnum (Solanales: Solanaceae) containing thin layer epicuticular waxes was analysed by thin-layer chromatography, infrared and gas liquid chromatography using standard hydrocarbons. Seventeen long chain alkanes (n-C(18) to n-C(34)) were identified and quantified. Hentriacontane (n-C(31)) was established as the major n-alkane, while nonadecane (n-C(19)) was the least abundant component of the extracted wax fraction. The carbon preference index calculated for the sample was 1.30, showing an odd to even carbon number predominance.

  14. Catalytic conversion of light alkanes

    SciTech Connect

    Lyons, J.E.

    1992-06-30

    The second Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between April 1, 1992 and June 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products that can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon uwspomdon fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE I).

  15. Increasing the octane number of gasoline using functionalized carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Kish, Sara Safari; Rashidi, Alimorad; Aghabozorg, Hamid Reza; Moradi, Leila

    2010-03-01

    The octane number is one of the characteristics of spark-ignition fuels such as gasoline. Octane number of fuels can be improved by addition of oxygenates such as ethanol, MTBE (methyl tert-butyl ether), TBF (tertiary butyl formate) and TBA (tertiary butyl alcohol) as well as their blends with gasoline that reduce the cost impact of fuels. Carbon nanotubes (CNTs) are as useful additives for increasing the octane number. Functionalized carbon nanotubes containing amide groups have a high reactivity and can react with many chemicals. These compounds can be solubilized in gasoline to increase the octane number. In this study, using octadecylamine and dodecylamine, CNTs were amidated and the amino-functionalized carbon nanotubes were added to gasoline. Research octane number analysis showed that these additives increase octane number of the desired samples. X-ray diffraction (XRD), Fourier transforms infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and thermal gravimetry analyses (TGA) were used for characterization of the prepared functionalized carbon nanotubes.

  16. Modeling SOA production from the oxidation of intermediate volatility alkanes

    NASA Astrophysics Data System (ADS)

    Aumont, B.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

    2012-12-01

    Secondary Organic Aerosols (SOA) production and ageing is a multigenerational oxidation process involving the formation of successive organic compounds with higher oxidation degree and lower vapour pressure. This process was investigated using the explicit oxidation model GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere). Results for the C8-C24 n-alkane series show the expected trends, i.e. (i) SOA yield grows with the carbon backbone of the parent hydrocarbon, (ii) SOA yields decreases with the decreasing pre-existing organic aerosol concentration, (iii) the number of generations required to describe SOA production increases when the pre-existing organic aerosol concentration decreases. Most SOA contributors were found to be not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA). Branched alkanes are more prone to fragment in the early stage of the oxidation than their corresponding linear analogues. Fragmentation is expected to alter both the yield and the mean oxidation state of the SOA. Here, GECKO-A is applied to generate highly detailed oxidation schemes for various series of branched and cyclised alkanes. Branching and cyclisation effects on SOA yields and oxidation states will be examined.

  17. Rapid analysis of 13C in plant-wax n-alkanes for reconstruction of terrestrial vegetation signals from aquatic sediments

    NASA Astrophysics Data System (ADS)

    McDuffee, Kelsey E.; Eglinton, Timothy I.; Sessions, Alex L.; Sylva, Sean; Wagner, Thomas; Hayes, John M.

    2004-10-01

    Long-chain, odd-carbon-numbered C25 to C35n-alkanes are characteristic components of epicuticular waxes produced by terrestrial higher plants. They are delivered to aquatic systems via eolian and fluvial transport and are preserved in underlying sediments. The isotopic compositions of these products can serve as records of past vegetation. We have developed a rapid method for stable carbon isotopic analyses of total plant-wax n-alkanes using a novel, moving-wire system coupled to an isotope-ratio mass spectrometer (MW-irMS). The n-alkane fractions are prepared from sediment samples by (1) saponification and extraction with organic solvents, (2) chromatographic separation using silica gel, (3) isolation of straight-chain carbon skeletons using a zeolite molecular sieve, and (4) oxidation and removal of unsaturated hydrocarbons with RuO4. Short-chain n-alkanes of nonvascular plant origin (alkane fractions essentially free of interfering components. The δ13C values obtained by MW-irMS did not differ significantly from weighted averages of individual n-alkane δ13C values obtained by irmGC-MS. Isotopic variations in compound-class n-alkane fractions from a latitudinal transect of core-top sediments from the Southwest African margin (3°N-28°S) were congruent with those measured by compound-specific isotopic analyses of plant-wax n-alkanes. The amplitude of the variations was smaller, indicating contributions from non-plant-wax hydrocarbons, but the measurements revealed variations in carbon isotopic composition that are consistent with vegetation zones on the adjacent continent.

  18. Rapid analysis of 13C in plant-wax n-alkanes for reconstruction of terrestrial vegetation signals from aquatic sediments

    NASA Astrophysics Data System (ADS)

    McDuffee, Kelsey E.; Eglinton, Timothy I.; Sessions, Alex L.; Sylva, Sean; Wagner, Thomas; Hayes, John M.

    2004-10-01

    Long-chain, odd-carbon-numbered C25 to C35 n-alkanes are characteristic components of epicuticular waxes produced by terrestrial higher plants. They are delivered to aquatic systems via eolian and fluvial transport and are preserved in underlying sediments. The isotopic compositions of these products can serve as records of past vegetation. We have developed a rapid method for stable carbon isotopic analyses of total plant-wax n-alkanes using a novel, moving-wire system coupled to an isotope-ratio mass spectrometer (MW-irMS). The n-alkane fractions are prepared from sediment samples by (1) saponification and extraction with organic solvents, (2) chromatographic separation using silica gel, (3) isolation of straight-chain carbon skeletons using a zeolite molecular sieve, and (4) oxidation and removal of unsaturated hydrocarbons with RuO4. Short-chain n-alkanes of nonvascular plant origin (alkane fractions essentially free of interfering components. The δ13C values obtained by MW-irMS did not differ significantly from weighted averages of individual n-alkane δ13C values obtained by irmGC-MS. Isotopic variations in compound-class n-alkane fractions from a latitudinal transect of core-top sediments from the Southwest African margin (3°N-28°S) were congruent with those measured by compound-specific isotopic analyses of plant-wax n-alkanes. The amplitude of the variations was smaller, indicating contributions from non-plant-wax hydrocarbons, but the measurements revealed variations in carbon isotopic composition that are consistent with vegetation zones on the adjacent continent.

  19. Environmental swap energy and role of configurational entropy in transfer of small molecules from water into alkanes

    NASA Astrophysics Data System (ADS)

    Smejtek, Pavel; Word, Robert C.

    2004-01-01

    We studied the effect of segmented solvent molecules on the free energy of transfer of small molecules from water into alkanes (hexane, heptane, octane, decane, dodecane, tetradecane, and hexadecane). For these alkanes we measured partition coefficients of benzene, 3-methylindole (3MI), 2,3,4,6-tetrachlorophenol (TeCP), and 2,4,6-tribromophenol (TriBP) at 3, 11, 20, 3, and 47 °C. For 3MI, TeCP, and TriBP the dependence of free energy of transfer on length of alkane chains was found to be very different from that for benzene. In contrast to benzene, the energy of transfer for 3MI, TeCP, and TriBP was independent of the number of carbons in alkanes. To interpret data, we used the classic Flory-Huggins (FH) theory of concentrated polymer solutions for the alkane phase. For benzene, the measured dependence of energy of transfer on the number of carbons in alkanes agreed well with predictions based on FH model in which the size of alkane segments was obtained from the ratio of molar volumes of alkanes and the solute. We show that for benzene, the energy of transfer can be divided into two components, one called environmental swap energy (ESE), and one representing the contribution of configurational entropy of alkane chains. For 3MI, TeCP, and TriBP the contribution of configurational entropy was not measurable even though the magnitude of the effect predicted from the FH model for short chain alkanes was as much as 20 times greater than experimental uncertainties. From the temperature dependence of ESE we obtained enthalpy and entropy of transfer for benzene, 3MI, TeCP, and TriBP. Experimental results are discussed in terms of a thermodynamic cycle considering creation of cavity, insertion of solute, and activation of solute-medium attractive interactions. Our results suggest that correcting experimental free energy of transfer by Flory-Huggins configurational entropy term is not generally appropriate and cannot be applied indiscriminately.

  20. Reflectance spectroscopy of organic compounds: 1. Alkanes

    USGS Publications Warehouse

    Clark, R.N.; Curchin, J.M.; Hoefen, T.M.; Swayze, G.A.

    2009-01-01

    Reflectance spectra of the organic compounds comprising the alkane series are presented from the ultraviolet to midinfrared, 0.35 to 15.5 /??m. Alkanes are hydrocarbon molecules containing only single carbon-carbon bonds, and are found naturally on the Earth and in the atmospheres of the giant planets and Saturn's moon, Titan. This paper presents the spectral properties of the alkanes as the first in a series of papers to build a spectral database of organic compounds for use in remote sensing studies. Applications range from mapping the environment on the Earth, to the search for organic molecules and life in the solar system and throughout the. universe. We show that the spectral reflectance properties of organic compounds are rich, with major diagnostic spectral features throughout the spectral range studied. Little to no spectral change was observed as a function of temperature and only small shifts and changes in the width of absorption bands were observed between liquids and solids, making remote detection of spectral properties throughout the solar system simpler. Some high molecular weight organic compounds contain single-bonded carbon chains and have spectra similar to alkanes even ' when they fall into other families. Small spectral differences are often present allowing discrimination among some compounds, further illustrating the need to catalog spectral properties for accurate remote sensing identification with spectroscopy.

  1. The influence of molecular structure and aerosol phase on the heterogeneous oxidation of normal and branched alkanes by OH.

    PubMed

    Ruehl, Christopher R; Nah, Theodora; Isaacman, Gabriel; Worton, David R; Chan, Arthur W H; Kolesar, Katheryn R; Cappa, Christopher D; Goldstein, Allen H; Wilson, Kevin R

    2013-05-16

    Insights into the influence of molecular structure and thermodynamic phase on the chemical mechanisms of hydroxyl radical-initiated heterogeneous oxidation are obtained by identifying reaction products of submicrometer particles composed of either n-octacosane (C28H58, a linear alkane) or squalane (C30H62, a highly branched alkane) and OH. A common pattern is observed in the positional isomers of octacosanone and octacosanol, with functionalization enhanced toward the end of the molecule. This suggests that relatively large linear alkanes are structured in submicrometer particles such that their ends are oriented toward the surface. For squalane, positional isomers of first-generation ketones and alcohols also form in distinct patterns. Ketones are favored on carbons adjacent to tertiary carbons, while hydroxyl groups are primarily found on tertiary carbons but also tend to form toward the end of the molecule. Some first-generation products, viz., hydroxycarbonyls and diols, contain two oxygen atoms. These results suggest that alkoxy radicals are important intermediates and undergo both intramolecular (isomerization) and intermolecular (chain propagation) hydrogen abstraction reactions. Oxidation products with carbon number less than the parent alkane's are observed to a much greater extent for squalane than for n-octacosane oxidation and can be explained by the preferential cleavage of bonds involving tertiary carbons.

  2. A DFT and ab initio benchmarking study of metal-alkane interactions and the activation of carbon-hydrogen bonds.

    PubMed

    Flener-Lovitt, Charity; Woon, David E; Dunning, Thom H; Girolami, Gregory S

    2010-02-01

    Density functional theory and ab initio methods have been used to calculate the structures and energies of minima and transition states for the reactions of methane coordinated to a transition metal. The reactions studied are reversible C-H bond activation of the coordinated methane ligand to form a transition metal methyl hydride complex and dissociation of the coordinated methane ligand. The reaction sequence can be summarized as L(x)M(CH(3))H <==> L(x)M(CH(4)) <==> L(x)M + CH(4), where L(x)M is the osmium-containing fragment (C(5)H(5))Os(R(2)PCH(2)PR(2))(+) and R is H or CH(3). Three-center metal-carbon-hydrogen interactions play an important role in this system. Both basis sets and functionals have been benchmarked in this work, including new correlation consistent basis sets for a third transition series element, osmium. Double zeta quality correlation consistent basis sets yield energies close to those from calculations with quadruple-zeta basis sets, with variations that are smaller than the differences between functionals. The energies of important species on the potential energy surface, calculated by using 10 DFT functionals, are compared both to experimental values and to CCSD(T) single point calculations. Kohn-Sham natural bond orbital descriptions are used to understand the differences between functionals. Older functionals favor electrostatic interactions over weak donor-acceptor interactions and, therefore, are not particularly well suited for describing systems--such as sigma-complexes--in which the latter are dominant. Newer kinetic and dispersion-corrected functionals such as MPW1K and M05-2X provide significantly better descriptions of the bonding interactions, as judged by their ability to predict energies closer to CCSD(T) values. Kohn-Sham and natural bond orbitals are used to differentiate between bonding descriptions. Our evaluations of these basis sets and DFT functionals lead us to recommend the use of dispersion corrected functionals in

  3. Evaluation of the organic matter sources using the δ13C composition of individual n-alkanes in sediments from Brazilian estuarine systems by GC/C/IRMS

    NASA Astrophysics Data System (ADS)

    Maioli, Otávio Luiz Gusso; de Oliveira, Cristiane Rossi; Dal Sasso, Marco Aurélio; Madureira, Luiz Augusto dos Santos; Azevedo, Débora de Almeida; de Aquino Neto, Francisco Radler

    2012-12-01

    The δ13C composition of individual n-alkanes (from C16 to C34) was measured from surface sediments of five Brazilian estuarine systems affected by different organic matter sources, such as harbor area, industries, urban centers and sugar cane crops, in order to determine the origins of the organic matter. The aliphatic hydrocarbon fraction was analyzed by gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS). The levels of n-alkanes in the studied areas ranged from 0.34 to 18.14 μg kg-1, being relatively low in comparison to high polluted environments. The Carbon Preference Index (CPI) calculated in the C23-C34 range indicates that n-alkanes are mainly inherited from cuticular waxes of higher plants. The δ13C composition of all n-alkanes detected in the sediment samples ranged from -39.6 to -18.3‰ showing different sources for the studied estuarine systems. Through Principal Component Analysis (PCA) it was possible to verify the petrogenic influence in the n-alkane sources, especially in the Paraíba do Sul sediment samples. Differences up to 15‰ of the δ13C values between n-alkanes of odd and even carbon number (C26 and C27) also indicated mixture of petrogenic and biogenic sources in Paraíba do Sul River. High (less negative) δ13C n-alkane values of odd carbon number were obtained from two sampling sites located close to an ethanol plant, indicating residues discharge of sugar cane (C4 plant). Influence of C3 plants that are the main components of dense ombrophile forest was observed in the Itajaí-Açu sediments by the decrease of δ13C (about 10‰ compared to the Paraíba do Sul River δ13C).

  4. Expanding the product profile of a microbial alkane biosynthetic pathway.

    PubMed

    Harger, Matthew; Zheng, Lei; Moon, Austin; Ager, Casey; An, Ju Hye; Choe, Chris; Lai, Yi-Ling; Mo, Benjamin; Zong, David; Smith, Matthew D; Egbert, Robert G; Mills, Jeremy H; Baker, David; Pultz, Ingrid Swanson; Siegel, Justin B

    2013-01-18

    Microbially produced alkanes are a new class of biofuels that closely match the chemical composition of petroleum-based fuels. Alkanes can be generated from the fatty acid biosynthetic pathway by the reduction of acyl-ACPs followed by decarbonylation of the resulting aldehydes. A current limitation of this pathway is the restricted product profile, which consists of n-alkanes of 13, 15, and 17 carbons in length. To expand the product profile, we incorporated a new part, FabH2 from Bacillus subtilis , an enzyme known to have a broader specificity profile for fatty acid initiation than the native FabH of Escherichia coli . When provided with the appropriate substrate, the addition of FabH2 resulted in an altered alkane product profile in which significant levels of n-alkanes of 14 and 16 carbons in length are produced. The production of even chain length alkanes represents initial steps toward the expansion of this recently discovered microbial alkane production pathway to synthesize complex fuels. This work was conceived and performed as part of the 2011 University of Washington international Genetically Engineered Machines (iGEM) project.

  5. Sophorolipids from Torulopsis bombicola: possible relation to alkane uptake.

    PubMed Central

    Ito, S; Inoue, S

    1982-01-01

    Torulopsis bombicola produces extracellular sophorolipids when it is grown on water-insoluble alkanes. Sophorolipids and related model compounds, which were not themselves used for growth, were found to stimulate markedly the growth of T. bombicola on alkanes. This stimulatory effect was restricted to growth on C10 to C20 alkanes, whereas no significantly influence was observed for growth on fatty alcohols, fatty acids, glucose, or glycerol. The nonionic methyl ester of the glycolipid supported the greatest cell yield. However, a number of synthetic nonionic surfactants were unable to replace the glycolipid. When organisms were grown on hexadecane, stimulation of growth by sophorolipids was observed almost exclusively with strains of Torulopsis yeasts. In contrast, the growth of other typical alkane-utilizing yeasts, such as candida and Pichia strains, was inhibited or not affected. It appears that sophorolipids are involved in alkane dissimilation by T. bombicola through an undetermined mechanism. PMID:7201782

  6. Global Civil Aviation Black Carbon Particle Mass and Number Emissions

    NASA Astrophysics Data System (ADS)

    Stettler, M. E. J.

    2015-12-01

    Black carbon (BC) is a product of incomplete combustion emitted by aircraft engines. In the atmosphere, BC particles strongly absorb incoming solar radiation and influence cloud formation processes leading to highly uncertain, but likely net positive warming of the earth's atmosphere. At cruise altitude, BC particle number emissions can influence the concentration of ice nuclei that can lead to contrail formation, with significant and highly uncertainty climate impacts. BC particles emitted by aircraft engines also degrade air quality in the vicinity of airports and globally. A significant contribution to the uncertainty in environmental impacts of aviation BC emissions is the uncertainty in emissions inventories. Previous work has shown that global aviation BC mass emissions are likely to have been underestimated by a factor of three. In this study, we present an updated global BC particle number inventory and evaluate parameters that contribute to uncertainty using global sensitivity analysis techniques. The method of calculating particle number from mass utilises a description of the mobility of fractal aggregates and uses the geometric mean diameter, geometric standard deviation, mass-mobility exponent, primary particle diameter and material density to relate the particle number concentration to the total mass concentration. Model results show good agreement with existing measurements of aircraft BC emissions at ground level and at cruise altitude. It is hoped that the results of this study can be applied to estimate direct and indirect climate impacts of aviation BC emissions in future studies.

  7. Possible origin of n -alkanes with a remarkable even-to-odd predominance in recent marine sediments

    NASA Astrophysics Data System (ADS)

    Nishimura, Mitsugu; Baker, Earl W.

    1986-02-01

    N- alkane distributions with a remarkable even-to-odd predominance (C 16-C 24) were found in marine surface sediments. The previously proposed diagenetic reduction of the corresponding n- fatty acids could not be considered as a source for these N- alkane. Based on a comparison of compositional features of n- alkane, n- fatty acid and n- alcohol distributions, carbon isotope analyses, and other geochemical parameters, the data indicate that the even-predominant n- alkanes were derived directly from marine bacteria.

  8. The vapor-particle partitioning of n-alkanes

    SciTech Connect

    Doskey, P.V.

    1994-04-01

    A mixed-phase partitioning model has been proposed to predict the distribution of n-alkanes between the vapor and particle phases in the atmosphere. n-Alkanes having terrestrial plant wax and petroleum origins are assumed to be associated with atmospheric particles as microcrystalline solids and subcooled liquids, respectively. The fraction of n-alkanes on atmospheric particles having plant wax and petroleum origins is estimated with carbon preference indices. Hypothetical terrestrial plant wax and petroleum mixtures are used to estimate the mole fractions of the n-alkanes in each phase and the molecular weights of the phases. Solid and subcooled liquid phase n-alkane vapor pressures are used in the model to predict the fraction of n-alkanes associated with particles in the atmosphere. Trends in the prediction of vapor-particle partitioning using these assumptions agree well with field observations. However, the fraction of particle phase n-alkanes predicted by the model was significantly different from the field observations.

  9. State-dependent rotational diffusion of tetracene in n-alkanes. Evidence for a dominant energy relaxation pathway.

    PubMed

    Mize, Hannah E; Blanchard, G J

    2013-12-19

    We have investigated the rotational diffusion of tetracene in the n-alkanes octane through hexadecane. Emission from the S1 state was monitored following excitation to the S1 state or the S2 state. Our data show that fast, non-radiative relaxation from S2 to S1 gives rise to local heating in the immediate vicinity of the chromophore. This local heating effect exhibits a solvent aliphatic chain length dependence for solvents C11 and longer, where solvents with an even number of carbons behave differently than those with an odd number of carbons. These data shed light on the possible origin(s) of odd-even effects in n-alkanes and suggest that a dominant intermolecular relaxation pathway for excess vibrational energy involves the S1 chromophore ring breathing mode (ca. 1383 cm(-1)) and the solvent terminal methyl group rocking mode (1375 cm(-1)). PMID:24295035

  10. State-dependent rotational diffusion of tetracene in n-alkanes. Evidence for a dominant energy relaxation pathway.

    PubMed

    Mize, Hannah E; Blanchard, G J

    2013-12-19

    We have investigated the rotational diffusion of tetracene in the n-alkanes octane through hexadecane. Emission from the S1 state was monitored following excitation to the S1 state or the S2 state. Our data show that fast, non-radiative relaxation from S2 to S1 gives rise to local heating in the immediate vicinity of the chromophore. This local heating effect exhibits a solvent aliphatic chain length dependence for solvents C11 and longer, where solvents with an even number of carbons behave differently than those with an odd number of carbons. These data shed light on the possible origin(s) of odd-even effects in n-alkanes and suggest that a dominant intermolecular relaxation pathway for excess vibrational energy involves the S1 chromophore ring breathing mode (ca. 1383 cm(-1)) and the solvent terminal methyl group rocking mode (1375 cm(-1)).

  11. QSAR models for predicting in vivo aquatic toxicity of chlorinated alkanes to fish.

    PubMed

    Zvinavashe, Elton; van den Berg, Hans; Soffers, Ans E M F; Vervoort, Jacques; Freidig, Andreas; Murk, Albertinka J; Rietjens, Ivonne M C M

    2008-03-01

    Quantitative structure-activity relationship (QSAR) models are expected to play a crucial role in reducing the number of animals to be used for toxicity testing resulting from the adoption of the new European Union chemical control system called Registration, Evaluation, and Authorization of Chemicals (REACH). The objective of the present study was to generate in vitro acute toxicity data that could be used to develop a QSAR model to describe acute in vivo toxicity of chlorinated alkanes. Cytotoxicity of a series of chlorinated alkanes to Chinese hamster ovary (CHO) cells was observed at concentrations similar to those that have been shown previously to be toxic to fish. Strong correlations exist between the acute in vitro toxicity of the chlorinated alkanes and (i) hydrophobicity [modeled by the calculated log K ow (octanol-water partition coefficient); r (2) = 0.883 and r int (2) = 0.854] and (ii) in vivo acute toxicity to fish ( r (2) = 0.758). A QSAR model has been developed to predict in vivo acute toxicity to fish, based on the in vitro data and even on in silico log K ow data only. The developed QSAR model is applicable to chlorinated alkanes with up to 10 carbon atoms, up to eight chlorine atoms, and log K ow values lying within the range from 1.71 to 5.70. Out of the 100204 compounds on the European Inventory of Existing Chemicals (EINECS), our QSAR model covers 77 (0.1%) of them. Our findings demonstrate that in vitro experiments and even in silico calculations can replace animal experiments in the prediction of the acute toxicity of chlorinated alkanes.

  12. Effect of Varying the 1-4 Intramolecular Scaling Factor in Atomistic Simulations of Long-Chain N-alkanes with the OPLS-AA Model

    SciTech Connect

    de Almeida, Valmor F; Ye, Xianggui; Cui, Shengting; Khomami, Bamin

    2013-01-01

    A comprehensive molecular dynamics simulation study of n-alkanes using the Optimized Potential for Liquid Simulation-All Atoms (OPLS-AA) force field at ambient condition has been performed. Our results indicate that while simulations with the OPLS-AA force field accurately predict the liquid state mass density for n-alkanes with carbon number equal or less than 10, for n-alkanes with carbon number equal or exceeding 12, the OPLS-AA force field with the standard scaling factor for the 1-4 intramolecular Van der Waals and electrostatic interaction gives rise to a quasi-crystalline structure. We found that accurate predictions of the liquid state properties are obtained by successively reducing the aforementioned scaling factor for each increase of the carbon number beyond n-dodecane. To better un-derstand the effects of reducing the scaling factor, we analyzed the variation of the torsion potential pro-file with the scaling factor, and the corresponding impact on the gauche-trans conformer distribution, heat of vaporization, melting point, and self-diffusion coefficient for n-dodecane. This relatively simple procedure thus allows for more accurate predictions of the thermo-physical properties of longer n-alkanes.

  13. Photochemical dimerization and functionalization of alkanes, ethers, primary alcohols and silanes

    DOEpatents

    Crabtree, Robert H.; Brown, Stephen H.

    1988-01-01

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary alcohols and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  14. Photochemical dimerization and functionalization of alkanes, ethers, primary alcohols and silanes

    DOEpatents

    Crabtree, R.H.; Brown, S.H.

    1988-02-16

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary alcohols and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  15. Isolating the non-polar contributions to the intermolecular potential for water-alkane interactions.

    PubMed

    Ballal, Deepti; Venkataraman, Pradeep; Fouad, Wael A; Cox, Kenneth R; Chapman, Walter G

    2014-08-14

    Intermolecular potential models for water and alkanes describe pure component properties fairly well, but fail to reproduce properties of water-alkane mixtures. Understanding interactions between water and non-polar molecules like alkanes is important not only for the hydrocarbon industry but has implications to biological processes as well. Although non-polar solutes in water have been widely studied, much less work has focused on water in non-polar solvents. In this study we calculate the solubility of water in different alkanes (methane to dodecane) at ambient conditions where the water content in alkanes is very low so that the non-polar water-alkane interactions determine solubility. Only the alkane-rich phase is simulated since the fugacity of water in the water rich phase is calculated from an accurate equation of state. Using the SPC/E model for water and TraPPE model for alkanes along with Lorentz-Berthelot mixing rules for the cross parameters produces a water solubility that is an order of magnitude lower than the experimental value. It is found that an effective water Lennard-Jones energy ε(W)/k = 220 K is required to match the experimental water solubility in TraPPE alkanes. This number is much higher than used in most simulation water models (SPC/E-ε(W)/k = 78.2 K). It is surprising that the interaction energy obtained here is also higher than the water-alkane interaction energy predicted by studies on solubility of alkanes in water. The reason for this high water-alkane interaction energy is not completely understood. Some factors that might contribute to the large interaction energy, such as polarizability of alkanes, octupole moment of methane, and clustering of water at low concentrations in alkanes, are examined. It is found that, though important, these factors do not completely explain the anomalously strong attraction between alkanes and water observed experimentally. PMID:25134597

  16. Isolating the non-polar contributions to the intermolecular potential for water-alkane interactions.

    PubMed

    Ballal, Deepti; Venkataraman, Pradeep; Fouad, Wael A; Cox, Kenneth R; Chapman, Walter G

    2014-08-14

    Intermolecular potential models for water and alkanes describe pure component properties fairly well, but fail to reproduce properties of water-alkane mixtures. Understanding interactions between water and non-polar molecules like alkanes is important not only for the hydrocarbon industry but has implications to biological processes as well. Although non-polar solutes in water have been widely studied, much less work has focused on water in non-polar solvents. In this study we calculate the solubility of water in different alkanes (methane to dodecane) at ambient conditions where the water content in alkanes is very low so that the non-polar water-alkane interactions determine solubility. Only the alkane-rich phase is simulated since the fugacity of water in the water rich phase is calculated from an accurate equation of state. Using the SPC/E model for water and TraPPE model for alkanes along with Lorentz-Berthelot mixing rules for the cross parameters produces a water solubility that is an order of magnitude lower than the experimental value. It is found that an effective water Lennard-Jones energy ε(W)/k = 220 K is required to match the experimental water solubility in TraPPE alkanes. This number is much higher than used in most simulation water models (SPC/E-ε(W)/k = 78.2 K). It is surprising that the interaction energy obtained here is also higher than the water-alkane interaction energy predicted by studies on solubility of alkanes in water. The reason for this high water-alkane interaction energy is not completely understood. Some factors that might contribute to the large interaction energy, such as polarizability of alkanes, octupole moment of methane, and clustering of water at low concentrations in alkanes, are examined. It is found that, though important, these factors do not completely explain the anomalously strong attraction between alkanes and water observed experimentally.

  17. Measurements of homogeneous nucleation in normal-alkanes

    NASA Astrophysics Data System (ADS)

    Kraack, H.; Sirota, E. B.; Deutsch, M.

    2000-04-01

    The homogeneous nucleation of normal-alkanes with carbon numbers 15⩽n⩽60 is studied by scanning calorimetry, using the droplet technique. Pure, nonemulsified samples show near-zero undercoolings below the melting point, Tm, except for both ends of the n-range, where undercoolings ΔT of up to 2 °C are observed. The emulsions have much larger undercoolings. The relative undercoolings show three regimes: A fast decreasing one, up to n=17, an anomalously low constant one, ΔT/Tm≈0.04, for 17⩽n⩽30, and a gradually increasing one for 32⩽n⩽60. A value of ΔT/Tm≈0.086 is reached at n=60. The connections of these results with the bulk rotator phases and the recently discovered surface freezing effect are discussed. Strong intrinsic interrelations among these are indicated.

  18. Regioselective alkane hydroxylation with a mutant AlkB enzyme

    DOEpatents

    Koch, Daniel J.; Arnold, Frances H.

    2012-11-13

    AlkB from Pseudomonas putida was engineered using in-vivo directed evolution to hydroxylate small chain alkanes. Mutant AlkB-BMO1 hydroxylates propane and butane at the terminal carbon at a rate greater than the wild-type to form 1-propanol and 1-butanol, respectively. Mutant AlkB-BMO2 similarly hydroxylates propane and butane at the terminal carbon at a rate greater than the wild-type to form 1-propanol and 1-butanol, respectively. These biocatalysts are highly active for small chain alkane substrates and their regioselectivity is retained in whole-cell biotransformations.

  19. A Comparison of the Monolayer Dynamics of the Branched Alkane Squalane and the Normal Alkane Tetracosane Adsorbed on Graphite

    NASA Astrophysics Data System (ADS)

    Enevoldsen, A. D.; Hansen, F. Y.; Diama, A.; Taub, H.

    2004-03-01

    Squalane is a branched alkane (C_30H_62) with 24 carbon atoms in its backbone, like the normal alkane tetracosane ( n-C_24H_50), and six symmetrically placed methyl side groups. In general, branched alkanes such as squalane are better lubricants than n-alkanes. We have studied the dynamics of the squalane and tetracosane monolayers by quasielastic neutron scattering and molecular dynamics (MD) simulations on two different time scales. Both experiments and simulations showed that diffusion at 260 K is about 2.5 times faster in the squalane than in the tetracosane system. It is somewhat surprising that the diffusion in a system with a branched alkane is faster than with a normal alkane. A possible explanation is that the squalane molecule does not bind as strongly to the surface as tetracosane, because the MD simulations have shown that the adsorbed molecules have a distorted backbone. This may also explain why the slow intramolecular motions associated with conformational changes are seen at lower temperatures in the squalane than the tetracosane monolayer where they are only observed near melting.

  20. Metabolism of Hydrocarbons in n-Alkane-Utilizing Anaerobic Bacteria.

    PubMed

    Wilkes, Heinz; Buckel, Wolfgang; Golding, Bernard T; Rabus, Ralf

    2016-01-01

    The glycyl radical enzyme-catalyzed addition of n-alkanes to fumarate creates a C-C-bond between two concomitantly formed stereogenic carbon centers. The configurations of the two diastereoisomers of the product resulting from n-hexane activation by the n-alkane-utilizing denitrifying bacterium strain HxN1, i.e. (1-methylpentyl)succinate, were assigned as (2S,1'R) and (2R,1'R). Experiments with stereospecifically deuterated n-(2,5-2H2)hexanes revealed that exclusively the pro-S hydrogen atom is abstracted from C2 of the n-alkane by the enzyme and later transferred back to C3 of the alkylsuccinate formed. These results indicate that the alkylsuccinate-forming reaction proceeds with an inversion of configuration at the carbon atom (C2) of the n-alkane forming the new C-C-bond, and thus stereochemically resembles a SN2-type reaction. Therefore, the reaction may occur in a concerted manner, which may avoid the highly energetic hex-2-yl radical as an intermediate. The reaction is associated with a significant primary kinetic isotope effect (kH/kD ≥3) for hydrogen, indicating that the homolytic C-H-bond cleavage is involved in the first irreversible step of the reaction mechanism. The (1-methylalkyl)succinate synthases of n-alkane-utilizing anaerobic bacteria apparently have very broad substrate ranges enabling them to activate not only aliphatic but also alkyl-aromatic hydrocarbons. Thus, two denitrifiers and one sulfate reducer were shown to convert the nongrowth substrate toluene to benzylsuccinate and further to the dead-end product benzoyl-CoA. For this purpose, however, the modified β-oxidation pathway known from alkylbenzene-utilizing bacteria was not employed, but rather the pathway used for n-alkane degradation involving CoA ligation, carbon skeleton rearrangement and decarboxylation. Furthermore, various n-alkane- and alkylbenzene-utilizing denitrifiers and sulfate reducers were found to be capable of forming benzyl alcohols from diverse alkylbenzenes

  1. Untypical even-to-odd predominance in the low-molecular n-alkanes of water, suspended matter, and bottom sediments in some regions of the Arctic Basin

    NASA Astrophysics Data System (ADS)

    Drozdova, Anastasia; Belyaev, Nikolay; Ponyaev, Mikhail

    2014-05-01

    Over the years, several studies have shown an unusual predominance of even-carbon number n-alkanes in dissolved and particulate phase samples and sediment samples from various regions of the World Ocean [Nachman, 1985; Nishimura and Baker, 1985; Elias et al., 1997]. Different possible sources were proposed such as diagenesis (diagenetic origin from co-occurring fatty acids and alcohols), direct microbial input, microbial degradation of algal detritus, etc. Some researchers, however, are incredulous about this phenomenon and consider relatively high content of even-carbon number n-alkanes as contamination during the experiments. We report here the results of GC and GC-MS analysis of water, suspended particulate matter and sediment samples collected during 7 marine and coastal scientific expeditions to the White and Kara Seas, and to the central Arctic Basin (2004-2013). Many of the above samples (more than 30) present n-alkane distribution with a strong even-carbon number predominance of n-C14H30, and n-C16H34. Maximum enrichment was observed in some suspended matter samples with predominance of n-C16H34. The origin of even-carbon number n-alkanes in marine ecosystems is still not clear. In Antarctic region n-C16 and n-C18 and other even chain n-alkanes were reported to be dominant in the samples of the sea-ice algae, zooplankton and fish [Green et al. 1997] however in the Arctic region this phenomenon has not been demonstrated yet. Increasing of bacteria number and δ13C values observed in course of the accompanying studies [Lein et al., 2013] suggest existence of mechanism of phytoplankton bacterial destruction in the Arctic ecosystems, leading to formation of even-carbon number n-alkanes. R.J. Nachman - Lipids, Vol. 20, No 9, pp. 629-633 (1985). M. Nishimura, E.W. Baker - Geochim. et Cosmochim. Acta, Vol. 50, pp. 299-305 (1986). V.O. Elias, B.R.T. Simoneit, J.N. Cardoso - Naturwissenschaften, Vol. 84, pp. 415-420 (1997). G. Green et al. - Marine Pollution

  2. Geomicrobiological linkages between short-chain alkane consumption and sulfate reduction rates in seep sediments

    PubMed Central

    Bose, Arpita; Rogers, Daniel R.; Adams, Melissa M.; Joye, Samantha B.; Girguis, Peter R.

    2013-01-01

    Marine hydrocarbon seeps are ecosystems that are rich in methane, and, in some cases, short-chain (C2–C5) and longer alkanes. C2–C4 alkanes such as ethane, propane, and butane can be significant components of seeping fluids. Some sulfate-reducing microbes oxidize short-chain alkanes anaerobically, and may play an important role in both the competition for sulfate and the local carbon budget. To better understand the anaerobic oxidation of short-chain n-alkanes coupled with sulfate-reduction, hydrocarbon-rich sediments from the Gulf of Mexico (GoM) were amended with artificial, sulfate-replete seawater and one of four n-alkanes (C1–C4) then incubated under strict anaerobic conditions. Measured rates of alkane oxidation and sulfate reduction closely follow stoichiometric predictions that assume the complete oxidation of alkanes to CO2 (though other sinks for alkane carbon likely exist). Changes in the δ13C of all the alkanes in the reactors show enrichment over the course of the incubation, with the C3 and C4 incubations showing the greatest enrichment (4.4 and 4.5‰, respectively). The concurrent depletion in the δ13C of dissolved inorganic carbon (DIC) implies a transfer of carbon from the alkane to the DIC pool (−3.5 and −6.7‰ for C3 and C4 incubations, respectively). Microbial community analyses reveal that certain members of the class Deltaproteobacteria are selectively enriched as the incubations degrade C1–C4 alkanes. Phylogenetic analyses indicate that distinct phylotypes are enriched in the ethane reactors, while phylotypes in the propane and butane reactors align with previously identified C3–C4 alkane-oxidizing sulfate-reducers. These data further constrain the potential influence of alkane oxidation on sulfate reduction rates (SRRs) in cold hydrocarbon-rich sediments, provide insight into their contribution to local carbon cycling, and illustrate the extent to which short-chain alkanes can serve as electron donors and govern microbial

  3. OH-initiated heterogeneous oxidation of cholestane: a model system for understanding the photochemical aging of cyclic alkane aerosols.

    PubMed

    Zhang, Haofei; Ruehl, Christopher R; Chan, Arthur W H; Nah, Theodora; Worton, David R; Isaacman, Gabriel; Goldstein, Allen H; Wilson, Kevin R

    2013-11-27

    Aerosols containing aliphatic hydrocarbons play a substantial role in the urban atmosphere. Cyclic alkanes constitute a large fraction of aliphatic hydrocarbon emissions originating from incomplete combustion of diesel fuel and motor oil. In the present study, cholestane (C27H48) is used as a model system to examine the OH-initiated heterogeneous oxidation pathways of cyclic alkanes in a photochemical flow tube reactor. Oxidation products are collected on filters and analyzed by a novel soft ionization two-dimensional gas chromatography/mass spectrometry technique. The analysis reveals that the first-generation functionalization products (cholestanones, cholestanals, and cholestanols) are the dominant reaction products that account for up to 70% by mass of the total speciated compounds. The ratio of first-generation carbonyls to alcohols is near unity at every oxidation level. Among the cholestanones/cholestanals, 55% are found to have the carbonyl group on the rings of the androstane skeleton, while 74% of cholestanols have the hydroxyl group on the rings. Particle-phase oxidation products with carbon numbers less than 27 (i.e., "fragmentation products") and higher-generation functionalization products are much less abundant. Carbon bond cleavage was found to occur only on the side chain. Tertiary-carbon alkoxy radicals are suggested to play an important role in governing both the distribution of functionalization products (via alkoxy radical isomerization and reaction with oxygen) and the fragmentation products (via alkoxy radical decomposition). These results provide new insights into the oxidation mechanism of cyclic alkanes.

  4. OH-initiated heterogeneous oxidation of cholestane: a model system for understanding the photochemical aging of cyclic alkane aerosols.

    PubMed

    Zhang, Haofei; Ruehl, Christopher R; Chan, Arthur W H; Nah, Theodora; Worton, David R; Isaacman, Gabriel; Goldstein, Allen H; Wilson, Kevin R

    2013-11-27

    Aerosols containing aliphatic hydrocarbons play a substantial role in the urban atmosphere. Cyclic alkanes constitute a large fraction of aliphatic hydrocarbon emissions originating from incomplete combustion of diesel fuel and motor oil. In the present study, cholestane (C27H48) is used as a model system to examine the OH-initiated heterogeneous oxidation pathways of cyclic alkanes in a photochemical flow tube reactor. Oxidation products are collected on filters and analyzed by a novel soft ionization two-dimensional gas chromatography/mass spectrometry technique. The analysis reveals that the first-generation functionalization products (cholestanones, cholestanals, and cholestanols) are the dominant reaction products that account for up to 70% by mass of the total speciated compounds. The ratio of first-generation carbonyls to alcohols is near unity at every oxidation level. Among the cholestanones/cholestanals, 55% are found to have the carbonyl group on the rings of the androstane skeleton, while 74% of cholestanols have the hydroxyl group on the rings. Particle-phase oxidation products with carbon numbers less than 27 (i.e., "fragmentation products") and higher-generation functionalization products are much less abundant. Carbon bond cleavage was found to occur only on the side chain. Tertiary-carbon alkoxy radicals are suggested to play an important role in governing both the distribution of functionalization products (via alkoxy radical isomerization and reaction with oxygen) and the fragmentation products (via alkoxy radical decomposition). These results provide new insights into the oxidation mechanism of cyclic alkanes. PMID:24152093

  5. Phase transition behavior of a series of even n-alkane C(n)/C(n+2) mixtures confined in microcapsules: from total miscibility to phase separation determined by confinement geometry and repulsion energy.

    PubMed

    Gao, Xia; Fu, Dongsheng; Su, Yunlan; Zhou, Yong; Wang, Dujin

    2013-11-01

    The phase behaviors of binary consecutive even normal alkane (n-alkane) mixtures (n-C(n)H(2n+2)/n-C(n+2)H(2n+6), with mass ratios of 90/10 and 10/90) with different average carbon numbers n¯ both in the bulk state (abbreviated as C(n)/C(n+2)) and in nearly monodisperse microcapsules (abbreviated as m-C(n)/C(n+2)), have been investigated by the combination of differential scanning calorimetry and temperature-dependent X-ray diffraction. The phase behavior of n-alkane mixtures gradually shifts from complete phase separation, partial miscibility to total miscibility in both bulk and microcapsules with the increase of average carbon numbers n¯. There are critical points for average carbon numbers of C(n)/C(n+2), where the corresponding mixtures exhibit coexistence of a triclinic phase (formed by alkane with a longer chain) and an orthorhombic ordered phase (formed by the two components of mixtures). Due to the confinement from hard shells of microcapsules, the critical points of m-C(n)/C(n+2) are smaller than those of C(n)/C(n+2). Such a phase behavior originates from the delicate combined action of confinement and repulsion energy for the encapsulated n-alkane mixtures with different average carbon numbers n¯. When n¯ is less than the critical point, the repulsion energy between the two kinds of molecules exceeds the suppression effect of confinement, and phase separation occurs in microcapsules. It is believed that the average carbon number is another important factor that exerts strong negative influence on the phase separation of m-C(n)/C(n+2) systems.

  6. Assimilation of chlorinated alkanes by hydrocarbon-utilizing fungi

    SciTech Connect

    Murphy, G.L.; Perry, J.J.

    1984-12-01

    The fatty acid compositions of two filamentous fungi (Cunninghamella elegans and Penicillium zonatum) and a yeast (Candida lipolytica) were determined after the organisms were grown on 1-chlorohexadecane or 1-chlorooctadecane. These organisms utilized the chlorinated alkanes as sole sources of carbon and energy. Analyses of the fatty acids present after growth on the chlorinated alkanes indicated that 60 to 70% of the total fatty acids in C. elegans were chlorinated. Approximately 50% of the fatty acids in C. lipolytica were also chlorinated. P. zonatum contained 20% 1-chlorohexadecanoic acid after growth on either substrate but did not incorporate C/sub 18/ chlorinated fatty acids.

  7. Identity and mechanisms of alkane-oxidizing metalloenzymes from deep-sea hydrothermal vents.

    PubMed

    Bertrand, Erin M; Keddis, Ramaydalis; Groves, John T; Vetriani, Costantino; Austin, Rachel Narehood

    2013-01-01

    Six aerobic alkanotrophs (organism that can metabolize alkanes as their sole carbon source) isolated from deep-sea hydrothermal vents were characterized using the radical clock substrate norcarane to determine the metalloenzyme and reaction mechanism used to oxidize alkanes. The organisms studied were Alcanivorax sp. strains EPR7 and MAR14, Marinobacter sp. strain EPR21, Nocardioides sp. strains EPR26w, EPR28w, and Parvibaculum hydrocarbonoclasticum strain EPR92. Each organism was able to grow on n-alkanes as the sole carbon source and therefore must express genes encoding an alkane-oxidizing enzyme. Results from the oxidation of the radical-clock diagnostic substrate norcarane demonstrated that five of the six organisms (EPR7, MAR14, EPR21, EPR26w, and EPR28w) used an alkane hydroxylase functionally similar to AlkB to catalyze the oxidation of medium-chain alkanes, while the sixth organism (EPR92) used an alkane-oxidizing cytochrome P450 (CYP)-like protein to catalyze the oxidation. DNA sequencing indicated that EPR7 and EPR21 possess genes encoding AlkB proteins, while sequencing results from EPR92 confirmed the presence of a gene encoding CYP-like alkane hydroxylase, consistent with the results from the norcarane experiments.

  8. Alkane oxidation with porphyrins and metal complexes thereof having haloalkyl side chains

    DOEpatents

    Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.; Bhinde, Manoj V.

    1998-01-01

    Transition metal complexes of meso-haloalkylporphyrins, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides.

  9. Alkane oxidation with porphyrins and metal complexes thereof having haloalkyl side chains

    DOEpatents

    Wijesekera, T.; Lyons, J.E.; Ellis, P.E. Jr.; Bhinde, M.V.

    1998-06-23

    Transition metal complexes of meso-haloalkylporphyrins are disclosed, wherein the haloalkyl groups contain 2 to 8 carbon atoms have been found to be highly effective catalysts for oxidation of alkanes and for the decomposition of hydroperoxides. 7 figs.

  10. Diamond like carbon coatings: Categorization by atomic number density

    NASA Technical Reports Server (NTRS)

    Angus, John C.

    1986-01-01

    Dense diamond-like hydrocarbon films grown at the NASA Lewis Research Center by radio frequency self bias discharge and by direct ion beam deposition were studied. A new method for categorizing hydrocarbons based on their atomic number density and elemental composition was developed and applied to the diamond-like hydrocarbon films. It was shown that the diamond-like hydrocarbon films are an entirely new class of hydrocarbons with atomic number densities lying between those of single crystal diamond and adamantanes. In addition, a major review article on these new materials was completed in cooperation with NASA Lewis Research Center personnel.

  11. Variation in n-Alkane Distributions of Modern Plants: Questioning Applications of n-Alkanes in Chemotaxonomy and Paleoecology

    NASA Astrophysics Data System (ADS)

    Bush, R. T.; McInerney, F. A.

    2010-12-01

    Long chain n-alkanes (n-C21 to n-C37) are synthesized as part of the epicuticular leaf wax of terrestrial plants and are among the most recognizable and widely used plant biomarkers. n-Alkane distributions have been utilized in previous studies on modern plant chemotaxonomy, testing whether taxa can be identified based on characteristic n-alkane profiles. Dominant n-alkanes (e.g. n-C27 or n-C31) have also been ascribed to major plant groups (e.g. trees or grasses respectively) and have been used in paleoecology studies to reconstruct fluctuations in plant functional types. However, many of these studies have been based on relatively few modern plant data; with the wealth of modern n-alkane studies, a more comprehensive analysis of n-alkanes in modern plants is now possible and can inform the usefulness of n-alkane distributions as paleoecological indicators. The work presented here is a combination of measurements made using plant leaves collected from the Chicago Botanic Garden and a compilation of published literature data from six continents. We categorized plants by type: angiosperms, gymnosperms, woody plants, forbs, grasses, ferns and pteridophytes, and mosses. We then quantified n-alkane distribution parameters such as carbon preference index (CPI), average chain length (ACL), and dispersion (a measure of the spread of the profile over multiple chain lengths) and used these to compare plant groups. Among all plants, one of the emergent correlations is a decrease in dispersion with increasing CPI. Within and among plant groups, n-alkane distributions show a very large range of variation, and the results show little or no correspondence between broad plant groups and a single dominant n-alkane or a ratio of n-alkanes. These findings are true both when data from six continents are combined and when plants from a given region are compared (North America). We also compared the n-alkane distributions of woody angiosperms, woody gymnosperms, and grasses with one

  12. Selective hydroxylation of alkanes by an extracellular fungal peroxygenase.

    PubMed

    Peter, Sebastian; Kinne, Matthias; Wang, Xiaoshi; Ullrich, René; Kayser, Gernot; Groves, John T; Hofrichter, Martin

    2011-10-01

    Fungal peroxygenases are novel extracellular heme-thiolate biocatalysts that are capable of catalyzing the selective monooxygenation of diverse organic compounds, using only H(2)O(2) as a cosubstrate. Little is known about the physiological role or the catalytic mechanism of these enzymes. We have found that the peroxygenase secreted by Agrocybe aegerita catalyzes the H(2)O(2)-dependent hydroxylation of linear alkanes at the 2-position and 3-position with high efficiency, as well as the regioselective monooxygenation of branched and cyclic alkanes. Experiments with n-heptane and n-octane showed that the hydroxylation proceeded with complete stereoselectivity for the (R)-enantiomer of the corresponding 3-alcohol. Investigations with a number of model substrates provided information about the route of alkane hydroxylation: (a) the hydroxylation of cyclohexane mediated by H(2)(18)(2) resulted in complete incorporation of (18)O into the hydroxyl group of the product cyclohexanol; (b) the hydroxylation of n-hexane-1,1,1,2,2,3,3-D(7) showed a large intramolecular deuterium isotope effect [(k(H)/k(D))(obs)] of 16.0 ± 1.0 for 2-hexanol and 8.9 ± 0.9 for 3-hexanol; and (c) the hydroxylation of the radical clock norcarane led to an estimated radical lifetime of 9.4 ps and an oxygen rebound rate of 1.06 × 10(11) s(-1). These results point to a hydrogen abstraction and oxygen rebound mechanism for alkane hydroxylation. The peroxygenase appeared to lack activity on long-chain alkanes (> C(16)) and highly branched alkanes (e.g. tetramethylpentane), but otherwise exhibited a broad substrate range. It may accordingly have a role in the bioconversion of natural and anthropogenic alkane-containing structures (including alkyl chains of complex biomaterials) in soils, plant litter, and wood. PMID:21812933

  13. Molecular screening for alkane hydroxylase genes in Gram-negative and Gram-positive strains.

    PubMed

    Smits, T H; Röthlisberger, M; Witholt, B; van Beilen, J B

    1999-08-01

    We have developed highly degenerate oligonucleotides for polymerase chain reaction (PCR) amplification of genes related to the Pseudomonas oleovorans GPo1 and Acinetobacter sp. ADP1 alkane hydroxylases, based on a number of highly conserved sequence motifs. In all Gram-negative and in two out of three Gram-positive strains able to grow on medium- (C6-C11) or long-chain n-alkanes (C12-C16), PCR products of the expected size were obtained. The PCR fragments were cloned and sequenced and found to encode peptides with 43.2-93.8% sequence identity to the corresponding fragment of the P. oleovorans GPo1 alkane hydroxylase. Strains that were unable to grow on n-alkanes did not yield PCR products with homology to alkane hydroxylase genes. The alkane hydroxylase genes of Acinetobacter calcoaceticus EB104 and Pseudomonas putida P1 were cloned using the PCR products as probes. The two genes allow an alkane hydroxylase-negative mutant of Acinetobacter sp. ADP1 and an Escherichia coli recombinant containing all P. oleovorans alk genes except alkB, respectively, to grow on n-alkanes, showing that the cloned genes do indeed encode alkane hydroxylases. PMID:11207749

  14. Incorporation of chlorinated alkanes into fatty acids of hydrocarbon-utilizing mycobacteria.

    PubMed

    Murphy, G L; Perry, J J

    1983-12-01

    The cellular fatty acid composition of Mycobacterium vaccae JOB5 and Mycobacterium convolutum R22 was examined after growth on n-alkanes and compared with the fatty acids of the organisms after growth on 1-chlorohexadecane and 1-chlorooctadecane. Growth on n-alkanes resulted in normal fatty acid profiles. Mass spectral analyses indicated that, after growth on the terminally chlorinated n-alkanes, 75 to 86% of the fatty acids in M. convolutum and ca. 55% of the fatty acids in M. vaccae contained chlorine. Neither organism could utilize chloroacetate or 3-chloropropionate as sole source of carbon and energy. When these compounds were added to a growth medium with n-hexadecane as substrate, there was no evidence that chlorinated fatty acids were produced. Terminally chlorinated n-alkanes can be added to the list of n-alkanes, alkenes, and cyclohexylalkane derivatives that can be directly incorporated into cellular fatty acids of hydrocarbon-utilizing organisms.

  15. Diffusion of squalene in n-alkanes and squalane.

    PubMed

    Kowert, Bruce A; Watson, Michael B; Dang, Nhan C

    2014-02-27

    Squalene, an intermediate in the biosynthesis of cholesterol, has a 24-carbon backbone with six methyl groups and six isolated double bonds. Capillary flow techniques have been used to determine its translational diffusion constant, D, at room temperature in squalane, n-C16, and three n-C8-squalane mixtures. The D values have a weaker dependence on viscosity, η, than predicted by the Stokes-Einstein relation, D = kBT/(6πηr). A fit to the modified relation, D/T = ASE/η(p), gives p = 0.820 ± 0.028; p = 1 for the Stokes-Einstein limit. The translational motion of squalene appears to be much like that of n-alkane solutes with comparable chain lengths; their D values show similar deviations from the Stokes-Einstein model. The n-alkane with the same carbon chain length as squalene, n-C24, has a near-equal p value of 0.844 ± 0.018 in n-alkane solvents. The values of the hydrodynamic radius, r, for n-C24, squalene, and other n-alkane solutes decrease as the viscosity increases and have a common dependence on the van der Waals volumes of the solute and solvent. The possibility of studying squalene in lipid droplets and membranes is discussed.

  16. Diffusion of squalene in n-alkanes and squalane.

    PubMed

    Kowert, Bruce A; Watson, Michael B; Dang, Nhan C

    2014-02-27

    Squalene, an intermediate in the biosynthesis of cholesterol, has a 24-carbon backbone with six methyl groups and six isolated double bonds. Capillary flow techniques have been used to determine its translational diffusion constant, D, at room temperature in squalane, n-C16, and three n-C8-squalane mixtures. The D values have a weaker dependence on viscosity, η, than predicted by the Stokes-Einstein relation, D = kBT/(6πηr). A fit to the modified relation, D/T = ASE/η(p), gives p = 0.820 ± 0.028; p = 1 for the Stokes-Einstein limit. The translational motion of squalene appears to be much like that of n-alkane solutes with comparable chain lengths; their D values show similar deviations from the Stokes-Einstein model. The n-alkane with the same carbon chain length as squalene, n-C24, has a near-equal p value of 0.844 ± 0.018 in n-alkane solvents. The values of the hydrodynamic radius, r, for n-C24, squalene, and other n-alkane solutes decrease as the viscosity increases and have a common dependence on the van der Waals volumes of the solute and solvent. The possibility of studying squalene in lipid droplets and membranes is discussed. PMID:24528091

  17. Integrated process for preparing a carboxylic acid from an alkane

    SciTech Connect

    Benderly, Abraham; Chadda, Nitin; Sevon, Douglass

    2011-12-20

    The present invention relates to an integrated process for producing unsaturated carboxylic acids from the corresponding C.sub.2-C.sub.4 alkane. The process begins with performance of thermally integrated dehydrogenation reactions which convert a C.sub.2-C.sub.4 alkane to its corresponding C.sub.2-C.sub.4 alkene, and which involve exothermically converting a portion of an alkane to its corresponding alkene by oxidative dehydrogenation in an exothermic reaction zone, in the presence of oxygen and a suitable catalyst, and then feeding the products of the exothermic reaction zone to an endothermic reaction zone wherein at least a portion of the remaining unconverted alkane is endothermically dehydrogenated to form an additional quantity of the same corresponding alkene, in the presence of carbon dioxide and an other suitable catalyst. The alkene products of the thermally integrated dehydrogenation reactions are then provided to a catalytic vapor phase partial oxidation process for conversion of the alkene to the corresponding unsaturated carboxylic acid or nitrile. Unreacted alkene and carbon dioxide are recovered from the oxidation product stream and recycled back to the thermally integrated dehydrogenation reactions.

  18. Surfactant-induced phases in water-supported alkane monolayers: I. Thermodynamics.

    PubMed

    Yefet, Shai; Sloutskin, Eli; Tamam, Lilach; Sapir, Zvi; Cohen, Asaf; Deutsch, Moshe; Ocko, Benjamin M

    2014-07-15

    Alkanes longer than n = 6 carbons do not spread on the water surface, but condense in a macroscopic lens. However, adding trimethylammonium-based surfactants, C(m)TAB, in submillimolar concentrations causes the alkanes to spread and form a single Langmuir-Gibbs (LG) monolayer of mixed alkanes and surfactant tails, which coexists with the alkane lenses. Upon cooling, this LG film surface-freezes at a temperature T(s) above the bulk freezing temperature T(b). The thermodynamics of surface freezing (SF) of these LG films is studied by surface tension measurements for a range of alkanes (n = 12-21) and surfactant alkyl lengths (m = 14, 16, 18), at several concentrations c. The surface freezing range T(s)-T(b) observed is up to 25 °C, an order of magnitude larger than the temperature range of SF monolayers on the surface of pure alkane melts. The measured (n,T) surface phase diagram is accounted for well by a model based on mixtures' theory, which includes an interchange energy term ω. ω is found to be negative, implying attraction between unlike species, rather than the repulsion found for SF of binary alkane mixtures. Thus, the surfactant/alkane mixing is a necessary condition for the occurrence of SF in these LG films. The X-ray derived structure of the films is presented in an accompanying paper. PMID:24918482

  19. Cloning and expression of three ladA-type alkane monooxygenase genes from an extremely thermophilic alkane-degrading bacterium Geobacillus thermoleovorans B23.

    PubMed

    Boonmak, Chanita; Takahashi, Yasunori; Morikawa, Masaaki

    2014-05-01

    An extremely thermophilic bacterium, Geobacillus thermoleovorans B23, is capable of degrading a broad range of alkanes (with carbon chain lengths ranging between C11 and C32) at 70 °C. Whole-genome sequence analysis revealed that unlike most alkane-degrading bacteria, strain B23 does not possess an alkB-type alkane monooxygenase gene. Instead, it possesses a cluster of three ladA-type genes, ladAαB23, ladAβB23, and ladB B23, on its chromosome, whose protein products share significant amino acid sequence identities, 49.8, 34.4, and 22.7 %, respectively, with that of ladA alkane monooxygenase gene found on a plasmid of Geobacillus thermodetrificans NG 80-2. Each of the three genes, ladAαB23, ladAβB23, and ladB B23, was heterologously expressed individually in an alkB1 deletion mutant strain, Pseudomonas fluorescens KOB2Δ1. It was found that all three genes were functional in P. fluorescens KOB2Δ1, and partially restored alkane degradation activity. In this study, we suggest that G. thermoleovorans B23 utilizes multiple LadA-type alkane monooxygenases for the degradation of a broad range of alkanes.

  20. High Temperature Chemical Kinetic Combustion Modeling of Lightly Methylated Alkanes

    SciTech Connect

    Sarathy, S M; Westbrook, C K; Pitz, W J; Mehl, M

    2011-03-01

    Conventional petroleum jet and diesel fuels, as well as alternative Fischer-Tropsch (FT) fuels and hydrotreated renewable jet (HRJ) fuels, contain high molecular weight lightly branched alkanes (i.e., methylalkanes) and straight chain alkanes (n-alkanes). Improving the combustion of these fuels in practical applications requires a fundamental understanding of large hydrocarbon combustion chemistry. This research project presents a detailed high temperature chemical kinetic mechanism for n-octane and three lightly branched isomers octane (i.e., 2-methylheptane, 3-methylheptane, and 2,5-dimethylhexane). The model is validated against experimental data from a variety of fundamental combustion devices. This new model is used to show how the location and number of methyl branches affects fuel reactivity including laminar flame speed and species formation.

  1. [Sources, Migration and Conversion of Dissolved Alkanes, Dissolved Fatty Acids in a Karst Underground River Water, in Chongqing Area].

    PubMed

    Liang, Zuo-bing; Sun, Yu-chuan; Wang, Zun-bo; Shi, Yang; Jiang, Ze-li; Zhang, Mei; Xie, Zheng-Lan; Liao, Yu

    2015-09-01

    Dissolved alkanes and dissolved fatty acids were collected from Qingmuguan underground river in July, October 2013. By gas chromatography-mass spectrometer (GC-MS), alkanes and fatty acids were quantitatively analyzed. The results showed that average contents of alkanes and fatty acids were 1 354 ng.L-1, 24203 ng.L-1 in July, and 667 ng.L-1, 2526 ng.L-1 in October respectively. With the increasing migration distance of dissolved alkanes and dissolved fatty acids in underground river, their contents decreased. Based on the molecular characteristic indices of alkanes, like CPI, OEP, Paq and R, dissolved alkanes were mainly originated from microorganisms in July, and aquatic plants in October. Saturated straight-chain fatty acid had the highest contents in all samples with the dominant peak in C16:0, combined with the characteristics of carbon peak, algae or bacteria might be the dominant source of dissolved fatty acids. PMID:26717680

  2. Solubility of gold nanoparticles as a function of ligand shell and alkane solvent.

    PubMed

    Lohman, Brandon C; Powell, Jeffrey A; Cingarapu, Sreeram; Aakeroy, Christer B; Chakrabarti, Amit; Klabunde, Kenneth J; Law, Bruce M; Sorensen, Christopher M

    2012-05-14

    The solubility of ca. 5.0 nm gold nanoparticles was studied systematically as a function of ligand shell and solvent. The ligands were octane-, decane-, dodecane- and hexadecanethiols; the solvents were the n-alkanes from hexane to hexadecane and toluene. Supernatant concentrations in equilibrium with precipitated superclusters of nanoparticles were measured at room temperature (23 °C) with UV-Vis spectrophotometry. The solubility of nanoparticles ligated with decane- and dodecanethiol was greatest in n-decane and n-dodecane, respectively. In contrast, the solubility of nanoparticles ligated with octane- and hexadecanethiol showed decreasing solubility with increasing solvent chain length. In addition the solubility of the octanethiol ligated system showed a nonmonotonic solvent carbon number functionality with even numbered solvents being better solvents than neighboring odd numbered solvents. PMID:22456604

  3. Solubility of gold nanoparticles as a function of ligand shell and alkane solvent.

    PubMed

    Lohman, Brandon C; Powell, Jeffrey A; Cingarapu, Sreeram; Aakeroy, Christer B; Chakrabarti, Amit; Klabunde, Kenneth J; Law, Bruce M; Sorensen, Christopher M

    2012-05-14

    The solubility of ca. 5.0 nm gold nanoparticles was studied systematically as a function of ligand shell and solvent. The ligands were octane-, decane-, dodecane- and hexadecanethiols; the solvents were the n-alkanes from hexane to hexadecane and toluene. Supernatant concentrations in equilibrium with precipitated superclusters of nanoparticles were measured at room temperature (23 °C) with UV-Vis spectrophotometry. The solubility of nanoparticles ligated with decane- and dodecanethiol was greatest in n-decane and n-dodecane, respectively. In contrast, the solubility of nanoparticles ligated with octane- and hexadecanethiol showed decreasing solubility with increasing solvent chain length. In addition the solubility of the octanethiol ligated system showed a nonmonotonic solvent carbon number functionality with even numbered solvents being better solvents than neighboring odd numbered solvents.

  4. Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

    DOEpatents

    Crabtree, Robert H.; Brown, Stephen H.

    1989-01-01

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  5. Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

    DOEpatents

    Crabtree, R.H.; Brown, S.H.

    1989-10-17

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  6. Adsorption and dissociation kinetics of alkanes on CaO(100)

    NASA Astrophysics Data System (ADS)

    Chakradhar, A.; Liu, Y.; Schmidt, J.; Kadossov, E.; Burghaus, U.

    2011-08-01

    The adsorption kinetics of ethane, butane, pentane, and hexane on CaO(100) have been studied by multi-mass thermal desorption (TDS) spectroscopy. The sample cleanliness was checked by Auger electron spectroscopy. A molecular and dissociative adsorption pathway was evident for the alkanes, except for ethane, which does not undergo bond activation. Two TDS peaks appeared when recording the parent mass, which are assigned to different adsorption sites/configurations of the molecularly adsorbed alkanes. Bond activation leads to desorption of hydrogen and several alkane fragments assigned to methane and ethylene formation. Only one TDS feature is seen in this case. Formation of carbon residuals was absent.

  7. Asynchronous evolution of the isotopic composition and amount of precipitation in north China during the Holocene revealed by a record of compound-specific carbon and hydrogen isotopes of long-chain n-alkanes from an alpine lake

    NASA Astrophysics Data System (ADS)

    Rao, Zhiguo; Jia, Guodong; Li, Yunxia; Chen, Jianhui; Xu, Qinghai; Chen, Fahu

    2016-07-01

    Both the timing of the maximum East Asian summer monsoon (EASM) intensity in monsoonal China and the environmental significance of the Chinese stalagmite oxygen isotopic record (δ18O) have been debated. Here, we present a ca. 120-year-resolution compound-specific carbon (δ13C) and hydrogen (δD) isotopes of terrestrial long-chain n-alkanes extracted from a well-dated sediment core from an alpine lake in north China. Our δ13C data, together with previously reported pollen data from a parallel core, demonstrate a humid mid-Holocene from ca. 8-5 ka BP. Assuming that the climatic humidity of north China is an indicator of the EASM intensity, then the maximum EASM intensity occurred in the mid-Holocene. Our δD data reveal a similar long-term trend to the δ18O record from nearby Lianhua Cave, indicating that the synchronous δD and δ18O records faithfully record the δD and δ18O of precipitation, respectively. The most negative δD and δ18O values occur in the early-mid Holocene, from ca. 11-5 ka BP. This contrast in the timing of isotopic variations demonstrates a complex relationship between the isotopic composition of precipitation and precipitation amount, or EASM intensity. Further comparisons indicate a possible linkage between the precipitation amount in north China and the west-east thermal gradient in the equatorial Pacific. In addition, the temperature of the moisture source area may play an important role in determining the isotopic composition of precipitation in monsoonal China.

  8. Difference equation model for isothermal gas chromatography expresses retention behavior of homologues of n-alkanes excluding the influence of holdup time.

    PubMed

    Wu, Liejun; Chen, Yongli; Caccamise, Sarah A L; Li, Qing X

    2012-10-19

    A difference equation (DE) model is developed using the methylene retention increment (Δtz) of n-alkanes to avoid the influence of gas holdup time (tM). The effects of the equation orders (1st-5th) on the accuracy of a curve fitting show that a linear equation (LE) is less satisfactory and it is not necessary to use a complicated cubic or higher order equation. The relationship between the logarithm of Δtz and the carbon number (z) of the n-alkanes under isothermal conditions closely follows the quadratic equation for C3-C30n-alkanes at column temperatures of 24-260 °C. The first and second order forward differences of the expression (Δlog Δtz and Δ2log Δtz, respectively) are linear and constant, respectively, which validates the DE model. This DE model lays a necessary foundation for further developing a retention model to accurately describe the relationship between the adjusted retention time and z of n-alkanes.

  9. Modular and selective biosynthesis of gasoline-range alkanes.

    PubMed

    Sheppard, Micah J; Kunjapur, Aditya M; Prather, Kristala L J

    2016-01-01

    Typical renewable liquid fuel alternatives to gasoline are not entirely compatible with current infrastructure. We have engineered Escherichia coli to selectively produce alkanes found in gasoline (propane, butane, pentane, heptane, and nonane) from renewable substrates such as glucose or glycerol. Our modular pathway framework achieves carbon-chain extension by two different mechanisms. A fatty acid synthesis route is used to generate longer chains heptane and nonane, while a more energy efficient alternative, reverse-β-oxidation, is used for synthesis of propane, butane, and pentane. We demonstrate that both upstream (thiolase) and intermediate (thioesterase) reactions can act as control points for chain-length specificity. Specific free fatty acids are subsequently converted to alkanes using a broad-specificity carboxylic acid reductase and a cyanobacterial aldehyde decarbonylase (AD). The selectivity obtained by different module pairings provides a foundation for tuning alkane product distribution for desired fuel properties. Alternate ADs that have greater activity on shorter substrates improve observed alkane titer. However, even in an engineered host strain that significantly reduces endogenous conversion of aldehyde intermediates to alcohol byproducts, AD activity is observed to be limiting for all chain lengths. Given these insights, we discuss guiding principles for pathway selection and potential opportunities for pathway improvement.

  10. Modular and selective biosynthesis of gasoline-range alkanes.

    PubMed

    Sheppard, Micah J; Kunjapur, Aditya M; Prather, Kristala L J

    2016-01-01

    Typical renewable liquid fuel alternatives to gasoline are not entirely compatible with current infrastructure. We have engineered Escherichia coli to selectively produce alkanes found in gasoline (propane, butane, pentane, heptane, and nonane) from renewable substrates such as glucose or glycerol. Our modular pathway framework achieves carbon-chain extension by two different mechanisms. A fatty acid synthesis route is used to generate longer chains heptane and nonane, while a more energy efficient alternative, reverse-β-oxidation, is used for synthesis of propane, butane, and pentane. We demonstrate that both upstream (thiolase) and intermediate (thioesterase) reactions can act as control points for chain-length specificity. Specific free fatty acids are subsequently converted to alkanes using a broad-specificity carboxylic acid reductase and a cyanobacterial aldehyde decarbonylase (AD). The selectivity obtained by different module pairings provides a foundation for tuning alkane product distribution for desired fuel properties. Alternate ADs that have greater activity on shorter substrates improve observed alkane titer. However, even in an engineered host strain that significantly reduces endogenous conversion of aldehyde intermediates to alcohol byproducts, AD activity is observed to be limiting for all chain lengths. Given these insights, we discuss guiding principles for pathway selection and potential opportunities for pathway improvement. PMID:26556131

  11. [Distribution Characteristics and Source Apportionment of n-Alkanes in Water from Yellow River in Henan Section].

    PubMed

    Feng, Jing-lan; Xi, Nan-nan; Zhang, Fei; Liu, Shu-hui; Sun, Jian-hui

    2016-03-15

    To investigate the distributions and possible sources of n-alkanes in water and suspended particulate matter from Yellow River in Henan section, 26 water and suspended particulate matter samples were collected in August 2010 and 22 n-alkanes (C₁₄-C₃₆) were quantitatively determined by gas chromatography-mass spectrometer (GC-MS). Potential sources of n-alkanes were analyzed using different characteristic parameters. The results indicated that total concentrations of 22 n-alkanes were 521-5,843 ng · L⁻¹ with a mean concentration of 1,409 ng · L⁻¹, while the total amounts of n-alkanes in the suspended particulate matter were 463-11,142 ng · L⁻¹ with a mean value of 1,951 ng · L⁻¹. The composition profiles of n-alkanes in water showed unimodal distribution with a peak at C₂₅ in water. However, the composition characteristics of n-alkanes in SPM were of bimodal type, but still with the advantage of high carbon hydrocarbons peak at C₂₅. Results of characteristic parameters including CPI, TAR, OEP and % WaxCn showed that n-alkanes in the studied area were derived mainly from combustion of fossil fuel, while terrestrial higher plant played a role in the existence of n-alkanes in water and suspended particulate matter from Yellow River in Henan section. PMID:27337879

  12. Mass dependence of the activation enthalpy and entropy of unentangled linear alkane chains.

    PubMed

    Jeong, Cheol; Douglas, Jack F

    2015-10-14

    The mass scaling of the self-diffusion coefficient D of polymers in the liquid state, D ∼ M(β), is one of the most basic characteristics of these complex fluids. Although traditional theories such as the Rouse and reptation models of unentangled and entangled polymer melts, respectively, predict that β is constant, this exponent for alkanes has been estimated experimentally to vary from -1.8 to -2.7 upon cooling. Significantly, β changes with temperature T under conditions where the chains are not entangled and at temperatures far above the glass transition temperature Tg where dynamic heterogeneity does not complicate the description of the liquid dynamics. Based on atomistic molecular dynamics simulations on unentangled linear alkanes in the melt, we find that the variation of β with T can be directly attributed to the dependence of the enthalpy ΔHa and entropy ΔSa of activation on the number of alkane backbone carbon atoms, n. In addition, we find a sharp change in the melt dynamics near a "critical" chain length, n ≈ 17. A close examination of this phenomenon indicates that a "buckling transition" from rod-like to coiled chain configurations occurs at this characteristic chain length and distinct entropy-enthalpy compensation relations, ΔSa ∝ ΔHa, hold on either side of this polymer conformational transition. We conclude that the activation free energy parameters exert a significant influence on the dynamics of polymer melts that is not anticipated by either the Rouse and reptation models. In addition to changes of ΔHa and ΔSa with M, we expect changes in these free energy parameters to be crucial for understanding the dynamics of polymer blends, nanocomposites, and confined polymers because of changes of the fluid free energy by interfacial interactions and geometrical confinement.

  13. Mass dependence of the activation enthalpy and entropy of unentangled linear alkane chains

    SciTech Connect

    Jeong, Cheol; Douglas, Jack F.

    2015-10-14

    The mass scaling of the self-diffusion coefficient D of polymers in the liquid state, D ∼ M{sup β}, is one of the most basic characteristics of these complex fluids. Although traditional theories such as the Rouse and reptation models of unentangled and entangled polymer melts, respectively, predict that β is constant, this exponent for alkanes has been estimated experimentally to vary from −1.8 to −2.7 upon cooling. Significantly, β changes with temperature T under conditions where the chains are not entangled and at temperatures far above the glass transition temperature T{sub g} where dynamic heterogeneity does not complicate the description of the liquid dynamics. Based on atomistic molecular dynamics simulations on unentangled linear alkanes in the melt, we find that the variation of β with T can be directly attributed to the dependence of the enthalpy ΔH{sub a} and entropy ΔS{sub a} of activation on the number of alkane backbone carbon atoms, n. In addition, we find a sharp change in the melt dynamics near a “critical” chain length, n ≈ 17. A close examination of this phenomenon indicates that a “buckling transition” from rod-like to coiled chain configurations occurs at this characteristic chain length and distinct entropy-enthalpy compensation relations, ΔS{sub a} ∝ ΔH{sub a}, hold on either side of this polymer conformational transition. We conclude that the activation free energy parameters exert a significant influence on the dynamics of polymer melts that is not anticipated by either the Rouse and reptation models. In addition to changes of ΔH{sub a} and ΔS{sub a} with M, we expect changes in these free energy parameters to be crucial for understanding the dynamics of polymer blends, nanocomposites, and confined polymers because of changes of the fluid free energy by interfacial interactions and geometrical confinement.

  14. Improved GC/MS method for quantitation of n-Alkanes in plant and fecal material

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A gas chromatography-mass spectrometry (GC/MS) method for the quantitation of n-alkanes (carbon backbones ranging from 21 to 36 carbon atoms) in forage and fecal samples has been developed. Automated solid-liquid extraction using elevated temperature and pressure minimized extraction time to 30 min...

  15. Alkane-Based Urethane Potting Compounds

    NASA Technical Reports Server (NTRS)

    Morris, D. E.

    1986-01-01

    New low viscosity urethanes easily mixed, molded, and outgassed. Alkane-based urethanes resist hydrolysis and oxidation and have excellent dielectric properties. Low-viscosity alkane-based urethane prepolymer prepared by one-step reaction of either isophorone diisocyanate or methyl-bis (4-cyclohexyl isocyanate) with hydrogenated, hydroxy-terminated polybutadiene (HTPBD).

  16. Removal of alkanes from drinking water using membrane technologies

    SciTech Connect

    Fronk, C.A.

    1995-10-01

    Increasingly, the public is concerned about the quality of its drinking water. The chlorinated alkanes are saturated, aliphatic, synthetic organic compounds (SOC`s). When hydrocarbon feedstocks are chlorinated, a wide variety of chlorocarbons and chlorohydrocarbons are produced that are used as industrial solvents, degreasers and intermediaries. Because compounds such as Carbon Tetrachloride and 1,2-Dichloroethane are widely used, they often find their way into drinking water, particularly groundwaters. Surface waters are somewhat less affected bemuse of the high volatility of many chlorinated alkanes. The Drinking Water Research Division is responsible for evaluating various membrane technologies that may be feasible for meeting Maximum Contaminant Levels. Several membrane processes are under investigation to determine their effectiveness in removing SOC`s from drinking water. One study addressed the removal of a variety of alkanes from spiked groundwater by six reverse osmosis membranes: a cellulose acetate, a polyamide (hollow fiber), and four different types of thin-film composite membranes. Progressive chlorination of methanes, ethanes and propanes produces compounds that exhibit differing physicochemical properties. The differences in compound properties have an effect on the removal of these compounds by reverse osmosis membranes. For example only 25% of the methylene chloride (Dichloromethane) was removed by one thin-film composite versus 90% removal of the carbon tetrachloride. In addition, the various membranes are made of different polymeric materials and showed a wide range of removals. Generally, the thin-film composite membranes out performed the other membranes and the more highly chlorinated the compound the better the removal. Pervaporation is yet another membrane process that may prove effective in removal of alkanes and future studies will address its usefulness as a drinking water.

  17. Classification of vegetable oils according to their botanical origin using n-alkane profiles established by GC-MS.

    PubMed

    Troya, F; Lerma-García, M J; Herrero-Martínez, J M; Simó-Alfonso, E F

    2015-01-15

    n-Alkane profiles established by gas chromatography-mass spectrometry (GC-MS) were used to classify vegetable oils according to their botanical origin. The n-alkanes present in corn, grapeseed, hazelnut, olive, peanut and sunflower oils were isolated by means of alkaline hydrolysis followed by silica gel column chromatography of the unsaponifiable fractions. The n-alkane fraction was constituted mainly of n-alkanes in the range C8-C35, although only those most abundant (15 n-alkanes, from 21 to 35 carbon No.) were used as original variables to construct linear discriminant analysis (LDA) models. Ratios of the peak areas selected by pairs were used as predictors. All the oils were correctly classified according to their botanical origin, with assignment probabilities higher than 95%, using an LDA model.

  18. Anaerobic oxidation of short-chain alkanes in hydrothermal sediments: potential influences on sulfur cycling and microbial diversity

    SciTech Connect

    Adams, MM; Hoarfrost, AL; Bose, A; Joye, SB; Girguis, PR

    2013-05-14

    Short-chain alkanes play a substantial role in carbon and sulfur cycling at hydrocarbon-rich environments globally, yet few studies have examined the metabolism of ethane (C-2), propane (C-3), and butane (C-4) in anoxic sediments in contrast to methane (C-1). In hydrothermal vent systems, short-chain alkanes are formed over relatively short geological time scales via thermogenic processes and often exist at high concentrations. The sediment-covered hydrothermal vent systems at Middle Valley (MV Juan de Fuca Ridge) are an ideal site for investigating the anaerobic oxidation of C-1-C-4 alkanes, given the elevated temperatures and dissolved hydrocarbon species characteristic of these metalliferous sediments. We examined whether MV microbial communities oxidized C-1-C-4 alkanes under mesophilic to thermophilic sulfate-reducing conditions. Here we present data from discrete temperature (25, 55, and 75 degrees C) anaerobic batch reactor incubations of MV sediments supplemented with individual alkanes. Co-registered alkane consumption and sulfate reduction (SR) measurements provide clear evidence for C-1-C-4 alkane oxidation linked to SR over time and across temperatures. In these anaerobic batch reactor sediments, 16S ribosomal RNA pyrosequencing revealed that Deltaproteobacteria, particularly a novel sulfate-reducing lineage, were the likely phylotypes mediating the oxidation of C-2-C-4 alkanes. Maximum C-1-C-4 alkane oxidation rates occurred at 55 degrees C, which reflects the mid-core sediment temperature profile and corroborates previous studies of rate maxima for the anaerobic oxidation of methane (AOM). Of the alkanes investigated, C-3 was oxidized at the highest rate over time, then C-4, C-2, and C-1, respectively. The implications of these results are discussed with respect to the potential competition between the anaerobic oxidation of C-2-C(4)alkanes with AOM for available oxidants and the influence on the fate of C-1 derived from these hydrothermal systems.

  19. [Effects of topographical condition and sampling number on the interpolation precision of forest litter carbon density].

    PubMed

    Zhang, Jia-jia; Fu, Wei-jun; Du, Qun; Zhang, Guo-jiang; Jiang, Pei-kun

    2013-08-01

    The territory of Zhejiang Province, East China was grouped into 3 topographical units (plain-coastal area, hill-basin area, and mountain area) to investigate the effects of topographical condition and sampling number on the Kriging interpolation precision of forest litter carbon density in the Province. The forest litter carbon density in the 3 topographical units showed a medium spatial correlation pattern, with the semi-variance nugget/sill ratio value ranged from 28.3% to 72.4%. The Kriging interpolation precision was in the order of plain-coastal area > hill-basin area > mountain area, indicating that the Kriging interpolation precision decreased with the increase of terrain complexity degree. Within the same topographical units, the Kriging interpolation precision improved with increasing sampling number, being most obvious in the mountain area. Therefore, under complicated topographical conditions, greater sampling number was required to achieve a high precision of Kriging interpolation. PMID:24380344

  20. Dielectric constant of liquid alkanes and hydrocarbon mixtures

    NASA Technical Reports Server (NTRS)

    Sen, A. D.; Anicich, V. G.; Arakelian, T.

    1992-01-01

    The complex dielectric constants of n-alkanes with two to seven carbon atoms have been measured. The measurements were conducted using a slotted-line technique at 1.2 GHz and at atmospheric pressure. The temperature was varied from the melting point to the boiling point of the respective alkanes. The real part of the dielectric constant was found to decrease with increasing temperature and correlate with the change in the molar volume. An upper limit to all the loss tangents was established at 0.001. The complex dielectric constants of a few mixtures of liquid alkanes were also measured at room temperature. For a pentane-octane mixture the real part of the dielectric constant could be explained by the Clausius-Mosotti theory. For the mixtures of n-hexane-ethylacetate and n-hexane-acetone the real part of the dielectric constants could be explained by the Onsager theory extended to mixtures. The dielectric constant of the n-hexane-acetone mixture displayed deviations from the Onsager theory at the highest fractions of acetone. The dipole moments of ethylacetate and acetone were determined for dilute mixtures using the Onsager theory and were found to be in agreement with their accepted gas-phase values. The loss tangents of the mixtures exhibited a linear relationship with the volume fraction for low concentrations of the polar liquids.

  1. Dielectric constant of liquid alkanes and hydrocarbon mixtures.

    PubMed

    Sen, A D; Anicich, V G; Arakelian, T

    1992-01-01

    The complex dielectric constants of n-alkanes with two to seven carbon atoms have been measured. The measurements were conducted using a slotted-line technique at 1.2 GHz and at atmospheric pressure. The temperature was varied from the melting point to the boiling point of the respective alkanes. The real part of the dielectric constant was found to decrease with increasing temperature and correlate with the change in the molar volume. An upper limit to all the loss tangents was established at 0.001. The complex dielectric constants of a few mixtures of liquid alkanes were also measured at room temperature. For a pentane-octane mixture the real part of the dielectric constant could be explained by the Clausius-Mosotti theory. For the mixtures of n-hexane-ethylacetate and n-hexane-acetone the real part of the dielectric constants could be explained by the Onsager theory extended to mixtures. The dielectric constant of the n-hexane-acetone mixture displayed deviations from the Onsager theory at the highest fractions of acetone. The dipole moments of ethylacetate and acetone were determined for dilute mixtures using the Onsager theory and were found to be in agreement with their accepted gas-phase values. The loss tangents of the mixtures exhibited a linear relationship with the volume fraction for low concentrations of the polar liquids.

  2. SST and terrestrial n-alkanes records in sediment of the Korean Plateau, East Sea (Japan Sea) during the last 400 kyr: Paleoceanographic and paleoclimatic implications

    NASA Astrophysics Data System (ADS)

    Hyun, Sangmin; Suh, Yean Jee; Kim, Jin Kyung

    2014-05-01

    SST variation was reconstructed using alkenones and their variation was compared with terrestrial n-alkanes signature from the sediment of the Korean Plateau, East Sea (Japan Sea) during the last 400 ka. SST variation showed glacial-interglacial time scale variation with a maximum temperature of 26 oC in MIS 7, and a minimum of 12 oC at MIS 2 and 6. The distribution of terrestrial n-alkanes signatures is characterized by the occurrence of high odd number predominance in most samples, however minor dominance of a specific compound (nC27 only) was the additional characteristic.bAverage Chain Length (ACL) and Carbon Preferences Index (ICP), derived from n-alkane distributions, showed a similar shifting between glacial-interglacial time-scale. This suggests that paleovegetation communities changed in response to paleoclimatological variations, and the input of terrestrial compound is strongly linked with paleoclimatology. In the previous work, isotopic composition of δ13C and δ15N of organic matter showed extreme temporal variation since MIS 11 suggesting influx of a large amount of terrestrial organic matters from the neighboring continent during MIS 2, 8 and 10. In particular, depleted values of δ13C during MIS 2, 8 and 10 were coincident with lower nitrogen isotope values indicating local paleoceanographic effects such as paleoproductivity changes. Decoupling of δ13C and δ15N during MIS 1, 3, 5, and 7, and coupling of the two during MIS 8 and 11 is observed, which can be interpreted as local productivity changes. The alkenones SST and n-alkanes signature coincided with carbon and nitrogen isotope variation in terms of glacial-interglacial time scale suggesting that the paleoenvironments in the East Sea is sensitive to the global climate changes associated with not only orbital-scale glacial-interglacial variations but also local paleceanographic variations.

  3. Characterization of the Medium- and Long-Chain n-Alkanes Degrading Pseudomonas aeruginosa Strain SJTD-1 and Its Alkane Hydroxylase Genes

    PubMed Central

    Liu, Huan; Xu, Jing; Liang, Rubing; Liu, Jianhua

    2014-01-01

    A gram-negative aliphatic hydrocarbon-degrading bacterium SJTD-1 isolated from oil-contaminated soil was identified as Pseudomonas aeruginosa by comparative analyses of the 16S rRNA sequence, phenotype, and physiological features. SJTD-1 could efficiently mineralize medium- and long-chain n-alkanes (C12-C30) as its sole carbon source within seven days, showing the most optimal growth on n-hexadecane, followed by n-octadecane, and n-eicosane. In 36 h, 500 mg/L of tetradecane, hexadecane, and octadecane were transformed completely; and 2 g/L n-hexadecane was degraded to undetectable levels within 72 h. Two putative alkane-degrading genes (gene 3623 and gene 4712) were characterized and our results indicated that their gene products were rate-limiting enzymes involved in the synergetic catabolism of C12–C16 alkanes. On the basis of bioinformatics and transcriptional analysis, two P450 monooxygenases, along with a putative AlmA-like oxygenase, were examined. Genetically defective mutants lacking the characteristic alkane hydroxylase failed to degrade n-octadecane, thereby suggesting a different catalytic mechanism for the microbial transformation of alkanes with chain lengths over C18. PMID:25165808

  4. Characterization of the medium- and long-chain n-alkanes degrading Pseudomonas aeruginosa strain SJTD-1 and its alkane hydroxylase genes.

    PubMed

    Liu, Huan; Xu, Jing; Liang, Rubing; Liu, Jianhua

    2014-01-01

    A gram-negative aliphatic hydrocarbon-degrading bacterium SJTD-1 isolated from oil-contaminated soil was identified as Pseudomonas aeruginosa by comparative analyses of the 16S rRNA sequence, phenotype, and physiological features. SJTD-1 could efficiently mineralize medium- and long-chain n-alkanes (C12-C30) as its sole carbon source within seven days, showing the most optimal growth on n-hexadecane, followed by n-octadecane, and n-eicosane. In 36 h, 500 mg/L of tetradecane, hexadecane, and octadecane were transformed completely; and 2 g/L n-hexadecane was degraded to undetectable levels within 72 h. Two putative alkane-degrading genes (gene 3623 and gene 4712) were characterized and our results indicated that their gene products were rate-limiting enzymes involved in the synergetic catabolism of C12-C16 alkanes. On the basis of bioinformatics and transcriptional analysis, two P450 monooxygenases, along with a putative AlmA-like oxygenase, were examined. Genetically defective mutants lacking the characteristic alkane hydroxylase failed to degrade n-octadecane, thereby suggesting a different catalytic mechanism for the microbial transformation of alkanes with chain lengths over C18. PMID:25165808

  5. Scalable and number-controlled synthesis of carbon nanotubes by nanostencil lithography.

    PubMed

    Choi, Jungwook; Koh, Kisik; Kim, Jongbaeg

    2013-01-01

    Controlled synthesis and integration of carbon nanotubes (CNTs) remain important areas of study to develop practical carbon-based nanodevices. A method of controlling the number of CNTs synthesized depending on the size of the catalyst was characterized using nanostencil lithography, and the critical dimension for the nanoaperture produced on a stencil mask used for growing individual CNTs was studied. The stencil mask was fabricated as a nanoaperture array down to 40 nm in diameter on a low-stress silicon nitride membrane. An iron catalyst used to synthesize CNTs was deposited through submicron patterns in the stencil mask onto a silicon substrate, and the profile of the patterned iron catalyst was analyzed using atomic force microscopy. The feasibility toward a scalable, number-, and location-controlled synthesis of CNTs was experimentally demonstrated based on the diameter and geometry of the apertures in the stencil mask. PMID:23759063

  6. Molecular distributions and compound-specific stable carbon isotopic compositions of lipids in wintertime aerosols from Beijing.

    PubMed

    Ren, Lujie; Fu, Pingqing; He, Yue; Hou, Juzhi; Chen, Jing; Pavuluri, Chandra Mouli; Sun, Yele; Wang, Zifa

    2016-01-01

    Molecular distributions and stable carbon isotopic compositions (δ(13)C) of n-alkanes, fatty acids and n-alcohols were investigated in urban aerosols from Beijing, northern China to better understand the sources and long-range atmospheric transport of terrestrial organic matter during polluted and clear days in winter. n-Alkanes (C19-C36), fatty acids (C8-C32) and n-alcohols (C16-C32) detected in Beijing aerosols are characterized by the predominance of C23, C16 and C28, respectively. Carbon preference index (CPI) values of n-alkanes, the ratios of the sum of odd-numbered n-alkanes to the sum of even-numbered n-alkanes, are close to 1, indicating a heavy influence of fossil fuel combustion. Relatively higher ratios of C(18:0+16:0)/C(18:n+16:1) (fatty acids) on clear days than polluted days indicate that long-distance transport and/or photochemical aging are more significant during clear days. δ(13)C values of n-alkanes and low molecular weight fatty acids (C16:0, C18:0) ranged from -34.1 to -24.7% and -26.9 to -24.6%, respectively, which are generally heavier on polluted days than those on clear days. Such a wide range suggests that atmospheric lipids in Beijing aerosols originate from multiple sources and encounter complicated atmospheric processes during long-range transport in North China. PMID:27270951

  7. Electron mobility, free ion yields, and electron thermalization distances in n-alkane liquids: Effect of chain length

    NASA Astrophysics Data System (ADS)

    Gee, Norman; Senanayake, P. Chandani; Freeman, Gordon R.

    1988-09-01

    The electron mobility μo was measured as a function of temperature in liquid n-hexane, n-heptane, n-octane, n-nonane, and n-undecane, and at 295 K in n-pentane. Combination of these with earlier measurements of ours showed that μ0 at 295 K decreased monotonically with increasing carbon chain length in n-alkane liquids from ethane to n-tetradecane. There was no significant difference between odd and even carbon number compounds. The results were in accord with two-state interpretations of electron transport. Free ion yields were measured in liquid n-Cx H2x+2 (4≤x≤14, except 13) and electron thermalization ranges bGP were estimated using the extended Onsager model. The zero field free ion yield G0fi at 295 K decreased with increasing chain length. The density-normalized thermalization range of electrons was bGPd=(41±1)×10-7 kg/m2 in all n-alkanes from C4 to C14 under the conditions of this study.

  8. The anaerobic degradation of gaseous, nonmethane alkanes — From in situ processes to microorganisms

    PubMed Central

    Musat, Florin

    2015-01-01

    The short chain, gaseous alkanes ethane, propane, n- and iso-butane are released in significant amounts into the atmosphere, where they contribute to tropospheric chemistry and ozone formation. Biodegradation of gaseous alkanes by aerobic microorganisms, mostly bacteria and fungi isolated from terrestrial environments, has been known for several decades. The first indications for short chain alkane anaerobic degradation were provided by geochemical studies of deep-sea environments around hydrocarbon seeps, and included the uncoupling of the sulfate-reduction and anaerobic oxidation of methane rates, the consumption of gaseous alkanes in anoxic sediments, or the enrichment in 13C of gases in interstitial water vs. the source gas. Microorganisms able to degrade gaseous alkanes were recently obtained from deep-sea and terrestrial sediments around hydrocarbon seeps. Up to date, only sulfate-reducing pure or enriched cultures with ethane, propane and n-butane have been reported. The only pure culture presently available, strain BuS5, is affiliated to the Desulfosarcina–Desulfococcus cluster of the Deltaproteobacteria. Other phylotypes involved in gaseous alkane degradation have been identified based on stable-isotope labeling and whole-cell hybridization. Under anoxic conditions, propane and n-butane are activated similar to the higher alkanes, by homolytic cleavage of the C—H bond of a subterminal carbon atom, and addition of the ensuing radical to fumarate, yielding methylalkylsuccinates. An additional mechanism of activation at the terminal carbon atoms was demonstrated for propane, which could in principle be employed also for the activation of ethane. PMID:25904994

  9. The anaerobic degradation of gaseous, nonmethane alkanes - From in situ processes to microorganisms.

    PubMed

    Musat, Florin

    2015-01-01

    The short chain, gaseous alkanes ethane, propane, n- and iso-butane are released in significant amounts into the atmosphere, where they contribute to tropospheric chemistry and ozone formation. Biodegradation of gaseous alkanes by aerobic microorganisms, mostly bacteria and fungi isolated from terrestrial environments, has been known for several decades. The first indications for short chain alkane anaerobic degradation were provided by geochemical studies of deep-sea environments around hydrocarbon seeps, and included the uncoupling of the sulfate-reduction and anaerobic oxidation of methane rates, the consumption of gaseous alkanes in anoxic sediments, or the enrichment in (13)C of gases in interstitial water vs. the source gas. Microorganisms able to degrade gaseous alkanes were recently obtained from deep-sea and terrestrial sediments around hydrocarbon seeps. Up to date, only sulfate-reducing pure or enriched cultures with ethane, propane and n-butane have been reported. The only pure culture presently available, strain BuS5, is affiliated to the Desulfosarcina-Desulfococcus cluster of the Deltaproteobacteria. Other phylotypes involved in gaseous alkane degradation have been identified based on stable-isotope labeling and whole-cell hybridization. Under anoxic conditions, propane and n-butane are activated similar to the higher alkanes, by homolytic cleavage of the C-H bond of a subterminal carbon atom, and addition of the ensuing radical to fumarate, yielding methylalkylsuccinates. An additional mechanism of activation at the terminal carbon atoms was demonstrated for propane, which could in principle be employed also for the activation of ethane. PMID:25904994

  10. Supported organoiridium catalysts for alkane dehydrogenation

    SciTech Connect

    Baker, R. Thomas; Sattelberger, Alfred P.; Li, Hongbo

    2013-09-03

    Solid supported organoiridium catalysts, a process for preparing such solid supported organoiridium catalysts, and the use of such solid supported organoiridium catalysts in dehydrogenation reactions of alkanes is provided. The catalysts can be easily recovered and recycled.

  11. Second virial coefficients, critical temperatures, and the molecular shapes of long n-alkanes

    NASA Astrophysics Data System (ADS)

    Vega, Carlos; López Rodríguez, Antonio

    1996-09-01

    The second virial coefficient for a molecular model of n-alkanes with up to 200 carbon atoms has been computed for temperatures in the range of 1000 Kalkanes. The Boyle temperature of n-alkanes is not much affected by the length of the chain for n-alkanes with more than 100 carbon atoms. According to the Flory theory, for infinitely long chains the Boyle temperature and the critical temperature, denoted as the θ temperature are the same. On this basis using the present model we find θ=1620 K as the critical temperature of polymethylene. Scaling laws for the square of the end-to-end distance and for the radius of gyration at several temperatures are analyzed. For high temperatures, the scaling laws correspond to good solvent conditions whereas at the θ temperature the scaling laws are those of an ideal chain. The shape of long n-alkanes at several temperatures is also analyzed. We find that the polymethylene chains present an anisotropy similar to that of a parallelepiped with a ratio of sizes of 1:1.7:3.6.

  12. Whole-cell bacterial bioreporter for actively searching and sensing of alkanes and oil spills.

    PubMed

    Zhang, Dayi; He, Yi; Wang, Yun; Wang, Hui; Wu, Lin; Aries, Eric; Huang, Wei E

    2012-01-01

    Acinetobacter baylyi ADP1 was found to tolerate seawater and have a special ability of adhering to an oil-water interface of 10-80 µm emulsified mineral and crude oil droplets. These properties make ADP1 an ideal bacterial chassis for constructing bioreporters that are able to actively search and sense oil spill in water and soils. Acinetobacter baylyi bioreporter ADPWH_alk was developed and applied to the detection of alkanes and alkenes in water, seawater and soils. Bioreporter ADPWH_alk was able to detect a broad range of alkanes and alkenes with carbon chain length from C7 to C36. So far, ADPWH_alk is the only bioreporter that is able to detect alkane with carbon chain length greater than C18. This bioreporter responded to the alkanes in about 30 min and it was independent to the cell growth phase because of two point mutations in alkM promoter recognized by alkane regulatory protein ALKR. ADPWH_alk was applied to detect mineral oil, Brent, Chestnut and Sirri crude oils in water and seawater in the range 0.1-100 mg l(-1), showing that the bioreporter oil detection was semi-quantitative. This study demonstrates that ADPWH_alk is a rapid, sensitive and semi-quantitative bioreporter that can be useful for environmental monitoring and assessment of oil spills in seawater and soils.

  13. Re-evaluation of effective carbon number (ECN) approach to predict response factors of 'compounds lacking authentic standards or surrogates' (CLASS) by thermal desorption analysis with GC-MS.

    PubMed

    Szulejko, Jan E; Kim, Ki-Hyun

    2014-12-01

    In our recent study, we experimentally demonstrated the feasibility of an effective carbon number (ECN) approach for the prediction of the response factor (RF) values of 'compounds lacking authentic standards or surrogates' (CLASS) using a certified 54-mix containing 38 halogenated analytes as a pseudo-unknown. Although our recent analysis performed well in terms of RF predictive power for a 25-component learning set (for both Q-MS and TOF-MS detection), large physically unrealistic negative ECN and carbon number equivalent (CNE) values were noted for TOF-MS detection, e.g., ECN (acetic acid)=-16.96. Hence, to further improve the ECN-based quantitation procedure of CLASS, we re-challenged RF vs. ECN linear regression analysis with additional descriptors (i.e., Cl, Br, CC, and a group ECN offset (Ok)) using the 1-point RF values. With an Ok, all compound classes, e.g., halo-alkanes/-alkenes and aromatics can now be fitted to yield consistently positive set of ECN values for most analytes (e.g., 3 outliers out of 29, Q-MS detection). In this way, we were able to further refine our approach so that the absolute percentage difference (PD)±standard deviation (SD) between mass detected vs. mass loaded is reduced from 39.0±34.1% (previous work) to 13.1±12.0% (this work) for 29 C1C4 halocarbons (Q-MS detector).

  14. Structural insights into diversity and n-alkane biodegradation mechanisms of alkane hydroxylases

    PubMed Central

    Ji, Yurui; Mao, Guannan; Wang, Yingying; Bartlam, Mark

    2013-01-01

    Environmental microbes utilize four degradation pathways for the oxidation of n-alkanes. Although the enzymes degrading n-alkanes in different microbes may vary, enzymes functioning in the first step in the aerobic degradation of alkanes all belong to the alkane hydroxylases. Alkane hydroxylases are a class of enzymes that insert oxygen atoms derived from molecular oxygen into different sites of the alkane terminus (or termini) depending on the type of enzymes. In this review, we summarize the different types of alkane hydroxylases, their degrading steps, and compare typical enzymes from various classes with regard to their three-dimensional structures, in order to provide insights into how the enzymes mediate their different roles in the degradation of n-alkanes and what determines their different substrate ranges. Through the above analyzes, the degrading mechanisms of enzymes can be elucidated and molecular biological methods can be utilized to expand their catalytic roles in the petrochemical industry or in bioremediation of oil-contaminated environments. PMID:23519435

  15. Regulation of the Alkane Hydroxylase CYP153 Gene in a Gram-Positive Alkane-Degrading Bacterium, Dietzia sp. Strain DQ12-45-1b

    PubMed Central

    Liang, Jie-Liang; JiangYang, Jing-Hong

    2015-01-01

    CYP153, one of the most common medium-chain n-alkane hydroxylases belonging to the cytochrome P450 superfamily, is widely expressed in n-alkane-degrading bacteria. CYP153 is also thought to cooperate with AlkB in degrading various n-alkanes. However, the mechanisms regulating the expression of the protein remain largely unknown. In this paper, we studied CYP153 gene transcription regulation by the potential AraC family regulator (CypR) located upstream of the CYP153 gene cluster in a broad-spectrum n-alkane-degrading Gram-positive bacterium, Dietzia sp. strain DQ12-45-1b. We first identified the transcriptional start site and the promoter of the CYP153 gene cluster. Sequence alignment of upstream regions of CYP153 gene clusters revealed high conservation in the −10 and −35 regions in Actinobacteria. Further analysis of the β-galactosidase activity in the CYP153 gene promoter-lacZ fusion cell indicated that the CYP153 gene promoter was induced by n-alkanes comprised of 8 to 14 carbon atoms, but not by derived decanol and decanic acid. Moreover, we constructed a cypR mutant strain and found that the CYP153 gene promoter activities and CYP153 gene transcriptional levels in the mutant strain were depressed compared with those in the wild-type strain in the presence of n-alkanes, suggesting that CypR served as an activator for the CYP153 gene promoter. By comparing CYP153 gene arrangements in Actinobacteria and Proteobacteria, we found that the AraC family regulator is ubiquitously located upstream of the CYP153 gene, suggesting its universal regulatory role in CYP153 gene transcription. We further hypothesize that the observed mode of CYP153 gene regulation is shared by many Actinobacteria. PMID:26567302

  16. Stable Isotope Labeled n-Alkanes to Assess Digesta Passage Kinetics through the Digestive Tract of Ruminants

    PubMed Central

    Warner, Daniel; Ferreira, Luis M. M.; Breuer, Michel J. H.; Dijkstra, Jan; Pellikaan, Wilbert F.

    2013-01-01

    We describe the use of carbon stable isotope (13C) labeled n-alkanes as a potential internal tracer to assess passage kinetics of ingested nutrients in ruminants. Plant cuticular n-alkanes originating from intrinsically 13C labeled ryegrass plants were pulse dosed intraruminally in four rumen-cannulated lactating dairy cows receiving four contrasting ryegrass silage treatments that differed in nitrogen fertilization level (45 or 90 kg nitrogen ha−1) and maturity (early or late). Passage kinetics through the gastrointestinal tract were derived from the δ13C (i.e. the ratio 13C:12C) in apparently undigested fecal material. Isotopic enrichment was observed in a wide range of long-chain n-alkanes (C27–C36) and passage kinetics were determined for the most abundant C29, C31 and C33 n-alkanes, for which a sufficiently high response signal was detected by combustion isotope ratio mass spectrometry. Basal diet treatment and carbon chain length of n-alkanes did not affect fractional passage rates from the rumen (K1) among individual n-alkanes (3.71–3.95%/h). Peak concentration time and transit time showed a quantitatively small, significant (p≤0.002) increase with carbon chain length. K1 estimates were comparable to those of the 13C labeled digestible dry matter fraction (3.38%/h; r = 0.61 to 0.71; p≤0.012). A literature review has shown that n-alkanes are not fermented by microorganisms in the rumen and affirms no preferential depletion of 13C versus 12C. Our results suggest that 13C labeled n-alkanes can be used as nutrient passage tracers and support the reliability of the δ13C signature of digestible feed nutrients as a tool to measure nutrient-specific passage kinetics. PMID:24124493

  17. Monocarboxylic acids from oxidation of acyclic isoprenoid alkanes by Mycobacterium fortuitum

    NASA Technical Reports Server (NTRS)

    Cox, R. E.; Maxwell, J. R.; Myers, R. N.

    1976-01-01

    Mycobacterium fortuitum utilizes certain stereoisomeric mixtures of individual multimethyl branched alkanes as sole carbon source, including 2,6(R), 10(S), 14(RS)-tetramethylhexadecane; 2,6(R), 10(S), 14(RS)-tetramethylheptadecane; 2,6(RS), 10(RS)-trimethyltetradecane, and 2,6(R), 10(S)-trimethylpentadecane. Products of oxidation isolated from the bacterial lipids were acids derived predominantly from oxidation of the isopropyl terminus of each alkane, except in the case of 2,6(RS), 10(RS)-trimethyltetradecane. With the latter, acids from oxidation at either terminus were detected in comparable proportions.

  18. Regioselective alkane hydroxylation with a mutant CYP153A6 enzyme

    DOEpatents

    Koch, Daniel J.; Arnold, Frances H.

    2013-01-29

    Cytochrome P450 CYP153A6 from Myobacterium sp. strain HXN1500 was engineered using in-vivo directed evolution to hydroxylate small-chain alkanes regioselectively. Mutant CYP153A6-BMO1 selectively hydroxylates butane and pentane at the terminal carbon to form 1-butanol and 1-pentanol, respectively, at rates greater than wild-type CYP153A6 enzymes. This biocatalyst is highly active for small-chain alkane substrates and the regioselectivity is retained in whole-cell biotransformations.

  19. Partial oxidation of {alpha}-olefins over iron antimony oxide - influence of carbon number

    SciTech Connect

    Steen, E. van; Schnobel, M.; O`Connor, C.T.

    1996-10-01

    Iron antimony oxide is a well known catalyst for the partial oxidation of propane and 1-butene. Kinetic studies of the partial oxidation of {alpha}-olefins (C{sub 2}-C{sub 9}) revealed that the activity showed a maximum at C{sub 4}. The main products of the partial oxidation of {alpha}-olefins (larger than C{sub 2}) are the conjugated alkenal (acrolein) and dienes. The selectivity to these desired products decreases with increasing chain length probably caused by both the decrease in number of allylic hydrogen atoms and the shielding of them. Ethene could only be oxidized at relatively high temperatures (over 450{degrees}C) and the only observed products were CO and CO{sub 2} indicating the need for the presence of allylic hydrogen for low temperature selective partial oxidation. Increasing the carbon number increases the yield of CO and CO{sub 2} due to shielding of the allylic hydrogen.

  20. Sesquiterpene, alkene, and alkane hydrocarbons in virgin olive oils of different varieties and geographical origins.

    PubMed

    Bortolomeazzi, R; Berno, P; Pizzale, L; Conte, L S

    2001-07-01

    The hydrocarbon fraction of 30 virgin olive oils was analyzed, focusing in particular on the sesquiterpenes. The oil samples were of different geographical origins and obtained from different olive varieties. The hydrocarbon fraction was isolated by silica gel column chromatography of the unsaponifiable fraction of the oils. The sesquiterpene hydrocarbons were then fractionated, on the basis of their degree of unsaturation, by AgNO3 TLC and silica gel AgNO3 column chromatography. The composition of the sesquiterpenes was more complex than previously reported. Among the 31 sesquiterpenes detected, 24 have been tentatively identified, by comparison of the linear retention indices on two capillary columns of different polarities and mass spectra with those reported in the literature. The total concentration of the sesquiterpenes in the oils analyzed ranged from about 2 to 37 ppm. Among the sesquiterpenes the more abundant were alpha-farnesene, alpha-copaene, eremophyllene, and alpha-muurolene. The alkenes present in the hydrocarbon fraction were isolated by TLC AgNO3 and characterized by GC-MS of their dimethyl disulfide derivatives. The series of n-Delta9-alkenes from C22 to C27, 8-heptadecene, and 6,10-dimethyl-1-undecene were detected. Among the n-alkanes, those with an odd number of carbon atoms predominated in all of the analyzed oils, the most common being C23, C25, C27, and C29. The concentration of the n-alkenes ranged from about 0.5 to 2 ppm, whereas for the n-alkanes the range was from 30 to 177 ppm.

  1. [Normal alkanes characteristic parameters of Jinzhou Bay surface sediments].

    PubMed

    Li, Ze-Li; Ma, Qi-Min; Cheng, Hai-Ou; Xu, Shao-Qing

    2011-11-01

    The concentration, composition and characteristic parameters of 18 surface sediment samples collected from Jinzhou Bay were studied. The samples were soxhlet-extracted with a mixture of 1: 1 (V/V) dichloromethane-hexane and analyzed by GC-MS after purification and concentration. Concentrations of n-alkanes vary from 1.9 to 4.2 microg x g(-1) with an average value of 2.6 microg x g(-1) dry weight. n-Alkanes distribution patterns of all positions were characterized by double peak-cluster, which means double sources from terrestrial and marine origin. The sum of nC25 to nC31 accounts for 20%-32% of the total n-alkanes, while the average value of L/H, C31/C19, TAR ratio are 0.67, 3.06, 2.02, respectively. All of these three indices suggest that the terrestrial contributions are higher than marine sources, especially for No. 2, 3 and 7 stations, which were influenced by riverinput nearby. Carbon Preference Index (CPI) ranges from 1.19 to 2.63 with an average value of 1.73, which is close to 1; the ratio of Pristane/Phytane (Pr/Ph) and unresolved/resolved compounds (U/R) range from 0.91 to 1.28, 2.2 to 4.3, respectively. All of these three parameters indicate that No. 13 and 15 stations are influenced by petroleum pollution. Comprehensive analysis of various parameters shows that Jinzhou Bay is threatened by both terrestrial inputs and petroleum hydrocarbons contaminations, which may relate to river discharging and port shipping in Jinzhou Bay. PMID:22295627

  2. Late Quaternary environmental changes inferred from n-alkane evidence in coastal area of southern Hainan Island, China

    NASA Astrophysics Data System (ADS)

    Wang, Mengyuan; Zheng, Zhuo

    2016-04-01

    The studied core was a coastal core in Hainan Island, China. It is in length of 49.01m and divided into four Units (MIS 1~MIS 6) according to lithology description. The Optically Stimulated Luminescence (OSL) attributes the sediments from Unit 3 to the Oxygen Isotope Stage of MIS 5e (Unit 3b and 3c) and 5d (Unit 3a). To interpret the origination of organic carbons and to reconstruct paleovegetation changes, n-alkane, δ13C and TOC have been used in the present research. The result of n-alkanes distribution indicates a series of changes of sedimentary environment and terrestrial input. The shallow water facies at Unit 2, 3a and 4 is mainly characterized by short carbon chain n-alkanes and relatively low concentration. Contrasting with that of deep-water marine facies of MIS 5e (Unit 3b), the n-alkane pattern is typical bimodal and the main peaks are both in short and long carbon chains. During Unit 3b-1 (MIS 5e), more terrestrial original n-alkanes contribute to the concentration of TOC than oceanic. Organic matter source is mainly terrestrial origination. Total organic matter input mechanism of TLG-01 correlates with sediment grain size (average grain size). Total organic carbon input is enhanced with the increasing of fine grain size component. The variation of CPI (25-33) value in this study correlates with hydrological energy. The highest CPI (25-33) value is shown in the high sea level period of MIS 5e, comparing with that in MIS 5d and MIS 1. High CPI value corresponds to high TOC and average grain size (Φ) value. In the weak hydrological energy sedimentary environment, more terrestrial organic matter, together with TOC, deposit in the study area. ACL (25-33) index display higher values in the interglacial period (MIS 5 and MIS 1) than MIS 3 (sediments weathered during MIS 2) and MIS 6. Paq proxy, together with δ13C, estimates the mangrove growing depth in MIS 5e. The correlation between δ13C and each carbon chain alkane state stabilize and turbulence of

  3. Distribution, activity and function of short-chain alkane degrading phylotypes in hydrothermal vent sediments

    NASA Astrophysics Data System (ADS)

    Adams, M. M.; Joye, S. B.; Hoarfrost, A.; Girguis, P. R.

    2012-12-01

    Global geochemical analyses suggest that C2-C4 short chain alkanes are a common component of the utilizable carbon pool in deep-sea sediments worldwide and have been found in diverse ecosystems. From a thermodynamic standpoint, the anaerobic microbial oxidation of these aliphatic hydrocarbons is more energetically yielding than the anaerobic oxidation of methane (AOM). Therefore, the preferential degradation of these hydrocarbons may compete with AOM for the use of oxidants such as sulfate, or other potential oxidants. Such processes could influence the fate of methane in the deep-sea. Sulfate-reducing bacteria (SRB) from hydrocarbon seep sediments of the Gulf of Mexico and Guaymas Basin have previously been enriched that anaerobically oxidize short chain alkanes to generate CO2 with the preferential utilization of 12C-enriched alkanes (Kniemeyer et al. 2007). Different temperature regimens along with multiple substrates were tested and a pure culture (deemed BuS5) was isolated from mesophilic enrichments with propane or n-butane as the sole carbon source. Through comparative sequence analysis, strain BuS5 was determined to cluster with the metabolically diverse Desulfosarcina / Desulfococcus cluster, which also contains the SRB found in consortia with anaerobic, methane-oxidizing archaea in seep sediments. Enrichments from a terrestrial, low temperature sulfidic hydrocarbon seep also corroborated that propane degradation occurred with most bacterial phylotypes surveyed belonging to the Deltaproteobacteria, particularly Desulfobacteraceae (Savage et al. 2011). To date, no microbes capable of ethane oxidation or anaerobic C2-C4 alkane oxidation at thermophilic temperature have been isolated. The sediment-covered, hydrothermal vent systems found at Middle Valley (Juan de Fuca Ridge, eastern Pacific Ocean) are a prime environment for investigating mesophilic to thermophilic anaerobic oxidation of short-chain alkanes, given the elevated temperatures and dissolved

  4. Diameter and wall number control of carbon nanotubes by chemical vapor deposition

    SciTech Connect

    Xie, Rongsi; Zhong, Guofang Zhang, Can; Chen, Bingan; Santiago Esconjauregui, C.; Robertson, John

    2013-12-28

    We analyze the relationship between the average wall number (N) and the diameter (d) for carbon nanotubes (CNTs) grown by chemical vapour deposition. It is found that N depends linearly on d for diameters in the range of 2.5–10 nm, while single wall nanotubes predominate for diameters under about 2.1 nm. The linear relationship is found to depend somewhat on the growth conditions. It is also verified that the mean diameter depends on the diameter of the originating catalyst nanoparticle, and thus on the initial catalyst thickness where a thin film catalyst is used. This simplifies the characterisation of CNTs by electron microscopy. We also find a linear relationship between nanotube diameter and initial catalyst film thickness.

  5. A hexanuclear mixed-valence oxovanadium(IV,V) complex as a highly efficient alkane oxidation catalyst.

    PubMed

    Sutradhar, Manas; Kirillova, Marina V; Guedes da Silva, M Fátima C; Martins, Luísa M D R S; Pombeiro, Armando J L

    2012-11-01

    The new hexanuclear mixed-valence vanadium complex [V(3)O(3)(OEt)(ashz)(2)(μ-OEt)](2) (1) with an N,O-donor ligand is reported. It acts as a highly efficient catalyst toward alkane oxidations by aqueous H(2)O(2). Remarkably, high turnover numbers up to 25000 with product yields of up to 27% (based on alkane) stand for one of the most active systems for such reactions.

  6. Improved Alkane Production in Nitrogen-Fixing and Halotolerant Cyanobacteria via Abiotic Stresses and Genetic Manipulation of Alkane Synthetic Genes.

    PubMed

    Kageyama, Hakuto; Waditee-Sirisattha, Rungaroon; Sirisattha, Sophon; Tanaka, Yoshito; Mahakhant, Aparat; Takabe, Teruhiro

    2015-07-01

    Cyanobacteria possess the unique capacity to produce alkane. In this study, effects of nitrogen deficiency and salt stress on biosynthesis of alkanes were investigated in three kinds of cyanobacteria. Intracellular alkane accumulation was increased in nitrogen-fixing cyanobacterium Anabaena sp. PCC7120, but decreased in non-diazotrophic cyanobacterium Synechococcus elongatus PCC7942 and constant in a halotolerant cyanobacterium Aphanothece halophytica under nitrogen-deficient condition. We also found that salt stress increased alkane accumulation in Anabaena sp. PCC7120 and A. halophytica. The expression levels of two alkane synthetic genes were not upregulated significantly under nitrogen deficiency or salt stress in Anabaena sp. PCC7120. The transformant Anabaena sp. PCC7120 cells with additional alkane synthetic gene set from A. halophytica increased intracellular alkane accumulation level compared to control cells. These results provide a prospect to improve bioproduction of alkanes in nitrogen-fixing halotolerant cyanobacteria via abiotic stresses and genetic engineering.

  7. Leaf wax n-alkane distributions in and across modern plants: Implications for paleoecology and chemotaxonomy

    NASA Astrophysics Data System (ADS)

    Bush, Rosemary T.; McInerney, Francesca A.

    2013-09-01

    Long chain (C21 to C37) n-alkanes are among the most long-lived and widely utilized terrestrial plant biomarkers. Dozens of studies have examined the range and variation of n-alkane chain-length abundances in modern plants from around the world, and n-alkane distributions have been used for a variety of purposes in paleoclimatology and paleoecology as well as chemotaxonomy. However, most of the paleoecological applications of n-alkane distributions have been based on a narrow set of modern data that cannot address intra- and inter-plant variability. Here, we present the results of a study using trees from near Chicago, IL, USA, as well as a meta-analysis of published data on modern plant n-alkane distributions. First, we test the conformity of n-alkane distributions in mature leaves across the canopy of 38 individual plants from 24 species as well as across a single growing season and find no significant differences for either canopy position or time of leaf collection. Second, we compile 2093 observations from 86 sources, including the new data here, to examine the generalities of n-alkane parameters such as carbon preference index (CPI), average chain length (ACL), and chain-length ratios for different plant groups. We show that angiosperms generally produce more n-alkanes than do gymnosperms, supporting previous observations, and furthermore that CPI values show such variation in modern plants that it is prudent to discard the use of CPI as a quantitative indicator of n-alkane degradation in sediments. We also test the hypotheses that certain n-alkane chain lengths predominate in and therefore can be representative of particular plant groups, namely, C23 and C25 in Sphagnum mosses, C27 and C29 in woody plants, and C31 in graminoids (grasses). We find that chain-length distributions are highly variable within plant groups, such that chemotaxonomic distinctions between grasses and woody plants are difficult to make based on n-alkane abundances. In contrast

  8. Fidelity of fossil n-alkanes from leaf to paleosol and applications to the Paleocene-Eocene Thermal Maximum

    NASA Astrophysics Data System (ADS)

    Bush, R. T.; McInerney, F. A.; Baczynski, A. A.; Wing, S. L.

    2011-12-01

    Long chain n-alkanes (C21-C35) are well-known as biomarkers of terrestrial plants. They can be preserved across a wide range of terrestrial and marine environments, survive in the sedimentary record for millions of years, and can serve as proxies for ancient environments. Most n-alkane records are derived from sediments rather than directly from fossil leaves. However, little is known about the fidelity of the n-alkane record: how and where leaf preservation relates to n-alkane preservation and how patterns of n-alkane carbon isotope ratios (δ13C) compare to living relatives. To examine these questions, we analyzed n-alkanes from fluvial sediments and individual leaf fossils collected in the Bighorn Basin, Wyoming, across the Paleocene-Eocene Thermal Maximum (PETM) carbon isotope excursion. We assessed the fidelity of the n-alkane signature from individual fossil leaves via three separate means. 1) Spatial variations were assessed by comparing n-alkane concentrations on a fossil leaf and in sediments both directly adjacent to the leaf and farther away. Absolute concentrations were greater within the compression fossil than in the directly adjacent sediment, which were in turn greater than in more distant sediment. 2) n-Alkane abundances and distributions were examined in fossil leaves having a range of preservational quality, from fossils with intact cuticle to carbonized fossils lacking cuticle and higher-order venation. The best preserved fossils preserved a higher concentration of n-alkanes and showed the most similar n-alkane distribution to living relatives. However, a strong odd over even predominance suggests a relatively unmodified plant source occurred in all samples regardless of preservation state. 3) n-Alkane δ13C values were measured for both fossil leaves and their living relatives. Both the saw-tooth pattern of δ13C values between odd and even chain lengths and the general decrease in δ13C values with increasing chain length are consistent with

  9. Investigating C4 Grass Contributions to N-alkane Based Paleoclimate Reconstructions

    NASA Astrophysics Data System (ADS)

    Doman, C. E.; Enders, S. K.; Chadwick, O.; Freeman, K. H.

    2014-12-01

    Plant wax n-alkanes are long-chain, saturated hydrocarbons contained within the protective waxy cuticle on leaves. These lipids are pervasive and persistent in soils and sediments and thus are ideal biomarkers of ancient terrestrial organic matter. In ecosystems dominated by C3 plants, the relationship between the carbon isotopic value of whole leaves and lipids is fairly well documented, but this relationship has not been fully investigated for plants that use C4 photosynthesis. In both cases, it is unclear if the isotopic relationships are sensitive to environmental conditions, or reflect inherited characteristics. This study used a natural climate gradient on the Kohala peninsula of Hawaii to investigate relationships between climate and the δ13C and δ2H values of n-alkanes in C3 and C4 plants. δ13C of C3 leaves and lipids decreased 5 ‰ from the driest to the wettest sites, consistent with published data. Carbon isotope values of C4 plants showed no relationship to moisture up to 1000 mm mean annual precipitation (MAP). Above this threshold, δ 13C values were around 10‰ more depleted, likely due to a combination of canopy effects and C4 grasses growing in an uncharacteristically wet and cold environment. In C3 plants, the fractionation between leaf and lipid carbon isotopes did not vary with MAP, which allows estimations of δ13C leaf to be made from alkanes preserved in ancient sediments. Along this transect, C3 plants produce around twice the quantity of n-alkanes as C4 grasses. C4 grasses produce longer carbon chains. As a result, n-alkanes in the geologic record will be biased towards C3 plants, but the presence of alkanes C33 and C35 indicate the contributions of C4 grasses. In both C3 and C4 plants, average chain length increased with mean annual precipitation, but the taxonomic differences in chain length were greater than environmental differences. Hydrogen isotopes of n-alkanes show no trends with MAP, but do show clear differences between plant

  10. Gas-phase study of Fe sup + -benzyne with alkanes

    SciTech Connect

    Yongqing Huang; Freiser, B.S. )

    1989-03-29

    The unimolecular chemistry of Fe{sup +}-benzyne and its reactivity with small alkanes in the gas phase are studied by Fourier transform mass spectrometry (FTMS). Collision-induced dissociation of Fe{sup +}-benzyne yields benzyne loss exclusively. In contrast, photodissociation of Fe{sup +}-benzyne yields not only cleavage of benzyne from Fe{sup +}, but competitive loss of C{sub 2}H{sub 2} and C{sub 4}H{sub 2} as well. The Fe{sup +}-benzyne is formed from chlorobenzene by loss of HCl. This dehydrochlorination of chlorobenzene also occurs in secondary reactions up to six times forming products of the type Fe{sup +}-polyphenylene. Fe{sup +}-benzyne reacts with alkanes larger than methane to form a wide variety of product ions by mechanisms including hydrogenation and methanation of the benzyne ligand. All of the product ions can be explained by mechanisms based on Fe{sup +} insertion into either C-C or C-H bonds as the reaction-initiating step, followed by either alkyl or H migration from Fe{sup +} onto the benzyne ligand or, alternatively, by the migratory insertion of benzyne into a metal-carbon or metal-hydrogen bond. Photodissociation and ion-molecule reaction studies yield a value for the metal-ligand bond energy of D{degree} (Fe{sup +}-benzyne) = 76 {plus minus} 10 kcal/mol.

  11. Direct hydrodeoxygenation of raw woody biomass into liquid alkanes.

    PubMed

    Xia, Qineng; Chen, Zongjia; Shao, Yi; Gong, Xueqing; Wang, Haifeng; Liu, Xiaohui; Parker, Stewart F; Han, Xue; Yang, Sihai; Wang, Yanqin

    2016-03-30

    Being the only sustainable source of organic carbon, biomass is playing an ever-increasingly important role in our energy landscape. The conversion of renewable lignocellulosic biomass into liquid fuels is particularly attractive but extremely challenging due to the inertness and complexity of lignocellulose. Here we describe the direct hydrodeoxygenation of raw woods into liquid alkanes with mass yields up to 28.1 wt% over a multifunctional Pt/NbOPO4 catalyst in cyclohexane. The superior performance of this catalyst allows simultaneous conversion of cellulose, hemicellulose and, more significantly, lignin fractions in the wood sawdust into hexane, pentane and alkylcyclohexanes, respectively. Investigation on the molecular mechanism reveals that a synergistic effect between Pt, NbOx species and acidic sites promotes this highly efficient hydrodeoxygenation of bulk lignocellulose. No chemical pretreatment of the raw woody biomass or separation is required for this one-pot process, which opens a general and energy-efficient route for converting raw lignocellulose into valuable alkanes.

  12. Direct hydrodeoxygenation of raw woody biomass into liquid alkanes.

    PubMed

    Xia, Qineng; Chen, Zongjia; Shao, Yi; Gong, Xueqing; Wang, Haifeng; Liu, Xiaohui; Parker, Stewart F; Han, Xue; Yang, Sihai; Wang, Yanqin

    2016-01-01

    Being the only sustainable source of organic carbon, biomass is playing an ever-increasingly important role in our energy landscape. The conversion of renewable lignocellulosic biomass into liquid fuels is particularly attractive but extremely challenging due to the inertness and complexity of lignocellulose. Here we describe the direct hydrodeoxygenation of raw woods into liquid alkanes with mass yields up to 28.1 wt% over a multifunctional Pt/NbOPO4 catalyst in cyclohexane. The superior performance of this catalyst allows simultaneous conversion of cellulose, hemicellulose and, more significantly, lignin fractions in the wood sawdust into hexane, pentane and alkylcyclohexanes, respectively. Investigation on the molecular mechanism reveals that a synergistic effect between Pt, NbOx species and acidic sites promotes this highly efficient hydrodeoxygenation of bulk lignocellulose. No chemical pretreatment of the raw woody biomass or separation is required for this one-pot process, which opens a general and energy-efficient route for converting raw lignocellulose into valuable alkanes. PMID:27025898

  13. Direct hydrodeoxygenation of raw woody biomass into liquid alkanes

    PubMed Central

    Xia, Qineng; Chen, Zongjia; Shao, Yi; Gong, Xueqing; Wang, Haifeng; Liu, Xiaohui; Parker, Stewart F.; Han, Xue; Yang, Sihai; Wang, Yanqin

    2016-01-01

    Being the only sustainable source of organic carbon, biomass is playing an ever-increasingly important role in our energy landscape. The conversion of renewable lignocellulosic biomass into liquid fuels is particularly attractive but extremely challenging due to the inertness and complexity of lignocellulose. Here we describe the direct hydrodeoxygenation of raw woods into liquid alkanes with mass yields up to 28.1 wt% over a multifunctional Pt/NbOPO4 catalyst in cyclohexane. The superior performance of this catalyst allows simultaneous conversion of cellulose, hemicellulose and, more significantly, lignin fractions in the wood sawdust into hexane, pentane and alkylcyclohexanes, respectively. Investigation on the molecular mechanism reveals that a synergistic effect between Pt, NbOx species and acidic sites promotes this highly efficient hydrodeoxygenation of bulk lignocellulose. No chemical pretreatment of the raw woody biomass or separation is required for this one-pot process, which opens a general and energy-efficient route for converting raw lignocellulose into valuable alkanes. PMID:27025898

  14. Nitrated metalloporphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, P.E. Jr.; Lyons, J.E.

    1994-01-18

    Compositions of matter comprising nitro-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has nitro groups attached thereto in meso and/or [beta]-pyrrolic positions.

  15. Nitrated metalloporphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, Jr., Paul E.; Lyons, James E.

    1992-01-01

    Alkanes are oxidized by contact with oxygen-containing gas in the presence as catalyst of a metalloporphyrin in which hydrogen atoms in the porphyrin ring have been replaced with one or more nitro groups. Hydrogen atoms in the porphyrin ring may also be substituted with halogen atoms.

  16. Nitrated metalloporphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, Jr., Paul E.; Lyons, James E.

    1994-01-01

    Compositions of matter comprising nitro-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has nitro groups attached thereto in meso and/or .beta.-pyrrolic positions.

  17. Accelerated Molecular Dynamics Simulation of Alkane Desorption

    NASA Astrophysics Data System (ADS)

    McLaughlin, Kelly; Fichthorn, Kristen

    2006-03-01

    Thermal desorption has been the focus of much surface science research. Studies of alkanes on graphite^1 and gold^2 have shown prefactors that are constant with alkane chain length but vary by over six orders of magnitude. Other studies on magnesium oxide^3 and gold^4 show a prefactor that increases with increasing chain length. We have developed an all-atom model to study alkane desorption from graphite. Transition state theory is used to obtain rate constants from the simulation. Accelerated MD is used to extend the desorption simulation to experimentally relevant temperatures. Our results show a prefactor that increases with increasing chain length. We predict that it will become constant as internal conformational changes occur significantly. We examine the effect of desorption environment through varying the alkane surface coverage. 1. K.R. Paserba and A.J. Gellman, J. Chem. Phys. 115, 6737 (2001). 2. S.M. Wetterer et al., J. Phys. Chem. 102, 9266 (1998). 3. S.L. Tait et al., J. Chem. Phys. 122, 164707 (2005). 4. K.A. Fichthorn and R.A. Miron, Phys. Rev. Lett. 89, 196103 (2002).

  18. Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

    NASA Astrophysics Data System (ADS)

    Aumont, B.; Valorso, R.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

    2012-06-01

    The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere). Gas phase oxidation schemes are generated for the C8-C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA) formation for various preexisting organic aerosol concentration (COA). As expected, simulation results show that (i) SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii) SOA yield decreases with decreasing COA, (iii) SOA production rates increase with increasing COA and (iv) the number of oxidation steps (i.e. generations) needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA), suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA) with large yields. The limitations of the model are discussed.

  19. Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

    NASA Astrophysics Data System (ADS)

    Aumont, B.; Valorso, R.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

    2012-08-01

    The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere). Gas phase oxidation schemes are generated for the C8-C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA) formation for various preexisting organic aerosol concentration (COA). As expected, simulation results show that (i) SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii) SOA yield decreases with decreasing COA, (iii) SOA production rates increase with increasing COA and (iv) the number of oxidation steps (i.e. generations) needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA), suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA) with large yields. The limitations of the model are discussed.

  20. Black Carbon Particle Number Distribution Measurements during the ATHENS-2013 Winter Campaign

    NASA Astrophysics Data System (ADS)

    Gkatzelis, Georgios; Papanastasiou, Dimitris; Florou, Kalliopi; Kaltsonoudis, Christos; Louvaris, Eyaggelos; Bezentakos, Spiridon; Biskos, Georgios; Pandis, Spuros

    2014-05-01

    Black Carbon (BC) particles emitted by anthropogenic sources play an important role both in climate change and in air quality degradation. Open burning in forests and savannas, combustion of diesel and solid fuels for cooking and heating in homes represent the majority of BC emissions. Earlier work has focused on the BC atmospheric direct radiative forcing that is mostly related to its mass concentration and optical properties of the corresponding particles. A variety of measurement techniques are used to measure the mass concentration of BC by taking advantage of its optical or physical properties. Moreover, the carbonaceous particles containing BC are also important for the indirect forcing of climate. This effect is mostly related to the number concentration of BC particles. The number distribution of BC particles especially below 100 nm is quite uncertain due to limitations of the existing measurement techniques. In this work we employed a thermodenuder-based method as an approach for the measurement of the BC number distribution. More specifically, we combined a thermodenuder (TD) operating at temperatures up to 300 ° C, with a Scanning Mobility Particle Sizer (SMPS) and a High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF AMS). Aerosol size and composition measurements were carried out both at ambient and at elevated TD temperatures in Athens field campaign during January and February of 2013. In parallel, a Multi-Angle Absorption Photometer (MAAP) provided information about the BC mass concentration while a Hygroscopic Tandem Differential Mobility Analyzer (HTDMA) measured the mixing state and the hygroscopicity of the particles as a function of their size. These measurements were then combined to estimate the number concentration of BC particles. Our analysis focused on different periods during the study. During some of them one source dominated the carbonaceous aerosol concentration. Such periods included rush hour traffic, nighttime wood

  1. Benzylic Phosphates in Friedel-Crafts Reactions with Activated and Unactivated Arenes: Access to Polyarylated Alkanes.

    PubMed

    Pallikonda, Gangaram; Chakravartya, Manab

    2016-03-01

    Easily reachable electron-poor/rich primary and secondary benzylic phosphates are suitably used as substrates for Friedel-Crafts benzylation reactions with only 1.2 equiv activated/deactivated arenes (no additional solvent) to access structurally and electronically diverse polyarylated alkanes with excellent yields and selectivities at room temperature. Specifically, diversely substituted di/triarylmethanes are generated within 2-30 min using this approach. A wide number of electron-poor polyarylated alkanes are easily accomplished through this route by just tuning the phosphates. PMID:26835977

  2. Transcriptional response of Desulfatibacillum alkenivorans AK-01 to growth on alkanes: insights from RT-qPCR and microarray analyses.

    PubMed

    Herath, Anjumala; Wawrik, Boris; Qin, Yujia; Zhou, Jizhong; Callaghan, Amy V

    2016-05-01

    Microbial transformation of n-alkanes in anaerobic ecosystems plays a pivotal role in biogeochemical carbon cycling and bioremediation, but the requisite genetic machinery is not well elucidated.Desulfatibacillum alkenivorans AK-01 utilizes n-alkanes (C13 to C18) and contains two genomic loci encoding alkylsuccinate synthase (ASS) gene clusters. ASS catalyzes alkane addition to fumarate to form methylalkylsuccinic acids. We hypothesized that the genes in the two clusters would be differentially expressed depending on the alkane substrate utilized for growth. RT-qPCR was used to investigate ass-gene expression across AK-01's known substrate range, and microarray-based transcriptomic analysis served to investigate whole-cell responses to growth on n-hexadecane versus hexadecanoate. RT-qPCR revealed induction of ass gene cluster 1 during growth on all tested alkane substrates, and the transcriptional start sites in cluster 1 were determined via 5'RACE. Induction of ass gene cluster 2 was not observed under the tested conditions. Transcriptomic analysis indicated that the upregulation of genes potentially involved in methylalkylsuccinate metabolism, including methylmalonyl-CoA mutase and a putative carboxyl transferase. These findings provide new directions for studying the transcriptional regulation of genes involved in alkane addition to fumarate, fumarate recycling and the processing of methylalkylsuccinates with regard to isolates, enrichment cultures and ecological datasets.

  3. Transcriptional response of Desulfatibacillum alkenivorans AK-01 to growth on alkanes: insights from RT-qPCR and microarray analyses.

    PubMed

    Herath, Anjumala; Wawrik, Boris; Qin, Yujia; Zhou, Jizhong; Callaghan, Amy V

    2016-05-01

    Microbial transformation of n-alkanes in anaerobic ecosystems plays a pivotal role in biogeochemical carbon cycling and bioremediation, but the requisite genetic machinery is not well elucidated.Desulfatibacillum alkenivorans AK-01 utilizes n-alkanes (C13 to C18) and contains two genomic loci encoding alkylsuccinate synthase (ASS) gene clusters. ASS catalyzes alkane addition to fumarate to form methylalkylsuccinic acids. We hypothesized that the genes in the two clusters would be differentially expressed depending on the alkane substrate utilized for growth. RT-qPCR was used to investigate ass-gene expression across AK-01's known substrate range, and microarray-based transcriptomic analysis served to investigate whole-cell responses to growth on n-hexadecane versus hexadecanoate. RT-qPCR revealed induction of ass gene cluster 1 during growth on all tested alkane substrates, and the transcriptional start sites in cluster 1 were determined via 5'RACE. Induction of ass gene cluster 2 was not observed under the tested conditions. Transcriptomic analysis indicated that the upregulation of genes potentially involved in methylalkylsuccinate metabolism, including methylmalonyl-CoA mutase and a putative carboxyl transferase. These findings provide new directions for studying the transcriptional regulation of genes involved in alkane addition to fumarate, fumarate recycling and the processing of methylalkylsuccinates with regard to isolates, enrichment cultures and ecological datasets. PMID:27009900

  4. Carbon monoxide improves neuronal differentiation and yield by increasing the functioning and number of mitochondria.

    PubMed

    Almeida, Ana S; Sonnewald, Ursula; Alves, Paula M; Vieira, Helena L A

    2016-08-01

    The process of cell differentiation goes hand-in-hand with metabolic adaptations, which are needed to provide energy and new metabolites. Carbon monoxide (CO) is an endogenous cytoprotective molecule able to inhibit cell death and improve mitochondrial metabolism. Neuronal differentiation processes were studied using the NT2 cell line, which is derived from human testicular embryonic teratocarcinoma and differentiates into post-mitotic neurons upon retinoic acid treatment. CO-releasing molecule A1 (CORM-A1) was used do deliver CO into cell culture. CO treatment improved NT2 neuronal differentiation and yield, since there were more neurons and the total cell number increased following the differentiation process. CO supplementation enhanced the mitochondrial population in post-mitotic neurons derived from NT2 cells, as indicated by an increase in mitochondrial DNA. CO treatment during neuronal differentiation increased the extent of the classical metabolic change that occurs during neuronal differentiation, from glycolytic to more oxidative metabolism, by decreasing the ratio of lactate production and glucose consumption. The expression of pyruvate and lactate dehydrogenases was higher, indicating an augmented oxidative metabolism. Moreover, these findings were corroborated by an increased percentage of (13) C incorporation from [U-(13) C]glucose into the tricarboxylic acid cycle metabolites malate and citrate, and also glutamate and aspartate in CO-treated cells. Finally, under low levels of oxygen (5%), which enhances glycolytic metabolism, some of the enhancing effects of CO on mitochondria were not observed. In conclusion, our data show that CO improves neuronal and mitochondrial yield by stimulation of tricarboxylic acid cycle activity, and thus oxidative metabolism of NT2 cells during the process of neuronal differentiation. The process of cell differentiation is coupled with metabolic adaptations. Carbon monoxide (CO) is an endogenous cytoprotective

  5. Stable alkanes containing very long carbon-carbon bonds.

    PubMed

    Fokin, Andrey A; Chernish, Lesya V; Gunchenko, Pavel A; Tikhonchuk, Evgeniya Yu; Hausmann, Heike; Serafin, Michael; Dahl, Jeremy E P; Carlson, Robert M K; Schreiner, Peter R

    2012-08-22

    The metal-induced coupling of tertiary diamondoid bromides gave highly sterically congested hydrocarbon (hetero)dimers with exceptionally long central C-C bonds of up to 1.71 Å in 2-(1-diamantyl)[121]tetramantane. Yet, these dimers are thermally very stable even at temperatures above 200 °C, which is not in line with common C-C bond length versus bond strengths correlations. We suggest that the extraordinary stabilization arises from numerous intramolecular van der Waals attractions between the neighboring H-terminated diamond-like surfaces. The C-C bond rotational dynamics of 1-(1-adamantyl)diamantane, 1-(1-diamantyl)diamantane, 2-(1-adamantyl)triamantane, 2-(1-diamantyl)triamantane, and 2-(1-diamantyl)[121]tetramantane were studied through variable-temperature (1)H- and (13)C NMR spectroscopies. The shapes of the inward (endo) CH surfaces determine the dynamic behavior, changing the central C-C bond rotation barriers from 7 to 33 kcal mol(-1). We probe the ability of popular density functional theory (DFT) approaches (including BLYP, B3LYP, B98, B3LYP-Dn, B97D, B3PW91, BHandHLYP, B3P86, PBE1PBE, wB97XD, and M06-2X) with 6-31G(d,p) and cc-pVDZ basis sets to describe such an unusual bonding situation. Only functionals accounting for dispersion are able to reproduce the experimental geometries, while most DFT functionals are able to reproduce the experimental rotational barriers due to error cancellations. Computations on larger diamondoids reveal that the interplay between the shapes and the sizes of the CH surfaces may even allow the preparation of open-shell alkyl radical dimers (and possibly polymers) that are strongly held together exclusively by dispersion forces.

  6. Stable alkanes containing very long carbon-carbon bonds.

    PubMed

    Fokin, Andrey A; Chernish, Lesya V; Gunchenko, Pavel A; Tikhonchuk, Evgeniya Yu; Hausmann, Heike; Serafin, Michael; Dahl, Jeremy E P; Carlson, Robert M K; Schreiner, Peter R

    2012-08-22

    The metal-induced coupling of tertiary diamondoid bromides gave highly sterically congested hydrocarbon (hetero)dimers with exceptionally long central C-C bonds of up to 1.71 Å in 2-(1-diamantyl)[121]tetramantane. Yet, these dimers are thermally very stable even at temperatures above 200 °C, which is not in line with common C-C bond length versus bond strengths correlations. We suggest that the extraordinary stabilization arises from numerous intramolecular van der Waals attractions between the neighboring H-terminated diamond-like surfaces. The C-C bond rotational dynamics of 1-(1-adamantyl)diamantane, 1-(1-diamantyl)diamantane, 2-(1-adamantyl)triamantane, 2-(1-diamantyl)triamantane, and 2-(1-diamantyl)[121]tetramantane were studied through variable-temperature (1)H- and (13)C NMR spectroscopies. The shapes of the inward (endo) CH surfaces determine the dynamic behavior, changing the central C-C bond rotation barriers from 7 to 33 kcal mol(-1). We probe the ability of popular density functional theory (DFT) approaches (including BLYP, B3LYP, B98, B3LYP-Dn, B97D, B3PW91, BHandHLYP, B3P86, PBE1PBE, wB97XD, and M06-2X) with 6-31G(d,p) and cc-pVDZ basis sets to describe such an unusual bonding situation. Only functionals accounting for dispersion are able to reproduce the experimental geometries, while most DFT functionals are able to reproduce the experimental rotational barriers due to error cancellations. Computations on larger diamondoids reveal that the interplay between the shapes and the sizes of the CH surfaces may even allow the preparation of open-shell alkyl radical dimers (and possibly polymers) that are strongly held together exclusively by dispersion forces. PMID:22835264

  7. Anaerobic oxidation of short-chain alkanes in hydrothermal sediments: potential influences on sulfur cycling and microbial diversity

    PubMed Central

    Adams, Melissa M.; Hoarfrost, Adrienne L.; Bose, Arpita; Joye, Samantha B.; Girguis, Peter R.

    2013-01-01

    Short-chain alkanes play a substantial role in carbon and sulfur cycling at hydrocarbon-rich environments globally, yet few studies have examined the metabolism of ethane (C2), propane (C3), and butane (C4) in anoxic sediments in contrast to methane (C1). In hydrothermal vent systems, short-chain alkanes are formed over relatively short geological time scales via thermogenic processes and often exist at high concentrations. The sediment-covered hydrothermal vent systems at Middle Valley (MV, Juan de Fuca Ridge) are an ideal site for investigating the anaerobic oxidation of C1–C4 alkanes, given the elevated temperatures and dissolved hydrocarbon species characteristic of these metalliferous sediments. We examined whether MV microbial communities oxidized C1–C4 alkanes under mesophilic to thermophilic sulfate-reducing conditions. Here we present data from discrete temperature (25, 55, and 75°C) anaerobic batch reactor incubations of MV sediments supplemented with individual alkanes. Co-registered alkane consumption and sulfate reduction (SR) measurements provide clear evidence for C1–C4 alkane oxidation linked to SR over time and across temperatures. In these anaerobic batch reactor sediments, 16S ribosomal RNA pyrosequencing revealed that Deltaproteobacteria, particularly a novel sulfate-reducing lineage, were the likely phylotypes mediating the oxidation of C2–C4 alkanes. Maximum C1–C4 alkane oxidation rates occurred at 55°C, which reflects the mid-core sediment temperature profile and corroborates previous studies of rate maxima for the anaerobic oxidation of methane (AOM). Of the alkanes investigated, C3 was oxidized at the highest rate over time, then C4, C2, and C1, respectively. The implications of these results are discussed with respect to the potential competition between the anaerobic oxidation of C2–C4alkanes with AOM for available oxidants and the influence on the fate of C1 derived from these hydrothermal systems. PMID:23717305

  8. Identification and quantification of mixed sources of oil spills based on distributions and isotope profiles of long-chain n-alkanes.

    PubMed

    Li, Yun; Xiong, Yongqiang

    2009-12-01

    Combined with quantitative determination of concentration and isotopic composition of petroleum hydrocarbons, weathering simulation experiments on artificially mixed oils and their two end-member oils are performed for identification and quantification of mixed sources. The >C(18)n-alkanes show no appreciable losses during a short-term weathering process. An approach based on distribution of long-chain n-alkanes (>C(18)) is suggested for estimating the contribution proportion of each source in mixed oils. Stable carbon isotope profile of individual n-alkanes is a powerful tool to differentiate sources of oil spills, but unavailable to accurately allocate each contribution due to a relatively large analytical error.

  9. Particle number scaling for diffusion-induced dissipation in graphene and carbon nanotube nanomechanical resonators

    NASA Astrophysics Data System (ADS)

    Rhén, Christin; Isacsson, Andreas

    2016-03-01

    When a contaminant diffuses on the surface of a nanomechanical resonator, the motions of the two become correlated. Despite being a high-order effect in the resonator-particle coupling, such correlations affect the system dynamics by inducing dissipation of the resonator energy. Here, we consider this diffusion-induced dissipation in the cases of multiple particles adsorbed on carbon nanotube and graphene resonators. By solving the stochastic equations of motion, we simulate the ringdown of the resonator, in order to determine the resonator energy decay rate. We find two different scalings with the number of adsorbed particles K and particle mass m . In the regime where the adsorbates are inertially trapped at an antinode of vibration, the dissipation rate Γ scales with the total adsorbed mass Γ ∝K m . In contrast, in the regime where particles diffuse freely over the resonator, the dissipation rate scales as the product of the total adsorbed mass and the individual particle mass: Γ ∝K m2 .

  10. Enhanced biodegradation of alkane hydrocarbons and crude oil by mixed strains and bacterial community analysis.

    PubMed

    Chen, Yu; Li, Chen; Zhou, Zhengxi; Wen, Jianping; You, Xueyi; Mao, Youzhi; Lu, Chunzhe; Huo, Guangxin; Jia, Xiaoqiang

    2014-04-01

    In this study, two strains, Acinetobacter sp. XM-02 and Pseudomonas sp. XM-01, were isolated from soil samples polluted by crude oil at Bohai offshore. The former one could degrade alkane hydrocarbons (crude oil and diesel, 1:4 (v/v)) and crude oil efficiently; the latter one failed to grow on alkane hydrocarbons but could produce rhamnolipid (a biosurfactant) with glycerol as sole carbon source. Compared with pure culture, mixed culture of the two strains showed higher capability in degrading alkane hydrocarbons and crude oil of which degradation rate were increased from 89.35 and 74.32 ± 4.09 to 97.41 and 87.29 ± 2.41 %, respectively. In the mixed culture, Acinetobacter sp. XM-02 grew fast with sufficient carbon source and produced intermediates which were subsequently utilized for the growth of Pseudomonas sp. XM-01 and then, rhamnolipid was produced by Pseudomonas sp. XM-01. Till the end of the process, Acinetobacter sp. XM-02 was inhibited by the rapid growth of Pseudomonas sp. XM-01. In addition, alkane hydrocarbon degradation rate of the mixed culture increased by 8.06 to 97.41 % compared with 87.29 % of the pure culture. The surface tension of medium dropping from 73.2 × 10(-3) to 28.6 × 10(-3) N/m. Based on newly found cooperation between the degrader and the coworking strain, rational investigations and optimal strategies to alkane hydrocarbons biodegradation were utilized for enhancing crude oil biodegradation. PMID:24532465

  11. Enhanced biodegradation of alkane hydrocarbons and crude oil by mixed strains and bacterial community analysis.

    PubMed

    Chen, Yu; Li, Chen; Zhou, Zhengxi; Wen, Jianping; You, Xueyi; Mao, Youzhi; Lu, Chunzhe; Huo, Guangxin; Jia, Xiaoqiang

    2014-04-01

    In this study, two strains, Acinetobacter sp. XM-02 and Pseudomonas sp. XM-01, were isolated from soil samples polluted by crude oil at Bohai offshore. The former one could degrade alkane hydrocarbons (crude oil and diesel, 1:4 (v/v)) and crude oil efficiently; the latter one failed to grow on alkane hydrocarbons but could produce rhamnolipid (a biosurfactant) with glycerol as sole carbon source. Compared with pure culture, mixed culture of the two strains showed higher capability in degrading alkane hydrocarbons and crude oil of which degradation rate were increased from 89.35 and 74.32 ± 4.09 to 97.41 and 87.29 ± 2.41 %, respectively. In the mixed culture, Acinetobacter sp. XM-02 grew fast with sufficient carbon source and produced intermediates which were subsequently utilized for the growth of Pseudomonas sp. XM-01 and then, rhamnolipid was produced by Pseudomonas sp. XM-01. Till the end of the process, Acinetobacter sp. XM-02 was inhibited by the rapid growth of Pseudomonas sp. XM-01. In addition, alkane hydrocarbon degradation rate of the mixed culture increased by 8.06 to 97.41 % compared with 87.29 % of the pure culture. The surface tension of medium dropping from 73.2 × 10(-3) to 28.6 × 10(-3) N/m. Based on newly found cooperation between the degrader and the coworking strain, rational investigations and optimal strategies to alkane hydrocarbons biodegradation were utilized for enhancing crude oil biodegradation.

  12. Alkyl nitrate formation from the reactions of C8-C14 n-alkanes with OH radicals in the presence of NO(x): measured yields with essential corrections for gas-wall partitioning.

    PubMed

    Yeh, Geoffrey K; Ziemann, Paul J

    2014-09-18

    In this study, C8-C14 n-alkanes were reacted with OH radicals in the presence of NO(x) in a Teflon film environmental chamber and isomer-specific yields of alkyl nitrates were determined using gas chromatography. Because results indicated significant losses of alkyl nitrates to chamber walls, gas-wall partitioning was investigated by monitoring the concentrations of a suite of synthesized alkyl nitrates added to the chamber. Gas-to-wall partitioning increased with increasing carbon number and with proximity of the nitrooxy group to the terminal carbon, with losses as high as 86%. The results were used to develop a structure-activity model to predict the effects of carbon number and isomer structure on gas-wall partitioning, which was used to correct the measured yields of alkyl nitrate isomers formed in chamber reactions. The resulting branching ratios for formation of secondary alkyl nitrates were similar for all isomers of a particular carbon number, and average values, which were almost identical to alkyl nitrate yields, were 0.219, 0.206, 0.254, 0.291, and 0.315 for reactions of n-octane, n-decane, n-dodecane, n-tridecane, and n-tetradecane, respectively. The increase in average branching ratios and alkyl nitrate yields with increasing carbon number to a plateau value of ∼0.30 at about C13-C14 is consistent with predictions of a previously developed model, indicating that the model is valid for alkane carbon numbers ≥C3.

  13. Alkyl nitrate formation from the reactions of C8-C14 n-alkanes with OH radicals in the presence of NO(x): measured yields with essential corrections for gas-wall partitioning.

    PubMed

    Yeh, Geoffrey K; Ziemann, Paul J

    2014-09-18

    In this study, C8-C14 n-alkanes were reacted with OH radicals in the presence of NO(x) in a Teflon film environmental chamber and isomer-specific yields of alkyl nitrates were determined using gas chromatography. Because results indicated significant losses of alkyl nitrates to chamber walls, gas-wall partitioning was investigated by monitoring the concentrations of a suite of synthesized alkyl nitrates added to the chamber. Gas-to-wall partitioning increased with increasing carbon number and with proximity of the nitrooxy group to the terminal carbon, with losses as high as 86%. The results were used to develop a structure-activity model to predict the effects of carbon number and isomer structure on gas-wall partitioning, which was used to correct the measured yields of alkyl nitrate isomers formed in chamber reactions. The resulting branching ratios for formation of secondary alkyl nitrates were similar for all isomers of a particular carbon number, and average values, which were almost identical to alkyl nitrate yields, were 0.219, 0.206, 0.254, 0.291, and 0.315 for reactions of n-octane, n-decane, n-dodecane, n-tridecane, and n-tetradecane, respectively. The increase in average branching ratios and alkyl nitrate yields with increasing carbon number to a plateau value of ∼0.30 at about C13-C14 is consistent with predictions of a previously developed model, indicating that the model is valid for alkane carbon numbers ≥C3. PMID:24654572

  14. Cool-flame Extinction During N-Alkane Droplet Combustion in Microgravity

    NASA Technical Reports Server (NTRS)

    Nayagam, Vedha; Dietrich, Daniel L.; Hicks, Michael C.; Williams, Forman A.

    2014-01-01

    Recent droplet combustion experiments onboard the International Space Station (ISS) have revealed that large n-alkane droplets can continue to burn quasi-steadily following radiative extinction in a low-temperature regime, characterized by negative-temperaturecoefficient (NTC) chemistry. In this study we report experimental observations of n-heptane, n-octane, and n-decane droplets of varying initial sizes burning in oxygen/nitrogen/carbon dioxide and oxygen/helium/nitrogen environments at 1.0, 0.7, and 0.5 atmospheric pressures. The oxygen concentration in these tests varied in the range of 14% to 25% by volume. Large n-alkane droplets exhibited quasi-steady low-temperature burning and extinction following radiative extinction of the visible flame while smaller droplets burned to completion or disruptively extinguished. A vapor-cloud formed in most cases slightly prior to or following the "cool flame" extinction. Results for droplet burning rates in both the hot-flame and cool-flame regimes as well as droplet extinction diameters at the end of each stage are presented. Time histories of radiant emission from the droplet captured using broadband radiometers are also presented. Remarkably the "cool flame" extinction diameters for all the three n-alkanes follow a trend reminiscent of the ignition delay times observed in previous studies. The similarities and differences among the n-alkanes during "cool flame" combustion are discussed using simplified theoretical models of the phenomenon

  15. Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

    DOEpatents

    Kung, Harold H.; Chaar, Mohamed A.

    1988-01-01

    Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons is carried out over metal vanadate catalysts under oxidizing conditions. The vanadate catalysts are represented by the formulas M.sub.3 (VO.sub.4).sub.2 and MV.sub.2 O.sub.6, M representing Mg, Zn, Ca, Pb, or Cd. The reaction is carried out in the presence of oxygen, but the formation of oxygenate by-products is suppressed.

  16. Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

    DOEpatents

    Kung, H.H.; Chaar, M.A.

    1988-10-11

    Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons is carried out over metal vanadate catalysts under oxidizing conditions. The vanadate catalysts are represented by the formulas M[sub 3](VO[sub 4])[sub 2] and MV[sub 2]O[sub 6], M representing Mg, Zn, Ca, Pb, or Cd. The reaction is carried out in the presence of oxygen, but the formation of oxygenate by-products is suppressed.

  17. [Composition of n-alkanes in soils of the Yellow River Estuary Wetlands and their potential as organic matter source indicators].

    PubMed

    Yao, Peng; Yin, Hong-Zhen; Yao, Qing-Zhen; Chen, Hong-Tao; Liu, Yue-Liang

    2012-10-01

    Abstract: Surface soil samples from the Yellow River Estuary Wetlands were analyzed for total organic carbon (TOC) and n-alkanes. Molecular indicators of n-alkanes were calculated and their potential as organic matter source indicators was discussed and compared among different sampling areas and times. C25-C33 n-alkanes with odd-to-even predominance were observed in most surface soils of the wetlands, suggesting the dominant contribution of terrestrial higher plants for the soil organic matter (SOM), and the ubiquitous presence of unresolved complex mixture indicated the presence of petroleum contamination. Total n-alkane concentrations in soils varied from 0.57 microg x g(-1) to 3.90 microg x g(-1), and distinct spatial and temporal differences were observed. In April 2009 (dry season), total n-alkane concentration was higher than that in June 2009 (during water-sediment regulation) with the maximum concentration observed at the core area of the wetlands, followed by the north side of the Yellow River after the last pontoon bridge, and the abandoned channel area of the Yellow River. The opposite trend of total n-alkane concentration was observed in June. The variation of total n-alkane concentration at two sampling time points were positively correlated with TOC and negatively correlated with sediment grain size, suggesting the influence of hydro-environment on the accumulation of soil organic matter. Molecular indicators of n-alkanes, such as average chain length (ACL), odd-even predominance (OEP), alkane index (AI), carbon preference index (CPI) and Terrigenous/ Aquatic Ratio (TAR) indicated that the maturity of organic matter in soils of the wetlands was low, and the dominant source of the SOM was terrestrial higher plants and mainly herbaceous plants. Compared with other indicators, TAR is better in reflecting the variation of hydro-environment.

  18. Measurement of black carbon and particle number emission factors from individual heavy-duty trucks.

    PubMed

    Ban-Weiss, George A; Lunden, Melissa M; Kirchstetter, Thomas W; Harley, Robert A

    2009-03-01

    Emission factors for black carbon (BC) and particle number (PN) were measured from 226 individual heavy-duty (HD) diesel trucks driving through a 1-km-long California highway tunnel in August 2006. Emission factors were based on concurrent increases in BC, PN, and CO2 concentrations (measured at 1 Hz) that corresponded to the passage of individual HD trucks. The distributions of BC and PN emission factors from individual HD trucks are skewed, meaning that a large fraction of pollution comes from a small fraction of the in-use vehicle fleet. The highest-emitting 10% of trucks were responsible for approximately 40% of total BC and PN emissions from all HD trucks. BC emissions were log-normally distributed with a mean emission factor of 1.7 g kg(-1) and maximum values of approximately 10 g kg(-1). Corresponding values for PN emission factors were 4.7 x 10(15) and 4 x 10(16) # kg(-1). There was minimal overlap among high-emitters of these two pollutants: only 1 of the 226 HD trucks measured was found to be among the highest 10% for both BC and PN. Monte Carlo resampling of the distribution of BC emission factors observed in this study revealed that uncertainties (1sigma) in extrapolating from a random sample of n HD trucks to a population mean emission factor ranged from +/- 43% for n=10 to +/- 8% for n=300, illustrating the importance of vehicle sample sizes in emissions studies. When n=10, sample means are more likely to be biased due to misrepresentation of high-emitters. As vehicles become cleaner on average in the future, skewness of the emissions distributions will increase, and thus sample sizes needed to extrapolate reliably from a subset of vehicles to the entire in-use vehicle fleet will become more of a challenge. PMID:19350913

  19. Measurement of Black Carbon and Particle Number Emission Factors from Individual Heavy-Duty Trucks

    SciTech Connect

    Ban-Weiss, George A.; Lunden, Melissa M.; Kirchstetter, Thomas W.; Harley, Robert A.

    2009-02-02

    Emission factors for black carbon (BC) and particle number (PN) were measured from 226 individual heavy-duty (HD) diesel-fueled trucks driving through a 1 km-long California highway tunnel in August 2006. Emission factors were based on concurrent increases in BC, PN, and CO{sub 2}B concentrations (measured at 1 Hz) that corresponded to the passage of individual HD trucks. The distributions of BC and PN emission factors from individual HD trucks are skewed, meaning that a large fraction of pollution comes from a small fraction of the in-use vehicle fleet. The highest-emitting 10% of trucks were responsible for {approx} 40% of total BC and PN emissions from all HD trucks. BC emissions were log-normally distributed with a mean emission factor of 1.7 g kg {sup -1} and maximum values of {approx} 10 g kg{sup -1}. Corresponding values for PN emission factors were 4.7 x 10{sup 15} and 4 x 10{sup 16} kg{sup -1}. There was minimal overlap among high-emitters of these two pollutants: only 1 of the 226 HD trucks measured was found to be among the highest 10% for both BC and PN. Monte Carlo resampling of the distribution of BC emission factors observed in this study revealed that uncertainties (1{sigma}) in extrapolating from a random sample of n HD trucks to a population mean emission factor ranged from {+-} 43% for n = 10 to {+-} 8% for n = 300, illustrating the importance of sufficiently large vehicle sample sizes in emissions studies. Studies with low sample sizes are also more easily biased due to misrepresentation of high-emitters. As vehicles become cleaner on average in future years, skewness of the emissions distributions will increase, and thus sample sizes needed to extrapolate reliably from a subset of vehicles to the entire in-use vehicle fleet are expected to become more of a challenge.

  20. Indoor air quality: Carbon monoxide, molds and beyond. Current issue paper number 198

    SciTech Connect

    Yeager, L.

    1999-09-01

    This paper provides an overview of several of the major indoor air pollutants and some of the ways in which indoor air quality is addressed by governments in the United States and Canada. The emphasis is on non-industrial settings. Pollutants discussed include carbon dioxide, tobacco smoke, radon, carbon monoxide, nitrogen dioxide, wood smoke and particles, volatile organic compounds, and molds.

  1. Alkane dehydrogenation catalyzed by rhodium(I) phosphine complexes. Observation of the stoichiometric alkane-to-rhodium hydrogen-transfer step

    SciTech Connect

    Shih, K.C.; Goldman, A.S. )

    1993-09-01

    RhL[sub 2]Cl (L = P[sup t]Pr[sub 3]) is found to dehydrogenate cyclooctane to give H[sub 2]RhL[sub 2]Cl and cyclooctene; this represents the first observation of the key hydrogen-transfer step proposed for related, catalytic alkane transfer-dehydrogenation systems. Using norbornene as a hydrogen acceptor, transfer-dehydrogenation is catalyzed but turnover numbers are low. 18 refs., 1 tab.

  2. Cooperative catalysis for the direct hydrodeoxygenation of vegetable oils into diesel-range alkanes over Pd/NbOPO4.

    PubMed

    Xia, Qineng; Zhuang, Xiaojing; Li, Molly Meng-Jung; Peng, Yung-Kang; Liu, Guoliang; Wu, Tai-Sing; Soo, Yun-Liang; Gong, Xue-Qing; Wang, Yanqin; Tsang, Shik Chi Edman

    2016-04-14

    Near quantitative carbon yields of diesel-range alkanes were achieved from the hydrodeoxygenation of triglycerides over Pd/NbOPO4 under mild conditions with no catalyst deactivation: catalyst characterization and theoretical calculations suggest that the high hydrodeoxygenation activity originated from the synergistic effect of Pd and strong Lewis acidity on the unique structure of NbOPO4. PMID:26998532

  3. Positron and electron scattering from alkane molecules. Normal- and cyclo-octane

    NASA Astrophysics Data System (ADS)

    Sueoka, O.; Makochekanwa, C.; Kimura, M.

    2006-03-01

    Total cross-sections (TCSs) for 0.2 1000 eV positrons and 0.4 1000 eV electrons colliding with normal-octane and cyclo-octane molecules have been studied using a relative measurement method. The TCS curves for positron and electron vary smoothly and compare well with other alkane molecules, in order of increasing carbon number. For positron scattering, weak humps at 1.5 2.5 eV for both normal- and cyclo-octane were observed. In the energy range lower than 2.2 eV, positron TCSs are roughly equal to or larger than electron TCSs. For electron scattering, a resonance peak at 8 eV and a shoulder at 25.0 eV were observed for both molecules. Over all the energy range, the TCS values for normal-octane are larger than those of cyclo-octane. The positron and electron TCS data for normal- and cyclo-octane molecules are briefly compared with those for normal- and cyclo-hexane.

  4. Prediction of the thermal conductivity of liquid N-alkanes over wide density ranges

    SciTech Connect

    Calado, J.C.G.; Fareleira, J.M.N.A.; Mardolcar, U.V.; De Castro, C.A.N.

    1987-01-01

    The thermal conductivity of liquids has been proved in the past to be difficult to predict with a reasonable accuracy, due to the lack of accurate experimental data and reliable prediction schemes. The proposed correlation scheme is constructed on a theoretically based treatment of the van der Waals model of a liquid, which permits the prediction of the density dependence and the thermal conductivity of liquid n-alkanes, methane to tridecane, for temperatures between 110 K and 370 K and pressures up to 0.6 MPa, i.e., for 0.3 less than or equal to T/T/sub c/ less than or equal to 0.7 and 2.4 less than or equal to rho/rho/sub c/ less than or equal to 3/7, with an accuracy of +- 1%, given a known value of the thermal conductivity of the fluid at the desired temperature. A generalization of the hard core volumes obtained, as a function of the number of carbon atoms, showed that it was possible to predict the thermal conductivity of pentane to tetradecane to within +- 2%, without the necessity of available experimental measurements.

  5. Concentrations and source variations of n-alkanes in a 21 m ice core and snow samples at Belukha glacier, Russian Altai mountains

    NASA Astrophysics Data System (ADS)

    Miyake, Takayuki; Nakazawa, Fumio; Sakugawa, Hiroshi; Takeuchi, Nozomu; Fujita, Koji; Ohta, Keiichi; Nakawo, Masayoshi

    Ice-core and snow samples collected on Belukha glacier, Russian Altai mountains, were analyzed for n-alkanes by gas chromatography. On the basis of the total concentrations (T-HCs), carbon preference index (CPI) values and the plant wax contributions (WaxCn), it is suggested that mountain glaciers on the Asian continent received higher loading of n-alkanes from natural and anthropogenic sources than the Greenland ice sheet. It appears that the loading and variation of n-alkanes on glaciers in the Altai are approximately the same as those of the mountain in general, because the concentrations, CPI values and WaxCn percentages of n-alkanes in Sofiyskiy glacier, also in the Russian Altai, are at the same levels as or slightly greater than those in ice-core and snow samples from Belukha glacier. It seems that the n-alkanes on Belukha glacier are derived mainly from higher plant wax and petroleum exhaust other than from diesel engines. Vertical profiles of T-HCs and CPI values of n-alkanes show that the non-WaxCn portions and T-HCs have recently increased with a decrease in CPI values on Belukha glacier. A similar trend of n-alkanes was reported for Sofiyskiy glacier, indicating that the influence of human activities has gradually increased around the Altai.

  6. Gene structure and regulation of alkane monooxygenases in propane-utilizing Mycobacterium sp. TY-6 and Pseudonocardia sp. TY-7.

    PubMed

    Kotani, Tetsuya; Kawashima, Yui; Yurimoto, Hiroya; Kato, Nobuo; Sakai, Yasuyoshi

    2006-09-01

    Mycobacterium sp. TY-6 and Pseudonocardia sp. TY-7 were isolated from soil samples as propane-utilizing bacteria and were found to be able to utilize various gaseous and liquid n-alkanes as carbon and energy sources. One gene cluster, M-prmABCD, and two gene clusters, P-prm1ABCD and P-prm2ABCD, were cloned from the genomes of Mycobacterium sp. TY-6 and Pseudonocardia sp. TY-7, respectively. These gene clusters are homologous to the gene cluster encoding the multicomponent propane monooxygenase (prmABCD) of Gordonia sp. TY-5. The expression of prm gene clusters in Mycobacterium sp. TY-6 and Pseudonocardia sp. TY-7 was shown to be induced by gaseous n-alkanes (C2-C4) except methane, suggesting that the products of these genes are involved in gaseous n-alkane oxidation. Homologous genes for an alkane hydroxylase system (alk system) involved in liquid n-alkane oxidation were also cloned from the genomic DNA of Mycobacterium sp. TY-6. The alk gene cluster was transcribed in response to liquid n-alkanes (C11-C15). These results indicate that Mycobacterium sp. TY-6 has two distinct gene clusters for multicomponent monooxygenases involved in alkane oxidation. Whole-cell reactions revealed that propane is oxidized to 1-propanol through terminal oxidation in Mycobacterium sp. TY-6 and that propane is oxidized to 1-propanol and 2-propanol through both terminal and subterminal oxidations in Pseudonocardia sp. TY-7. This study reveals the diversity of propane metabolism present in microorganisms. PMID:17046531

  7. Technical Note: n-Alkane lipid biomarkers in loess: post-sedimentary or syn-sedimentary?

    NASA Astrophysics Data System (ADS)

    Zech, M.; Kreutzer, S.; Goslar, T.; Meszner, S.; Krause, T.; Faust, D.; Fuchs, M.

    2012-07-01

    There is an ongoing discussion whether n-alkane biomarkers - and organic matter (OM) from loess in general - reflect a syn-sedimentary paleoenvironmental and paleoclimate signal or whether they are significantly a post-sedimentary feature contaminated by root-derived OM. We present first radiocarbon data for the n-alkane fraction of lipid extracts and for the first time luminescence ages for the Middle to Late Weichselian loess-paleosol sequence of Gleina in Saxony, Germany. Comparison of these biomarker ages with sedimentation ages as assessed by optically stimulated luminescence (OSL) dating shows that one n-alkane sample features a syn-sedimentary age (14C: 29.2 ± 1.4 kyr cal BP versus OSL: 27.3 ± 3.0 kyr). By contrast, the 14C ages derived from the other n-alkane samples are clearly younger (20.3 ± 0.7 kyr cal BP, 22.1 ± 0.7 kyr cal BP and 29.8 ± 1.4 kyr cal BP) than the corresponding OSL ages (26.6 ± 3.1 kyr, 32.0 ± 3.5 kyr and 45.6 ± 5.3 kyr). This finding suggests that a post-sedimentary n-alkane contamination presumably by roots has occurred. In order to estimate the post-sedimentary n-alkane contamination more quantitatively, we applied a 14C mass balance calculation based on the measured pMC (percent modern carbon) values, the calculated syn-sedimentary pMC values and pMC values suspected to reflect likely time points of post-sedimentary contamination (current, modern, 3 kyr, 6 kyr and 9 kyr). Accordingly, current and modern root-contamination would account for up to 7%, a 3 kyr old root-contamination for up to 10%, and an Early and Middle Holocene root-contamination for up to 20% of the total sedimentary n-alkane pool. We acknowledge and encourage that these first radiocarbon results need further confirmation both from other loess-paleosol sequences and for different biomarkers, e.g. carboxylic acids or alcohols as further lipid biomarkers.

  8. Extension of Pitzer corresponding states correlations using new vapor pressure measurements of the n-alkanes C sub 10 to C sub 28

    SciTech Connect

    Morgan, D.L.; Kobayashi, R.

    1989-12-31

    Direct vapor pressure measurements of zone-refined n-alkane samples in the carbon number range from C{sub 10} to C{sub 28} (decane, dodecane, tetradecane, hexadecane, octadecane, nonadecane, eicosane, docosane, tetracosane, and octacosane) have been obtained. The overall range of the new measurements are from 0.1 to 1400 kPa and from 323 to 588{degree}K with expected accuracies given by (0.00015P + 0.0048)kPa and 0.03{degree}K. The vapor pressure data have been regressed to Wagner-type equations using critical parameters developed. To extend the range of the Wagner equations toward low reduced temperatures, an alternative set of conformal'' equations were constructed using two real-fluid corresponding states principle (CSP) methods. Using n-alkane vapor pressure data in the range from C{sub 1} to C{sub 36}, the acentric factor ranges of Pitzer-type CSP correlations for vapor pressures and heats of vaporization were extended. In a first approach dubbed PERT2'', a set of conformal'' Wagner equations was generalized by including a second order perturbation term in Pitzer's acentric factor expansion for In(P{sub r}). In a second approach, input parameters (P{sub c},{omega}) were determined from vapor pressure data for accurate pairs of vapor pressure and heat of vaporization reference equations based on methane and octane (C{sub 1}/C{sub 8}). Input parameters (T{sub c},P{sub c},{omega}) for n-alkanes have been correlated and tabulated out to C{sub 36} for both of these approaches. Ratios of the parameters for the two methods can be interpreted in terms of shape factor'' effects. 83 refs., 23 figs., 25 tabs.

  9. Thermal analysis of n-alkane phase change material mixtures

    SciTech Connect

    Chio, Y.I.; Choi, E.; Lorsch, H.G.

    1991-03-31

    Tests were performed to characterize the thermal behavior of it number of n-alkanes to be used as phase change materials (PCMs) in district cooling applications. Hexadecane and tetradecane were mixed in different fractions, and their thermal behavior was experimentally evaluated. Test results for melting temperature and fusion energy for laboratory grade hexadecane and tetradecane showed good agreement with datain the literature. However, values for commercial grade hexadecane were found to be considerably lower. In the range of temperatures of interest for district cooling, mixtures of tetradecane and hexadecane can be treated as homogeneous substances. However, their heats of fusion are slightly lower than those of the pure substances. Their melting temperatures are also lower by an amount that can be predicted.

  10. Characterization of a Novel Rieske-Type Alkane Monooxygenase System in Pusillimonas sp. Strain T7-7

    PubMed Central

    Li, Ping; Wang, Lei

    2013-01-01

    The cold-tolerant bacterium Pusillimonas sp. strain T7-7 is able to utilize diesel oils (C5 to C30 alkanes) as a sole carbon and energy source. In the present study, bioinformatics, proteomics, and real-time reverse transcriptase PCR approaches were used to identify the alkane hydroxylation system present in this bacterium. This system is composed of a Rieske-type monooxygenase, a ferredoxin, and an NADH-dependent reductase. The function of the monooxygenase, which consists of one large (46.711 kDa) and one small (15.355 kDa) subunit, was further studied using in vitro biochemical analysis and in vivo heterologous functional complementation tests. The purified large subunit of the monooxygenase was able to oxidize alkanes ranging from pentane (C5) to tetracosane (C24) using NADH as a cofactor, with greatest activity on the C15 substrate. The large subunit also showed activity on several alkane derivatives, including nitromethane and methane sulfonic acid, but it did not act on any aromatic hydrocarbons. The optimal reaction condition of the large subunit is pH 7.5 at 30°C. Fe2+ can enhance the activity of the enzyme evidently. This is the first time that an alkane monooxygenase system belonging to the Rieske non-heme iron oxygenase family has been identified in a bacterium. PMID:23417490

  11. Detailed chemical kinetic models for large n-alkanes and iso-alkanes found in conventional and F-T diesel fuels

    SciTech Connect

    Westbrook, C K; Pitz, W J; Mehl, M; Curran, H J

    2009-03-09

    n-Hexadecane and 2,2,4,4,6,8,8-heptamethylnonane represent the primary reference fuels for diesel that are used to determine cetane number, a measure of the ignition property of diesel fuel. With the development of chemical kinetics models for both primary reference fuels, a new capability is now available to model diesel fuel ignition. Additionally, we have developed chemical kinetic models for a whole series of large n-alkanes and a large iso-alkane to represent these chemical classes in fuel surrogates for conventional and future fuels. These chemical kinetic models are used to predict the effect of the aforementioned fuel components on ignition characteristics under conditions found in internal combustion engines.

  12. Structures with high number density of carbon nanotubes and 3-dimensional distribution

    NASA Technical Reports Server (NTRS)

    Chen, Zheng (Inventor); Tzeng, Yonhua (Inventor)

    2002-01-01

    A composite is described having a three dimensional distribution of carbon nanotubes. The critical aspect of such composites is a nonwoven network of randomly oriented fibers connected at their junctions to afford macropores in the spaces between the fibers. A variety of fibers may be employed, including metallic fibers, and especially nickel fibers. The composite has quite desirable properties for cold field electron emission applications, such as a relatively low turn-on electric field, high electric field enhancement factors, and high current densities. The composites of this invention also show favorable properties for other an electrode applications. Several methods, which also have general application in carbon nanotube production, of preparing these composites are described and employ a liquid feedstock of oxyhydrocarbons as carbon nanotube precursors.

  13. n-Alkane lipid biomarkers in loess: post-sedimentary or syn-sedimentary?

    NASA Astrophysics Data System (ADS)

    Zech, Michael; Kreutzer, Sebastian; Goslar, Tomasz; Meszner, Sascha; Krause, Tobias; Faust, Dominik; Fuchs, Markus

    2013-04-01

    There is an ongoing discussion whether n-alkane biomarkers - and organic matter (OM) from loess in general - reflect a syn-sedimentary paleoenvironmental and paleoclimate signal or whether they are significantly a post-sedimentary feature contaminated by root-derived OM (Zech et al., 2012, 2013; Wiesenberg and Gocke, 2013). We present first radiocarbon data for the n-alkane fraction of lipid extracts and for the first time luminescence ages for the Middle to Late Weichselian loess-paleosol sequence of Gleina in Saxony, Germany. Comparison of these biomarker ages with sedimentation ages as assessed by optically stimulated luminescence (OSL) dating shows that one n-alkane sample features a syn-sedimentary age (14C: 29.2 ± 1.4 kyr calBP versus OSL: 27.3 ± 3.0 kyr). By contrast, the 14C ages derived from the other n-alkane samples are clearly younger (20.3 ± 0.7 kyr calBP, 22.1 ± 0.7 kyr calBP and 29.8 ± 1.4 kyr calBP) than the corresponding OSL ages (26.6 ± 3.1 kyr, 32.0 ± 3.5 kyr and 45.6 ± 5.3 kyr). This finding suggests that a post-sedimentary n-alkane contamination presumably by roots has occurred. In order to estimate the post-sedimentary n-alkane contamination more quantitatively, we applied a 14C mass balance calculation based on the measured pMC (percent modern carbon) values, the calculated syn-sedimentary pMC values and pMC values suspected to reflect likely time points of post-sedimentary contamination (modern, last decades, 3 kyr, 6 kyr and 9 kyr). Accordingly, modern and last decadal root-contamination would account for up to 7%, a 3 kyr old root-contamination for up to 10%, and an Early and Middle Holocene root-contamination for up to 20% of the total sedimentary n-alkane pool. We acknowledge and encourage that these first radiocarbon results need further confirmation both from other loess-paleosol sequences and for different biomarkers, e.g. carboxylic acids or alcohols as further lipid biomarkers. Zech, M., Kreutzer, S., Goslar, T., Meszner, S

  14. An analysis of organic matter sources for surface sediments in the central South Yellow Sea, China: evidence based on macroelements and n-alkanes.

    PubMed

    Zhang, Shengyin; Li, Shuanglin; Dong, Heping; Zhao, Qingfang; Lu, Xinchuan; Shi, Ji'an

    2014-11-15

    By analyzing the composition of n-alkane and macroelements in the surface sediments of the central South Yellow Sea of China, we evaluated the influencing factors on the distribution of organic matter. The analysis indicates that the distribution of total organic carbon (TOC) was low in the west and high in the east, and TOC was more related to Al2O3 content than medium diameter (MD). The composition of n-alkanes indicated the organic matter was mainly derived from terrestrial higher plants. Contributions from herbaceous plants and woody plants were comparable. The comprehensive analysis of the parameters of macroelements and n-alkanes showed the terrestrial organic matter in the central South Yellow Sea was mainly from the input of the modern Yellow River and old Yellow River. However, some samples exhibited evident input characteristics from petroleum sources, which changed the original n-alkanes of organic matter in sediments.

  15. Diffusion of Trace Alkanes in Polyethylene: Spin-Echo Measurements and Monte-Carlo Simulations

    NASA Astrophysics Data System (ADS)

    von Meerwall, E.; Lin, H.; Mattice, W. L.

    2006-03-01

    We have performed pulsed-gradient NMR diffusion (D) measurements on five n-alkanes (24, 28, 36, 44, and 60 carbons) in a polyethylene (PE) host (M = 33 kDa) as function of concentration c (2-10 wt.%) at 180 deg. C. Monte-Carlo simulations on the second-nearest-neighbor diamond lattice (38, 46, 62, and 78 carbons) at c between 2 and 15 wt.% in a host of PE (M = 4.5 kDa) explored static and dynamic properties. The bridging method uses beads combining adjacent moieties and incorporates two-bead moves; it permits detailed reconstruction of the chain molecules at any stage. It uses discretized short-range rotational isomeric state and long-range intra- and interchain Lennard-Jones potentials. For both experiment and simulation, trace D was obtained by extrapolating D(c) to c = 0 using the Fujita-Doolittle equation with known chain-end free-volume parameters. A ratio of 330 Monte-Carlo steps per picosecond brings simulation into congruence with experiment; this factor is identical to that required for PE melts. The applicability of the Rouse model is approached only for the largest alkanes, but the M(alkane)-dependence of trace D is seen to be in transition from the Rouse-like 1/M-scaling to a steeper value characteristic of reptation with constraint release.

  16. Conversion of raw lignocellulosic biomass into branched long-chain alkanes through three tandem steps.

    PubMed

    Li, Chunrui; Ding, Daqian; Xia, Qineng; Liu, Xiaohui; Wang, Yanqin

    2016-07-01

    Synthesis of branched long-chain alkanes from renewable biomass has attracted intensive interest in recent years, but the feedstock for this synthesis is restricted to platform chemicals. Here, we develop an effective and energy-efficient process to convert raw lignocellulosic biomass (e.g., corncob) into branched diesel-range alkanes through three tandem steps for the first time. Furfural and isopropyl levulinate (LA ester) were prepared from hemicellulose and cellulose fractions of corncob in toluene/water biphasic system with added isopropanol, which was followed by double aldol condensation of furfural with LA ester into C15 oxygenates and the final hydrodeoxygenation of C15 oxygenates into branched long-chain alkanes. The core point of this tandem process is the addition of isopropanol in the first step, which enables the spontaneous transfer of levulinic acid (LA) into the toluene phase in the form of LA ester through esterification, resulting in LA ester co-existing with furfural in the same phase, which is the basis for double aldol condensation in the toluene phase. Moreover, the acidic aqueous phase and toluene can be reused and the residues, including lignin and humins in aqueous phase, can be separated and carbonized to porous carbon materials. PMID:27241180

  17. Numerical and experimental studies of ethanol flames and autoignition theory for higher alkanes

    NASA Astrophysics Data System (ADS)

    Saxena, Priyank

    In order to enhance the fuel efficiency of an engine and to control pollutant formation, an improved understanding of the combustion chemistry of the fuels at a fundamental level is paramount. This knowledge can be gained by developing detailed reaction mechanisms of the fuels for various combustion processes and by studying combustion analytically employing reduced-chemistry descriptions. There is a need for small detailed reaction mechanisms for alkane and alcohol fuels with reduced uncertainties in their combustion chemistry that are computationally cheaper in multidimensional CFD calculations. Detailed mechanisms are the starting points in identifying reduced-chemistry descriptions of combustion processes to study problems analytically. This research includes numerical, experimental and analytical studies. The first part of the dissertation consists of numerical and experimental studies of ethanol flames. Although ethanol has gained popularity as a possible low-pollution source of renewable energy, significant uncertainties remain in its combustion chemistry. To begin to address ethanol combustion, first a relatively small detailed reaction mechanism, commonly known as the San Diego Mech, is developed for the combustion of hydrogen, carbon monoxide, formaldehyde, methane, methanol, ethane, ethylene, and acetylene, in air or oxygen-inert mixtures. This mechanism is tested for autoignition, premixed-flame burning velocities, and structures and extinction of diffusion flames and of partially premixed flames of many of these fuels. The reduction in uncertainties in the combustion chemistry can best be achieved by consistently updating a reaction mechanism with reaction rate data for the elementary steps based on newer studies in literature and by testing it against as many experimental conditions as available. The results of such a testing for abovementioned fuels are reported here along with the modifications of reaction-rate parameters of the most important

  18. Molecular dynamics study of solubilization of immiscible solutes by a micelle: Free energy of transfer of alkanes from water to the micelle core by thermodynamic integration method.

    PubMed

    Fujimoto, K; Yoshii, N; Okazaki, S

    2010-08-21

    Free energy of transfer, DeltaG(w-->m), from water phase to a sodium dodecyl sulfate (SDS) micelle core has been calculated for a series of hydrophobic solutes originally immiscible with water by thermodynamic integration method combined with molecular dynamics calculations. The calculated free energy of transfer is in good correspondence to the experiment as well as the theoretical free energy of transfer. The calculated DeltaG(w-->m)'s are all negative, implying that the alkane molecules are more stable in the micelle than in the water phase. It decreases almost linearly as a function of the number of carbon atoms of the alkanes longer than methane with a decrement of 3.3 kJ mol(-1) per one methylene group. The calculated free energy of transfer indicates that, for example, at the micelle concentration of 50 CMC (critical micelle concentration), about only 1 of 6 micelles or 1 of 32 000 micelles does not contain a solute methane or n-octane molecule, respectively. PMID:20726656

  19. Molecular dynamics study of solubilization of immiscible solutes by a micelle: Free energy of transfer of alkanes from water to the micelle core by thermodynamic integration method

    NASA Astrophysics Data System (ADS)

    Fujimoto, K.; Yoshii, N.; Okazaki, S.

    2010-08-01

    Free energy of transfer, ΔGw→m, from water phase to a sodium dodecyl sulfate (SDS) micelle core has been calculated for a series of hydrophobic solutes originally immiscible with water by thermodynamic integration method combined with molecular dynamics calculations. The calculated free energy of transfer is in good correspondence to the experiment as well as the theoretical free energy of transfer. The calculated ΔGw→m's are all negative, implying that the alkane molecules are more stable in the micelle than in the water phase. It decreases almost linearly as a function of the number of carbon atoms of the alkanes longer than methane with a decrement of 3.3 kJ mol-1 per one methylene group. The calculated free energy of transfer indicates that, for example, at the micelle concentration of 50 CMC (critical micelle concentration), about only 1 of 6 micelles or 1 of 32 000 micelles does not contain a solute methane or n-octane molecule, respectively.

  20. Concentrations and δ²H values of cuticular n-alkanes vary significantly among plant organs, species and habitats in grasses from an alpine and a temperate European grassland.

    PubMed

    Gamarra, Bruno; Kahmen, Ansgar

    2015-08-01

    n-Alkanes are long-chained hydrocarbons contained in the cuticle of terrestrial plants. Their hydrogen isotope ratios (δ(2)H) have been used as a proxy for environmental and plant ecophysiological processes. Calibration studies designed to resolve the mechanisms that determine the δ(2)H values of n-alkanes have exclusively focused on n-alkanes derived from leaves. It is, however, unclear in which quantities n-alkanes are also produced by other plant organs such as roots or inflorescences, or whether different plant organs produce distinct n-alkane δ(2)H values. To resolve these open questions, we sampled leaves, sheaths, stems, inflorescences and roots from a total of 15 species of European C3 grasses in an alpine and a temperate grassland in Switzerland. Our data show slightly increased n-alkane concentrations and n-alkane δ(2)H values in the alpine compared to the temperate grassland. More importantly, inflorescences had typically much higher n-alkane concentrations than other organs while roots had very low n-alkane concentrations. Most interestingly, the δ(2)H values of the carbon autonomous plant organs leaves, sheaths and stems were in general depleted compared to the overall mean δ(2)H value of a species, while non-carbon autonomous organs such as roots and inflorescences show δ(2)H values that are higher compared to the overall mean δ(2)H value of a species. We attribute organ-specific δ(2)H values to differences in the H-NADPH biosynthetic origin in different plant organs as a function of their carbon relationships. Finally, we employed simple mass balance calculations to show that leaves are in fact the main source of n-alkanes in the sediment. As such, studies assessing the environmental and physiological drivers of n-alkanes that focus on leaves produce relationships that can be employed to interpret the δ(2)H values of n-alkanes derived from sediments. This is despite the significant differences that we found among the δ(2)H values in the

  1. Products of Chemistry: Alkanes: Abundant, Pervasive, Important, and Essential.

    ERIC Educational Resources Information Center

    Seymour, Raymond B.

    1989-01-01

    Discusses the history and commercialization of alkanes. Examines the nomenclature and uses of alkanes. Studies polymerization and several types of polyethylenes: low-density, high-density, low-molecular-weight, cross-linked, linear low-density, and ultrahigh-molecular-weight. Includes a glossary of hydrocarbon terms. (MVL)

  2. 40 CFR 721.536 - Halogenated phenyl alkane.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halogenated phenyl alkane. 721.536 Section 721.536 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.536 Halogenated phenyl alkane....

  3. 40 CFR 721.535 - Halogenated alkane (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.535 Halogenated alkane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated alkane (PMN P-01-433) is...

  4. 40 CFR 721.535 - Halogenated alkane (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.535 Halogenated alkane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated alkane (PMN P-01-433) is...

  5. 40 CFR 721.536 - Halogenated phenyl alkane.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.536 Halogenated phenyl alkane. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated phenyl alkane (PMN P-89-867)...

  6. 40 CFR 721.536 - Halogenated phenyl alkane.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.536 Halogenated phenyl alkane. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated phenyl alkane (PMN P-89-867)...

  7. Diverse Bacterial Groups Contribute to the Alkane Degradation Potential of Chronically Polluted Subantarctic Coastal Sediments.

    PubMed

    Guibert, Lilian M; Loviso, Claudia L; Borglin, Sharon; Jansson, Janet K; Dionisi, Hebe M; Lozada, Mariana

    2016-01-01

    We aimed to gain insight into the alkane degradation potential of microbial communities from chronically polluted sediments of a subantarctic coastal environment using a combination of metagenomic approaches. A total of 6178 sequences annotated as alkane-1-monooxygenases (EC 1.14.15.3) were retrieved from a shotgun metagenomic dataset that included two sites analyzed in triplicate. The majority of the sequences binned with AlkB described in Bacteroidetes (32 ± 13 %) or Proteobacteria (29 ± 7 %), although a large proportion remained unclassified at the phylum level. Operational taxonomic unit (OTU)-based analyses showed small differences in AlkB distribution among samples that could be correlated with alkane concentrations, as well as with site-specific variations in pH and salinity. A number of low-abundance OTUs, mostly affiliated with Actinobacterial sequences, were found to be only present in the most contaminated samples. On the other hand, the molecular screening of a large-insert metagenomic library of intertidal sediments from one of the sampling sites identified two genomic fragments containing novel alkB gene sequences, as well as various contiguous genes related to lipid metabolism. Both genomic fragments were affiliated with the phylum Planctomycetes, and one could be further assigned to the genus Rhodopirellula due to the presence of a partial sequence of the 23S ribosomal RNA (rRNA) gene. This work highlights the diversity of bacterial groups contributing to the alkane degradation potential and reveals patterns of functional diversity in relation with environmental stressors in a chronically polluted, high-latitude coastal environment. In addition, alkane biodegradation genes are described for the first time in members of Planctomycetes.

  8. Using n-alkanes to estimate diet composition of herbivores: a novel mathematical approach.

    PubMed

    Barcia, P; Bugalho, M N; Campagnolo, M L; Cerdeira, J O

    2007-02-01

    N-alkanes are long-chain saturated hydrocarbons occurring in plant cuticles that can be used as chemical markers for estimating the diet composition of herbivores. An important constraint of using n-alkanes to estimate diet composition with currently employed mathematical procedures is that the number of markers must be equal or larger than the number of diet components. This is a considerable limitation when dealing with free-ranging herbivores feeding on complex plant communities. We present a novel approach for the estimation of diet composition using n-alkanes which applies equally to cases where the number of markers is lower, equal or greater than the number of plant species in the diet. The model uses linear programming to estimate the minimum and maximum proportions of each plant in the diet, and avoids the need for grouping species in order to reduce the number of estimated dietary components. We illustrate the model with two data sets of n-alkane content of plants and faeces obtained from a sheep grazing experiment conducted in Australia and a red deer study in Portugal. Our results are consistent with previous studies on those data sets and provide additional information on the proportions of individual species in the diet. Results show that sheep included in the diet high proportions of white clover (from 0.25 to 0.37), and relatively high proportions of grasses (e.g. brome from 0.14 to 0.26) but tended to avoid Lotus spp. (always less than 0.04 of the diet). For red deer we found high proportions of legumes (e.g. Trifolium angustifolium and Vicia sativa reaching maximum proportions of 0.42 and 0.30 of the diet, respectively) with grasses being less important and Cistus ladanifer, a browse, also having relevance (from 0.21 to 0.42 of the diet).

  9. Alkanes in benthic organisms from the Buccaneer oil field

    SciTech Connect

    Middleditch, B.S.; Basile, B.

    1980-06-01

    About 200 g per day of alkanes are present in brine discharged from each of two production platforms in the Buccaneer oil field in the NW Gulf of Mexico. These alkanes disperse rapidly in the water column, so that seawater concentrations of petroleum alkanes in this region are generally very low. They can be taken up to some extent by plankton, fish, and barnacles, but the petroleum alkane concentrations in these organisms are also relatively low. The largest pool of petroleum alkanes is in the surficial sediments, where concentrations of up to 25 ppM are observed, with concentration gradients extending more than 20 m from the production platforms. Organisms are examined which are exposed to these sediments and, for comparison, other specimens from control sites around structures from which there are no discharges.

  10. Utilization of n-Alkanes by Cladosporium resinae

    PubMed Central

    Teh, J. S.; Lee, K. H.

    1973-01-01

    Four different isolates of Cladosporium resinae from Australian soils were tested for their ability to utilize liquid n-alkanes ranging from n-hexane to n-octadecane under standard conditions. The isolates were unable to make use of n-hexane, n-heptane, and n-octane for growth. In fact, these hydrocarbons, particularly n-hexane, exerted an inhibitory effect on spore germination and mycelial growth. All higher n-alkanes from n-nonane to n-octadecane were assimilated by the fungus, although only limited growth occurred on n-nonane and n-decane. The long chain n-alkanes (C14 to C18) supported good growth of all isolates, but there was no obvious correlation between cell yields and chain lengths of these n-alkanes. Variation in growth responses to individual n-alkane among the different isolates was also observed. The cause of this variation is unknown. PMID:4735447

  11. Molecular distributions and compound-specific stable carbon isotopic compositions of lipids in wintertime aerosols from Beijing

    NASA Astrophysics Data System (ADS)

    Ren, Lujie; Fu, Pingqing; He, Yue; Hou, Juzhi; Chen, Jing; Pavuluri, Chandra Mouli; Sun, Yele; Wang, Zifa

    2016-06-01

    Molecular distributions and stable carbon isotopic compositions (δ13C) of n-alkanes, fatty acids and n-alcohols were investigated in urban aerosols from Beijing, northern China to better understand the sources and long-range atmospheric transport of terrestrial organic matter during polluted and clear days in winter. n-Alkanes (C19–C36), fatty acids (C8–C32) and n-alcohols (C16–C32) detected in Beijing aerosols are characterized by the predominance of C23, C16 and C28, respectively. Carbon preference index (CPI) values of n-alkanes, the ratios of the sum of odd-numbered n-alkanes to the sum of even-numbered n-alkanes, are close to 1, indicating a heavy influence of fossil fuel combustion. Relatively higher ratios of C(18:0+16:0)/C(18:n+16:1) (fatty acids) on clear days than polluted days indicate that long-distance transport and/or photochemical aging are more significant during clear days. δ13C values of n-alkanes and low molecular weight fatty acids (C16:0, C18:0) ranged from –34.1 to ‑24.7% and ‑26.9 to ‑24.6%, respectively, which are generally heavier on polluted days than those on clear days. Such a wide range suggests that atmospheric lipids in Beijing aerosols originate from multiple sources and encounter complicated atmospheric processes during long-range transport in North China.

  12. Molecular distributions and compound-specific stable carbon isotopic compositions of lipids in wintertime aerosols from Beijing

    PubMed Central

    Ren, Lujie; Fu, Pingqing; He, Yue; Hou, Juzhi; Chen, Jing; Pavuluri, Chandra Mouli; Sun, Yele; Wang, Zifa

    2016-01-01

    Molecular distributions and stable carbon isotopic compositions (δ13C) of n-alkanes, fatty acids and n-alcohols were investigated in urban aerosols from Beijing, northern China to better understand the sources and long-range atmospheric transport of terrestrial organic matter during polluted and clear days in winter. n-Alkanes (C19–C36), fatty acids (C8–C32) and n-alcohols (C16–C32) detected in Beijing aerosols are characterized by the predominance of C23, C16 and C28, respectively. Carbon preference index (CPI) values of n-alkanes, the ratios of the sum of odd-numbered n-alkanes to the sum of even-numbered n-alkanes, are close to 1, indicating a heavy influence of fossil fuel combustion. Relatively higher ratios of C(18:0+16:0)/C(18:n+16:1) (fatty acids) on clear days than polluted days indicate that long-distance transport and/or photochemical aging are more significant during clear days. δ13C values of n-alkanes and low molecular weight fatty acids (C16:0, C18:0) ranged from –34.1 to −24.7% and −26.9 to −24.6%, respectively, which are generally heavier on polluted days than those on clear days. Such a wide range suggests that atmospheric lipids in Beijing aerosols originate from multiple sources and encounter complicated atmospheric processes during long-range transport in North China. PMID:27270951

  13. Spectroscopy of the tilde A state of NO-alkane complexes (alkane = methane, ethane, propane, and n-butane)

    NASA Astrophysics Data System (ADS)

    Tamé-Reyes, Victor M.; Gardner, Adrian M.; Harris, Joe P.; McDaniel, Jodie; Wright, Timothy G.

    2012-12-01

    We have recorded (1+1) resonance-enhanced multiphoton ionization spectra of complexes formed between NO and the alkanes: CH4, C2H6, C3H8, and n-C4H10. The spectra correspond to the tilde A ← tilde X transition, which is a NO-localized 3s ← 2pπ* transition. In line with previous work, the spectrum for NO-CH4 has well-defined structure, but this is only partially resolved for the other complexes. The spectra recorded in the NO+-alkane mass channels all show a slowly rising onset, followed by a sharp offset, which is associated with dissociation of NO-alkane, from which binding energies in the tilde X and tilde A states are deduced. Beyond this sharp offset, there is a further rise in signal, which is attributed to fragmentation of higher complexes, NO-(alkane)n. Analysis of these features allows binding energies for (NO-alkane) ... alkane to be estimated, and these suggest that in the NO-(alkane)2 complexes, the second alkane molecule is bound to the first, rather than to NO. Calculated structures for the 1:1 complexes are reported, as well as binding energies.

  14. The Effect of Terminal Substitution on the Helical Carbon Structure of Fluoro-Alkane Chains: a Pure Rotational Study of CH2OH-Cn-1F2n-1 (n = 4, 5,& 6)

    NASA Astrophysics Data System (ADS)

    Schwartz, Aaron Z. A.; Maturo, Mark P.; Obenchain, Daniel A.; Cooke, S. A.

    2016-06-01

    Continuing a series of studies to investigate the change in structure of hydrocarbons as the amount of fluorination is increased to varying degrees of substitution, we present a survey on the change in the helical nature of the fluorinated carbon backbone when a -CH2OH group is substituted for a terminal - CF3 group. Spectra for 1H,1H-heptafluorobutan-1-ol, 1H,1H-nonafluoropentan-1-ol, and 1H,1H-undecafluorohexan-1-ol were collected separately using a chirped-pulse FTMW spectrometer in the range of 7-13 GHz. Only one conformation was observed for each molecule. Additional measurements of the 1H,1H-heptafluorobutan-1-ol were completed using a Balle-Flygare cavity instrument. Assignments of the singly-substituted 13C isotopologues of the 1H,1H-heptafluorobutan-1-ol were also measured. A comparison of both ab initio and experimental structures will be presented.

  15. Selective Adsorption of n-Alkanes from n-Octane on Metal-Organic Frameworks: Length Selectivity.

    PubMed

    Bhadra, Biswa Nath; Jhung, Sung Hwa

    2016-03-01

    The liquid-phase adsorption of n-alkanes (from n-octane (C8) solvent) with different chain lengths was carried out over three metal-organic frameworks (MOFs), viz., metal-azolate framework-6 (MAF-6), copper-benzenetricarboxylate (Cu-BTC), and iron-benzenetricarboxylate (MIL-100(Fe)), and a conventional adsorbent activated carbon (AC). MAF-6 and Cu-BTC were found to have significant selectivity for the adsorption of n-dodecane (C12) and n-heptane (C7), respectively, from C8. Selectivity for C12 on MAF-6 was also observed in competitive adsorption from binary adsorbate systems. To understand the selective adsorption of C12 on MAF-6 more, the adsorption of C12 from C8 over MAF-6 was investigated in detail and compared with that over AC. The obtained selectivities over MAF-6 and Cu-BTC for C12 and C7, respectively, might be explained by the similarity between cavity size of adsorbents and molecular length of n-alkanes. In the case of AC and MIL-100(Fe), no specific adsorption selectivity was observed because the cavity sizes of the two adsorbents are larger than the size of the n-alkanes used in this study. The adsorption capacities (qt) of n-alkanes over AC and MIL-100(Fe) decreased and increased, respectively, as the polarity (or length) of the adsorbates increased, probably because of nonpolar and polar interactions between the adsorbents and n-alkanes. On the basis of the results obtained, it can be concluded that matching the cavity size (of adsorbents) with the molecular length (of n-alknaes) is more important parameter than the MOF's hydrophilicity/hydrophobicity for the selective adsorption/separation of alkanes.

  16. High-order harmonic generation in alkanes

    SciTech Connect

    Altucci, C.; Velotta, R.; Heesel, E.; Springate, E.; Marangos, J. P.; Vozzi, C.; Benedetti, E.; Calegari, F.; Sansone, G.; Stagira, S.; Nisoli, M.; Tosa, V.

    2006-04-15

    We have investigated the process of high-order harmonic generation in light alkanes by using femtosecond laser pulses. We show the experimental results cannot be matched by a model that assumes a single active electron only in a hydrogenic s orbital. Clear evidences are shown of the important role played by the p-like character originating from the covalent C-H bond. By constructing a suitable mixture of s-type and p-type atomic wave functions, an excellent agreement between measurements in methane and simulations is found, thus confirming the validity of the developed method as a general tool for the analysis of high-order harmonic generation in complex molecules.

  17. Novel phase behavior in normal alkanes

    SciTech Connect

    Sirota, E.B.; King, H.E. Jr.; Hughes, G.J.; Wan, W.K. )

    1992-01-27

    X-ray scattering studies on aligned films of binary mixtures of the normal alkanes C{sub 23}H{sub 48} and C{sub 28}H{sub 58} reveal, for the first time in such materials, the existence of a new equilibrium phase having the symmetry of a smectic crystal, possibly a hexatic. This phase occurs between the hexagonally packed {ital R}{sub II} and the lower-temperature orthorhombic {ital R}{sub I}, plastic crystalline, layered, rotator phases. We argue that this loss of order is due to local distortion fluctuations in the hexagonal phase. Furthermore, we have identified an {ital ABC}-to-{ital ABAB} restacking transition within the ordered {ital R}{sub II} phase.

  18. Upgrading light hydrocarbons via tandem catalysis: a dual homogeneous Ta/Ir system for alkane/alkene coupling.

    PubMed

    Leitch, David C; Lam, Yan Choi; Labinger, Jay A; Bercaw, John E

    2013-07-17

    Light alkanes and alkenes are abundant but are underutilized as energy carriers because of their high volatility and low energy density. A tandem catalytic approach for the coupling of alkanes and alkenes has been developed in order to upgrade these light hydrocarbons into heavier fuel molecules. This process involves alkane dehydrogenation by a pincer-ligated iridium complex and alkene dimerization by a Cp*TaCl2(alkene) catalyst. These two homogeneous catalysts operate with up to 60/30 cooperative turnovers (Ir/Ta) in the dimerization of 1-hexene/n-heptane, giving C13/C14 products in 40% yield. This dual system can also effect the catalytic dimerization of n-heptane (neohexene as the H2 acceptor) with cooperative turnover numbers of 22/3 (Ir/Ta).

  19. Molecular, 13C, and 14C evidence for the allochthonous and ancient origin of C 16C 18n-alkanes in modern soils

    NASA Astrophysics Data System (ADS)

    Lichtfouse, Éric; Bardoux, Gerard; Mariotti, Andre; Balesdent, Jerome; Ballentine, Donna C.; Macko, Stephen A.

    1997-05-01

    The heterogeneous isotopic composition of C 3 and C 4 plants can be used to to follow the fate of plant carbon into soil organic molecules. Thus, after 23 years of maize cropping (C 4) on a soil which was previously under C 3 vegetation, C 25C 33 soil n-alkanes are 13C-enriched up to 9ℵ. relatively to the initial C 3 soil, reflecting the input of 13C-enriched n-alkanes from maize waxes. In sharp contrast, C 16C 18 soil n-alkanes do not show any significant 13C/ 12C variation over the same time interval. This absence of isotopic variation, along with consideration of their relative concentration, absolute concentration, and biodegradability, demonstrate that these substances must represent a regular input from an external source. Evidence of a large contribution of an ancient source, amounting to more than 65% of the alkane fraction, is given by a 14C-age of 8510 yrs BP. Moreover, short-chain n-alkanes from soils, diesel fuel, diesel automobile exhaust, and petroleum products exhibit similar distributions and δ 13C values. These findings suggests that C 16C 18 soil n-alkanes represent a non-point source pollution of ancient hydrocarbons either carried by aerosols or entering the soil via continuous hydrocarbon seepage from the deep sedimentary rocks of the Paris basin.

  20. Long-chain alkane production by the yeast Saccharomyces cerevisiae.

    PubMed

    Buijs, Nicolaas A; Zhou, Yongjin J; Siewers, Verena; Nielsen, Jens

    2015-06-01

    In the past decade industrial-scale production of renewable transportation biofuels has been developed as an alternative to fossil fuels, with ethanol as the most prominent biofuel and yeast as the production organism of choice. However, ethanol is a less efficient substitute fuel for heavy-duty and maritime transportation as well as aviation due to its low energy density. Therefore, new types of biofuels, such as alkanes, are being developed that can be used as drop-in fuels and can substitute gasoline, diesel, and kerosene. Here, we describe for the first time the heterologous biosynthesis of long-chain alkanes by the yeast Saccharomyces cerevisiae. We show that elimination of the hexadecenal dehydrogenase Hfd1 and expression of a redox system are essential for alkane biosynthesis in yeast. Deletion of HFD1 together with expression of an alkane biosynthesis pathway resulted in the production of the alkanes tridecane, pentadecane, and heptadecane. Our study provides a proof of principle for producing long-chain alkanes in the industrial workhorse S. cerevisiae, which was so far limited to bacteria. We anticipate that these findings will be a key factor for further yeast engineering to enable industrial production of alkane based drop-in biofuels, which can allow the biofuel industry to diversify beyond bioethanol.

  1. Long-chain alkane production by the yeast Saccharomyces cerevisiae.

    PubMed

    Buijs, Nicolaas A; Zhou, Yongjin J; Siewers, Verena; Nielsen, Jens

    2015-06-01

    In the past decade industrial-scale production of renewable transportation biofuels has been developed as an alternative to fossil fuels, with ethanol as the most prominent biofuel and yeast as the production organism of choice. However, ethanol is a less efficient substitute fuel for heavy-duty and maritime transportation as well as aviation due to its low energy density. Therefore, new types of biofuels, such as alkanes, are being developed that can be used as drop-in fuels and can substitute gasoline, diesel, and kerosene. Here, we describe for the first time the heterologous biosynthesis of long-chain alkanes by the yeast Saccharomyces cerevisiae. We show that elimination of the hexadecenal dehydrogenase Hfd1 and expression of a redox system are essential for alkane biosynthesis in yeast. Deletion of HFD1 together with expression of an alkane biosynthesis pathway resulted in the production of the alkanes tridecane, pentadecane, and heptadecane. Our study provides a proof of principle for producing long-chain alkanes in the industrial workhorse S. cerevisiae, which was so far limited to bacteria. We anticipate that these findings will be a key factor for further yeast engineering to enable industrial production of alkane based drop-in biofuels, which can allow the biofuel industry to diversify beyond bioethanol. PMID:25545362

  2. Fossil Leaves and Fossil Leaf n-Alkanes: Reconstructing the First Closed Canopied Rainforests

    NASA Astrophysics Data System (ADS)

    Graham, H. V.; Freeman, K. H.

    2013-12-01

    Although the age and location is disputed, the rise of the first closed-canopy forest is likely linked with the expansion of angiosperms in the late Cretacous or early Cenozoic. The carbon isotope 'canopy effect' reflects the extent of canopy closure, and is well documented in δ13C values of the leaves and leaf lipids in modern forests. To test the extent of canopy closure among the oldest documented angiosperm tropical forests, we analyzed isotopic characteristics of leaf fossils and leaf waxes from the Guaduas and Cerrejón Formations. The Guaduas Fm. (Maastrichtian) contains some of the earliest angiosperm fossils in the Neotropics, and both leaf morphology and pollen records at this site suggest an open-canopy structure. The Cerrejón Fm. (Paleocene) contains what are believed to be the first recorded fossil leaves from a closed-canopy forest. We analyzed the bulk carbon isotope content (δ13Cleaf) of 199 fossil leaves, as well as the n-alkane concentration and chain-length distribution, and δ13C of alkanes (δ13Clipid) of 73 fossil leaves and adjacent sediment samples. Fossil leaves are dominated by eudicots and include ten modern plant families (Apocynaceae, Bombaceae, Euphorbaceae, Fabaceae, Lauraceae, Malvaceae, Meliaceae, Menispermaceae, Moraceae, Sapotaceae). We interpreted extent of canopy coverage based on the range of δ13Cleaf values. The narrow range of δ13C values in leaves from the Guaduas Fm (2.7‰) is consistent with an open canopy. A significantly wider range in values (6.3‰) suggests a closed-canopy signature for site 0315 of the Cerrejón Fm,. In contrast, at Site 0318, a lacustrine deposit, leaves had a narrow range (3.3‰) in δ13C values, and this is not consistent with a closed-canopy, but is consistent with leaf assemblages from a forest edge. Leaves that accumulate in lake sediments tend to be biased toward plants living at the lake edge, which do not experience closed-canopy conditions, and do not express the isotopic

  3. Catalytic conversion of light alkanes. Quarterly progress report, April 1--June 30, 1992

    SciTech Connect

    Lyons, J.E.

    1992-06-30

    The second Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between April 1, 1992 and June 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products that can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon uwspomdon fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE I).

  4. Catalytic conversion of light alkanes: Quarterly report, January 1-March 31, 1992

    SciTech Connect

    Biscardi, J.; Bowden, P.T.; Durante, V.A.; Ellis, P.E. Jr.; Gray, H.B.; Gorbey, R.G.; Hayes, R.C.; Hodge, J.; Hughes, M.; Langdale, W.A.; Lyons, J.E.; Marcus, B.; Messick, D.; Merrill, R.A.; Moore, F.A.; Myers, H.K. Jr.; Seitzer, W.H.; Shaikh, S.N.; Tsao, W.H.; Wagner, R.W.; Warren, R.W.; Wijesekera, T.P.

    1997-05-01

    The first Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between January 1. 1992 and March 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products which can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon transportation fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient porphryinic macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE III).

  5. Catalytic conversion of light alkanes phase II. Topical report, January 1990--January 1993

    SciTech Connect

    1998-12-31

    The Topical Report on Phase II of the project entitled, Catalytic Conversion of Light Alkanes reviews work done between January 1, 1990 and September 30, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products which can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon transportation fuel. This Topical Report documents our efforts to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. Research on the Cooperative Agreement is divided into three Phases relating to three molecular environments for the active catalytic species that we are trying to generate. In this report we present our work on catalysts which have oxidation-active metals in polyoxoanions (PHASE II).

  6. The Effects of Vegetation Barriers on Near-road Ultrafine Particle Number and Carbon Monoxide Concentrations

    EPA Science Inventory

    Numerous studies have shown that people living in near-roadway communities (within 100 m of the road) are exposed to high ultrafine particle (UFP) number concentrations, which may be associated with adverse health effects. Vegetation barriers have been shown to affect pollutant t...

  7. Lithium carbonate therapy for cluster headache. Changes in number of platelets, and serotonin and histamine levels.

    PubMed

    Medina, J L; Fareed, J; Diamond, S

    1980-09-01

    Three groups of patients were studied: Group A consisted of 12 patients with cluster headache that was treated with lithium carbonate. Group B consisted of six patients with cluster headache that was managed with other drugs. Group C consisted of five patients with muscle contraction headache who received lithium. Serum lithium levels, platelet count, platelet serotonin levels, and platelet-rich plasma histamine levels were determined before and during therapy. The frequency of the headache and levels of serotonin and histamine tended to follow a parallel course in groups A and B: as the headache frequency dropped, serotonin and histamine levels fell. The stable period was characterized by little change in serotonin and histamine levels. Recurrences of headaches were accompanied by a return of serotonin and histamine to pretreatment levels. The course of cluster headache is related to changes in serotonin and histamine levels. Lithium, by modifying the headache course, changes serotonin and histamine levels. PMID:7417056

  8. High Diversity of Anaerobic Alkane-Degrading Microbial Communities in Marine Seep Sediments Based on (1-methylalkyl)succinate Synthase Genes

    PubMed Central

    Stagars, Marion H.; Ruff, S. Emil; Amann, Rudolf; Knittel, Katrin

    2016-01-01

    Alkanes comprise a substantial fraction of crude oil and are prevalent at marine seeps. These environments are typically anoxic and host diverse microbial communities that grow on alkanes. The most widely distributed mechanism of anaerobic alkane activation is the addition of alkanes to fumarate by (1-methylalkyl)succinate synthase (Mas). Here we studied the diversity of MasD, the catalytic subunit of the enzyme, in 12 marine sediments sampled at seven seeps. We aimed to identify cosmopolitan species as well as to identify factors structuring the alkane-degrading community. Using next generation sequencing we obtained a total of 420 MasD species-level operational taxonomic units (OTU0.96) at 96% amino acid identity. Diversity analysis shows a high richness and evenness of alkane-degrading bacteria. Sites with similar hydrocarbon composition harbored similar alkane-degrading communities based on MasD genes; the MasD community structure is clearly driven by the hydrocarbon source available at the various seeps. Two of the detected OTU0.96 were cosmopolitan and abundant while 75% were locally restricted, suggesting the presence of few abundant and globally distributed alkane degraders as well as specialized variants that have developed under specific conditions at the diverse seep environments. Of the three MasD clades identified, the most diverse was affiliated with Deltaproteobacteria. A second clade was affiliated with both Deltaproteobacteria and Firmicutes likely indicating lateral gene transfer events. The third clade was only distantly related to known alkane-degrading organisms and comprises new divergent lineages of MasD homologs, which might belong to an overlooked phylum of alkane-degrading bacteria. In addition, masD geneFISH allowed for the in situ identification and quantification of the target guild in alkane-degrading enrichment cultures. Altogether, these findings suggest an unexpectedly high number of yet unknown groups of anaerobic alkane degraders

  9. Regulation of alkane degradation pathway by a TetR family repressor via an autoregulation positive feedback mechanism in a Gram-positive Dietzia bacterium.

    PubMed

    Liang, Jie-Liang; Nie, Yong; Wang, Miaoxiao; Xiong, Guangming; Wang, Yi-Ping; Maser, Edmund; Wu, Xiao-Lei

    2016-01-01

    n-Alkanes are ubiquitous in nature and serve as important carbon sources for both Gram-positive and Gram-negative bacteria. Hydroxylation of n-alkanes by alkane monooxygenases is the first and most critical step in n-alkane metabolism. However, regulation of alkane degradation genes in Gram-positive bacteria remains poorly characterized. We therefore explored the transcriptional regulation of an alkB-type alkane hydroxylase-rubredoxin fusion gene, alkW1, from Dietzia sp. DQ12-45-1b. The alkW1 promoter was characterized and so was the putative TetR family regulator, AlkX, located downstream of alkW1 gene. We further identified an unusually long 48 bp inverted repeat upstream of alkW1 and demonstrated the binding of AlkX to this operator. Analytical ultracentrifugation and microcalorimetric results indicated that AlkX formed stable dimers in solution and two dimers bound to one operator in a positive cooperative fashion characterized by a Hill coefficient of 1.64 (± 0.03) [k(D)  = 1.06 (± 0.16) μM, k(D) ' = 0.05 (± 0.01) μM]. However, the DNA-binding affinity was disrupted in the presence of long-chain fatty acids (C10-C24), suggesting that AlkX can sense the concentrations of n-alkane degradation metabolites. A model was therefore proposed where AlkX controls alkW1 expression in a metabolite-dependent manner. Bioinformatic analysis revealed that the alkane hydroxylase gene regulation mechanism may be common among Actinobacteria.

  10. Heterogeneity of Alkane Chain Length in Freshwater and Marine Cyanobacteria

    PubMed Central

    Shakeel, Tabinda; Fatma, Zia; Fatma, Tasneem; Yazdani, Syed Shams

    2015-01-01

    The potential utilization of cyanobacteria for the biological production of alkanes represents an exceptional system for the next generation of biofuels. Here, we analyzed a diverse group of freshwater and marine cyanobacterial isolates from Indian culture collections for their ability to produce both alkanes and alkenes. Among the 50 cyanobacterial isolates screened, 32 isolates; 14 freshwater and 18 marine isolates; produced predominantly alkanes. The GC-MS/MS profiles revealed a higher percentage of pentadecane and heptadecane production for marine and freshwater strains, respectively. Oscillatoria species were found to be the highest producers of alkanes. Among the freshwater isolates, Oscillatoria CCC305 produced the maximum alkane level with 0.43 μg/mg dry cell weight, while Oscillatoria formosa BDU30603 was the highest producer among the marine isolates with 0.13 μg/mg dry cell weight. Culturing these strains under different media compositions showed that the alkane chain length was not influenced by the growth medium but was rather an inherent property of the strains. Analysis of the cellular fatty acid content indicated the presence of predominantly C16 chain length fatty acids in marine strains, while the proportion of C18 chain length fatty acids increased in the majority of freshwater strains. These results correlated with alkane chain length specificity of marine and freshwater isolates indicating that alkane chain lengths may be primarily determined by the fatty acid synthesis pathway. Moreover, the phylogenetic analysis showed clustering of pentadecane-producing marine strains that was distinct from heptadecane-producing freshwater strains strongly suggesting a close association between alkane chain length and the cyanobacteria habitat. PMID:25853127

  11. Large odd-numbered carbon clusters from fullerene-ozone reactions. (Reannouncement with new availability information). Technical report

    SciTech Connect

    McElvany, S.W.; Callahan, J.H.; Ross, M.M.; Lamb, L.D.; Huffman, D.R.

    1993-06-11

    The odd-numbered carbon clusters C119, C129 and C139 have been observed in the mass spectra of toluene extracts of fullerene soots and of the products of ozone-fullerene reactions. Specifically, ozone-C60 reactions yield C119, and ozone-C70 reactions yield C139, and ozone-(C60/C70) reactions produce C119, C129, and C139. These unexpected species correspond to dimers of C60, C60/C70, and C70, respectively, less one carbon atom, and are stable gas-phase ions with behavior similar to that of fullerenes. The results suggest a new route to functionalization and derivatization of fullerenes through controlled ozone-catalyzed cage-opening reactions.

  12. Properties of Ga-containing pentasils in aromatization of lower alkanes after repeated reaction-regeneration cycles

    SciTech Connect

    Vosmerikov, A.V.; Barbashin, Y.E.; Erofeev, V.I.

    1995-10-20

    Variation of catalytic and acidic properties of gallium-containing zeolite catalysts in aromatization of lower alkanes after several reaction-regeneration cycles has been examined. The catalytic activity only slightly decreases from cycle to cycle, and a relatively large number of oxidative regenerations can be performed.

  13. Angiosperm n-alkane distribution patterns and the geologic record of C4 grassland evolution

    NASA Astrophysics Data System (ADS)

    Henderson, A.; Graham, H. V.; Patzkowsky, M.; Fox, D. L.; Freeman, K. H.

    2012-12-01

    n-Alkane average chain-length (ACL) patterns vary regionally with community composition and climate. To clarify the influence of phylogenetic and community patterns, we compiled and analyzed a global database of published n-alkane abundance for n-C27 to C35 homologs in modern plant specimens (n=205). ACL for waxes in C4 non-woody plants are longer than for woody plants, suggesting ACL can serve as an indicator of the three-dimensional structure of local vegetation. Further, these findings suggest compound-specific isotopic data for longer alkane homologs (C31, C33, C35) will proportionately represent non-woody vegetation and isotope measurements of C29 are more representative of woody vegetation. Thus, the combination of ACL and carbon isotope compositions should allow us to disentangle C3 woody, C3 non-woody, and C4 non-woody signals in terrestrial paleorecords. Application of this approach to the geologic record of Miocene C4 grassland expansion in the US Great Plains and the Siwaliks in Pakistan illustrate two very different transition scenarios. Alkane-specific isotopic data indicate C4 grasslands appeared 2.5 Ma in the Great Plains and 6.5 Ma in the Siwaliks, and ACL analysis indicates that this transition involved the replacement of woody vegetation in the US and the replacement of C3 grasses in Pakistan. Our analysis illustrates that, consistent with differences in the timing of C4 grassland, the drivers of change were likely not the same in these regions. Oxygen isotope records suggest that the more recent transition in the Great Plains was associated with climate cooling and possibly changes in disturbance regimes and that the transition in the Siwaliks was likely associated with warming and drying.

  14. Heterochromatin domain number correlates with X-ray and carbon-ion radiation resistance in cancer cells.

    PubMed

    Sato, Katsutoshi; Imai, Takashi; Okayasu, Ryuichi; Shimokawa, Takashi

    2014-10-01

    Although it is known that cancer cells can develop radiation resistance after repeated exposures to X rays, the underlying mechanisms and characteristics of this radiation-induced resistance of cancer cells are not well understood. Additionally, it is not known whether cells that develop X-ray resistance also would develop resistance to other types of radiation such as heavy-ions including carbon ions (C-ion). In this study, we established X-ray resistant cancer cell lines by delivering repeated exposures to X rays, and then assessed whether the cells were resistant to carbon ions. The mouse squamous cell carcinoma cell line, NR-S1, was X irradiated six times with 10 Gy, and the X-ray resistant cancer cells named X60 and ten subclones were established. Significant X-ray resistance was induced in four of the subclones (X60, X60-H2, X60-A3 and X60-B12). The X60 cells and all of the subclones were resistant to carbon ions. The correlation analysis between radioresistance and morphological characteristics of these cells showed that X-ray (R=0.74) and C-ion (R=0.79) resistance correlated strongly with the number of heterochromatin domains. Moreover, the numbers of γ-H2AX foci remaining in irradiated X60 cells and radioresistant subclones X60-A3 and X60-H2 were lower than in the NR-S1 cells after X-ray or C-ion irradiation, indicating that X60 cells and the radioresistant subclones rapidly repaired the DNA double-strand breaks compared with NR-S1 cells. Our findings suggest that the underlying causal mechanisms of X-ray and C-ion radiation resistance may overlap, and that an increase in heterochromatin domain number may be an indicator of X-ray and C-ion resistance.

  15. From carbon numbers to ecosystem services: usable results comparing natural versus managed lands

    NASA Astrophysics Data System (ADS)

    Bachelet, D. M.; Ferschweiler, K.; Sheehan, T.; Sleeter, B. M.; Zhu, Z.

    2015-12-01

    We ran the MC2 dynamic vegetation model for the conterminous US at 30 arc sec with and without land use and fire suppression for several climate change scenarios. We translated model results into key ecosystem services (ES) such as climate regulation through carbon uptake and sequestration (global climate) or through transpiration (regional climate) as well as water provision through runoff and throughflow. We also projected timber production and gauged the risk of production lost to fire and/or drought by simulating fuel loads and forest vigor annually through the 21st century. We calculated the rising irrigation demand for agricultural land which, coupled with available information on groundwater resources, could help plan for future cropping systems. By combining these results we can evaluate land cover value across the country in terms of quantity and quality of services rendered. By comparing projections with and without landuse and fire suppression we can illustrate differences in regulating and provisioning services between managed and natural lands.

  16. Quantification of Biogenic Volatile Organic Compounds with a Flame Ionization Detector Using the Effective Carbon Number Concept

    NASA Astrophysics Data System (ADS)

    Faiola, C. L.; Erickson, M. H.; Fricaud, V. L.; Wallace, H. W.; Jobson, B. T.; VanReken, T. M.

    2011-12-01

    Biogenic volatile organic compounds (BVOCs) are emitted into the atmosphere by plants and include structurally complex organic molecules such as monoterpenes, sesquiterpenes, and their oxygenated derivatives. These BVOCs are among the principle factors influencing the oxidative capacity of the atmosphere in forested regions. BVOC emission rates are often measured by collecting samples onto adsorptive cartridges in the field and then transporting these samples to the laboratory for chromatographic analysis. One of the most commonly used detectors in gas chromatography is the flame ionization detector (FID) due to its broad linear range, high sensitivity, and predictable response to many compounds. The FID response to saturated aliphatic molecules is proportional to carbon number. However, deviations occur as the complexity of the molecular structure increases. To account for these deviations, Sternberg et al. (1962) developed the effective carbon number (ECN) concept, which describes the number of carbons the FID "effectively" responds to. The ECN of a complex molecule can be estimated from the number and type of functional groups present, allowing an estimate of relative response factors for quantification. This approach is particularly useful for applications where samples contain a mixture of organic compounds and standards are not realistically accessible- a common predicament for environmental measurements. ECNs for a limited number of compounds with varying functional groups have been quantified in previous studies. However, there remain large gaps in the variety of compounds for which published data are available. This results in higher than necessary uncertainties when quantifying compounds that are structurally dissimilar to those that have been reported in the literature. The purpose of this study was to determine the ECN for a variety of terpenoid compounds to enable improved quantification of BVOC measurements. A dynamic dilution system was developed to

  17. Quantitative Vapor-phase IR Intensities and DFT Computations to Predict Absolute IR Spectra based on Molecular Structure: I. Alkanes

    SciTech Connect

    Williams, Stephen D.; Johnson, Timothy J.; Sharpe, Steven W.; Yavelak, Veronica; Oats, R. P.; Brauer, Carolyn S.

    2013-11-13

    Recently recorded quantitative IR spectra of a variety of gas-phase alkanes are shown to have integrated intensities in both the C-H stretching and C-H bending regions that depend linearly on the molecular size, i.e. the number of C-H bonds. This result is well predicted from CH4 to C15H32 by DFT computations of IR spectra at the B3LYP/6-31+G(d,p) level of DFT theory. A simple model predicting the absolute IR band intensities of alkanes based only on structural formula is proposed: For the C-H stretching band near 2930 cm-1 this is given by (in km/mol): CH¬_str = (34±3)*CH – (41±60) where CH is number of C-H bonds in the alkane. The linearity is explained in terms of coordinated motion of methylene groups rather than the summed intensities of autonomous -CH2- units. The effect of alkyl chain length on the intensity of a C-H bending mode is explored and interpreted in terms of conformer distribution. The relative intensity contribution of a methyl mode compared to the total C-H stretch intensity is shown to be linear in the number of terminal methyl groups in the alkane, and can be used to predict quantitative spectra a priori based on structure alone.

  18. Process for converting light alkanes to higher hydrocarbons

    DOEpatents

    Noceti, Richard P.; Taylor, Charles E.

    1988-01-01

    A process is disclosed for the production of aromatic-rich, gasoline boiling range hydrocarbons from the lower alkanes, particularly from methane. The process is carried out in two stages. In the first, alkane is reacted with oxygen and hydrogen chloride over an oxyhydrochlorination catalyst such as copper chloride with minor proportions of potassium chloride and rare earth chloride. This produces an intermediate gaseous mixture containing water and chlorinated alkanes. The chlorinated alkanes are contacted with a crystalline aluminosilicate catalyst in the hydrogen or metal promoted form to produce gasoline range hydrocarbons with a high proportion of aromatics and a small percentage of light hydrocarbons (C.sub.2 -C.sub.4). The light hydrocarbons can be recycled for further processing over the oxyhydrochlorination catalyst.

  19. The effects of vegetation barriers on near-road ultrafine particle number and carbon monoxide concentrations.

    PubMed

    Lin, Ming-Yeng; Hagler, Gayle; Baldauf, Richard; Isakov, Vlad; Lin, Hong-Yiou; Khlystov, Andrey

    2016-05-15

    Numerous studies have shown that people living in near-roadway communities (within 100 m of the road) are exposed to high ultrafine particle (UFP) number concentrations, which may be associated with adverse health effects. Vegetation barriers have been shown to affect pollutant transport via particle deposition to leaves and altering the dispersion of emission plumes, which in turn would modify the exposure of near-roadway communities to traffic-related UFPs. In this study, both stationary (equipped with a Scanning Mobility Particle Sizer, SMPS) and mobile (equipped with Fast Mobility Particle Sizer, FMPS) measurements were conducted to investigate the effects of vegetation barriers on downwind UFP (particle diameters ranging from 14 to 102 nm) concentrations at two sites in North Carolina, USA. One site had mainly deciduous vegetation while the other was primarily coniferous; both sites have a nearby open field without the vegetation barriers along the same stretch of limited access road, which served as a reference. During downwind conditions (traffic emissions transported towards the vegetation barrier) and when the wind speed was above or equal to 0.5m/s, field measurements indicated that vegetation barriers with full foliage reduced UFP and CO concentrations by 37.7-63.6% and 23.6-56.1%, respectively. When the test was repeated at the same sites during winter periods when deciduous foliage was reduced, the deciduous barrier during winter showed no significant change in UFP concentration before and after the barrier. Results from the stationary (using SMPS) and mobile (using FMPS) measurements for UFP total number concentrations generally agreed to within 20%. PMID:26930311

  20. The effects of vegetation barriers on near-road ultrafine particle number and carbon monoxide concentrations.

    PubMed

    Lin, Ming-Yeng; Hagler, Gayle; Baldauf, Richard; Isakov, Vlad; Lin, Hong-Yiou; Khlystov, Andrey

    2016-05-15

    Numerous studies have shown that people living in near-roadway communities (within 100 m of the road) are exposed to high ultrafine particle (UFP) number concentrations, which may be associated with adverse health effects. Vegetation barriers have been shown to affect pollutant transport via particle deposition to leaves and altering the dispersion of emission plumes, which in turn would modify the exposure of near-roadway communities to traffic-related UFPs. In this study, both stationary (equipped with a Scanning Mobility Particle Sizer, SMPS) and mobile (equipped with Fast Mobility Particle Sizer, FMPS) measurements were conducted to investigate the effects of vegetation barriers on downwind UFP (particle diameters ranging from 14 to 102 nm) concentrations at two sites in North Carolina, USA. One site had mainly deciduous vegetation while the other was primarily coniferous; both sites have a nearby open field without the vegetation barriers along the same stretch of limited access road, which served as a reference. During downwind conditions (traffic emissions transported towards the vegetation barrier) and when the wind speed was above or equal to 0.5m/s, field measurements indicated that vegetation barriers with full foliage reduced UFP and CO concentrations by 37.7-63.6% and 23.6-56.1%, respectively. When the test was repeated at the same sites during winter periods when deciduous foliage was reduced, the deciduous barrier during winter showed no significant change in UFP concentration before and after the barrier. Results from the stationary (using SMPS) and mobile (using FMPS) measurements for UFP total number concentrations generally agreed to within 20%.

  1. Photovoltaic response of carbon nanotube-silicon heterojunctions: effect of nanotube film thickness and number of walls.

    PubMed

    Castrucci, P; Del Gobbo, S; Camilli, L; Scarselli, M; Casciardi, S; Tombolini, F; Convertino, A; Fortunato, G; De Crescenzi, M

    2011-10-01

    We report on the multiwall carbon nanotube application as energy conversion material to fabricate thin film solar cells, with nanotubes acting as photogeneration sites as well as charge separators, collectors and carrier transporters. The device consists of a semitransparent thin film of nanotubes coating a n-type crystalline silicon substrate. Under illumination electron-hole (e-h) pairs, generated in the nanotubes and in the silicon substrate underneath, are split and charges are transported through the nanotubes (electrons) and the n-Si (holes). We found that a suitable thickness of the nanotube thin film, high density of Schottky junctions between nanotubes and n-Si and lowest number of nanotube walls are all fundamental parameters to improve the device incident photon to electron conversion efficiency. Multiwall carbon nanotubes have been synthesized by chemical vapour deposition in an ultra high vacuum chamber by evaporating a given amount of iron at room temperature and then exposing the substrate kept at 800 degrees C at acetylene gas. The amount of deposited iron is found to directly affect the nanotube size distribution (inner and outer diameter) and therefore the number of walls of the nanotubes.

  2. Quantification of biogenic volatile organic compounds with a flame ionization detector using the effective carbon number concept

    NASA Astrophysics Data System (ADS)

    Faiola, C. L.; Erickson, M. H.; Fricaud, V. L.; Jobson, B. T.; VanReken, T. M.

    2012-03-01

    Biogenic volatile organic compounds (BVOCs) are emitted into the atmosphere by plants and include isoprene, monoterpenes, sesquiterpenes, and their oxygenated derivatives. These BVOCs are among the principal factors influencing the oxidative capacity of the atmosphere in forested regions. BVOC emission rates are often measured by collecting samples onto adsorptive cartridges in the field and then transporting these samples to the laboratory for chromatographic analysis. One of the most commonly used detectors in chromatographic analysis is the flame ionization detector (FID). For quantitative analysis with an FID, relative response factors may be estimated using the effective carbon number (ECN) concept. The purpose of this study was to determine the ECN for a variety of terpenoid compounds to enable improved quantification of BVOC measurements. A dynamic dilution system was developed to make quantitative gas standards of VOCs with mixing ratios from 20-55 ppb. For each experiment using this system, one terpene standard was co-injected with an internal reference, n-octane, and analyzed via an automated cryofocusing system interfaced to a gas chromatograph flame ionization detector and mass spectrometer (GC/MS/FID). The ECNs of 16 compounds (14 BVOCs) were evaluated with this approach, with each test compound analyzed at least three times. The difference between the actual carbon number and measured ECN ranged from -24% to -2%. The difference between theoretical ECN and measured ECN ranged from -22% to 9%. Measured ECN values were within 10% of theoretical ECN values for most terpenoid compounds.

  3. Quantification of biogenic volatile organic compounds with a flame ionization detector using the effective carbon number concept

    NASA Astrophysics Data System (ADS)

    Faiola, C. L.; Erickson, M. H.; Fricaud, V. L.; Jobson, B. T.; VanReken, T. M.

    2012-08-01

    Biogenic volatile organic compounds (BVOCs) are emitted into the atmosphere by plants and include isoprene, monoterpenes, sesquiterpenes, and their oxygenated derivatives. These BVOCs are among the principal factors influencing the oxidative capacity of the atmosphere in forested regions. BVOC emission rates are often measured by collecting samples onto adsorptive cartridges in the field and then transporting these samples to the laboratory for chromatographic analysis. One of the most commonly used detectors in chromatographic analysis is the flame ionization detector (FID). For quantitative analysis with an FID, relative response factors may be estimated using the effective carbon number (ECN) concept. The purpose of this study was to determine the ECN for a variety of terpenoid compounds to enable improved quantification of BVOC measurements. A dynamic dilution system was developed to make quantitative gas standards of VOCs with mixing ratios from 20-55 ppb. For each experiment using this system, one terpene standard was co-injected with an internal reference, n-octane, and analyzed via an automated cryofocusing system interfaced to a gas chromatograph flame ionization detector and mass spectrometer (GC/MS/FID). The ECNs of 16 compounds (14 BVOCs) were evaluated with this approach, with each test compound analyzed at least three times. The difference between the actual carbon number and measured ECN ranged from -24% to -2%. The difference between theoretical ECN and measured ECN ranged from -22% to 9%. Measured ECN values were within 10% of theoretical ECN values for most terpenoid compounds.

  4. Isolation and characterization of alkane degrading bacteria from petroleum reservoir waste water in Iran (Kerman and Tehran provenances).

    PubMed

    Hassanshahian, Mehdi; Ahmadinejad, Mohammad; Tebyanian, Hamid; Kariminik, Ashraf

    2013-08-15

    Petroleum products spill and leakage have become two major environmental challenges in Iran. Sampling was performed in the petroleum reservoir waste water of Tehran and Kerman Provinces of Iran. Alkane degrading bacteria were isolated by enrichment in a Bushnel-Hass medium, with hexadecane as sole source of carbon and energy. The isolated strains were identified by amplification of 16S rDNA gene and sequencing. Specific primers were used for identification of alkane hydroxylase gene. Fifteen alkane degrading bacteria were isolated and 8 strains were selected as powerful degradative bacteria. These 8 strains relate to Rhodococcus jostii, Stenotrophomonas maltophilia, Achromobacter piechaudii, Tsukamurella tyrosinosolvens, Pseudomonas fluorescens, Rhodococcus erythropolis, Stenotrophomonas maltophilia, Pseudomonas aeruginosa genera. The optimum concentration of hexadecane that allowed high growth was 2.5%. Gas chromatography results show that all strains can degrade approximately half of hexadecane in one week of incubation. All of the strains have alkane hydroxylase gene which are important for biodegradation. As a result, this study indicates that there is a high diversity of degradative bacteria in petroleum reservoir waste water in Iran.

  5. Contribution of cyanobacterial alkane production to the ocean hydrocarbon cycle.

    PubMed

    Lea-Smith, David J; Biller, Steven J; Davey, Matthew P; Cotton, Charles A R; Perez Sepulveda, Blanca M; Turchyn, Alexandra V; Scanlan, David J; Smith, Alison G; Chisholm, Sallie W; Howe, Christopher J

    2015-11-01

    Hydrocarbons are ubiquitous in the ocean, where alkanes such as pentadecane and heptadecane can be found even in waters minimally polluted with crude oil. Populations of hydrocarbon-degrading bacteria, which are responsible for the turnover of these compounds, are also found throughout marine systems, including in unpolluted waters. These observations suggest the existence of an unknown and widespread source of hydrocarbons in the oceans. Here, we report that strains of the two most abundant marine cyanobacteria, Prochlorococcus and Synechococcus, produce and accumulate hydrocarbons, predominantly C15 and C17 alkanes, between 0.022 and 0.368% of dry cell weight. Based on global population sizes and turnover rates, we estimate that these species have the capacity to produce 2-540 pg alkanes per mL per day, which translates into a global ocean yield of ∼ 308-771 million tons of hydrocarbons annually. We also demonstrate that both obligate and facultative marine hydrocarbon-degrading bacteria can consume cyanobacterial alkanes, which likely prevents these hydrocarbons from accumulating in the environment. Our findings implicate cyanobacteria and hydrocarbon degraders as key players in a notable internal hydrocarbon cycle within the upper ocean, where alkanes are continually produced and subsequently consumed within days. Furthermore we show that cyanobacterial alkane production is likely sufficient to sustain populations of hydrocarbon-degrading bacteria, whose abundances can rapidly expand upon localized release of crude oil from natural seepage and human activities.

  6. Contribution of cyanobacterial alkane production to the ocean hydrocarbon cycle

    PubMed Central

    Lea-Smith, David J.; Biller, Steven J.; Davey, Matthew P.; Cotton, Charles A. R.; Perez Sepulveda, Blanca M.; Turchyn, Alexandra V.; Scanlan, David J.; Smith, Alison G.; Chisholm, Sallie W.; Howe, Christopher J.

    2015-01-01

    Hydrocarbons are ubiquitous in the ocean, where alkanes such as pentadecane and heptadecane can be found even in waters minimally polluted with crude oil. Populations of hydrocarbon-degrading bacteria, which are responsible for the turnover of these compounds, are also found throughout marine systems, including in unpolluted waters. These observations suggest the existence of an unknown and widespread source of hydrocarbons in the oceans. Here, we report that strains of the two most abundant marine cyanobacteria, Prochlorococcus and Synechococcus, produce and accumulate hydrocarbons, predominantly C15 and C17 alkanes, between 0.022 and 0.368% of dry cell weight. Based on global population sizes and turnover rates, we estimate that these species have the capacity to produce 2–540 pg alkanes per mL per day, which translates into a global ocean yield of ∼308–771 million tons of hydrocarbons annually. We also demonstrate that both obligate and facultative marine hydrocarbon-degrading bacteria can consume cyanobacterial alkanes, which likely prevents these hydrocarbons from accumulating in the environment. Our findings implicate cyanobacteria and hydrocarbon degraders as key players in a notable internal hydrocarbon cycle within the upper ocean, where alkanes are continually produced and subsequently consumed within days. Furthermore we show that cyanobacterial alkane production is likely sufficient to sustain populations of hydrocarbon-degrading bacteria, whose abundances can rapidly expand upon localized release of crude oil from natural seepage and human activities. PMID:26438854

  7. Measuring and modelling the local-scale spatio-temporal variation of urban particle number size distributions and black carbon

    NASA Astrophysics Data System (ADS)

    Ruths, Matthias; von Bismarck-Osten, Clemens; Weber, Stephan

    2014-10-01

    Mobile measurements were performed to study the spatio-temporal variation of particle number size distributions (NSD) in the range 11 < Dp < 365 nm as well as total particle number and black carbon concentrations in Braunschweig, Germany during the winter and summer period 2012/2013. The study area of about 1 km2 consisted of six different outdoor microenvironments (ME) that were classified according to different traffic intensities and dominant land use types along the measurement route. Highest averaged total number concentrations measured at roadside (RO) were 2.5 × 104 pt cm-3 (with a maximum of 7.6 × 104 pt cm-3) during winter and about 1.2 × 104 pt cm-3 on average during the summer campaign. Measurement spots which are more distant to traffic were characterised by lower concentrations of 1.6 × 104 pt cm-3 and 9.0 × 103 pt cm-3 during winter and summer, respectively. Black carbon (BC) concentrations were also clearly related to traffic emissions and resulted in concentrations of 2.8 μg m-3 on average (absolute maximum of 6.2 μg m-3) at RO-sites. The concentrations of particles and BC in the different ME (aggregated from the single measurement spots) documented the concentration of both metrics to be a function of distance of the measurement to fresh traffic emissions. A multiple regression based model was established to identify significant parameters which can be used to model the microscale variation of particle NSD in the outdoor ME. Two models with different numbers of input parameters were calculated. The first contained all measured parameters as input, the second only a reduced number consisting of TNC, BC and wind speed. Both models worked convincingly, even the approach with the limited number of input parameters. The average size integrated (TNC) deviation to observed data in all ME during both seasons was <13%. The best agreement between model and observations is given for the near-traffic ME.

  8. Alkane biosynthesis by decarbonylation of aldehyde catalyzed by a microsomal preparation from Botryococcus braunii.

    PubMed

    Dennis, M W; Kolattukudy, P E

    1991-06-01

    The final step in the synthesis of n-hydrocarbons in an animal and a higher plant involves enzymatic decarbonylation of aldehydes to the corresponding alkanes by loss of the carbonyl carbon. Whether such a novel reaction is involved in hydrocarbon synthesis in the colonial microalga, Botryococcus braunii, which is known to produce unusually high levels (up to 32% of dry weight) of n-C27, C29, and C31 alka-dienes and -trienes, was investigated. Dithioerythritol severely inhibited the incorporation of [1-14C]acetate into these hydrocarbons with accumulation of the label in the aldehyde fraction in the B. braunii cells. Microsomal preparations of the alga synthesized alkane from fatty acid and aldehyde in the absence of O2. Conversion of fatty acid to alkane required CoA, ATP, and NADH, whereas conversion of aldehyde to alkane did not require the addition of cofactors. That the alkane synthesis involves a decarbonylation was shown by the production of CO and heptadecane from octadecanal. CO was identified by adsorption to RhCl[(C6H6)3P]3. The decarbonylase had a pH optimum at 7.0, an apparent Km of 65 microM, a Vmax of 1.36 nmol/min/mg and was inhibited by the metal chelators EDTA, O-phenanthroline and 8-hydroxyquinoline. It was stimulated nearly threefold by 2 mM ascorbate and inhibited by the presence of O2. A partial (28%) retention of the aldehydic hydrogen of [1-3H]octadecanal in the heptadecane was observed; the remaining 3H was lost to H2O. The microsomal preparation also catalyzed the oxidation of 14CO to 14CO2, with a pH optimum of 7.0. This accounts for the nonstoichiometry of CO to heptadecane observed. In vivo studies with 14CO showed that the label was incorporated into metabolic products. This metabolic conversion of CO, not found in the previously examined hydrocarbon synthesizing systems, may be necessary for organisms that produce large amounts of hydrocarbons such as the present alga. The mechanism of the decarbonylation and the nature of the

  9. Reversible Interconversion between Alkanes, Alkenes, Alcohols and Ketones under Hydrothermal Conditions

    NASA Astrophysics Data System (ADS)

    Shipp, J.; Hartnett, H. E.; Gould, I. R.; Shock, E.; Williams, L. B.

    2011-12-01

    Many transformation reactions involving hydrocarbons that occur in deep sedimentary systems and determine petroleum compositions occur in the presence of H2O. Hydrothermal transformations of organic material are thought to provide carbon sources for microbes in deep ocean sediments. Hydrothermal conditions may also mimic the conditions where life developed on an early Earth. Nevertheless, much remains to be learned about the mechanisms of hydrothermal organic reactions, including ways in which various reactions are interrelated and how reactions compete with each other. It can be argued that metastable equilibrium states develop over geological timescales and at geochemically relevant temperatures, suggesting that reactions occur under thermodynamic rather than kinetic control. The extent to which reactions are reversible, and how product distributions are determined, are primary tests of the metastable equilibrium model. Seewald (2001, GCA 65, 1641-1664) showed that under hydrothermal conditions and in the presence of a redox buffer, simple alkanes and alkenes undergo oxidation, reduction, and hydration reactions. He proposed a reaction scheme where alkanes interconvert with alkenes, followed by stepwise hydration of alkenes to alcohols, oxidation to ketones, and finally conversion to carboxylic acids, which can undergo decarboxylation. Here we describe experiments that further develop the scope of these functional group interconversions, determine relative reaction kinetics, and provide insight into competing reactions. Hydrothermal experiments were performed at 300°C and 100 MPa in gold capsules for 12 to 144 hours. The reactant structures were based on cyclohexane with one and two methyl groups that served as regio- and stereochemical markers for the reactions. Starting with the alkanes, the observed products include the corresponding alkenes, alcohols, ketones and enones, in support of the Seewald reaction scheme. Our experiments add a branch to this scheme

  10. Anaerobic Coculture of Microalgae with Thermosipho globiformans and Methanocaldococcus jannaschii at 68°C Enhances Generation of n-Alkane-Rich Biofuels after Pyrolysis

    PubMed Central

    Matsuyama, Shigeru; Igarashi, Kensuke; Utsumi, Motoo; Shiraiwa, Yoshihiro; Kuwabara, Tomohiko

    2013-01-01

    We tested different alga-bacterium-archaeon consortia to investigate the production of oil-like mixtures, expecting that n-alkane-rich biofuels might be synthesized after pyrolysis. Thermosipho globiformans and Methanocaldococcus jannaschii were cocultured at 68°C with microalgae for 9 days under two anaerobic conditions, followed by pyrolysis at 300°C for 4 days. Arthrospira platensis (Cyanobacteria), Dunaliella tertiolecta (Chlorophyta), Emiliania huxleyi (Haptophyta), and Euglena gracilis (Euglenophyta) served as microalgal raw materials. D. tertiolecta, E. huxleyi, and E. gracilis cocultured with the bacterium and archaeon inhibited their growth and CH4 production. E. huxleyi had the strongest inhibitory effect. Biofuel generation was enhanced by reducing impurities containing alkanenitriles during pyrolysis. The composition and amounts of n-alkanes produced by pyrolysis were closely related to the lipid contents and composition of the microalgae. Pyrolysis of A. platensis and D. tertiolecta containing mainly phospholipids and glycolipids generated short-carbon-chain n-alkanes (n-tridecane to n-nonadecane) and considerable amounts of isoprenoids. E. gracilis also produced mainly short n-alkanes. In contrast, E. huxleyi containing long-chain (31 and 33 carbon atoms) alkenes and very long-chain (37 to 39 carbon atoms) alkenones, in addition to phospholipids and glycolipids, generated a high yield of n-alkanes of various lengths (n-tridecane to n-pentatriacontane). The gas chromatography-mass spectrometry (GC-MS) profiles of these n-alkanes were similar to those of native petroleum crude oils despite containing a considerable amount of n-hentriacontane. The ratio of phytane to n-octadecane was also similar to that of native crude oils. PMID:23183975

  11. Influence of carbon dioxide on numbers of Culicoides midges collected with suction light traps in South Africa.

    PubMed

    Venter, G J; Boikanyo, S N B; Majatladi, D M; Morey, L

    2016-03-01

    To implement risk management against diseases transmitted by species of Culicoides Latreille, 1809 (Diptera: Ceratopogonidae), it is essential to identify all potential vectors. Light traps are the most commonly used tool for the collection of Culicoides midges. Given the indiscriminate artificial attraction of light, traps will collect all night-flying insects rather than only livestock-associated Culicoides midges. Factors that may increase the efficacy of traps, especially for livestock-associated Culicoides midges, require investigation. In the present study, results obtained with Centers for Disease Control (CDC) and Onderstepoort light traps baited with carbon dioxide (CO2 ) were compared with those of unbaited controls. Comparisons were made using two replicates of a 4 × 4 randomized Latin square design. With both trap types, the mean numbers of Culicoides midges collected in 16 baited traps were higher than those caught in 16 unbaited traps. Although exceptionally low numbers were collected with the CDC traps, the increases in the numbers and frequency of collection of Culicoides imicola Kieffer, 1913 were more pronounced in the CDC traps compared with the Onderstepoort traps. These results indicate that the addition of CO2 may increase the efficiency of these traps for the collection of C. imicola and other livestock-associated Culicoides species. PMID:26522279

  12. Controlling the number of walls in multi walled carbon nanotubes/alumina hybrid compound via ball milling of precipitate catalyst

    NASA Astrophysics Data System (ADS)

    Nosbi, Norlin; Akil, Hazizan Md

    2015-06-01

    This paper reports the influence of milling time on the structure and properties of the precipitate catalyst of multi walled carbon nanotubes (MWCNT)/alumina hybrid compound, produced through the chemical vapour deposition (CVD) process. For this purpose, light green precipitate consisted of aluminium, nickel(II) nitrate hexahydrate and sodium hydroxide mixture was placed in a planetary mill equipped with alumina vials using alumina balls at 300 rpm rotation speed for various milling time (5-15 h) prior to calcinations and CVD process. The compound was characterized using various techniques. Based on high-resolution transmission electron microscopy analysis, increasing the milling time up to 15 h decreased the diameter of MWCNT from 32.3 to 13.1 nm. It was noticed that the milling time had a significant effect on MWCNT wall thickness, whereby increasing the milling time from 0 to 15 h reduced the number of walls from 29 to 12. It was also interesting to note that the carbon content increased from 23.29 wt.% to 36.37 wt.% with increasing milling time.

  13. Modeling SOA formation from alkanes and alkenes in chamber experiments: effect of gas/wall partitioning of organic vapors.

    NASA Astrophysics Data System (ADS)

    Stéphanie La, Yuyi; Camredon, Marie; Ziemann, Paul; Ouzebidour, Farida; Valorso, Richard; Madronich, Sasha; Lee-Taylor, Julia; Hodzic, Alma; Aumont, Bernard

    2014-05-01

    Oxidation products of Intermediate Volatility Organic Compounds (IVOC) are expected to be the major precursors of secondary organic aerosols (SOA). Laboratory experiments were conducted this last decade in the Riverside APRC chamber to study IVOC oxidative mechanisms and SOA formation processes for a large set of linear, branched and cyclic aliphatic hydrocarbons (Ziemann, 2011). This dataset are used here to assess the explicit oxidation model GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) (Aumont et al., 2005). The simulated SOA yields agree with the general trends observed in the chamber experiments. They are (i) increasing with the increasing carbon number; (ii) decreasing with increasing methyl branch number; and (iii) increasing for cyclic compounds compared to their corresponding linear analogues. However, simulated SOA yields are systematically overestimated regardless of the precursors, suggesting missing processes in the model. In this study, we assess whether gas-to-wall partitioning of organic vapors can explain these model/observation mismatches (Matsunaga and Ziemann, 2010). First results show that GECKO-A outputs better match the observations when wall uptake of organic vapors is taken into account. Effects of gas/wall partitioning on SOA yields and composition will be presented. Preliminary results suggest that wall uptake is a major process influencing SOA production in the Teflon chambers. References Aumont, B., Szopa, S., Madronich, S.: Modelling the evolution of organic carbon during its gas-phase tropospheric oxidation: development of an explicit model based on a self generating approach. Atmos.Chem.Phys., 5, 2497-2517 (2005). P. J. Ziemann: Effects of molecular structure on the chemistry of aerosol formation from the OH-radical-initiated oxidation of alkanes and alkenes, Int. Rev.Phys.Chem., 30:2, 161-195 (2011). Matsunaga, A., Ziemann, P. J.: Gas-wall partitioning of organic compounds in a Teflon film

  14. Mg2+-Dependent Control of the Spatial Arrangement of Rhodococcus erythropolis PR4 Cells in Aqueous-Alkane Two Phase Culture Containing n-Dodecane

    PubMed Central

    Takihara, Hayato; Akase, Yumiko; Sunairi, Michio; Iwabuchi, Noriyuki

    2016-01-01

    We recently reported that a close relationship exists between alkane carbon-chain length, cell growth, and translocation frequency in Rhodococcus. In the present study, we examined the regulation of the spatial arrangement of cells in aqueous-alkane two phase cultures. An analysis of the effects of minerals on cell localization revealed that changes in the concentration of MgSO4 in two phase cultures containing n-dodecane (C12) altered cell localization from translocation to adhesion and vice versa. Our results indicate that the spatial arrangement of cells in two phase culture systems is controlled through the regulation of MgSO4 concentrations. PMID:27180641

  15. Flow paths and chemical reactivity of CO2 in carbonates using Mercury-Intrusion Capillary Pressure data and dimensionless numbers

    NASA Astrophysics Data System (ADS)

    Vialle, S.; Dvorkin, J. P.; Mavko, G. M.

    2012-12-01

    Experiments performed earlier by Vialle and Vanorio (2011) [1] have showed that the injection of CO2-rich water (pH=3.2) in various calcite limestones lead to heterogeneous dissolution of the pore structure, inducing secondary porosity and changing the rock stiffness. The presence of oil in the pore space affects the magnitude of these changes by lowering the reactive surface area. We present here a semi-quantitative analysis at the mesoscale to investigate how different initial pore microgeometries and heterogeneities in pore microgeometry affect the fluid-rock interactions. In particular, we aim at quantitatively explaining (1) why, in clean samples, higher-porosity micrite with rounded grains appears to be more affected by dissolution than tight micrite and spar cement and (2) why, for the same number of pore volumes of fluid injected, the magnitude of the changes in porosity (and subsequently elastic properties) differs among the studied rock samples. Rock microgeometry is studied by classical rock-physics methods, He-pycnometry and Mercury-Intrusion Capillary Pressure (MICP) tests, as well as by Scanning Electron Microscopy (SEM) imaging. Experiments were performed on subsamples (~0.5cm3) extracted from core plugs (~12cm3): two Fontainebleau sandstones, to serve as benchmarks, and two calcite carbonates from two different geological formations. In order to relate pore microgeometry to flow paths and chemical reactivity of CO2 in carbonate rocks, we chose to work at a scale that lies between the pore scale and the core scale. The method consists of physically subdividing the core plugs under examination into subsets based on the pore-throat sizes; these subsets correspond to three types of microstructure: "macropores", "microporous rounded micrite", and "spar cement"/"tight micrite". The dimensionless Péclet (Pe) and Damkhöler (Da) numbers, defined as the ratio between the advection rate and the diffusion rate, and as the ratio between the reaction rate and

  16. Influence of alkane chain length on adsorption on an α-alumina surface by MD simulations

    NASA Astrophysics Data System (ADS)

    Turgut, C.; Pandiyan, S.; Mether, L.; Belmahi, M.; Nordlund, K.; Philipp, P.

    2015-06-01

    Plasma surface techniques provide both an efficient and ecological tool for the functionalization of surfaces. Hence, a proper understanding of the plasma-surface interactions of precursors and radicals during the deposition process is of great importance. Especially during the initial deposition process, the deposition of molecules and fragments is difficult to investigate by experimental techniques and import insights can be obtained by molecular dynamics simulations. In this work, the reactive force field developed by the group of Kieffer at the University of Michigan was used to study the adsorption of single linear alkane chains on an α-alumina surface. The chain length was changed from 6 backbone carbon atoms to 16 carbon atoms, the deposition energy from 0.01 to 10 eV and the incidence angle from 0° to 60° with respect to the surface normal. Results show that the adsorption depends a lot on the ratio of deposition energy to alkane chain length and the incidence angle. More grazing incidence reduces the adsorption probability and a low ratio of energy to chain length increases it.

  17. Diffusion of Benzene and Alkylbenzenes in n-Alkanes.

    PubMed

    Kowert, Bruce A; Register, Paul M

    2015-10-01

    The translational diffusion constants, D, of benzene and a series of alkylbenzenes have been determined in four n-alkanes at room temperature using capillary flow techniques. The alkylbenzenes are toluene, ethylbenzene, 1-phenylpropane, 1-phenylpentane, 1-phenyloctane, 1-phenylundecane, 1-phenyltetradecane, and 1-phenylheptadecane. The n-alkanes are n-nonane, n-decane, n-dodecane, and n-pentadecane. Ratios of the solutes' D values are independent of solvent and in general agreement with the predictions of diffusion models for cylinders and lollipops. For the latter, an alkylbenzene's phenyl ring is the lollipop's candy; the alkyl chain is its handle. A model that considers the solutes to be spheres with volumes determined by the van der Waals increments of their constituent atoms is not in agreement with experiment. The diffusion constants of 1-alkene and n-alkane solutes in n-alkane solvents also are compared with the cylinder model; reasonably good agreement is found. The n-alkanes are relatively extended, and this appears to be the case for the alkyl chains of the 1-alkenes and alkylbenzenes as well. PMID:26417941

  18. Alkane desaturation by concerted double hydrogen atom transfer to benzyne.

    PubMed

    Niu, Dawen; Willoughby, Patrick H; Woods, Brian P; Baire, Beeraiah; Hoye, Thomas R

    2013-09-26

    The removal of two vicinal hydrogen atoms from an alkane to produce an alkene is a challenge for synthetic chemists. In nature, desaturases and acetylenases are adept at achieving this essential oxidative functionalization reaction, for example during the biosynthesis of unsaturated fatty acids, eicosanoids, gibberellins and carotenoids. Alkane-to-alkene conversion almost always involves one or more chemical intermediates in a multistep reaction pathway; these may be either isolable species (such as alcohols or alkyl halides) or reactive intermediates (such as carbocations, alkyl radicals, or σ-alkyl-metal species). Here we report a desaturation reaction of simple, unactivated alkanes that is mechanistically unique. We show that benzynes are capable of the concerted removal of two vicinal hydrogen atoms from a hydrocarbon. The discovery of this exothermic, net redox process was enabled by the simple thermal generation of reactive benzyne intermediates through the hexadehydro-Diels-Alder cycloisomerization reaction of triyne substrates. We are not aware of any single-step, bimolecular reaction in which two hydrogen atoms are simultaneously transferred from a saturated alkane. Computational studies indicate a preferred geometry with eclipsed vicinal C-H bonds in the alkane donor.

  19. Carbon-Nanotubes-Supported Pd Nanoparticles for Alcohol Oxidations in Fuel Cells: Effect of Number of Nanotube Walls on Activity.

    PubMed

    Zhang, Jin; Lu, Shanfu; Xiang, Yan; Shen, Pei Kang; Liu, Jian; Jiang, San Ping

    2015-09-01

    Carbon nanotubes (CNTs) are well known electrocatalyst supports due to their high electrical conductivity, structural stability, and high surface area. Here, we demonstrate that the number of inner tubes or walls of CNTs also have a significant promotion effect on the activity of supported Pd nanoparticles (NPs) for alcohol oxidation reactions of direct alcohol fuel cells (DAFCs). Pd NPs with similar particle size (2.1-2.8 nm) were uniformly assembled on CNTs with different number of walls. The results indicate that Pd NPs supported on triple-walled CNTs (TWNTs) have the highest mass activity and stability for methanol, ethanol, and ethylene glycol oxidation reactions, as compared to Pd NPs supported on single-walled and multi-walled CNTs. Such a specific promotion effect of TWNTs on the electrocatalytic activity of Pd NPs is not related to the contribution of metal impurities in CNTs, oxygen-functional groups of CNTs or surface area of CNTs and Pd NPs. A facile charge transfer mechanism via electron tunneling between the outer wall and inner tubes of CNTs under electrochemical driving force is proposed for the significant promotion effect of TWNTs for the alcohol oxidation reactions in alkaline solutions.

  20. Discrimination of the prochiral hydrogens at the C-2 position of n-alkanes by the methane/ammonia monooxygenase family proteins.

    PubMed

    Miyaji, Akimitsu; Miyoshi, Teppei; Motokura, Ken; Baba, Toshihide

    2015-08-14

    The selectivity of ammonia monooxygenase from Nitrosomonas europaea (AMO-Ne) for the oxidation of C4-C8n-alkanes to the corresponding alcohol isomers was examined to show the ability of AMO-Ne to recognize the n-alkane orientation within the catalytic site. AMO-Ne in whole cells produces 1- and 2-alcohols from C4-C8n-alkanes, and the regioselectivity is dependent on the length of the carbon chain. 2-Alcohols produced from C4-C7n-alkanes were predominantly either the R- or S-enantiomers, while 2-octanol produced from n-octane was racemic. These results indicate that AMO-Ne can discriminate between the prochiral hydrogens at the C-2 position, with the degree of discrimination varying according to the n-alkane. Compared to the particulate methane monooxygenase (pMMO) of Methylococcus capsulatus (Bath) and that of Methylosinus trichosporium OB3b, AMO-Ne showed a distinct ability to discriminate between the orientation of n-butane and n-pentane in the catalytic site.

  1. Final Technical Report "Catalytic Hydrogenation of Carbon Monoxide and Olefin Oxidation" Grant number : DE-FG02-86ER13615

    SciTech Connect

    Wayland, B.B.

    2009-08-31

    Title: Catalytic Hydrogenation of Carbon Monoxide and Olefin Oxidation Grant No. DE-FG02-86ER13615 PI: Wayland, B. B. (wayland@sas.upenn.edu) Abstract Development of new mechanistic strategies and catalyst materials for activation of CO, H2, CH4, C2H4, O2, and related substrates relevant to the conversion of carbon monoxide, alkanes, and alkenes to organic oxygenates are central objectives encompassed by this program. Design and synthesis of metal complexes that manifest reactivity patterns associated with potential pathways for the hydrogenation of carbon monoxide through metallo-formyl (M-CHO), dimetal ketone (M-C(O)-M), and dimetal dionyl (M-C(O)-C(O)-M) species is one major focus. Hydrocarbon oxidation using molecular oxygen is a central goal for methane activation and functionalization as well as regioselective oxidation of olefins. Discovery of new reactivity patterns and control of selectivity are pursued through designing new metal complexes and adjusting reaction conditions. Variation of reaction media promotes distinct reaction pathways that control both reaction rates and selectivities. Dimetalloradical diporphyrin complexes preorganize transition states for substrate reactions that involve two metal centers and manifest large rate increases over mono-metalloradical reactions of hydrogen, methane, and other small molecule substrates. Another broad goal and recurring theme of this program is to contribute to the thermodynamic database for a wide scope of organo-metal transformations in a range of reaction media. One of the most complete descriptions of equilibrium thermodynamics for organometallic reactions in water and methanol is emerging from the study of rhodium porphyrin substrate reactions in aqueous and alcoholic media. Water soluble group nine metalloporphyrins manifest remarkably versatile substrate reactivity in aqueous and alcoholic media which includes producing rhodium formyl (Rh-CHO) and hydroxy methyl (Rh-CH2OH) species. Exploratory

  2. Microbial production of short-chain alkanes.

    PubMed

    Choi, Yong Jun; Lee, Sang Yup

    2013-10-24

    Increasing concerns about limited fossil fuels and global environmental problems have focused attention on the need to develop sustainable biofuels from renewable resources. Although microbial production of diesel has been reported, production of another much in demand transport fuel, petrol (gasoline), has not yet been demonstrated. Here we report the development of platform Escherichia coli strains that are capable of producing short-chain alkanes (SCAs; petrol), free fatty acids (FFAs), fatty esters and fatty alcohols through the fatty acyl (acyl carrier protein (ACP)) to fatty acid to fatty acyl-CoA pathway. First, the β-oxidation pathway was blocked by deleting the fadE gene to prevent the degradation of fatty acyl-CoAs generated in vivo. To increase the formation of short-chain fatty acids suitable for subsequent conversion to SCAs in vivo, the activity of 3-oxoacyl-ACP synthase (FabH), which is inhibited by unsaturated fatty acyl-ACPs, was enhanced to promote the initiation of fatty acid biosynthesis by deleting the fadR gene; deletion of the fadR gene prevents upregulation of the fabA and fabB genes responsible for unsaturated fatty acids biosynthesis. A modified thioesterase was used to convert short-chain fatty acyl-ACPs to the corresponding FFAs, which were then converted to SCAs by the sequential reactions of E. coli fatty acyl-CoA synthetase, Clostridium acetobutylicum fatty acyl-CoA reductase and Arabidopsis thaliana fatty aldehyde decarbonylase. The final engineered strain produced up to 580.8 mg l(-1) of SCAs consisting of nonane (327.8 mg l(-1)), dodecane (136.5 mg l(-1)), tridecane (64.8 mg l(-1)), 2-methyl-dodecane (42.8 mg l(-1)) and tetradecane (8.9 mg l(-1)), together with small amounts of other hydrocarbons. Furthermore, this platform strain could produce short-chain FFAs using a fadD-deleted strain, and short-chain fatty esters by introducing the Acinetobacter sp. ADP1 wax ester synthase (atfA) and the E. coli mutant

  3. Alkanes in shrimp from the Buccaneer Oil Field

    SciTech Connect

    Middleditch, B.S.; Basile, B.; Chang, E.S.

    1982-07-01

    A total of 36 samples of shrimp were examined from the region of the Buccaneer oil field, eighteen of which were representatives of the commercial species Penaeus aztecus and the rest were various other species: Penaeus duorarum (pink shrimp), Trachypenaeus duorarum (sugar shrimp), Squilla empusa (mantis shrimp), and Sicyonia dorsalis (chevron shrimp). The alkanes and deuteriated alkanes were completely separated by GC, so a mass spectrometer was not required for their detection and quantitation. To confirm the identities of individual compounds, however, some samples were examined by combined gas chromatography-mass spectrometry. Results show that only thirteen of the forty shrimp collected from the region of the Buccaneer oil field contained petroleum alkanes, and the majority of these were obtained from trawls immediately adjacent to the production platforms. It appears that shrimp caught in the region of the Buccaneer oil field are not appreciably tainted with hydrocarbons discharged from the production platforms. (JMT)

  4. Infrared Spectroscopic Investigation on CH Bond Acidity in Cationic Alkanes

    NASA Astrophysics Data System (ADS)

    Matsuda, Yoshiyuki; Xie, Min; Fujii, Asuka

    2016-06-01

    We have demonstrated large enhancements of CH bond acidities in alcohol, ether, and amine cations through infrared predissociation spectroscopy based on the vacuum ultraviolet photoionization detection. In this study, we investigate for the cationic alkanes (pentane, hexane, and heptane) with different alkyl chain lengths. The σ electrons are ejected in the ionization of alkanes, while nonbonding electrons are ejected in ionization of alcohols, ethers, and amines. Nevertheless, the acidity enhancements of CH in these cationic alkanes have also been demonstrated by infrared spectroscopy. The correlations of their CH bond acidities with the alkyl chain lengths as well as the mechanisms of their acidity enhancements will be discussed by comparison of infrared spectra and theoretical calculations.

  5. Thermal decomposition of n-alkanes under supercritical conditions

    SciTech Connect

    Yu, J.; Eser, S.

    1996-10-01

    The future aircraft fuel system may be operating at temperatures above the critical points of fuels. Currently there is very limited information on the thermal stability of hydrocarbon fuels under supercritical conditions. In this work, the thermal stressing experiments of n-decane, n-dodecane, n-tetradecane, their mixtures, and an n-paraffin mixture, Norpar-13, was carried out under supercritical conditions. The experimental results indicated that the thermal decomposition of n-alkanes can be represented well by the first-order kinetics. Pressure has significant effects on the first-order rate constant and product distribution in the near-critical region. The major products are a series of n-alkanes and 1-alkenes. The relative yields of n-alkanes and 1-alkenes depend on the reaction conditions. The first-order rate constants for the thermal decomposition of individual compounds in a mixture are different from those obtained for the decomposition of pure compounds.

  6. Surface crystallization in normal-alkanes and alcohols

    SciTech Connect

    Deutsch, M.; Ocko, B.M.; Wu, X.Z. |; Sirota, E.B.; Sinha, S.K.

    1995-06-01

    A new, rare surface freezing, phenomenon is observed in molten normal-alkanes and their derivatives (alcohols, thiols, etc.). X-ray and surface tension measurements show the formation of a crystalline monolayer on the surface of the liquid alkane at temperatures up to 3 C above the bulk solidification temperature, T{sub f}. For alcohols, a single bilayer is formed. In both cases, the molecules in the layer are hexagonally packed and oriented normal to the surface for short chain lengths, and tilted for long ones. In both cases the single layer persists down to T{sub f}. In terms of wetting theory, this constitutes a very limited partial wetting of the liquid surface by the crystalline layer. The new surface phase is obtained only for chain lengths 14 < n {le} 50 in alkanes, and 16 < n < 30 in alcohols. The measurements are satisfactorily accounted for within a simple theory based on surface energy considerations.

  7. Alkanes and alkenes conversion to high octane gasoline

    SciTech Connect

    Harandi, M.N.; Owen, H.

    1989-07-25

    This patent describes a process for the conversion of lower alkane and alkene hydrocarbons to high octane gasoline. It comprises: contacting a hydrocarbon feedstock comprising lower alkanes and alkenes with a fluidized bed of acidic, shape selective metallosiliate catalyst in a first conversion zone under high temperature alkane conversion conditions wherein the feedstock contains an amount of lower alkene sufficient to provide an exotherm sufficient to maintain near isothermal reaction conditions whereby an effluent stream is produced comprising higher aliphatic hydrocarbons rich in aromatics; contacting the effluent stream with a fluidized bed of acidic, medium pore metallosilicate catalyst in a second conversion zone at moderate temperature under oligonerization and alkylation conditions whereby a C/sub 5/ + gasoline boiling range product is produced rich in alkylated aromatics.

  8. Catalytic, mild, and selective oxyfunctionalization of linear alkanes: current challenges.

    PubMed

    Bordeaux, Mélanie; Galarneau, Anne; Drone, Jullien

    2012-10-22

    Selective catalysts for sustainable oxidation of alkanes are highly demanded because of the abundance of these molecules in the environment, the possibility to transform them into higher-value compounds, such as chemicals or synthetic fuels, and the fact that, kinetically speaking, this is a difficult reaction. Numerous chemical and biological catalysts have been developed in the lasts decades for this purpose, rendering the overview over this field of chemistry difficult. After giving a definition of the ideal catalyst for alkane oxyfunctionalization, this review aims to present the catalysts available today that are closest to ideal.

  9. Modeling of alkane emissions from a wood stain

    SciTech Connect

    Chang, J.C.S.; Guo, Z.

    1993-01-01

    The article discusses full-scale residential house tests to evaluate the effects of organic emissions from a wood finishing product--wood stain--on indoor air quality (IAQ). The test house concentrations of three alkane species, nonane, decane, and undecane, were measured as a function of time after the application of the wood stain. It was found that the test house concentrations can be simulated by an integrated IAQ model which takes into consideration source, sink, and ventilation effects. The alkane emissions were controlled by an evaporation-like process.

  10. Hydrocarbon and elemental carbon signatures in a tropical wetland: biogeochemical evidence of forest fire and vegetation changes.

    PubMed

    Tareq, Shafi M; Tanoue, Eiichiro; Tsuji, H; Tanaka, Noriyuki; Ohta, Keiichi

    2005-06-01

    Evidence of changing vegetation in the tropical wetland (Rawa Danau, west Java, Indonesia) over the past 7428 years is illustrated by elemental (soot) carbon (EC) and n-alkane composition of sedimentary geolipids. In this study, vegetation changes and relevant controlling factors (e.g. forest fire and climate change) were documented on a decadal to centennial scale. The n-alkane composition that changes with depth might record changes in sources of organic matter (OM) in the wetland. The presence of EC (0.01-0.24% of organic carbon: OC) during late (0-1700 cal. year BP) and mid (3500-4500 cal. year BP) Holocene (at depths 0-50 cm, and 160-210 cm) indicated that large-scale forest fires severely affected the tropical vegetation. The hydrocarbon indices (CPI: carbon preference index, MCN: mean carbon number, and HVI: hydrocarbon vegetation index) significantly correlated with one another while a comparison of EC profile with the profiles of hydrocarbon indices indicated that n-alkane composition of the geolipid in lake sediment could record signatures of changes in catchment vegetation. Forest fire and vegetation changes might be related to regional climatic shifts relating to ENSO activity as well as being influenced by human influences. PMID:15894051

  11. Determination of car on-road black carbon and particle number emission factors and comparison between mobile and stationary measurements

    NASA Astrophysics Data System (ADS)

    Ježek, I.; Drinovec, L.; Ferrero, L.; Carriero, M.; Močnik, G.

    2015-01-01

    We have used two methods for measuring emission factors (EFs) in real driving conditions on five cars in a controlled environment: the stationary method, where the investigated vehicle drives by the stationary measurement platform and the composition of the plume is measured, and the chasing method, where a mobile measurement platform drives behind the investigated vehicle. We measured EFs of black carbon and particle number concentration. The stationary method was tested for repeatability at different speeds and on a slope. The chasing method was tested on a test track and compared to the portable emission measurement system. We further developed the data processing algorithm for both methods, trying to improve consistency, determine the plume duration, limit the background influence and facilitate automatic processing of measurements. The comparison of emission factors determined by the two methods showed good agreement. EFs of a single car measured with either method have a specific distribution with a characteristic value and a long tail of super emissions. Measuring EFs at different speeds or slopes did not significantly influence the EFs of different cars; hence, we propose a new description of vehicle emissions that is not related to kinematic or engine parameters, and we rather describe the vehicle EF with a characteristic value and a super emission tail.

  12. Determination of car on-road black carbon and particle number emission factors and comparison between mobile and stationary measurements

    NASA Astrophysics Data System (ADS)

    Ježek, I.; Drinovec, L.; Ferrero, L.; Carriero, M.; Močnik, G.

    2014-06-01

    We have used two methods for measuring emission factors (EF) in real driving conditions on five cars in a controlled environment: the stationary method, where the investigated vehicle drives by the stationary measurement platform and the composition of the plume is measured; and the chasing method, where a mobile measurement platform drives behind the investigated vehicle. We measured EF of black carbon and particle number concentration. The stationary method was tested for repeatability at different speeds and on a slope. The chasing method was tested on a test track and compared to the portable emission measurement system. We further developed the data processing algorithm for both methods, trying to improve consistency, determine the plume duration, limit the background influence and facilitate automatic processing of measurements. The comparison of emission factors determined by the two methods showed good agreement. EFs of a single car measured with either method have a specific distribution with a characteristic value and a long tail of super emissions. Measuring EFs at different speeds or slopes did not significantly influence the EFs of different cars, hence we propose a new description of vehicle emissions that is not related to kinematic or engine parameters, rather we describe the vehicle EF with a characteristic value and a "super emission" tail.

  13. Natural gas constituent and carbon isotopic composition in petroliferous basins, China

    NASA Astrophysics Data System (ADS)

    Zhu, Guangyou; Wang, Zhengjun; Dai, Jinxing; Su, Jing

    2014-02-01

    There are abundant gas resources in petroliferous basins of China. Large to midsize gas fields are found in Eastern, central and Western of China. However, origin, constituents and isotopic composition of natural gas in different gas fields are varied distinctly, and some present strong chemical secondary alteration and show variation both in age and space. Based on the systematic analysis of constituents and carbon isotope of a large number of gas samples, combined with the geological characteristics, this paper classifies the origins of the gases, explores the gas isotope characteristics and evolutionary regulation with the variation time and space, and further discusses the distinctive geochemistry of the gases in China. These gases are dominated by dry gas, its methane carbon isotope values range from -10‰ to -70‰, ethane from -16‰ to -52‰, propane from -13‰ to -43‰, and butane from -18‰ to -34‰. The carbon isotopes of most gases show the characteristics of humic-derived gas and crude oil cracked gas. In addition, large primary biogenic gas fields have been discovered in the Qaidam basin; inorganic-derived alkane gases have been discovered in deep of the Songliao Basin. Half of these gas fields are characterized by the alkane carbon isotope reversal in different degrees. Research indicates there are several reasons can result in carbon isotope reversal. Firstly, gas charge of different genetic types or different source in one gas reservoir may cause carbon isotope reversal. Besides, high-over mature evolution of gas can also lead to the carbon isotopic reversal of alkanes. Thirdly, secondary alteration of hydrocarbons may also result in abnormal distribution of carbon isotope, isotope transforms to unusual light and heavy.

  14. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

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

  15. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

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

  16. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

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

  17. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2010 CFR

    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...

  18. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  19. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  20. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  1. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  2. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  3. Hydrogen isotope composition of leaf wax n-alkanes in Arabidopsis lines with different transpiration rates

    NASA Astrophysics Data System (ADS)

    Pedentchouk, N.; Lawson, T.; Eley, Y.; McAusland, L.

    2012-04-01

    Stable isotopic compositions of oxygen and hydrogen are used widely to investigate modern and ancient water cycles. The D/H composition of organic compounds derived from terrestrial plants has recently attracted significant attention as a proxy for palaeohydrology. However, the role of various plant physiological and biochemical factors in controlling the D/H signature of leaf wax lipids in extant plants remains unclear. The focus of this study is to investigate the effect of plant transpiration on the D/H composition of n-alkanes in terrestrial plants. This experiment includes 4 varieties of Arabidopsis thaliana that differ with respect to stomatal density and stomatal geometry. All 4 varieties were grown indoors under identical temperature, relative humidity, light and watering regimes and then sampled for leaf wax and leaf water stable isotopic measurements. During growth, stomatal conductance to carbon dioxide and water vapour were also determined. We found that the plants varied significantly in terms of their transpiration rates. Transpiration rates were significantly higher in Arabidopsis ost1 and ost1-1 varieties (2.4 and 3.2 mmol m-2 s-1, respectively) than in Arabidopsis RbohD and Col-0 (1.5 and 1.4). However, hydrogen isotope measurements of n-alkanes extracted from leaf waxes revealed a very different pattern. Varieties ost1, ost1-1, and RbohD have very similar deltaD values of n-C29 alkane (-125, -128, and -127 per mil), whereas the deltaD value of Col-0 is more negative (-137 per mil). The initial results of this work suggest that plant transpiration is decoupled from the D/H composition of n-alkanes. In other words, physical processes that affect water vapour movement between the plant and its environment apparently cannot account for the stable hydrogen isotope composition of organic compounds that comprise leaf waxes. Additional, perhaps biochemical, processes that affect hydrogen isotope fractionation during photosynthesis might need to be invoked

  4. Conformational equilibria of alkanes in aqueous solution: relationship to water structure near hydrophobic solutes.

    PubMed Central

    Ashbaugh, H S; Garde, S; Hummer, G; Kaler, E W; Paulaitis, M E

    1999-01-01

    Conformational free energies of butane, pentane, and hexane in water are calculated from molecular simulations with explicit waters and from a simple molecular theory in which the local hydration structure is estimated based on a proximity approximation. This proximity approximation uses only the two nearest carbon atoms on the alkane to predict the local water density at a given point in space. Conformational free energies of hydration are subsequently calculated using a free energy perturbation method. Quantitative agreement is found between the free energies obtained from simulations and theory. Moreover, free energy calculations using this proximity approximation are approximately four orders of magnitude faster than those based on explicit water simulations. Our results demonstrate the accuracy and utility of the proximity approximation for predicting water structure as the basis for a quantitative description of n-alkane conformational equilibria in water. In addition, the proximity approximation provides a molecular foundation for extending predictions of water structure and hydration thermodynamic properties of simple hydrophobic solutes to larger clusters or assemblies of hydrophobic solutes. PMID:10423414

  5. Removal of chlorinated and non-chlorinated alkanes in a trickle-bed biofilter

    SciTech Connect

    Klasson, K.T.; Davison, B.H.; Barton, J.W.; Jacobs, J.E.

    1998-01-01

    Increasing restrictions in emissions from a variety of industrial settings demand low cost removal of dilute contaminants in air. Many of these contaminants such as volatile organic components (VOCs) and sulfur compounds are biodegradable and can be removed from air streams via biofiltration. The simplest form of biofiltration consists of compost-based systems. More advanced systems designed for unique contaminants are biofilters with bioactive structured packing operating in trickle-bed mode. These advanced systems rely on a microbial consortium capable of degrading the contaminants of concern and the consortium usually is isolated or enriched from a more complex microbial mixture. This paper describes the use of a trickle-bed reactor seeded with a microbial consortium enriched from a methanotrophic culture. The microbial consortium has been found to degrade chlorinated alkanes as the sole carbon source. Degradation rates of alkane mixtures are presented for the trickle-bed as well as results from batch cultures experiments designed to study degradation of various chlorinated and non-chlorinated VOCs.

  6. On droplet combustion of biodiesel fuel mixed with diesel/alkanes in microgravity condition

    SciTech Connect

    Pan, Kuo-Long; Li, Je-Wei; Chen, Chien-Pei; Wang, Ching-Hua

    2009-10-15

    The burning characteristics of a biodiesel droplet mixed with diesel or alkanes such as dodecane and hexadecane were experimentally studied in a reduced-gravity environment so as to create a spherically symmetrical flame without the influence of natural convection due to buoyancy. Small droplets on the order of 500 {mu}m in diameter were initially injected via a piezoelectric technique onto the cross point intersected by two thin carbon fibers; these were prepared inside a combustion chamber that was housed in a drag shield, which was freely dropped onto a foam cushion. It was found that, for single component droplets, the tendency to form a rigid soot shell was relatively small for biodiesel fuel as compared to that exhibited by the other tested fuels. The soot created drifted away readily, showing a puffing phenomenon; this could be related to the distinct molecular structure of biodiesel leading to unique soot layers that were more vulnerable to oxidative reactivity as compared to the soot generated by diesel or alkanes. The addition of biodiesel to these more traditional fuels also presented better performance with respect to annihilating the soot shell, particularly for diesel. The burning rate generally follows that of multi-component fuels, by some means in terms of a lever rule, whereas the mixture of biodiesel and dodecane exhibits a somewhat nonlinear relation with the added fraction of dodecane. This might be related to the formation of a soot shell. (author)

  7. Catalytic production of branched small alkanes from biohydrocarbons.

    PubMed

    Oya, Shin-ichi; Kanno, Daisuke; Watanabe, Hideo; Tamura, Masazumi; Nakagawa, Yoshinao; Tomishige, Keiichi

    2015-08-10

    Squalane, C30 algae-derived branched hydrocarbon, was successfully converted to smaller hydrocarbons without skeletal isomerization and aromatization over ruthenium on ceria (Ru/CeO2 ). The internal CH2 CH2 bonds located between branches are preferably dissociated to give branched alkanes with very simple distribution as compared with conventional methods using metal-acid bifunctional catalysts.

  8. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, P.E. Jr.; Lyons, J.E.

    1993-05-18

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso- and/or [beta]-pyrrolic positions.

  9. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, P.E. Jr.; Lyons, J.E.

    1995-01-17

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or [beta]-pyrrolic positions.

  10. Improving alkane synthesis in Escherichia coli via metabolic engineering.

    PubMed

    Song, Xuejiao; Yu, Haiying; Zhu, Kun

    2016-01-01

    Concerns about energy security and global petroleum supply have made the production of renewable biofuels an industrial imperative. The ideal biofuels are n-alkanes in that they are chemically and structurally identical to the fossil fuels and can "drop in" to the transportation infrastructure. In this work, an Escherichia coli strain that produces n-alkanes was constructed by heterologous expression of acyl-acyl carrier protein (ACP) reductase (AAR) and aldehyde deformylating oxygenase (ADO) from Synechococcus elongatus PCC7942. The accumulation of alkanes ranged from 3.1 to 24.0 mg/L using different expressing strategies. Deletion of yqhD, an inherent aldehyde reductase in E. coli, or overexpression of fadR, an activator for fatty acid biosynthesis, exhibited a nearly twofold increase in alkane titers, respectively. Combining yqhD deletion and fadR overexpression resulted in a production titer of 255.6 mg/L in E. coli, and heptadecene was the most abundant product. PMID:26476644

  11. 40 CFR 721.10704 - Aryl-substituted alkane.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... reporting. (1) The chemical substance identified generically as an aryl-substituted alkane (PMN P-12-548) is subject to reporting under this section for the significant new uses described in paragraph (a)(2) of this... communication program. Requirements as specified in § 721.72(a), (b), (c), (d), (e) (concentration set at...

  12. MODELING OF ALKANE EMISSIONS FROM A WOOD STAIN

    EPA Science Inventory

    The article discusses full-scale residential house tests to evaluate the effects of organic emissions from a wood finishing product--wood stain--on indoor air quality (IAQ). The test house concentrations of three alkane species, nonane, decane, and undecane, were measured as a fu...

  13. Diverse alkane hydroxylase genes in microorganisms and environments

    PubMed Central

    Nie, Yong; Chi, Chang-Qiao; Fang, Hui; Liang, Jie-Liang; Lu, She-Lian; Lai, Guo-Li; Tang, Yue-Qin; Wu, Xiao-Lei

    2014-01-01

    AlkB and CYP153 are important alkane hydroxylases responsible for aerobic alkane degradation in bioremediation of oil-polluted environments and microbial enhanced oil recovery. Since their distribution in nature is not clear, we made the investigation among thus-far sequenced 3,979 microbial genomes and 137 metagenomes from terrestrial, freshwater, and marine environments. Hundreds of diverse alkB and CYP153 genes including many novel ones were found in bacterial genomes, whereas none were found in archaeal genomes. Moreover, these genes were detected with different distributional patterns in the terrestrial, freshwater, and marine metagenomes. Hints for horizontal gene transfer, gene duplication, and gene fusion were found, which together are likely responsible for diversifying the alkB and CYP153 genes adapt to the ubiquitous distribution of different alkanes in nature. In addition, different distributions of these genes between bacterial genomes and metagenomes suggested the potentially important roles of unknown or less common alkane degraders in nature. PMID:24829093

  14. Cyano- and polycyanometalloporphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, Jr., Paul E.; Lyons, James E.

    1992-01-01

    Alkanes are oxidized by contact with oxygen-containing gas in the presence as catalyst of a metalloporphyrin in which hydrogen atoms in the porphyrin ring have been substituted with one or more cyano groups. Hydrogen atoms in the porphyrin ring may also be substituted with halogen atoms.

  15. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, Jr., Paul E.; Lyons, James E.

    1995-01-01

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

  16. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, Jr., Paul E.; Lyons, James E.

    1993-01-01

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

  17. Improving alkane synthesis in Escherichia coli via metabolic engineering.

    PubMed

    Song, Xuejiao; Yu, Haiying; Zhu, Kun

    2016-01-01

    Concerns about energy security and global petroleum supply have made the production of renewable biofuels an industrial imperative. The ideal biofuels are n-alkanes in that they are chemically and structurally identical to the fossil fuels and can "drop in" to the transportation infrastructure. In this work, an Escherichia coli strain that produces n-alkanes was constructed by heterologous expression of acyl-acyl carrier protein (ACP) reductase (AAR) and aldehyde deformylating oxygenase (ADO) from Synechococcus elongatus PCC7942. The accumulation of alkanes ranged from 3.1 to 24.0 mg/L using different expressing strategies. Deletion of yqhD, an inherent aldehyde reductase in E. coli, or overexpression of fadR, an activator for fatty acid biosynthesis, exhibited a nearly twofold increase in alkane titers, respectively. Combining yqhD deletion and fadR overexpression resulted in a production titer of 255.6 mg/L in E. coli, and heptadecene was the most abundant product.

  18. Catalytic oxidation of light alkanes in presence of a base

    DOEpatents

    Bhinde, Manoj V.; Bierl, Thomas W.

    1998-01-01

    The presence of a base in the reaction mixture in a metal-ligand catalyzed partial oxidation of alkanes results in sustained catalyst activity, and in greater percent conversion as compared with oxidation in the absence of base, while maintaining satisfactory selectivity for the desired oxidation, for example the oxidation of isobutane to isobutanol.

  19. Catalytic oxidation of light alkanes in presence of a base

    DOEpatents

    Bhinde, M.V.; Bierl, T.W.

    1998-03-03

    The presence of a base in the reaction mixture in a metal-ligand catalyzed partial oxidation of alkanes results in sustained catalyst activity, and in greater percent conversion as compared with oxidation in the absence of base, while maintaining satisfactory selectivity for the desired oxidation, for example the oxidation of isobutane to isobutanol. 1 fig.

  20. Pathway of n-Alkane Oxidation in Cladosporium resinae

    PubMed Central

    Walker, J. D.; Cooney, J. J.

    1973-01-01

    Pathways of initial oxidation of n-alkanes were examined in two strains of Cladosporium resinae. Cells grow on dodecane and hexadecane and their primary alcohol and monoic acid derivatives. The homologous aldehydes do not support growth but are oxidized by intact cells and by cell-free preparations. Hexane and its derivatives support little or no growth, but cell extracts oxidize hexane, hexanol, and hexanal. Alkane oxidation by extracts is stimulated by reduced nicotinamide adenine dinucleotide (phosphate). Alcohol and aldehyde oxidation are stimulated by nicotinamide adenine dinucleotide (phosphate), and reduced coenzymes accumulate in the presence of cyanide or azide. Extracts supplied with 14C-hexadecane convert it to the alcohol, aldehyde, and acid. Therefore, the major pathway for initial oxidation of n-alkanes is via the primary alcohol, aldehyde, and monoic acid, and the system can act on short-, intermediate-, and long-chain substrates. Thus, filamentous fungi appear to oxidize n-alkanes by pathways similar to those used by bacteria and yeasts. PMID:4146874

  1. Two-stage process for conversion of alkanes to gasoline

    SciTech Connect

    Harandi, M.N.; Owen, H.

    1989-08-22

    This patent describes an improvement in a two-stage process for upgrading hydrocarbons in at least four reaction zones cooperating to produce gasoline range hydrocarbons from lower alkanes. The reaction zones comprising first reaction zone to crack gas oil range hydrocarbons utilizing a large pore cracking catalyst, a second reaction zone in which the large pore catalyst is oxidatively regenerated, a third reaction zone in which an external catalyst cooler autogeneously cools regenerated catalyst by dehydrogenation of the lower alkane stream to produce an olefinic effluent, and a fourth reaction zone in which the olefinic effluent is oligomerized to the gasoline range hydrocarbons. The improvement comprising: a first stage, comprising utilizing excess heat from the second reaction zone: contacting the hot fluid catalytic cracking catalyst with C/sub 3//sup +/ alkanes in the third reaction zone to provide conversion of the alkanes to olefins which leave the third reaction zone as the olefinic effluent separated from catalyst; returning a specified amount of separate fluid catalytic cracking catalyst from the third reaction zone directly to the first or second reaction zone; a second state comprising passing the olefinic effluent from the third reaction zone to a fourth reaction zone for oligomerizing olefins to gasoline range hydrocarbons contacting the olefinic effluent with a medium pore zeolite catalyst effective; recovering a gasoline range hydrocarbon stream from the effluent of the fourth reaction zone.

  2. Origins of n-alkanes, carbonyl compounds and molecular biomarkers in atmospheric fine and coarse particles of Athens, Greece.

    PubMed

    Andreou, G; Rapsomanikis, S

    2009-10-15

    The abundance and origin of aliphatic hydrocarbons, carbonyl compounds and molecular biomarkers found in the aliphatic fraction of PM(10-2.5) and PM(2.5) in the centre of Athens Greece are discussed in an attempt to reveal seasonal air pollution characteristics of the conurbation. Each extract was fractionated into individual compound classes and was analyzed using gas chromatography coupled to mass spectrometry. Normal alkanes, ranging from C(14) to C(35), were abundant in PM(10-2.5) and PM(2.5) samples during both sampling campaigns. The daily concentration of total n-alkanes was up to 438 ng m(-3) for PM(10-2.5) and up to 511 ng m(-3) for PM(2.5). Additionally, gaseous concentrations of n-alkanes were calculated, revealing that the relative proportions between gaseous and particle phases of individual compounds may differ significantly between summer and late winter. Normal alkanals and alkan-2-ones were only detected in the fine fraction of particulate matter and their concentrations were much lower than the n-alkane concentrations. Several geochemical parameters were used to qualitatively reconcile the sources of organic aerosol. The carbon preference index (CPI) of the coarse particles in August had the highest value, while in March the leaf wax contribution decreased significantly and the CPI value was very close to unity for both sites. Maximum concentrations of carbonyl compounds were reported in the range of C(15)-C(20), demonstrating that they were formed from anthropogenic activity or from atmospheric oxidative processes. 6, 10, 14-trimethylpentadecan-2-one, a marker of biogenic input, was also detected in our samples. Molecular biomarker compounds confirmed that ca. 60% of the aliphatic fraction on the sampled atmospheric particles originated from petroleum and not from any contemporary biogenic sources. Pristane and phytane were detected in the fine fraction with their presence indicating sources of fossil fuel in the range of C(16)-C(20). At all

  3. Crystallization features of normal alkanes in confined geometry.

    PubMed

    Su, Yunlan; Liu, Guoming; Xie, Baoquan; Fu, Dongsheng; Wang, Dujin

    2014-01-21

    How polymers crystallize can greatly affect their thermal and mechanical properties, which influence the practical applications of these materials. Polymeric materials, such as block copolymers, graft polymers, and polymer blends, have complex molecular structures. Due to the multiple hierarchical structures and different size domains in polymer systems, confined hard environments for polymer crystallization exist widely in these materials. The confined geometry is closely related to both the phase metastability and lifetime of polymer. This affects the phase miscibility, microphase separation, and crystallization behaviors and determines both the performance of polymer materials and how easily these materials can be processed. Furthermore, the size effect of metastable states needs to be clarified in polymers. However, scientists find it difficult to propose a quantitative formula to describe the transition dynamics of metastable states in these complex systems. Normal alkanes [CnH2n+2, n-alkanes], especially linear saturated hydrocarbons, can provide a well-defined model system for studying the complex crystallization behaviors of polymer materials, surfactants, and lipids. Therefore, a deeper investigation of normal alkane phase behavior in confinement will help scientists to understand the crystalline phase transition and ultimate properties of many polymeric materials, especially polyolefins. In this Account, we provide an in-depth look at the research concerning the confined crystallization behavior of n-alkanes and binary mixtures in microcapsules by our laboratory and others. Since 2006, our group has developed a technique for synthesizing nearly monodispersed n-alkane containing microcapsules with controllable size and surface porous morphology. We applied an in situ polymerization method, using melamine-formaldehyde resin as shell material and nonionic surfactants as emulsifiers. The solid shell of microcapsules can provide a stable three-dimensional (3-D

  4. Catalytic oxidation of alkanes by a (salen)osmium(VI) nitrido complex using H2O2 as the terminal oxidant.

    PubMed

    Chen, Man; Pan, Yi; Kwong, Hoi-Ki; Zeng, Raymond J; Lau, Kai-Chung; Lau, Tai-Chu

    2015-09-14

    The osmium(VI) nitrido complex, [Os(VI)(N)(L)(CH3OH)](+) (1, L = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion) is an efficient catalyst for the oxidation of alkanes under ambient conditions using H2O2 as the oxidant. Alkanes are oxidized to the corresponding alcohols and ketones, with yields up to 75% and turnover numbers up to 2230. Experimental and computational studies are consistent with a mechanism that involves O-atom transfer from H2O2 to [Os(VI)(N)(L)](+) to generate an [Os(VIII)(N)(O)(L)](+) active intermediate.

  5. On-bicycle exposure to particulate air pollution: Particle number, black carbon, PM2.5, and particle size

    NASA Astrophysics Data System (ADS)

    Hankey, Steve; Marshall, Julian D.

    2015-12-01

    Inhalation of air pollution during transport is an important exposure pathway, especially for certain modes of travel and types of particles. We measured concentrations of particulate air pollution (particle number [PN], black carbon [BC], fine particles [PM2.5], particle size) using a mobile, bicycle-based monitoring platform during morning and afternoon rush-hour to explore patterns of exposure while cycling (34 days between August 14 and October 16, 2012 in Minneapolis, MN). Measurements were geo-located at 1 ​s intervals along 3 prescribed monitoring routes totaling 85 h (1426 km) of monitoring. Mean morning [afternoon] on-road concentrations were 32,500 [16,600] pt cm-3, 2.5 [0.7] μg m-3 BC, 8.7 [8.3] μg m-3 PM2.5, and 42 [39] nm particle diameter. Concentrations were correlated with street functional class and declined within small distances from a major road (e.g., for PN and BC, mean concentration decreased ∼20% by moving 1 block away from major roads to adjacent local roads). We estimate the share of on-bicycle exposure attributable to near-traffic emissions (vs. regional pollution) is ∼50% for PN and BC; ∼25% for PM2.5. Regression models of instantaneous traffic volumes, derived from on-bicycle video recordings of nearby traffic, quantify the increase in particle-concentrations associated with each passing vehicle; for example, trucks were associated with acute, high concentration exposure events (average concentration-increase per truck: 31,000 pt cm-3, 1.0 μg m-3 PM2.5, 1.6 μg m-3 BC). Our findings could be used to inform design of low-exposure bicycle networks in urban areas.

  6. Sequential chemical oxidation and aerobic biodegradation of equivalent carbon number-based hydrocarbon fractions in jet fuel.

    PubMed

    Xie, Guibo; Barcelona, Michael J

    2003-10-15

    Remediation of petroleum mixtures is complicated by the differing environmental degradabilities of hundreds of individual hydrocarbons in the mixtures. By grouping the individual hydrocarbons into a few fractions based on equivalent carbon number (EC), the present study examined the chemical and biological degradation of the fractions. With or without prechemical oxidation (25 days) by three oxidants (KMnO4, H202, MgO2), sterile and live microcosms were constituted with aquifer samples for aerobic biodegradation (134 days) of JP-4 jet fuel. Eighty-seven hydrocarbons were recovered and grouped into nine EC fractions. The apparent removal and actual transformation rate constants were estimated for both chemical and biological degradations. The data show that prechemical oxidations facilitated removal of total petroleum hydrocarbons (TPH) (up to 80%) within shorter times (<50 days) than biological alone. KMnO4 and H202 were better oxidants in terms of mass reduction in shorter times yet to some extent inhibited the subsequent microbial activity. MgO2 was a moderate oxidant with less inhibition of microbial activity. Selective degradation of the EC fractions was observed for both chemical and biological processes. The biological processes were much less effective than the prechemical oxidations in transforming aromatic fractions, the more toxic fractions. The favorable substrates (i.e., aliphatic EC approximately 10) for microbial growth were also those most subject to chemical oxidation. The results suggest that for remediation of petroleum contaminants, sequential chemical and biological technologies may surpass biological alone and more moderate oxidants such as MgO2 may be better candidates. More work is needed on the optimal dose and residence time for applied oxidants and on the application to engineering design and formulation of cleanup standards.

  7. Dependence on chain length of NMR relaxation times in mixtures of alkanes

    NASA Astrophysics Data System (ADS)

    Freed, Denise E.

    2007-05-01

    Many naturally occurring fluids, such as crude oils, consist of a very large number of components. It is often of interest to determine the composition of the fluids in situ. Diffusion coefficients and nuclear magnetic resonance (NMR) relaxation times can be measured in situ and depend on the size of the molecules. It has been shown [D. E. Freed et al., Phys. Rev. Lett. 94, 067602 (2005)] that the diffusion coefficient of each component in a mixture of alkanes follows a scaling law in the chain length of that molecule and in the mean chain length of the mixture, and these relations were used to determine the chain length distribution of crude oils from NMR diffusion measurements. In this paper, the behavior of NMR relaxation times in mixtures of chain molecules is addressed. The author explains why one would expect scaling laws for the transverse and longitudinal relaxation times of mixtures of short chain molecules and mixtures of alkanes, in particular. It is shown how the power law dependence on the chain length can be calculated from the scaling laws for the translational diffusion coefficients. The author fits the literature data for NMR relaxation in binary mixtures of alkanes and finds that its dependence on chain length agrees with the theory. Lastly, it is shown how the scaling laws in the chain length and the mean chain length can be used to determine the chain length distribution in crude oils that are high in saturates. A good fit is obtained between the NMR-derived chain length distributions and the ones from gas chromatography.

  8. Re-assessing the role of plant community change and climate in the PETM n-alkane record

    NASA Astrophysics Data System (ADS)

    Bush, R. T.; Baczynski, A. A.; McInerney, F. A.; Chen, D.

    2012-12-01

    The terrestrial leaf wax n-alkane record of the Paleocene-Eocene Thermal Maximum (PETM) in the Bighorn Basin, Wyoming, shows large excursions in both carbon isotope (δ13C) values and n-alkane average chain length (ACL). At the onset of the PETM, ACL values increase from ~28.5 to ~30.1 while the negative carbon isotope excursion (CIE) is 4-6‰ in magnitude and larger than δ13C records from other materials. It has been hypothesized previously that both the ACL excursion and the large magnitude of the CIE were caused by a concurrent turnover in the local flora from a mixed conifer/angiosperm community before the PETM to a different suite of angiosperm species during the PETM. Here, we present the results of a meta-analysis of data (>2000 data from 89 sources, both published and unpublished) on n-alkane amounts and chain length distributions in modern plants from around the world. We applied the data in two sets of comparisons: 1) within and among plant groups such as herbs and graminoids, and 2) between plants and climate, using reported collection locations for outdoor plants and climate values generated via GIS extraction of WorldClim modeled data. We show that angiosperms, as group, produce more n-alkanes than do gymnosperms by 1-2 orders of magnitude, and this means that the gymnosperm contribution to a mixed soil n-alkane pool would be negligible, even in an ecosystem where gymnosperms dominated (i.e. the pre/post-PETM ecosystems). The modern plant data also demonstrate that turnover of the plant community during the PETM, even among only the angiosperm species, is likely not the source of the observed ACL excursion. First, we constructed "representative" groups of PETM and pre/post-PETM communities using living relative species at the Chicago Botanic Garden and find no significant difference in chain length distributions between the two groups. Second and moreover, the modern plant data reveal that n-alkane chain length distributions are tremendously variable

  9. Quantifying Dimer and Trimer Formation of Tri-n-butyl Phosphates in Different Alkane Diluents: FTIR Study.

    PubMed

    Vo, Quynh N; Unangst, Jaclynn L; Nguyen, Hung D; Nilsson, Mikael

    2016-07-21

    Tri-n-butyl phosphate (TBP), a representative of neutral organophosphorous metal-ion-extracting reagents, is an important ligand used in solvent extraction processes for the recovery of uranium and plutonium from spent nuclear fuel, as well as other non-nuclear applications. Ligand-ligand and organic solvent-ligand interactions play an important role in these processes. The self-association behavior of TBP in various alkane diluents of different chain lengths (8, 12, and 16 carbons) and a branched alkane (iso-octane) was investigated by Fourier transform infrared spectroscopic measurements. By careful deconvolution of the spectra into multiple peaks, our results indicate that TBP self-associates to form not only dimers, as previous studies showed, but also trimers in the practical concentration range. Using a mathematical fitting procedure, the dimerization and trimerization constants were determined. As expected, these equilibrium constants are dependent on the solvent used. As the alkane chain for linear hydrocarbon solvents becomes longer, dimerization decreases whereas trimerization increases. For the more branched hydrocarbon, we observe a significantly higher dimerization constant. These effects are most likely due to the intermolecular van der Waals interactions between the butyl tails of each TBP molecule and the diluent hydrocarbon chain as all solvents in this study are relatively nonpolar. PMID:27399338

  10. Diverse sulfate-reducing bacteria of the Desulfosarcina/Desulfococcus clade are the key alkane degraders at marine seeps.

    PubMed

    Kleindienst, Sara; Herbst, Florian-Alexander; Stagars, Marion; von Netzer, Frederick; von Bergen, Martin; Seifert, Jana; Peplies, Jörg; Amann, Rudolf; Musat, Florin; Lueders, Tillmann; Knittel, Katrin

    2014-10-01

    Biogeochemical and microbiological data indicate that the anaerobic oxidation of non-methane hydrocarbons by sulfate-reducing bacteria (SRB) has an important role in carbon and sulfur cycling at marine seeps. Yet, little is known about the bacterial hydrocarbon degraders active in situ. Here, we provide the link between previous biogeochemical measurements and the cultivation of degraders by direct identification of SRB responsible for butane and dodecane degradation in complex on-site microbiota. Two contrasting seep sediments from Mediterranean Amon mud volcano and Guaymas Basin (Gulf of California) were incubated with (13)C-labeled butane or dodecane under sulfate-reducing conditions and analyzed via complementary stable isotope probing (SIP) techniques. Using DNA- and rRNA-SIP, we identified four specialized clades of alkane oxidizers within Desulfobacteraceae to be distinctively active in oxidation of short- and long-chain alkanes. All clades belong to the Desulfosarcina/Desulfococcus (DSS) clade, substantiating the crucial role of these bacteria in anaerobic hydrocarbon degradation at marine seeps. The identification of key enzymes of anaerobic alkane degradation, subsequent β-oxidation and the reverse Wood-Ljungdahl pathway for complete substrate oxidation by protein-SIP further corroborated the importance of the DSS clade and indicated that biochemical pathways, analog to those discovered in the laboratory, are of great relevance for natural settings. The high diversity within identified subclades together with their capability to initiate alkane degradation and growth within days to weeks after substrate amendment suggest an overlooked potential of marine benthic microbiota to react to natural changes in seepage, as well as to massive hydrocarbon input, for example, as encountered during anthropogenic oil spills.

  11. Diverse sulfate-reducing bacteria of the Desulfosarcina/Desulfococcus clade are the key alkane degraders at marine seeps

    PubMed Central

    Kleindienst, Sara; Herbst, Florian-Alexander; Stagars, Marion; von Netzer, Frederick; von Bergen, Martin; Seifert, Jana; Peplies, Jörg; Amann, Rudolf; Musat, Florin; Lueders, Tillmann; Knittel, Katrin

    2014-01-01

    Biogeochemical and microbiological data indicate that the anaerobic oxidation of non-methane hydrocarbons by sulfate-reducing bacteria (SRB) has an important role in carbon and sulfur cycling at marine seeps. Yet, little is known about the bacterial hydrocarbon degraders active in situ. Here, we provide the link between previous biogeochemical measurements and the cultivation of degraders by direct identification of SRB responsible for butane and dodecane degradation in complex on-site microbiota. Two contrasting seep sediments from Mediterranean Amon mud volcano and Guaymas Basin (Gulf of California) were incubated with 13C-labeled butane or dodecane under sulfate-reducing conditions and analyzed via complementary stable isotope probing (SIP) techniques. Using DNA- and rRNA-SIP, we identified four specialized clades of alkane oxidizers within Desulfobacteraceae to be distinctively active in oxidation of short- and long-chain alkanes. All clades belong to the Desulfosarcina/Desulfococcus (DSS) clade, substantiating the crucial role of these bacteria in anaerobic hydrocarbon degradation at marine seeps. The identification of key enzymes of anaerobic alkane degradation, subsequent β-oxidation and the reverse Wood–Ljungdahl pathway for complete substrate oxidation by protein-SIP further corroborated the importance of the DSS clade and indicated that biochemical pathways, analog to those discovered in the laboratory, are of great relevance for natural settings. The high diversity within identified subclades together with their capability to initiate alkane degradation and growth within days to weeks after substrate amendment suggest an overlooked potential of marine benthic microbiota to react to natural changes in seepage, as well as to massive hydrocarbon input, for example, as encountered during anthropogenic oil spills. PMID:24722631

  12. Effects of solvent density on retention in gas-liquid chromatography. I. Alkanes solutes in polyethylene glycol stationary phases.

    PubMed

    González, F R; Pérez-Parajón, J; García-Domínguez, J A

    2002-04-12

    Gas-liquid chromatographic columns were prepared coating silica capillaries with poly(oxyethylene) polymers of different molecular mass distributions, in the range of low number-average molar masses, where the density still varies significantly. A novel, high-temperature, rapid evaporation method was developed and applied to the static coating of the low-molecular-mass stationary phases. The analysis of alkanes retention data from these columns reveals that the dependence of the partition coefficient with the solvent macroscopic density is mainly due to a variation of entropy. Enthalpies of solute transfer contribute poorly to the observed variations of retention. Since the alkanes solubility diminishes with the increasing solvent density, and this variation is weakly dependent with temperature, it is concluded that the decrease of free-volume in the liquid is responsible for this behavior.

  13. POSSIBLE LATE MIDDLE ORDOVICIAN ORGANIC CARBON ISOTOPE EXCURSION: EVIDENCE FROM ORDOVICIAN OILS AND HYDROCARBON SOURCE ROCKS, MID-CONTINENT AND EAST-CENTRAL UNITED STATES.

    USGS Publications Warehouse

    Hatch, Joseph R.; Jacobson, Stephen R.; Witzke, Brian J.; Risatti, J. Bruno; Anders, Donald E.; Watney, W. Lynn; Newell, K. David; Vuletich, April K.

    1987-01-01

    Oils generated by Middle Ordovician rocks are found throughout the Mid-Continent and east-central regions of the United States. Gas chromatographic characteristics of these oils include a relatively high abundance of n-alkanes with carbon numbers less than 20, a strong predominance of odd-numbered n-alkanes between C//1//0 and C//2//0, and relatively small amounts of branched and cyclic alkanes. The wide ranges in delta **1**3C for oils and rock extracts reflect a major, positive excursion(s) in organic matter delta **1**3C in late Middle Ordovician rocks. This excursion has at least regional significance in that it can be documented in sections 480 mi apart in south-central Kansas and eastern Iowa. The distance may be as much as 930 mi. The parallel shifts in organic and carbonate delta **1**3C in core samples from 1 E. M. Greene well, Washington County, Iowa, imply changes in the isotope composition of the ocean-atmosphere carbon reservoir. These and other aspects of the subject are discussed.

  14. A Process for Microbial Hydrocarbon Synthesis: Overproduction of Fatty Acids in Escherichia coli and Catalytic Conversion to Alkanes

    PubMed Central

    Lennen, Rebecca M.; Braden, Drew J.; West, Ryan M.; Dumesic, James A.; Pfleger, Brian F.

    2013-01-01

    The development of renewable alternatives to diesel and jet fuels is highly desirable for the heavy transportation sector, and would offer benefits over the production and use of short-chain alcohols for personal transportation. Here, we report the development of a metabolically engineered strain of Escherichia coli that overproduces medium-chain length fatty acids via three basic modifications: elimination of β-oxidation, overexpression of the four subunits of acetyl-CoA carboxylase, and expression of a plant acyl–acyl carrier protein (ACP) thioesterase from Umbellularia californica (BTE). The expression level of BTE was optimized by comparing fatty acid production from strains harboring BTE on plasmids with four different copy numbers. Expression of BTE from low copy number plasmids resulted in the highest fatty acid production. Up to a seven-fold increase in total fatty acid production was observed in engineered strains over a negative control strain (lacking β-oxidation), with a composition dominated by C12 and C14 saturated and unsaturated fatty acids. Next, a strategy for producing undecane via a combination of biotechnology and heterogeneous catalysis is demonstrated. Fatty acids were extracted from a culture of an overproducing strain into an alkane phase and fed to a Pd/C plug flow reactor, where the extracted fatty acids were decarboxylated into saturated alkanes. The result is an enriched alkane stream that can be recycled for continuous extractions. Complete conversion of C12 fatty acids extracted from culture to alkanes has been demonstrated yielding a concentration of 0.44 g L−1 (culture volume) undecane. PMID:20073090

  15. Impacts of Conformational Geometries in Fluorinated Alkanes.

    PubMed

    Brandenburg, Tim; Golnak, Ronny; Nagasaka, Masanari; Atak, Kaan; Sreekantan Nair Lalithambika, Sreeju; Kosugi, Nobuhiro; Aziz, Emad F

    2016-01-01

    Research of blood substitute formulations and their base materials is of high scientific interest. Especially fluorinated microemulsions based on perfluorocarbons, with their interesting chemical properties, offer opportunities for applications in biomedicine and physical chemistry. In this work, carbon K-edge absorption spectra of liquid perfluoroalkanes and their parent hydrocarbons are presented and compared. Based on soft X-ray absorption, a comprehensive picture of the electronic structure is provided with the aid of time dependent density functional theory. We have observed that conformational geometries mainly influence the chemical and electronic interactions in the presented liquid materials, leading to a direct association of conformational geometries to the dissolving capacity of the presented perfluorocarbons with other solvents like water and possibly gases like oxygen. PMID:27527753

  16. Impacts of Conformational Geometries in Fluorinated Alkanes

    PubMed Central

    Brandenburg, Tim; Golnak, Ronny; Nagasaka, Masanari; Atak, Kaan; Sreekantan Nair Lalithambika, Sreeju; Kosugi, Nobuhiro; Aziz, Emad F.

    2016-01-01

    Research of blood substitute formulations and their base materials is of high scientific interest. Especially fluorinated microemulsions based on perfluorocarbons, with their interesting chemical properties, offer opportunities for applications in biomedicine and physical chemistry. In this work, carbon K-edge absorption spectra of liquid perfluoroalkanes and their parent hydrocarbons are presented and compared. Based on soft X-ray absorption, a comprehensive picture of the electronic structure is provided with the aid of time dependent density functional theory. We have observed that conformational geometries mainly influence the chemical and electronic interactions in the presented liquid materials, leading to a direct association of conformational geometries to the dissolving capacity of the presented perfluorocarbons with other solvents like water and possibly gases like oxygen. PMID:27527753

  17. Impacts of Conformational Geometries in Fluorinated Alkanes

    NASA Astrophysics Data System (ADS)

    Brandenburg, Tim; Golnak, Ronny; Nagasaka, Masanari; Atak, Kaan; Sreekantan Nair Lalithambika, Sreeju; Kosugi, Nobuhiro; Aziz, Emad F.

    2016-08-01

    Research of blood substitute formulations and their base materials is of high scientific interest. Especially fluorinated microemulsions based on perfluorocarbons, with their interesting chemical properties, offer opportunities for applications in biomedicine and physical chemistry. In this work, carbon K-edge absorption spectra of liquid perfluoroalkanes and their parent hydrocarbons are presented and compared. Based on soft X-ray absorption, a comprehensive picture of the electronic structure is provided with the aid of time dependent density functional theory. We have observed that conformational geometries mainly influence the chemical and electronic interactions in the presented liquid materials, leading to a direct association of conformational geometries to the dissolving capacity of the presented perfluorocarbons with other solvents like water and possibly gases like oxygen.

  18. Comparative study of normal and branched alkane monolayer films adsorbed on a solid surface. II. Dynamics

    NASA Astrophysics Data System (ADS)

    Enevoldsen, A. D.; Hansen, F. Y.; Diama, A.; Taub, H.; Dimeo, R. M.; Neumann, D. A.; Copley, J. R. D.

    2007-03-01

    The dynamics of monolayer films of the n-alkane tetracosane (n-C24H52) and the branched alkane squalane (C30H62) adsorbed on graphite have been studied by quasielastic and inelastic neutron scattering and molecular dynamics (MD) simulations. Both molecules have 24 carbon atoms along their carbon backbone, and squalane has an additional six methyl side groups symmetrically placed along its length. The authors' principal objective has been to determine the influence of the side groups on the dynamics of the squalane monolayer and thereby assess its potential as a nanoscale lubricant. To investigate the dynamics of these monolayers they used both the disk chopper spectrometer (DCS) and the high flux backscattering spectrometer (HFBS) at the National Institute of Standards and Technology. These instruments made it possible to study dynamical processes such as molecular diffusive motions and vibrations on very different time scales: 1-40ps (DCS) and 0.1-4ns (HFBS). The MD simulations were done on corresponding time scales and were used to interpret the neutron spectra. The authors found that the dynamics of the two monolayers are qualitatively similar on the respective time scales and that there are only small quantitative differences that can be understood in terms of the different masses and moments of inertia of the two molecules. In the course of this study, the authors developed a procedure to separate out the low-frequency vibrational modes in the spectra, thereby facilitating an analysis of the quasielastic scattering. They conclude that there are no major differences in the monolayer dynamics caused by intramolecular branching. It remains to be seen whether this similarity in monolayer dynamics also holds for the lubricating properties of these molecules in confined geometries.

  19. Quantifying sources of methane using light alkanes in the Los Angeles basin, California

    NASA Astrophysics Data System (ADS)

    Peischl, J.; Ryerson, T. B.; Brioude, J.; Aikin, K. C.; Andrews, A. E.; Atlas, E.; Blake, D.; Daube, B. C.; Gouw, J. A.; Dlugokencky, E.; Frost, G. J.; Gentner, D. R.; Gilman, J. B.; Goldstein, A. H.; Harley, R. A.; Holloway, J. S.; Kofler, J.; Kuster, W. C.; Lang, P. M.; Novelli, P. C.; Santoni, G. W.; Trainer, M.; Wofsy, S. C.; Parrish, D. D.

    2013-05-01

    Methane (CH4), carbon dioxide (CO2), carbon monoxide (CO), and C2-C5 alkanes were measured throughout the Los Angeles (L.A.) basin in May and June 2010. We use these data to show that the emission ratios of CH4/CO and CH4/CO2 in the L.A. basin are larger than expected from population-apportioned bottom-up state inventories, consistent with previously published work. We use experimentally determined CH4/CO and CH4/CO2 emission ratios in combination with annual State of California CO and CO2 inventories to derive a yearly emission rate of CH4 to the L.A. basin. We further use the airborne measurements to directly derive CH4 emission rates from dairy operations in Chino, and from the two largest landfills in the L.A. basin, and show these sources are accurately represented in the California Air Resources Board greenhouse gas inventory for CH4. We then use measurements of C2-C5 alkanes to quantify the relative contribution of other CH4 sources in the L.A. basin, with results differing from those of previous studies. The atmospheric data are consistent with the majority of CH4 emissions in the region coming from fugitive losses from natural gas in pipelines and urban distribution systems and/or geologic seeps, as well as landfills and dairies. The local oil and gas industry also provides a significant source of CH4 in the area. The addition of CH4 emissions from natural gas pipelines and urban distribution systems and/or geologic seeps and from the local oil and gas industry is sufficient to account for the differences between the top-down and bottom-up CH4 inventories identified in previously published work.

  20. Controlling Morphology and Molecular Packing of Alkane Substituted Phthalocyanine Blend Bulk Heterojunction Solar Cells†

    PubMed Central

    Jurow, Matthew J.; Hageman, Brian A.; Nam, Chang-Yong; Pabon, Cesar; Black, Charles T.

    2013-01-01

    Systematic changes in the exocyclic substiution of core phthalocyanine platform tune the absorption properties to yield commercially viable dyes that function as the primary light absorbers in organic bulk heterojunction solar cells. Blends of these complementary phthalocyanines absorb a broader portion of the solar spectrum compared to a single dye, thereby increasing solar cell performance. We correlate grazing incidence small angle x-ray scattering structural data with solar cell performance to elucidate the role of nanomorphology of active layers composed of blends of phthalocyanines and a fullerene derivative. A highly reproducible device architecture is used to assure accuracy and is relevant to films for solar windows in urban settings. We demonstrate that the number and structure of the exocyclic motifs dictate phase formation, hierarchical organization, and nanostructure, thus can be employed to tailor active layer morphology to enhance exciton dissociation and charge collection efficiencies in the photovoltaic devices. These studies reveal that disordered films make better solar cells, short alkanes increase the optical density of the active layer, and branched alkanes inhibit unproductive homogeneous molecular alignment. PMID:23589766

  1. A unified single-event microkinetic model for alkane hydroconversion in different aggregation states on Pt/H-USY-zeolites.

    PubMed

    Laxmi Narasimhan, C S; Thybaut, Joris W; Martens, Johan A; Jacobs, Pierre A; Denayer, Joeri F; Marin, Guy B

    2006-04-01

    A single-event microkinetic model for the catalytic hydroconversion of hydrocarbons on Pt/H-US-Y bifunctional zeolite catalysts developed for low-pressure vapor phase conditions was extended to cover high-pressure vapor phase and liquid phase conditions. The effect of the density of the bulk hydrocarbon phase on the physisorption as well as on the protonation steps of the reaction network was accounted for explicitly and can be interpreted in terms of "compression" of the hydrocarbon sorbate inside the zeolite pores and "solvation" of the catalyst framework by the dense bulk hydrocarbon phase. The bulk phase density effect on the physisorbed state is described via a single excess free enthalpy of physisorption. A dense bulk hydrocarbon phase destabilizes the sorbate molecules inside the catalyst pores. An expression of the excess free enthalpy of physisorption involving the fugacity coefficient and a zeolite dependent factor allows description of physisorption data. Typical excess free enthalpy values are in the range 1.5-5.1 kJ mol(-1) increasing with carbon number in the series of C5-C16 alkanes. At high-pressure vapor phase and liquid phase conditions, the excess standard protonation enthalpy is estimated at -7.8 kJ mol(-1) leading to relatively more stable carbenium ions at dense bulk phase conditions. As a result of the excess physisorption and protonation properties, the lightest hydrocarbons in mixtures are more competitive at dense phase conditions and their conversion is enhanced compared to low-density conditions. PMID:16570981

  2. Flash Points of Secondary Alcohol and n-Alkane Mixtures.

    PubMed

    Esina, Zoya N; Miroshnikov, Alexander M; Korchuganova, Margarita R

    2015-11-19

    The flash point is one of the most important characteristics used to assess the ignition hazard of mixtures of flammable liquids. To determine the flash points of mixtures of secondary alcohols with n-alkanes, it is necessary to calculate the activity coefficients. In this paper, we use a model that allows us to obtain enthalpy of fusion and enthalpy of vaporization data of the pure components to calculate the liquid-solid equilibrium (LSE) and vapor-liquid equilibrium (VLE). Enthalpy of fusion and enthalpy of vaporization data of secondary alcohols in the literature are limited; thus, the prediction of these characteristics was performed using the method of thermodynamic similarity. Additionally, the empirical models provided the critical temperatures and boiling temperatures of the secondary alcohols. The modeled melting enthalpy and enthalpy of vaporization as well as the calculated LSE and VLE flash points were determined for the secondary alcohol and n-alkane mixtures. PMID:26491811

  3. Influence of high biomass concentrations on alkane solubilities.

    PubMed

    Davison, B H; Barton, J W; Klasson, K T; Francisco, A B

    2000-05-01

    Alkane solubilities were measured experimentally for high-density biomass. The resulting Henry's law constants for propane were found to decrease significantly for both dense yeast suspensions and an actual propane-degrading biofilm consortium. At the biomass densities of a typical biofilm, propane solubility was about an order of magnitude greater than that in pure water. For example, a dense biofilm had a propane Henry's law constant of 0.09+/-0.04 atm m(3) mol(-1) compared to 0.6+/-0.1 atm m(3) mol(-1) measured in pure water. The results were modeled with mixing rules and compared with octanol-water mixtures. Hydrogels (agar) and salts decreased the alkane solubility. By considering a theoretical solubility of propane in dry biomass, estimates were made of intrinsic Henry's law constants for propane in pure yeast and biomass, which were 13+/-2 and 5+/-2 atm kg biomass mol(-1) for yeast and biofilm consortium, respectively.

  4. Site isolation in vanadium phosphorus oxide alkane oxidation

    SciTech Connect

    Thompson, M R; Ebner, J R

    1991-06-01

    Single crystal X-ray diffraction studies of vanadyl pyrophosphate indicate that at least two polytypical structures exists for this active and selective alkane oxidation catalyst. The crystal structures of these materials differ with respect to the symmetry and direction of columns of vanadyl groups within the unit cell. Single crystals of vanadyl pyrophosphate have been generated at extreme temperatures not often experienced by microcrystalline catalysts. The crystallography of the system suggests that other crystalline modifications or disordered phases might also exist. Zeroth-order models of crystal surface termination of vanadyl pyrophosphate have been constructed which conceptually illustrate the ability of vanadyl pyrophosphate to accommodate varying amounts of surface phosphorus parallel to (1,0,0), (0,1,0) and (0,2,4). Pyrophosphate termination of surfaces parallel to (1,0,0) likely results in the isolation of clusters of reactive centers and limits overoxidation of the alkane substrate. 23 refs., 6 figs.

  5. Multi-stage conversion of alkanes to gasoline

    SciTech Connect

    Harandi, M.N.; Owen, H.

    1991-09-17

    This patent describes improvement in a facility for converting alkanes into gasoline, the facility including a fluid catalytic cracking system and an olefin oligomerization reactor. The improvement comprises: a first valved conduit means for withdrawing a controlled stream of the regenerated catalyst from the first regenerator means; a dehydrogenation reactor in valved communication with the first regenerator means, through the first valved conduit means the dehydrogenation reactor having a dehydrogenation zone at a temperature below those prevailing in the first regeneration zone, the dehydrogenation reactor being located externally relative to the fluid catalytic cracker reactor and first regenerator; means for introducing a lower alkane feedstream into the dehydrogenation zone in an amount sufficient to maintain hot withdrawn catalyst in a state of fluidization in the dehydrogenation reactor while the catalyst is being cooled therein; a second valved conduit means for transporting cooled catalyst from the dehydrogenation zone to the first regeneration zone.

  6. Monitoring the alkane monooxygenase gene alkB in different soil interfaces during plant litter degradation of C3 and C4 plants

    NASA Astrophysics Data System (ADS)

    Schulz, S.; Munch, J. C.; Schloter, M.

    2009-04-01

    Hydrocarbons like n-alkanes are ubiquitous in the environment as a result of anthropogenic contamination (e.g. oil spills) as well as a part of an ecosystem's biomass. For example n-alkanes become released during plant litter degradation; consequently they become a high abundant carbon source for microorganism. One possibility for the prokaryotic hydrocarbon metabolisation is an aerobic degradation pathway where the initial step is catalysed by the membrane bound alkane monooxygenase alkB. We analysed the influence of alkanes on the abundance of the alkB gene in different interfaces of the litter-soil system during the degradation of maize and pea litter. Therefore soil samples of a sandy and a loamy soil have been incubated with straw of maize and pea plants up to 30 weeks with constant soil moisture and temperature. Using quantitative real-time PCR we were able to monitor the changes of the abundance and the expression rates of alkB. In our experiments we focused on the straw layer, the litter/soil interface and the soil 1 cm below this interface (bulk soil). Our results clearly demonstrate time and space dependent abundance patterns of alkB genes and transcripts in the different layers studied, which are additionally shaped by the soil type used.

  7. At what chain length do unbranched alkanes prefer folded conformations?

    PubMed

    Byrd, Jason N; Bartlett, Rodney J; Montgomery, John A

    2014-03-01

    Short unbranched alkanes are known to prefer linear conformations, whereas long unbranched alkanes are folded. It is not known with certainty at what chain length the linear conformation is no longer the global minimum. To clarify this point, we use ab initio and density functional methods to compute the relative energies of the linear and hairpin alkane conformers for increasing chain lengths. Extensive electronic structure calculations are performed to obtain optimized geometries, harmonic frequencies, and accurate single point energies for the selected alkane conformers from octane through octadecane. Benchmark CCSD(T)/cc-pVTZ single point calculations are performed for chains through tetradecane, whereas approximate methods are required for the longer chains up to octadecane. Using frozen natural orbitals to unambiguously truncate the virtual orbital space, we are able to compute composite CCSD FNO(T) single point energies for all the chain lengths. This approximate composite method has significant computational savings compared to full CCSD(T) while retaining ∼0.15 kcal/mol accuracy compared to the benchmark results. More approximate dual-basis resolution-of-the-identity double-hybrid DFT calculations are also performed and shown to have reasonable 0.2-0.4 kcal/mol errors compared with our benchmark values. After including contributions from temperature dependent internal energy shifts, we find the preference for folded conformations to lie between hexadecane and octadecane, in excellent agreement with recent experiments [ Lüttschwager , N. O. ; Wassermann , T. N. ; Mata , R. A. ; Suhm , M. A. Angew. Chem. Int. Ed. 2013 , 52 , 463 ]. PMID:24524689

  8. CRADA Final Report for CRADA Number NFE-10-02991 "Development and Commercialization of Alternative Carbon Precursors and Conversion Technologies"

    SciTech Connect

    Norris, Rober; Paulauskas, Felix; Naskar, Amit; Kaufman, Michael; Yarborough, Ken; Derstine, Chris

    2013-10-01

    The overall objective of the collaborative research performed by the Oak Ridge National Laboratory (ORNL) and the Dow Chemical Company under this Cooperative Research And Development Agreement (CRADA NFE-10-02991) was to develop and establish pathways to commercialize new carbon fiber precursor and conversion technology. This technology is to produce alternative polymer fiber precursor formulations as well as scaled energy-efficient advanced conversion technology to enable continuous mode conversion to obtain carbonized fibers that are technically and economically viable in industrial markets such as transportation, wind energy, infrastructure and oil drilling applications. There have been efforts in the past to produce a low cost carbon fiber. These attempts have to be interpreted against the backdrop of the market needs at the time, which were strictly military aircraft and high-end aerospace components. In fact, manufacturing costs have been reduced from those days to current practice, where both process optimization and volume production have enabled carbon fiber to become available at prices below $20/lb. However, the requirements of the lucrative aerospace market limits further price reductions from current practice. This approach is different because specific industrial applications are targeted, most specifically wind turbine blade and light vehicle transportation, where aircraft grade carbon fiber is not required. As a result, researchers are free to adjust both manufacturing process and precursor chemistry to meet the relaxed physical specifications at a lower cost. This report documents the approach and findings of this cooperative research in alternative precursors and advanced conversion for production of cost-effective carbon fiber for energy missions. Due to export control, proprietary restrictions, and CRADA protected data considerations, specific design details and processing parameters are not included in this report.

  9. Inhibition of firefly luciferase by alkane analogues.

    PubMed

    Takehara, Kô; Kamaya, Hiroshi; Ueda, Issaku

    2005-01-18

    We reported that anesthetics increased the partial molal volume of firefly luciferase (FFL), while long-chain fatty acids (LCFA) decreased it. The present study measured the actions of dodecanol (neutral), dodecanoic acid (negatively charged), and dodecylamine (positively charged) hydrophobic molecules on FFL. The interaction modes are measured by (1) ATP-induced bioluminescence of FFL and (2) fluorescence of 2-(p-toluidino)naphthalene-6-sulfonate (TNS). TNS fluoresces brightly in hydrophobic media. It competes with the substrate luciferin on the FFL binding. From the Scatchard plot of TNS titration, the maximum binding number of TNS was 0.83, and its binding constant was 8.27 x 10(5) M(-1). Job's plot also showed that the binding number is 0.89. From the TNS titration of FFL, the binding constant was estimated to be 8.8 x 10(5) M(-1). Dodecanoic acid quenched the TNS fluorescence entirely. Dodecanol quenched about 25% of the fluorescence, whereas dodecylamine increased it. By comparing the fluorescence of TNS and bioluminescence of FFL, the binding modes and the inhibition mechanisms of these dodecane analogues are classified in three different modes: competitive (dodecanoic acid), noncompetitive (dodecylamine), and mixed (dodecanol).

  10. Hydrogenotrophic denitrification process efficiency and the number of denitrifying bacteria (MPN) in the sequencing batch biofilm reactor (SBBR) with platinum and carbon anodes.

    PubMed

    Kłodowska, Izabella; Rodziewicz, Joanna; Janczukowicz, Wojciech; Gotkowska-Płachta, Anna; Cydzik-Kwiatkowska, Agnieszka

    2016-01-01

    This work reports on the effect of electric current density and anode material (platinum, carbon) on the concentration of oxidized and mineral forms of nitrogen, on physical parameters (pH, redox potential, electrical conductivity) and the number of denitrifying bacteria in the biofilm (MPN). Experiments were conducted under anaerobic conditions without and with the flow of electric current (with density of 79 mA · m(-2) and 132 mA · m(-2)). Results obtained in the study enabled concluding that increasing density of electric current caused a decreasing concentration of nitrate in the reactor with platinum anode (R1) and carbon anode (R2). Its concentration depended on anode material. The highest hydrogenotrophic denitrification efficiency was achieved in R2 in which the process was aided by inorganic carbon (CO2) that originated from carbon anode oxidation and the electrical conductivity of wastewater increased as a result of the presence of HCO3(-) and CO3(2-) ions. Strong oxidizing properties of the platinum anode (R1) prevented the accumulation of adverse forms of nitrogen, including nitrite and ammonia. The increase in electric current density affected also a lower number of denitrifying bacteria (MPN) in the biofilm in both reactors (R1 and R2). Metal oxides accumulated on the surface of the cathode had a toxic effect upon microorganisms and impaired the production of a hydrogen donor.

  11. Hydrogenotrophic denitrification process efficiency and the number of denitrifying bacteria (MPN) in the sequencing batch biofilm reactor (SBBR) with platinum and carbon anodes.

    PubMed

    Kłodowska, Izabella; Rodziewicz, Joanna; Janczukowicz, Wojciech; Gotkowska-Płachta, Anna; Cydzik-Kwiatkowska, Agnieszka

    2016-01-01

    This work reports on the effect of electric current density and anode material (platinum, carbon) on the concentration of oxidized and mineral forms of nitrogen, on physical parameters (pH, redox potential, electrical conductivity) and the number of denitrifying bacteria in the biofilm (MPN). Experiments were conducted under anaerobic conditions without and with the flow of electric current (with density of 79 mA · m(-2) and 132 mA · m(-2)). Results obtained in the study enabled concluding that increasing density of electric current caused a decreasing concentration of nitrate in the reactor with platinum anode (R1) and carbon anode (R2). Its concentration depended on anode material. The highest hydrogenotrophic denitrification efficiency was achieved in R2 in which the process was aided by inorganic carbon (CO2) that originated from carbon anode oxidation and the electrical conductivity of wastewater increased as a result of the presence of HCO3(-) and CO3(2-) ions. Strong oxidizing properties of the platinum anode (R1) prevented the accumulation of adverse forms of nitrogen, including nitrite and ammonia. The increase in electric current density affected also a lower number of denitrifying bacteria (MPN) in the biofilm in both reactors (R1 and R2). Metal oxides accumulated on the surface of the cathode had a toxic effect upon microorganisms and impaired the production of a hydrogen donor. PMID:26809836

  12. Short-chain alkane cycling in deep Gulf of Mexico cold-seep sediments

    NASA Astrophysics Data System (ADS)

    Sibert, R.; Joye, S. B.; Hunter, K.

    2015-12-01

    Mixtures of light hydrocarbon gases are common in deep Gulf of Mexico cold-seep sediments, and are typically dissolved in pore fluids, adsorbed to sediment particles, trapped in methane ice, or as free gas. The dominant component in these natural gas mixtures is usually methane (>80% C1), but ethane (C2) and propane (C3) are nearly always present in trace amounts (<1% total). The processes that control the concentration and isotopic signature of these gases in sediments are well explained for methane, but the controls for C2/C3 cycling are still a relative mystery. Methane production proceeds in deep anoxic sediments by either 1) thermocatalytic cracking of fossil organic matter, or 2) as a direct product of microbial metabolism, i.e. methanogenesis. In surface sediments, it appears that both microbial consumption and chemical deposition of methane (i.e. as methane clathrate) ensures that >95% of the methane produced at depth never reaches the water column. Production of C1 and C2 in deep-sea sediments has been historically attributed only to thermocatalytic processes, though limited data suggests production of C2/C3 compounds through the activity of archaea at depth. Furthermore, carbon isotopic data on ethane and propane from deep cores of Gulf of Mexico sediments suggest alkanogenesis at >3 m depth in the sediment column and alkane oxidation in uppermost oxidant-rich sediments. Additional studies have also isolated microorganisms capable of oxidizing ethane and propane in the laboratory, but field studies of microbial-driven dynamics of C2/C3 gases in cold-seep sediments are rare. Here, we present the results of a series of incubation experiments using sediment slurries culled from surface sediments from one of the most prolific natural oil and gas seeps in the Gulf of Mexico. Rates of alkane oxidation were measured under a variety of conditions to assess the surface-driven microbial controls on C2/C3 cycling in cold-seep environments. Such microbial processes

  13. Contact forces at the sliding interface: Mixed versus pure model alkane monolayers

    NASA Astrophysics Data System (ADS)

    Mikulski, Paul T.; Gao, Guangtu; Chateauneuf, Ginger M.; Harrison, Judith A.

    2005-01-01

    Classical molecular dynamics simulations of an amorphous carbon tip sliding against monolayers of n-alkane chains are presented. The tribological behavior of tightly packed, pure monolayers composed of chains containing 14 carbon atoms is compared to mixed monolayers that randomly combine equal amounts of 12- and 16-carbon-atom chains. When sliding in the direction of chain cant under repulsive (positive) loads, pure monolayers consistently show lower friction than mixed monolayers. The distribution of contact forces between individual monolayer chain groups and the tip shows pure and mixed monolayers resist tip motion similarly. In contrast, the contact forces "pushing" the tip along differ in the two monolayers. The pure monolayers exhibit a high level of symmetry between resisting and pushing forces which results in a lower net friction. Both systems exhibit a marked friction anisotropy. The contact force distribution changes dramatically as a result of the change in sliding direction, resulting in an increase in friction. Upon continued sliding in the direction perpendicular to chain cant, both types of monolayers are often capable of transitioning to a state where the chains are primarily oriented with the cant along the sliding direction. A large change in the distribution of contact forces and a reduction in friction accompany this transition.

  14. Abiogenic formation of alkanes in the Earth's crust as a minor source for global hydrocarbon reservoirs.

    PubMed

    Sherwood Lollar, B; Westgate, T D; Ward, J A; Slater, G F; Lacrampe-Couloume, G

    2002-04-01

    Natural hydrocarbons are largely formed by the thermal decomposition of organic matter (thermogenesis) or by microbial processes (bacteriogenesis). But the discovery of methane at an East Pacific Rise hydrothermal vent and in other crustal fluids supports the occurrence of an abiogenic source of hydrocarbons. These abiogenic hydrocarbons are generally formed by the reduction of carbon dioxide, a process which is thought to occur during magma cooling and-more commonly-in hydrothermal systems during water-rock interactions, for example involving Fischer-Tropsch reactions and the serpentinization of ultramafic rocks. Suggestions that abiogenic hydrocarbons make a significant contribution to economic hydrocarbon reservoirs have been difficult to resolve, in part owing to uncertainty in the carbon isotopic signatures for abiogenic versus thermogenic hydrocarbons. Here, using carbon and hydrogen isotope analyses of abiogenic methane and higher hydrocarbons in crystalline rocks of the Canadian shield, we show a clear distinction between abiogenic and thermogenic hydrocarbons. The progressive isotopic trends for the series of C1-C4 alkanes indicate that hydrocarbon formation occurs by way of polymerization of methane precursors. Given that these trends are not observed in the isotopic signatures of economic gas reservoirs, we can now rule out the presence of a globally significant abiogenic source of hydrocarbons. PMID:11932741

  15. Laboratory spectroscopic analyses of electron irradiated alkanes and alkenes in solar system ices

    NASA Astrophysics Data System (ADS)

    Hand, K. P.; Carlson, R. W.

    2012-03-01

    We report results from laboratory experiments of 10 keV electron irradiation of thin ice films of water and short-chain hydrocarbons at ˜10-8 Torr and temperatures ranging from 70-100 K. Hydrocarbon mixtures include water with C3H8, C3H6, C4H10 (butane and isobutane), and C4H8, (1-butene and cis/trans-2-butene). The double bonds of the alkenes in our initial mixtures were rapidly destroyed or converted to single carbon bonds, covalent bonds with hydrogen, bonds with -OH (hydroxyl), bonds with oxygen (C-O), or double bonds with oxygen (carbonyl). Spectra resulting from irradiation of alkane and alkene ices are largely indistinguishable; the initial differences in film composition are destroyed and the resulting mixture includes long-chain, branched aliphatics, aldehydes, ketones, esters, and alcohols. Methane was observed as a product during radiolysis but CO was largely absent. We find that while some of the carbon is oxidized and lost to CO2 formation, some carbon is sequestered into highly refractory, long-chain aliphatic compounds that remain as a thin residue even after the ice film has been raised to standard temperature and pressure. We conclude that the high availability of hydrogen in our experiments leads to the formation of the formyl radical which then serves as the precursor for formaldehyde and polymerization of longer hydrocarbon chains.

  16. Abiogenic formation of alkanes in the Earth's crust as a minor source for global hydrocarbon reservoirs.

    PubMed

    Sherwood Lollar, B; Westgate, T D; Ward, J A; Slater, G F; Lacrampe-Couloume, G

    2002-04-01

    Natural hydrocarbons are largely formed by the thermal decomposition of organic matter (thermogenesis) or by microbial processes (bacteriogenesis). But the discovery of methane at an East Pacific Rise hydrothermal vent and in other crustal fluids supports the occurrence of an abiogenic source of hydrocarbons. These abiogenic hydrocarbons are generally formed by the reduction of carbon dioxide, a process which is thought to occur during magma cooling and-more commonly-in hydrothermal systems during water-rock interactions, for example involving Fischer-Tropsch reactions and the serpentinization of ultramafic rocks. Suggestions that abiogenic hydrocarbons make a significant contribution to economic hydrocarbon reservoirs have been difficult to resolve, in part owing to uncertainty in the carbon isotopic signatures for abiogenic versus thermogenic hydrocarbons. Here, using carbon and hydrogen isotope analyses of abiogenic methane and higher hydrocarbons in crystalline rocks of the Canadian shield, we show a clear distinction between abiogenic and thermogenic hydrocarbons. The progressive isotopic trends for the series of C1-C4 alkanes indicate that hydrocarbon formation occurs by way of polymerization of methane precursors. Given that these trends are not observed in the isotopic signatures of economic gas reservoirs, we can now rule out the presence of a globally significant abiogenic source of hydrocarbons.

  17. Draft Genome Sequence of Gordonia sihwensis Strain 9, a Branched Alkane-Degrading Bacterium

    PubMed Central

    Brown, Lisa M.; Gunasekera, Thusitha S.; Striebich, Richard C.

    2016-01-01

    Gordonia sihwensis strain 9 is a Gram-positive bacterium capable of efficient aerobic degradation of branched and normal alkanes. The draft genome of G. sihwensis S9 is 4.16 Mb in size, with 3,686 coding sequences and 68.1% G+C content. Alkane monooxygenase and P-450 cytochrome genes required for alkane degradation are predicted in G. sihwensis S9. PMID:27340079

  18. Fundamental Flame Velocities of Pure Hydrocarbons I : Alkanes, Alkenes, Alkynes Benzene, and Cyclohexane

    NASA Technical Reports Server (NTRS)

    Gerstein, Melvin; Levine, Oscar; Wong, Edgar L

    1950-01-01

    The flame velocities of 37 pure hydrocarbons including normal and branched alkanes, alkenes, and alkynes; as well as benzene and cyclohexane, together with the experimental technique employed are presented. The normal alkanes have about the same flame velocity from ethane through heptane with methane being about 16 percent lower. Unsaturation increases the flame velocity in the order of alkanes, alkenes, and alkynes. Branching reduces the flame velocity.

  19. Comparative study of normal and branched alkane monolayer films adsorbed on a solid surface. I. Structure

    NASA Astrophysics Data System (ADS)

    Enevoldsen, A. D.; Hansen, F. Y.; Diama, A.; Criswell, L.; Taub, H.

    2007-03-01

    The structure of a monolayer film of the branched alkane squalane (C30H62) adsorbed on graphite has been studied by neutron diffraction and molecular dynamics (MD) simulations and compared with a similar study of the n-alkane tetracosane (n-C24H52). Both molecules have 24 carbon atoms along their backbone and squalane has, in addition, six methyl side groups. Upon adsorption, there are significant differences as well as similarities in the behavior of these molecular films. Both molecules form ordered structures at low temperatures; however, while the melting point of the two-dimensional (2D) tetracosane film is roughly the same as the bulk melting point, the surface strongly stabilizes the 2D squalane film such that its melting point is 91K above its value in bulk. Therefore, squalane, like tetracosane, will be a poor lubricant in those nanoscale devices that require a fluid lubricant at room temperature. The neutron diffraction data show that the translational order in the squalane monolayer is significantly less than in the tetracosane monolayer. The authors' MD simulations suggest that this is caused by a distortion of the squalane molecules upon adsorption on the graphite surface. When the molecules are allowed to relax on the surface, they distort such that all six methyl groups point away from the surface. This results in a reduction in the monolayer's translational order characterized by a decrease in its coherence length and hence a broadening of the diffraction peaks. The MD simulations also show that the melting mechanism in the squalane monolayer is the same footprint reduction mechanism found in the tetracosane monolayer, where a chain melting drives the lattice melting.

  20. Comparative study of normal and branched alkane monolayer films adsorbed on a solid surface. I. Structure.

    PubMed

    Enevoldsen, A D; Hansen, F Y; Diama, A; Criswell, L; Taub, H

    2007-03-14

    The structure of a monolayer film of the branched alkane squalane (C30H62) adsorbed on graphite has been studied by neutron diffraction and molecular dynamics (MD) simulations and compared with a similar study of the n-alkane tetracosane (n-C24H52). Both molecules have 24 carbon atoms along their backbone and squalane has, in addition, six methyl side groups. Upon adsorption, there are significant differences as well as similarities in the behavior of these molecular films. Both molecules form ordered structures at low temperatures; however, while the melting point of the two-dimensional (2D) tetracosane film is roughly the same as the bulk melting point, the surface strongly stabilizes the 2D squalane film such that its melting point is 91 K above its value in bulk. Therefore, squalane, like tetracosane, will be a poor lubricant in those nanoscale devices that require a fluid lubricant at room temperature. The neutron diffraction data show that the translational order in the squalane monolayer is significantly less than in the tetracosane monolayer. The authors' MD simulations suggest that this is caused by a distortion of the squalane molecules upon adsorption on the graphite surface. When the molecules are allowed to relax on the surface, they distort such that all six methyl groups point away from the surface. This results in a reduction in the monolayer's translational order characterized by a decrease in its coherence length and hence a broadening of the diffraction peaks. The MD simulations also show that the melting mechanism in the squalane monolayer is the same footprint reduction mechanism found in the tetracosane monolayer, where a chain melting drives the lattice melting.

  1. Gas-Phase Reactions of Atomic Gold Cations with Linear Alkanes (C2-C9).

    PubMed

    Zhang, Ting; Li, Zi-Yu; Zhang, Mei-Qi; He, Sheng-Gui

    2016-06-30

    To develop proper ionization methods for alkanes, the reactivity of bare or ligated transition metal ions toward alkanes has attracted increasing interests. In this study, the reactions of the gold cations with linear alkanes from ethane up to nonane (CnH2n+2, n = 2-9) under mild conditions have been characterized by mass spectrometry and density functional theory calculations. When reacting with Au(+), small alkanes (n = 2-6) were confirmed to follow specific reaction channels of dehydrogenation for ethane and hydride transfer for others to generate product ions characteristic of the original alkanes, which indicates that Au(+) can act as a reagent ion to ionize alkanes from ethane to n-hexane. Strong dependence of the chain length of alkanes was observed for the rate constants and reaction efficiencies. Extensive fragmentation took place for larger alkanes (n > 6). Theoretical results show that the fragmentation induced by the hydride transfer occurs after the release of AuH. Moreover, the fragmentation of n-heptane was successfully avoided when the reaction took place in a high-pressure reactor. This implies that Au(+) is a potential reagent ion to ionize linear and even the branched alkanes. PMID:27266670

  2. Identification and use of an alkane transporter plug-in for applications in biocatalysis and whole-cell biosensing of alkanes

    NASA Astrophysics Data System (ADS)

    Grant, Chris; Deszcz, Dawid; Wei, Yu-Chia; Martínez-Torres, Rubéns Julio; Morris, Phattaraporn; Folliard, Thomas; Sreenivasan, Rakesh; Ward, John; Dalby, Paul; Woodley, John M.; Baganz, Frank

    2014-07-01

    Effective application of whole-cell devices in synthetic biology and biocatalysis will always require consideration of the uptake of molecules of interest into the cell. Here we demonstrate that the AlkL protein from Pseudomonas putida GPo1 is an alkane import protein capable of industrially relevant rates of uptake of C7-C16 n-alkanes. Without alkL expression, native E.coli n-alkane uptake was the rate-limiting step in both the whole-cell bioconversion of C7-C16 n-alkanes and in the activation of a whole-cell alkane biosensor by C10 and C11 alkanes. By coexpression of alkL as a transporter plug-in, specific yields improved by up to 100-fold for bioxidation of >C12 alkanes to fatty alcohols and acids. The alkL protein was shown to be toxic to the host when overexpressed but when expressed from a vector capable of controlled induction, yields of alkane oxidation were improved a further 10-fold (8 g/L and 1.7 g/g of total oxidized products). Further testing of activity on n-octane with the controlled expression vector revealed the highest reported rates of 120 μmol/min/g and 1 g/L/h total oxidized products. This is the first time AlkL has been shown to directly facilitate enhanced uptake of C10-C16 alkanes and represents the highest reported gain in product yields resulting from its use.

  3. Preliminary assessment of halogenated alkanes as vapor-phase tracers

    SciTech Connect

    Adams, Michael C.; Moore, Joseph N.; Hirtz, Paul

    1991-01-01

    New tracers are needed to evaluate the efficiency of injection strategies in vapor-dominated environments. One group of compounds that seems to meet the requirements for vapor-phase tracing are the halogenated alkanes (HCFCs). HCFCs are generally nontoxic, and extrapolation of tabulated thermodynamic data indicate that they will be thermally stable and nonreactive in a geothermal environment. The solubilities and stabilities of these compounds, which form several homologous series, vary according to the substituent ratios of fluorine, chlorine, and hydrogen. Laboratory and field tests that will further define the suitability of HCFCs as vapor-phase tracers are under way.

  4. Polarizabilities and van der Waals C6 coefficients of fullerenes from an atomistic electrodynamics model: Anomalous scaling with number of carbon atoms.

    PubMed

    Saidi, Wissam A; Norman, Patrick

    2016-07-14

    The van der Waals C6 coefficients of fullerenes are shown to exhibit an anomalous dependence on the number of carbon atoms N such that C6 ∝ N(2.2) as predicted using state-of-the-art quantum mechanical calculations based on fullerenes with small sizes, and N(2.75) as predicted using a classical-metallic spherical-shell approximation of the fullerenes. We use an atomistic electrodynamics model where each carbon atom is described by a polarizable object to extend the quantum mechanical calculations to larger fullerenes. The parameters of this model are optimized to describe accurately the static and complex polarizabilities of the fullerenes by fitting against accurate ab initio calculations. This model shows that C6 ∝ N(2.8), which is supportive of the classical-metallic spherical-shell approximation. Additionally, we show that the anomalous dependence of the polarizability on N is attributed to the electric charge term, while the dipole-dipole term scales almost linearly with the number of carbon atoms. PMID:27421409

  5. Polarizabilities and van der Waals C6 coefficients of fullerenes from an atomistic electrodynamics model: Anomalous scaling with number of carbon atoms.

    PubMed

    Saidi, Wissam A; Norman, Patrick

    2016-07-14

    The van der Waals C6 coefficients of fullerenes are shown to exhibit an anomalous dependence on the number of carbon atoms N such that C6 ∝ N(2.2) as predicted using state-of-the-art quantum mechanical calculations based on fullerenes with small sizes, and N(2.75) as predicted using a classical-metallic spherical-shell approximation of the fullerenes. We use an atomistic electrodynamics model where each carbon atom is described by a polarizable object to extend the quantum mechanical calculations to larger fullerenes. The parameters of this model are optimized to describe accurately the static and complex polarizabilities of the fullerenes by fitting against accurate ab initio calculations. This model shows that C6 ∝ N(2.8), which is supportive of the classical-metallic spherical-shell approximation. Additionally, we show that the anomalous dependence of the polarizability on N is attributed to the electric charge term, while the dipole-dipole term scales almost linearly with the number of carbon atoms.

  6. Polarizabilities and van der Waals C6 coefficients of fullerenes from an atomistic electrodynamics model: Anomalous scaling with number of carbon atoms

    NASA Astrophysics Data System (ADS)

    Saidi, Wissam A.; Norman, Patrick

    2016-07-01

    The van der Waals C6 coefficients of fullerenes are shown to exhibit an anomalous dependence on the number of carbon atoms N such that C6 ∝ N2.2 as predicted using state-of-the-art quantum mechanical calculations based on fullerenes with small sizes, and N2.75 as predicted using a classical-metallic spherical-shell approximation of the fullerenes. We use an atomistic electrodynamics model where each carbon atom is described by a polarizable object to extend the quantum mechanical calculations to larger fullerenes. The parameters of this model are optimized to describe accurately the static and complex polarizabilities of the fullerenes by fitting against accurate ab initio calculations. This model shows that C6 ∝ N2.8, which is supportive of the classical-metallic spherical-shell approximation. Additionally, we show that the anomalous dependence of the polarizability on N is attributed to the electric charge term, while the dipole-dipole term scales almost linearly with the number of carbon atoms.

  7. Effect of alkane chain length and counterion on the freezing transition of cationic surfactant adsorbed film at alkane mixture - water interfaces.

    PubMed

    Tokiwa, Yuhei; Sakamoto, Hiroyasu; Takiue, Takanori; Aratono, Makoto; Matsubara, Hiroki

    2015-05-21

    Penetration of alkane molecules into the adsorbed film gives rise to a surface freezing transition of cationic surfactant at the alkane-water interface. To examine the effect of the alkane chain length and counterion on the surface freezing, we employed interfacial tensiometry and ellipsometry to study the interface of cetyltrimethylammonium bromide and cetyltrimethylammonium chloride aqueous solutions against dodecane, tetradecane, hexadecane, and their mixtures. Applying theoretical equations to the experimental results obtained, we found that the alkane molecules that have the same chain length as the surfactant adsorb preferentially into the surface freezing film. Furthermore, we demonstrated that the freezing transition temperature of cationic surfactant adsorbed film was independent of the kind of counterion. PMID:25932500

  8. Hydrogen-transferring pyrolysis of long-chain alkanes and thermal stability improvement of jet fuels by hydrogen donors

    SciTech Connect

    Song, C.; Lai, W.C.; Schobert, H.H. . Fuel Science Program)

    1994-03-01

    Hydrogen-transferring pyrolysis refers to the thermal decomposition of hydrocarbons in the presence of hydrogen donors. Relative to the pyrolysis of pure n-tetradecane (C[sub 14]H[sub 28]) at 450 C, adding 10 vol % of H-donor tetralin suppressed n-C[sub 14] conversion by 68 % after 12 min of residence time, by about 66% after 21 min, and by 37% after 30 min. The presence of tetralin not only inhibited the n-C[sub 14] decomposition, but also altered the product distribution. The decomposition and isomerization of primary radicals are strongly suppressed, leading to a much higher ratio of the 1-alkene to n-alkane with 12 carbon atoms and slightly higher alkene/alkane ratio for the other product groups. The overall reaction mechanism for the initial stage of hydrogen-transferring pyrolysis is characterized by a one-step [beta]-scission of secondary radical followed by H-abstraction of the resulting primary radical. Moreover, desirable effects of the H-donor are also observed even after 240 min at 450 C, especially for inhibiting solid deposition. The authors also examined the effect of tetralin addition on the deposit formation from a paraffinic jet fuel JP-8 which is rich in C[sub 9]-C[sub 16] long-chain alkanes, and an aromatic compound, n-butylbenzene. Adding 10 vol % tetralin to a JP-8 jet fuel, n-C[sub 14], and n-butylbenzene reduced the formation of deposits by 90% (from 3.1 to 0.3 wt %), 77 % (from 3.0 to 0.7 wt %), and 54 % (from 5.6 to 2.6 wt %), respectively. These results suggest that, by taking advantage of H-transferring pyrolysis, hydrocarbon jet fuels may be used at high operating temperatures with little or no solid deposition.

  9. Multiple sources of alkanes in Quaternary oceanic sediment of Antarctica

    USGS Publications Warehouse

    Kvenvolden, K.A.; Rapp, J.B.; Golan-Bac, M.; Hostettler, F.D.

    1987-01-01

    Normal alkanes (n-C13n-C36), isoprenoid hydrocarbons (i-C15, i-C16, i-C18, i-C19, and i-C20) triterpanes (C27C32), and (C27C29) are present in low concentrations offshore Antarctica in near-surface, Quaternary sediment of the Wilkes Land continental margin and of the western Ross Sea. The distributions of these hydrocarbons are interpreted relative to possible sources and processes. The hydrocarbons appear to be mixtures of primary and recycled material from marine and terrigenous sources. The n-alkanes are most abundant and are characterized by two distinct populations, one of probable marine origin and the other likely from terrigenous, vascular plant sources. Because the continent of Antarctica today is devoid of higher plants, the plant-derived hydrocarbons in these offshore sediments probably came from wind-blown material and recycled Antarctic sediment that contains land-plant remains from an earlier period of time. Isoprenoid hydrocarbons are partially recycled and mainly of marine origin; the dominance of pristane over phytane suggests oxic paleoenvironmental conditions. Both modern and ancient triterpanes and steranes are present, and the distribution of these indicates a mixture of primary and recycled bacterial, algal, and possible higher-plant materials. Although the sampled sediments were deposited during the Quaternary, they apparently contain a significant component of hydrocarbons of pre-Quaternary age. ?? 1987.

  10. Geologic seepage of methane and light alkanes in Los Angeles

    NASA Astrophysics Data System (ADS)

    Doezema, L. A.; Chang, K.; Baril, R.; Nwachuku, I.; Contreras, P.; Marquez, A.; Howard, D.

    2013-12-01

    Natural geologic seepage of methane from underground oil and natural gas reservoirs has been suggested to be an underreported part of the global methane budget. Other light alkanes are also given off in combination with the methane seepage, making it possible that geologic seepage is also a potentially significant global source of these light alkanes. This study reports C1-C5 findings from geologic seepage made in the Los Angeles region. Microseepage, invisible escape of gases, was measured primarily at Kenneth Hahn Regional Park, while macroseepage, the visible release of gases, was measured at the La Brea Tar Pits. Samples were collected using stainless steel canisters and flux chambers and were analyzed using gas chromatography with flame ionization detectors (GC-FID). Average microseepage flux rates of 0.95 μg m-2 h-1 for ethane and 0.51 μg m-2 h-1 were found for propane, while average macroseepage rates for methane, ethane, and propane were 664, 19.8, and 18.1 mg m-2 h-1 respectively. Relationships between microseepage flux rate and location of underground oil and natural deposit and earthquake fault lines are presented. Additionally, the relative importance of findings in context with global budgets and local air quality is discussed.

  11. Supercritical carbon dioxide-soluble ligands for extracting actinide metal ions from porous solids (EMSP Project Number 64965)

    SciTech Connect

    Dietz, M. L.; Barrans, Jr., R. E.; Herlinger, A. W.; Brennecke, J. F.

    2000-04-24

    The objective of this project is to develop novel, substituted diphosphonic acid ligands that can be used for supercritical carbon dioxide extraction (SCDE) of actinide ions from solid wastes. Specifically, selected diphosphonic acids, which are known to form extremely stable complexes with actinides in aqueous and organic solution, are to be rendered carbon dioxide-soluble by the introduction of appropriate alkyl- or silicon-containing substituents. The metal complexation chemistry of these new ligands in SC-CO{sub 2} will then be investigated and techniques for their use in actinide extraction from porous solids developed. This report summarizes the work performed during the first 1.3 years of a 3-year program. Because the planned studies of metal complexation and the development of techniques for actinide removal from solids are dependent on the availability of suitable ligands, efforts to date have focused primarily on the synthesis of selected alkyl- or silicon-containing diphosphonic acids. The authors' principal targets have been derivatives in which the silicon-containing groups either serve as the ester function or are attached to the anchor carbon of the diphosphonic acid. Because methylenediphosphonic acid (MDPA) is commercially available and because its esterification with simple alcohols to yield symmetrical diesters is well-established, their initial studies have focused on this ligand and its reactions with silyl alcohols. Success has been achieved in the reaction of MDPA and its ethylene, propylene, and butylene analogs with 3-(trimethylsilyl)-1-propanol. Using a procedure similar to that previously employed for the synthesis of C-8 dialkylmethylenediphosphonic acids, this series of alkylenediphosphonic acids has been esterified in good yield (ca. 60%) to the symmetrically-substituted diesters. Vapor phase osmometric and cryoscopic studies of these compounds in toluene and 1-decanol, respectively, indicate that their aggregation properties closely

  12. 40 CFR 721.2625 - Reaction product of alkane-diol and epichlorohydrin.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction product of alkane-diol and... Specific Chemical Substances § 721.2625 Reaction product of alkane-diol and epichlorohydrin. (a) Chemical... as reaction product of alkanediol and epichlorohydrin (PMN P-89-760) is subject to reporting...

  13. 40 CFR 721.2625 - Reaction product of alkane-diol and epichlorohydrin.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of alkane-diol and... Specific Chemical Substances § 721.2625 Reaction product of alkane-diol and epichlorohydrin. (a) Chemical... as reaction product of alkanediol and epichlorohydrin (PMN P-89-760) is subject to reporting...

  14. 40 CFR 721.2625 - Reaction product of alkane-diol and epichlorohydrin.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of alkane-diol and... Specific Chemical Substances § 721.2625 Reaction product of alkane-diol and epichlorohydrin. (a) Chemical... as reaction product of alkanediol and epichlorohydrin (PMN P-89-760) is subject to reporting...

  15. 40 CFR 721.2625 - Reaction product of alkane-diol and epichlorohydrin.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction product of alkane-diol and... Specific Chemical Substances § 721.2625 Reaction product of alkane-diol and epichlorohydrin. (a) Chemical... as reaction product of alkanediol and epichlorohydrin (PMN P-89-760) is subject to reporting...

  16. 40 CFR 721.2625 - Reaction product of alkane-diol and epichlorohydrin.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction product of alkane-diol and... Specific Chemical Substances § 721.2625 Reaction product of alkane-diol and epichlorohydrin. (a) Chemical... as reaction product of alkanediol and epichlorohydrin (PMN P-89-760) is subject to reporting...

  17. Carbon Species in Serpentinites and Gabbros Underlying the Lost City Hydrothermal Field, Southern Atlantis Massif (30°N, MAR)

    NASA Astrophysics Data System (ADS)

    Delacour, A.; Schaeffer, P.; Bernasconi, S. M.; Frueh-Green, G. L.

    2006-12-01

    Serpentinization of oceanic peridotites results in the production of volatile-rich (methane and hydrogen) fluids and other light hydrocarbons, and is characteristic of the low-temperature (<90°C) fluids actively venting at the Lost City Hydrothermal Field (LCHF; 30°N near the MAR). Carbon contents and carbon isotope compositions have been measured from serpentinized peridotites and gabbros in the basement of the LCHF with the goal to better understand carbon sources and carbon cycling during serpentinization and hydrothermal venting. The serpentinites have total carbon contents (TC) of 60 to 820 ppm, and up to 1.7 wt% in samples containing carbonate veins. C-isotope compositions of the TC range from -24.9 to +2.3‰, whereby positive δ13C values are correlated with serpentinites with carbonate veins and indicate a marine carbon input. The non-carbonate carbon content (TOC: total organic carbon and graphite residual after HCl dissolution) of the serpentinites is from 55 to 280 ppm, with δ13CTOC ranging from -29.5 to -21.5‰. The gabbros show a wider range of TC and δ13CTC, but have δ13CTOC in the same range as the serpentinites. The TOC isotopic compositions may reflect hydrocarbon production during serpentinization or the presence of organic compounds within the samples. To constrain the origin further, organic compounds were extracted from selected serpentinites. The saturated hydrocarbon fractions show a predominance of n-alkanes and an unresolved complex mixture. Long chain n- alkanes show no odd over even carbon number predominance, indicating no contamination by higher plants waxes from recent material. Although n-alkanes can be biogenic or be produced abiotically by Fischer Tropsch-type reactions, the occurrence of the isoprenoids norpristane, pristane, phytane and squalane clearly indicate a biogenic origin, possibly incorporated into the serpentinites during fluid-rock interaction. Compound- specific C-isotope analyses show relatively constant

  18. A Model of Reduced Kinetics for Alkane Oxidation Using Constituents and Species for N-Heptane

    NASA Technical Reports Server (NTRS)

    Harstad, Kenneth G.; Bellan, Josette

    2011-01-01

    The reduction of elementary or skeletal oxidation kinetics to a subgroup of tractable reactions for inclusion in turbulent combustion codes has been the subject of numerous studies. The skeletal mechanism is obtained from the elementary mechanism by removing from it reactions that are considered negligible for the intent of the specific study considered. As of now, there are many chemical reduction methodologies. A methodology for deriving a reduced kinetic mechanism for alkane oxidation is described and applied to n-heptane. The model is based on partitioning the species of the skeletal kinetic mechanism into lights, defined as those having a carbon number smaller than 3, and heavies, which are the complement of the species ensemble. For modeling purposes, the heavy species are mathematically decomposed into constituents, which are similar but not identical to groups in the group additivity theory. From analysis of the LLNL (Lawrence Livermore National Laboratory) skeletal mechanism in conjunction with CHEMKIN II, it is shown that a similarity variable can be formed such that the appropriately non-dimensionalized global constituent molar density exhibits a self-similar behavior over a very wide range of equivalence ratios, initial pressures and initial temperatures that is of interest for predicting n-heptane oxidation. Furthermore, the oxygen and water molar densities are shown to display a quasi-linear behavior with respect to the similarity variable. The light species ensemble is partitioned into quasi-steady and unsteady species. The reduced model is based on concepts consistent with those of Large Eddy Simulation (LES) in which functional forms are used to replace the small scales eliminated through filtering of the governing equations; in LES, these small scales are unimportant as far as the overwhelming part of dynamic energy is concerned. Here, the scales thought unimportant for recovering the thermodynamic energy are removed. The concept is tested by

  19. Adsorption of proteins at the aqueous solution/alkane interface: Co-adsorption of protein and alkane.

    PubMed

    Miller, R; Aksenenko, E V; Zinkovych, I I; Fainerman, V B

    2015-08-01

    The equations of state, adsorption isotherms and functions of the distribution of protein molecules in liquid interfacial layers with respect to molar area and the equations for their viscoelastic behavior are presented. This theory was used to determine the adsorption characteristics of β-casein and β-lactoglobulin at water/oil interfaces. The experimental results are shown to be describable quite adequately by the proposed theory with consistent model parameters. The data analysis demonstrated that the β-casein molecule adsorbed at equilibrium conditions is more unfolded as compared with dynamic conditions, and this fact causes the significant increase of the adsorption equilibrium constant. The theory assumes the adsorption of protein molecules from the aqueous solution and a competitive adsorption of alkane molecules from the alkane phase. The comparison of the experimental equilibrium interfacial tension isotherms for β-lactoglobulin at the solution/hexane interface with data calculated using the proposed theoretical model demonstrates that the assumption of a competitive adsorption is essential, and the influence of the hexane molecules on the shape of the adsorption isotherm does in fact exist.

  20. Estimation of the Number of Cross-Links of Multi-walled Carbon Nanotube Films Formed by a Dehydration Condensation Reaction

    NASA Astrophysics Data System (ADS)

    Ogino, S.; Sato, Y.; Yamamoto, G.; Sasamori, K.; Kimura, H.; Hashida, T.; Motomiiya, K.; Jeyadevan, B.; Tohji, K.

    2007-03-01

    Preparation procedure of multi-walled carbon nanotube (MWCNT) films shows as follows. First, as-grown MWCNTs heated in the air and treated with hydrochloric acid to remove amorphous carbon and catalytic metal particles respectively. Then, the o1btained MWCNT samples were treated with nitric acid at 373K to add carboxylic acid and hydroxyl groups on their surface. Finally, MWCNT films were prepared by employing a condensation reaction utilizing 1,3-dicyclohexylcarbodiimide (DCC) to cross-link each MWCNT with chemical bonds. Morphological changes in the resultant MWCNT films were monitored using scanning electron microscopy, and showed that the MWCNTs were randomly intertwined in the films. The prepared MWCNT films were 17mm in diameter and 20μm in thickness, and the apparent density was 0.59 g/cm3. Fourier transform-infrared spectroscopy confirmed that each MWCNT modified with carboxylic acid and hydroxyl groups was cross-linked through the ester bond. It was found that the ratio of the number of ester cross-links and carbon atoms of the nanotubes per unit apparent volume (cm3) of condensed-MWCNT films was 5.23×10-3 using TGA. The tensile strength and Vickers hardness of condensed-MWCNT films achieved an average of 15MPa and 9.2MPa, respectively, and was greater than those of free-standing MWCNT films without ester bond.

  1. Bulk and compound-specific isotope analysis of long-chain n-alkanes from a 85,000 year sediment core from Lake Peten Petén Itzá, Guatemala

    NASA Astrophysics Data System (ADS)

    Mays, J.; Brenner, M.; Curtis, J. H.; Curtis, K.; Hodell, D. A.; Correa-Metrio, A.; Escobar, J.; Dutton, A. L.; Zimmerman, A. R.; Guilderson, T. P.

    2013-12-01

    Sediment core PI-6 from Lake Petén Itzá, Guatemala possesses an 85-ka record of climate from lowland Central America. Variations in sediment lithology suggest large, abrupt changes in precipitation during the last glacial and deglacial periods, and into the early Holocene. Study of cores from nearby Lake Quexil demonstrated the utility of using the carbon isotopic composition of leaf wax n-alkanes to infer changes in terrestrial vegetation (Huang et al. 2001). Forty-nine samples were taken from composite Petén Itzá core PI-6 to measure carbon isotopes of bulk organic carbon and long-chain n alkanes. Changes in δ13C values indicate shifts in the relative proportion of C3 to C4 biomass. The record shows largest δ13C variations are associated with Heinrich Events. Carbon isotope values in sediments deposited during the Last Glacial Maximum (LGM) indicate moderate precipitation and little rainfall fluctuation. The deglacial was a period of pronounced climate variability, e.g. the Bölling-Allerod and Younger Dryas. Arid times of the deglacial were inferred from samples with the greatest δ13C values in organic matter, reflecting the largest proportion of C4 plants. Such inferences are supported by stable isotope measurements on ostracod shells and analysis of pollen from the same sample depths in core PI-6. Carbon stable isotope measures on bulk organic carbon and n alkane compounds show similar trends throughout the record and the C:N ratio of Petén Itzá sediments indicates a predominantly allochthonous source for bulk organic matter. Hence, isotope measures on bulk organic carbon (δ13CTOC) in sediments from this lake are sufficient to infer climate-driven shifts in vegetation, making n-alkane extraction and isotope analysis superfluous.

  2. 40 CFR 721.10625 - Distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... benzene by-product, brominated and bromo diphenyl alkane (generic). 721.10625 Section 721.10625 Protection... Distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane (generic). (a... generically as distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane...

  3. 40 CFR 721.10625 - Distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... benzene by-product, brominated and bromo diphenyl alkane (generic). 721.10625 Section 721.10625 Protection... Distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane (generic). (a... generically as distillation bottoms, alkylated benzene by-product, brominated and bromo diphenyl alkane...

  4. 40 CFR 721.10178 - Distillates (Fischer-Tropsch), hydroisomerized middle, C10-13-branched alkane fraction.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...), hydroisomerized middle, C10-13-branched alkane fraction. 721.10178 Section 721.10178 Protection of Environment...), hydroisomerized middle, C10-13-branched alkane fraction. (a) Chemical substance and significant new uses subject... middle, C10-13-branched alkane fraction (PMN P-04-319; CAS No. 642928-30-1) is subject to reporting...

  5. 40 CFR 721.10178 - Distillates (Fischer-Tropsch), hydroisomerized middle, C10-13-branched alkane fraction.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...), hydroisomerized middle, C10-13-branched alkane fraction. 721.10178 Section 721.10178 Protection of Environment...), hydroisomerized middle, C10-13-branched alkane fraction. (a) Chemical substance and significant new uses subject... middle, C10-13-branched alkane fraction (PMN P-04-319; CAS No. 642928-30-1) is subject to reporting...

  6. Pre-Existing Carbon Structure and Its Effect on Site-Specific Carbon Isotopes in Small Organic Molecules

    NASA Astrophysics Data System (ADS)

    Piasecki, A.; Eiler, J. M.

    2014-12-01

    The ability to measure site-specific isotopes in organic molecules allows for better understanding of the mechanisms of their biosynthetic and/or catagenic formation and destruction. Here we examine for site-specific isotopic composition of propane from natural and synthetic sources using novel instruments and techniques gas source mass spectrometry 1, and discuss the possible relationship of our findings to recent independent evidence from NMR measurements for the isotopic structures of long-chain alkanes2. A recent NMR study2 demonstrates that n-alkanes can be divided into three groups according to their site-specific carbon isotope structure: long (C16+) even carbon number, long (C17+) odd carbon number , and short (C11-C15). We modeled the isotopic site-specific composition of propane derived from these three distinct groups. If propane is cleaved from such long-chain hydrocarbons without fractionation, the long odd-numbered and the shorter alkanes would produce propane with an average terminal position 6-7‰ lighter than the center position, while the long even-numbered chain compounds would produce propane with a terminal position averaging around 7‰ heavier than the center. If, instead the fractionation associated with cleaving propane from such parent molecules is ~10‰ (as seems likely), then these average terminal — center differences should be decreased by ~5 ‰ (i.e., to -11-12 and +1-2 ‰, respectively). We will compare these predictions with our previous demonstrations of the changes in bulk and site specific compositions in propane due to isotope exchange equilibria, diffusion and conventional models of kerogen 'cracking', and will use these models as a framework for interpreting the observed site-specific isotopic compositions of propane from diverse natural gas deposits. 1. Piasecki, A. et al. Site-Specific Carbon Isotope Measurement of Organics by Gas Source Mass Spectrometry. Mineralogical Magazine 77, (2013). 2. Gilbert, A., Yamada, K

  7. Copper-Catalyzed Intermolecular Amidation and Imidation of Unactivated Alkanes

    PubMed Central

    2015-01-01

    We report a set of rare copper-catalyzed reactions of alkanes with simple amides, sulfonamides, and imides (i.e., benzamides, tosylamides, carbamates, and phthalimide) to form the corresponding N-alkyl products. The reactions lead to functionalization at secondary C–H bonds over tertiary C–H bonds and even occur at primary C–H bonds. [(phen)Cu(phth)] (1-phth) and [(phen)Cu(phth)2] (1-phth2), which are potential intermediates in the reaction, have been isolated and fully characterized. The stoichiometric reactions of 1-phth and 1-phth2 with alkanes, alkyl radicals, and radical probes were investigated to elucidate the mechanism of the amidation. The catalytic and stoichiometric reactions require both copper and tBuOOtBu for the generation of N-alkyl product. Neither 1-phth nor 1-phth2 reacted with excess cyclohexane at 100 °C without tBuOOtBu. However, the reactions of 1-phth and 1-phth2 with tBuOOtBu afforded N-cyclohexylphthalimide (Cy-phth), N-methylphthalimide, and tert-butoxycyclohexane (Cy-OtBu) in approximate ratios of 70:20:30, respectively. Reactions with radical traps support the intermediacy of a tert-butoxy radical, which forms an alkyl radical intermediate. The intermediacy of an alkyl radical was evidenced by the catalytic reaction of cyclohexane with benzamide in the presence of CBr4, which formed exclusively bromocyclohexane. Furthermore, stoichiometric reactions of [(phen)Cu(phth)2] with tBuOOtBu and (Ph(Me)2CO)2 at 100 °C without cyclohexane afforded N-methylphthalimide (Me-phth) from β-Me scission of the alkoxy radicals to form a methyl radical. Separate reactions of cyclohexane and d12-cyclohexane with benzamide showed that the turnover-limiting step in the catalytic reaction is the C–H cleavage of cyclohexane by a tert-butoxy radical. These mechanistic data imply that the tert-butoxy radical reacts with the C–H bonds of alkanes, and the subsequent alkyl radical combines with 1-phth2 to form the corresponding N-alkyl imide product

  8. Climate variation and terrigenous input in the Tagus prodelta reconstructed through the use of N-alkanes and Uk'37

    NASA Astrophysics Data System (ADS)

    Rodrigues, T.; Grimalt, J.; Flores, J.; Lebreiro, S.; Abrantes, F.

    2003-04-01

    Sea surface temperatures and river input have been reconstructed for the last 13,5kyr based on long chain alkenones and n-alkanes respectively, using a sedimentary sequence recovered from the Tagus prodelta (Portuguese Margin, 38ºN, 9ºW; PO287-26-1B; D13902; D13882). A preliminary age model has been constructed using five 14C AMS dating and correlation to core SU8118. In the upper part of this sequence temperatures ranged between 15ºC and 19ºC, exhibiting the lowest values during the Little Ice Age. This low temperature interval is marked by a general increase in organic carbon and total C37 alkenones pointing to increasing productivity. Minima sea surface temperature occur during the Younger Dryas event centred at about 12cal.kyr B.P. and the Allerød-Bølling interstadial occurs at the end of the sequence. The SST minima are concurrent with increases in tetra unsaturated alkenone (%C37:4), possibly reflecting the influence of less saline waters originated from iceberg melting. N-alkanes and n-alcohols exhibit the same trend indicating very good preservation of organic matter throughout the sequence. In addition, the strong agreement between these two proxies and C37 alkenones suggest river input as the main source of nutrients for the increased coccolith production in the area which in terms of coccolith assemblages were dominated by G. oceanica and other small gephyrocapsid.

  9. Biodegradation of low-molecular-weight alkanes under mesophilic, sulfate-reducing conditions: metabolic intermediates and community patterns.

    PubMed

    Savage, Kristen N; Krumholz, Lee R; Gieg, Lisa M; Parisi, Victoria A; Suflita, Joseph M; Allen, Jon; Philp, R Paul; Elshahed, Mostafa S

    2010-06-01

    We evaluated the ability of the native microbiota in a low-temperature, sulfidic natural hydrocarbon seep (Zodletone) to metabolize short-chain hydrocarbons. n-Propane and n-pentane were metabolized under sulfate-reducing conditions in initial enrichments and in sediment-free subcultures. Carbon isotope analysis of residual propane in active enrichments showed that propane became enriched in (13)C by 6.7 (+/-2.0) per thousand, indicating a biological mechanism for propane loss. The detection of n-propylsuccinic and isopropylsuccinic acids in active propane-degrading enrichments provided evidence for anaerobic biodegradation via a fumarate addition pathway. A eubacterial 16S rRNA gene survey of sediment-free enrichments showed that the majority of the sequenced clones were phylogenetically affiliated within the Deltaproteobacteria. Such sequences were most closely affiliated with clones retrieved from hydrocarbon-impacted marine ecosystems, volatile fatty acid metabolizers, hydrogen users, and with a novel Deltaproteobacterial lineage. Other cloned sequences were affiliated with the Firmicutes and Chloroflexi phyla. The sequenced clones were only distantly (<95%) related to other reported low-molecular-weight alkane-degrading sulfate-reducing populations. This work documents the potential for anaerobic short-chain n-alkane metabolism for the first time in a terrestrial environment, provides evidence for a fumarate addition mechanism for n-propane activation under these conditions, and reveals microbial community members present in such enrichments.

  10. Hydrocarbons, the advanced biofuels produced by different organisms, the evidence that alkanes in petroleum can be renewable.

    PubMed

    Fu, Wen-Juan; Chi, Zhe; Ma, Zai-Chao; Zhou, Hai-Xiang; Liu, Guang-Lei; Lee, Ching-Fu; Chi, Zhen-Ming

    2015-09-01

    It is generally regarded that the petroleum cannot be renewable. However, in recent years, it has been found that many marine cyanobacteria, some eubacteria, engineered Escherichia coli, some endophytic fungi, engineered yeasts, some marine yeasts, plants, and insects can synthesize hydrocarbons with different carbon lengths. If the organisms, especially some native microorganisms and engineered bacteria and yeasts, can synthesize and secret a large amount of hydrocarbons within a short period, alkanes in the petroleum can be renewable. It has been documented that there are eight pathways for hydrocarbon biosynthesis in different organisms. Unfortunately, most of native microorganisms, engineered E. coli and engineered yeasts, only synthesize a small amount of intracellular and extracellular hydrocarbons. Recently, Aureobasidium pullulans var. melanogenum isolated from a mangrove ecosystem has been found to be able to synthesize and secret over 21.5 g/l long-chain hydrocarbons with a yield of 0.275 g/g glucose and a productivity of 0.193 g/l/h within 5 days. The yeast may have highly potential applications in alkane production.

  11. [The diversity of alkane degrading bacteria in the enrichments with deep sea sediment of the South China Sea].

    PubMed

    Liu, Zhen; Shao, Zong-Ze

    2007-10-01

    Deep sea sediment samples of the South Sea of China were used for isolation and biodiversity examination of hydrocarbon degrading bacterium. 48 isolates were obtained from the enrichments with hexadecane as the sole carbon sources. Among them, 27 isolates were capable of degrading alkane; and 4 could produce biosurfactant significantly as determined by the surface tension measurement. 2 isolates belonging to Dietzia maris lowered water surface tension to 33 mN/m. This is the first report about D. maris in biosurfactant production. The results of polymerase chain reaction (PCR) followed by Denaturing Gradient Gel Electrophoresis (DGGE) and DNA sequencing suggested that Bacillus was the dominant member in the hexadecane enriched communities. Isolates of Bacillus aquimaris were demonstrated to be the most predominant degraders in all 7 samples at 2 sampling sites. In addition, Sporosarcina, Halomonas and Brevibacterium were also found as one of the dominant members in some samples. Therefore, species of Bacillus might play an important role in alkane degradation in the sediments of the sampling sites.

  12. The Genome of the Moderate Halophile Amycolicicoccus subflavus DQS3-9A1T Reveals Four Alkane Hydroxylation Systems and Provides Some Clues on the Genetic Basis for Its Adaptation to a Petroleum Environment

    PubMed Central

    Nie, Yong; Fang, Hui; Li, Yan; Chi, Chang-Qiao; Tang, Yue-Qin; Wu, Xiao-Lei

    2013-01-01

    The moderate halophile Amycolicicoccus subflavus DQS3-9A1T is the type strain of a novel species in the recently described novel genus Amycolicicoccus, which was isolated from oil mud precipitated from oil produced water. The complete genome of A. subflavus DQS3-9A1T has been sequenced and is characteristic of harboring the genes for adaption to the harsh petroleum environment with salinity, high osmotic pressure, and poor nutrient levels. Firstly, it characteristically contains four types of alkane hydroxylases, including the integral-membrane non-heme iron monooxygenase (AlkB) and cytochrome P450 CYP153, a long-chain alkane monooxygenase (LadA) and propane monooxygenase. It also accommodates complete pathways for the response to osmotic pressure. Physiological tests proved that the strain could grow on n-alkanes ranging from C10 to C36 and propane as the sole carbon sources, with the differential induction of four kinds of alkane hydroxylase coding genes. In addition, the strain could grow in 1–12% NaCl with the putative genes responsible for osmotic stresses induced as expected. These results reveal the effective adaptation of the strain DQS3-9A1T to harsh oil environment and provide a genome platform to investigate the global regulation of different alkane metabolisms in bacteria that are crucially important for petroleum degradation. To our knowledge, this is the first report to describe the co-existence of such four types of alkane hydroxylases in a bacterial strain. PMID:23967144

  13. The genome of the moderate halophile Amycolicicoccus subflavus DQS3-9A1(T) reveals four alkane hydroxylation systems and provides some clues on the genetic basis for its adaptation to a petroleum environment.

    PubMed

    Nie, Yong; Fang, Hui; Li, Yan; Chi, Chang-Qiao; Tang, Yue-Qin; Wu, Xiao-Lei

    2013-01-01

    The moderate halophile Amycolicicoccus subflavus DQS3-9A1(T) is the type strain of a novel species in the recently described novel genus Amycolicicoccus, which was isolated from oil mud precipitated from oil produced water. The complete genome of A. subflavus DQS3-9A1(T) has been sequenced and is characteristic of harboring the genes for adaption to the harsh petroleum environment with salinity, high osmotic pressure, and poor nutrient levels. Firstly, it characteristically contains four types of alkane hydroxylases, including the integral-membrane non-heme iron monooxygenase (AlkB) and cytochrome P450 CYP153, a long-chain alkane monooxygenase (LadA) and propane monooxygenase. It also accommodates complete pathways for the response to osmotic pressure. Physiological tests proved that the strain could grow on n-alkanes ranging from C10 to C36 and propane as the sole carbon sources, with the differential induction of four kinds of alkane hydroxylase coding genes. In addition, the strain could grow in 1-12% NaCl with the putative genes responsible for osmotic stresses induced as expected. These results reveal the effective adaptation of the strain DQS3-9A1(T) to harsh oil environment and provide a genome platform to investigate the global regulation of different alkane metabolisms in bacteria that are crucially important for petroleum degradation. To our knowledge, this is the first report to describe the co-existence of such four types of alkane hydroxylases in a bacterial strain.

  14. Morphological Transformations in Solid Domains of Alkanes on Surfactant Solutions.

    PubMed

    Matsubara, Hiroki; Takaichi, Tetsumasa; Takiue, Takanori; Aratono, Makoto; Toyoda, Aya; Iimura, Kenichi; Ash, Philip A; Bain, Colin D

    2013-03-21

    Alkanes on surfactant solutions can form three distinct phases at the air-solution interface, a liquid phase (L), a solid monolayer phase (S1), and a hybrid bilayer phase (S2). Phase coexistence between any two, or all three, of these phases has been observed by Brewster angle microscopy of tetradecane, hexadecane, and their mixtures on solutions of tetradecyltrimethylammonium bromide. The morphologies of the domains depend on the competition between line tension and electrostatic interactions, which are essentially different depending on the pair of phases in contact. Domains of S1 in the L phase are long and thin; however, long, thin domains of L in an S1 phase are not stable but break up into a string of small circular domains. The bilayer S2 domains are always circular, owing to the dominance of line tension on the morphology. PMID:26291344

  15. Environmental chemistry and toxicology of polychlorinated n-alkanes.

    PubMed

    Tomy, G T; Fisk, A T; Westmore, J B; Muir, D C

    1998-01-01

    Polychlorinated-n-alkanes (PCAs) or chlorinated paraffins consist of C10 to C30 n-alkanes with chlorine content from 30% to 70% by mass. PCAs are used as high-temperature lubricants, plasticizers, flame retardants, and additives in adhesives, paints, rubber, and sealants. This review presents the existing data on the environmental chemistry and toxicology of PCAs and a preliminary exposure and risk assessment. There is limited information on the levels, fate, or biological effects of PCAs in the environment. This results both from the difficulty associated with quantifying PCAs, because of the complexity inherent to commercial formulations, and from the limited knowledge of their physicochemical properties and biodegradation rates. There are indications that PCAs are widespread environmental contaminants at ng/L levels in surface waters and ng/g (wet wt) levels in biota. However, environmental measurements of PCAs are very limited in the U.S. and Canada, and are only slightly more detailed in western Europe. Assuming that reported water concentrations are mainly caused by the short chain (C10-C13) compounds, aquatic organisms may be at risk from exposure to PCAs. Fugacity level II modeling for two representative PCAs, using the best available physicochemical property data and estimated degradation rates, suggested that C16C24Cl10 would achieve higher concentrations in biota, sediment, and soil than C12H20Cl6 because of slower degradation rates and lower water solubility. Environmental residence time of C16H24Cl10 is estimated to be 520 d compared to 210 d for C12H20Cl6. Future studies will require better analytical methods and reference materials certified for PCA content. Additional data are needed to evaluate exposure of biota to PCAs in the environment, particularly in light of their continued production and usage around the globe. PMID:9751033

  16. Enhancing Alkane Production in Cyanobacterial Lipid Droplets: A ModeFl Platform for Industrially Relevant Compound Production

    PubMed Central

    Peramuna, Anantha; Morton, Ray; Summers, Michael L.

    2015-01-01

    Cyanobacterial lipid droplets (LDs) are packed with hydrophobic energy-dense compounds and have great potential for biotechnological expression and the compartmentalization of high value compounds. Nostoc punctiforme normally accumulates LDs containing neutral lipids, and small amounts of heptadecane, during the stationary phase of growth. In this study, we further enhanced heptadecane production in N. punctiforme by introducing extrachromosomal copies of aar/adc genes, and report the discovery of a putative novel lipase encoded by Npun_F5141, which further enhanced alkane production. Extra copies of all three genes in high light conditions resulted in a 16-fold higher accumulation of heptadecane compared to the wild type strain in the exponential phase. LD accumulation during exponential phase also increased massively to accommodate the heptadecane production. A large number of small, less fluorescent LDs were observed at the cell periphery in exponential growth phase, whereas fewer number of highly fluorescent, much larger LDs were localized towards the center of the cell in the stationary phase. These advances demonstrate that cyanobacterial LDs are an ideal model platform to make industrially relevant compounds, such as alkanes, during exponential growth, and provide insight into LD formation in cyanobacteria. PMID:25821934

  17. Isolation and characterization of different bacterial strains for bioremediation of n-alkanes and polycyclic aromatic hydrocarbons.

    PubMed

    Guermouche M'rassi, A; Bensalah, F; Gury, J; Duran, R

    2015-10-01

    Crude oil is a common environmental pollutant composed of a large number of both aromatic and aliphatic hydrocarbons. Biodegradation is carried out by microbial communities that are important in determining the fate of pollutants in the environment. The intrinsic biodegradability of the hydrocarbons and the distribution in the environment of competent degrading microorganisms are crucial information for the implementation of bioremediation processes. In the present study, the biodegradation capacities of various bacteria toward aliphatic and aromatic hydrocarbons were determined. The purpose of the study was to isolate and characterize hydrocarbon-degrading bacteria from contaminated soil of a refinery in Arzew, Algeria. A collection of 150 bacterial strains was obtained; the bacterial isolates were identified by 16S rRNA gene sequencing and their ability to degrade hydrocarbon compounds characterized. The isolated strains were mainly affiliated to the Gamma-Proteobacteria class. Among them, Pseudomonas spp. had the ability to metabolize high molecular weight hydrocarbon compounds such as pristane (C19) at 35.11 % by strain LGM22 and benzo[a] pyrene (C20) at 33.93 % by strain LGM11. Some strains were able to grow on all the hydrocarbons tested including octadecane, squalene, phenanthrene, and pyrene. Some strains were specialized degrading only few substrates. In contrast, the strain LGM2 designated as Pseudomonas sp. was found able to degrade both linear and branched alkanes as well as low and high poly-aromatic hydrocarbons (PAHs). The alkB gene involved in alkane degradation was detected in LGM2 and other Pseudomonas-related isolates. The capabilities of the isolated bacterial strains to degrade alkanes and PAHs should be of great practical significance in bioremediation of oil-contaminated environments.

  18. A model of reduced kinetics for alkane oxidation using constituents and species: Proof of concept for n-heptane

    SciTech Connect

    Harstad, Kenneth; Bellan, Josette

    2010-08-15

    A methodology for deriving a reduced kinetic mechanism for alkane oxidation is described and applied to n-heptane. The model is based on partitioning the species of the skeletal kinetic mechanism into lights, defined as those having a carbon number smaller than 3, and heavies, which are the complement in the species ensemble. For modeling purposes, the heavy species are mathematically decomposed into constituents, which are similar but not identical to groups in the group additivity theory. From analysis of the LLNL skeletal mechanism in conjunction with CHEMKIN II, it is shown that a similarity variable can be formed such that the appropriately scaled global constituent molar density exhibits a self-similar behavior over a very wide range of equivalence ratios, initial pressures and initial temperatures that is of interest for predicting n-heptane oxidation. Furthermore, the oxygen and water molar densities are shown to display a quasi-linear behavior with respect to the similarity variable. The light species ensemble is partitioned into quasi-steady and unsteady species. The concept is tested by using tabular information from the LLNL skeletal mechanism in conjunction with CHEMKIN II. The test reveals that the similarity concept is indeed justified and that the combustion temperature is well predicted, but that the ignition time is overpredicted. To palliate this deficiency, functional modeling is incorporated into our conceptual reduction. Due to the reduction process, models are also included for the global constituent molar density, the kinetics-induced enthalpy evolution of the heavy species, the contribution to the reaction rate of the unsteady lights from the heavies, the molar density evolution of oxygen and water, the mole fractions of the quasi-steady light species and the mean molar heat capacity of the heavy species. The model is compact in that there are only nine species-related progress variables. Results are presented comparing the performance of

  19. Measuring long chain alkanes in diesel engine exhaust by thermal desorption PTR-MS

    NASA Astrophysics Data System (ADS)

    Erickson, M. H.; Gueneron, M.; Jobson, B. T.

    2013-07-01

    A method using thermal desorption sampling and analysis by PTR-MS to measure long chain alkanes (C12-C18) and other larger organics associated with diesel engine exhaust emissions is described. Long chain alkanes undergo dissociative proton transfer reactions forming a series of fragment ions with formula CnH2n+1. The PTR-MS is insensitive to n-alkanes less than C8 but displays an increasing sensitivity for larger alkanes. Fragment ion distribution and sensitivity is a function of drift conditions. At 80 Td the most abundant ion fragments from C10 to C16 n-alkanes were m/z 57, 71 and 85. The mass spectrum of gasoline and diesel fuel at 80 Td displayed ion group patterns that can be related to known fuel constituents, such as alkanes, alkylbenzenes and cycloalkanes, and other compound groups that are inferred from molecular weight distributions such as dihydronapthalenes and naphthenic monoaromatics. It is shown that thermal desorption sampling of gasoline and diesel engine exhausts at 80 Td allows for discrimination against light alkanes and alkenes which are a major constituent of both exhausts, allowing for quantification of higher molecular weight alkanes from the abundance of CnH2n+1 fragment ions. Using this approach, the molar abundance of C12-C18 alkanes in diesel engine exhaust was found to be 75% that of the total C1-C4 alkylbenzene abundance. While the PTR-MS mass spectra of gasoline and diesel exhaust looked similar, the abundance of higher molecular weight compounds relative to that of C4-alkylbenzenes was much greater in diesel engine exhaust. The abundance patterns of compounds determined by thermal desorption sampling may allow for emission profiles to be developed to better quantify the relative contributions of diesel and gasoline exhaust emissions of larger organic compounds to urban air concentrations.

  20. Light alkane conversion processes - Suprabiotic catalyst systems for selective oxidation of light alkane gases to fuel oxygenates.

    SciTech Connect

    Lyons, J.E.

    1992-07-01

    The objective of the work presented in this paper is to develop new, efficient catalysts for the selective transformation of the light alkanes in natural gas to alcohols for use as liquid transportation fuels, fuel precursors and chemical products. There currently exists no DIRECT one-step catalytic air-oxidation process to convert these substrates to alcohols. Such a one-step route would represent superior useful technology for the utilization of natural gas and similar refinery-derived light hydrocarbon streams. Processes for converting natural gas or its components (methane, ethane, propane, and the butanes) to alcohols for use as motor fuels, fuel additives or fuel precursors will not only add a valuable alternative to crude oil but will produce a clean-burning, high octane alternative to conventional gasoline.

  1. Light alkane conversion processes - Suprabiotic catalyst systems for selective oxidation of light alkane gases to fuel oxygenates

    SciTech Connect

    Lyons, J.E.

    1992-01-01

    The objective of the work presented in this paper is to develop new, efficient catalysts for the selective transformation of the light alkanes in natural gas to alcohols for use as liquid transportation fuels, fuel precursors and chemical products. There currently exists no DIRECT one-step catalytic air-oxidation process to convert these substrates to alcohols. Such a one-step route would represent superior useful technology for the utilization of natural gas and similar refinery-derived light hydrocarbon streams. Processes for converting natural gas or its components (methane, ethane, propane, and the butanes) to alcohols for use as motor fuels, fuel additives or fuel precursors will not only add a valuable alternative to crude oil but will produce a clean-burning, high octane alternative to conventional gasoline.

  2. Are δ13C values of n-alkanes affected by atmospheric CO2 concentrations? Results from a free-air CO2 enrichment (FACE) experiment.

    NASA Astrophysics Data System (ADS)

    Sandquist, D. R.; Williams, D. G.; Shuman, B. N.; Kim, S.; Chen, J.; Macdonald, C.

    2015-12-01

    Compound-specific carbon isotope (δ13C) analyses of leaf waxes (i.e., n-alkanes) can be linked to large-scale shifts in vegetation, such as dominant taxa, functional types, life-forms and photosynthetic pathways that are usually coupled with environmental changes in climate. However using these δ13C values to interpret finer-scale ecosystem properties, including climate attributes such as CO2 concentrations, is difficult owing to uncertainty in the magnitude of internal biosynthetic fractionations that determine the δ13C of waxes relative to that of bulk leaf material. We investigated the composition, abundance and δ13C of n-alkanes in the aboveground biomass of a C4 grass and a C3 grass exposed to experimentally controlled CO2 at ambient [490ppm] and elevated [630ppm] levels within natural grassland in Wyoming. The δ13C values of bulk tissues were predictably different based on the C3 and C4 photosynthetic pathways, but the difference between bulk tissue and n-alkanes (ɛlipid), for both C29 and C31, was consistently greater in the C4 grass. The magnitudes of these ɛlipid values were large (- 7‰ to -15‰) relative to those found in most other studies. CO2 concentration of the growing environment also had a significant effect on n-alkane δ13C values, with consistently higher values of ~ 2‰ under elevated CO2 found in both species and in both a wet and a dry year. These results underscore the importance of recognizing potential abiotic effects on leaf wax δ13C values, in addition to the biotic drivers their variation, when interpreting climate from leaf-wax biomarkers of terrestrial ecosystems.

  3. Degradation of Hydrocarbons by Members of the Genus Candida II. Oxidation of n-Alkanes and 1-Alkenes by Candida lipolytica

    PubMed Central

    Klug, M. J.; Markovetz, A. J.

    1967-01-01

    Candida lipolytica ATCC 8661 was grown in a mineral-salts hydrocarbon medium. n-Alkanes and 1-alkenes with 14 through 18 carbon atoms were used as substrates. Ether extracts of culture fluids and cells obtained from cultures grown on the various substrates were analyzed by thin-layer and gas-liquid chromatography. Analyses of fluids from cultures grown on n-alkanes indicated a predominance of fatty acids and alcohols of the same chain length as the substrate. In addition, numerous other fatty acids and alcohols were present. Analyses of saponifiable and nonsaponifiable material obtained from the cells revealed essentially the same products. The presence of primary and secondary alcohols, as well as fatty acids, of the same chain length as the n-alkane substrate suggested that attack on both the methyl and α-methylene group was occurring. The significance of these two mechanisms in the degradation of n-alkanes by this organism was not evident from the data presented. Analyses of fluids from cultures grown on 1-alkenes indicated the presence of 1,2-diols, as well as ω-unsaturated fatty acids, of the same chain length as the substrate. Alcohols present were all unsaturated. Saponifiable and nonsaponifiable material obtained from cells contained essentially the same products. The presence of 1,2-diols and ω-unsaturated fatty acids of the same chain length as the substrate from cultures grown on 1-alkenes indicated that both the terminal methyl group and the terminal double bond were being attacked. PMID:6025303

  4. Influence of the hydrogenation step on selectivity during the nonoxidative oligomerization of methane to alkanes on Pt/SiO{sub 2} catalysts (EUROPt-1)

    SciTech Connect

    Marceau, E.; Tatiboueet, J.M.; Che, M.; Saint-Just, J.

    1999-04-25

    Methane oligomerization to alkanes can be accomplished on supported platinum via a two-step procedure: formation of carbonaceous species on the metallic surface by methane adsorption, followed by hydrogenation of these species. Temperature-programmed oxidation (TPO) experiments performed after hydrogenation steps of various durations show that the hydrogenation of a carbonaceous deposit obtained at 300 C on the reference Pt/SiO{sub 2} catalyst EUROPt-1 is not a fast process. Two groups of surface carbonaceous species have been characterized through their different reactivities toward oxygen, but at 300 C their reactivities toward hydrogen are similar. Among alkanes up to C{sub 5}, methane is the main product of hydrogenation, corresponding to one-half of the surface carbon reactive toward hydrogen; linear and branched alkanes are produced from the other half of the reactive carbonaceous species. On EUROPt-1, mainly ethane and n-pentane are produced during the first minutes of reaction, while on a sintered catalyst the initial production in n-pentane is negligible. The release of n-pentane during an intermediate purge with inert gas on EUROPt-1 shows that C-C bonds can form already during methane adsorption, leading to C{sub 5} precursors on specific active sites of this catalyst. A model of formation of C{sub 5} precursors is proposed by analogy with the organometallic chemistry of molecular hydrocarbon platinacycles. The subsequent production of alkanes (C{sub 2} > C{sub 3} > C{sub 4} > C{sub 5}) could be described through a statistical model of dynamic coupling between carbonaceous species involving hydrogen, rather than by hydrogenolysis of heavier carbonaceous species. However, this latter mechanism is likely to predominate for the production of C{sub 6}-C{sub 8} compounds.

  5. Prototheca zopfii Kruger strain UMK-13 growth on acetate or n-alkanes

    SciTech Connect

    Koenig, D.W.; Ward, H.B.

    1983-01-01

    A new strain of Prototheca zopfii Kruger was grown on acetate or on pure n-alkanes. A maximum acetate-supported exponential growth of 12 divisions day/sup -1/ occurred at pH 5 and 30/sup 0/C. At 25/sup 0/C, growth on n-alkanes was almost as fast, but no growth occurred at 30/sup 0/C. After 3 days at 25/sup 0/C, 34 to 45% of the n-alkanes had been removed, whereas at 21/sup 0/C and slower growth, utilization was twofold greater after 15 days. Rates of growth and utilization increased markedly after a point of sudden emulsification.

  6. Particulate PAHs and n-alkanes in the air over Southern and Eastern Mediterranean Sea.

    PubMed

    Romagnoli, Paola; Balducci, Catia; Perilli, Mattia; Perreca, Erica; Cecinato, Angelo

    2016-09-01

    Particulate polycyclic aromatic hydrocarbons, n-alkanes and polar organic compounds were investigated in the marine atmosphere of Southern and Eastern Mediterranean Sea, in the frame of the scientific cruise of Urania ship between 27 July and 11 August 2013. The PM10 fraction of aerosol to which most organic substances are associated, were collected daily; contemporarily, gaseous regulated toxicants (ozone, nitrogen oxides and carbon oxide) and carbonyls were recorded. Samplings were carried out in front of Palermo and Messina, respectively the start and end harbors, and along the cruise, both in movement (transects, N = 14) and at stops (N = 11). Total PAHs ranged from 0.06 ng/m(3) up to 1.8 ng/m(3), with the maximums observed close to harbors. Unlike total concentrations that were in general comparable, the percent composition of PAHs was distinct for harbors, transects and stops, which allowed to draw insights about the pollution sources impact. Concentrations of n-alkanes (C18-C35) ranging from 6.7 to 43 ng/m(3) were quantified. The carbonyls evaluation revealed relatively high concentrations of formaldehyde (∼4-24 μg/m(3)) and acetone (∼5-35 μg/m(3)) near harbors, and of acrolein (up to 12 μg/m(3)) offshore, while benzaldehyde was quite independent of the site type (≈0.5 μg/m(3)). Nicotine and caffeine were detected, at different extents (0.0-2.2 ng/m(3) and 0.01-0.17 ng/m(3), respectively), in ca. 70% and 100% of samples. Alkyl phthalates ranged from 2.7 to 67 ng/m(3) and showed variable percentages in the samples. Finally, traces of N,N-diethyl-meta-toluene amide (up to 0.4 ng/m(3)) were found at all sites. PMID:27341155

  7. Development of a Carbon Number Polarity Grid SOA Model with the use of Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere

    NASA Astrophysics Data System (ADS)

    Chung, S. H.; Lee-Taylor, J.; Asher, W.; Hodzic, A.; Madronich, S.; Aumont, B.; Pankow, J. F.; Barsanti, K. C.

    2012-12-01

    A major weakness in current air quality and climate models is the ability to simulate secondary organic aerosol (SOA) levels and physiochemical properties accurately. A new approach to model SOA formation is the carbon number (nc) polarity grid (CNPG) framework. The CNPG framework makes use of a nc vs. polarity grid for representing relevant organic compounds and their time-dependent concentrations. The nc vs polarity grid is well suited for modeling SOA because nc together with some suitable measure of total molecular polarity provides the minimum yet sufficient formation for estimating the parameters required to calculate partitioning coefficients. Furthermore, CNPG allows consideration of the effects of variation in the activity coefficients of the partitioning compounds, variation in the mean molecular weight of the absorbing organic phase, water uptake, and the possibility of phase separation in the organic aerosol phase. In this work, we use the GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) chemistry mechanism to produce the chemical structures of SOA precursor oxidization products and their time-dependent concentrations. The SIMPOL group contribution method is used to calculate the enthalpy of vaporization ΔHvap for each product. The total molecular polarity is then calculated as ΔHvap,diff, the difference between each compound's ΔHvap and that of its carbon-number equivalent straight-chain hydrocarbon. The gas- and particle-phase concentrations of each compound are mapped onto the nc vs polarity grid as a function of time to evaluate the time evolution of SOA-relevant oxidation products and to help guide lumping strategies for reducing complexity. In addition to using ΔHvap,diff, use of other measures of polarity will also be explored. Initial SOA precursor studies include toluene (C7) + n-heptadecane (C17) and α-pinene, under atmospherically relevant conditions. Results will be discussed in the context of the

  8. Liquid alkanes with targeted molecular weights from biomass-derived carbohydrates.

    PubMed

    West, Ryan M; Liu, Zhen Y; Peter, Maximilian; Dumesic, James A

    2008-01-01

    Liquid transportation fuels must burn cleanly and have high energy densities, criteria that are currently fulfilled by petroleum, a non-renewable resource, the combustion of which leads to increasing levels of atmospheric CO(2). An attractive approach for the production of transportation fuels from renewable biomass resources is to convert carbohydrates into alkanes with targeted molecular weights, such as C(8)-C(15) for jet-fuel applications. Targeted n-alkanes can be produced directly from fructose by an integrated process involving first the dehydration of this C(6) sugar to form 5-hydroxymethylfurfural, followed by controlled formation of C-C bonds with acetone to form C(9) and C(15) compounds, and completed by hydrogenation and hydrodeoxygenation reactions to form the corresponding n-alkanes. Analogous reactions are demonstrated starting with 5-methylfurfural or 2-furaldehyde, with the latter leading to C(8) and C(13) n-alkanes. PMID:18702136

  9. Draft Genome Sequence of the Versatile Alkane-Degrading Bacterium Aquabacterium sp. Strain NJ1

    PubMed Central

    Shiwa, Yuh; Yoshikawa, Hirofumi; Zylstra, Gerben J.

    2014-01-01

    The draft genome sequence of a soil bacterium, Aquabacterium sp. strain NJ1, capable of utilizing both liquid and solid alkanes, was deciphered. This is the first report of an Aquabacterium genome sequence. PMID:25477416

  10. Modeling the Role of Alkanes, Polycyclic Aromatic Hydrocarbons, and Their Oligomers in Secondary Organic Aerosol Formation

    EPA Science Inventory

    A computationally efficient method to treat secondary organic aerosol (SOA) from various length and structure alkanes as well as SOA from polycyclic aromatic hydrocarbons (PAHs) is implemented in the Community Multiscale Air Quality (CMAQ) model to predict aerosol concentrations ...

  11. Conformational problem of alkanes in liquid crystals by NMR spectroscopy: a mini-review.

    PubMed

    Weber, Adrian C J; Chen, Daniel H J

    2014-10-01

    Recent discoveries of the role of alkane flexibility in determining liquid-crystal behaviour are surveyed. With the impetus for understanding the alkane conformational problem established, recent model dependent (1)H NMR work on the topic will be reviewed where progress is made but the need to circumvent models eventually becomes evident. A closer look at the rigid basic units of alkanes will provide the way forward where it is shown that the orientational ordering and anisotropic potentials of these molecules dissolved in liquid crystals scale with each other. Once this relationship is established, a series of works using anisotropic and isotropic (1)H NMR spectroscopy to study alkane conformational statistics will be covered, wherein the influence of the gas, isotropic condensed and anisotropic condensed phases will be described. PMID:25142124

  12. Liquid-Phase Exfoliation of Graphite into Single- and Few-Layer Graphene with α-Functionalized Alkanes.

    PubMed

    Haar, Sébastien; Bruna, Matteo; Lian, Jian Xiang; Tomarchio, Flavia; Olivier, Yoann; Mazzaro, Raffaello; Morandi, Vittorio; Moran, Joseph; Ferrari, Andrea C; Beljonne, David; Ciesielski, Artur; Samorì, Paolo

    2016-07-21

    Graphene has unique physical and chemical properties, making it appealing for a number of applications in optoelectronics, sensing, photonics, composites, and smart coatings, just to cite a few. These require the development of production processes that are inexpensive and up-scalable. These criteria are met in liquid-phase exfoliation (LPE), a technique that can be enhanced when specific organic molecules are used. Here we report the exfoliation of graphite in N-methyl-2-pyrrolidinone, in the presence of heneicosane linear alkanes terminated with different head groups. These molecules act as stabilizing agents during exfoliation. The efficiency of the exfoliation in terms of the concentration of exfoliated single- and few-layer graphene flakes depends on the functional head group determining the strength of the molecular dimerization through dipole-dipole interactions. A thermodynamic analysis is carried out to interpret the impact of the termination group of the alkyl chain on the exfoliation yield. This combines molecular dynamics and molecular mechanics to rationalize the role of functionalized alkanes in the dispersion and stabilization process, which is ultimately attributed to a synergistic effect of the interactions between the molecules, graphene, and the solvent. PMID:27349897

  13. Adsorption of linear alkanes on Cu(111): Temperature and chain-length dependence of the softened vibrational mode

    NASA Astrophysics Data System (ADS)

    Fosser, Kari A.; Kang, Joo H.; Nuzzo, Ralph G.; Wöll, Christof

    2007-05-01

    The vibrational spectra of linear alkanes, with lengths ranging from n-propane to n-octane, were examined on a copper surface by reflection-absorption infrared spectroscopy. The appearance and frequency of the "soft mode," a feature routinely seen in studies of saturated hydrocarbons adsorbed on metals, were examined and compared between the different adsorbates. The frequency of the mode was found to be dependent on both the number of methylene units of each alkane as well as specific aspects of the order of the monolayer phase. Studies of monolayer coverages at different temperatures provide insights into the nature of the two-dimensional (2D) melting transitions of these adlayer structures, ones that can be inferred from observed shifts in the soft vibrational modes appearing in the C-H stretching region of the infrared spectrum. These studies support recently reported hypotheses as to the origins of such soft modes: the metal-hydrogen interactions that mediate them and the dynamics that underlay their pronounced temperature dependencies. The present data strongly support a model for the 2D to one-dimensional order-order phase transition arising via a continuous rather than discrete first-order process.

  14. Liquid-Phase Exfoliation of Graphite into Single- and Few-Layer Graphene with α-Functionalized Alkanes.

    PubMed

    Haar, Sébastien; Bruna, Matteo; Lian, Jian Xiang; Tomarchio, Flavia; Olivier, Yoann; Mazzaro, Raffaello; Morandi, Vittorio; Moran, Joseph; Ferrari, Andrea C; Beljonne, David; Ciesielski, Artur; Samorì, Paolo

    2016-07-21

    Graphene has unique physical and chemical properties, making it appealing for a number of applications in optoelectronics, sensing, photonics, composites, and smart coatings, just to cite a few. These require the development of production processes that are inexpensive and up-scalable. These criteria are met in liquid-phase exfoliation (LPE), a technique that can be enhanced when specific organic molecules are used. Here we report the exfoliation of graphite in N-methyl-2-pyrrolidinone, in the presence of heneicosane linear alkanes terminated with different head groups. These molecules act as stabilizing agents during exfoliation. The efficiency of the exfoliation in terms of the concentration of exfoliated single- and few-layer graphene flakes depends on the functional head group determining the strength of the molecular dimerization through dipole-dipole interactions. A thermodynamic analysis is carried out to interpret the impact of the termination group of the alkyl chain on the exfoliation yield. This combines molecular dynamics and molecular mechanics to rationalize the role of functionalized alkanes in the dispersion and stabilization process, which is ultimately attributed to a synergistic effect of the interactions between the molecules, graphene, and the solvent.

  15. Biodegradation of variable-chain-length n-alkanes in Rhodococcus opacus R7 and the involvement of an alkane hydroxylase system in the metabolism

    PubMed Central

    2014-01-01

    Rhodococcus opacus R7 is a Gram-positive bacterium isolated from a polycyclic aromatic hydrocarbon contaminated soil for its versatile metabolism; indeed the strain is able to grow on naphthalene, o-xylene, and several long- and medium-chain n-alkanes. In this work we determined the degradation of n-alkanes in Rhodococcus opacus R7 in presence of n-dodecane (C12), n-hexadecane (C16), n-eicosane (C20), n-tetracosane (C24) and the metabolic pathway in presence of C12. The consumption rate of C12 was 88%, of C16 was 69%, of C20 was 51% and of C24 it was 78%. The decrement of the degradation rate seems to be correlated to the length of the aliphatic chain of these hydrocarbons. On the basis of the metabolic intermediates determined by the R7 growth on C12, our data indicated that R. opacus R7 metabolizes medium-chain n-alkanes by the primary alcohol formation. This represents a difference in comparison with other Rhodococcus strains, in which a mixture of the two alcohols was observed. By GC-MSD analysis we also identified the monocarboxylic acid, confirming the terminal oxidation. Moreover, the alkB gene cluster from R. opacus R7 was isolated and its involvement in the n-alkane degradation system was investigated by the cloning of this genomic region into a shuttle-vector E. coli-Rhodococcus to evaluate the alkane hydroxylase activity. Our results showed an increased biodegradation of C12 in the recombinant strain R. erythropolis AP (pTipQT1-alkR7) in comparison with the wild type strain R. erythropolis AP. These data supported the involvement of the alkB gene cluster in the n-alkane degradation in the R7 strain. PMID:25401074

  16. n-alkanes as a substratum for riboflavin production. I. Investigations of the dynamics of the flavinogenesis in chosen yeasts of the genus candida.

    PubMed

    Olczyk, C

    1978-01-01

    For the first time the flavinogenic abilities of Candida flareri on a simple, fully defined medium with hydrocarbons were demonstrated. C flareri and C. guilliermondi on a synthetic medium with biotin and n-alkanes (n-decane and hexadecane) overproduce riboflavin with a considerable but varying efficiency. Among the two hydrocarbons examined n-hexadecane proved to be a more favourable source of carbon for the biosynthesis of this vitamin than n-decane. The quantities of riboflavin accumulated by C. flareri in an aerated culture are twice higher than those for C. guilliermondii (50.5 microgram/ml on hexadecane) in analogous conditions. PMID:643742

  17. Measuring long chain alkanes in diesel engine exhaust by thermal desorption PTR-MS

    NASA Astrophysics Data System (ADS)

    Erickson, M. H.; Gueneron, M.; Jobson, B. T.

    2014-01-01

    A method using thermal desorption sampling and analysis by proton transfer reaction mass spectrometry (PTR-MS) to measure long chain alkanes (C12-C18) and other larger organics associated with diesel engine exhaust emissions is described. Long chain alkanes undergo dissociative proton transfer reactions forming a series of fragment ions with formula CnH2n+1. The PTR-MS is insensitive to n-alkanes less than C8 but displays an increasing sensitivity for larger alkanes. Fragment ion distribution and sensitivity is a function of drift conditions. At 80 Td the most abundant ion fragments from C10 to C16 n-alkanes were m/z 57, 71 and 85. The mass spectrum of gasoline and diesel fuel at 80 Td displayed ion group patterns that can be related to known fuel constituents, such as alkanes, alkylbenzenes and cycloalkanes, and other compound groups that are inferred from molecular weight distributions such as dihydronapthalenes and naphthenic monoaromatics. It is shown that thermal desorption sampling of gasoline and diesel engine exhausts at 80 Td allows for discrimination against volatile organic compounds, allowing for quantification of long chain alkanes from the abundance of CnH2n+1 fragment ions. The total abundance of long chain alkanes in diesel engine exhaust was measured to be similar to the total abundance of C1-C4 alkylbenzene compounds. The abundance patterns of compounds determined by thermal desorption sampling may allow for emission profiles to be developed to better quantify the relative contributions of diesel and gasoline exhaust emissions on organic compounds concentrations in urban air.

  18. Two distinct monooxygenases for alkane oxidation in Nocardioides sp. strain CF8.

    PubMed

    Hamamura, N; Yeager, C M; Arp, D J

    2001-11-01

    Alkane monooxygenases in Nocardioides sp. strain CF8 were examined at the physiological and genetic levels. Strain CF8 can utilize alkanes ranging in chain length from C(2) to C(16). Butane degradation by butane-grown cells was strongly inhibited by allylthiourea, a copper-selective chelator, while hexane-, octane-, and decane-grown cells showed detectable butane degradation activity in the presence of allylthiourea. Growth on butane and hexane was strongly inhibited by 1-hexyne, while 1-hexyne did not affect growth on octane or decane. A specific 30-kDa acetylene-binding polypeptide was observed for butane-, hexane-, octane-, and decane-grown cells but was absent from cells grown with octane or decane in the presence of 1-hexyne. These results suggest the presence of two monooxygenases in strain CF8. Degenerate primers designed for PCR amplification of genes related to the binuclear-iron-containing alkane hydroxylase from Pseudomonas oleovorans were used to clone a related gene from strain CF8. Reverse transcription-PCR and Northern blot analysis showed that this gene encoding a binuclear-iron-containing alkane hydroxylase was expressed in cells grown on alkanes above C(6). These results indicate the presence of two distinct monooxygenases for alkane oxidation in Nocardioides sp. strain CF8. PMID:11679317

  19. Marine hydrocarbonoclastic bacteria as whole-cell biosensors for n-alkanes.

    PubMed

    Sevilla, Emma; Yuste, Luis; Rojo, Fernando

    2015-07-01

    Whole-cell biosensors offer potentially useful, cost-effective systems for the in-situ monitoring of seawater for hydrocarbons derived from accidental spills. The present work compares the performance of a biosensor system for the detection of alkanes in seawater, hosted in either Escherichia coli (commonly employed in whole-cell biosensors but not optimized for alkane assimilation) or different marine bacteria specialized in assimilating alkanes. The sensor system was based on the Pseudomonas putida AlkS regulatory protein and the PalkB promoter fused to a gene encoding the green fluorescent protein. While the E. coli sensor provided the fastest response to pure alkanes (25-fold induction after 2 h under the conditions used), a sensor based on Alcanivorax borkumensis was slower, requiring 3-4 h to reach similar induction values. However, the A. borkumensis sensor showed a fourfold lower detection threshold for octane (0.5 μM), and was also better at sensing the alkanes present in petrol. At petrol concentrations of 0.0125%, the A. borkumensis sensor rendered a sevenfold induction, while E. coli sensor showed no response. We discuss possible explanations to this behaviour in terms of the cellular adaptations to alkane uptake and the basal fluorescence produced by each bacterial strain, which was lowest for A. borkumensis. PMID:25874658

  20. Alkanes in flower surface waxes of Momordica cochinchinensis influence attraction to Aulacophora foveicollis Lucas (Coleoptera: Chrysomelidae).

    PubMed

    Mukherjee, A; Sarkar, N; Barik, A

    2013-08-01

    Extraction, thin-layer chromatography, and gas chromatography-mass spectrophotometry analyses revealed 15 alkanes representing 97.14% of the total alkanes in the surface waxes of Momordica cochinchinensis Spreng flowers. Nonacosane was the prevailing alkane followed by hexatriacontane, nonadecane, heptacosane, and hentriacontane, accounting for 39.08%, 24.24%, 13.52%, 6.32%, and 5.12%, respectively. The alkanes from flower surface waxes followed by a synthetic mixture of alkanes mimicking alkanes of flower surface waxes elicited attraction of the female insect, Aulacophora foveicollis Lucas (Coleoptera: Chrysomelidae) between 2 and 10-μg/mL concentrations in a Y-shaped glass tube olfactometer bioassay under laboratory conditions. Synthetic nonadecane from 178.28-891.37 ng, heptacosane from 118.14-590.72 ng, and nonacosane at 784.73 ng showed attraction of the insect. A synthetic mixture of 534.82 ng nonadecane, 354.43 ng heptacosane, and 2,354.18 ng nonacosane elicited highest attraction of A. foveicollis. PMID:23949856

  1. Alkanes in flower surface waxes of Momordica cochinchinensis influence attraction to Aulacophora foveicollis Lucas (Coleoptera: Chrysomelidae).

    PubMed

    Mukherjee, A; Sarkar, N; Barik, A

    2013-08-01

    Extraction, thin-layer chromatography, and gas chromatography-mass spectrophotometry analyses revealed 15 alkanes representing 97.14% of the total alkanes in the surface waxes of Momordica cochinchinensis Spreng flowers. Nonacosane was the prevailing alkane followed by hexatriacontane, nonadecane, heptacosane, and hentriacontane, accounting for 39.08%, 24.24%, 13.52%, 6.32%, and 5.12%, respectively. The alkanes from flower surface waxes followed by a synthetic mixture of alkanes mimicking alkanes of flower surface waxes elicited attraction of the female insect, Aulacophora foveicollis Lucas (Coleoptera: Chrysomelidae) between 2 and 10-μg/mL concentrations in a Y-shaped glass tube olfactometer bioassay under laboratory conditions. Synthetic nonadecane from 178.28-891.37 ng, heptacosane from 118.14-590.72 ng, and nonacosane at 784.73 ng showed attraction of the insect. A synthetic mixture of 534.82 ng nonadecane, 354.43 ng heptacosane, and 2,354.18 ng nonacosane elicited highest attraction of A. foveicollis.

  2. Marine hydrocarbonoclastic bacteria as whole-cell biosensors for n-alkanes

    PubMed Central

    Sevilla, Emma; Yuste, Luis; Rojo, Fernando

    2015-01-01

    Whole-cell biosensors offer potentially useful, cost-effective systems for the in-situ monitoring of seawater for hydrocarbons derived from accidental spills. The present work compares the performance of a biosensor system for the detection of alkanes in seawater, hosted in either Escherichia coli (commonly employed in whole-cell biosensors but not optimized for alkane assimilation) or different marine bacteria specialized in assimilating alkanes. The sensor system was based on the Pseudomonas putida AlkS regulatory protein and the PalkB promoter fused to a gene encoding the green fluorescent protein. While the E. coli sensor provided the fastest response to pure alkanes (25-fold induction after 2 h under the conditions used), a sensor based on Alcanivorax borkumensis was slower, requiring 3–4 h to reach similar induction values. However, the A. borkumensis sensor showed a fourfold lower detection threshold for octane (0.5 μM), and was also better at sensing the alkanes present in petrol. At petrol concentrations of 0.0125%, the A. borkumensis sensor rendered a sevenfold induction, while E. coli sensor showed no response. We discuss possible explanations to this behaviour in terms of the cellular adaptations to alkane uptake and the basal fluorescence produced by each bacterial strain, which was lowest for A. borkumensis. PMID:25874658

  3. Marine hydrocarbonoclastic bacteria as whole-cell biosensors for n-alkanes.

    PubMed

    Sevilla, Emma; Yuste, Luis; Rojo, Fernando

    2015-07-01

    Whole-cell biosensors offer potentially useful, cost-effective systems for the in-situ monitoring of seawater for hydrocarbons derived from accidental spills. The present work compares the performance of a biosensor system for the detection of alkanes in seawater, hosted in either Escherichia coli (commonly employed in whole-cell biosensors but not optimized for alkane assimilation) or different marine bacteria specialized in assimilating alkanes. The sensor system was based on the Pseudomonas putida AlkS regulatory protein and the PalkB promoter fused to a gene encoding the green fluorescent protein. While the E. coli sensor provided the fastest response to pure alkanes (25-fold induction after 2 h under the conditions used), a sensor based on Alcanivorax borkumensis was slower, requiring 3-4 h to reach similar induction values. However, the A. borkumensis sensor showed a fourfold lower detection threshold for octane (0.5 μM), and was also better at sensing the alkanes present in petrol. At petrol concentrations of 0.0125%, the A. borkumensis sensor rendered a sevenfold induction, while E. coli sensor showed no response. We discuss possible explanations to this behaviour in terms of the cellular adaptations to alkane uptake and the basal fluorescence produced by each bacterial strain, which was lowest for A. borkumensis.

  4. Bulk and Compound-Specific Isotope Analysis of Long-Chain, n-alkanes From a 85-kyr Core From Lake Peten Itza, Guatemala

    NASA Astrophysics Data System (ADS)

    Mays, J. L.; Brenner, M.; Bush, M. B.; Correa, A.; Curtis, J. H.; Hodell, D. A.

    2007-12-01

    Drill cores obtained from Lake Petén Itzá, Guatemala, contain a ~85-kyr record of terrestrial climate from lowland Central America. Variations in sediment lithology suggest rapid changes in precipitation during the last glacial and deglacial periods. Previous work in nearby Lake Quexil demonstrated the utility of using the carbon isotopic compositions of leaf wax n-alkanes to infer changes in terrestrial vegetation (Huang et al., 2001). Here we report carbon isotopes of bulk organic and long-chain n-alkanes in 60 samples to reconstruct changes in the relative proportion of C3 and C4 biomass in the watershed under changing climate and atmospheric CO2 conditions during the past 85 kyrs. Compound-specific carbon isotope results are compared directly with pollen analysis from the same samples. Huang, Y., F.A. Street-Perrott, S.E. Metcalfe, M. Brenner, M. Moreland, and K.H. Freeman. 2001. Climate change as the dominant control on glacial-interglacial variations in C3 and C4 plant abundance. Science 293:1647-1651.

  5. Characterization of phospholipid+semifluorinated alkane vesicle system.

    PubMed

    Sabín, Juan; Ruso, Juan M; González-Pérez, Alfredo; Prieto, Gerardo; Sarmiento, Félix

    2006-01-15

    The aim of this study is to characterize vesicles obtained by the incorporation of the semifluorinated alkane, (perfluoro-n-hexyl)ethane (diblock F6H2) to a standard lipid, egg yolk phosphatidylcholine (PC). Large unilamellar vesicles (LUVs), prepared by extrusion, were characterized by fluorescence spectroscopy, zeta potential (zeta-potential) and light scattering. By using the fluorescence spectroscopy technique, the anisotropy of l,6-diphenyl-l,3,5-hexatriene (DPH) probe at different temperatures was determined. It was demonstrated that F6H2 is placed inside of the lipid bilayer and that the hydrocarbon acyl chain in the bilayers has higher viscosity in the presence of fluoroalkane. The zeta-potential of the PC-F6H2 system is negative and increases (in absolute value) from -10 to -19 mV when the temperature rises from 10 to 25 degrees C, this last value keeping practically constant with a further increase of temperature. The adsorption of K+ ions on the liposome surface was measured by zeta-potential. This adsorption originates a sudden increase of the initial zeta-potential followed by a slight decrease with K+ concentration. The application of the DLVO theory of colloidal stability showed a growing dependence of the DLVO potential with K+ concentration and consequently a increasing stability.

  6. Alkane functionalization at ([mu]-Oxo)diiron(III) centers

    SciTech Connect

    Leising, R.A.; Kim, J.; Perez, M.A.; Que, L. Jr. )

    1993-10-20

    The reactivity of ([mu]-oxo)diferric complexes with [sup t]BuOOH (TBHP) for the functionalization of alkanes in CH[sub 3]CN has been investigated as part of our efforts to model dinuclear sites in nonheme iron enzymes. [Fe[sub 2](TPA)[sub 2]O(OAc)](CIO[sub 4])[sub 3] (1) (TPA = tris(2-pyridylmethyl)amine, OAc = acetate) is an efficient catalyst for cyclohexane oxidation, affording cyclohexanol (A, 9 equiv), cyclohexanone (K, 11 equiv), and (tert-butylperoxy)cyclohexane (P, 16 equiv) in 0.25 h at ambient temperature and pressure under an argon atmosphere. The catalyst is remarkably robust, as indicated by the [sup 1]H NMR and UV-vis spectra of the reaction mixture during the catalytic reaction and by its ability to maintain its turnover efficiency with subsequent additions of oxidant. The catalytic mechanism for TBHP utilization was explored by observing the effects of varying the tripodal ligands on the ([mu]-oxo)([mu]-carboxylato)diferric catalysts and varying the bridge on Fe[sub 2]O(TPA)[sub 2] catalysts. The (A + K)/P ratio increased as the ligands became more electron donating. Solvent also played an important role in determining the partitioning of products between A + K and P, with benzonitrile favoring hydroxylated products at the expense of P and pyridine having the opposite effect. 49 refs., 2 figs., 3 tabs.

  7. Expression of an alkane monooxygenase (alkB) gene and methyl tert-butyl ether co-metabolic oxidation in Pseudomonas citronellolis.

    PubMed

    Bravo, Ana Luisa; Sigala, Juan Carlos; Le Borgne, Sylvie; Morales, Marcia

    2015-04-01

    Pseudomonas citronellolis UAM-Ps1 co-metabolically transforms methyl tert-butyl ether (MTBE) to tert-butyl alcohol with n-pentane (2.6 mM), n-octane (1.5 mM) or dicyclopropylketone (DCPK) (4.4 mM), a gratuitous inducer of alkane hydroxylase (AlkB) activity. The reverse transcription quantitative real-time PCR was used to quantify the alkane monooxygenase (alkB) gene expression. The alkB gene was expressed in the presence of n-alkanes and DCPK and MTBE oxidation occurred only in cultures when alkB was transcribed. A correlation between the number of alkB transcripts and MTBE consumption was found (ΜΤΒΕ consumption in μmol = 1.44e(-13) x DNA copies, R(2) = 0.99) when MTBE (0.84 mM) was added. Furthermore, alkB was cloned and expressed into Escherichia coli and the recombinant AlkB had a molecular weight of 42 kDa. This is the first report where the expression of alkB is related to the co-metabolic oxidation of MTBE. PMID:25432418

  8. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    SciTech Connect

    Getsoian, Andrew “Bean”; Das, Ujjal; Camacho-Bunquin, Jeffrey; Zhang, Guanghui; Gallagher, James R.; Hu, Bo; Cheah, Singfoong; Schaidle, Joshua A.; Ruddy, Daniel A.; Hensley, Jesse E.; Krause, Theodore R.; Curtiss, Larry A.; Miller, Jeffrey T.; Hock, Adam S.

    2016-01-01

    Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. These findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

  9. Expression of an alkane monooxygenase (alkB) gene and methyl tert-butyl ether co-metabolic oxidation in Pseudomonas citronellolis.

    PubMed

    Bravo, Ana Luisa; Sigala, Juan Carlos; Le Borgne, Sylvie; Morales, Marcia

    2015-04-01

    Pseudomonas citronellolis UAM-Ps1 co-metabolically transforms methyl tert-butyl ether (MTBE) to tert-butyl alcohol with n-pentane (2.6 mM), n-octane (1.5 mM) or dicyclopropylketone (DCPK) (4.4 mM), a gratuitous inducer of alkane hydroxylase (AlkB) activity. The reverse transcription quantitative real-time PCR was used to quantify the alkane monooxygenase (alkB) gene expression. The alkB gene was expressed in the presence of n-alkanes and DCPK and MTBE oxidation occurred only in cultures when alkB was transcribed. A correlation between the number of alkB transcripts and MTBE consumption was found (ΜΤΒΕ consumption in μmol = 1.44e(-13) x DNA copies, R(2) = 0.99) when MTBE (0.84 mM) was added. Furthermore, alkB was cloned and expressed into Escherichia coli and the recombinant AlkB had a molecular weight of 42 kDa. This is the first report where the expression of alkB is related to the co-metabolic oxidation of MTBE.

  10. Carbon Nanosheets and Nanostructured Electrodes in Organic Photovoltaic Devices: Cooperative Research and Development Final Report, CRADA Number CRD-08-321

    SciTech Connect

    Olson, D.

    2012-04-01

    Carbon nanosheet thin films were employed as nanostructured electrodes in organic solar cells. Due to the nanostructured texture of the carbon nanosheet electrodes, there was an increase in performance over standard ITO electrodes with very thick active layers. ZnO deposited via atomic layer deposition (ALD) was used as a hole blocking layer to provide for carrier selectivity of the carbon nanosheets.

  11. The carbon isotope biogeochemistry of the individual hydrocarbons in bat guano and the ecology of the insectivorous bats in the region of Carlsbad, New Mexico

    NASA Astrophysics Data System (ADS)

    Des Marais, David J.; Mitchell, J. M.; Meinschein, W. G.; Hayes, J. M.

    1980-12-01

    The structures and 13C contents of individual alkanes extracted from bat guano found in the Carlsbad region of New Mexico can be related to both the photosynthetic pathways of the local plants and the feeding habits of the insects that support the bats. Carbon isotopic analyses show that equivalent numbers of C 3 and C 4 native plant species occupy the Pecos River Valley, a very significant feeding area for the Carlsbad bats. During the seasons when bats frequent the area, the agricultural crops consist principally of alfalfa and cotton, both C 3 plants. The molecular composition of the bat guano hydrocarbons is fully consistent with an insect origin. Two isotopically distinct groups of insect branched alkanes were discerned. These two groups of alkanes derived from two chemotaxonomically distinct populations of insects possessing distinctly different feeding habits. It is possible that one population grazes predominantly on crops whereas the other population prefers native vegetation. This and other isotopic evidence suggests that crop pests constitute a major percentage of the bats' diet. Because the guano sample was less than 40 years old, this material reflects the present day plant community in the Pecos River Valley. Future studies of more ancient guano deposits should reveal a measurable influence of both natural and man-induced vegetative changes with time upon the 13C content of the bat guano hydrocarbons.

  12. Assessment of the GECKO-A modeling tool using chamber observations for C12 alkanes

    NASA Astrophysics Data System (ADS)

    Aumont, B.; La, S.; Ouzebidour, F.; Valorso, R.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J. M.; Hodzic, A.; Madronich, S.; Yee, L. D.; Loza, C. L.; Craven, J. S.; Zhang, X.; Seinfeld, J.

    2013-12-01

    Secondary Organic Aerosol (SOA) production and ageing is the result of atmospheric oxidation processes leading to the progressive formation of organic species with higher oxidation state and lower volatility. Explicit chemical mechanisms reflect our understanding of these multigenerational oxidation steps. Major uncertainties remain concerning the processes leading to SOA formation and the development, assessment and improvement of such explicit schemes is therefore a key issue. The development of explicit mechanism to describe the oxidation of long chain hydrocarbons is however a challenge. Indeed, explicit oxidation schemes involve a large number of reactions and secondary organic species, far exceeding the size of chemical schemes that can be written manually. The chemical mechanism generator GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) is a computer program designed to overcome this difficulty. GECKO-A generates gas phase oxidation schemes according to a prescribed protocol assigning reaction pathways and kinetics data on the basis of experimental data and structure-activity relationships. In this study, we examine the ability of the generated schemes to explain SOA formation observed in the Caltech Environmental Chambers from various C12 alkane isomers and under high NOx and low NOx conditions. First results show that the model overestimates both the SOA yields and the O/C ratios. Various sensitivity tests are performed to explore processes that might be responsible for these disagreements.

  13. A 25,000-year record of climate-induced changes in lowland vegetation of eastern equatorial Africa revealed by the stable carbon-isotopic composition of fossil plant leaf waxes

    NASA Astrophysics Data System (ADS)

    Sinninghe Damsté, Jaap S.; Verschuren, Dirk; Ossebaar, Jort; Blokker, Jord; van Houten, Rianne; van der Meer, Marcel T. J.; Plessen, Birgit; Schouten, Stefan

    2011-02-01

    The debate of climate versus CO2 in controlling the long-term dynamics of tropical African vegetation has focused on events at the upper tree-line, since the relevant paleodata tend to be from mid-elevation sites (~ 2000-3000 m). Less well known is the relative importance of CO2 in regulating the dynamics of tropical lowland (< 1500 m) vegetation, particularly that of the dry open woodlands, bush- and grasslands covering much of eastern equatorial Africa. Here we examine the stable carbon isotopic composition of n-alkanes in the sediment record of Lake Challa, a lowland crater lake near Mt. Kilimanjaro, covering the last 25,000 years. The distributions of the n-alkanes, with dominance of the long-chain odd-carbon-numbered components, and their isotopic composition reveal a mixed origin. The C23 and C25n-alkanes are depleted in 13C, with δ13C values between - 30 and - 50‰. In shallow lakes these n-alkanes are thought to derive from non-emergent aquatic plants, but this is unlikely in this steep-sided crater lake as it lacks a significant littoral habitat. The C27+n-alkanes are predominantly derived from leaf wax lipids of terrestrial plants, brought into the lake predominantly by local soil run-off. Their δ13C values, in particular that of the n-C31 alkane, reveal a marked transition in local lowland vegetation from being dominated (~ 70-100%) by C4 plants during the glacial period until 16.5 cal kyr BP, to a more mixed C3/C4 composition (~ 30-60% C4) during the Holocene. The start of the late-glacial trend towards a greater proportion of C3 plants coincided with the start of increasing monsoon rainfall, ~ 1500 years after the onset of the rise in atmospheric CO2 and ~ 3500 years after the onset of post-glacial warming. The transition was interrupted during the dry Younger Dryas period (13.0-11.7 cal kyr BP), when C4 plants again became much more prevalent, almost reaching their glacial-period abundance. Notably, the principal trend in leaf-wax δ13C values

  14. Conversion of alkanes to linear alkylsilanes using an iridium-iron-catalysed tandem dehydrogenation-isomerization-hydrosilylation.

    PubMed

    Jia, Xiangqing; Huang, Zheng

    2016-02-01

    The conversion of inexpensive, saturated hydrocarbon feedstocks into value-added speciality chemicals using regiospecific, catalytic functionalization of alkanes is a major goal of organometallic chemistry. Linear alkylsilanes represent one such speciality chemical-they have a wide range of applications, including release coatings, silicone rubbers and moulding products. Direct, selective, functionalization of alkanes at primary C-H bonds is difficult and, to date, methods for catalytically converting alkanes into linear alkylsilanes are unknown. Here, we report a well-defined, dual-catalyst system for one-pot, two-step alkane silylations. The system comprises a pincer-ligated Ir catalyst for alkane dehydrogenation and an Fe catalyst that effects a subsequent tandem olefin isomerization-hydrosilylation. This method exhibits exclusive regioselectivity for the production of terminally functionalized alkylsilanes. This dual-catalyst strategy has also been applied to regioselective alkane borylations to form linear alkylboronate esters. PMID:26791899

  15. Conversion of alkanes to linear alkylsilanes using an iridium-iron-catalysed tandem dehydrogenation-isomerization-hydrosilylation

    NASA Astrophysics Data System (ADS)

    Jia, Xiangqing; Huang, Zheng

    2016-02-01

    The conversion of inexpensive, saturated hydrocarbon feedstocks into value-added speciality chemicals using regiospecific, catalytic functionalization of alkanes is a major goal of organometallic chemistry. Linear alkylsilanes represent one such speciality chemical—they have a wide range of applications, including release coatings, silicone rubbers and moulding products. Direct, selective, functionalization of alkanes at primary C-H bonds is difficult and, to date, methods for catalytically converting alkanes into linear alkylsilanes are unknown. Here, we report a well-defined, dual-catalyst system for one-pot, two-step alkane silylations. The system comprises a pincer-ligated Ir catalyst for alkane dehydrogenation and an Fe catalyst that effects a subsequent tandem olefin isomerization-hydrosilylation. This method exhibits exclusive regioselectivity for the production of terminally functionalized alkylsilanes. This dual-catalyst strategy has also been applied to regioselective alkane borylations to form linear alkylboronate esters.

  16. Neutron diffraction and quasielastic neutron scattering studies of films of intermediate-length alkanes adsorbed on a graphite surface

    NASA Astrophysics Data System (ADS)

    Diama, Armand

    Over the past several years, we have conducted a variety of elastic neutron diffraction and quasielastic neutron scattering experiments to study the structure and the dynamics of films of two intermediate-length alkane molecules (C nH2n+2), adsorbed on a graphite basal-plane surface. The two molecules are the normal alkane n-tetracosane [n-CH 3(CH2)22CH3] and the branched alkane squalane (C30H62 or 2, 6, 10, 15, 19, 23-hexamethyltetracosane) whose carbon backbone is the same length as teteracosane. The temperature dependence of the monolayer structure of tetracosane and squalane was investigated using elastic neutron diffraction and evidence of two phase transitions was observed. Both the low-coverage tetracosane (C 24H50) and squalane (C30H62) monolayers have crystalline-to-"smectic" and "smectic"-to-isotropic fluid phase transitions upon heating. The diffusive motion in the tetracosane and squalane monolayers has been investigated by quasielastic neutron scattering. Two different quasielastic neutron scattering spectrometers at the Center for Neutron Research, National Institute of Standards and Technology (NIST) have been used. The spectrometers differ in both their dynamic range and energy resolution allowing molecular motions to be investigated on time scales in the range 10-13--10 -9 s. On these time scales, we observe evidence of translational, rotational, and intermolecular diffusive motions in the tetracosane and squalane monolayers. We conclude that the molecular diffusive motion in the two monolayers is qualitatively similar. Thus, despite the three methyl sidegroups at each end of the squalane molecule, its monolayer structure, phase transitions, and dynamics are qualitatively similar to that of a monolayer of the unbranched tetracosane molecules. With the higher resolution spectrometer at NIST, we have also investigated the molecular diffusive motion in multilayer tetracosane films. The analysis of our measurements indicates slower diffusive motion in

  17. Emissions of organic aerosol mass, black carbon, particle number, and regulated and unregulated gases from scooters and light and heavy duty vehicles with different fuels

    NASA Astrophysics Data System (ADS)

    Chirico, R.; Clairotte, M.; Adam, T. W.; Giechaskiel, B.; Heringa, M. F.; Elsasser, M.; Martini, G.; Manfredi, U.; Streibel, T.; Sklorz, M.; Zimmermann, R.; DeCarlo, P. F.; Astorga, C.; Baltensperger, U.; Prevot, A. S. H.

    2014-06-01

    A sampling campaign with seven different types of vehicles was conducted in 2009 at the vehicle test facilities of the Joint Research Centre (JRC) in Ispra (Italy). The vehicles chosen were representative of some categories circulating in Europe and were fueled either with standard gasoline or diesel and some with blends of rapeseed methyl ester biodiesel. The aim of this work was to improve the knowledge about the emission factors of gas phase and particle-associated regulated and unregulated species from vehicle exhaust. Unregulated species such as black carbon (BC), primary organic aerosol (OA) content, particle number (PN), monocyclic and polycyclic aromatic hydrocarbons (PAHs) and a~selection of unregulated gaseous compounds, including nitrous acid (N2O), ammonia (NH3), hydrogen cyanide (HCN), formaldehyde (HCHO), acetaldehyde (CH3CHO), sulfur dioxide (SO2), and methane (CH4), were measured in real time with a suite of instruments including a high-resolution aerosol time-of-flight mass spectrometer, a resonance enhanced multi-photon ionization time-of-flight mass spectrometer, and a high resolution Fourier transform infrared spectrometer. Diesel vehicles, without particle filters, featured the highest values for particle number, followed by gasoline vehicles and scooters. The particles from diesel and gasoline vehicles were mostly made of BC with a low fraction of OA, while the particles from the scooters were mainly composed of OA. Scooters were characterized by super high emissions factors for OA, which were orders of magnitude higher than for the other vehicles. The heavy duty diesel vehicle (HDDV) featured the highest nitrogen oxides (NOx) emissions, while the scooters had the highest emissions for total hydrocarbons and aromatic compounds due to the unburned and partially burned gasoline and lubricant oil mixture. Generally, vehicles fuelled with biodiesel blends showed lower emission factors of OA and total aromatics than those from the standard fuels

  18. Long-term observations of tropospheric particle number size distributions and equivalent black carbon mass concentrations in the German Ultrafine Aerosol Network (GUAN)

    NASA Astrophysics Data System (ADS)

    Birmili, Wolfram; Weinhold, Kay; Rasch, Fabian; Sonntag, André; Sun, Jia; Merkel, Maik; Wiedensohler, Alfred; Bastian, Susanne; Schladitz, Alexander; Löschau, Gunter; Cyrys, Josef; Pitz, Mike; Gu, Jianwei; Kusch, Thomas; Flentje, Harald; Quass, Ulrich; Kaminski, Heinz; Kuhlbusch, Thomas A. J.; Meinhardt, Frank; Schwerin, Andreas; Bath, Olaf; Ries, Ludwig; Gerwig, Holger; Wirtz, Klaus; Fiebig, Markus

    2016-08-01

    The German Ultrafine Aerosol Network (GUAN) is a cooperative atmospheric observation network, which aims at improving the scientific understanding of aerosol-related effects in the troposphere. The network addresses research questions dedicated to both climate- and health-related effects. GUAN's core activity has been the continuous collection of tropospheric particle number size distributions and black carbon mass concentrations at 17 observation sites in Germany. These sites cover various environmental settings including urban traffic, urban background, rural background, and Alpine mountains. In association with partner projects, GUAN has implemented a high degree of harmonisation of instrumentation, operating procedures, and data evaluation procedures. The quality of the measurement data is assured by laboratory intercomparisons as well as on-site comparisons with reference instruments. This paper describes the measurement sites, instrumentation, quality assurance, and data evaluation procedures in the network as well as the EBAS repository, where the data sets can be obtained (doi:10.5072/guan).

  19. Berberine cation: A fluorescent chemosensor for alkanes and other low-polarity compounds. An explanation of this phenomenon

    PubMed

    Cossio; Arrieta; Cebolla; Membrado; Vela; Garriga; Domingo

    2000-07-27

    Alkanes in the presence of berberine sulfate provide an enhancement of fluorescent signal, which depends on alkane concentration and structure, when the system is irradiated with monochromatic UV light. Computational analysis suggests that an ion-induced dipole between alkanes and berberine sulfate is responsible for this phenomenon. This interaction can properly model the experimentally obtained fluorescent response. The proposed explanation allows other interacting systems to be designed, which have been experimentally confirmed. PMID:10930271

  20. Berberine cation: A fluorescent chemosensor for alkanes and other low-polarity compounds. An explanation of this phenomenon

    PubMed

    Cossio; Arrieta; Cebolla; Membrado; Vela; Garriga; Domingo

    2000-07-27

    Alkanes in the presence of berberine sulfate provide an enhancement of fluorescent signal, which depends on alkane concentration and structure, when the system is irradiated with monochromatic UV light. Computational analysis suggests that an ion-induced dipole between alkanes and berberine sulfate is responsible for this phenomenon. This interaction can properly model the experimentally obtained fluorescent response. The proposed explanation allows other interacting systems to be designed, which have been experimentally confirmed.

  1. Photochemical properties of some Cl-containing halogenated alkanes.

    PubMed

    Orkin, V L; Khamaganov, V G; Kasimovskaya, E E; Guschin, A G

    2013-07-01

    Rate constants for the gas-phase reactions of OH radicals with three partially halogenated alkanes, CH3Cl (kMC), CHFClCFCl2 (k122a), and CH2FCFCl2 (k132c), were measured using a discharge flow-electron paramagnetic resonance technique over the temperature range from 298 to 460 K. The temperature dependences of the rate constants can be represented by the expressions kMC(298-460 K) = (3.09 ± 0.94) × 10(-12) exp[-(1411 ± 85)/T] cm(3) molecule(-1) s(-1), k122a(298-460 K) = (1.26 ± 0.24) × 10(-12) exp[-(1298 ± 66)/T] cm(3) molecule(-1) s(-1), and k132c(298-370 K) = (8.1 ± 2.2) × 10(-13) exp[-(1247 ± 89)/T] cm(3) molecule(-1) s(-1). The atmospheric lifetimes of CH3Cl, CHFClCFCl2, and CH2FCFCl2 due to their reaction with OH were estimated to be 1.6, 3.5, and 4.5 years, respectively. The UV absorption cross sections of halogenated ethanes, CHFClCFCl2, and CH2FCFCl2, were measured at T = 295 K between 190 and 240 nm, as were those for CHCl2CF2Cl (HCFC-122), CHCl2CF3 (HCFC-123), CHFClCF2Cl (HCFC-123a), and CH3CFCl2 (HCFC-141b). The atmospheric lifetimes due to stratospheric photolysis were also estimated. PMID:23725515

  2. Characterization of sorbent properties of soil organic matter and carbonaceous geosorbents using n-alkanes and cycloalkanes as molecular probes

    SciTech Connect

    Satoshi Endo; Peter Grathwohl; Stefan B. Haderlein; Torsten C. Schmidt

    2009-01-15

    Nonspecific interactions and modes (i.e., adsorption vs absorption) of sorption by noncondensed, amorphous organic phases (here termed organic matter; OM) in soils and by rigid, aromatic, and condensed phases (termed carbonaceous geosorbents; CGs) were investigated using n-alkanes and cycloalkanes as molecular probes. Sorption isotherms of and cyclooctane from water for seven CGs (charcoal, lignite coke, activated carbon, graphite, partially oxidized graphite, diesel soot, bituminous coal), four sorbents with a predominance of OM (lignite, peat, two sapric soils), and two soils containing OM and high amounts of CGs were measured in batch systems. The peat and the sapric soils showed extensively linear sorption, while the CGs exhibited highly nonlinear and strong (K{sub oc} values being up to 105 times those for the OM-rich materials at low concentrations) sorption for the alkanes studied, showing that enhanced sorption by CGs can occur to completely apolar sorbates that do not undergo any specific interaction. The n-octane-to-cyclooctane sorption coefficient ratios for adsorption to CGs were {ge}1, being distinctly different from those for absorption to the OM-rich materials. The measured sorption isotherms and the CG compositions in the soils determined by quantitative petrography analysis suggest, however, that CGs occurring in soils may be far less effective sorbents than the reference CGs used in the sorption experiments at least for nonspecifically interacting sorbates, probably because of competitive sorption and/or pore blocking by natural OM. The presented approaches and results offer a basis for interpreting sorption data for other organic compounds, as nonspecific interactions and sorption modes are relevant for any compound. 47 refs., 4 figs., 2 tabs.

  3. Cyclooctane metathesis catalyzed by silica-supported tungsten pentamethyl [(≡SiO)W(Me)5]: distribution of macrocyclic alkanes.

    PubMed

    Riache, Nassima; Callens, Emmanuel; Samantaray, Manoja K; Kharbatia, Najeh M; Atiqullah, Muhammad; Basset, Jean-Marie

    2014-11-10

    Metathesis of cyclic alkanes catalyzed by the new surface complex [(≡SiO)W(Me)5] affords a wide distribution of cyclic and macrocyclic alkanes. The major products with the formula C(n)H(2n) are the result of either a ring contraction or ring expansion of cyclooctane leading to lower unsubstituted cyclic alkanes (5≤n≤7) and to an unprecedented distribution of unsubstituted macrocyclic alkanes (12≤n≤40), respectively, identified by GC/MS and by NMR spectroscopies.

  4. Thermo-mechanical characteristics of UV-irradiated polyurethane elastomers extended with α, ω-alkane diols

    NASA Astrophysics Data System (ADS)

    Zia, Khalid Mahmood; Bhatti, Ijaz Ahmad; Barikani, Mehdi; Zuber, Mohammad; Sheikh, Munir Ahmad

    2009-05-01

    A series of polyurethane elastomers were prepared by the reaction of poly ɛ-caprolactone and 4,4'-diphenylmethane diisocyanate. The prepolymer was extended using α, ω-alkane diols as chain extenders having 2-10 methylene units in their structure. The synthesized samples were irradiated for 50, 100 and 200 h in an ultra violet (UV) exposure unit. Modifications in the chemical structure before and after irradiation were characterized using Fourier Transform Infrared spectroscopy. The thermal and mechanical properties were affected by the ultra violet irradiation time and the number of methylene units in the chain extenders. The experimental results indicated that the morphological structure changed during irradiation as a consequence of hard segment and soft segment degradation.

  5. Thermal analysis of n-alkane phase change material mixtures. Progress report, January 1, 1991--March 31, 1991

    SciTech Connect

    Chio, Y.I.; Choi, E.; Lorsch, H.G.

    1991-03-31

    Tests were performed to characterize the thermal behavior of it number of n-alkanes to be used as phase change materials (PCMs) in district cooling applications. Hexadecane and tetradecane were mixed in different fractions, and their thermal behavior was experimentally evaluated. Test results for melting temperature and fusion energy for laboratory grade hexadecane and tetradecane showed good agreement with datain the literature. However, values for commercial grade hexadecane were found to be considerably lower. In the range of temperatures of interest for district cooling, mixtures of tetradecane and hexadecane can be treated as homogeneous substances. However, their heats of fusion are slightly lower than those of the pure substances. Their melting temperatures are also lower by an amount that can be predicted.

  6. Comparing the accuracy of high-dimensional neural network potentials and the systematic molecular fragmentation method: A benchmark study for all-trans alkanes

    NASA Astrophysics Data System (ADS)

    Gastegger, Michael; Kauffmann, Clemens; Behler, Jörg; Marquetand, Philipp

    2016-05-01

    Many approaches, which have been developed to express the potential energy of large systems, exploit the locality of the atomic interactions. A prominent example is the fragmentation methods in which the quantum chemical calculations are carried out for overlapping small fragments of a given molecule that are then combined in a second step to yield the system's total energy. Here we compare the accuracy of the systematic molecular fragmentation approach with the performance of high-dimensional neural network (HDNN) potentials introduced by Behler and Parrinello. HDNN potentials are similar in spirit to the fragmentation approach in that the total energy is constructed as a sum of environment-dependent atomic energies, which are derived indirectly from electronic structure calculations. As a benchmark set, we use all-trans alkanes containing up to eleven carbon atoms at the coupled cluster level of theory. These molecules have been chosen because they allow to extrapolate reliable reference energies for very long chains, enabling an assessment of the energies obtained by both methods for alkanes including up to 10 000 carbon atoms. We find that both methods predict high-quality energies with the HDNN potentials yielding smaller errors with respect to the coupled cluster reference.

  7. Crystal structures of eight mono-methyl alkanes (C26–C32) via single-crystal and powder diffraction and DFT-D optimization

    PubMed Central

    Brooks, Lee; Brunelli, Michela; Pattison, Philip; Jones, Graeme R.; Fitch, Andrew

    2015-01-01

    The crystal structures of eight mono-methyl alkanes have been determined from single-crystal or high-resolution powder X-ray diffraction using synchrotron radiation. Mono-methyl alkanes can be found on the cuticles of insects and are believed to act as recognition pheromones in some social species, e.g. ants, wasps etc. The molecules were synthesized as pure S enantiomers and are (S)-9-methylpentacosane, C26H54; (S)-9-methylheptacosane and (S)-11-methylheptacosane, C28H58; (S)-7-methylnonacosane, (S)-9-methylnonacosane, (S)-11-methylnonacosane and (S)-13-methylnonacosane, C30H62; and (S)-9-methylhentriacontane, C32H66. All crystallize in space group P21. Depending on the position of the methyl group on the carbon chain, two packing schemes are observed, in which the molecules pack together hexagonally as linear rods with terminal and side methyl groups clustering to form distinct motifs. Carbon-chain torsion angles deviate by less than 10° from the fully extended conformation, but with one packing form showing greater curvature than the other near the position of the methyl side group. The crystal structures are optimized by dispersion-corrected DFT calculations, because of the difficulties in refining accurate structural parameters from powder diffraction data from relatively poorly crystalline materials. PMID:26306191

  8. Ubiquitous Presence and Novel Diversity of Anaerobic Alkane Degraders in Cold Marine Sediments

    PubMed Central

    Gittel, Antje; Donhauser, Johanna; Røy, Hans; Girguis, Peter R.; Jørgensen, Bo B.; Kjeldsen, Kasper U.

    2015-01-01

    Alkanes are major constituents of crude oil and are released to the marine environment by natural seepage and from anthropogenic sources. Due to their chemical inertness, their removal from anoxic marine sediments is primarily controlled by the activity of anaerobic alkane-degrading microorganisms. To facilitate comprehensive cultivation-independent surveys of the diversity and distribution of anaerobic alkane degraders, we designed novel PCR primers that cover all known diversity of the 1-methylalkyl succinate synthase gene (masD/assA), which catalyzes the initial activation of alkanes. We studied masD/assA gene diversity in pristine and seepage-impacted Danish coastal sediments, as well as in sediments and alkane-degrading enrichment cultures from the Middle Valley (MV) hydrothermal vent system in the Pacific Northwest. MasD/assA genes were ubiquitously present, and the primers captured the diversity of both known and previously undiscovered masD/assA gene diversity. Seepage sediments were dominated by a single masD/assA gene cluster, which is presumably indicative of a substrate-adapted community, while pristine sediments harbored a diverse range of masD/assA phylotypes including those present in seepage sediments. This rare biosphere of anaerobic alkane degraders will likely increase in abundance in the event of seepage or accidental oil spillage. Nanomolar concentrations of short-chain alkanes (SCA) were detected in pristine and seepage sediments. Interestingly, anaerobic alkane degraders closely related to strain BuS5, the only SCA degrader in pure culture, were found in mesophilic MV enrichments, but not in cold sediments from Danish waters. We propose that the new masD/assA gene lineages in these sediments represent novel phylotypes that are either fueled by naturally occurring low levels of SCA or that metabolize medium- to long-chain alkanes. Our study highlights that masD/assA genes are a relevant diagnostic marker to identify seepage and microseepage, e

  9. Ubiquitous Presence and Novel Diversity of Anaerobic Alkane Degraders in Cold Marine Sediments.

    PubMed

    Gittel, Antje; Donhauser, Johanna; Røy, Hans; Girguis, Peter R; Jørgensen, Bo B; Kjeldsen, Kasper U

    2015-01-01

    Alkanes are major constituents of crude oil and are released to the marine environment by natural seepage and from anthropogenic sources. Due to their chemical inertness, their removal from anoxic marine sediments is primarily controlled by the activity of anaerobic alkane-degrading microorganisms. To facilitate comprehensive cultivation-independent surveys of the diversity and distribution of anaerobic alkane degraders, we designed novel PCR primers that cover all known diversity of the 1-methylalkyl succinate synthase gene (masD/assA), which catalyzes the initial activation of alkanes. We studied masD/assA gene diversity in pristine and seepage-impacted Danish coastal sediments, as well as in sediments and alkane-degrading enrichment cultures from the Middle Valley (MV) hydrothermal vent system in the Pacific Northwest. MasD/assA genes were ubiquitously present, and the primers captured the diversity of both known and previously undiscovered masD/assA gene diversity. Seepage sediments were dominated by a single masD/assA gene cluster, which is presumably indicative of a substrate-adapted community, while pristine sediments harbored a diverse range of masD/assA phylotypes including those present in seepage sediments. This rare biosphere of anaerobic alkane degraders will likely increase in abundance in the event of seepage or accidental oil spillage. Nanomolar concentrations of short-chain alkanes (SCA) were detected in pristine and seepage sediments. Interestingly, anaerobic alkane degraders closely related to strain BuS5, the only SCA degrader in pure culture, were found in mesophilic MV enrichments, but not in cold sediments from Danish waters. We propose that the new masD/assA gene lineages in these sediments represent novel phylotypes that are either fueled by naturally occurring low levels of SCA or that metabolize medium- to long-chain alkanes. Our study highlights that masD/assA genes are a relevant diagnostic marker to identify seepage and microseepage, e

  10. Biogeographic variation of foliar n-alkanes of Juniperus communis var. saxatilis Pallas from the Balkans.

    PubMed

    Rajčević, Nemanja; Janaćković, Pedja; Dodoš, Tanja; Tešević, Vele; Marin, Petar D

    2014-12-01

    The composition of the epicuticular n-alkanes isolated from the leaves of ten populations of Juniperus communis L. var. saxatilis Pallas from central (continental) and western (coastal) areas of the Balkan Peninsula was characterized by GC-FID and GC/MS analyses. In the leaf waxes, 14 n-alkane homologues with chain-lengths ranging from C22 to C35 were identified. All samples were dominated by n-tritriacontane (C33 ), but differences in two other dominant n-alkanes allowed separating the coastal from the continental populations. Several statistical methods (ANOVA, principal component, discriminant, and cluster analyses as well as the Mantel test) were deployed to analyze the diversity and variability of the epicuticular-leaf-n-alkane patterns of the ten natural populations of J. communis var. saxatilis and their relation to different geographic and bioclimatic parameters. Cluster analysis showed a high correlation of the leaf-n-alkane patterns with the geographical distribution of the investigated samples, differentiating the coastal from the continental populations of this taxon. Several bioclimatic parameters related to aridity were highly correlated with this differentiation.

  11. Toward aldehyde and alkane production by removing aldehyde reductase activity in Escherichia coli

    PubMed Central

    Rodriguez, Gabriel M.; Atsumi, Shota

    2015-01-01

    Advances in synthetic biology and metabolic engineering have enabled the construction of novel biological routes to valuable chemicals using suitable microbial hosts. Aldehydes serve as chemical feedstocks in the synthesis of rubbers, plastics, and other larger molecules. Microbial production of alkanes is dependent on the formation of a fatty aldehyde intermediate which is converted to an alkane by an aldehyde deformylating oxygenase (ADO). However, microbial hosts such as Escherichia coli are plagued by many highly active endogenous aldehyde reductases (ALRs) that convert aldehydes to alcohols, which greatly complicates strain engineering for aldehyde and alkane production. It has been shown that the endogenous ALR activity outcompetes the ADO enzyme for fatty aldehyde substrate. The large degree of ALR redundancy coupled with an incomplete database of ALRs represents a significant obstacle in engineering E. coli for either aldehyde or alkane production. In this study, we identified 44 ALR candidates encoded in the E. coli genome using bioinformatics tools, and undertook a comprehensive screening by measuring the ability of these enzymes to produce isobutanol. From the pool of 44 candidates, we found five new ALRs using this screening method (YahK, DkgA, GldA, YbbO, and YghA). Combined deletions of all 13 known ALRs resulted in a 90–99% reduction in endogenous ALR activity for a wide range of aldehyde substrates (C2–C12). Elucidation of the ALRs found in E. coli could guide one in reducing competing alcohol formation during alkane or aldehyde production. PMID:25108218

  12. ClogP(alk): a method for predicting alkane/water partition coefficient.

    PubMed

    Kenny, Peter W; Montanari, Carlos A; Prokopczyk, Igor M

    2013-05-01

    Alkane/water partition coefficients (P(alk)) are less familiar to the molecular design community than their 1-octanol/water equivalents and access to both data and prediction tools is much more limited. A method for predicting alkane/water partition coefficient from molecular structure is introduced. The basis for the ClogP(alk) model is the strong (R² = 0.987) relationship between alkane/water partition coefficient and molecular surface area (MSA) that was observed for saturated hydrocarbons. The model treats a molecule as a perturbation of a saturated hydrocarbon molecule with the same MSA and uses increments defined for functional groups to quantify the extent to which logP(alk) is perturbed by the introduction each functional group. Interactions between functional groups, such as intramolecular hydrogen bonds are also parameterized within a perturbation framework. The functional groups and interactions between them are specified substructurally in a transparent and reproducible manner using SMARTS notation. The ClogP(alk) model was parameterized using data measured for structurally prototypical compounds that dominate the literature on alkane/water partition coefficients and then validated using an external test set of 100 alkane/water logP measurements, the majority of which were for drugs.

  13. n-Alkane distributions as indicators of novel ecosystem development in western boreal forest soils

    NASA Astrophysics Data System (ADS)

    Norris, Charlotte; Dungait, Jennifer; Quideau, Sylvie

    2013-04-01

    Novel ecosystem development is occurring within the western boreal forest of Canada due to land reclamation following surface mining in the Athabasca Oil Sands Region. Sphagnum peat is the primary organic matter amendment used to reconstruct soils in the novel ecosystems. We hypothesised that ecosystem recovery would be indicated by an increasing similarity in the biomolecular characteristics of novel reconstructed soil organic matter (SOM) derived from peat to those of natural boreal ecosystems. In this study, we evaluated the use of the homologous series of very long chain (>C20) n-alkanes with odd-over-even predominance as biomarker signatures to monitor the re-establishment of boreal forests on reconstructed soils. The lipids were extracted from dominant vegetation inputs and SOM from a series of natural and novel ecosystem reference plots. We observed unique very long n-alkane signatures of the source vegetation, e.g. Sphagnum sp. was dominated by C31 and aspen (Populus tremuloides Michx.) leaves by C25. Greater concentrations of very long chain n-alkanes were extracted from natural than novel ecosystem SOM (p<0.01), and their distribution differed between the two systems (p<0.001) and reflected the dominant vegetation input. Our results indicate that further research is required to clarify the influence of vegetation or disturbance on the signature of very long chain n-alkanes in SOM; however, the use of n-alkanes as biomarkers of ecosystem development is a promising method.

  14. Effects of fuel properties on the burning characteristics of collision-merged alkane/water droplets

    SciTech Connect

    Wang, C.H.; Pan, K.L.; Huang, W.C.; Wen, H.C.; Yang, J.Y.; Law, C.K.

    2008-04-15

    The combustion characteristics of freely falling droplets, individually generated by the merging of colliding alkane and water droplets, were experimentally investigated. The outcome of the collision droplets was first studied and then the subsequent burning processes such as the flame appearance, ignition and burning behaviors were recorded, through either visual observation or microphotography with the aid of stroboscopic lighting. If the merged droplets were exhibited in an insertive manner, while the water droplet inserted into the alkane droplet, these yield the burning behaviors prior to the end of flame were very much similar to that of pure alkane. The burning was ended with droplet extinction for lower-C alkane, and with either droplet ''flash vaporization'' or extinction for hexadecane. And if the merged droplets were in adhesive manner, for hexadecane with large water content, they either could not be ignited for the large merged droplets, or be ignited with a much prolonged ignition delay, followed by a soot-reducing flame and an ending of droplet extinction for the small merged droplets. ''Homogeneous'' explosion was not observed in any of the tests, and ''heterogeneous'' explosion, induced by trapped air bubbles, occasionally occurred for merged droplets with C-atom in alkane is higher than dodecane. And the sudden disappearance of droplet definitely decreased the burning time and thus enhanced the burning intensity. Besides, the fuel mass consumption rates were increased, even in the cases that having droplet extinction, because of the enlargement of the surface area due to the stuffing of water droplet. (author)

  15. Transferable Anisotropic United-Atom Force Field Based on the Mie Potential for Phase Equilibrium Calculations: n-Alkanes and n-Olefins.

    PubMed

    Hemmen, Andrea; Gross, Joachim

    2015-09-01

    A new transferable force field parametrization for n-alkanes and n-olefins is proposed in this work. A united-atom approach is taken, where hydrogen atoms are lumped with neighboring atoms to single interaction sites. A comprehensive study is conducted for alkanes, optimizing van der Waals force field parameters in 6 dimensions. A Mie n-6 potential is considered for the van der Waals interaction, where for n-alkanes we simultaneously optimize the energy parameters ϵCH3 and ϵCH2 as well as the size parameters σCH3 and σCH2 of the CH3(sp(3)) and CH2(sp(3)) groups. Further, the repulsive exponent n of the Mie n-6 potential is varied. Moreover, we investigate the bond length toward the terminal CH3 group as a degree of freedom. According to the AUA (anisotropic united-atom) force field, the bond length between the terminal CH3 group and the neighboring interaction site should be increased by Δl compared with the carbon-carbon distance in order to better account for the hydrogen atoms. The parameter Δl is considered as a degree of freedom. The intramolecular force field parametrization is taken from existing force fields. A single objective function for the optimization is defined as squared relative deviations in vapor pressure and in liquid density of propane, n-butane, n-hexane, and n-octane. A similar study is also done for olefins, where the objective function includes 1-butene, 1-hexene, 1-octene, cis-2-pentene, and trans-2-pentene. Molecular simulations are performed in the grand canonical ensemble with transition-matrix sampling where the phase equilibrium properties are obtained with the histogram reweighting technique. The 6-dimensional optimization of strongly correlated parameters is possible, because the analytic PC-SAFT equation of state is used to locally correlate simulation results. The procedure is iterative but leads to very efficient convergence. An implementation is proposed, where the converged result is not affected (disturbed) by the

  16. Black carbon, particle number concentration and nitrogen oxide emission factors of random in-use vehicles measured with the on-road chasing method

    NASA Astrophysics Data System (ADS)

    Ježek, I.; Katrašnik, T.; Westerdahl, D.; Močnik, G.

    2015-06-01

    The chasing method was used in an on-road measurement campaign, and emission factors (EF) of black carbon (BC), particle number (PN) and nitrogen oxides (NOx) were determined for 139 individual vehicles of different types encountered on the roads. The aggregated results provide EFs for BC, NOx and PN for three vehicle categories: goods vehicles, gasoline and diesel passenger cars. This is the first on-road measurement study where BC EFs of numerous individual diesel cars were determined in real-world driving conditions. We found good agreement between EFs of goods vehicles determined in this campaign and the results of previous studies that used either chasing or remote sensing measurement techniques. The composition of the sampled car fleet determined from the national vehicle registry information is reflective of Eurostat statistical data on the Slovenian and European vehicle fleet. The median BC EF of diesel and gasoline cars that were in use for less than 5 years, decreased by 60 and 47% from those in use for 5-10 years, respectively, the median NOx and PN EFs, of goods vehicles that were in use for less than five years, decreased from those in use for 5-10 years by 52 and 67%, respectively. The influence of engine maximum power of the measured EFs showed an increase in NOx EF from least to more powerful vehicles with diesel engines. Finally a disproportionate contribution of high emitters to the total emissions of the measured fleet was found; the top 25% of emitting diesel cars contributed 63, 47 and 61% of BC, NOx and PN emissions respectively. With the combination of relatively simple on-road measurements with sophisticated post processing individual vehicles EF can be determined and useful information about the fleet emissions can be obtained by exactly representing vehicles which contribute disproportionally to vehicle fleet emissions; and monitor how the numerous emission reduction approaches are reflected in on-road driving conditions.

  17. Land Use Regression Models of On-Road Particulate Air Pollution (Particle Number, Black Carbon, PM2.5, Particle Size) Using Mobile Monitoring.

    PubMed

    Hankey, Steve; Marshall, Julian D

    2015-08-01

    Land Use Regression (LUR) models typically use fixed-site monitoring; here, we employ mobile monitoring as a cost-effective alternative for LUR development. We use bicycle-based, mobile measurements (∼85 h) during rush-hour in Minneapolis, MN to build LUR models for particulate concentrations (particle number [PN], black carbon [BC], fine particulate matter [PM2.5], particle size). We developed and examined 1224 separate LUR models by varying pollutant, time-of-day, and method of spatial and temporal smoothing of the time-series data. Our base-case LUR models had modest goodness-of-fit (adjusted R(2): ∼0.5 [PN], ∼0.4 [PM2.5], 0.35 [BC], ∼0.25 [particle size]), low bias (<4%) and absolute bias (2-18%), and included predictor variables that captured proximity to and density of emission sources. The spatial density of our measurements resulted in a large model-building data set (n = 1101 concentration estimates); ∼25% of buffer variables were selected at spatial scales of <100m, suggesting that on-road particle concentrations change on small spatial scales. LUR model-R(2) improved as sampling runs were completed, with diminishing benefits after ∼40 h of data collection. Spatial autocorrelation of model residuals indicated that models performed poorly where spatiotemporal resolution of emission sources (i.e., traffic congestion) was poor. Our findings suggest that LUR modeling from mobile measurements is possible, but that more work could usefully inform best practices.

  18. Applicability of a noise-based model to estimate in-traffic exposure to black carbon and particle number concentrations in different cultures.

    PubMed

    Dekoninck, Luc; Botteldooren, Dick; Panis, Luc Int; Hankey, Steve; Jain, Grishma; S, Karthik; Marshall, Julian

    2015-01-01

    Several studies show that a significant portion of daily air pollution exposure, in particular black carbon (BC), occurs during transport. In a previous work, a model for the in-traffic exposure of bicyclists to BC was proposed based on spectral evaluation of mobile noise measurements and validated with BC measurements in Ghent, Belgium. In this paper, applicability of this model in a different cultural context with a totally different traffic and mobility situation is presented. In addition, a similar modeling approach is tested for particle number (PN) concentration. Indirectly assessing BC and PN exposure through a model based on noise measurements is advantageous because of the availability of very affordable noise monitoring devices. Our previous work showed that a model including specific spectral components of the noise that relate to engine and rolling emission and basic meteorological data, could be quite accurate. Moreover, including a background concentration adjustment improved the model considerably. To explore whether this model could also be used in a different context, with or without tuning of the model parameters, a study was conducted in Bangalore, India. Noise measurement equipment, data storage, data processing, continent, country, measurement operators, vehicle fleet, driving behavior, biking facilities, background concentration, and meteorology are all very different from the first measurement campaign in Belgium. More than 24h of combined in-traffic noise, BC, and PN measurements were collected. It was shown that the noise-based BC exposure model gives good predictions in Bangalore and that the same approach is also successful for PN. Cross validation of the model parameters was used to compare factors that impact exposure across study sites. A pooled model (combining the measurements of the two locations) results in a correlation of 0.84 when fitting the total trip exposure in Bangalore. Estimating particulate matter exposure with traffic

  19. Land Use Regression Models of On-Road Particulate Air Pollution (Particle Number, Black Carbon, PM2.5, Particle Size) Using Mobile Monitoring.

    PubMed

    Hankey, Steve; Marshall, Julian D

    2015-08-01

    Land Use Regression (LUR) models typically use fixed-site monitoring; here, we employ mobile monitoring as a cost-effective alternative for LUR development. We use bicycle-based, mobile measurements (∼85 h) during rush-hour in Minneapolis, MN to build LUR models for particulate concentrations (particle number [PN], black carbon [BC], fine particulate matter [PM2.5], particle size). We developed and examined 1224 separate LUR models by varying pollutant, time-of-day, and method of spatial and temporal smoothing of the time-series data. Our base-case LUR models had modest goodness-of-fit (adjusted R(2): ∼0.5 [PN], ∼0.4 [PM2.5], 0.35 [BC], ∼0.25 [particle size]), low bias (<4%) and absolute bias (2-18%), and included predictor variables that captured proximity to and density of emission sources. The spatial density of our measurements resulted in a large model-building data set (n = 1101 concentration estimates); ∼25% of buffer variables were selected at spatial scales of <100m, suggesting that on-road particle concentrations change on small spatial scales. LUR model-R(2) improved as sampling runs were completed, with diminishing benefits after ∼40 h of data collection. Spatial autocorrelation of model residuals indicated that models performed poorly where spatiotemporal resolution of emission sources (i.e., traffic congestion) was poor. Our findings suggest that LUR modeling from mobile measurements is possible, but that more work could usefully inform best practices. PMID:26134458

  20. Applicability of a noise-based model to estimate in-traffic exposure to black carbon and particle number concentrations in different cultures.

    PubMed

    Dekoninck, Luc; Botteldooren, Dick; Panis, Luc Int; Hankey, Steve; Jain, Grishma; S, Karthik; Marshall, Julian

    2015-01-01

    Several studies show that a significant portion of daily air pollution exposure, in particular black carbon (BC), occurs during transport. In a previous work, a model for the in-traffic exposure of bicyclists to BC was proposed based on spectral evaluation of mobile noise measurements and validated with BC measurements in Ghent, Belgium. In this paper, applicability of this model in a different cultural context with a totally different traffic and mobility situation is presented. In addition, a similar modeling approach is tested for particle number (PN) concentration. Indirectly assessing BC and PN exposure through a model based on noise measurements is advantageous because of the availability of very affordable noise monitoring devices. Our previous work showed that a model including specific spectral components of the noise that relate to engine and rolling emission and basic meteorological data, could be quite accurate. Moreover, including a background concentration adjustment improved the model considerably. To explore whether this model could also be used in a different context, with or without tuning of the model parameters, a study was conducted in Bangalore, India. Noise measurement equipment, data storage, data processing, continent, country, measurement operators, vehicle fleet, driving behavior, biking facilities, background concentration, and meteorology are all very different from the first measurement campaign in Belgium. More than 24h of combined in-traffic noise, BC, and PN measurements were collected. It was shown that the noise-based BC exposure model gives good predictions in Bangalore and that the same approach is also successful for PN. Cross validation of the model parameters was used to compare factors that impact exposure across study sites. A pooled model (combining the measurements of the two locations) results in a correlation of 0.84 when fitting the total trip exposure in Bangalore. Estimating particulate matter exposure with traffic

  1. The synergetic effect of starch and alpha amylase on the biodegradation of n-alkanes.

    PubMed

    Karimi, M; Biria, D

    2016-06-01

    The impact of adding soluble starch on biodegradation of n-alkanes (C10-C14) by Bacillus subtilis TB1 was investigated. Gas chromatography was employed to measure the residual hydrocarbons in the system. It was observed that the efficiency of biodegradation improved with the presence of starch and the obtained residual hydrocarbons in the system were 53% less than the samples without starch. The produced bacterial enzymes were studied through electrophoresis and reverse zymography for explaining the observations. The results indicated that the produced amylase by the bacteria can degrade hydrocarbons and the same was obtained by the application of a commercial alpha amylase sample. In addition, in silico docking of alpha-amylase with n-alkanes with different molecular weights was studied by Molegro virtual docker which showed high negative binding energies and further substantiated the experimental observations. Overall, the findings confirmed the catalytic effect of alpha amylase on n-alkanes degradation.

  2. Catalytic dehydroaromatization of n-alkanes by pincer-ligated iridium complexes

    NASA Astrophysics Data System (ADS)

    Ahuja, Ritu; Punji, Benudhar; Findlater, Michael; Supplee, Carolyn; Schinski, William; Brookhart, Maurice; Goldman, Alan S.

    2011-02-01

    Aromatic hydrocarbons are among the most important building blocks in the chemical industry. Benzene, toluene and xylenes are obtained from the high temperature thermolysis of alkanes. Higher alkylaromatics are generally derived from arene-olefin coupling, which gives branched products—that is, secondary alkyl arenes—with olefins higher than ethylene. The dehydrogenation of acyclic alkanes to give alkylaromatics can be achieved using heterogeneous catalysts at high temperatures, but with low yields and low selectivity. We present here the first catalytic conversion of n-alkanes to alkylaromatics using homogeneous or molecular catalysts—specifically ‘pincer’-ligated iridium complexes—and olefinic hydrogen acceptors. For example, the reaction of n-octane affords up to 86% yield of aromatic product, primarily o-xylene and secondarily ethylbenzene. In the case of n-decane and n-dodecane, the resulting alkylarenes are exclusively unbranched (that is, n-alkyl-substituted), with selectivity for the corresponding o-(n-alkyl)toluene.

  3. The synergetic effect of starch and alpha amylase on the biodegradation of n-alkanes.

    PubMed

    Karimi, M; Biria, D

    2016-06-01

    The impact of adding soluble starch on biodegradation of n-alkanes (C10-C14) by Bacillus subtilis TB1 was investigated. Gas chromatography was employed to measure the residual hydrocarbons in the system. It was observed that the efficiency of biodegradation improved with the presence of starch and the obtained residual hydrocarbons in the system were 53% less than the samples without starch. The produced bacterial enzymes were studied through electrophoresis and reverse zymography for explaining the observations. The results indicated that the produced amylase by the bacteria can degrade hydrocarbons and the same was obtained by the application of a commercial alpha amylase sample. In addition, in silico docking of alpha-amylase with n-alkanes with different molecular weights was studied by Molegro virtual docker which showed high negative binding energies and further substantiated the experimental observations. Overall, the findings confirmed the catalytic effect of alpha amylase on n-alkanes degradation. PMID:26971168

  4. Dehydrogenation of n-alkanes catalyzed by iridium ``pincer`` complexes: Regioselective formation of {alpha}-olefins

    SciTech Connect

    Liu, F.; Singh, B.; Goldman, A.S.; Pak, E.B.; Jensen, C.M.

    1999-04-28

    The development of methods for the functionalization of alkanes is of cardinal importance in catalytic chemistry. A specific functionalization of particularly great potential value is the conversion of n-alkanes to the corresponding 1-alkenes ({alpha}-olefins) since these serve as precursors for a wide range of commodity-scale chemicals (>2 {times} 10{sup 9} kg/yr). Such a conversion is also an intriguing challenge as viewed from a fundamental perspective. n-Alkanes are the simplest organic molecules with the potential to undergo regioselective transformations; {alpha}-olefins are the thermodynamically least stable of the corresponding double-bond isomers and any mechanism for their formation must presumably involve activation of the strongest bond (primary C-{single_bond}H) in the molecule.

  5. Mie potentials for phase equilibria calculations: application to alkanes and perfluoroalkanes.

    PubMed

    Potoff, Jeffrey J; Bernard-Brunel, Damien A

    2009-11-01

    Transferable united-atom force fields, based on n - 6 Lennard-Jones potentials, are presented for normal alkanes and perfluorocarbons. It is shown that by varying the repulsive exponent the range of the potential can be altered, leading to improved predictions of vapor pressures while also reproducing saturated liquid densities to high accuracy. Histogram-reweighting Monte Carlo simulations in the grand canonical ensemble are used to determine the vapor liquid coexistence curves, vapor pressures, heats of vaporization, and critical points for normal alkanes methane through tetradecane, and perfluorocarbons perfluoromethane through perfluorooctane. For all molecules studied, saturated liquid densities are reproduced to within 1% of experiment. Vapor pressures for normal alkanes and perfluorocarbons were predicted to within 3% and 6% of experiment, respectively. Calculations performed for binary mixture vapor-liquid equilibria for propane + pentane show excellent agreement with experiment, while slight deviations are observed for the ethane + perfluoroethane mixture.

  6. Elevation-dependent changes in n-alkane δD and soil GDGTs across the South Central Andes

    NASA Astrophysics Data System (ADS)

    Nieto-Moreno, Vanesa; Rohrmann, Alexander; van der Meer, Marcel T. J.; Sinninghe Damsté, Jaap S.; Sachse, Dirk; Tofelde, Stefanie; Niedermeyer, Eva M.; Strecker, Manfred R.; Mulch, Andreas

    2016-11-01

    Surface uplift of large plateaus may significantly influence regional climate and more specifically precipitation patterns and temperature, sometimes complicating paleoaltimetry interpretations. Thus, understanding the topographic evolution of tectonically active mountain belts benefits from continued development of reliable proxies to reduce uncertainties in paleoaltimetry reconstructions. Lipid biomarker-based proxies provide a novel approach to stable isotope paleoaltimetry and complement authigenic or pedogenic mineral proxy materials, in particular outside semi-arid climate zones where soil carbonates are not abundant but (soil) organic matter has a high preservation potential. Here we present δD values of soil-derived n-alkanes and mean annual air temperature (MAT) estimates based on branched glycerol dialkyl glycerol tetraether (brGDGT) distributions to assess their potential for paleoelevation reconstructions in the southern central Andes. We analyzed soil samples across two environmental and hydrological gradients that include a hillslope (26-28°S) and a valley (22-24°S) transect on the windward flanks of Central Andean Eastern Cordillera in NW Argentina. Our results show that present-day n-alkane δD values and brGDGT-based MAT estimates are both linearly related with elevation and in good agreement with present-day climate conditions. Soil n-alkanes show a δD lapse rate (Δ (δD)) of - 1.64 ‰ / 100 m (R2 = 0.91, p < 0.01) at the hillslope transect, within the range of δD lapse rates from precipitation and surface waters in other tropical regions in the Andes like the Eastern Cordillera in Colombia and Bolivia and the Equatorial and Peruvian Andes. BrGDGT-derived soil temperatures are similar to monitored winter temperatures in the region and show a lapse rate of ΔT = - 0.51 °C / 100 m (R2 = 0.91, p < 0.01), comparable with lapse rates from in situ soil temperature measurements, satellite-derived land-surface temperatures at this transect, and

  7. Leaf wax composition and carbon isotopes vary among major conifer groups

    NASA Astrophysics Data System (ADS)

    Diefendorf, Aaron F.; Leslie, Andrew B.; Wing, Scott L.

    2015-12-01

    Leaf waxes (e.g. n-alkanes, n-alkanoic acids) and their carbon isotopes (δ13C) are commonly used to track past changes in the carbon cycle, water availability, and plant ecophysiology. Previous studies indicated that conifers have lower n-alkane concentrations than angiosperms and that 13C fractionation during n-alkane synthesis (εn-alkane) is smaller than in angiosperms. These prior studies, however, sampled a limited phylogenetic and geographic subset of conifers, leaving out many important subtropical and Southern Hemisphere groups that were once widespread and common components of fossil assemblages. To expand on previous work, we collected 43 conifer species (and Ginkgo biloba) from the University of California Botanical Garden at Berkeley, sampling all extant conifer families and almost two-thirds of extant genera. We find that Pinaceae, including many North American species used in previous studies, have very low or no n-alkanes. However, other conifer groups have significant concentrations of n-alkanes, especially Southern Hemisphere Araucariaceae and Podocarpaceae (monkey puzzles, Norfolk Island pines, and yellowwoods), and many species of Cupressaceae (junipers and relatives). Within the Cupressaceae, we find total n-alkane concentrations are high in subfamilies Cupressoideae and Callitroideae, but significantly lower in the early diverging taxodioid lineages (including bald cypress and redwood). Individual n-alkane chain lengths have a weak phylogenetic signal, except for n-C29 alkane, but when combined using average chain length (ACL), a strong phylogenetic signal emerges. The strong phylogenetic signal in ACL, observed in the context of a common growth environment for all plants we sampled, suggests that ACL is strongly influenced by factors other than climate. An analysis of εn-alkane indicates a strong phylogenetic signal in which the smallest biosynthetic fractionation occurs in Pinaceae and the largest in Taxaceae (yews and relatives). The

  8. Statistically designed study of the variables and parameters of carbon dioxide equations of state

    SciTech Connect

    Donohue, M.D.; Naiman, D.Q.; Jin, Gang; Loehe, J.R.

    1991-05-01

    Carbon dioxide is used widely in enhanced oil recovery (EOR) processes to maximize the production of crude oil from aging and nearly depleted oil wells. Carbon dioxide also is encountered in many processes related to oil recovery. Accurate representations of the properties of carbon dioxide, and its mixtures with hydrocarbons, play a critical role in a number of enhanced oil recovery operations. One of the first tasks of this project was to select an equation of state to calculate the properties of carbon dioxide and its mixtures. The equations simplicity, accuracy, and reliability in representing phase behavior and thermodynamic properties of mixtures containing carbon dioxide with hydrocarbons at conditions relevant to enhanced oil recovery were taken into account. We also have determined the thermodynamic properties that are important to enhanced oil recovery and the ranges of temperature, pressure and composition that are important. We chose twelve equations of state for preliminary studies to be evaluated against these criteria. All of these equations were tested for pure carbon dioxide and eleven were tested for pure alkanes and their mixtures with carbon dioxide. Two equations, the ALS equation and the ESD equation, were selected for detailed statistical analysis. 54 refs., 41 figs., 36 tabs.

  9. Pulse radiolysis of alkanes: A time-resolved electron paramagnetic resonance study

    SciTech Connect

    Shkrob, I.A.; Trifunac, A.D.

    1994-02-14

    Time-resolved spin-echo-detected electron paramagnetic resonance (EPR) was applied to examine short-lived alkyl radicals formed in pulse radiolysis of liquid alkanes. It was found that the ratio of yields of penultimate and interior radicals in n-alkanes at the instant of their generation is temperature-independent and is ca. 1.25 times greater than the statistical quantity. This higher-than-statistical production of penultimate radicals indicates that the fast ion molecule reactions involving radical cations are a significant route of radical generation. The analysis of spin-echo kinetics in n-alkanes suggests that the alkyl radicals are emissively polarized in spur reactions. this initial polarization rapidly increases with shortening of the aliphatic chain. Another finding is that a long-chain structure of these radicals results in much higher rate of Heisenberg spin exchange relative to the recombination rate. The relative yields of hydrogen abstraction and fragmentation for various branched alkanes are estimated. It is concluded that the fragmentation occurs prior to the formation of radicals in an excited precursor species. Effects of phenolic and alkene additives in radiolysis of n-alkanes are examined. It is demonstrated that phenoxy radicals are produced in dissociative capture of electrons and alkane holes. Another route is a reaction of phenols with free hydrogen atoms. A rapid transfer of singlet correlation from the geminate radical ion pairs is responsible for unusual polarization patterns in the phenoxy and cyclohexadienyl radicals. The significance of these results in the context of cross-linking in polyethylene and higher paraffins is discussed. 56 refs.

  10. Structure and Mass Transport Characteristics at the Intrinsic Liquid-Vapor Interfaces of Alkanes.

    PubMed

    Chilukoti, Hari Krishna; Kikugawa, Gota; Ohara, Taku

    2016-07-28

    In this paper, an instantaneous interface definition has been used to study the intrinsic structure and self-diffusion coefficient in the vicinity of the liquid-vapor interfaces of decane and tetracosane at three different temperatures using molecular dynamics simulations, and the results have been compared with those obtained on the basis of the conventional Gibbs dividing surface (time- and space-averaged interface). The alkane molecules were modeled using the united atom NERD force field. Partial layered structures of alkane molecules at the liquid-vapor interface are observed as a pinned structure of alkane liquids based on the intrinsic interface. This kind of characteristic has not been observed in the density profiles obtained based on the Gibbs dividing surface. By examining the orientation order parameter and radius of gyration of the alkane molecules, it was observed that the alkane molecules were preferentially oriented to be more parallel to the intrinsic interface than to the Gibbs dividing surface, and the shape of the alkane molecules is slightly changed in the vicinity of the liquid-vapor interfaces. The self-diffusion coefficient parallel to the intrinsic interface was examined using the Green-Kubo relation, where the projection of the velocity in the parallel direction to the local intrinsic interface is used in the velocity correlation function. It was found that the self-diffusion coefficient in the direction parallel to the intrinsic interface changes as the position approaches the interface in a more obvious manner as compared with the self-diffusion coefficient obtained with respect to the Gibbs dividing surface. These results suggest that the use of an instantaneous interface definition allowed us to capture sharp variations in transport properties which are originating due to steeper structure at the liquid-vapor interfaces.

  11. Structure and Mass Transport Characteristics at the Intrinsic Liquid-Vapor Interfaces of Alkanes.

    PubMed

    Chilukoti, Hari Krishna; Kikugawa, Gota; Ohara, Taku

    2016-07-28

    In this paper, an instantaneous interface definition has been used to study the intrinsic structure and self-diffusion coefficient in the vicinity of the liquid-vapor interfaces of decane and tetracosane at three different temperatures using molecular dynamics simulations, and the results have been compared with those obtained on the basis of the conventional Gibbs dividing surface (time- and space-averaged interface). The alkane molecules were modeled using the united atom NERD force field. Partial layered structures of alkane molecules at the liquid-vapor interface are observed as a pinned structure of alkane liquids based on the intrinsic interface. This kind of characteristic has not been observed in the density profiles obtained based on the Gibbs dividing surface. By examining the orientation order parameter and radius of gyration of the alkane molecules, it was observed that the alkane molecules were preferentially oriented to be more parallel to the intrinsic interface than to the Gibbs dividing surface, and the shape of the alkane molecules is slightly changed in the vicinity of the liquid-vapor interfaces. The self-diffusion coefficient parallel to the intrinsic interface was examined using the Green-Kubo relation, where the projection of the velocity in the parallel direction to the local intrinsic interface is used in the velocity correlation function. It was found that the self-diffusion coefficient in the direction parallel to the intrinsic interface changes as the position approaches the interface in a more obvious manner as compared with the self-diffusion coefficient obtained with respect to the Gibbs dividing surface. These results suggest that the use of an instantaneous interface definition allowed us to capture sharp variations in transport properties which are originating due to steeper structure at the liquid-vapor interfaces. PMID:27387788

  12. Self-assembly of long chain alkanes and their derivatives on graphite

    NASA Astrophysics Data System (ADS)

    Yang, Teng; Berber, Savas; Tománek, David; Liu, Jun-Fu; Miller, Glen P.

    2008-03-01

    We combine scanning tunneling microscopy (STM) measurements with ab initio calculations to study the self-assembly of long chain alkanes and related alcohol and carboxylic acid molecules on graphite. For each system, we identify the optimum adsorption geometry and explain the energetic origin of the domain formation observed in the STM images. Our results for the hierarchy of adsorbate-adsorbate and adsorbate-substrate interactions provide a quantitative basis to understand the ordering of long chain alkanes in self-assembled monolayers and ways to modify it using alcohol and acid functional groups.

  13. Self-assembly of long chain alkanes and their derivatives on graphite.

    PubMed

    Yang, Teng; Berber, Savas; Liu, Jun-Fu; Miller, Glen P; Tománek, David

    2008-03-28

    We combine scanning tunneling microscopy (STM) measurements with ab initio calculations to study the self-assembly of long chain alkanes and related alcohol and carboxylic acid molecules on graphite. For each system, we identify the optimum adsorption geometry and explain the energetic origin of the domain formation observed in the STM images. Our results for the hierarchy of adsorbate-adsorbate and adsorbate-substrate interactions provide a quantitative basis to understand the ordering of long chain alkanes in self-assembled monolayers and ways to modify it using alcohol and acid functional groups.

  14. Mass effect on the Soret coefficient in n-alkane mixtures.

    PubMed

    Alonso de Mezquia, David; Bou-Ali, M Mounir; Madariaga, J Antonio; Santamaría, Carlos

    2014-02-28

    We have determined the Soret coefficient of different equimolar and non equimolar n-alkane mixtures from measurements of the molecular diffusion and thermal diffusion coefficients. It is shown that equimolar mixtures behave as isotopic-like mixtures in which only the mass effect contributes to the Soret effect. In non equimolar mixtures, a small linear dependence with the molar fraction is observed. Finally, we have obtained a new correlation, which allows the determination of the Soret coefficient of n-alkane mixtures using the data of viscosity, the thermal expansion coefficient of the pure components, and the density of the equimolar mixture. PMID:24588181

  15. Mass effect on the Soret coefficient in n-alkane mixtures

    SciTech Connect

    Alonso de Mezquia, David; Mounir Bou-Ali, M.; Madariaga, J. Antonio; Santamaría, Carlos

    2014-02-28

    We have determined the Soret coefficient of different equimolar and non equimolar n-alkane mixtures from measurements of the molecular diffusion and thermal diffusion coefficients. It is shown that equimolar mixtures behave as isotopic-like mixtures in which only the mass effect contributes to the Soret effect. In non equimolar mixtures, a small linear dependence with the molar fraction is observed. Finally, we have obtained a new correlation, which allows the determination of the Soret coefficient of n-alkane mixtures using the data of viscosity, the thermal expansion coefficient of the pure components, and the density of the equimolar mixture.

  16. 40 CFR 721.10145 - Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Modified reaction products of alkyl... Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino compound... identified generically as modified reaction products of alkyl alcohol, halogenated alkane,...

  17. 40 CFR 721.10145 - Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Modified reaction products of alkyl... Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino compound... identified generically as modified reaction products of alkyl alcohol, halogenated alkane,...

  18. 40 CFR 721.10145 - Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Modified reaction products of alkyl... Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino compound... identified generically as modified reaction products of alkyl alcohol, halogenated alkane,...

  19. 40 CFR 721.10145 - Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Modified reaction products of alkyl... Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino compound... identified generically as modified reaction products of alkyl alcohol, halogenated alkane,...

  20. 40 CFR 721.10145 - Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Modified reaction products of alkyl... Modified reaction products of alkyl alcohol, halogenated alkane, substituted epoxide, and amino compound... identified generically as modified reaction products of alkyl alcohol, halogenated alkane,...

  1. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Naphtha (Fischer-Tropsch), C4-11... Significant New Uses for Specific Chemical Substances § 721.10103 Naphtha (Fischer-Tropsch), C4-11-alkane... substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  2. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Naphtha (Fischer-Tropsch), C4-11... Significant New Uses for Specific Chemical Substances § 721.10103 Naphtha (Fischer-Tropsch), C4-11-alkane... substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  3. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Naphtha (Fischer-Tropsch), C4-11... Significant New Uses for Specific Chemical Substances § 721.10103 Naphtha (Fischer-Tropsch), C4-11-alkane... substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  4. 40 CFR 721.10103 - Naphtha (Fischer-Tropsch), C4-11-alkane, branched and linear.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Naphtha (Fischer-Tropsch), C4-11... Significant New Uses for Specific Chemical Substances § 721.10103 Naphtha (Fischer-Tropsch), C4-11-alkane... substance identified as naphtha (fischer-tropsch), C4-11-alkane, branched and linear (PMN P-04-235; CAS...

  5. Enhanced Translocation and Growth of Rhodococcus erythropolis PR4 in the Alkane Phase of Aqueous-Alkane Two Phase Cultures Were Mediated by GroEL2 Overexpression

    PubMed Central

    Takihara, Hayato; Ogihara, Jun; Yoshida, Takao; Okuda, Shujiro; Nakajima, Mutsuyasu; Iwabuchi, Noriyuki; Sunairi, Michio

    2014-01-01

    We previously reported that R. erythropolis PR4 translocated from the aqueous to the alkane phase, and then grew in two phase cultures to which long-chain alkanes had been added. This was considered to be beneficial for bioremediation. In the present study, we investigated the proteins involved in the translocation of R. erythropolis PR4. The results of our proteogenomic analysis suggested that GroEL2 was upregulated more in cells that translocated inside of the pristane (C19) phase than in those located at the aqueous-alkane interface attached to the n-dodecane (C12) surface. PR4 (pK4-EL2-1) and PR4 (pK4-ΔEL2-1) strains were constructed to confirm the effects of the upregulation of GroEL2 in translocated cells. The expression of GroEL2 in PR4 (pK4-EL2-1) was 15.5-fold higher than that in PR4 (pK4-ΔEL2-1) in two phase cultures containing C12. The growth and cell surface lipophilicity of PR4 were enhanced by the introduction of pK4-EL2-1. These results suggested that the plasmid overexpression of groEL2 in PR4 (pK4-EL2-1) led to changes in cell localization, enhanced growth, and increased cell surface lipophilicity. Thus, we concluded that the overexpression of GroEL2 may play an important role in increasing the organic solvent tolerance of R. erythropolis PR4 in aqueous-alkane two phase cultures. PMID:25311591

  6. Chronic toxicity of a mixture of chlorinated alkanes and alkenes in ICR mice.

    PubMed

    Wang, Fun-In; Kuo, Min-Liang; Shun, Chia-Tung; Ma, Yee-Chung; Wang, Jung-Der; Ueng, Tzuu-Huei

    2002-02-01

    The aim of this study was to determine the chronic toxicity of a mixture of chlorinated alkanes and alkenes (CA) consisting of chloroform, 1,1-dichloroethane, 1,1-dichloroethylene, 1,1,1-trichloroethane, trichloroethylene, and tetrachloroethylene. These chlorinated organic solvents were present in the underground water near an electronic appliances manufactory in Taoyuan, Taiwan. Male and female weanling ICR mice were treated with low-, medium-, and high-dose CA mixtures in drinking water for 16 and 18 mo, respectively. A significant number of male mice treated with the high-dose CA mixture developed tail alopecia and deformation, which was not prominent in CA-treated female mice. Medium- and high-dose CA mixtures induced marginal increases of liver and lung weights, blood urea nitrogen, and serum creatinine levels in male mice. In female mice, the high-dose CA mixture increased liver, kidney, and uterus and ovary total weights, without affecting serum biochemistry parameters. CA mixtures had no effects on the total glutathione content or the level of glutathione S-transferase activity in the livers and kid- neys of male and female mice. Treatments with CA mixtures produced a trend of increasing frequency of hepatocelluar neoplasms in male mice, compared to male and female controls and CA-treated female mice. The high-dose CA mixture induced a significantly higher incidence of mammary adenocarcinoma in female mice. The calculated odds ratios of mammary adenocarcinoma in female mice induced by low-, medium-, and high-dose CA mixtures were 1.14, 1.37, and 3.53 times that of the controls, respectively. The low-dose CA mixture induced a higher incidence of cysts and inflammation in and around the ovaries. This study has demonstrated that the CA mixture is a potential carcinogen to male and female mice. These animal toxicology data may be important in assessing the health effects of individuals exposed to the CA mixture.

  7. Black carbon, particle number concentration and nitrogen oxide emission factors of random in-use vehicles measured with the on-road chasing method

    NASA Astrophysics Data System (ADS)

    Ježek, I.; Katrašnik, T.; Westerdahl, D.; Močnik, G.

    2015-10-01

    The chasing method was used in an on-road measurement campaign, and emission factors (EF) of black carbon (BC), particle number (PN) and nitrogen oxides (NOx) were determined for 139 individual vehicles of different types encountered on the roads. The aggregated results provide EFs for BC, NOx and PN for three vehicle categories: goods vehicles, gasoline and diesel passenger cars. This is the first on-road measurement study where BC EFs of numerous individual diesel cars were determined in real-world driving conditions. We found good agreement between EFs of goods vehicles determined in this campaign and the results of previous studies that used either chasing or remote-sensing measurement techniques. The composition of the sampled car fleet determined from the national vehicle registry information is reflective of Eurostat statistical data on the Slovenian and European vehicle fleet. The median BC EF of diesel and gasoline cars that were in use for less than 5 years decreased by 60 and 47 % from those in use for 5-10 years, respectively; the median NOx and PN EFs of goods vehicles that were in use for less than 5 years decreased from those in use for 5-10 years by 52 and 67 %, respectively. Surprisingly, we found an increase of BC EFs in the newer goods vehicle fleet compared to the 5-10-year old one. The influence of engine maximum power of the measured EFs showed an increase in NOx EF from least to more powerful vehicles with diesel engines. Finally, a disproportionate contribution of high emitters to the total emissions of the measured fleet was found; the top 25 % of emitting diesel cars contributed 63, 47 and 61 % of BC, NOx and PN emissions respectively. With the combination of relatively simple on-road measurements and sophisticated post processing, individual vehicle EF can be determined and useful information about the fleet emissions can be obtained by exactly representing vehicles which contribute disproportionally to vehicle fleet emissions; and

  8. Three years of aerosol mass, black carbon and particle number concentrations at Montsec (southern Pyrenees, 1570 m a.s.l.)

    NASA Astrophysics Data System (ADS)

    Ripoll, A.; Pey, J.; Minguillón, M. C.; Pérez, N.; Pandolfi, M.; Querol, X.; Alastuey, A.

    2014-04-01

    Time variation of mass particulate matter (PM1 and PM1&minus10), black carbon (BC) and number of particles (N3: number of particles with an aerodynamic diameter higher than 3 nm, and N10: higher than 10 nm) concentrations at the high-altitude site of Montsec (MSC) in the southern Pyrenees was interpreted for the period 2010-2012. At MSC, PM10 (12 μg m-3) and N7 (2140 # cm-3) three-year arithmetic average concentrations were higher than those measured at other high-altitude sites in central Europe during the same period (PM10: 3-9 μg m-3 and N: 634-2070 # cm-3). By contrast, BC concentrations at MSC (0.2 μg m-3) were equal to or even lower than those measured at these European sites (0.2-0.4 μg m-3). These differences were attributed to the higher relevance of Saharan dust transport and to the higher importance of the biogenic precursor emissions and new particle formation (NPF) processes, and to the lower influence of anthropogenic emissions at MSC. The different time variation of PM and BC concentrations compared with that of N suggests that these aerosol parameters were governed by diverse factors at MSC. Both PM and BC concentrations showed marked differences for different meteorological scenarios, with enhanced concentrations under North African air outbreaks (PM1&minus10: 13 μg m-3, PM1: 8 μg m-3 and BC: 0.3 μg m-3) and low concentrations when Atlantic advections occurred (PM1-10: 5 μg m-3, PM1: 4 μg m-3 and BC: 0.1 μg m-3). PM and BC concentrations increased in summer, with a secondary maximum in early spring, and were at their lowest in winter, due to the contrasting origin of the air masses in the warmer seasons (spring and summer) and in the colder seasons (autumn and winter). The maximum in the warmer seasons was attributed to long-range transport processes that mask the breezes and regional transport breaking the daily cycles of these pollutants. By contrast, PM and BC concentrations showed clear diurnal cycles, with maxima at midday in the

  9. Maturation of Green River Shale Kerogen with Hydrous Pyrolysis: Characterization of Geochemical Biomarkers and Carbon Isotopes

    NASA Astrophysics Data System (ADS)

    Fu, Q.; Darnell, M.; Bissada, K. K.

    2014-12-01

    To fully understand controlling factors of organic compound generation during oil shale maturation, and systematically assess associated carbon isotope values, a series of hydrous pyrolysis experiments are performed. Kerogen was isolated from Green River shale by a set of acid treatment. Experiments are conducted at 350 °C and 300 bars of total pressure with running time of 24, 48 and 72 hours, respectively. In each experiment, the reactor contains 1.5 grams of kerogen and 30 grams of deionized water. After experiments, gaseous products are removed under cryogenic conditions for chemical and carbon isotope analyses (GC-IRMS). The bitumen product is retrieved and separated into saturated hydrocarbons, aromatics, resins, and asphaltenes (SARA) by HPLC before subsequent analyses (GC, GC-MS, and IRMS). The gaseous compounds from experiments consisted of CO2 and C1 to C4 hydrocarbons. Semiquantitative analysis indicates the yield of n-alkanes decreases with carbon number, with CO2 being more abundant than all alkanes. The δ13C value of alkanes increases with molecular weight, with CO2 having the highest value. Methane and ethane become enriched in 13C with time. In bitumen products, gravimetric analysis has shown that the abundance of aromatics increases with time, while that of asphaltenes decreases. After 72 hours, the weight percentages of saturated hydrocarbons, aromatics, resins and asphaltenes are 2.6, 42.3, 40.1, and 15.0, respectively. High resolution GC-MS results indicate low kerogen maturation after 72 hours using saturated biomarker compounds as thermal maturity indicator, such as 22S/(22S + 22R) of C31 to C35 homohopanes, tricyclics/17(H)-hopanes, and Ts/(Ts + Tm). Bulk carbon isotope value of bitumen decreases with time, with 2.5‰ lighter than original kerogen after 72 hours. In terms of different groups, saturated hydrocarbons and resins become depleted in 13C with longer reaction time, while aromatics and asphaltenes become enriched in 13C

  10. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: explicit modeling of SOA formation from alkane and alkene oxidation

    NASA Astrophysics Data System (ADS)

    La, Y. S.; Camredon, M.; Ziemann, P. J.; Valorso, R.; Matsunaga, A.; Lannuque, V.; Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.

    2016-02-01

    Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool, which explicitly represents SOA formation and gas-wall partitioning. The model was compared with 41 smog chamber experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NOx conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas-wall mass transfer, the vapor pressure of the species and the duration of the experiments. This work suggests that SOA yields inferred from chamber experiments could be underestimated up a factor of 2 due to the loss of organic vapors to chamber walls.

  11. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: explicit modeling of SOA formation from alkane and alkene oxidation

    NASA Astrophysics Data System (ADS)

    La, Y. S.; Camredon, M.; Ziemann, P. J.; Valorso, R.; Matsunaga, A.; Lannuque, V.; Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.

    2015-09-01

    Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool which explicitly represents SOA formation and gas/wall partitioning. The model was compared with 41 smog chamber experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NOx conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas/wall mass transfer, the vapor pressure of the species and the duration of the experiments. This work suggests that SOA yields inferred from chamber experiments could be underestimated up to 0.35 yield unit due to the loss of organic vapors to chamber walls.

  12. 40 CFR 721.10148 - Acryloxy alkanoic alkane derivative with mixed metal oxides (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... with mixed metal oxides (generic). 721.10148 Section 721.10148 Protection of Environment ENVIRONMENTAL... mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as acryloxy alkanoic alkane derivative with mixed...

  13. 40 CFR 721.10148 - Acryloxy alkanoic alkane derivative with mixed metal oxides (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... with mixed metal oxides (generic). 721.10148 Section 721.10148 Protection of Environment ENVIRONMENTAL... mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as acryloxy alkanoic alkane derivative with mixed...

  14. Anaerobic biodegradation of long-chain n-alkanes under sulfate-reducing conditions

    SciTech Connect

    Caldwell, M.E.; Suflita, J.M.; Garrett, R.M.; Prince, R.C.

    1998-07-15

    The ability of anaerobic microorganisms to degrade a wide variety of crude oil components was investigated using chronically hydrocarbon-contaminated marine sediments as the source of inoculum. When sulfate reduction was the predominant electron-accepting process, gas chromatographic analysis revealed almost complete n-alkane removal (C{sub 15}-C{sub 34}) from a weathered oil within 201 d of incubation. No alteration of the oil was detected in sterile control incubations or when nitrate served as an alternate electron acceptor. The amount of sulfate reduced in the oil-amended nonsterile incubations was more than enough to account for the complete mineralization of the n-alkane fraction of the oil; no loss of this anion was observed in sterile control incubations. The mineralization of the alkanes was confirmed using {sup 14}C-14,15-octacosane (C{sub 28}H{sub 58}), with 97% of the radioactivity recovered as {sup 14}CO{sub 2}. These findings extend the range of hydrocarbons known to be amenable to anaerobic biodegradation. Moreover, the rapid and extensive alteration in the n-alkanes can no longer be considered a defining characteristic of aerobic oil biodegradation processes alone.

  15. Microstructure of High Pressure Polyolefin/n-Alkane & Dimethyl Ether Solutions

    NASA Astrophysics Data System (ADS)

    van Zanten, John; McHugh, Mark; Li, Dan; Guney-Altay, Ozge; Dinoia, Todd; Kermis, Thomas; Park, Il-Hyun

    2003-03-01

    A series of dilute and semi-dilute poly(ethylene-co-1-butene)/n-alkane and dimethyl ether (DME) solutions have been investigated with high pressure small angle neutron scattering and dynamic light scattering. The n-alkane solvents considered in these investigations were ethane, propane, butane and pentane. The solutions have been examined at 110-150 °C and at pressures up to ˜2500 bar. In the semi-dilute concentration range, the classic high concentration isotopic labeling technique is used in conjunction with small angle neutron scattering to determine both the solution correlation length and coil dimensions for poly(ethylene-co-1-butene) dissolved in either ethane, pentane or DME. Chain collapse is observed upon approach to the phase boundary in n-alkane solutions but is absent in DME solutions. For the dilute solution regime, solutions of varying concentration in all of the n-alkanes and DME are considered in order to determine both the polymer diffusion coefficient at infinite dilution as well as the dynamic second viral coefficient which is primarily dominated by the second osmotic virial coefficient. The polymer coil hydrodynamic radii behavior in dilute solutions is essentially the same as that observed for the semi-dilute solutions. Coil behavior in the dilute and semi-dilute concentration regimes is compared and contrasted.

  16. Interrogation of Chesapeake Bay sediment microbial communities for intrinsic alkane-utilizing potential under anaerobic conditions.

    PubMed

    Johnson, Jamie M; Wawrik, Boris; Isom, Catherine; Boling, Wilford B; Callaghan, Amy V

    2015-02-01

    Based on the transient exposure of Chesapeake Bay sediments to hydrocarbons and the metabolic versatility of known anaerobic alkane-degrading microorganisms, it was hypothesized that distinct Bay sediment communities, governed by geochemical gradients, would have intrinsic alkane-utilizing potential under sulfate-reducing and/or methanogenic conditions. Sediment cores were collected along a transect of the Bay. Community DNA was interrogated via pyrosequencing of 16S rRNA genes, PCR of anaerobic hydrocarbon activation genes, and qPCR of 16S rRNA genes and genes involved in sulfate reduction/methanogenesis. Site sediments were used to establish microcosms amended with n-hexadecane under sulfate-reducing and methanogenic conditions. Sequencing of 16S rRNA genes indicated that sediments associated with hypoxic water columns contained significantly greater proportions of Bacteria and Archaea consistent with syntrophic degradation of organic matter and methanogenesis compared to less reduced sediments. Microbial taxa frequently associated with hydrocarbon-degrading communities were found throughout the Bay, and the genetic potential for hydrocarbon metabolism was demonstrated via the detection of benzyl-(bssA) and alkylsuccinate synthase (assA) genes. Although microcosm studies did not indicate sulfidogenic alkane degradation, the data suggested that methanogenic conversion of alkanes was occurring. These findings highlight the potential role that anaerobic microorganisms could play in the bioremediation of hydrocarbons in the Bay. PMID:25764556

  17. Interrogation of Chesapeake Bay sediment microbial communities for intrinsic alkane-utilizing potential under anaerobic conditions.

    PubMed

    Johnson, Jamie M; Wawrik, Boris; Isom, Catherine; Boling, Wilford B; Callaghan, Amy V

    2015-02-01

    Based on the transient exposure of Chesapeake Bay sediments to hydrocarbons and the metabolic versatility of known anaerobic alkane-degrading microorganisms, it was hypothesized that distinct Bay sediment communities, governed by geochemical gradients, would have intrinsic alkane-utilizing potential under sulfate-reducing and/or methanogenic conditions. Sediment cores were collected along a transect of the Bay. Community DNA was interrogated via pyrosequencing of 16S rRNA genes, PCR of anaerobic hydrocarbon activation genes, and qPCR of 16S rRNA genes and genes involved in sulfate reduction/methanogenesis. Site sediments were used to establish microcosms amended with n-hexadecane under sulfate-reducing and methanogenic conditions. Sequencing of 16S rRNA genes indicated that sediments associated with hypoxic water columns contained significantly greater proportions of Bacteria and Archaea consistent with syntrophic degradation of organic matter and methanogenesis compared to less reduced sediments. Microbial taxa frequently associated with hydrocarbon-degrading communities were found throughout the Bay, and the genetic potential for hydrocarbon metabolism was demonstrated via the detection of benzyl-(bssA) and alkylsuccinate synthase (assA) genes. Although microcosm studies did not indicate sulfidogenic alkane degradation, the data suggested that methanogenic conversion of alkanes was occurring. These findings highlight the potential role that anaerobic microorganisms could play in the bioremediation of hydrocarbons in the Bay.

  18. 40 CFR 721.10148 - Acryloxy alkanoic alkane derivative with mixed metal oxides (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... with mixed metal oxides (generic). 721.10148 Section 721.10148 Protection of Environment ENVIRONMENTAL... mixed metal oxides (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as acryloxy alkanoic alkane derivative with mixed...

  19. Iridium complexes of new NCP pincer ligands: catalytic alkane dehydrogenation and alkene isomerization.

    PubMed

    Jia, Xiangqing; Zhang, Lei; Qin, Chuan; Leng, Xuebing; Huang, Zheng

    2014-09-28

    Iridium complexes of novel NCP pincer ligands containing pyridine and phosphinite arms have been synthesized. One Ir complex shows good catalytic activity for alkane dehydrogenation, and all complexes are highly active for olefin isomerization. A combination of the Ir complex and a (PNN)Fe pincer complex catalyzes the formation of linear alkylboronates selectively from internal olefins via sequential olefin isomerization-hydroboration.

  20. Biosurfactant-mediated biodegradation of straight and methyl-branched alkanes by Pseudomonas aeruginosa ATCC 55925

    PubMed Central

    2011-01-01

    Accidental oil spills and waste disposal are important sources for environmental pollution. We investigated the biodegradation of alkanes by Pseudomonas aeruginosa ATCC 55925 in relation to a rhamnolipid surfactant produced by the same bacterial strain. Results showed that the linear C11-C21 compounds in a heating oil sample degraded from 6% to 100%, whereas the iso-alkanes tended to be recalcitrant unless they were exposed to the biosurfactant; under such condition total biodegradation was achieved. Only the biodegradation of the commercial C12-C19 alkanes could be demonstrated, ranging from 23% to 100%, depending on the experimental conditions. Pristane (a C19 branched alkane) only biodegraded when present alone with the biosurfactant and when included in an artificial mixture even without the biosurfactant. In all cases the biosurfactant significantly enhanced biodegradation. The electron scanning microscopy showed that cells depicted several adaptations to growth on hydrocarbons, such as biopolymeric spheres with embedded cells distributed over different layers on the spherical surfaces and cells linked to each other by extracellular appendages. Electron transmission microscopy revealed transparent inclusions, which were associated with hydrocarbon based-culture cells. These patterns of hydrocarbon biodegradation and cell adaptations depended on the substrate bioavailability, type and length of hydrocarbon. PMID:21906343