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Sample records for methane ethane propane

  1. Identification of Methane, Ethane, and Propane Oxidizing Bacteria at Marine Hydrocarbon Seeps by Stable Isotope Probing

    NASA Astrophysics Data System (ADS)

    Redmond, M.; Ding, H.; Friedrich, M. W.; Valentine, D. L.

    2008-12-01

    Hydrocarbon seeps emit substantial amounts of oil and natural gas into the marine environment, where they can be oxidized by microorganisms in the sediment and water column. Here, we used stable isotope probing of DNA and lipid biomarkers to identify the microorganisms actively consuming 13C-labeled natural gas compounds in seep sediment samples. Surface sediment was collected from the Coal Oil Point seep field (offshore Santa Barbara, California, USA) and incubated under aerobic conditions with 13C labeled methane, ethane, or propane for up to 37 days, with sediment sub-samples taken at 3-4 intermediate time points. DNA was extracted from sediment and separated by CsCl density gradient centrifugation. The microbial community in each fraction was profiled using T-RFLP, and bacterial 16S rRNA gene clone libraries were constructed from un-incubated hydrocarbon seep sediment and selected isotopically 'heavy' (13C) and 'light' (12C) gradient fractions from ethane incubations. All clone libraries were dominated by sequences from members of the family Rhodobacteraceae (>25% of sequences) and a diverse group of Gammaproteobacteria, including sequences related to those of methylotrophs and to those of bacteria known to consume the longer-chain alkanes present in crude oil. After 14 days of incubation, the relative abundance of Rhodobacteraceae was higher in 'heavy' fractions from the 13C-ethane incubation than in 'light' fractions, suggesting incorporation of 13C label. The Rhodobacteraceae are very diverse metabolically, but have often been observed in abundance in oil contaminated seawater. Several members of this group have been shown to oxidize longer chain alkanes (C10 or higher), but none have been previously linked to the consumption of the gaseous alkanes ethane, propane, and butane. For the final time point, 13C content of phospholipid fatty acids (PLFA) were also analyzed, showing substantial incorporation of 13C over 37 days. In the methane incubation

  2. Sorption of methane, ethane, propane, butane, carbon dioxide, and nitrogen on kerogen

    NASA Astrophysics Data System (ADS)

    Pribylov, A. A.; Skibitskaya, N. A.; Zekel', L. A.

    2014-06-01

    Sorption isotherms of nitrogen, methane (in the pressure range of 0.1-40 MPa), ethane (0.1-3.7MPa), propane (0.01-1 MPa), butane (0.01-0.2 MPa), and carbon dioxide (0.1-6 MPa) are measured on two adsorbents with kerogen contents of 16 and 75% at temperatures of 303, 323, 343 K. Adsorption volumes are calculated for all adsorption systems using two independent methods. The BET technique is used to determine the surface area values of the two adsorbents on the basis of sorption data for ethane, propane, butane, and carbon dioxide. The initial and isosteric adheat of sorption values are calculated on the basis of sorption isotherms of ethane, propane, butane, carbon dioxide measured at three temperatures. It is found from comparing the dependences of isosteric heat of sorption on the two adsorbents that molecules of the above gases diffuse into its bulk (adsorbent 2) in addition to sorbing on the outside surface formed by kerogen molecules, while sorption of the same gases on the rock (adsorbent 1) is similar to sorption on a smooth hard adsorbent surface.

  3. Liquid-state theory of hydrocarbon-water systems: Application to methane, ethane, and propane

    SciTech Connect

    Lue, L.; Blankschtein, D.

    1992-10-15

    The authors studied the structural and bulk thermodynamic properties of hydrocarbon (methane, ethane, and propane)-water systems as well as pure water using the site-site Ornstein-Zernike (SSOZ) equation under a variety of different closure relations in order to compare the quantitative predictive capabilities of the various closures. For the hydrocarbon-water systems, the simple point-charge(SPC) potential was used to model water, and the optimized potentials for liquid, simulation (OPLS) were used to model the hydrocarbons. 69 refs., 11 figs., 8 tabs.

  4. Improvement of gas hydrate preservation by increasing compression pressure to simple hydrates of methane, ethane, and propane

    NASA Astrophysics Data System (ADS)

    Kida, Masato; Jin, Yusuke; Watanabe, Mizuho; Murayama, Tetsuro; Nagao, Jiro

    2017-09-01

    In this report, we describe the dissociation behavior of gas hydrate grains pressed at 1 and 6 MPa. Certain simple gas hydrates in powder form show anomalous preservation phenomenon under their thermodynamic unstable condition. Investigation of simple hydrates of methane, ethane, and propane reveals that high pressure applied to the gas hydrate particles enhances their preservation effects. Application of high pressure increases the dissociation temperature of methane hydrate and has a restrictive effect against the dissociation of ethane and propane hydrate grains. These improvements of gas hydrate preservation by increasing pressure to the initial gas hydrate particles imply that appropriate pressure applied to gas hydrate particles enhances gas hydrate preservation effects.

  5. Raman spectra of methane, ethylene, ethane, dimethyl ether, formaldehyde and propane for combustion applications

    NASA Astrophysics Data System (ADS)

    Magnotti, G.; KC, U.; Varghese, P. L.; Barlow, R. S.

    2015-09-01

    Spontaneous Raman scattering measurements of temperature and major species concentration in hydrocarbon-air flames require detailed knowledge of the Raman spectra of the hydrocarbons present when fuels more complex than methane are used. Although hydrocarbon spectra have been extensively studied at room temperature, there are no data available at higher temperatures. Quantum mechanical calculations, when available are not sufficiently accurate for combustion applications. This work presents experimental measurements of spontaneous Stokes-Raman scattering spectra of methane, ethylene, ethane, dimethyl ether, formaldehyde and propane in the temperature range 300-860 K. Raman spectra from heated hydrocarbons jets have been collected with a higher resolution than is generally employed for Raman measurements in combustion applications. A set of synthetic spectra have been generated for each hydrocarbon, providing the basis for extrapolation to higher temperatures. The spectra provided here will enable simultaneous measurements of multiple hydrocarbons in flames. This capability will greatly extend the range of applicability of Raman measurements in combustion applications. In addition, the experimental spectra provide a validation dataset for quantum mechanical models.

  6. The SPASIBA force field of aldehydes. Part I: Structure and vibrational wavenumbers of methanal, ethanal and propanal

    NASA Astrophysics Data System (ADS)

    Zanoun, A.; Durier, V.; Belaidi, A.; Vergoten, G.

    1999-02-01

    The SPASIBA vibrational spectroscopic force field has been developed for the aldehyde function. The tested molecules are methanal, ethanal, propanal and some of their deuterated analogues. The parameters have been obtained by fitting calculated and observed vibrational wavenumbers. A set of 34 independant force constants has been found to correctly describe the structure and vibrational spectra. The average error between predicted and observed vibrational wavenumber is 16 cm -1.

  7. Prediction of equilibrium distributions of isotopologues for methane, ethane and propane using density functional theory

    NASA Astrophysics Data System (ADS)

    Piasecki, Alison; Sessions, Alex; Peterson, Brian; Eiler, John

    2016-10-01

    Many previous studies have examined abundances of deuterium (D) and 13C within small organic molecules. Recent advances in analytical instrumentation add the abilities to measure site-specific and multiply substituted isotopologues of natural organics. Here we perform first-principles calculations of the equilibrium distributions of 13C and D in the volatile alkanes (including both single and multiple substitutions), as a guide to the interpretation of current measurements and as a basis for anticipating isotope effects that might be examined with future analytical techniques. The models we present illustrate several common themes of the isotopic structures of the small alkanes, including; temperature dependent enrichment of clumped isotope species, with amplitudes in the order D-D > 13C-D > 13C-13C; similarity in strength of such clumped isotope effects between different molecules (e.g., 13C-D clumping is ∼5‰ enriched at 300 K in methane, ethane and propane); a ∼10× contrast between the amplitudes of stronger adjacent substitution of two heavy isotopes vs. weaker non-adjacent substitution; temperature-dependent site-specific fractionation of D and 13C into interior positions of molecules relative to terminal methyl groups; and a relatively simple additive effect to the overall amplitude of enrichment when clumped and site specific effects combine in the same isotopologue. We suggest that the most promising tools suggested by our results are isotopic thermometers based on site-specific distribution of deuterium, which exhibits strong (∼100‰), highly temperature dependent fractionation between methyl groups and methylene carbon positions in propane (and likely other larger n-alkanes).

  8. Kinetic mechanism of plasma recombination in methane, ethane and propane after high-voltage nanosecond discharge

    NASA Astrophysics Data System (ADS)

    Anokhin, E. M.; Popov, M. A.; Kochetov, I. V.; Starikovskiy, A. Yu; Aleksandrov, N. L.

    2016-08-01

    The results of the experimental and numerical study of high-voltage nanosecond discharge afterglow in pure methane, ethane and propane are presented for room temperature and pressures from 2 to 20 Torr. Time-resolved electron density during the plasma decay was measured with a microwave interferometer for initial electron densities in the range between 5  ×  1010 and 3  ×  1012 cm-3 and the effective recombination coefficients were obtained. Measured effective recombination coefficients increased with gas pressure and were much higher than the recombination coefficients for simple molecular hydrocarbon ions. The properties of plasma in the discharge afterglow were numerically simulated by solving the balance equations for charged particles and electron temperature. Calculations showed that electrons had time to thermalize prior to the recombination. The measured data were interpreted under the assumption that cluster hydrocarbon ions are formed during the plasma decay that is controlled by the dissociative electron recombination with these ions at electron room temperature. Based on the analysis of the experimental data, the rates of three-body formation of cluster ions and recombination coefficients for these ions were estimated.

  9. Phase diagrams for clathrate hydrates of methane, ethane, and propane from first-principles thermodynamics.

    PubMed

    Cao, Xiaoxiao; Huang, Yingying; Li, Wenbo; Zheng, Zhaoyang; Jiang, Xue; Su, Yan; Zhao, Jijun; Liu, Changling

    2016-01-28

    Natural gas hydrates are inclusion compounds composed of major light hydrocarbon gaseous molecules (CH4, C2H6, and C3H8) and a water clathrate framework. Understanding the phase stability and formation conditions of natural gas hydrates is crucial for their future exploitation and applications and requires an accurate description of intermolecular interactions. Previous ab initio calculations on gas hydrates were mainly limited by the cluster models, whereas the phase diagram and equilibrium conditions of hydrate formation were usually investigated using the thermodynamic models or empirical molecular simulations. For the first time, we construct the chemical potential phase diagrams of type II clathrate hydrates encapsulated with methane/ethane/propane guest molecules using first-principles thermodynamics. We find that the partially occupied structures (136H2O·1CH4, 136H2O·16CH4, 136H2O·20CH4, 136H2O·1C2H6, and 136H2O·1C3H8) and fully occupied structures (136H2O·24CH4, 136H2O·8C2H6, and 136H2O·8C3H8) are thermodynamically favorable under given pressure-temperature (p-T) conditions. The theoretically predicted equilibrium pressures for pure CH4, C2H6 and C3H8 hydrates at the phase transition point are consistent with the experimental data. These results provide valuable guidance for establishing the relationship between the accurate description of intermolecular noncovalent interactions and the p-T equilibrium conditions of clathrate hydrates and other molecular crystals.

  10. Synergistic effect of mixing dimethyl ether with methane, ethane, propane, and ethylene fuels on polycyclic aromatic hydrocarbon and soot formation

    SciTech Connect

    Yoon, S.S.; Anh, D.H.; Chung, S.H.

    2008-08-15

    Characteristics of polycyclic aromatic hydrocarbon (PAH) and soot formation in counterflow diffusion flames of methane, ethane, propane, and ethylene fuels mixed with dimethyl ether (DME) have been investigated. Planar laser-induced incandescence and fluorescence techniques were employed to measure relative soot volume fractions and PAH concentrations, respectively. Results showed that even though DME is known to be a clean fuel in terms of soot formation, DME mixture with ethylene fuel increases PAH and soot formation significantly as compared to the pure ethylene case, while the mixture of DME with methane, ethane, and propane decreases PAH and soot formation. Numerical calculations adopting a detailed kinetics showed that DME can be decomposed to produce a relatively large number of methyl radicals in the low-temperature region where PAH forms and grows; thus the mixture of DME with ethylene increases CH{sub 3} radicals significantly in the PAH formation region. Considering that the increase in the concentration of O radicals is minimal in the PAH formation region with DME mixture, the enhancement of PAH and soot formation in the mixture flames of DME and ethylene can be explained based on the role of methyl radicals in PAH and soot formation. Methyl radicals can increase the concentration of propargyls, which could enhance incipient benzene ring formation through the propargyl recombination reaction and subsequent PAH growth. Thus, the result substantiates the importance of methyl radicals in PAH and soot formation, especially in the PAH formation region of diffusion flames. (author)

  11. Acetonitrile cluster solvation in a cryogenic ethane-methane-propane liquid: Implications for Titan lake chemistry.

    PubMed

    Corrales, L René; Yi, Thomas D; Trumbo, Samantha K; Shalloway, David; Lunine, Jonathan I; Usher, David A

    2017-03-14

    The atmosphere of Titan, Saturn's largest moon, exhibits interesting UV- and radiation-driven chemistry between nitrogen and methane, resulting in dipolar, nitrile-containing molecules. The assembly and subsequent solvation of such molecules in the alkane lakes and seas found on the moon's surface are of particular interest for investigating the possibility of prebiotic chemistry in Titan's hydrophobic seas. Here we characterize the solvation of acetonitrile, a product of Titan's atmospheric radiation chemistry tentatively detected on Titan's surface [H. B. Niemann et al., Nature 438, 779-784 (2005)], in an alkane mixture estimated to match a postulated composition of the smaller lakes during cycles of active drying and rewetting. Molecular dynamics simulations are employed to determine the potential of mean force of acetonitrile (CH3CN) clusters moving from the alkane vapor into the bulk liquid. We find that the clusters prefer the alkane liquid to the vapor and do not dissociate in the bulk liquid. This opens up the possibility that acetonitrile-based microscopic polar chemistry may be possible in the otherwise nonpolar Titan lakes.

  12. Acetonitrile cluster solvation in a cryogenic ethane-methane-propane liquid: Implications for Titan lake chemistry

    NASA Astrophysics Data System (ADS)

    Corrales, L. René; Yi, Thomas D.; Trumbo, Samantha K.; Shalloway, David; Lunine, Jonathan I.; Usher, David A.

    2017-03-01

    The atmosphere of Titan, Saturn's largest moon, exhibits interesting UV- and radiation-driven chemistry between nitrogen and methane, resulting in dipolar, nitrile-containing molecules. The assembly and subsequent solvation of such molecules in the alkane lakes and seas found on the moon's surface are of particular interest for investigating the possibility of prebiotic chemistry in Titan's hydrophobic seas. Here we characterize the solvation of acetonitrile, a product of Titan's atmospheric radiation chemistry tentatively detected on Titan's surface [H. B. Niemann et al., Nature 438, 779-784 (2005)], in an alkane mixture estimated to match a postulated composition of the smaller lakes during cycles of active drying and rewetting. Molecular dynamics simulations are employed to determine the potential of mean force of acetonitrile (CH3CN) clusters moving from the alkane vapor into the bulk liquid. We find that the clusters prefer the alkane liquid to the vapor and do not dissociate in the bulk liquid. This opens up the possibility that acetonitrile-based microscopic polar chemistry may be possible in the otherwise nonpolar Titan lakes.

  13. Desorption Kinetics of Ar, Kr, Xe, N2, O2, CO, Methane, Ethane, and Propane from Graphene and Amorphous Solid Water Surfaces

    SciTech Connect

    Smith, R. Scott; May, Robert A.; Kay, Bruce D.

    2016-03-03

    The desorption kinetics for Ar, Kr, Xe, N2, O2, CO, methane, ethane, and propane from grapheme covered Pt(111) and amorphous solid water (ASW) surfaces are investigated using temperature programmed desorption (TPD). The TPD spectra for all of the adsorbates from graphene have well-resolved first, second, third, and multi- layer desorption peaks. The alignment of the leading edges is consistent the zero-order desorption for all of the adsorbates. An Arrhenius analysis is used to obtain desorption energies and prefactors for desorption from graphene for all of the adsorbates. In contrast, the leading desorption edges for the adsorbates from ASW do not align (for coverages < 2 ML). The non-alignment of TPD leading edges suggests that there are multiple desorption binding sites on the ASW surface. Inversion analysis is used to obtain the coverage dependent desorption energies and prefactors for desorption from ASW for all of the adsorbates.

  14. Development of a pre-concentration system and auto-analyzer for dissolved methane, ethane, propane, and butane concentration measurements with a GC-FID

    NASA Astrophysics Data System (ADS)

    Chepigin, A.; Leonte, M.; Colombo, F.; Kessler, J. D.

    2014-12-01

    Dissolved methane, ethane, propane, and butane concentrations in natural waters are traditionally measured using a headspace equilibration technique and gas chromatograph with flame ionization detector (GC-FID). While a relatively simple technique, headspace equilibration suffers from slow equilibration times and loss of sensitivity due to concentration dilution with the pure gas headspace. Here we present a newly developed pre-concentration system and auto-analyzer for use with a GC-FID. This system decreases the time required for each analysis by eliminating the headspace equilibration time, increases the sensitivity and precision with a rapid pre-concentration step, and minimized operator time with an autoanalyzer. In this method, samples are collected from Niskin bottles in newly developed 1 L plastic sample bags rather than glass vials. Immediately following sample collection, the sample bags are placed in an incubator and individually connected to a multiport sampling valve. Water is pumped automatically from the desired sample bag through a small (6.5 mL) Liqui-Cel® membrane contactor where the dissolved gas is vacuum extracted and directly flushed into the GC sample loop. The gases of interest are preferentially extracted with the Liqui-Cel and thus a natural pre-concentration effect is obtained. Daily method calibration is achieved in the field with a five-point calibration curve that is created by analyzing gas standard-spiked water stored in 5 L gas-impermeable bags. Our system has been shown to substantially pre-concentrate the dissolved gases of interest and produce a highly linear response of peak areas to dissolved gas concentration. The system retains the high accuracy, precision, and wide range of measurable concentrations of the headspace equilibration method while simultaneously increasing the sensitivity due to the pre-concentration step. The time and labor involved in the headspace equilibration method is eliminated and replaced with the

  15. Marine microbes rapidly adapt to consume ethane, propane, and butane within the dissolved hydrocarbon plume of a natural seep

    NASA Astrophysics Data System (ADS)

    Mendes, Stephanie D.; Redmond, Molly C.; Voigritter, Karl; Perez, Christian; Scarlett, Rachel; Valentine, David L.

    2015-03-01

    Simple hydrocarbon gases containing two to four carbons (ethane, propane, and butane) are among the most abundant compounds present in petroleum reservoirs, and are introduced into the ocean through natural seepage and industrial discharge. Yet little is known about the bacterial consumption of these compounds in ocean waters. To assess the timing by which microbes metabolize these gases, we conducted a three-phase study that tested and applied a radiotracer-based method to quantify the oxidation rates of ethane, propane, and butane in fresh seawater samples. Phase 1 involved the synthesis of tritiated ethane, propane, and butane using Grignard reagents and tritiated water. Phase 2 was a systematic assessment of experimental conditions, wherein the indigenous microbial community was found to rapidly oxidize ethane, propane, and butane. Phase 3 was the application of this tritium method near the Coal Oil Point seeps, offshore California. Spatial and temporal patterns of ethane, propane, and butane oxidation down current from the hydrocarbon seeps demonstrated that >99% of these gases are metabolized within 1.3 days following initial exposure. The oxidation of ethane outpaced oxidation of propane and butane with patterns indicating the microbial community responded to these gases by rapid adaptation or growth. Methane oxidation responded the slowest in plume waters. Estimates based on the observed metabolic rates and carbon mass balance suggest that ethane, propane, and butane-consuming microorganisms may transiently account for a majority of the total microbial community in these impacted waters.

  16. Titan ocean: Ethane, methane, nitrogen

    NASA Astrophysics Data System (ADS)

    Bell, Peter M.

    Detection of the atmosphere of Saturn's satellite Titan by the Voyager I spacecraft indicated an abundance of only 3 mol % methane (CH4). Recently J.I. Lunine, D.J. Stevenson, and Y.L. Yung calculated that 3 mol % methane is sufficiently low to preclude the stable coexistence of liquid methane on Titan's surface, which has a temperature of 94 K (Science, 222, 1229, 1983). Instead, Lunine et al. suggest that Titan's atmospheric methane may have broken down by a catalyzed photochemical reaction to ethane (C2H6). The resulting ocean would consist of a mixture of C2H6 and CH4 in the proportion of 3 to 1.

  17. Ethane and propane in the Southern marine troposphere

    NASA Astrophysics Data System (ADS)

    Clarkson, T. S.; Martin, R. J.; Rudolph, J.

    Nearly 500 measurements of the ethane and propane mixing ratios have been made in clean marine air at Baring Head (New Zealand) and Scott Base (Antarctica) between 1991 and 1996. The annual averages of the mixing ratios (285 and 40 ppt) are lower than previously reported for the Southern Hemisphere. A striking feature of the seasonal cycle is the abrupt drop in mixing ratios of both compounds around November and a corresponding increase in the ethane/propane ratio (from about 7 in winter to > 10 in summer), suggesting a sharp decrease in Southern Hemisphere sources (e.g. biomass burning or fossil gas emissions) of these compounds in the spring. From a simple budget estimate it is concluded that biomass burning is most likely the dominant source of ethane and propane in the Southern Hemisphere. The seasonal variability of the emissions which are required to balance the Southern Hemisphere propane budget agrees very well with the seasonality derived for ethane emissions in a previous study.

  18. Liquid Ethane and Methane on Titan

    NASA Astrophysics Data System (ADS)

    Clark, Roger Nelson; Curchin, J.; Brown, R. H.; Barnes, J. W.; Jaumann, R.; Soderblom, L.; Cruikshank, D. P.; Lunine, J.; Stephan, K.; Hoefen, T. H.; Le Mouelic, S.; Sotin, C.; Baines, K.; Buratti, B.; Nicholson, P.

    2008-09-01

    Absorption coefficients for liquid methane and ethane were derived in a 1-bar nitrogen atmosphere at 90K. Ethane and methane were condensed in an aluminum sample cup, and a 2-way transmission spectrum was measured. Different path lengths up to 14 mm allowed a wide range of absorption coefficients to be measured, and covered the range needed to compare to spectra of Titan in the 1- to 5-micron atmospheric windows. The data were used to compute possible liquid absorption in spectra from the Cassini Visual and Infrared Mapping Spectrometer (VIMS) and were compared to global VIMS data for Titan. The laboratory data show that both liquid methane and ethane have a strong absorption band near 4.97 microns that is detectable by VIMS. A liquid lake thickness of 3 mm (6 mm path length) would result in an absorption band depth of about 65% for methane and 85% for ethane. Ethane has a 2.02-micron absorption with a strength similar to the 4.97-micron absorption, and methane has an absorption that is 10x weaker. Continuum absorption would result in the following surface reflectance levels (at VIMS wavelengths and resolution). Examining VIMS Titan data, we find that for most of the surface, we detect no liquid methane or ethane. In a few locations VIMS data indicate liquid methane or ethane, but at less than about 1-mm total path length.

  19. Mid-Ir Cavity Ringdown Spectroscopy Measurements of Atmospheric Ethane to Methane Ratio for Methane Source Attribution

    NASA Astrophysics Data System (ADS)

    Shen, L.; Bui, T. Q.; Okumura, M.

    2016-12-01

    Atmospheric methane is a very important greenhouse gas. Source of methane plumes could be attributed using isotopic composition measurements and methane coemitting gas (ethane, propane, and butane) detections. Since isotopic source attribution process requires sensitive detection of more than three methane isotopologues (12CH4, 13CH4, and 12CH3D), we choose to measure the highest abundant coemitting gas, ethane. Ethane to methane ratio from biogenic and thermogenic sources have known to vary from 0.1% to 30%. In this work, we demonstrated a mid-IR (3.3 µm) cw cavity ringdown spectrometer capable of measuring atmospheric ethane abundance and ethane to methane ratio. This technique utilizes the long effective pathlengh of cavity ringdown spectroscopy to increase sensitivity of atmospheric ethane detection. Our spectrometer can measure atmospheric ethane concentration as low as 70 ppb. We have demonstrated the capability of this instrument by measuring the atmospheric ethane composition and ethane to methane ration in ambient air in Pasadena, California and soil gas samples collected from the Porter Ranch SoCal Gas Storage Facility.

  20. Origins and trends in ethane and propane in the United Kingdom from 1993 to 2012

    NASA Astrophysics Data System (ADS)

    Derwent, R. G.; Field, R. A.; Dumitrean, P.; Murrells, T. P.; Telling, S. P.

    2017-05-01

    Continuous, high frequency in situ observations of ethane and propane began in the United Kingdom in 1993 and have continued through to the present day at a range of kerbside, urban background and rural locations. Whilst other monitored C2 - C8 hydrocarbons have shown dramatic declines in concentrations by close to or over an order of magnitude, ethane and propane levels have remained at or close to their 1993 values. Urban ethane sources appear to be dominated by natural gas leakage. Background levels of ethane associated with long range transport are rising. However, natural gas leakage is not the sole source of urban propane. Oil and gas operations lead to elevated propane levels in urban centres when important refinery operations are located nearby. Weekend versus weekday average diurnal curves for ethane and propane at an urban background site in London show the importance of natural gas leakage for both ethane and propane, and road traffic sources for propane. The road traffic source of propane was tentatively identified as arising from petrol-engined motor vehicle refuelling and showed a strong downwards trend at the long-running urban background and rural sites. The natural gas leakage source of ethane and propane in the observations exhibits an upwards trend whereas that in the UK emission inventory trends downwards. Also, inventory emissions for natural gas leakage appeared to be significantly underestimated compared with the observations. In addition, the observed ethane to propane ratio found here for natural gas leakage strongly disagreed with the inventory ratio.

  1. Reversal of global atmospheric ethane and propane trends largely due to US oil and natural gas production

    NASA Astrophysics Data System (ADS)

    Helmig, Detlev; Rossabi, Samuel; Hueber, Jacques; Tans, Pieter; Montzka, Stephen A.; Masarie, Ken; Thoning, Kirk; Plass-Duelmer, Christian; Claude, Anja; Carpenter, Lucy J.; Lewis, Alastair C.; Punjabi, Shalini; Reimann, Stefan; Vollmer, Martin K.; Steinbrecher, Rainer; Hannigan, James W.; Emmons, Louisa K.; Mahieu, Emmanuel; Franco, Bruno; Smale, Dan; Pozzer, Andrea

    2016-07-01

    Non-methane hydrocarbons such as ethane are important precursors to tropospheric ozone and aerosols. Using data from a global surface network and atmospheric column observations we show that the steady decline in the ethane mole fraction that began in the 1970s halted between 2005 and 2010 in most of the Northern Hemisphere and has since reversed. We calculate a yearly increase in ethane emissions in the Northern Hemisphere of 0.42 (+/-0.19) Tg yr-1 between mid-2009 and mid-2014. The largest increases in ethane and the shorter-lived propane are seen over the central and eastern USA, with a spatial distribution that suggests North American oil and natural gas development as the primary source of increasing emissions. By including other co-emitted oil and natural gas non-methane hydrocarbons, we estimate a Northern Hemisphere total non-methane hydrocarbon yearly emission increase of 1.2 (+/-0.8) Tg yr-1. Atmospheric chemical transport modelling suggests that these emissions could augment summertime mean surface ozone by several nanomoles per mole near oil and natural gas production regions. Methane/ethane oil and natural gas emission ratios could suggest a significant increase in associated methane emissions; however, this increase is inconsistent with observed leak rates in production regions and changes in methane's global isotopic ratio.

  2. Demonstration of an ethane spectrometer for methane source identification.

    PubMed

    Yacovitch, Tara I; Herndon, Scott C; Roscioli, Joseph R; Floerchinger, Cody; McGovern, Ryan M; Agnese, Michael; Pétron, Gabrielle; Kofler, Jonathan; Sweeney, Colm; Karion, Anna; Conley, Stephen A; Kort, Eric A; Nähle, Lars; Fischer, Marc; Hildebrandt, Lars; Koeth, Johannes; McManus, J Barry; Nelson, David D; Zahniser, Mark S; Kolb, Charles E

    2014-07-15

    Methane is an important greenhouse gas and tropospheric ozone precursor. Simultaneous observation of ethane with methane can help identify specific methane source types. Aerodyne Ethane-Mini spectrometers, employing recently available mid-infrared distributed feedback tunable diode lasers (DFB-TDL), provide 1 s ethane measurements with sub-ppb precision. In this work, an Ethane-Mini spectrometer has been integrated into two mobile sampling platforms, a ground vehicle and a small airplane, and used to measure ethane/methane enhancement ratios downwind of methane sources. Methane emissions with precisely known sources are shown to have ethane/methane enhancement ratios that differ greatly depending on the source type. Large differences between biogenic and thermogenic sources are observed. Variation within thermogenic sources are detected and tabulated. Methane emitters are classified by their expected ethane content. Categories include the following: biogenic (<0.2%), dry gas (1-6%), wet gas (>6%), pipeline grade natural gas (<15%), and processed natural gas liquids (>30%). Regional scale observations in the Dallas/Fort Worth area of Texas show two distinct ethane/methane enhancement ratios bridged by a transitional region. These results demonstrate the usefulness of continuous and fast ethane measurements in experimental studies of methane emissions, particularly in the oil and natural gas sector.

  3. Raman studies of methane-ethane hydrate metastability.

    PubMed

    Ohno, Hiroshi; Strobel, Timothy A; Dec, Steven F; Sloan, E Dendy; Koh, Carolyn A

    2009-03-05

    The interconversion of methane-ethane hydrate from metastable to stable structures was studied using Raman spectroscopy. sI and sII hydrates were synthesized from methane-ethane gas mixtures of 65% or 93% methane in ethane and water, both with and without the kinetic hydrate inhibitor, poly(N-vinylcaprolactam). The observed faster structural conversion rate in the higher methane concentration atmosphere can be explained in terms of the differences in driving force (difference in chemical potential of water in sI and sII hydrates) and kinetics (mass transfer of gas and water rearrangement). The kinetic hydrate inhibitor increased the conversion rate at 65% methane in ethane (sI is thermodynamically stable) but retards the rate at 93% methane in ethane (sII is thermodynamically stable), implying there is a complex interaction between the polymer, water, and hydrate guests at crystal surfaces.

  4. Novel Pt/Mg(In)(Al)O catalysts for ethane and propane dehydrogenation

    SciTech Connect

    Sun, Pingping; Siddiqi, Georges; Vining, William C.; Chi, Miaofang; Bell, Alexis T.

    2011-10-28

    Catalysts for the dehydrogenation of light alkanes were prepared by dispersing Pt on the surface of a calcined hydrotalcite-like support containing indium, Mg(In)(Al)O. Upon reduction in H{sub 2} at temperatures above 673 K, bimetallic particles of PtIn are observed by TEM, which have an average diameter of 1 nm. Analysis of Pt LIII-edge extended X-ray absorption fine structure (EXAFS) data shows that the In content of the bimetallic particles increases with increasing bulk In/Pt ratio and reduction temperature. Pt LIII-edge X-ray absorption near edge structure (XANES) indicates that an increasing donation of electronic charge from In to Pt occurs with increasing In content in the PtIn particles. The activity and selectivity of the Pt/Mg(In)(Al)O catalysts for ethane and propane dehydrogenation reactions are strongly dependent on the bulk In/Pt ratio. For both reactants, maximum activity was achieved for a bulk In/Pt ratio of 0.48, and at this In/Pt ratio, the selectivity to alkene was nearly 100%. Coke deposition was observed after catalyst use for either ethane or propane dehydrogenation, and it was observed that the alloying of Pt with In greatly reduced the amount of coke deposited. Characterization of the deposit by Raman spectroscopy indicates that the coke is present as highly disordered graphite particles <30 nm in diameter. While the amount of coke deposited during ethane and propane dehydrogenation are comparable, the effects on activity are dependent on reactant composition. Coke deposition had no effect on ethane dehydrogenation activity, but caused a loss in propane dehydrogenation activity. This difference is attributed to the greater ease with which coke produced on the surface of PtIn nanoparticles migrates to the support during ethane dehydrogenation versus propane dehydrogenation.

  5. Attainable superheat of ethane-methane solutions

    NASA Astrophysics Data System (ADS)

    Baidakov, V. G.; Pankov, A. S.

    2013-12-01

    Methods of measuring lifetime and continuous pressure decrease were used to study kinetics of spontaneous boiling-up of superheated ethane-methane solutions. The attainable superheats of solutions at two pressure values (1.0 and 1.6 MPa) and two concentrations of methane (2.1 and 6.0 mole %) were determined experimentally in the range of nucleation rate J = 1·104-3·108 s-1m-3. At temperatures 266.5, 270.0, and 273.15 K, the attainable stretching of the studied solutions was measured. The experimental results were compared with the theory of homogeneous nucleation. At nucleation rates J ≥ 2.5·106 s-1m-3, there is a fair agreement of the theory and experiment. The discrepancy in attainable superheat temperatures T n does not exceed 0.8 K. It is shown that significant underheating of solution to theoretical values T n at J < 2.5·106 s-1m-3 cannot be bound only with heterogeneous nucleation but is conditioned by other factors as well.

  6. Trapping of methane and ethane in Titan surface materials

    NASA Astrophysics Data System (ADS)

    Cable, M. L.; Hodyss, R. P.; Choukroun, M.; Markus, C.; Beauchamp, P. M.

    2013-12-01

    We present a series of cryogenic Raman and infrared spectra demonstrating that solid benzene (as well as other putative Titan surface materials) can trap significant amounts of ethane and methane within its crystal structure at Titan surface temperatures. This is analogous to the well-known ability of water ice to trap volatile species well above their sublimation temperatures (e.g., Bar-Nun et al. 1985 , Icarus, 63, 317). Experiments also suggest that liquid ethane can permeate and adsorb onto solid benzene, implying that lake edges and evaporite basins on Titan may hold important quantities of ethane. These results can help explain the release of methane observed at the Huygens landing site (Nieman et al. 2010, JGR 115, E12006), and point toward a large possible reservoir of methane and ethane hidden within Titan's surface organics.

  7. Methane, Ethane, and Nitrogen Liquid Stability on Titan

    NASA Astrophysics Data System (ADS)

    Hanley, Jennifer; Thompson, Garrett Leland; Roe, Henry G.; Grundy, Will; Tegler, Stephen C.; Lindberg, Gerrick Eugene; Trilling, David E.

    2016-10-01

    Previous studies have shown that the lakes of Titan are composed of methane and/or ethane, but the relative proportions are mostly unclear. Understanding the past and current stability of these lakes requires characterizing the interactions of liquid methane and ethane, along with nitrogen. Previous studies have shown that the freezing point of methane is depressed when mixed with nitrogen. Our cryogenic laboratory setup allows us to explore ices down to 30 K through imaging and transmission spectroscopy. Recent work (see Thompson et al., this conference) discovered that although methane and ethane have similar freezing points, when mixed they can remain liquid down to 72 K. Concurrently with the freezing point measurements we acquire transmission spectra of these mixtures to understand how the spectral features change with concentration and temperature. Any mixing of these two species together will depress the freezing point of the lake below Titan's surface temperature, preventing them from freezing. Also, when ethane ice forms, it freezes on the bottom of the liquid, while methane ice freezes at the top of the liquid, implying ethane ice is denser than the solution, while methane ice is less dense; this holds for all concentrations. We will present new results exploring the ternary system of methane, ethane and nitrogen. In particular we will map out the N2-C2H6 liquidus, as has been done for CH4-N2, as well as explore the effect of nitrogen on the eutectic of the methane-ethane system. This behavior has implications for not only the lakes on the surface of Titan, but also for the evaporation/condensation/cloud cycle in the atmosphere. These results will help interpretation of future observational data, and guide current theoretical models.

  8. Airborne Ethane Observations in the Barnett Shale: Quantification of Ethane Flux and Attribution of Methane Emissions.

    PubMed

    Smith, Mackenzie L; Kort, Eric A; Karion, Anna; Sweeney, Colm; Herndon, Scott C; Yacovitch, Tara I

    2015-07-07

    We present high time resolution airborne ethane (C2H6) and methane (CH4) measurements made in March and October 2013 as part of the Barnett Coordinated Campaign over the Barnett Shale formation in Texas. Ethane fluxes are quantified using a downwind flight strategy, a first demonstration of this approach for C2H6. Additionally, ethane-to-methane emissions ratios (C2H6:CH4) of point sources were observationally determined from simultaneous airborne C2H6 and CH4 measurements during a survey flight over the source region. Distinct C2H6:CH4 × 100% molar ratios of 0.0%, 1.8%, and 9.6%, indicative of microbial, low-C2H6 fossil, and high-C2H6 fossil sources, respectively, emerged in observations over the emissions source region of the Barnett Shale. Ethane-to-methane correlations were used in conjunction with C2H6 and CH4 fluxes to quantify the fraction of CH4 emissions derived from fossil and microbial sources. On the basis of two analyses, we find 71-85% of the observed methane emissions quantified in the Barnett Shale are derived from fossil sources. The average ethane flux observed from the studied region of the Barnett Shale was 6.6 ± 0.2 × 10(3) kg hr(-1) and consistent across six days in spring and fall of 2013.

  9. Investigation of Compton profiles of molecular methane and ethane

    SciTech Connect

    Zhao, Xiao-Li; Xu, Long-Quan; Kang, Xu; Liu, Ya-Wei; Ni, Dong-Dong; Zhu, Lin-Fan; Yang, Ke Ma, Yong-Peng; Yan, Shuai

    2015-02-28

    The Compton profiles of methane and ethane molecules have been determined at an incident photon energy of 20 keV based on the third generation synchrotron radiation, and the statistical accuracy of 0.2% is achieved near p{sub z} = 0. The density functional theory with aug-cc-pVTZ basis set was used to calculate the Compton profiles of methane and ethane. The present experimental Compton profiles are in better agreement with the theoretical calculations in the whole p{sub z} region than the previous experimental results, which indicates that the present experimental Compton profiles are accurate enough to serve as the benchmark data for methane and ethane molecules.

  10. Reactions of O/1D/ with methane and ethane.

    NASA Technical Reports Server (NTRS)

    Lin, C.-L.; Demore, W. B.

    1973-01-01

    Mixtures of nitrous oxide and methane and mixtures of nitrous oxide and ethane were photolyzed with 1849-A light. The reaction products were analyzed chromatographically. It was found that the reaction of the excited atomic oxygen with methane gives mainly CH3 and OH radicals as initial products, along with about 9% of formaldehyde and molecular hydrogen. The reaction of the excited atomic oxygen with ethane gives C2H5, OH, CH3 and CH2OH as major initial products, with only a few per cent of molecular hydrogen.

  11. Experimental investigations about the effect of trace amount of propane on the formation of mixed hydrates of methane and propane

    NASA Astrophysics Data System (ADS)

    Cai, W.; Lu, H.; Huang, X.

    2016-12-01

    In natural gas hydrates, some heavy hydrocarbons are always detected in addition to methane. However, it is still not well understood how the trace amount of heavy gas affect the hydrate properties. Intensive studies have been carried out to study the thermodynamic properties and structure types of mixed gases hydrates, but comparatively few investigations have been carried out on the cage occupancies of guest molecules in mixed gases hydrates. For understanding how trace amount of propane affects the formation of mixed methane-propane hydrates, X-ray diffraction, Raman spectroscopy, and gas chromatography were applied to the synthesized mixed methane-propane hydrate specimens, to get their structural characteristics (structure type, structural parameters, cage occupancy, etc.) and gas compositions. The mixed methane-propane hydrates were prepared by reacting fine ice powders with various gas mixtures of methane and propane. When the propane content was below 0.4%, the hydrates synthesized were found containing both sI methane hydrate and sII methane-propane hydrate; while the hydrates were found always sII when propane was over certain content. Detail studies about the cage occupancies of propane and methane in sII hydrate revealed that: 1) with the increase in propane content of methane-propane mixture, the occupancy of propane in large cage increased as accompanied with the decrease in methane occupancy in large cage, however the occupancy of methane in small cage didn't experience significant change; 2) temperature and pressure seemed no obvious influence on cage occupancy.

  12. Second and third virial coefficients for methane + ethane and methane + ethane + carbon dioxide at (300 and 320) K

    SciTech Connect

    Hou, H.; Holste, J.C.; Hall, K.R.; Marsh, K.N.; Gammon, B.E.

    1996-03-01

    Measurements of pVT made using the Burnett technique at (300 and 320) K are reported for methane, ethane, three x{sub 1} methane + (1 {minus} x{sub 1}) ethane mixtures with x{sub 1} = 0.30623, 0.49971, and 0.70090, and two x{sub 1} methane + x{sub 2} ethane + (1 {minus} x{sub 1} {minus} x{sub 2}) carbon dioxide mixtures with x{sub 1} = 0.32125, x{sub 2} = 0.34099 and x{sub 1} = 0.24759, x{sub 2} = 0.56013. Second virial coefficients have been calculated from these results for the pure fluids, and the binary and ternary mixtures. Cross second and third virial coefficients have been derived, including the cross third virial coefficient which describes the simultaneous unlike interaction between methane, ethane, and carbon dioxide. The experimental results were used to test an approximation to the virial equation which greatly simplifies calculations for multicomponent mixtures and which requires only experimental virial coefficients for binary mixtures. Values calculated using the model agree with experimental values within the estimated uncertainties. The results are compared with literature values, where available.

  13. Structural changes and preferential cage occupancy of ethane hydrate and methane-ethane mixed gas hydrate under very high pressure.

    PubMed

    Hirai, Hisako; Takahara, Naoya; Kawamura, Taro; Yamamoto, Yoshitaka; Yagi, Takehiko

    2008-12-14

    High-pressure experiments of ethane hydrate and methane-ethane mixed hydrates with five compositions were performed using a diamond anvil cell in a pressure range of 0.1-2.8 GPa at room temperature. X-ray diffractometry and Raman spectroscopy showed structural changes as follows. The initial structure, structure I (sI), of ethane hydrate was retained up to 2.1 GPa without any structural change. For the mixed hydrates, sI was widely distributed throughout the region examined except for the methane-rich and lower pressure regions. For the ethane-rich and intermediate composition regions (73 mol % ethane sample and 53% sample), sI was maintained up to 2.1 GPa. With increasing methane component (34% and 30% samples), sI existed at pressures from 0.1 to about 1.0 GPa. Hexagonal structure (sH) appeared in addition to sI at 1.3 GPa for the 34% sample and at 1.1 GPa for the 30% sample. By further increasing the methane component (22% sample), structure II (sII) existed solely up to 0.3 GPa. From 0.3 to 0.6 GPa, sII and sI coexisted, and from 0.6 to 1.0 GPa only sI existed. At 1.2 GPa sH appeared, and sH and sI coexisted up to 2.1 GPa. Above 2.1 GPa, ethane hydrate and all of the mixed hydrates decomposed into ice VI and ethane fluid or methane-ethane fluid, respectively. The Raman study revealed that occupation of the small cages by ethane molecules occurred above 0.1 GPa in ethane hydrate and continued up to decomposition at 2.1 GPa, although it is thought that ethane molecules are contained only in the large cage.

  14. Adsorption of methane, ethane, and ethylene on zeolite

    SciTech Connect

    Berlier, K.; Olivier, M.G.; Jadot, R.

    1995-11-01

    Adsorption isotherms at 283 and 303 K of methane, ethane, and ethylene on zeolite G5 have been obtained. Measurements have been made at pressures up to 1,200 kPa using an automated apparatus based on the volumetric method. This study is linked to a modeling interest because of the structure simplicity of the adsorbate molecules and because of the known geometric structure of the adsorbent.

  15. Effect of catalyst structure on oxidative dehydrogenation of ethane and propane on alumina-supported vanadia

    SciTech Connect

    Argyle, Morris D.; Chen, Kaidong; Bell, Alexis T.; Iglesia, Enrique

    2001-09-11

    The catalytic properties of Al2O3-supported vanadia with a wide range of VOx surface density (1.4-34.2 V/nm2) and structure were examined for the oxidative dehydrogenation of ethane and propane. UV-visible and Raman spectra showed that vanadia is dispersed predominantly as isolated monovanadate species below {approx}2.3 V/nm2. As surface densities increase, two-dimensional polyvanadates appear (2.3-7.0 V/nm2) along with increasing amounts of V2O5 crystallites at surface densities above 7.0 V/nm2. The rate constant for oxidative dehydrogenation (k1) and its ratio with alkane and alkene combustion (k2/k1 and k3/k1, respectively) were compared for both alkane reactants as a function of vanadia surface density. Propene formation rates (per V-atom) are {approx}8 times higher than ethene formation rates at a given reaction temperature, but the apparent ODH activation energies (E1) are similar for the two reactants and relatively insensitive to vanadia surface density. Ethene and propene formation rates (per V-atom) are strongly influenced by vanadia surface density and reach a maximum value at intermediate surface densities ({approx}8 V/nm2). The ratio of k2/k1 depends weakly on reaction temperature, indicating that activation energies for alkane combustion and ODH reactions are similar. The ratio of k2/k1 is independent of surface density for ethane, but increase slightly with vanadia surface density for propane, suggesting that isolated structures prevalent at low surface densities are slightly more selective for alkane dehydrogenation reactions. The ratio of k3/k1 decreases markedly with increasing reaction temperature for both ethane and propane ODH. Thus, the apparent activation energy for alkene combustion (E3) is much lower than that for alkane dehydrogenation (E1) and the difference between these two activation energies decreases with increasing surface density. The lower alkene selectivities observed at high vanadia surface densities are attributed to an

  16. Laboratory studies, analysis, and interpretation of the spectra of hydrocarbons present in planetary atmospheres including cyanoacetylene, acetylene, propane, and ethane

    NASA Technical Reports Server (NTRS)

    Blass, William E.; Daunt, Stephen J.; Peters, Antoni V.; Weber, Mark C.

    1990-01-01

    Combining broadband Fourier transform spectrometers (FTS) from the McMath facility at NSO and from NRC in Ottawa and narrow band TDL data from the laboratories with computational physics techniques has produced a broad range of results for the study of planetary atmospheres. Motivation for the effort flows from the Voyager/IRIS observations and the needs of Voyager analysis for laboratory results. In addition, anticipation of the Cassini mission adds incentive to pursue studies of observed and potentially observable constituents of planetary atmospheres. Current studies include cyanoacetylene, acetylene, propane, and ethane. Particular attention is devoted to cyanoacetylen (H3CN) which is observed in the atmosphere of Titan. The results of a high resolution infrared laboratory study of the line positions of the 663, 449, and 22.5/cm fundamental bands are presented. Line position, reproducible to better than 5 MHz for the first two bands, are available for infrared astrophysical searches. Intensity and broadening studies are in progress. Acetylene is a nearly ubiquitous atmospheric constituent of the outer planets and Titan due to the nature of methane photochemistry. Results of ambient temperature absolute intensity measurements are presented for the fundamental and two two-quantum hotband in the 730/cm region. Low temperature hotband intensity and linewidth measurements are planned.

  17. Airborne Ethane Observations over the Barnett and Bakken Shale Formations: Quantification of Ethane Fluxes and Attribution of Methane Emissions

    NASA Astrophysics Data System (ADS)

    Smith, M. L.; Kort, E. A.; Karion, A.; Sweeney, C.; Peischl, J.; Ryerson, T. B.

    2014-12-01

    The largest emissions sources of methane, a potent greenhouse gas and the primary component of natural gas, are the fossil fuel sector and microbial processes that occur in agricultural settings, landfills, and wetlands. Attribution of methane to these different source sectors has proven difficult, as evidenced by persistent disagreement between the annual emissions estimated from atmospheric observations (top-down) and from inventories (bottom-up). Given the rapidly changing natural gas infrastructure in North America, and the implications of associated rapid changes in emissions of methane for climate, it is crucial we improve our ability to quantify and understand current and future methane emissions. Here, we present evidence that continuous in-situ airborne observations of ethane, which is a tracer for fossil fuel emissions, are a new and useful tool for attribution of methane emissions to specific source sectors. Additionally, with these new airborne observations we present the first tightly constrained ethane emissions estimates of oil and gas production fields using the well-known mass balance method. The ratios of ethane-to-methane (C2H6:CH4) of specific methane emissions sources were studied over regions of high oil and gas production from the Barnett, TX and Bakken, ND shale plays, using continuous (1Hz frequency) airborne ethane measurements paired with simultaneous methane measurements. Despite the complex mixture of sources in the Barnett region, the methane emissions were well-characterized by distinct C2H6:CH4 relationships indicative of a high-ethane fossil fuel source (e.g., "wet" gas), a low-ethane fossil fuel source (e.g., "dry" gas), and an ethane-free, or microbial source. The defined set of C2H6:CH4 that characterized the emissions input to the atmosphere was used in conjunction with the total ethane and methane fluxes to place bounds on the fraction of methane emissions attributable to each source. Additionally, substantial ethane fluxes

  18. Enhancing aerobic biodegradation of 1,2-dibromoethane in groundwater using ethane or propane and inorganic nutrients

    NASA Astrophysics Data System (ADS)

    Hatzinger, Paul B.; Streger, Sheryl H.; Begley, James F.

    2015-01-01

    1,2-Dibromoethane (ethylene dibromide; EDB) is a probable human carcinogen that was previously used as both a soil fumigant and a scavenger in leaded gasoline. EDB has been observed to persist in soils and groundwater, particularly under oxic conditions. The objective of this study was to evaluate options to enhance the aerobic degradation of EDB in groundwater, with a particular focus on possible in situ remediation strategies. Propane gas and ethane gas were observed to significantly stimulate the biodegradation of EDB in microcosms constructed with aquifer solids and groundwater from the FS-12 EDB plume at Joint Base Cape Cod (Cape Cod, MA), but only after inorganic nutrients were added. Ethene gas was also effective, but rates were appreciably slower than for ethane and propane. EDB was reduced to < 0.02 μg/L, the Massachusetts state Maximum Contaminant Level (MCL), in microcosms that received ethane gas and inorganic nutrients. An enrichment culture (BE-3R) that grew on ethane or propane gas but not EDB was obtained from the site materials. The degradation of EDB by this culture was inhibited by acetylene gas, suggesting that degradation is catalyzed by a monooxygenase enzyme. The BE-3R culture was also observed to biodegrade 1,2-dichloroethane (DCA), a compound commonly used in conjunction with EDB as a lead scavenger in gasoline. The data suggest that addition of ethane or propane gas with inorganic nutrients may be a viable option to enhance degradation of EDB in groundwater aquifers to below current state or federal MCL values.

  19. Preindustrial atmospheric ethane levels inferred from polar ice cores: A constraint on the geologic sources of atmospheric ethane and methane

    NASA Astrophysics Data System (ADS)

    Nicewonger, Melinda R.; Verhulst, Kristal R.; Aydin, Murat; Saltzman, Eric S.

    2016-01-01

    Ethane levels were measured in air extracted from Greenland and Antarctic ice cores ranging in age from 994 to 1918 Common Era (C.E.) There is good temporal overlap between the two data sets from 1600 to 1750 C.E. with ethane levels stable at 397 ± 28 parts per trillion (ppt) (±2 standard error (s.e.)) over Greenland and 103 ± 9 ppt over Antarctica. The observed north/south interpolar ratio of ethane (3.9 ± 0.1, 1σ) implies considerably more ethane emissions in the Northern Hemisphere than in the Southern Hemisphere, suggesting geologic ethane sources contribute significantly to the preindustrial ethane budget. Box model simulations based on these data constrain the global geologic emissions of ethane to 2.2-3.5 Tg yr-1 and biomass burning emissions to 1.2-2.5 Tg yr-1 during the preindustrial era. The results suggest biomass burning emissions likely increased since the preindustrial period. Biomass burning and geologic outgassing are also sources of atmospheric methane. The results place constraints on preindustrial methane emissions from these sources.

  20. Long-term Decline of Global Atmospheric Ethane Concentrations and Implications for Methane

    NASA Astrophysics Data System (ADS)

    Blake, D. R.; Simpson, I. J.; Sulbaek Andersen, M.; Meinardi, S.; Bruhwiler, L.; Blake, N. J.; Helmig, D.

    2012-12-01

    Methane (CH4) and ethane (C2H6) are the most abundant hydrocarbons in the remote atmosphere. Both are precursors to tropospheric ozone (O3) and methane is a potent greenhouse gas. Here we present the longest continuous record of global atmospheric ethane levels. We show that global ethane emission rates decreased from 14.3 to 11.3 Tg yr-1, or 21% from 1984-2010. Based on simulations using the TM5 atmospheric tracer transport model, ethane's long-term global decline is attributed to decreasing fugitive emissions from ethane's fossil fuel source—most likely reduced venting and flaring of natural gas in oil fields—rather than declines in its other major sources, biofuel use and biomass burning. In addition, our calculated top-down estimates of ethane's global emission rates agree well with recent bottom-up estimates from the literature, which suggests that the ethane budget is quite well balanced and unlikely to have any additional major sources. Ethane's major emission sources are shared with methane, and recent studies have disagreed on whether reduced fossil fuel or microbial emissions have caused methane's growth rate to slow (Aydin et al., 2011; Kai et al., 2011). Because methane and ethane are emitted from fossil fuel sources with characteristic emission ratios, our long-term ethane record can be used to quantitatively investigate methane's slowing growth rate. We show that reduced fugitive fossil fuel emissions account for at least 10-21 Tg yr-1 (30-70%) of the decrease in methane's global emissions, significantly contributing to methane's slowing growth rate since the mid-1980s.

  1. Performance of an Experimental Annular Turbojet Combustor with Methane and Propane

    NASA Technical Reports Server (NTRS)

    Norgren, Carl T

    1957-01-01

    Combustion efficiencies obtained with gaseous methane were compared with reported data obtained with gaseous propane for the same experimental combustor configuration. The combustion efficiencies obtained with methane were 98, 91, and 77 percent at simulated flight altitudes of 56,000, 70,000 and 80,000 feet, corresponding to combustor inlet-air pressures from 15 to 5 inches of mercury absolute. Combustion efficiencies with propane were equivalent to those with methane up to a simulated altitude of 70,000 feet. At the most severe conditions investigated propane operated with a higher efficiency and over a wider range of fuel-air ratio than methane.

  2. The solubility of ethane, propane, and carbon dioxide in aqueous solutions of sodium cumene sulfonate.

    PubMed

    King, A D

    2004-05-01

    Measurements have been made to determine the solubilities of ethane, C2H6, propane, C3H8, and carbon dioxide, CO2, in aqueous solutions of sodium cumene sulfonate (NaCS) at 25 degrees C. The solubilities measured for each gas satisfy Henry's law at all concentrations of NaCS. The solubilities of C2H6 and C3H8 exhibit quite similar behavior with respect to added NaCS. The solubilities of these two gases are very low in pure water and are found to be nearly independent of NaCS concentration over a concentration range of 0-0.4 mol NaCS/kg H2O. At intermediate concentrations of NaCS, the solubilities of C2H6 and C3H8 exhibit a gradual increase with added NaCS concentrations ranging from 0.4 to 2.0 mol NaCS/kg H2O. At NaCS concentrations greater than 2.0 mol NaCS/kg H2O, the solubilities of these two gases increase with added NaCS in an approximately linear manner, with the solubility of C3H8 increasing more rapidly than that for C2H6 (by a factor of approximately 2.5). CO2 is much more soluble in pure water than the hydrocarbon gases and exhibits markedly different behavior with respect to added NaCS. The solubility of CO2 decreases with added NaCS over a concentration range of 0-0.9 mol NaCS/kg H2O, passes through a minimum at a concentration of approximately 1.0 mol NaCS/kg H2O, and then increases with added NaCS at higher NaCS concentrations in a manner similar to that observed with C2H6 and C3H8. The trends in solubility observed for these three gases dissolved in aqueous solutions of NaCS resemble those found previously with aqueous solutions of ordinary surfactants. The solubility data measured for these three gases can be interpreted surprisingly well in terms of the mass-action model for micellization, in which salting-out effects due to monomer salt ions suppress gas solubility at low NaCS concentrations and gas solubilization by small micelles of NaCS acts to enhance gas solubility at the higher NaCS concentrations.

  3. Development of a Flight Instrument for in situ Measurements of Ethane and Methane

    NASA Astrophysics Data System (ADS)

    Wilkerson, J. P.; Sayres, D. S.; Anderson, J. G.

    2015-12-01

    Methane emissions data for natural gas and oil fields have high uncertainty. Better quantifying these emissions is crucial to establish an accurate methane budget for the United States. One obstacle is that these emissions often occur in areas near livestock facilities where biogenic methane abounds. Measuring ethane, which has no biogenic source, along with methane can tease these sources apart. However, ethane is typically measured by taking whole-air samples. This tactic has lower spatial resolution than making in situ measurements and requires the measurer to anticipate the location of emission plumes. This leaves unexpected plumes uncharacterized. Using Re-injection Mirror Integrated Cavity Output Spectroscopy (RIM-ICOS), we can measure both methane and ethane in flight, allowing us to establish more accurate fugitive emissions data that can more readily distinguish between different sources of this greenhouse gas.

  4. Nitrogen, methane, and ethane sorption on activated carbon

    NASA Astrophysics Data System (ADS)

    Tzabar, N.; Grossman, G.

    2011-09-01

    Joule-Thomson (JT) sorption cryocoolers rely on sorption compressors that provide a continuous flow with predetermined high and low pressures without any vibration emission. These cryocoolers may operate with different fluids, in accordance with the desired cold temperature. Nitrogen, methane, and ethane are prevalent candidate fluids for sorption cryocoolers, providing cold temperatures of about 80 K, 120 K, and 185 K, respectively. In order to develop a sorption compressor it is necessary to know the sorption characteristics of the fluid on the selected adsorbent. In this work we present experimental sorption measurements of the mentioned fluids on a commercial pelleted activated carbon. The Langmuir, Freundlich, and Sips models are fitted to the experimental results and further modified to incorporate the temperature dependence, in order to extend the prediction of sorption properties into wider ranges of temperature and pressure. It appears that each fluid has a different model that best fits its characteristics. Finally, the isosteric heat of adsorption is calculated for the three mentioned fluids as a function of the adsorption coverage and polynomial regressions are obtained for it.

  5. Long-term decline of global atmospheric ethane concentrations and implications for methane.

    PubMed

    Simpson, Isobel J; Sulbaek Andersen, Mads P; Meinardi, Simone; Bruhwiler, Lori; Blake, Nicola J; Helmig, Detlev; Rowland, F Sherwood; Blake, Donald R

    2012-08-23

    After methane, ethane is the most abundant hydrocarbon in the remote atmosphere. It is a precursor to tropospheric ozone and it influences the atmosphere's oxidative capacity through its reaction with the hydroxyl radical, ethane's primary atmospheric sink. Here we present the longest continuous record of global atmospheric ethane levels. We show that global ethane emission rates decreased from 14.3 to 11.3 teragrams per year, or by 21 per cent, from 1984 to 2010. We attribute this to decreasing fugitive emissions from ethane's fossil fuel source--most probably decreased venting and flaring of natural gas in oil fields--rather than a decline in its other major sources, biofuel use and biomass burning. Ethane's major emission sources are shared with methane, and recent studies have disagreed on whether reduced fossil fuel or microbial emissions have caused methane's atmospheric growth rate to slow. Our findings suggest that reduced fugitive fossil fuel emissions account for at least 10-21 teragrams per year (30-70 per cent) of the decrease in methane's global emissions, significantly contributing to methane's slowing atmospheric growth rate since the mid-1980s.

  6. Study on synchronous detection method of methane and ethane with laser absorption spectroscopy technology

    NASA Astrophysics Data System (ADS)

    He, Ying; Zhang, Yu-jun; You, Kun; Gao, Yan-wei; Chen, Chen; Liu, Jian-guo; Liu, Wen-qing

    2016-10-01

    The main ingredient of mash gas is alkenes, and methane is the most parts of mash gas and ethane is a small portion of it. Fast, accurate, real-time measurement of methane and ethane concentration is an important task for preventing coal mining disaster. In this research, a monitoring system with tunable diode laser absorption spectroscopy (TDLAS) technology has been set up for simultaneous measurement of methane and ethane, and a DFB laser at wavelength of 1.653μm was used as the laser source. The absorption spectroscopy information of methane and ethane, especially the characteristic of the spectrum peak positions and relative intensity were determined by available spectral structures from previous study and available database. Then, the concentration inversion algorithm method based on the spectral resolution and feature extraction was designed for methane and ethane synchronous detection. At last, the continuously experimental results obtained by different concentration of methane and ethane sample gases with the multiple reflection cell and the standard distribution system. In this experiment, the standard distribution system made with the standard gas and two high precision mass flow meters of D07 Sevenstar series whose flow velocity is 1l/min and 5l/min respectively. When the multiple reflection cell work stably, the biggest detection error of methane concentration inversion was 3.7%, and the biggest detection error of ethane was 4.8%. So it is verified that this concentration inversion algorithm works stably and reliably. Thus, this technology could realize the real-time, fast and continuous measurement requirement of mash gas and it will provide the effective technical support to coal mining production in safety for our country.

  7. Activation of methane and ethane and their selective oxidation to the alcohols in protic media

    SciTech Connect

    Sen, A.; Benvenuto, M.A.; Lin, M.; Hutson, A.C.; Basickes, N. )

    1994-02-09

    The selective oxidation of methane and ethane to the alcohols in solvents ranging from strong acids to neutral aqueous medium has been studied. In 98% sulfuric acid, methane is oxidized to CH[sub 3]OSO[sub 3]H by a variety of 1e[sup [minus

  8. Microwave Spectrum and Structure of the Methane-Propane Complex

    NASA Astrophysics Data System (ADS)

    Peterson, Karen I.; Lin, Wei; Arsenault, Eric A.; Choi, Yoon Jeong; Novick, Stewart E.

    2017-06-01

    Methane is exceptional in its solid-phase orientational disorder that persists down to 24 K. Only below that temperature does the structure become partially ordered, and full crystallinity requires even lower temperatures and high pressures. Not surprisingly, methane appears to freely rotate in most van der Waals complexes, although two notable exceptions are CH_4-HF and CH_4-C_5H_5N. Of interest to us is how alkane interactions affect the methane rotation. Except for CH_4-CH_4, rotationally-resolved spectra of alkane-alkane complexes have not been studied. To fill this void, we present the microwave spectrum of CH_4-C_3H_8 which is the smallest alkane complex with a practical dipole moment. The microwave spectrum of CH_4-C_3H_8 was measured using the Fourier Transform microwave spectrometer at Wesleyan University. In the region between 7100 and 25300 MHz, we observed approximately 70 transitions that could plausibly be attributed to the CH_4-C_3H_8 complex (requiring high power and the proper mixture of gases). Of these, 16 were assigned to the A-state (lowest internal rotor state of methane) and four to the F-state. The A-state transitions were fitted with a Watson Hamiltonian using nine spectroscopic constants of which A = 7553.8144(97) MHz, B = 2483.9183(35) MHz, and C = 2041.8630(21) MHz. The A rotational constant is only 1.5 MHz higher than that of Ar-C_3H_8 and, since the a-axis of the complex passes approximately through the centers of mass of the subunits, this indicates a similar relative orientation. Thus, we find that the CH_4 is located above the plane of the propane. The center-of-mass separation of the subunits in CH_4-C_3H_8 is calculated to be 3.993 Å, 0.16 Å longer than the Ar-C_3H_8 distance of 3.825 Å, a reasonable difference considering the larger van der Waals radius of CH_4. The four F-state lines, which were about twice as strong as the A-state lines, could be fitted to A, B, and C rotational constants, and further analysis is in progress.

  9. Demonstration of a Fast, Precise Propane Measurement Using Infrared Spectroscopy

    NASA Astrophysics Data System (ADS)

    Zahniser, M. S.; Roscioli, J. R.; Nelson, D. D.; Herndon, S. C.

    2016-12-01

    Propane is one of the primary components of emissions from natural gas extraction and processing activities. In addition to being an air pollutant, its ratio to other hydrocarbons such as methane and ethane can serve as a "fingerprint" of a particular facility or process, aiding in identifying emission sources. Quantifying propane has typically required laboratory analysis of flask samples, resulting in low temporal resolution and making plume-based measurements infeasible. Here we demonstrate fast (1-second), high precision (<300 ppt) measurements of propane using high resolution mid-infrared spectroscopy at 2967 wavenumbers. In addition, we explore the impact of nearby water and ethane absorption lines on the accuracy and precision of the propane measurement. Finally, we discuss development of a dual-laser instrument capable of simultaneous measurements of methane, ethane, and propane (the C1-C3 compounds), all within a small spatial package that can be easily deployed aboard a mobile platform.

  10. Ethane's 12C/13C Ratio in Titan: Implications for Methane Replenishment

    NASA Technical Reports Server (NTRS)

    Jennings, Donald E.; Nixon, C. A.; Romani, P. N.; Bjoraker, G. L.; Sada, P. V.; Lunsford, A. W.; Boyle, R. J.; Hesman, B. E.; McCabe, G. H.

    2009-01-01

    As the .main destination of carbon in the destruction of methane in the atmosphere of Titan, ethane provides information about the carbon isotopic composition of the reservoir from which methane is replenished. If the amount of methane entering the atmosphere is presently equal to the amount converted to ethane, the 12C/13C ratio in ethane should be close to the ratio in the reservoir. We have measured the 12C/13C ratio in ethane both with Cassini CIRS(exp 1) and from the ground and find that it is very close to the telluric standard and outer planet values (89), consistent with a primordial origin for the methane reservoir. The lower 12C/13C ratio measured for methane by Huygens GCMS (82.3) can be explained if the conversion of CH4 to CH3 (and C2H6) favors 12C over 13C with a carbon kinetic isotope effect of 1.08. The time required for the atmospheric methane to reach equilibrium, i.e., for replenishment to equal destruction, is approximately 5 methane atmospheric lifetimes.

  11. Recent decreases in fossil-fuel emissions of ethane and methane derived from firn air.

    PubMed

    Aydin, Murat; Verhulst, Kristal R; Saltzman, Eric S; Battle, Mark O; Montzka, Stephen A; Blake, Donald R; Tang, Qi; Prather, Michael J

    2011-08-10

    Methane and ethane are the most abundant hydrocarbons in the atmosphere and they affect both atmospheric chemistry and climate. Both gases are emitted from fossil fuels and biomass burning, whereas methane (CH(4)) alone has large sources from wetlands, agriculture, landfills and waste water. Here we use measurements in firn (perennial snowpack) air from Greenland and Antarctica to reconstruct the atmospheric variability of ethane (C(2)H(6)) during the twentieth century. Ethane levels rose from early in the century until the 1980s, when the trend reversed, with a period of decline over the next 20 years. We find that this variability was primarily driven by changes in ethane emissions from fossil fuels; these emissions peaked in the 1960s and 1970s at 14-16 teragrams per year (1 Tg = 10(12) g) and dropped to 8-10 Tg  yr(-1) by the turn of the century. The reduction in fossil-fuel sources is probably related to changes in light hydrocarbon emissions associated with petroleum production and use. The ethane-based fossil-fuel emission history is strikingly different from bottom-up estimates of methane emissions from fossil-fuel use, and implies that the fossil-fuel source of methane started to decline in the 1980s and probably caused the late twentieth century slow-down in the growth rate of atmospheric methane.

  12. Experimental determination of acetylene and ethylene solubility in liquid methane and ethane: Implications to Titan's surface

    NASA Astrophysics Data System (ADS)

    Singh, S.; Combe, J.-Ph.; Cordier, D.; Wagner, A.; Chevrier, V. F.; McMahon, Z.

    2017-07-01

    In this study, the solubility of acetylene (or ethyne, C2H2) and ethylene (or ethene, C2H4) in liquid methane (CH4) and ethane (C2H6) has been experimentally determined at Titan surface temperature (90 K) and pressure (1.5 bars). As predicted by theoretical models, the solubilities of acetylene and ethylene are very large at Titan temperature and these species are most likely to be abundantly present in the lakes and as evaporites on the shores or dry lake beds. Our results indicate the solubility of 4.9 × 10-2 mole fraction for acetylene in methane and 48 × 10-2 mole fraction in ethane; for ethylene, 5.6 × 10-1 mole fraction in methane and 4.8 × 10-1 mole fraction in ethane. Assuming the mole fractions from atmospheric models in the lower stratosphere and equilibrium with the surface, we determined that the lakes on Titan that cover ∼400,000 km2 are not saturated. The liquid lakes on Titan act as an important reservoir for both acetylene and ethylene. Assuming difference of methane and ethane content in the lakes at different latitudes, the difference in solubility in liquid methane and ethane, solutes in lakes may change with the temporal evolution (such as; evaporation and condensation) over seasons and geological time scales.

  13. Theoretical investigation of the elimination and addition reactions of methane and ethane with nickel

    SciTech Connect

    Blomberg, M.R.A.; Brandemark, U.; Siegbahn, P.E.M.

    1983-08-24

    Contracted CI calculations have been performed to study the mechanisms for the concerted elimination and addition reactions of ethane and methane with nickel. It is found that the /sup 1/A/sub 1/ state of nickel-ethane and the /sup 1/A' state of nickel-methane behave very similarly. The elimination barrier, for example, is computed to be 34 kcal/mol for methane and 37 kcal/mol for ethane. For the addition reaction a somewhat larger difference is obtained, the activation energy of methane being 54 kcal/mol and of ethane (breaking the C-C bond) 42 kcal/mol. This difference in activation energy can be explained by the difference in the bond strength of the C-H bond in methane and the C-C bond in ethane, the C-H bond being 16 kcal/mol stronger. The difference between these two systems on one side and H/sub 2/ on the other is large; H/sub 2/ has a computed addition barrier to nickel of only 3 kcal/mol. The hydrogen atoms can much more easily form bonds in several directions at the same time than methyl groups, and this difference leads to higher activation energies for reactions involving methyl groups. For all three systems the reaction takes place with nickel in a d/sup 9/ state and with a large extent of d involvement in the bonding at the bent equilibrium geometry. 23 references, 3 figures, 5 tables.

  14. C-12/C-13 Ratio in Ethane on Titan and Implications for Methane's Replenishment

    NASA Technical Reports Server (NTRS)

    Jennings, Donald E.; Romani, Paul N.; Bjoraker, Gordon L.; Sada, Pedro V.; Nixon, Conor A.; Lunsford, Allen W.; Boyle, Robert J.; Hesman, Brigette E.; McCabe, George H.

    2009-01-01

    The C-12/C-13 abundance ratio in ethane in the atmosphere of Titan has been measured at 822 cm(sup -1) from high spectral resolution ground-based observations. The value 89(8), coincides with the telluric standard and also agrees with the ratio seen in the outer planets. It is almost identical to the result for ethane on Titan found by the composite infrared spectrometer (CIRS) on Cassini. The C-12/C-13 ratio for ethane is higher than the ratio measured in atmospheric methane by Cassini/Huygens GCMS, 82.3(l), representing an enrichment of C-12 in the ethane that might be explained by a kinetic isotope effect of approximately 1.1 in the formation of methyl radicals. If methane is being continuously resupplied to balance photochemical destruction, then we expect the isotopic composition in the ethane product to equilibrate at close to the same C-12/C-13 ratio as that in the supply. The telluric value of the ratio in ethane then implies that the methane reservoir is primordial.

  15. 12C/13C ratio in ethane on titan and implications for methane's replenishment.

    PubMed

    Jennings, Donald E; Romani, Paul N; Bjoraker, Gordon L; Sada, Pedro V; Nixon, Conor A; Lunsford, Allen W; Boyle, Robert J; Hesman, Brigette E; McCabe, George H

    2009-10-22

    The (12)C/(13)C abundance ratio in ethane in the atmosphere of Titan has been measured at 822 cm(-1) from high spectral resolution ground-based observations. The value, 89(8), coincides with the telluric standard and also agrees with the ratio seen in the outer planets. It is almost identical to the result for ethane on Titan found by the composite infrared spectrometer (CIRS) on Cassini. The (12)C/(13)C ratio for ethane is higher than the ratio measured in atmospheric methane by Cassini/Huygens GCMS, 82.3(1), representing an enrichment of (12)C in the ethane that might be explained by a kinetic isotope effect of approximately 1.1 in the formation of methyl radicals. If methane is being continuously resupplied to balance photochemical destruction, then we expect the isotopic composition in the ethane product to equilibrate at close to the same (12)C/(13)C ratio as that in the supply. The telluric value of the ratio in ethane then implies that the methane reservoir is primordial.

  16. Methane, black carbon, and ethane emissions from natural gas flares in the Bakken Shale, ND.

    PubMed

    Gvakharia, Alexander; Kort, Eric A; Brandt, Adam R; Peischl, Jeff; Ryerson, Thomas B; Schwarz, Joshua P; Smith, Mackenzie L; Sweeney, Colm

    2017-04-12

    Incomplete combustion during flaring can lead to production of black carbon (BC) and loss of methane and other pollutants to the atmosphere, impacting climate and air quality. However, few studies have measured flare efficiency in a real-world setting. We use airborne data of plume samples from 37 unique flares in the Bakken region of North Dakota in May 2014 to calculate emission factors for BC, methane, ethane, and combustion efficiency for methane and ethane. We find no clear relationship between emission factors and aircraft-level wind speed, nor between methane and BC emission factors. Observed median combustion efficiencies for methane and ethane are close to expected values for typical flares according to the US EPA (98%). However, we find that the efficiency distribution is skewed, exhibiting lognormal behavior. This suggests incomplete combustion from flares contributes almost 1/5 of the total field emissions of methane and ethane measured in the Bakken shale, more than double the expected value if 98\\% efficiency was representative. BC emission factors also have a skewed distribution, but we find lower emission values than previous studies. The direct observation for the first time of a heavy-tail emissions distribution from flares suggests the need to consider skewed distributions when assessing flare impacts globally.

  17. Cooling rate and ice-crystal measurement in biological specimens plunged into liquid ethane, propane, and Freon 22.

    PubMed

    Ryan, K P; Bald, W B; Neumann, K; Simonsberger, P; Purse, D H; Nicholson, D N

    1990-06-01

    Specimens sandwiched between copper planchettes were plunged up to a depth of 430 mm into coolants used for cryofixation. Hydrated gelatin containing a miniature thermocouple was used to mimic the behaviour of tissue during freezing. Gelatin and red blood cells were used for ice-crystal analysis. Ethane produced the fastest cooling rates and the smallest ice-crystal profiles, and Freon 22 produced the slowest cooling rates and the largest crystal profiles. Smaller crystal profiles were often seen in the centre of the specimens than in subsurface zones. The results show that ethane, rather than propane, should be used for freezing metal-sandwiched freeze-fracture specimens by the plunging method, and probably also in the jet-cooling method. They further suggest that good cryofixation could occur at the centre of thin specimens rather than only at their surfaces. Comparison between theoretical and experimental ice-crystal sizes was satisfactory, indicating that where the experimental parameters can be defined then realistic predictions can be made regarding cryofixation results.

  18. Methane source identification in Boston, Massachusetts using isotopic and ethane measurements

    NASA Astrophysics Data System (ADS)

    Down, A.; Jackson, R. B.; Plata, D.; McKain, K.; Wofsy, S. C.; Rella, C.; Crosson, E.; Phillips, N. G.

    2012-12-01

    Methane has substantial greenhouse warming potential and is the principle component of natural gas. Fugitive natural gas emissions could be a significant source of methane to the atmosphere. However, the cumulative magnitude of natural gas leaks is not yet well constrained. We used a combination of point source measurements and ambient monitoring to characterize the methane sources in the Boston urban area. We developed distinct fingerprints for natural gas and multiple biogenic methane sources based on hydrocarbon concentration and isotopic composition. We combine these data with periodic measurements of atmospheric methane and ethane concentration to estimate the fractional contribution of natural gas and biogenic methane sources to the cumulative urban methane flux in Boston. These results are used to inform an inverse model of urban methane concentration and emissions.

  19. 20th century ethane variability from polar firn air and implications for the methane budget

    NASA Astrophysics Data System (ADS)

    Saltzman, E. S.; Verhulst, K. R.; Aydin, K. M.; Battle, M. O.; Montzka, S. A.; Tang, Q.; Prather, M. J.

    2010-12-01

    Methane and ethane are the most abundant hydrocarbons in the atmosphere and they impact both atmospheric chemistry and climate. Both gases are emitted from fossil fuels and biomass burning, while methane alone has large sources from wetlands, agriculture, landfills and wastewater. Here we use measurements in firn air from Greenland and Antarctica to reconstruct the atmospheric variability of ethane during the 20th century. Ethane levels rose from early in the century until the 1980’s when the trend reverses, with a period of decline over the next 20 years. This variability is primarily driven by changes in ethane emissions from fossil fuels that peaked in the 1960’s and 1970’s at 14-16 Tg/y and dropped to 8-10 Tg/y before the end of the century. The reduction in fossil-fuel sources is likely related to changes in light hydrocarbon recovery during petroleum production and use. The ethane-based emission history implies that the decline in the fossil-fuel source of methane may have started prior to the 1980’s and that the magnitude of the decline is larger than previous estimates.

  20. ANALYSIS OF DISSOLVED METHANE, ETHANE, AND ETHYLENE IN GROUND WATER BY A STANDARD GAS CHROMATOGRAPHIC TECHNIQUE

    EPA Science Inventory

    The measurement of dissolved gases such as methane, ethane, and ethylene in ground water is important in determining whether intrinsic bioremediation is occurring in a fuel- or solvent-contaminated aquifer. A simple procedure is described for the collection and subsequent analys...

  1. ANALYSIS OF DISSOLVED METHANE, ETHANE, AND ETHYLENE IN GROUND WATER BY A STANDARD GAS CHROMATOGRAPHIC TECHNIQUE

    EPA Science Inventory

    The measurement of dissolved gases such as methane, ethane, and ethylene in ground water is important in determining whether intrinsic bioremediation is occurring in a fuel- or solvent-contaminated aquifer. A simple procedure is described for the collection and subsequent analys...

  2. Ethane and propane emissions to the ocean and atmosphere from 550-1200 m seeps in the Gulf of Mexico

    NASA Astrophysics Data System (ADS)

    Solomon, E. A.; Kastner, M.; Leifer, I.

    2009-12-01

    Ethane (C2) and propane (C3) are highly reactive trace gases in the atmosphere that are important precursors of organic aerosols and contribute to ozone formation. The global flux of C2 and C3 based on tropospheric removal are 13-15.5 and 12 Tg/yr, respectively. Current emission inventories that include fossil fuel, biomass burning, biofuels, and waste treatment underestimate the global flux by ~2-5 Tg/yr. Previous studies have indicated that the open ocean contributes only marginally to global C2 and C3 budgets, but very few studies have investigated the natural emissions from marine seeps and their potential significance to global C2 and C3 fluxes. During a recent study at 3 seeps at depths from 550-600 m in the Gulf of Mexico (GOM), a submersible was used to collect water column samples immediately adjacent to 5 bubble plumes from the seafloor vents to the sea surface. Bottom water C2 and C3 concentrations above the seeps ranged from 24.3-2220 and 15.8-385 nM, respectively. Ethane and propane concentrations decrease by ~50-95% in the bottom 200 m. Mixed layer C2 and C3 concentrations were extremely high ranging from 6.3-147 and 4.0-110 nM. These mixed layer C2 and C3 concentrations are up to 1×105 and 5×105 times saturation with respect to atmospheric equilibrium. In general, C1/C2 and C2/C3 ratios decrease from the seafloor to the mixed layer with surface ratios lower than previously reported from marine seeps and the ocean, indicating preferential loss of light hydrocarbons from the plumes during water column transit. Preliminary results from numerical bubble models show the importance of bubble plume-driven upwelling flows, bubble size, and pressure effects for enhancing hydrocarbon transfer to the mixed layer. Based on contemporaneous wind speeds at the study sites, preliminary estimates for the diffusive C2 and C3 fluxes to the atmosphere above the seeps range from 10-400 μmol/m2d; 2-4 orders of magnitude greater than estimates from the open ocean

  3. Renewed methane increase (2007-2014): contribution of oil and natural gas emissions determined from methane and ethane column observations

    NASA Astrophysics Data System (ADS)

    Hausmann, Petra; Sussmann, Ralf; Smale, Dan

    2016-04-01

    Harmonized time series of column-averaged mole fractions of atmospheric methane and ethane over the period 1999-2014 are derived from solar Fourier transform infrared (FTIR) measurements at the Zugspitze summit (47° N, 2964 m a.s.l.) and at Lauder (45° S, 370 m a.s.l.). Long-term trend analysis reveals a consistent renewed methane increase since 2007 of 6.2 [5.6, 6.9] ppb yr-1 at the Zugspitze and 6.0 [5.3, 6.7] ppb yr-1 at Lauder (95 % confidence intervals). Several recent studies provide pieces of evidence that the renewed methane increase is most likely driven by two main factors: (i) increased methane emissions from tropical wetlands, followed by (ii) increased thermogenic methane emissions due to growing oil and natural gas production. Here, we quantify the magnitude of the second class of sources, using long-term measurements of atmospheric ethane as tracer for thermogenic methane emissions. In 2007, after years of weak decline, the Zugspitze ethane time series shows the sudden onset of a significant positive trend (2.3 [1.8, 2.8] × 10-2 ppb yr-1 for 2007-2014), while a negative trend persists at Lauder after 2007 (-0.4 [-0.6, -0.1] × 10-2 ppb yr-1). Zugspitze methane and ethane time series are significantly correlated for the period 2007-2014 and can be assigned to thermogenic methane emissions with an ethane-to-methane ratio of 10-21 %. We present optimized emission scenarios for 2007-2014 derived from an atmospheric two-box model. From our trend observations we infer a total ethane emission increase over the period 2007-2014 from oil and natural gas sources of 1-11 Tg yr-1 along with an overall methane emission increase of 24-45 Tg yr-1. Based on these results, the oil and natural gas emission contribution C to the renewed methane increase is deduced using three different emission scenarios with dedicated ranges of methane-to-ethane ratios (MER). Reference scenario 1 assumes an oil and gas emission combination with MER = 3.3-7.6, which results in a

  4. Real-Time Measurements of Ethane for Source Attribution of Methane Plumes from Oil and Gas Facilities

    NASA Astrophysics Data System (ADS)

    Yacovitch, T. I.; Floerchinger, C.; Roscioli, J. R.; Herndon, S.; Fortner, E.; Knighton, W. B.; Petron, G.; Sweeney, C.; Karion, A.; Kofler, J.; Iglesias, G.; Zavala, M. A.; Molina, L. T.

    2013-12-01

    The Aerodyne Mobile Lab has conducted several recent studies of the methane emissions from Oil and Gas facilities at varying stages of production: well-heads; processing facilities; and compressor stations. Accurate quantification of methane emission rates are can be complicated by other local sources, notably livestock and microbial production. Methane emissions from oil and gas facilities are always accompanied by small amounts of ethane, while biogenic plumes contain no ethane. A prototype ethane spectrometer based on the Aerodyne-Mini chassis, has been deployed to oil and gas facilities in the Veracruz region of Mexico, as part of the 2013 Short-Lived Climate-Forcing project, and during ground-based measurements in the Barnett Shale in Texas as part of the Barnett Oil and Gas Observation Study. These results suggest a source-dependence in the ethane-to-methane ratio in oil and gas emissions. The results will be contrasted with 13CH4 methane isotope ratios determined using Aerodyne's Methane-Dual instrument. The limits and advantages of ethane-methane ratios and methane isotopes will be discussed. In the current instrumentation, the precision of determined ethane-to-methane ratios in a single plume encounter exceeds the analogous carbon isotope quantification.

  5. Understanding methane variability from 1980 - 2015 using inversions of methane, δ13C and ethane

    NASA Astrophysics Data System (ADS)

    Thompson, Rona; Nisbet, Euan

    2017-04-01

    Atmospheric methane (CH4) increased globally during the 20th century, from a pre-industrial value of approximately 722 ppb to 1773 ppb in 1999. The upward trend, however, was interrupted between 1999 and 2006, when the atmospheric growth rate of CH4 was close to zero. From 2007, atmospheric CH4 started to increase again and, in 2014, the growth rate was substantially faster (12.5 ppb/y) than in any other year since 2007. Changes in the atmospheric growth rate indicate changes in the balance of CH4 sources and sinks, however, the cause of the 1999-2006 stabilization and subsequent rise in atmospheric CH4, and its attribution to different sources is still not fully resolved. Various explanations have been proposed for the pause in the growth, including a reduction in fossil fuel and wetland emissions, and for its renewed increase, such as increasing emissions from wetlands, enteric fermentation, and fossil fuels, as well as a decline in the OH sink. To better constrain the sources and sinks of CH4, we have performed an inversion using the AGAGE 12-box model of the atmosphere using atmospheric observations of CH4, δ13C, and of ethane. Using observations of these 3 atmospheric tracers simultaneously, a stronger constraint is placed on the different sources, as well as the principal atmospheric sink via oxidation by OH. In the model, we account for all emissions grouped into microbial, fossil fuel, biomass burning, landfill and ocean sources, as well as the soil oxidation sink. We also account for the atmospheric sink of CH4 and ethane via oxidation by OH and Cl radicals. The modelled lifetimes of CH4 and ethane were 8.2 years and 1.3 months, respectively. Inversions were also performed in which the OH sink was optimized simultaneously with the emissions. We find that fossil fuel emissions were underestimated in the northern mid to high latitudes in the 1980s but were overestimated from the mid 1990s onwards with respect to the prior (EDGAR-4.2), and that there is no

  6. Methane and Ethane Measurements from a New TCCON Station in Los Angeles

    NASA Astrophysics Data System (ADS)

    Wunch, D.; Roehl, C. M.; Blavier, J. L.; Allen, N.; Treffers, R.; Toon, G. C.; Wennberg, P. O.

    2012-12-01

    The Los Angeles urban region emits large amounts of methane (~0.44Tg/year) into the atmosphere. It is currently unclear exactly how much of this is biogenic (landfills, cattle), and how much is from natural gas (natural seeps or fugitive emissions from the natural gas infrastructure). Since natural gas contains ethane, whereas biogenic emissions contain none, simultaneous measurements of ethane and methane offer the possibility of separating the biogenic versus natural gas emissions of methane. We investigate this using total column measurements from a new Total Carbon Column Observing Network (TCCON) remote sensing station in the Los Angeles suburb of Pasadena, which began measurements in July 2012. These measurements will be put into the context of historical remote sensing and in situ measurements described by Wennberg et al., 2012 (doi:10.1021/es301138y).

  7. AIRBORNE, OPTICAL REMOTE SENSNG OF METHANE AND ETHANE FOR NATURAL GAS PIPELINE LEAK DETECTION

    SciTech Connect

    Jerry Myers

    2005-04-15

    Ophir Corporation was awarded a contract by the U. S. Department of Energy, National Energy Technology Laboratory under the Project Title ''Airborne, Optical Remote Sensing of Methane and Ethane for Natural Gas Pipeline Leak Detection'' on October 14, 2002. The scope of the work involved designing and developing an airborne, optical remote sensor capable of sensing methane and, if possible, ethane for the detection of natural gas pipeline leaks. Flight testing using a custom dual wavelength, high power fiber amplifier was initiated in February 2005. Ophir successfully demonstrated the airborne system, showing that it was capable of discerning small amounts of methane from a simulated pipeline leak. Leak rates as low as 150 standard cubic feet per hour (scf/h) were detected by the airborne sensor.

  8. Dissociation behavior of methane--ethane mixed gas hydrate coexisting structures I and II.

    PubMed

    Kida, Masato; Jin, Yusuke; Takahashi, Nobuo; Nagao, Jiro; Narita, Hideo

    2010-09-09

    Dissociation behavior of methane-ethane mixed gas hydrate coexisting structures I and II at constant temperatures less than 223 K was studied with use of powder X-ray diffraction and solid-state (13)C NMR techniques. The diffraction patterns at temperatures less than 203 K showed both structures I and II simultaneously convert to Ih during the dissociation, but the diffraction pattern at temperatures greater than 208 K showed different dissociation behavior between structures I and II. Although the diffraction peaks from structure II decreased during measurement at constant temperatures greater than 208 K, those from structure I increased at the initial step of dissociation and then disappeared. This anomalous behavior of the methane-ethane mixed gas hydrate coexisting structures I and II was examined by using the (13)C NMR technique. The (13)C NMR spectra revealed that the anomalous behavior results from the formation of ethane-rich structure I. The structure I hydrate formation was associated with the dissociation rate of the initial methane-ethane mixed gas hydrate.

  9. Estimates of methane and ethane emissions from the Texas Barnett Shale

    NASA Astrophysics Data System (ADS)

    Karion, A.; Sweeney, C.; Yacovitch, T.; Petron, G.; Wolter, S.; Conley, S. A.; Hardesty, R. M.; Brewer, A.; Kofler, J.; Newberger, T.; Herndon, S.; Miller, B. R.; Montzka, S. A.; Rella, C.; Crosson, E.; Tsai, T.; Tans, P. P.

    2013-12-01

    The recent development of horizontal drilling technology by the oil and gas industry has dramatically increased onshore U.S. natural gas and oil production in the last several years. This production boom has led to wide-spread interest from the policy and scientific communities in quantifying the climate impact of the use of natural gas as a replacement for coal. Because the primary component of natural gas is methane, a powerful greenhouse gas, natural gas leakage into the atmosphere affects its climate impact. Several recent scientific field studies have focused on using atmospheric measurements to estimate this leakage in different producing basins. Methane can be measured precisely with commercial analyzers, and deployment of such analyzers on aircraft, coupled with meteorological measurements, can allow scientists to estimate emissions from regions of concentrated production. Ethane and other light hydrocarbons, also components of raw gas, can be used as tracers for differentiating natural gas emissions from those of other methane sources, such as agriculture or landfills, which do not contain any non-methane hydrocarbons such as ethane. Here we present results from one such field campaign in the Barnett Shale near Fort Worth, Texas, in March 2013. Several 4-hour flights were conducted over the natural gas and oil production region with a small single-engine aircraft instrumented with analyzers for measuring ambient methane, carbon monoxide, carbon dioxide, and ethane at high frequencies (0.3-1Hz). The aircraft also measured horizontal winds, temperature, humidity, and pressure, and collected whole air samples in flasks analyzed later for several light hydrocarbons. In addition to the aircraft, a ground-based High-Resolution Doppler Lidar was deployed in the basin to measure profiles of horizontal winds and estimate the boundary layer height 24 hours a day over the campaign period. The aircraft and lidar measurements are used together to estimate methane and

  10. Three-dimensional methane fingerprinting using simultaneous measurements of ethane and deuterium and 13C isotopologues of methane

    NASA Astrophysics Data System (ADS)

    Fleck, Derek; Hoffnagle, John; Saad, Nabil; He, Yonggang

    2017-04-01

    Methane is a growing source of energy in the world that is the source of heat for billions of people which offers efficient burning and is sufficiently cleaner than coal. With an increase in global demand and a move toward methane sequestration, methods for monitoring and distinguishing origins of gas are essential. Methane identification is not only necessary for source discrimination, but also aids in gas and oil exploration by mapping reservoir types and distinguish between gas well, oil wells, or dry wells. Presence of ethane, longer hydrocarbons and measurements of δ13C in CH4 can distinguish the stage the gas was produced, while deuterium in CH4,δD, can further classify natural gas reservoir types. This study describes an analyzer used for measuring methane sources and mapping them to determine sources and processes these gasses originate from. This has been done by developing cavity ring-down analyzer that measures both δ13C and δD in CH4, as well as the ethane to methane ratio (C2:C1). For a continuous flow sample at 10,000ppm CH4, δ13C and δD can be measured to <0.06‰ in 5 minutes, while C2:C1 ratio is measured to <0.05% in 5 minutes. Using these measurements has allowed for discrimination of biogenic and thermogenic samples, as well as processes such as shallow gas migration in which thermogenic gas is stripped of hydrocarbons.

  11. Bottom-up simulations of methane and ethane emissions from global oil and gas systems 1980 to 2012

    NASA Astrophysics Data System (ADS)

    Höglund-Isaksson, Lena

    2017-02-01

    Existing bottom-up emission inventories of methane from global oil and gas systems do not satisfactorily explain year-on-year variation in atmospheric methane estimated by top-down models. Using a novel bottom-up approach this study quantifies and attributes methane and ethane emissions from global oil and gas production from 1980 to 2012. Country-specific information on associated gas flows from published sources are combined with inter-annual variations in observed flaring of associated gas from satellite images from 1994 to 2010, to arrive at country-specific annual estimates of methane and ethane emissions from flows of associated gas. Results confirm trends from top-down models and indicate considerably higher methane and ethane emissions from oil production than previously shown in bottom-up inventories for this time period.

  12. Hydrogen Safety Issues Compared to Safety Issues with Methane andPropane

    SciTech Connect

    Green, Michael A.

    2005-08-20

    The hydrogen economy is not possible if the safety standards currently applied to liquid hydrogen and hydrogen gas by many laboratories are applied to devices that use either liquid or gaseous hydrogen. Methane and propane are commonly used by ordinary people without the special training. This report asks, 'How is hydrogen different from flammable gasses that are commonly being used all over the world?' This report compares the properties of hydrogen, methane and propane and how these properties may relate to safety when they are used in both the liquid and gaseous state. Through such an analysis, sensible safety standards for the large-scale (or even small-scale) use of liquid and gaseous hydrogen systems can be developed. This paper is meant to promote discussion of issues related to hydrogen safety so that engineers designing equipment can factor sensible safety standards into their designs.

  13. Elastic wave speeds and moduli in polycrystalline ice Ih, si methane hydrate, and sll methane-ethane hydrate

    USGS Publications Warehouse

    Helgerud, M.B.; Waite, W.F.; Kirby, S.H.; Nur, A.

    2009-01-01

    We used ultrasonic pulse transmission to measure compressional, P, and shear, S, wave speeds in laboratory-formed polycrystalline ice Ih, si methane hydrate, and sll methane-ethane hydrate. From the wave speed's linear dependence on temperature and pressure and from the sample's calculated density, we derived expressions for bulk, shear, and compressional wave moduli and Poisson's ratio from -20 to 15??C and 22.4 to 32.8 MPa for ice Ih, -20 to 15??C and 30.5 to 97.7 MPa for si methane hydrate, and -20 to 10??C and 30.5 to 91.6 MPa for sll methane-ethane hydrate. All three materials had comparable P and S wave speeds and decreasing shear wave speeds with increasing applied pressure. Each material also showed evidence of rapid intergranular bonding, with a corresponding increase in wave speed, in response to pauses in sample deformation. There were also key differences. Resistance to uniaxial compaction, indicated by the pressure required to compact initially porous samples, was significantly lower for ice Ih than for either hydrate. The ice Ih shear modulus decreased with increasing pressure, in contrast to the increase measured in both hydrates ?? 2009.

  14. Ethene/ethane and propene/propane separation via the olefin and paraffin selective metal-organic framework adsorbents CPO-27 and ZIF-8.

    PubMed

    Böhme, Ulrike; Barth, Benjamin; Paula, Carolin; Kuhnt, Andreas; Schwieger, Wilhelm; Mundstock, Alexander; Caro, Jürgen; Hartmann, Martin

    2013-07-09

    Two types of metal-organic frameworks (MOFs) have been synthesized and evaluated in the separation of C2 and C3 olefins and paraffins. Whereas Co2(dhtp) (=Co-CPO-27 = Co-MOF-74) and Mg2(dhtp) show an adsorption selectivity for the olefins ethene and propene over the paraffins ethane and propane, the zeolitic imidazolate framework ZIF-8 behaves in the opposite way and preferentially adsorbs the alkane. Consequently, in breakthrough experiments, the olefins or paraffins, respectively, can be separated.

  15. Experimental study of surface tension of ethane-methane solution in temperature range 213-283 K

    NASA Astrophysics Data System (ADS)

    Andbaeva, V. N.; Khotienkova, M. N.

    2013-09-01

    The differential variation of the method of capillary rise was used to measure the capillary constant and to determine the surface tension of ethane-methane solution at "high" temperatures. Measurements were performed on the isotherms in the range of temperatures 213.15 ÷ 283.15 K at pressures up to 4 MPa. Decrease of ethane surface tension with the increase of pressure and concentration of methane in the solution is shown. The experimental data are compared with the results of surface tension calculation according to Rowlinson theory. Methane adsorption in the interface layer of solution is calculated.

  16. The Global Search for Abiogenic GHGs, via Methane Isotopes and Ethane

    NASA Astrophysics Data System (ADS)

    Malina, Edward; Muller, Jan-Peter; Walton, David; Potts, Dale

    2015-04-01

    The importance of Methane as an anthropogenic Green House Gas (GHG) is well recognized in the scientific community, and is second only to Carbon Dioxide in terms of influence on the Earth's radiation budget (Parker, et al, 2011) suggesting that the ability to apportion the source of the methane (whether it is biogenic, abiogenic or thermogenic) has never been more important. It has been proposed (Etiope, 2009) that it may be possible to distinguish between a biogenic methane source (e.g. bacteria fermentation) and an abiogenic source (e.g. gas seepage or fugitive emissions) via the retrieval of the abundances of methane isotopes (12CH4 and 13CH4) and through the ratio of ethane (C2H6) to methane (CH4) concentrations. Using ultra fine spectroscopy (<0.2cm-1 spectral resolution) from Fourier Transform Spectrometers (FTS) based on the SCISAT-1 (ACE-FTS) and GOSAT (TANSO-FTS) we are developing a retrieval scheme to map global emissions of abiogenic and biogenic methane, and provide insight into how these variations in methane might drive atmospheric chemistry, focusing on the lower levels of the atmosphere. Using HiTran2012 simulations, we show that it is possible to distinguish between methane isotopes using the FTS based instruments on ACE and GOSAT, and retrieve the abundances in the Short Wave Infra-red (SWIR) at 1.65μm, 2.3μm, 3.3μm and Thermal IR, 7.8μm wavebands for methane, and the 3.3μm and 7μm wavebands for ethane. Initially we use the spectral line database HITRAN to determine the most appropriate spectral waveband to retrieve methane isotopes (and ethane) with minimal water vapour, CO2 and NO2 impact. Following this, we have evaluated the detectability of these trace gases using the more sophisticated Radiative Transfer Models (RTMs) SCIATRAN, the Oxford RFM and MODTRAN 5 in the SWIR, in order to determine the barriers to retrieving methane isotopes in both ACE (limb profile) and GOSAT (nadir measurements) instruments, including a preliminary

  17. Analysis of Ignition Behavior in a Turbocharged Direct Injection Dual Fuel Engine Using Propane and Methane as Primary Fuels

    SciTech Connect

    Polk, A. C.; Gibson, C. M.; Shoemaker, N. T.; Srinivasan, K. K.; Krishnan, S. R.

    2013-05-24

    This paper presents experimental analyses of the ignition delay (ID) behavior for diesel-ignited propane and diesel-ignited methane dual fuel combustion. Two sets of experiments were performed at a constant speed (1800 rev/min) using a 4-cylinder direct injection diesel engine with the stock ECU and a wastegated turbocharger. First, the effects of fuel-air equivalence ratios (© pilot ¼ 0.2-0.6 and © overall ¼ 0.2-0.9) on IDs were quantified. Second, the effects of gaseous fuel percent energy substitution (PES) and brake mean effective pressure (BMEP) (from 2.5 to 10 bar) on IDs were investigated. With constant © pilot (> 0.5), increasing © overall with propane initially decreased ID but eventually led to premature propane autoignition; however, the corresponding effects with methane were relatively minor. Cyclic variations in the start of combustion (SOC) increased with increasing © overall (at constant © pilot), more significantly for propane than for methane. With increasing PES at constant BMEP, the ID showed a nonlinear (initially increasing and later decreasing) trend at low BMEPs for propane but a linearly decreasing trend at high BMEPs. For methane, increasing PES only increased IDs at all BMEPs. At low BMEPs, increasing PES led to significantly higher cyclic SOC variations and SOC advancement for both propane and methane. Finally, the engine ignition delay (EID) was also shown to be a useful metric to understand the influence of ID on dual fuel combustion.

  18. Comparative study of two theoretical models of methane and ethane steam reforming process

    NASA Astrophysics Data System (ADS)

    Brus, Grzegorz; Kaczmarczyk Marcin Tomiczek, Robert; Mozdzierz, Marcin

    2016-09-01

    From the chemical point of view the reforming process of heavy hydrocarbons such as Associated Petroleum Gas (APG) is very complex. One of the main issue is a set of undesired chemical reactions that causes deposition of solid carbon and consequently block catalytic property of a reactor. The experimental investigation is crucial to design APG reforming reactors. However, the experiment needs to be preceded by careful thermodynamical analysis to design safe operation conditions. In case of small number of reactants and reactions such as in case of steam reforming of pure methane, the problem can be solved by treating each equilibrium reaction constant as an element of the system of non-linear equations. The system of equations can be solved by Newton-Raphson method. However in case of large number of reactants and reaction, such as in case of APG reforming this method is inefficient. A large number of strongly non-linear equations leads often to converge problem. In this paper the authors suggest to use different approach called Parametric Equation Method. In this method a system of non-linear equations is replaced by a set of single non-linear equations solved separately. The methods were used to simulate steam reforming of methane-ethane rich fuel. The results of computations from both methods were juxtaposed and comparative study were conducted. Finally safe operation conditions for steam reforming of methane-ethane fuel were calculated and presented.

  19. Natural gas fugitive emissions rates constrained by global atmospheric methane and ethane.

    PubMed

    Schwietzke, Stefan; Griffin, W Michael; Matthews, H Scott; Bruhwiler, Lori M P

    2014-07-15

    The amount of methane emissions released by the natural gas (NG) industry is a critical and uncertain value for various industry and policy decisions, such as for determining the climate implications of using NG over coal. Previous studies have estimated fugitive emissions rates (FER)--the fraction of produced NG (mainly methane and ethane) escaped to the atmosphere--between 1 and 9%. Most of these studies rely on few and outdated measurements, and some may represent only temporal/regional NG industry snapshots. This study estimates NG industry representative FER using global atmospheric methane and ethane measurements over three decades, and literature ranges of (i) tracer gas atmospheric lifetimes, (ii) non-NG source estimates, and (iii) fossil fuel fugitive gas hydrocarbon compositions. The modeling suggests an upper bound global average FER of 5% during 2006-2011, and a most likely FER of 2-4% since 2000, trending downward. These results do not account for highly uncertain natural hydrocarbon seepage, which could lower the FER. Further emissions reductions by the NG industry may be needed to ensure climate benefits over coal during the next few decades.

  20. Promotional mechanism of propane on selective catalytic reduction of NOx by methane over In/H-BEA at low temperature

    NASA Astrophysics Data System (ADS)

    Pan, Hua; Jian, Yanfei; Yu, Yanke; Chen, Ningna; He, Chi; He, Cheng

    2016-12-01

    Effects of propane/methane ratios on NOx reduction by mixtures of methane and propane over In/H-BEA catalyst were investigated at temperatures ranging from 250 to 550 °C. The higher catalytic activity of In/H-BEA was exhibited for CH4-SCR at high temperatures above 450 °C, while the higher NOx conversion was achieved in C3H8-SCR at below 425 °C. A broadened temperature window and enhanced CO2 selectivity were achieved by combining of methane and propane as the co-reductant. The mixtures with propane/methane of 1/2 showed the most superior T50 (325 °C) and T90 (500 °C) temperatures for NOx reduction over In/H-BEA catalyst. For the promotion mechanism of propane on NO reduction by methane at low temperature, the formation of carbonaceous species (e.g. R-COOH) were enhanced by the activation of C3H8 on Brønsted acid sites at low temperature, and further promoted the generation of sbnd NCO species, which was a crucial determining step for NO reduction.

  1. Numerical Study of Contaminant Effects on Combustion of Hydrogen, Ethane, and Methane in Air

    NASA Technical Reports Server (NTRS)

    Lai, H. T.; Thomas, S. R.

    1995-01-01

    A numerical study was performed to assess the effects of vitiated air on the chemical kinetics of hydrogen, ethane, and methane combustion with air. A series of calculations in static reacting systems was performed, where the initial temperature was specified and reactions occurred at constant pressure. Three different types of test flow contaminants were considered: NP, H2O, and a combustion of H2O and CO2. These contaminants are present in the test flows of facilities used for hypersonic propulsion testing. The results were computed using a detailed reaction mechanism and are presented in terms of ignition and reaction times. Calculations were made for a wide range of contaminant concentrations, temperatures and pressures. The results indicate a pronounced kinetic effect over a range of temperatures, especially with NO contamination and, to a lesser degree, with H2O contamination. In all cases studied, CO2 remained kinetically inert, but had a thermodynamic effect on results by acting as a third body. The largest effect is observed with combustion using hydrogen fuel, less effect is seen with combustion of ethane, and little effect of contaminants is shown with methane combustion.

  2. AIRBORNE, OPTICAL REMOTE SENSING OF METHANE AND ETHANE FOR NATURAL GAS PIPLINE LEAK DETECTION

    SciTech Connect

    Jerry Myers

    2004-05-12

    Ophir Corporation was awarded a contract by the U. S. Department of Energy, National Energy Technology Laboratory under the Project Title ''Airborne, Optical Remote Sensing of Methane and Ethane for Natural Gas Pipeline Leak Detection'' on October 14, 2002. The third six-month technical report contains a summary of the progress made towards finalizing the design and assembling the airborne, remote methane and ethane sensor. The vendor has been chosen and is on contract to develop the light source with the appropriate linewidth and spectral shape to best utilize the Ophir gas correlation software. Ophir has expanded upon the target reflectance testing begun in the previous performance period by replacing the experimental receiving optics with the proposed airborne large aperture telescope, which is theoretically capable of capturing many times more signal return. The data gathered from these tests has shown the importance of optimizing the fiber optic receiving fiber to the receiving optic and has helped Ophir to optimize the design of the gas cells and narrowband optical filters. Finally, Ophir will discuss remaining project issues that may impact the success of the project.

  3. Active Thermochemical Tables: Sequential Bond Dissociation Enthalpies of Methane, Ethane, and Methanol and the Related Thermochemistry.

    PubMed

    Ruscic, Branko

    2015-07-16

    Active Thermochemical Tables (ATcT) thermochemistry for the sequential bond dissociations of methane, ethane, and methanol systems were obtained by analyzing and solving a very large thermochemical network (TN). Values for all possible C-H, C-C, C-O, and O-H bond dissociation enthalpies at 298.15 K (BDE298) and bond dissociation energies at 0 K (D0) are presented. The corresponding ATcT standard gas-phase enthalpies of formation of the resulting CHn, n = 4-0 species (methane, methyl, methylene, methylidyne, and carbon atom), C2Hn, n = 6-0 species (ethane, ethyl, ethylene, ethylidene, vinyl, ethylidyne, acetylene, vinylidene, ethynyl, and ethynylene), and COHn, n = 4-0 species (methanol, hydroxymethyl, methoxy, formaldehyde, hydroxymethylene, formyl, isoformyl, and carbon monoxide) are also presented. The ATcT thermochemistry of carbon dioxide, water, hydroxyl, and carbon, oxygen, and hydrogen atoms is also included, together with the sequential BDEs of CO2 and H2O. The provenances of the ATcT enthalpies of formation, which are quite distributed and involve a large number of relevant determinations, are analyzed by variance decomposition and discussed in terms of principal contributions. The underlying reasons for periodic appearances of remarkably low and/or unusually high BDEs, alternating along the dissociation sequences, are analyzed and quantitatively rationalized. The present ATcT results are the most accurate thermochemical values currently available for these species.

  4. Active Thermochemical Tables: Sequential Bond Dissociation Enthalpies of Methane, Ethane, and Methanol, and the Related Thermochemistry

    SciTech Connect

    Ruscic, Branko

    2015-07-16

    Active Thermochemical Tables (ATcT) thermochemistry for the sequential bond dissociations of methane, ethane, and methanol systems were obtained by analyzing and solving a very large thermochemical network (TN). Values for all possible C–H, C–C, C–O, and O–H bond dissociation enthalpies at 298.15 K (BDE298) and bond dissociation energies at 0 K (D0) are presented. The corresponding ATcT standard gas-phase enthalpies of formation of the resulting CHn, n = 4–0 species (methane, methyl, methylene, methylidyne, and carbon atom), C2Hn, n = 6–0 species (ethane, ethyl, ethylene, ethylidene, vinyl, ethylidyne, acetylene, vinylidene, ethynyl, and ethynylene), and COHn, n = 4–0 species (methanol, hydroxymethyl, methoxy, formaldehyde, hydroxymethylene, formyl, isoformyl, and carbon monoxide) are also presented. The ATcT thermochemistry of carbon dioxide, water, hydroxyl, and carbon, oxygen, and hydrogen atoms is also included, together with the sequential BDEs of CO2 and H2O. The provenances of the ATcT enthalpies of formation, which are quite distributed and involve a large number of relevant determinations, are analyzed by variance decomposition and discussed in terms of principal contributions. The underlying reasons for periodic appearances of remarkably low and/or unusually high BDEs, alternating along the dissociation sequences, are analyzed and quantitatively rationalized. The present ATcT results are the most accurate thermochemical values currently available for these species.

  5. Active Thermochemical Tables: Sequential Bond Dissociation Enthalpies of Methane, Ethane, and Methanol and the Related Thermochemistry

    DOE PAGES

    Ruscic, Branko

    2015-03-31

    Active Thermochemical Tables (ATcT) thermochemistry for the sequential bond dissociations of methane, ethane, and methanol systems were obtained by analyzing and solving a very large thermochemical network (TN). Values for all possible C–H, C–C, C–O, and O–H bond dissociation enthalpies at 298.15 K (BDE298) and bond dissociation energies at 0 K (D0) are presented. The corresponding ATcT standard gas-phase enthalpies of formation of the resulting CHn, n = 4–0 species (methane, methyl, methylene, methylidyne, and carbon atom), C2Hn, n = 6–0 species (ethane, ethyl, ethylene, ethylidene, vinyl, ethylidyne, acetylene, vinylidene, ethynyl, and ethynylene), and COHn, n = 4–0 species (methanol,more » hydroxymethyl, methoxy, formaldehyde, hydroxymethylene, formyl, isoformyl, and carbon monoxide) are also presented. The ATcT thermochemistry of carbon dioxide, water, hydroxyl, and carbon, oxygen, and hydrogen atoms is also included, together with the sequential BDEs of CO2 and H2O. The provenances of the ATcT enthalpies of formation, which are quite distributed and involve a large number of relevant determinations, are analyzed by variance decomposition and discussed in terms of principal contributions. The underlying reasons for periodic appearances of remarkably low and/or unusually high BDEs, alternating along the dissociation sequences, are analyzed and quantitatively rationalized. The present ATcT results are the most accurate thermochemical values currently available for these species.« less

  6. AIRBORNE, OPTICAL REMOTE SENSING OF METHANE AND ETHANE FOR NATURAL GAS PIPELINE LEAK DETECTION

    SciTech Connect

    Jerry Myers

    2003-11-12

    Ophir Corporation was awarded a contract by the U. S. Department of Energy, National Energy Technology Laboratory under the Project Title ''Airborne, Optical Remote Sensing of Methane and Ethane for Natural Gas Pipeline Leak Detection'' on October 14, 2002. This second six-month technical report summarizes the progress made towards defining, designing, and developing the hardware and software segments of the airborne, optical remote methane and ethane sensor. The most challenging task to date has been to identify a vendor capable of designing and developing a light source with the appropriate output wavelength and power. This report will document the work that has been done to identify design requirements, and potential vendors for the light source. Significant progress has also been made in characterizing the amount of light return available from a remote target at various distances from the light source. A great deal of time has been spent conducting laboratory and long-optical path target reflectance measurements. This is important since it helps to establish the overall optical output requirements for the sensor. It also reduces the relative uncertainty and risk associated with developing a custom light source. The data gathered from the optical path testing has been translated to the airborne transceiver design in such areas as: fiber coupling, optical detector selection, gas filters, and software analysis. Ophir will next, summarize the design progress of the transceiver hardware and software development. Finally, Ophir will discuss remaining project issues that may impact the success of the project.

  7. Vertical and meridional distribution of ethane, acetylene and propane in Saturn’s stratosphere from CIRS/Cassini limb observations

    NASA Astrophysics Data System (ADS)

    Guerlet, Sandrine; Fouchet, Thierry; Bézard, Bruno; Simon-Miller, Amy A.; Michael Flasar, F.

    2009-09-01

    Measuring the spatial distribution of chemical compounds in Saturn's stratosphere is critical to better understand the planet's photochemistry and dynamics. Here we present an analysis of infrared spectra in the range 600-1400 cm -1 acquired in limb geometry by the Cassini spacecraft between March 2005 and January 2008. We first determine the vertical temperature profiles from 3 to 0.01 hPa, at latitudes ranging from 70°N to 80°S. We infer a similar meridional temperature gradient at 1-2 hPa as in recent previous studies [Fletcher, L.N., Irwin, P.G.J., Teanby, N.A., Orton, G.S., Parrish, P.D., de Kok, R., Howett, C., Calcutt, S.B., Bowles, N., Taylor, F.W., 2007. Icarus 189, 457-478; Howett, C.J.A., Irwin, P.G.J., Teanby, N.A., Simon-Miller, A., Calcutt, S.B., Fletcher, L.N., de Kok, R., 2007. Icarus 190, 556-572]. We then retrieve the vertical profiles of C2H6 and C2H2 from 3 to 0.01 hPa and of C3H8 around 1 hPa. At 1 hPa, the meridional variation of C2H2 is found to follow the yearly averaged solar insolation, except for a strong equatorial mole fraction of 8×10-7, nearly two times higher than expected. This enhancement in abundance can be explained by the descent of hydrocarbon-rich air, with a vertical wind speed at the equator of 0.25±0.1 mm/s at 1 hPa and 0.4±0.15 mm/s at 0.1 hPa. The ethane distribution is relatively uniform at 1 hPa, with only a moderate 25% increase from 35°S to 80°S. Propane is found to increase from north to south by a factor of 1.9, suggesting that its lifetime may be shorter than Saturn's year at 1 hPa. At high altitudes (1 Pa), C2H2 and C2H6 abundances depart significantly from the photochemical model predictions of Moses and Greathouse [Moses, J.I., Greathouse, T.K., 2005. J. Geophys. Res. 110, 9007], except at high southern latitudes (62, 70 and 80°S) and near the equator. The observed abundances are found strongly depleted in the 20-40°S region and enhanced in the 20-30°N region, the latter coinciding with the ring

  8. AIRBORNE, OPTICAL REMOTE SENSING OF METHANE AND ETHANE FOR NATURAL GAS PIPELINE LEAK DETECTION

    SciTech Connect

    Jerry Myers

    2003-05-13

    Ophir Corporation was awarded a contract by the U. S. Department of Energy, National Energy Technology Laboratory under the Project Title ''Airborne, Optical Remote Sensing of Methane and Ethane for Natural Gas Pipeline Leak Detection'' on October 14, 2002. This six-month technical report summarizes the progress for each of the proposed tasks, discusses project concerns, and outlines near-term goals. Ophir has completed a data survey of two major natural gas pipeline companies on the design requirements for an airborne, optical remote sensor. The results of this survey are disclosed in this report. A substantial amount of time was spent on modeling the expected optical signal at the receiver at different absorption wavelengths, and determining the impact of noise sources such as solar background, signal shot noise, and electronic noise on methane and ethane gas detection. Based upon the signal to noise modeling and industry input, Ophir finalized the design requirements for the airborne sensor, and released the critical sensor light source design requirements to qualified vendors. Responses from the vendors indicated that the light source was not commercially available, and will require a research and development effort to produce. Three vendors have responded positively with proposed design solutions. Ophir has decided to conduct short path optical laboratory experiments to verify the existence of methane and absorption at the specified wavelength, prior to proceeding with the light source selection. Techniques to eliminate common mode noise were also evaluated during the laboratory tests. Finally, Ophir has included a summary of the potential concerns for project success and has established future goals.

  9. Measured temperature and pressure dependence of V-p and V-s in compacted, polycrystalline sI methane and sII methane-ethane hydrate

    NASA Astrophysics Data System (ADS)

    Helgerud, M. B.; Waite, W. F.; Kirby, S. H.; Nur, A.

    2003-01-01

    We report on compressional- and shear-wave-speed measurements made on compacted polycrystalline sI methane and sII methane-ethane hydrate. The gas hydrate samples are synthesized directly in the measurement apparatus by warming granulated ice to 17degreesC in the presence of a clathrate-forming gas at high pressure (methane for sI, 90.2% methane, 9.8% ethane for sII). Porosity is eliminated after hydrate synthesis by compacting the sample in the synthesis pressure vessel between a hydraulic ram and a fixed end-plug, both containing shear-wave transducers. Wave-speed measurements are made between -20 and 15degreesC and 0 to 105 MPa applied piston pressure.

  10. Measured temperature and pressure dependence of Vp and Vs in compacted, polycrystalline sI methane and sII methane-ethane hydrate

    USGS Publications Warehouse

    Helgerud, M.B.; Waite, W.F.; Kirby, S.H.; Nur, A.

    2003-01-01

    We report on compressional- and shear-wave-speed measurements made on compacted polycrystalline sI methane and sII methane-ethane hydrate. The gas hydrate samples are synthesized directly in the measurement apparatus by warming granulated ice to 17??C in the presence of a clathrate-forming gas at high pressure (methane for sI, 90.2% methane, 9.8% ethane for sII). Porosity is eliminated after hydrate synthesis by compacting the sample in the synthesis pressure vessel between a hydraulic ram and a fixed end-plug, both containing shear-wave transducers. Wave-speed measurements are made between -20 and 15??C and 0 to 105 MPa applied piston pressure.

  11. METABOLISM OF CHLORINATED METHANES, ETHANES, AND ETHYLENES BY A MIXED BACTERIAL CUTLURE GROWING ON METHANE

    EPA Science Inventory

    Soil was taken from the top 10 cm of a soil column that removed halogenated aliphatic hydrocarbons in the presence of natural gas. This soil was used as an enrichment inoculum to determine that the removals seen in the soil column were in fact of a microbiological nature. Methane...

  12. METABOLISM OF CHLORINATED METHANES, ETHANES, AND ETHYLENES BY A MIXED BACTERIAL CUTLURE GROWING ON METHANE

    EPA Science Inventory

    Soil was taken from the top 10 cm of a soil column that removed halogenated aliphatic hydrocarbons in the presence of natural gas. This soil was used as an enrichment inoculum to determine that the removals seen in the soil column were in fact of a microbiological nature. Methane...

  13. Contribution of oil and natural gas production to renewed increase of atmospheric methane (2007-2014): top-down estimate from ethane and methane column observations

    NASA Astrophysics Data System (ADS)

    Hausmann, P.; Sussmann, R.; Smale, D.

    2015-12-01

    Harmonized time series of column-averaged mole fractions of atmospheric methane and ethane over the period 1999-2014 are derived from solar Fourier transform infrared (FTIR) measurements at the Zugspitze summit (47° N, 2964 m a.s.l.) and at Lauder (45° S, 370 m a.s.l.). Long-term trend analysis reveals a consistent renewed methane increase since 2007 of 6.2 [5.6, 6.9] ppb yr-1 at the Zugspitze and 6.0 [5.3, 6.7] ppb yr-1 at Lauder (95 % confidence intervals). Several recent studies provide pieces of evidence that the renewed methane increase is most likely driven by two main factors: (i) increased methane emissions from tropical wetlands, followed by (ii) increased thermogenic methane emissions due to growing oil and natural gas production. Here, we quantify the magnitude of the second class of sources, using long-term measurements of atmospheric ethane as tracer for thermogenic methane emissions. In 2007, after years of weak decline, the Zugspitze ethane time series shows the sudden onset of a significant positive trend (2.3 [1.8, 2.8] × 10-2 ppb yr-1 for 2007-2014), while a negative trend persists at Lauder after 2007 (-0.4 [-0.6, -0.1] × 10-2 ppb yr-1). Zugspitze methane and ethane time series are significantly correlated for the period 2007-2014 and can be assigned to thermogenic methane emissions with an ethane-to-methane ratio of 10-21 %. We present optimized emission scenarios for 2007-2014 derived from an atmospheric two-box model. From our trend observations we infer a total ethane emission increase over the period 2007-2014 from oil and natural gas sources of 1-11 Tg yr-1 along with an overall methane emission increase of 24-45 Tg yr-1. Based on these results, the oil and natural gas emission contribution C to the renewed methane increase is deduced using three different emission scenarios with dedicated ranges of methane-to-ethane ratios (MER). Reference scenario 1 assumes an oil and gas emission combination with MER = 3.3-7.6, which results in a

  14. Comparison of Propane and Methane Performance and Emissions in a Turbocharged Direct Injection Dual Fuel Engine

    SciTech Connect

    Gibson, C. M.; Polk, A. C.; Shoemaker, N. T.; Srinivasan, K. K.; Krishnan, S. R.

    2011-01-01

    With increasingly restrictive NO x and particulate matter emissions standards, the recent discovery of new natural gas reserves, and the possibility of producing propane efficiently from biomass sources, dual fueling strategies have become more attractive. This paper presents experimental results from dual fuel operation of a four-cylinder turbocharged direct injection (DI) diesel engine with propane or methane (a natural gas surrogate) as the primary fuel and diesel as the ignition source. Experiments were performed with the stock engine control unit at a constant speed of 1800 rpm, and a wide range of brake mean effective pressures (BMEPs) (2.7-11.6 bars) and percent energy substitutions (PESs) of C 3 H 8 and CH 4. Brake thermal efficiencies (BTEs) and emissions (NO x, smoke, total hydrocarbons (THCs), CO, and CO 2) were measured. Maximum PES levels of about 80-95% with CH 4 and 40-92% with C 3 H 8 were achieved. Maximum PES was limited by poor combustion efficiencies and engine misfire at low loads for both C 3 H 8 and CH 4, and the onset of knock above 9 bar BMEP for C 3 H 8. While dual fuel BTEs were lower than straight diesel BTEs at low loads, they approached diesel BTE values at high loads. For dual fuel operation, NO x and smoke reductions (from diesel values) were as high as 66-68% and 97%, respectively, but CO and THC emissions were significantly higher with increasing PES at all engine loads

  15. A Low Temperature Eutectic Methane-Ethane Liquid: A Potential Geologic Fluid in the Outermost Solar System

    NASA Astrophysics Data System (ADS)

    Thompson, Garrett Leland; Hanley, Jennifer; Grundy, Will; Tegler, Stephen C.; Roe, Henry G.; Lindberg, Gerrick Eugene; Trilling, David E.

    2016-10-01

    Many icy bodies and moons in the solar system contain methane and ethane, including Titan, Triton, Pluto, Eris, Makemake, and likely others. The material properties of these species and their interactions with one another are still inadequately characterized. To provide insight into the behaviors of these species we conducted a series of laboratory experiments to map the liquidus line as a function of temperature and composition. The interaction of ethane and methane yields a eutectic mixture and depresses the freezing point to ~72 K, almost 20 K colder than the normal freezing points of either pure species. The eutectic composition is 64% CH4 and 36% C2H6. This phenomenon may enable geological processes involving liquids in the near surface environments of bodies once thought too cold and/or that have surface pressures too low to support liquid phases. The addition of other cosmochemically abundant species may suppress freezing points even further (see Hanley et al., this conference).

  16. Contribution of oil and natural gas production to renewed increase in atmospheric methane (2007-2014): top-down estimate from ethane and methane column observations

    NASA Astrophysics Data System (ADS)

    Hausmann, Petra; Sussmann, Ralf; Smale, Dan

    2016-03-01

    Harmonized time series of column-averaged mole fractions of atmospheric methane and ethane over the period 1999-2014 are derived from solar Fourier transform infrared (FTIR) measurements at the Zugspitze summit (47° N, 11° E; 2964 m a.s.l.) and at Lauder (45° S, 170° E; 370 m a.s.l.). Long-term trend analysis reveals a consistent renewed methane increase since 2007 of 6.2 [5.6, 6.9] ppb yr-1 (parts-per-billion per year) at the Zugspitze and 6.0 [5.3, 6.7] ppb yr-1 at Lauder (95 % confidence intervals). Several recent studies provide pieces of evidence that the renewed methane increase is most likely driven by two main factors: (i) increased methane emissions from tropical wetlands, followed by (ii) increased thermogenic methane emissions due to growing oil and natural gas production. Here, we quantify the magnitude of the second class of sources, using long-term measurements of atmospheric ethane as a tracer for thermogenic methane emissions. In 2007, after years of weak decline, the Zugspitze ethane time series shows the sudden onset of a significant positive trend (2.3 [1.8, 2.8] × 10-2 ppb yr-1 for 2007-2014), while a negative trend persists at Lauder after 2007 (-0.4 [-0.6, -0.1] × 10-2 ppb yr-1). Zugspitze methane and ethane time series are significantly correlated for the period 2007-2014 and can be assigned to thermogenic methane emissions with an ethane-to-methane ratio (EMR) of 12-19 %. We present optimized emission scenarios for 2007-2014 derived from an atmospheric two-box model. From our trend observations we infer a total ethane emission increase over the period 2007-2014 from oil and natural gas sources of 1-11 Tg yr-1 along with an overall methane emission increase of 24-45 Tg yr-1. Based on these results, the oil and natural gas emission contribution (C) to the renewed methane increase is deduced using three different emission scenarios with dedicated EMR ranges. Reference scenario 1 assumes an oil and gas emission combination with EMR = 7

  17. Separating methane emissions from biogenic sources and natural gas by vertical column enhancements of ammonia, ethane, and methane in the Colorado Front Range

    NASA Astrophysics Data System (ADS)

    Chiu, R.; Volkamer, R. M.; Blumenstock, T.; Hase, F.; Hannigan, J. W.; Kille, N.; Frey, M.; Kumar Sha, M.; Orphal, J.

    2015-12-01

    Methane sources in the Colorado Front Range include biogenic sources from cattle feedlots and natural gas operations. Although numerous studies have measured methane emissions, there remains significant uncertainty regarding the relative contributions of these various methane emission sources. Here we present data from a March 2015 field campaign that deployed two Bruker EM27 Sun Fourier Transform Spectrometers (FTS) and the University of Colorado Solar Occultation Flux (CU-SOF) FTS in Eaton, Colorado; the former were used to measure enhancements in the methane vertical column densities (VCD), while the latter was used to measure ethane and ammonia VCDs. A third EM27 FTS was deployed to a background site in Westminster, Colorado which was far removed from cattle and petroleum operations. Northerly winds make possible the determination of methane VCD column enhancement from Westminster to Eaton. All instruments were compared during several background days at the National Center for Atmospheric Research (NCAR) in Boulder, Colorado. This presentation explores the potential of methane source attribution using ammonia as a tracer for feedlot emissions and ethane as a tracer for petroleum emissions.

  18. Methane Fingerprinting: Isotopic Methane and Ethane-to-Methane Ratio Analysis Using a Cavity Ring-Down Spectrometer

    NASA Astrophysics Data System (ADS)

    Saad, Nabil; Fleck, Derek; Hoffnagle, John

    2016-04-01

    Emissions of Natural gas, and methane (CH4) specifically, have come under increased scrutiny by virtue of methane's 28-36x greenhouse warming potential compared to carbon dioxide (CO2) while accounting for 10% of the total greenhouse gas emissions in the US. Large uncontrolled leaks, such as the recent Aliso Canyon leak, originating from uncapped wells, coal mines and storage facilities have increased the total global contribution of methane missions even further. Determining the specific fingerprint of methane sources, by quantifying δ13C values and C2:C1 ratios, provides the means to understand methane producing processes and allows for sources of methane to be mapped and classified through these processes; i.e. biogenic vs. thermogenic, wet vs dry. In this study we present a fully developed Cavity Ring-Down Spectrometer (CRDS) that precisely measures 12CH4 concentration and its 13CH4 isotope concentration, yielding δ13C measurements, C2H6 concentration, along with CO2 and H2O. This provides real-time continuous measurements without an upfront separation requirement or multiple analyses to derive the origin of the gas samples. The highly sensitive analyzer allows for measurements of scarce molecules down to sub-ppb 1-σ precision in 5 minutes of measurement: with CH4 <0.1ppb, δ13C <1‰ C2H6 <1ppb and CO2 <1ppm. To complement this work, we provide the analysis of different methane sources providing a 2-dimensional mapping of methane sources as functions of δ13C and C2:C1 ratios, which can be thought of as a modified Bernard Plot. This dual ratio mapping can be used to discriminate between naturally occurring biogenic methane sources, naturally occurring enriched thermogenic sources, and natural gas distribution sources. This also shows future promise in aiding gas and oil exploration, in distinguishing oil vs coal gases, as well as a valuable tool in the development of methane sequestration.

  19. Quantification of Methane and Ethane Emissions from the San Juan Basin

    NASA Astrophysics Data System (ADS)

    Smith, M. L.; Kort, E. A.; Karion, A.; Sweeney, C.; Gvakharia, A.

    2015-12-01

    Methane (CH4), a potent greenhouse gas, and the primary component of natural gas, is emitted from areas of high fossil fuel production and processing. Recently, persistent and large methane emissions (~0.59 Tg yr-1) from the four corners area of the United States have been identified using satellite (SCIAMACHY) observations taken over the years 2003 to 2009. These emissions appear to be the largest CH4 anomaly (positive deviation above background values) in the contiguous U.S., and exceed bottom-up inventory estimates for the area by 1.8 to 3.5 times. The majority of emissions sources expected to contribute to this anomalous CH4 signal are located in the San Juan basin of New Mexico, and include harvesting and processing of natural gas, coal, and coalbed CH4. The magnitude of CH4 emissions from the San Juan basin have not yet been directly quantified using airborne measurements. Additionally, changing fossil fuel-related activities in the basin may have altered the magnitude of CH4 emissions compared to estimates derived from 2003-2009 satellite measurements. Here, we present in-situ airborne observations of CH4 over the San Juan basin, which allow tight quantification of CH4 fluxes using the mass balance method. Observations over the basin were taken for multiple wind directions on multiple days in April, 2015 to obtain a robust estimate of CH4 emissions. The flux of ethane (C2H6), the second most abundant component of natural gas and a tracer species indicative of fossil-derived CH4, was also quantified. Substantial C2H6 emissions may affect regional air quality and chemistry through its influence on tropospheric ozone production.

  20. Phase equilibria of the system methane-ethane from temperature scaling Gibbs Ensemble Monte Carlo simulation

    NASA Astrophysics Data System (ADS)

    Zhang, Zhigang; Duan, Zhenhao

    2002-10-01

    A new technique of temperature scaling method combined with the conventional Gibbs Ensemble Monte Carlo simulation was used to study liquid-vapor phase equilibria of the methane-ethane (CH 4-C 2H 6) system. With this efficient method, a new set of united-atom Lennard-Jones potential parameters for pure C 2H 6 was found to be more accurate than those of previous models in the prediction of phase equilibria. Using the optimized potentials for liquid simulations (OPLS) potential for CH 4 and the potential of this study for C 2H 6, together with a simple mixing rule, we simulated the equilibrium compositions and densities of the CH 4-C 2H 6 mixtures with accuracy close to experiments. The simulated data are supplements to experiments, and may cover a larger temperature-pressure-composition space than experiments. Compared with some well-established equations of state such as Peng-Robinson equation of state (PR-EQS), the simulated results are found to be closer to experiments, at least in some temperature and pressure ranges.

  1. Fate and transport of dissolved methane and ethane in cretaceous shales of the Williston Basin, Canada

    NASA Astrophysics Data System (ADS)

    Jim Hendry, M.; Lee Barbour, S.; Schmeling, Erin E.; Mundle, Scott O. C.; Huang, M.

    2016-08-01

    Baseline characteristics of dissolved methane (CH4) and ethane (C2H6) and their stable isotopes in thick, low hydraulic conductivity, Cretaceous shales were determined using high-resolution core profiling at four sites in the Williston Basin (WB), Canada. Positive correlations with the conservative natural tracer Cl- reflected a lack of measureable production or consumption of gases in the shale to the depth investigated (150 m below ground, BG) and suggest CH4 and C2H6 concentrations near the interface with overlying Quaternary sediments are controlled by lateral migration and dilution in permeable zones. Curvilinear increasing concentrations with depth in the shale at all sites coupled with 1-D solute transport modeling suggest long-term (over millions of years) upward diffusion of CH4 and C2H6 from deeper WB sources, likely the Second White Speckled Shale Formation (SWSS; ˜790 m BG). δ13C-CH4 profiles in the shale are consistent with upward diffusional fractionation of isotopes from the SWSS. Distinct CH4 and C2H6 isotope values of gases in the shales versus 13C-enriched thermogenic isotopic signatures of CH4 and C2H6 in deeper oil-producing WB intervals could be used to identify fugitive gases originating deeper in the Basin.

  2. Ring-polymer molecular dynamics studies on the rate coefficient of the abstraction channel of hydrogen plus ethane, propane, and dimethyl ether

    NASA Astrophysics Data System (ADS)

    Meng, Qingyong; Chen, Jun

    2017-01-01

    To accurately compute the rates of the abstraction channels of hydrogen plus ethane (Et), propane (Pr), and dimethyl ether (DME), ring-polymer molecular dynamics (RPMD) method is used in conjunction with the recently constructed local permutation invariant polynomial neural-networks potential energy surface of the parent H + CH4 system [Q. Meng et al., J. Chem. Phys. 144, 154312 (2016)]. For H + Et, one of the H atoms in CH4 of the parent system is replaced by a methyl group, while for the H + DME reaction, it is replaced by the methoxyl group. For the H + Pr reaction, replacing one of the H atoms in CH4 by an ethyl group, the terminal channel is built, meanwhile the middle channel is considered through replacing two H atoms in CH4 by two methyl groups. Since the potential energy barriers of the title reactions must differ from the H + CH4 barrier, the corrections have to be made by computing the ratio of free-energy barriers between H + CH4 and the title reactions at coupled cluster with a full treatment singles and doubles (where the triples contribution is calculated by perturbation theory, that is, CCSD(T)) level. Comparing the present RPMD rates with the previous theoretical and experimental results, good agreement can be found. Moreover, probable reasons for the deviation between the present RPMD rates and the previous experimental ones are discussed.

  3. Effect of Initial Mixture Temperature on Flame Speed of Methane-Air, Propane-Air, and Ethylene-Air Mixtures

    NASA Technical Reports Server (NTRS)

    Dugger, Gordon L

    1952-01-01

    Flame speeds based on the outer edge of the shadow cast by the laminar Bunsen cone were determined as functions of composition for methane-air mixtures at initial mixture temperatures ranging from -132 degrees to 342 degrees c and for propane-air and ethylene-air mixtures at initial mixture temperatures ranging from -73 degrees to 344 degrees c. The data showed that maximum flame speed increased with temperature at an increasing rate. The percentage change in flame speed with change in initial temperature for the three fuels followed the decreasing order, methane, propane, and ethylene. Empirical equations were determined for maximum flame speed as a function of initial temperature over the temperature range covered for each fuel. The observed effect of temperature on flame speed for each of the fuels was reasonably well predicted by either the thermal theory as presented by Semenov or the square-root law of Tanford and Pease.

  4. A comparative study of diesel ignited methane and propane dual fuel low temperature combustion in a single cylinder research engine

    NASA Astrophysics Data System (ADS)

    Raihan, Mostafa Shameem

    The objective of this thesis is to investigate and compare the performance and emissions characteristics of diesel-ignited methane and diesel-ignited propane dual fuel LTC in a single cylinder research engine (SCRE) at a constant engine load of 5.1 bar net indicated mean effective pressure (IMEP) and at a constant engine speed of 1500 RPM. Percentage of energy substitution of propane or methane (0 - 90 percent), diesel injection timing (SOI: 355 CAD -- 280 CAD), rail pressure (200 bar -- 1300 bar) and boost pressure (1.1 bar -- 1.8 bar) were varied to quantify their impact on engine performance and engine-out ISNOx, ISHC, ISCO, and smoke emissions. Advancing SOI to 310 CAD and beyond yielded simultaneous ISNOx and smoke emissions. A rail pressure of 500 bar was the optimal one for both fueling combinations while increasing boost pressure over 1.2 bar had a very little effect on ISNOx and smoke emissions.

  5. Continuous spectroscopic measurement of methane isotopes and ethane made on board an aircraft: instrument configuration and characterisation

    NASA Astrophysics Data System (ADS)

    Pitt, Joseph; Young, Stuart; Hopkins, James; Lee, James; Bauguitte, Stéphane; Dorsey, James; Allen, Grant; Gallagher, Martin; Yacovitch, Tara; Zahniser, Mark; Fisher, Rebecca; Lowry, Dave; Nisbet, Euan

    2017-04-01

    We describe the configuration of two commercially available absorption spectrometers for use on board the UK Facility for Airborne Atmospheric Research (FAAM) aircraft. A dual laser instrument has been used to make continuous measurements of the atmospheric 13CH4:12CH4 ratio and ethane mole fraction, using an interband cascade laser (ICL) and a recently developed type of diode laser respectively. Simultaneous measurements of atmospheric ethane have also been made using a single laser instrument employing an ICL, enabling instrument inter-comparison. Instrument performance is evaluated over a series of test flights, and initial results from the MOYA (Methane Observations and Yearly Assessments) campaign, targeting biomass burning plumes in west Africa, are also presented. We describe the calibration procedure and data analysis approaches for methane isotope measurement, involving calibration over a range of methane isotopic composition and methane mole fraction. We assess the effectiveness of this calibration technique during the first MOYA campaign period using measurements of a target cylinder of known composition.

  6. Kinetic modeling of propane aromatization reaction over HZSM-5 and GaHZSM-5

    SciTech Connect

    Lukyanov, D.B.; Gnep, N.S.; Guisnet, M.R. . Catalyse en Chimie Organique)

    1995-02-01

    A detailed kinetic model for a propane aromatization reaction over HZSM-5 and GaHZSM-5 is developed. Kinetic modeling results show that propane transformation over HZSM-5 occurs via protolytic cracking and hydrogen transfer routes. The contributions of both routes in propane conversion are established. Rate constants of propane transformation steps are found to be at least 1,000 times lower than the rate constants of diene formation steps, which, in turn, are the slowest among the acid-catalyzed olefin aromatization steps. Gallium introduced into ZSM-5 catalyst is active in dehydrogenation of propane into propene, of olefins into dienes, and of naphthenes into aromatics. At the same time, gallium species catalyze propane transformation into methane and ethene hydrogenation into ethane. Both latter reactions appear to be the main reasons for the limit to aromatics selectivity over GaHZSM-5 catalysts.

  7. Estimates of Methane and Ethane Emissions from the Barnett Shale Using Atmospheric Measurements

    NASA Astrophysics Data System (ADS)

    Karion, A.; Sweeney, C.; Kort, E. A.; Shepson, P. B.; Conley, S. A.; Lauvaux, T.; Davis, K. J.; Deng, A.; Lyon, D. R.; Smith, M. L.

    2015-12-01

    Recent development of horizontal drilling technology and advances in hydraulic fracturing techniques by the oil and gas industry have dramatically increased onshore U.S. natural gas and oil production in the last several years. The primary component of natural gas is methane (CH4), a powerful greenhouse gas; therefore, natural gas leakage into the atmosphere affects its climate impact. We present estimates of regional methane (CH4) and ethane (C2H6) emissions from oil and natural gas operations in the Barnett Shale, Texas, made in March and October 2013 as part of the Environmental Defense Fund's Barnett Coordinated Campaign. The Barnett is one of the largest production basins in the United States, with 8% of total U.S. natural gas production, and thus, our results represent a crucial step toward determining the greenhouse gas footprint of U.S. onshore natural gas production. Using a mass balance approach on eight different flight days the total CH4 emissions for the region are estimated to be 76 ± 13x 103 kg/hr, or 0.66 ± 0.11 Tg CH4 /yr; (95% CI). Repeated mass balance flights in the same basin on eight different days and two seasons demonstrate the consistency of the mass balance approach. On the basis of airborne C2H6 and CH4 measurements, we find 71-85% of the observed CH4 emissions quantified in the Barnett Shale are derived from fossil sources. The average C2H6 flux was 6.6 ± 0.2 x 103 kg/hr and consistent across six days in spring and fall of 2013. This result is the first demonstration of this approach for C2H6. We estimate that 60±11x103 kg CH4/hr (95% CI) are emitted by natural gas and oil operations, including production, processing, and distribution in the urban areas of Dallas and Fort Worth. This estimate is significantly higher than emissions reported by the EDGAR inventory or by industry to EPA's Greenhouse Gas Reporting Program.

  8. Photoabsorption cross sections of methane and ethane, 1380-1600 A, at T equals 295 K and T equals 200 K. [in Jupiter atmosphere

    NASA Technical Reports Server (NTRS)

    Mount, G. H.; Moos, H. W.

    1978-01-01

    Photoabsorption cross sections of methane and ethane have been determined in the wavelength range from 1380 to 1600 A at room (295 K) and dry-ice (200 K) temperatures. It is found that the room-temperature ethane data are in excellent agreement with the older measurements of Okabe and Becker (1963) rather than with more recent determinations and that a small systematic blueshift occurs at the foot of the molecular absorption edges of both gases as the gases are cooled from room temperature to 200 K, a value close to the actual temperature of the Jovian atmosphere. It is concluded that methane photoabsorption will dominate until its cross section is about 0.01 that of ethane, which occurs at about 1440 A, and that ethane should be the dominant photoabsorber in the Jovian atmosphere in the region from above 1440 A to not farther than 1575 A.

  9. Rapid analysis of dissolved methane, ethylene, acetylene and ethane using partition coefficients and headspace-gas chromatography.

    PubMed

    Lomond, Jasmine S; Tong, Anthony Z

    2011-01-01

    Analysis of dissolved methane, ethylene, acetylene, and ethane in water is crucial in evaluating anaerobic activity and investigating the sources of hydrocarbon contamination in aquatic environments. A rapid chromatographic method based on phase equilibrium between water and its headspace is developed for these analytes. The new method requires minimal sample preparation and no special apparatus except those associated with gas chromatography. Instead of Henry's Law used in similar previous studies, partition coefficients are used for the first time to calculate concentrations of dissolved hydrocarbon gases, which considerably simplifies the calculation involved. Partition coefficients are determined to be 128, 27.9, 1.28, and 96.3 at 30°C for methane, ethylene, acetylene, and ethane, respectively. It was discovered that the volume ratio of gas-to-liquid phase is critical to the accuracy of the measurements. The method performance can be readily improved by reducing the volume ratio of the two phases. Method validation shows less than 6% variation in accuracy and precision except at low levels of methane where interferences occur in ambient air. Method detection limits are determined to be in the low ng/L range for all analytes. The performance of the method is further tested using environmental samples collected from various sites in Nova Scotia.

  10. Pathways and kinetics of methane and ethane C-H bond cleavage on PdO(101)

    NASA Astrophysics Data System (ADS)

    Antony, Abbin; Asthagiri, Aravind; Weaver, Jason F.

    2013-09-01

    We used conventional density functional theory (DFT) and dispersion-corrected DFT (DFT-D3) calculations to investigate C-H bond activation pathways for methane and ethane σ-complexes adsorbed on the PdO(101) surface. The DFT-D3 calculations predict lower and more physically realistic values of the apparent C-H bond cleavage barriers, which are defined relative to the gas-phase energy level, while giving nearly the same energy differences between stationary states as predicted by conventional DFT for a given reaction pathway. For the stable CH4 η2 complex on PdO(101), DFT-D3 predicts that the C-H bond cleavage barriers are 55.2 and 16.1 kJ/mol relative to the initial molecularly adsorbed and gaseous states, respectively. We also predict that dehydrogenation of the resulting CH3 groups and conversion to CH3O species are significantly more energetically demanding than the initial C-H bond activation of CH4 on PdO(101). Using DFT-D3, we find that an η2 and an η1 ethane complex can undergo C-H bond cleavage on PdO(101) with intrinsic energy barriers that are similar to that of the methane complex, but with apparent barriers that are close to zero. We also investigated the dissociation kinetics of methane and ethane on PdO(101) using microkinetic models, with parameters derived from the DFT-D3 relaxed structures. We find that a so-called 3N - 2 model, in which two frustrated adsorbate motions are treated as free motions, predicts desorption pre-factors and alkane dissociation probabilities that agree well with estimates obtained from the literature. The microkinetic simulations demonstrate the importance of accurately describing entropic contributions in kinetic simulations of alkane dissociative chemisorption.

  11. Fugitive methane emission pinpointing and source attribution using ethane measurements in a portable cavity ring-down analyzer

    NASA Astrophysics Data System (ADS)

    Fleck, Derek; Hoffnagle, John; Yiu, John; Chong, Johnston; Tan, Sze

    2017-04-01

    Methane source pinpointing and attribution is ever more important because of the vast network of natural gas distribution which has led to a very large emission sources. Ethane can be used as a tracer to distinguish gas sources between biogenic and natural gas. Having this measurement sensitive enough can even distinguish between gas distributors, or maturity through gas wetness. Here we present data obtained using a portable cavity ring-down spectrometer weighing less than 11 kg and consuming less than 35W that simultaneously measures methane and ethane with a raw 1-σ precision of 50ppb and 4.5ppb, respectively at 2 Hz. These precisions allow for a C2:C1 ratio 1-σ measurement of <0.1% above 10ppm in a single measurement. Utilizing a second onboard laser allows for a high precision methane only mode used for surveying and pinpointing. This mode measures at a rate faster than 4Hz with a 1-σ precision of <3ppb. Because methane seepages are highly variable due to air turbulence and mixing right above the ground, correlations in the variations in C2H6 and CH4 are used to derive a source C2:C1. Additional hardware is needed for steady state concentration measurements to reliably measure the C2:C1 ratio instantaneously. Source discrimination data of local leaks and methane sources using this analysis method are presented. Additionally, two-dimensional plume snapshots are constructed using an integrated onboard GPS to visualize horizontal plane gas propagation.

  12. Intermolecular hydrogen transfer between guest species in small and large cages of methane + propane mixed gas hydrates.

    PubMed

    Sugahara, Takeshi; Kobayashi, Yusuke; Tani, Atsushi; Inoue, Tatsuya; Ohgaki, Kazunari

    2012-03-15

    To investigate the molecular interaction between guest species inside of the small and large cages of methane + propane mixed gas hydrates, thermal stabilities of the methyl radical (possibly induced in small cages) and the normal propyl and isopropyl radicals (induced in large cages) were investigated by means of electron spin resonance measurements. The increase of the total amount of the normal propyl and isopropyl radicals reveals that the methyl radical in the small cage withdraws one hydrogen atom from the propane molecule enclathrated in the adjacent large cage of the structure-II hydrate. A guest species in a hydrate cage has the ability to interact closely with the other one in the adjacent cages. The clathrate hydrate may be utilized as a possible nanoscale reaction field.

  13. Experimental reflectance study of methane and ethane ice at Titan's surface conditions

    NASA Astrophysics Data System (ADS)

    Singh, G.; Singh, S.; Wagner, A.; Chevrier, V. F.; Combe, J.-P.; Gainor, M.

    2017-10-01

    Cassini's Visible and Infrared Mapping Spectrometer (VIMS) has provided evidence of several different hydrocarbons on the surface of Titan using seven atmospheric windows. Methane (CH4) and ethane (C2H6) are suggested to exist in both the liquid and solid states on Titan. Even if the average surface temperature (90-94 K) of Titan is clearly in the liquid stability field of both CH4 and C2H6, the particles can condense in the atmosphere (˜65 km for C2H6 and lower stratosphere for CH4 Anderson et al. in Icarus, 243:129-138, 2014) and precipitate allowing them to melt and/or sublimate. It is also suggested that these liquids can freeze on the surface due to evaporative cooling. We conducted a laboratory study at Titan surface conditions to determine the phase change of CH4 and C2H6 and to test if they would freeze on the surface of Titan. Using NIR reflectance spectroscopy, we calculated the reflectivity ratio (R_{solid}/R_{liquid}) of CH4 and C2H6 of 1.08 and 1.36, respectively, suggesting an 8% increase in reflectivity for CH4 and a 36% increase for C2H6 during phase change. The low albedo in liquid phase for both CH4 and C2H6 is consistent with observations made by VIMS in both Titan's northern and southern latitudes. We also find the evaporation rate of amorphous CH4 close to Titan conditions, which is 9.0 ± 0.3 × 10^{-5} kg s^{-1} m^{-2} at 87 K and we estimated a sublimation rate of 0.22 × 10^{-5} kg s^{-1} m^{-2} at 83 K for a 1.5 bar N2 atmosphere. The freezing rate of ˜46 m/year for C2H6 was observed whereas, for CH4, we observed that CH4 does not freeze at 87 K due to a high N2 dissolution rate. However, the viscosity of CH4 increases with a decreasing temperature that results in amorphous CH4. The results show a remarkable difference between the formation of ice for two liquids with different N2 dissolution rates. Consequently, using the results obtained from the laboratory study we predict that the observed change is albedo during and after rainfall

  14. Flame Speeds of Methane-Air, Propane-Air, and Ethylene-Air Mixtures at Low Initial Temperatures

    NASA Technical Reports Server (NTRS)

    Dugger, Gordon L; Heimel, Sheldon

    1952-01-01

    Flame speeds were determined for methane-air, propane-air, and ethylene-air mixtures at -73 C and for methane-air mixtures at -132 C. The data extend the curves of maximum flame speed against initial mixture temperature previously established for the range from room temperature to 344 C. Empirical equations for maximum flame speed u(cm/ sec) as a function of initial mixture temperature T(sub O) were determined to be as follows: for methane, for T(sub O) from 141 to 615 K, u = 8 + 0.000160 T(sub O)(exp 2.11); for propane, for T(sub O) from 200 to 616 K, u = 10 + 0.000342 T(sub O)(exp 2.00); for ethylene, for T(sub O) from 200 to 617 K, u = 10 + 0.00259 T(sub O)(exp 1.74). Relative flame speeds at low initial temperatures were predicted within approximately 20 percent by either the thermal theory as presented by Semenov or by the diffusion theory of Tanford and Pease. The same order was found previously for high initial temperatures. The low-temperature data were also found to extend the linear correlations between maximum flame speed and calculated equilibrium active-radical concentrations, which were established by the previously reported high-temperature data.

  15. Quantifying the Loss of Processed Natural Gas Within California's South Coast Air Basin Using Long-term Measurements of Ethane and Methane

    NASA Astrophysics Data System (ADS)

    Wunch, D.; Toon, G. C.; Hedelius, J.; Vizenor, N.; Roehl, C. M.; Saad, K.; Blavier, J. F.; Blake, D. R.; Wennberg, P. O.

    2016-12-01

    In California's South Coast Air Basin (SoCAB), the methane emissions inferred from atmospheric measurements exceed estimates based on inventories. We seek to provide insight into the sources of the discrepancy with two records of atmospheric trace gas total column abundances in the SoCAB: one temporally sparse dataset that began in the late 1980s, and a temporally dense dataset that began in 2012. We use their measurements of ethane and methane to partition the sources of the excess methane. The early few years of the sparse record show a rapid decline in ethane emissions at a much faster rate than decreasing vehicle exhaust or natural gas and crude oil production can explain. Between 2010 and 2015, ethane emissions have grown gradually, which is in contrast to the steady production of natural gas liquids over that time. Since 2012, ethane to methane ratios in the natural gas withdrawn from a storage facility within the SoCAB have been increasing; these ratios are tracked in our atmospheric measurements with about half of the rate of increase. From this, we infer that about half of the excess methane in the SoCAB between 2012-­2015 is attributable to losses from the natural gas infrastructure.

  16. Bacterial ethane formation from reduced, ethylated sulfur compounds in anoxic sediments

    USGS Publications Warehouse

    Oremland, R.S.; Whiticar, Michael J.; Strohmaier, F.E.; Kiene, R.P.

    1988-01-01

    Trace levels of ethane were produced biologically in anoxic sediment slurries from five chemically different aquatic environments. Gases from these locations displayed biogenic characteristics, having 12C-enriched values of ??13CH4 (-62 to -86%.), ??13C2H6 (-35 to -55%.) and high ratios (720 to 140,000) of CH4 [C2H6 + C3H8]. Endogenous production of ethane by slurries was inhibited by autoclaving or by addition of the inhibitor of methanogenic bacteria, 2-bromoethanesulfonic acid (BES). Ethane formation was stimulated markedly by ethanethiol (ESH), and, to a lesser extent, by diethylsulfide (DES). Formation of methane and ethane in ESH- or DES-amended slurries was blocked by BES. Experiments showed that ethionine (or an analogous compound) could be a precursor of ESH. Ethylamine or ethanol additions to slurries caused only a minor stimulation of ethane formation. Similarly, propanethiol additions resulted in only a minor enhancement of propane formation. Cell suspensions of a methyltrophic methanogen produced traces of ethane when incubated in the presence of DES, although the organism did not grow on this compound. These results indicate that methanogenic bacteria produce ethane from the traces of ethylated sulfur compounds present in recent sediments. Preliminary estimates of stable carbon isotope fractionation associated with sediment methane formation from dimethylsulfide was about 40%., while ethane formation from DES and ESH was only 4. 6 and 6.5%., respectively. ?? 1988.

  17. Fugitive Emissions Attribution via Simultaneous Measurement of Ethane and Methane Isotopic Signature in Vehicle-based Surveys

    NASA Astrophysics Data System (ADS)

    Marshall, A. D.; Williams, J. P.; Baillie, J.; MacKay, K.; Risk, D. A.; Fleck, D.

    2016-12-01

    Detecting and attributing sub-regulatory fugitive emissions in the energy sector remains a priority for industry and environmental groups alike. Vehicle-based geochemical emission detection and attribution is seeing increasingly widespread use. In order to distinguish between biogenic and thermogenic emission sources, these techniques rely on tracer species like δ13C of methane (δ13CH4). In this study, we assessed the performance of the new Picarro G2210-i, a cavity ring-down spectroscopy (CRDS) analyzer that measures δ13CH4 and ethane (C2H6) simultaneously to provide increased thermogenic tracer power. In the lab, we assessed drift and other performance characteristics relative to a G2201-i (existing isotopic CH4 and carbon dioxide analyzer). We performed model experiments to synthetically assess the new analyzer's utility for oil and gas developments with differing levels of ethane. Lastly, we also conducted survey drives in a high-ethane oilfield using both the G2210-i and G2201-i. Results were very positive. The G2210-i showed minimal drift, as expected. Allan deviation experiments showed that the G2210-i has a precision of 0.482 ppb for CH4 and 3.15 ppb for C2H6 for 1Hz measurements. Computational experiments confirmed that the resolution of C2H6 is sufficient for detecting and attributing thermogenic CH4 at distance in oil and gas settings, which was further validated in the field where we measured simultaneous departures in δ13CH4 and C2H6 within plumes from venting infrastructure. C2:C1 ratios also proved very useful for attribution. As we move to reduce emissions from the energy industry, this analyzer presents new analytical possibilities that will be of high value to industry stakeholders.

  18. 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

    2013-10-02

    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

  19. Mobile Measurement of Methane and Ethane for the Detection and Attribution of Natural Gas Pipeline Leaks Using Off-Axis Integrated Output Spectroscopy

    NASA Astrophysics Data System (ADS)

    Leen, J. B.; Spillane, S.; Gardner, A.; Hansen, P. C.; Gupta, M.; Baer, D. S.

    2015-12-01

    Natural gas leaks pose a risk to public safety both because of potential explosions as well as from the greenhouse gas potential of fugitive methane. The rapid and cost effective detection of leaks in natural gas distribution is critical to providing a system that is safe for the public and the environment. Detection of methane from a mobile platform (vehicles, aircraft, etc.) is an accepted method of identifying leaks. A robust approach to differentiating pipeline gas (thermogenic) from other biogenic sources is the detection of ethane along with methane. Ethane is present in nearly all thermogenic gas but not in biogenic sources and its presence can be used to positively identify a gas sample. We present a mobile system for the simultaneous measurement of methane and ethane that is capable of detecting pipeline leaks and differentiating pipeline gas from other biogenic sources such as landfills, swamps, sewers, and enteric fermentation. The mobile system consists of a high precision GPS, sonic anemometer, and methane/ethane analyzer based on off-axis integrated cavity output spectroscopy (OA-ICOS). In order to minimize the system cost and facilitate the wide use of mobile leak detection, the analyzer operates in the near-infrared portion of the spectrum where lasers and optics are significantly less costly than in the mid-infrared. The analyzer is capable of detecting methane with a precision of <2 ppb (1σ in 1 sec) and detecting ethane with a precision of <30 ppb (1σ in 1 sec). Additionally, measurement rates of 5 Hz allow for detection of leaks at speeds up to 50 mph. The sonic anemometer, GPS and analyzer inlet are mounted to a generic roof rack for attachment to available fleet vehicles. The system can detect leaks having a downwind concentration of as little as 10 ppb of methane above ambient, while leaks 500 ppb above ambient can be identified as thermogenic with greater than 99% certainty (for gas with 6% ethane). Finally, analysis of wind data provides

  20. Quantifying the loss of processed natural gas within California's South Coast Air Basin using long-term measurements of ethane and methane

    NASA Astrophysics Data System (ADS)

    Wunch, Debra; Toon, Geoffrey C.; Hedelius, Jacob K.; Vizenor, Nicholas; Roehl, Coleen M.; Saad, Katherine M.; Blavier, Jean-François L.; Blake, Donald R.; Wennberg, Paul O.

    2016-11-01

    Methane emissions inventories for Southern California's South Coast Air Basin (SoCAB) have underestimated emissions from atmospheric measurements. To provide insight into the sources of the discrepancy, we analyze records of atmospheric trace gas total column abundances in the SoCAB starting in the late 1980s to produce annual estimates of the ethane emissions from 1989 to 2015 and methane emissions from 2007 to 2015. The first decade of measurements shows a rapid decline in ethane emissions coincident with decreasing natural gas and crude oil production in the basin. Between 2010 and 2015, however, ethane emissions have grown gradually from about 13 ± 5 to about 23 ± 3 Gg yr-1, despite the steady production of natural gas and oil over that time period. The methane emissions record begins with 1 year of measurements in 2007 and continuous measurements from 2011 to 2016 and shows little trend over time, with an average emission rate of 413 ± 86 Gg yr-1. Since 2012, ethane to methane ratios in the natural gas withdrawn from a storage facility within the SoCAB have been increasing by 0.62 ± 0.05 % yr-1, consistent with the ratios measured in the delivered gas. Our atmospheric measurements also show an increase in these ratios but with a slope of 0.36 ± 0.08 % yr-1, or 58 ± 13 % of the slope calculated from the withdrawn gas. From this, we infer that more than half of the excess methane in the SoCAB between 2012 and 2015 is attributable to losses from the natural gas infrastructure.

  1. Non-oxidative coupling reaction of methane to ethane and hydrogen catalyzed by the silica-supported tantalum hydride: ([triple bond]SiO)2Ta-H.

    PubMed

    Soulivong, Daravong; Norsic, Sébastien; Taoufik, Mostafa; Copéret, Christophe; Thivolle-Cazat, Jean; Chakka, Sudhakar; Basset, Jean-Marie

    2008-04-16

    Silica-supported tantalum hydride, (SiO)2Ta-H (1), proves to be the first single-site catalyst for the direct non-oxidative coupling transformation of methane into ethane and hydrogen at moderate temperatures, with a high selectivity (>98%). The reaction likely involves the tantalum-methyl-methylidene species as a key intermediate, where the methyl ligand can migrate onto the tantalum-methylidene affording the tantalum-ethyl.

  2. CRYOCHEM calculation: Minor components influence solid solutions in nitrogen-methane atmospheres - ethane on Titan and carbon monoxide on Pluto

    NASA Astrophysics Data System (ADS)

    Tan, S. P.; Kargel, J. S.; Adidharma, H.; Marion, G. M.

    2016-12-01

    In the extremely cold conditions on Triton, Pluto and other Kuiper Belt Objects, and Titan's tropopause and lower stratosphere, the atmospheres as a whole, not components individually, are subject to freeze into solid phases as solutions, notpure ices. This is in contrast to water ice in Earth's atmosphere, where the atmosphere stays in gaseous phase when water freezes into a solid phase of presumably pure water due to the much higher temperatures involved. A molecular-based thermodynamic model for cryogenic chemical systems, referred to as CRYOCHEM, has been developed to include the phase equilibria involving multi-component solid solutions. Calculations using CRYOCHEM, therefore, can provide us with compositions of solid solutions that are in equilibrium with the gaseous atmosphere. There is no longer a need to assume pure solids conventionally used in modeling, or even as binary (two-component) mixtures, which commonly consider only nitrogen and methane. Two examples will be discussed: (1) on Titan where ethane plays a significant role in precipitation of high-altitude solid aerosols; and (2) on Pluto where carbon monoxide may also play some important role in the sublimation/condensation cycle at the surface and shallow subsurface, e.g., zone of solid-state greenhouse heating. The presence of these third components essentially affects the solid-gas phase equilibria of nitrogen-methane binary system at their respective conditions on Titan and Pluto, the information of which is useful for future modeling, including those on other bodies in the outer Solar System and comets that share similar volatiles.

  3. Autoignited laminar lifted flames of methane, ethylene, ethane, and n-butane jets in coflow air with elevated temperature

    SciTech Connect

    Choi, B.C.; Chung, S.H.

    2010-12-15

    The autoignition characteristics of laminar lifted flames of methane, ethylene, ethane, and n-butane fuels have been investigated experimentally in coflow air with elevated temperature over 800 K. The lifted flames were categorized into three regimes depending on the initial temperature and fuel mole fraction: (1) non-autoignited lifted flame, (2) autoignited lifted flame with tribrachial (or triple) edge, and (3) autoignited lifted flame with mild combustion. For the non-autoignited lifted flames at relatively low temperature, the existence of lifted flame depended on the Schmidt number of fuel, such that only the fuels with Sc > 1 exhibited stationary lifted flames. The balance mechanism between the propagation speed of tribrachial flame and local flow velocity stabilized the lifted flames. At relatively high initial temperatures, either autoignited lifted flames having tribrachial edge or autoignited lifted flames with mild combustion existed regardless of the Schmidt number of fuel. The adiabatic ignition delay time played a crucial role for the stabilization of autoignited flames. Especially, heat loss during the ignition process should be accounted for, such that the characteristic convection time, defined by the autoignition height divided by jet velocity was correlated well with the square of the adiabatic ignition delay time for the critical autoignition conditions. The liftoff height was also correlated well with the square of the adiabatic ignition delay time. (author)

  4. Spin-orbit relaxation and quenching of cesium 72P in mixtures of helium, methane, and ethane

    NASA Astrophysics Data System (ADS)

    Brown, Kirk C.; Perram, Glen P.

    2012-02-01

    The fine-structure mixing and quenching cross sections of the cesium 72P state in mixtures of helium, methane, and ethane were measured using laser-induced fluorescence techniques. This research was performed to study the kinetics associated with an optically pumped blue cesium laser operating on the 72P1/2-6S1/2 transition. Fluorescence decay curves from pulsed-laser experiments were analyzed as a function of buffer gas density at cell temperatures near 393 K. The fine-structure mixing cross sections for He, CH4, and C2H6 are 14±3, 35±6, and 73±10 Å2, respectively. The 2P3/2 state is quenched more rapidly than the 2P1/2 state. A model that includes the effects of radiation trapping and independent quenching cross sections for each fine-structure sublevel is compared to the experimental data. The rapid quenching negatively impacts the performance of a recently demonstrated optically pumped blue laser. We compare the cross sections for alkali-metal and noble gases and extend the adiabaticity analysis to the higher-lying excited states.

  5. Measurement of methane and other light hydrocarbons in the troposphere and lower stratosphere

    NASA Technical Reports Server (NTRS)

    Aikin, A. C.; Gallagher, C. C.; Spicer, C. W.; Holdren, M. W.

    1987-01-01

    The volume mixing ratios of methane, acetylene, ethane, and propane were measured in the troposphere and stratosphere on April 5, 1984, at 33 deg N, over New Mexico, using the technique of grab sampling by evacuated spheres on a balloon platform. Tropospheric volume mixing ratios were CH4, 1.59 ppm; C2H2, 358 ppt (parts per trillion); C2H6, 365 ppt; and C3H8, 1440 ppt. In the stratosphere, acetylene was 60 ppt. For ethane and propane the mixing ratios at 11.6 km were 441 ppt and 84 ppt, respectively.

  6. Microbial Oxidation of Ethane within Seep Sediment at Coal Oil Point, Santa Barbara, CA

    NASA Astrophysics Data System (ADS)

    Mendes, S. D.; Duncombe, R.; Scarlett, R. D.; Shaffer, J.; Lensch, S.; Valentine, D. L.

    2013-12-01

    The hydrocarbon seep field at Coal Oil Point (COP), off the coast of Santa Barbara, California, releases more than 10^10 g of thermogenic natural gas each year. Only a fraction of this methane, ethane, propane, and butane reaches the atmosphere, and is instead consumed by marine microbes in both the sediment and water column. Bacterial respiration of these gases has been observed in aerobic and anaerobic conditions, with the exception of ethane (aerobic only) (Kniemeyer et. al 2007). This work seeks to quantify the rate of ethane oxidation (both aerobic and anaerobic) in marine sediment. A series of experiments, to be conducted using COP seep sediment aboard the R/V Atlantis in October 2013, will test how varying oxygen conditions impact ethane oxidation rate. Oxidation rates will be quantified using sensitive 3H-ethane tracers. Preliminary data from Shane's Seep, located within the COP seep field, indicates that ethane oxidation is restricted to the top 6 cm of sediment. This suggests that oxygen is a limiting factor, but further work is needed to establish if ethane oxidation is restricted to exclusively aerobic environments.

  7. Evaluating ethane and methane emissions associated with the development of oil and natural gas extraction in North America

    NASA Astrophysics Data System (ADS)

    Franco, B.; Mahieu, E.; Emmons, L. K.; Tzompa-Sosa, Z. A.; Fischer, E. V.; Sudo, K.; Bovy, B.; Conway, S.; Griffin, D.; Hannigan, J. W.; Strong, K.; Walker, K. A.

    2016-04-01

    Sharp rises in the atmospheric abundance of ethane (C2H6) have been detected from 2009 onwards in the Northern Hemisphere as a result of the unprecedented growth in the exploitation of shale gas and tight oil reservoirs in North America. Using time series of C2H6 total columns derived from ground-based Fourier transform infrared (FTIR) observations made at five selected Network for the Detection of Atmospheric Composition Change sites, we characterize the recent C2H6 evolution and determine growth rates of ˜5% yr-1 at mid-latitudes and of ˜3% yr-1 at remote sites. Results from CAM-chem simulations with the Hemispheric Transport of Air Pollutants, Phase II bottom-up inventory for anthropogenic emissions are found to greatly underestimate the current C2H6 abundances. Doubling global emissions is required to reconcile the simulations and the observations prior to 2009. We further estimate that North American anthropogenic C2H6 emissions have increased from 1.6 Tg yr-1 in 2008 to 2.8 Tg yr-1 in 2014, i.e. by 75% over these six years. We also completed a second simulation with new top-down emissions of C2H6 from North American oil and gas activities, biofuel consumption and biomass burning, inferred from space-borne observations of methane (CH4) from Greenhouse Gases Observing SATellite. In this simulation, GEOS-Chem is able to reproduce FTIR measurements at the mid-latitudinal sites, underscoring the impact of the North American oil and gas development on the current C2H6 abundance. Finally we estimate that the North American oil and gas emissions of CH4, a major greenhouse gas, grew from 20 to 35 Tg yr-1 over the period 2008-2014, in association with the recent C2H6 rise.

  8. Propane poisoning

    MedlinePlus

    Propane is a colorless and odorless flammable gas that can turn into liquid under very cold temperatures. This article discusses the harmful effects from breathing in or swallowing propane. Breathing in or swallowing propane can be ...

  9. The MOYA aircraft campaign: First measurements of methane, ethane and C-13 isotopes from West African biomass burning and other regional sources using the UK FAAM aircraft

    NASA Astrophysics Data System (ADS)

    Allen, Grant; Pitt, Joseph; Lee, James; Hopkins, James; Young, Stuart; Bauguitte, Stéphane; Gallagher, Martin; Fisher, Rebecca; Lowry, David; Nisbet, Euan

    2017-04-01

    Global methane concentrations continue to rise due to an imbalance between sources and sinks. There remains little consensus on the relative components of the manifold source types and their geographical origin. The Global Methane Budget and Yearly Assessments (MOYA) project is tasked with better characterising the global methane budget through an augmented global measurement and modelling programme. As part of MOYA, the UK's Facility for Airborne Atmospheric Measurement (FAAM), will fly four campaigns based out of West Africa and Ascension Island in the period 2017-2019, to focus on the important role of tropical sources. The first of these, to be conducted in late February 2017, will focus on the biomass burning season in West Africa. This paper will present the plan for future FAAM MOYA campaigns and report on our first aircraft data gathered in the West African region. The new addition of an interband cascade laser spectrometer to the FAAM aircraft, flown in this campaign for the first time, promises to provide the first real-time, continuous, and simultaneous, airborne measurements of methane, ethane and methane C-13 isotopologues. Together, these measurements, when interpreted in combination with other trace gases and aerosol measured on the aircraft, will serve as case studies to inform modelling of regional and global fluxes through their isotopic fingerprints.

  10. Kinetics of methane-ethane gas replacement in clathrate-hydrates studied by time-resolved neutron diffraction and Raman spectroscopy.

    PubMed

    Murshed, M Mangir; Schmidt, Burkhard C; Kuhs, Werner F

    2010-01-14

    The kinetics of CH(4)-C(2)H(6) replacement in gas hydrates has been studied by in situ neutron diffraction and Raman spectroscopy. Deuterated ethane structure type I (C(2)H(6) sI) hydrates were transformed in a closed volume into methane-ethane mixed structure type II (CH(4)-C(2)H(6) sII) hydrates at 5 MPa and various temperatures in the vicinity of 0 degrees C while followed by time-resolved neutron powder diffraction on D20 at ILL, Grenoble. The role of available surface area of the sI starting material on the formation kinetics of sII hydrates was studied. Ex situ Raman spectroscopic investigations were carried out to crosscheck the gas composition and the distribution of the gas species over the cages as a function of structure type and compared to the in situ neutron results. Raman micromapping on single hydrate grains showed compositional and structural gradients between the surface and core of the transformed hydrates. Moreover, the observed methane-ethane ratio is very far from the one expected for a formation from a constantly equilibrated gas phase. The results also prove that gas replacement in CH(4)-C(2)H(6) hydrates is a regrowth process involving the nucleation of new crystallites commencing at the surface of the parent C(2)H(6) sI hydrate with a progressively shrinking core of unreacted material. The time-resolved neutron diffraction results clearly indicate an increasing diffusion limitation of the exchange process. This diffusion limitation leads to a progressive slowing down of the exchange reaction and is likely to be responsible for the incomplete exchange of the gases.

  11. Measurement of position-specific 13C isotopic composition of propane at the nanomole level

    NASA Astrophysics Data System (ADS)

    Gilbert, Alexis; Yamada, Keita; Suda, Konomi; Ueno, Yuichiro; Yoshida, Naohiro

    2016-03-01

    We have developed a novel method for analyzing intramolecular carbon isotopic distribution of propane as a potential new tracer of its origin. The method is based on on-line pyrolysis of propane followed by analysis of carbon isotope ratios of the pyrolytic products methane, ethylene and ethane. Using propane samples spiked with 13C at the terminal methyl carbon, we characterize the origin of the pyrolytic fragments. We show that the exchange between C-atoms during the pyrolytic process is negligible, and thus that relative intramolecular isotope composition can be calculated. Preliminary data from 3 samples show that site-preference (SP) values, defined as the difference of δ13C values between terminal and sub-terminal C-atom positions of propane, range from -1.8‰ to -12.9‰. In addition, SP value obtained using our method for a thermogenic natural gas sample is consistent with that expected from theoretical models of thermal cracking, suggesting that the isotope fractionation associated with propane pyrolysis is negligible. The method will provide novel insights into the characterization of the origin of propane and will help better understand the biogeochemistry of natural gas deposits.

  12. Propane Basics

    SciTech Connect

    NREL

    2010-03-01

    Propane powers about 190,000 vehicles in the U.S. and more than 14 million worldwide. Propane vehicles are a good choice for many fleet applications including school buses, shuttle buses, taxies and light-duty trucks.

  13. How Do Perfluorinated Alkanoic Acids Elicit Cytochrome P450 to Catalyze Methane Hydroxylation? An MD and QM/MM Study

    PubMed Central

    Li, Chunsen; Shaik, Sason

    2013-01-01

    Recent experimental studies show that usage of perfluoro decanoic acid (PFDA), as a dummy substrate, can elicit P450BM3 to perform hydroxylation of small alkanes, such as methane (ref. 17) and propane (ref. 17 and ref. 18). To comprehend the mechanism whereby PFDA operates to potentiate P450BM3 to catalyze the hydroxylation of small alkanes, we used molecular dynamics (MD) and hybrid quantum mechanical / molecular mechanical (QM/MM) calculations. The MD results show that without the PFDA, methane escapes the active site, while the presence of PFDA can potentially induce a productive Cpd I-Methane juxtaposition for rapid oxidation. Nevertheless, when only a single methane molecule is present near the PFDA, it still escapes the pocket within less than a nanosecond. However, when three methane molecules are present in the pocket, they alternate quasi-periodically such that at all times (within 10 ns), a molecule of methane is always present in the proximity of Cpd I in a reactive conformation. Our results further demonstrate that the PFDA does not exert any electrostatic catalysis, whether the PFDA is in the protonated or deprotonated forms. Taken together, we conclude that methane hydroxylation requires, in addition to PFDA, a high partial pressure of methane that will cause a high methane concentration in the active site. Further study of ethane and propane hydroxylations demonstrates that higher alkane concentration is helpful for all the three small alkanes. Thus for the smallest alkane, methane, at least three molecules are necessary whereas for the larger ethane, two molecules are needed to force one ethane to be closer to Cpd I. Finally, for propane a second molecule is helpful but not absolutely necessary; for this molecule the PFDA may well be sufficient to keep propane close to Cpd I for efficient oxidation. We therefore propose that high alkane pressure should assist small alkane hydroxylation by P450 in a manner inversely proportional to the size of the

  14. How Do Perfluorinated Alkanoic Acids Elicit Cytochrome P450 to Catalyze Methane Hydroxylation? An MD and QM/MM Study.

    PubMed

    Li, Chunsen; Shaik, Sason

    2013-03-07

    Recent experimental studies show that usage of perfluoro decanoic acid (PFDA), as a dummy substrate, can elicit P450BM3 to perform hydroxylation of small alkanes, such as methane (ref. 17) and propane (ref. 17 and ref. 18). To comprehend the mechanism whereby PFDA operates to potentiate P450BM3 to catalyze the hydroxylation of small alkanes, we used molecular dynamics (MD) and hybrid quantum mechanical / molecular mechanical (QM/MM) calculations. The MD results show that without the PFDA, methane escapes the active site, while the presence of PFDA can potentially induce a productive Cpd I-Methane juxtaposition for rapid oxidation. Nevertheless, when only a single methane molecule is present near the PFDA, it still escapes the pocket within less than a nanosecond. However, when three methane molecules are present in the pocket, they alternate quasi-periodically such that at all times (within 10 ns), a molecule of methane is always present in the proximity of Cpd I in a reactive conformation. Our results further demonstrate that the PFDA does not exert any electrostatic catalysis, whether the PFDA is in the protonated or deprotonated forms. Taken together, we conclude that methane hydroxylation requires, in addition to PFDA, a high partial pressure of methane that will cause a high methane concentration in the active site. Further study of ethane and propane hydroxylations demonstrates that higher alkane concentration is helpful for all the three small alkanes. Thus for the smallest alkane, methane, at least three molecules are necessary whereas for the larger ethane, two molecules are needed to force one ethane to be closer to Cpd I. Finally, for propane a second molecule is helpful but not absolutely necessary; for this molecule the PFDA may well be sufficient to keep propane close to Cpd I for efficient oxidation. We therefore propose that high alkane pressure should assist small alkane hydroxylation by P450 in a manner inversely proportional to the size of the

  15. Propane Update.

    ERIC Educational Resources Information Center

    Brantner, Max

    1984-01-01

    Reports on a northern Illinois school bus fleet converted to propane fuel in 1981 and 1982. Includes tables showing, first, total annual fuel costs before and after conversion and, second, fuel efficiency for 16 buses using propane and three using gasoline. Notes precautions for propane use. (MCG)

  16. Propane Update.

    ERIC Educational Resources Information Center

    Brantner, Max

    1984-01-01

    Reports on a northern Illinois school bus fleet converted to propane fuel in 1981 and 1982. Includes tables showing, first, total annual fuel costs before and after conversion and, second, fuel efficiency for 16 buses using propane and three using gasoline. Notes precautions for propane use. (MCG)

  17. Parametric performance of circumferentially grooved heat pipes with homogeneous and graded-porosity slab wicks at cryogenic temperatures. [methane and ethane working fluids

    NASA Technical Reports Server (NTRS)

    Groll, M.; Pittman, R. B.; Eninger, J. E.

    1976-01-01

    A recently developed, potentially high-performance nonarterial wick was extensively tested. This slab wick has an axially varying porosity which can be tailored to match the local stress imposed on the wick. The purpose of the tests was to establish the usefulness of the graded-porosity slab wick at cryogenic temperatures between 110 and 260 K, with methane and ethane as working fluids. For comparison, a homogeneous (i.e., uniform porosity) slab wick was also tested. The tests included: maximum heat pipe performance as a function of fluid inventory, maximum performance as a function of operating temperature, maximum performance as a function of evaporator elevation, and influence of slab wick orientation on performance. The experimental data were compared with theoretical predictions obtained with the GRADE computer program.

  18. Global corresponding states representation of the interfacial tension and capillary constant for the binary mixtures argon + krypton, methane + krypton, and krypton + ethane

    SciTech Connect

    Holcomb, C.D.; Zollweg, J.A. )

    1993-05-06

    Corresponding states theories for surface tension and capillary constant have been evaluated using constant liquid mole fraction and constant [open quotes]fugacity fraction[close quotes] reference fluids for three binary systems. Experimental vapor-liquid equilibria, capillary constant, and surface tension data for argon + krypton, methane + krypton, and krypton + ethane systems were measured from 125 K to the critical line. These results form a database for phase behavior of varying complexity between simple compounds. The database has been used to compare the [open quotes]fugacity fraction[close quotes] corresponding states theory for capillary constant and surface tension with the traditional corresponding states theory which uses as a reference fluid a liquid with constant mole fraction. The database was also used to test the Moldover and Rainwater prediction for the surface tension coefficient in the fugacity fraction corresponding states theory. 33 refs., 11 figs., 10 tabs.

  19. Relative rate studies of the reactions of chlorine atoms with simple alkanes and the chlorinated methanes

    SciTech Connect

    Wingen, L.; Lee, J.J.; Neavyn, R.

    1995-12-01

    The reactions of chlorine atoms with organics are of interest because atomic chlorine is a potential tropospheric oxidant. Relative rate constants for the reaction of pairs of simple alkanes (ethane/propane, ethane/n-butane, and isobutane/n-butane) and the chlorinated methanes (chloromethane, dichloromethane, and chloroform relative to methane) were measured, using the photolysis of Cl{sub 2} as the source of chlorine atoms and following the loss of the organics by GC-FID. The ratios of the relative rate constants were in excellent agreement with the literature except for ethane/n-butane, where our results are approximately 20% lower than recently published values, and for chloroform/methane, where our value is approximately 50% higher than the values recommended by JPL and JPCRD. Our results will be compard to previously published relative rate studies as well as to the results of absolute rate constant studies, and the differences will be discussed.

  20. Time-resolved infrared (TRIR) study on the formation and reactivity of organometallic methane and ethane complexes in room temperature solution

    PubMed Central

    Cowan, Alexander J.; Portius, Peter; Kawanami, Hajime K.; Jina, Omar S.; Grills, David C.; Sun, Xue-Zhong; McMaster, Jonathan; George, Michael W.

    2007-01-01

    We have used fast time-resolved infrared spectroscopy to characterize a series of organometallic methane and ethane complexes in solution at room temperature: W(CO)5(CH4) and M(η5C5R5)(CO)2(L) [where M = Mn or Re, R = H or CH3 (Re only); and L = CH4 or C2H6]. In all cases, the methane complexes are found to be short-lived and significantly more reactive than the analogous n-heptane complexes. Re(Cp)(CO)2(CH4) and Re(Cp*)(CO)2(L) [Cp* = η5C5(CH3)5 and L = CH4, C2H6] were found to be in rapid equilibrium with the alkyl hydride complexes. In the presence of CO, both alkane and alkyl hydride complexes decay at the same rate. We have used picosecond time-resolved infrared spectroscopy to directly monitor the photolysis of Re(Cp*)(CO)3 in scCH4 and demonstrated that the initially generated Re(Cp*)(CO)2(CH4) forms an equilibrium mixture of Re(Cp*)(CO)2(CH4)/Re(Cp*)(CO)2(CH3)H within the first few nanoseconds (τ = 2 ns). The ratio of alkane to alkyl hydride complexes varies in the order Re(Cp)(CO)2(C2H6):Re(Cp)(CO)2(C2H5)H > Re(Cp*)(CO)2(C2H6):Re(Cp*)(CO)2(C2H5)H ≈ Re(Cp)(CO)2(CH4):Re(Cp)(CO)2(CH3)H > Re(Cp*)(CO)2(CH4):Re(Cp*)(CO)2(CH3)H. Activation parameters for the reactions of the organometallic methane and ethane complexes with CO have been measured, and the ΔH‡ values represent lower limits for the CH4 binding enthalpies to the metal center of WCH4 (30 kJ·mol−1), MnCH4 (39 kJ·mol−1), and ReCH4 (51 kJ·mol−1) bonds in W(CO)5(CH4), Mn(Cp)(CO)2(CH4), and Re(Cp)(CO)2(CH4), respectively. PMID:17409190

  1. Time-resolved infrared (TRIR) study on the formation and reactivity of organometallic methane and ethane complexes in room temperature solution.

    PubMed

    Cowan, Alexander J; Portius, Peter; Kawanami, Hajime K; Jina, Omar S; Grills, David C; Sun, Xue-Zhong; McMaster, Jonathan; George, Michael W

    2007-04-24

    We have used fast time-resolved infrared spectroscopy to characterize a series of organometallic methane and ethane complexes in solution at room temperature: W(CO)5(CH4) and M(eta5-C5R5)(CO)2(L) [where M = Mn or Re, R = H or CH3 (Re only); and L = CH4 or C2H6]. In all cases, the methane complexes are found to be short-lived and significantly more reactive than the analogous n-heptane complexes. Re(Cp)(CO)2(CH4) and Re(Cp*)(CO)2(L) [Cp* = eta5-C5(CH3)(5) and L = CH4, C2H6] were found to be in rapid equilibrium with the alkyl hydride complexes. In the presence of CO, both alkane and alkyl hydride complexes decay at the same rate. We have used picosecond time-resolved infrared spectroscopy to directly monitor the photolysis of Re(Cp*)(CO)3 in scCH4 and demonstrated that the initially generated Re(Cp*)(CO)2(CH4) forms an equilibrium mixture of Re(Cp*)(CO)2(CH4)/Re(Cp*)(CO)2(CH3)H within the first few nanoseconds (tau = 2 ns). The ratio of alkane to alkyl hydride complexes varies in the order Re(Cp)(CO)2(C2H6):Re(Cp)(CO)2(C2H5)H > Re(Cp*)(CO)2(C2H6):Re(Cp*)(CO)2(C2H5)H approximately equal to Re(Cp)(CO)2(CH4):Re(Cp)(CO)2(CH3)H > Re(Cp*)(CO)2(CH4):Re(Cp*)(CO)2(CH3)H. Activation parameters for the reactions of the organometallic methane and ethane complexes with CO have been measured, and the DeltaH++ values represent lower limits for the CH4 binding enthalpies to the metal center of W-CH4 (30 kJ.mol(-1)), Mn-CH4 (39 kJ.mol(-1)), and Re-CH4 (51 kJ.mol(-1)) bonds in W(CO)5(CH4), Mn(Cp)(CO)2(CH4), and Re(Cp)(CO)2(CH4), respectively.

  2. Propane fear

    SciTech Connect

    Begley, R.

    1992-02-12

    A minor feature of a Congressional energy bill is causing consternation for a number of propane-consuming chemical companies. The firms are fighting the bill`s inclusion of liquefied petroleum gas (LPG) on a list of alternative fuels that can be used to meet its urban fleet vehicles requirements. The firms fear that this added use would drive up the price of propane-an LPG-for homeowners, farmers, and themselves. Speaking for the Propane Consumers Coalition, a Dow Chemical spokesman says 7.7 million households use propane, as does agriculture, and current demand is such that December saw a 23-year low in US inventories. The US depends on imports of propane, he says, and about half the propane sold in the US is derived from the refining of oil, much of which is also imported. Adding demand for vehicle fuel would drive up imports and process, the spokesman says, thereby damaging all users, including the petrochemical industry.

  3. Oxidative Condensation of Methane — a New Pathway to the Synthesis of Ethane, Ethylene, and Other Hydrocarbons

    NASA Astrophysics Data System (ADS)

    Minachev, Khabib M.; Usachev, Nikolay Ya; Udut, V. N.; Khodakov, Yu S.

    1988-03-01

    During the last five years, the chemistry of methane has been enriched by the possibility of obtaining C2 and other hydrocarbons as a result of the oxidative condensation of methane in the presence of a series of catalytic systems. The availability of the starting materials (CH4 and O2) leads to extensive prospects for the replacement of the petroleum raw materials by natural gas in single-stage syntheses of valuable compounds and in the first place ethylene. This review gives a systematic account of the results of the selection of effective catalysts and surveys the information leading to the elucidation of the mechanism for the formation of the products of the extensive oxidation and oxidative condensation of methane. The bibliography includes 118 references.

  4. Diffusion of methane and other alkanes in metal-organic frameworks for natural gas storage

    SciTech Connect

    Borah, B; Zhang, HD; Snurr, RQ

    2015-03-03

    Diffusion of methane, ethane, propane and n-butane was studied within the micropores of several metal organic frameworks (MOFs) of varying topologies, including the MOFs PCN-14, NU-125, NU-1100 and DUT-49. Diffusion coefficients of the pure components, as well as methane/ethane, methane/ propane and methane/butane binary mixtures, were calculated using molecular dynamics simulations to understand the effect of the longer alkanes on uptake of natural gas in MOB. The calculated self diffusion coefficients of all four components are on the order of 10(-8) m(2)/s. The diffusion coefficients of the pure components decrease as a function of chain length in all of the MOFs studied and show different behaviour as a function of loading in different MOB. The self-diffusivities follow the trend DPCN-14 < DNU-125 approximate to DNU-1100 < DDUT-49, which is exactly the reverse order of the densities of the MOFs: PCN-14 > NU-125 approximate to NU-1100 > DUT-49. By comparing the diffusion of pure methane and methane mixtures vvith the higher alkancs, it is observed that the diffusivity of methane is unaffected by the presence of the higher alkanes in the MOFs considered, indicating that the diffusion path of methane is not blocked by the higher alkanes present in natural gas. (C) 2014 Elsevier Ltd. All rights reserved.

  5. Detection of abundant ethane and methane, along with carbon monoxide and water, in comet C/1996 B2 Hyakutake: evidence for interstellar origin.

    PubMed

    Mumma, M J; DiSanti, M A; Dello Russo, N; Fomenkova, M; Magee-Sauer, K; Kaminski, C D; Xie, D X

    1996-05-31

    The saturated hydrocarbons ethane (C2H6) and methane (CH4) along with carbon monoxide (CO) and water (H2O) were detected in comet C/1996 B2 Hyakutake with the use of high-resolution infrared spectroscopy at the NASA Infrared Telescope Facility on Mauna Kea, Hawaii. The inferred production rates of molecular gases from the icy, cometary nucleus (in molecules per second) are 6.4 X 10(26) for C2H6, 1.2 X 10(27) for CH4, 9.8 X 10(27) for CO, and 1.7 X 10(29) for H2O. An abundance of C2H6 comparable to that of CH4 implies that ices in C/1996 B2 Hyakutake did not originate in a thermochemically equilibrated region of the solar nebula. The abundances are consistent with a kinetically controlled production process, but production of C2H6 by gas-phase ion molecule reactions in the natal cloud core is energetically forbidden. The high C2H6/CH4 ratio is consistent with production of C2H6 in icy grain mantles in the natal cloud, either by photolysis of CH4-rich ice or by hydrogen-addition reactions to acetylene condensed from the gas phase.

  6. Development of highly sensitive sensor system for methane utilizing cataluminescence.

    PubMed

    Gong, Gu; Zhu, Hua

    2016-02-01

    A gaseous sensor system was developed for the detection of methane based on its cataluminescence emission. Cataluminescence characteristics and optimal conditions were studied in detail under optimized experimental conditions. Results showed that the methane cataluminescence sensor system could cover a linear detection range from 10 to 5800 ppm (R = 0.9963, n = 7) and the detection limit was about 7 ppm (S/N = 3), which was below the standard permitted concentration. Moreover, a linear discriminant analysis method was used to test the recognizable performance of the methane sensor. It was found that methane, ethane, propane and pentane could be distinguished clearly. Its methane sensing properties, including improved sensitivity, selectivity, stability and recognition demonstrated the TiO2/SnO2 materials to be promising candidates for constructing a cataluminescence-based gas sensor that could be used for detecting explosive gas contaminants.

  7. Position-specific and clumped stable isotope studies: comparison of the Urey and path-integral approaches for carbon dioxide, nitrous oxide, methane, and propane.

    PubMed

    Webb, Michael A; Miller, Thomas F

    2014-01-16

    We combine path-integral Monte Carlo methods with high-quality potential energy surfaces to compute equilibrium isotope effects in a variety of systems relevant to 'clumped' isotope analysis and isotope geochemistry, including CO2, N2O, methane, and propane. Through a systematic study of heavy-atom isotope-exchange reactions, we quantify and analyze errors that arise in the widely used Urey model for predicting equilibrium constants of isotope-exchange reactions using reduced partition function ratios. These results illustrate that the Urey model relies on a nontrivial cancellation of errors that can shift the apparent equilibrium temperature by as much as 35 K for a given distribution of isotopologues. The calculations reported here provide the same level of precision as the best existing analytical instrumentation, resolving the relative enrichment of certain isotopologues to as little as 0.01‰. These findings demonstrate path-integral methods to be a rigorous and viable alternative to more approximate methods for heavy-atom geochemical applications.

  8. Rate constants and temperature dependences for the reactions of hydroxyl radical with several halogenated methanes, ethanes, and propanes by relative rate measurements

    NASA Technical Reports Server (NTRS)

    Hsu, K.-J.; DeMore, W. B.

    1995-01-01

    Rate constants of 15 OH reactions with halogen-substituted alkanes, C1 to C3, were studied using a relative rate technique in the temperature range 283-403 K. Compounds studied were CHF2Cl (22), CHF2Br (22B), CH3F (41), CH2F2 (32), CHF3 (23), CHClFCCl2F (122a), CHCl2CF3 (123), CHClFCF3 (124), CH3CF3 (143a), CH3CH2F (161), CF3CHFCF3 (227ea), CF3CH2CF3 (236fa), CF3CHFCHF2 (236ea), and CHF2CF2CH2F (245ca). Using CH4, CH3CCl3, CF3CF2H, and C2H6 as primary reference standards (JPL 92-20 rate constants), absolute rate constants are derived. Results are in good agreement with previous experimental results for six of the compounds studied, including CHF2Cl, CHF2Br, CH2F2, CH3CF3, CHFClCFCl2, and CF3CHFCF3. For the remainder the relative rate constants are lower than those derived from experiments in which OH loss was used to measure the reaction rate. Comparisons of the derived Arrhenius A factors with previous literature transition-state calculations show order of magnitude agreement in most cases. However, the experimental A factors show a much closer proportionality to the number of H atoms in the molecule than is evident from the transition state calculations. For most of the compounds studied, an A factor of (8 +/- 3)E-13 cm(exp 3)/(molecule s) per C-H bond is observed. A new measurement of the ratio k(CH3CCl3)/k(CH4) is reported that is in good agreement with previous data.

  9. Low-temperature superacid catalysis: Reactions of n - butane and propane catalyzed by iron- and manganese-promoted sulfated zirconia

    SciTech Connect

    Tsz-Keung, Cheung; d`Itri, J.L.; Lange, F.C.; Gates, B.C.

    1995-12-31

    The primary goal of this project is to evaluate the potential value of solid superacid catalysts of the sulfated zirconia type for light hydrocarbon conversion. The key experiments catalytic testing of the performance of such catalysts in a flow reactor fed with streams containing, for example, n-butane or propane. Fe- and Mn-promoted sulfated zirconia was used to catalyze the conversion of n-butane at atmospheric pressure, 225-450{degrees}C, and n-butane partial pressures in the range of 0.0025-0.01 atm. At temperatures <225{degrees}C, these reactions were accompanied by cracking; at temperatures >350{degrees}C, cracking and isomerization occurred. Catalyst deactivation, resulting at least in part from coke formation, was rapid. The primary cracking products were methane, ethane, ethylene, and propylene. The observation of these products along with an ethane/ethylene molar ratio of nearly 1 at 450{degrees}C is consistent with cracking occurring, at least in part, by the Haag-Dessau mechanism, whereby the strongly acidic catalyst protonates n-butane to give carbonium ions. The rate of methane formation from n-butane cracking catalyzed by Fe- and Mn-promoted sulfated zirconia at 450{degrees}C was about 3 x 10{sup -8} mol/(g of catalyst {center_dot}s). The observation of butanes, pentanes, and methane as products is consistent with Olah superacid chemistry, whereby propane is first protonated by a very strong acid to form a carbonium ion. The carbonium ion then decomposes into methane and an ethyl cation which undergoes oligocondensation reactions with propane to form higher molecular weight alkanes. The results are consistent with the identification of iron- and manganese-promoted sulfated zirconia as a superacid.

  10. Use of propane as a quench gas in argon-filled proportional counters and comparison with other quench gases

    NASA Technical Reports Server (NTRS)

    Agrawal, P. C.; Ramsey, B. D.

    1988-01-01

    An experimental investigation of propane and six other quench gases was carried out in argon-filled proportional counters. The objective of the study was to find the best gas mixture for optimizing the gas gain and the energy resolution as well as to understand the role of the ionization potential of quench gases in determining these parameters. It was found that the best gas gains and energy resolutions are obtained with propane, ethane, and isobutane in that order. The ionization potentials of these three lie below the argon metastable potentials and have the lowest value of resonance defect compared to the other quench gases. The better results obtained with these mixtures can be explained by an increased ionization yield resulting from the Penning effect. Propylene and trans-2-butene give inferior performance compared to the above three gases. Methane and carbon dioxide, the most commonly used quench gases in the argon-filled detectors, provide the worst results.

  11. Use of propane as a quench gas in argon-filled proportional counters and comparison with other quench gases

    NASA Technical Reports Server (NTRS)

    Agrawal, P. C.; Ramsey, B. D.

    1988-01-01

    An experimental investigation of propane and six other quench gases was carried out in argon-filled proportional counters. The objective of the study was to find the best gas mixture for optimizing the gas gain and the energy resolution as well as to understand the role of the ionization potential of quench gases in determining these parameters. It was found that the best gas gains and energy resolutions are obtained with propane, ethane, and isobutane in that order. The ionization potentials of these three lie below the argon metastable potentials and have the lowest value of resonance defect compared to the other quench gases. The better results obtained with these mixtures can be explained by an increased ionization yield resulting from the Penning effect. Propylene and trans-2-butene give inferior performance compared to the above three gases. Methane and carbon dioxide, the most commonly used quench gases in the argon-filled detectors, provide the worst results.

  12. 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.

  13. Methane-derived hydrocarbons produced under upper-mantle conditions

    SciTech Connect

    Kolesnikov, Anton; Kutcherov, Vladimir G.; Goncharov, Alexander F.

    2009-08-13

    There is widespread evidence that petroleum originates from biological processes. Whether hydrocarbons can also be produced from abiogenic precursor molecules under the high-pressure, high-temperature conditions characteristic of the upper mantle remains an open question. It has been proposed that hydrocarbons generated in the upper mantle could be transported through deep faults to shallower regions in the Earth's crust, and contribute to petroleum reserves. Here we use in situ Raman spectroscopy in laser-heated diamond anvil cells to monitor the chemical reactivity of methane and ethane under upper-mantle conditions. We show that when methane is exposed to pressures higher than 2 GPa, and to temperatures in the range of 1,000-1,500 K, it partially reacts to form saturated hydrocarbons containing 2-4 carbons (ethane, propane and butane) and molecular hydrogen and graphite. Conversely, exposure of ethane to similar conditions results in the production of methane, suggesting that the synthesis of saturated hydrocarbons is reversible. Our results support the suggestion that hydrocarbons heavier than methane can be produced by abiogenic processes in the upper mantle.

  14. Activation of methane by transition metal-substituted aluminophosphate molecular sieves

    SciTech Connect

    Maroni, V A; Willms, K A; Nguyen, Hiephoa; Iton, L E

    1989-12-01

    Recent experiments in our laboratory have demonstrated that aluminophosphate molecular sieves substituted with cobalt and cobalt/silicon combinations and having the AlPO{sub 4}-34 or AlPO{sub 4}-5 structure activate methane starting at {approximately}350{degree}C. Between 400 and 500{degree}C the rate of methane conversion increases steadily with typical conversion efficiencies at 500{degree}C ranging from 15 to 60%. The cobalt and silicon substituted AlPO{sub 4}-34 structure (CoAPSO-34) produces ethylene, ethane, propylene, and propane in varying proportions, depending on reactions conditions. The cobalt-substituted AlPO{sub 4}-5 (CoAPSO-5) produces propylene in very high yield with ethane, ethylene, and propane also seen. Analogous aluminophosphate molecular sieves substituted with magnesium or silicon, but containing no transition metal (e.g., SAPO-34, MAPO-5), do not activate methane under the conditions described above. The activation mechanism is based on reduction of the cobalt(III) form of the molecular sieve to the cobalt(II) form with accompanying oxidative dehydrogenation of the methane. Reoxidation of the cobalt(II) for to the cobalt(III) form can be done either chemically (e.g., using O{sub 2}) or electrochemically. 7 refs., 2 figs., 1 tab.

  15. Photocatalytic oxidation of methane over silver decorated zinc oxide nanocatalysts.

    PubMed

    Chen, Xuxing; Li, Yunpeng; Pan, Xiaoyang; Cortie, David; Huang, Xintang; Yi, Zhiguo

    2016-07-20

    The search for active catalysts that efficiently oxidize methane under ambient conditions remains a challenging task for both C1 utilization and atmospheric cleansing. Here, we show that when the particle size of zinc oxide is reduced down to the nanoscale, it exhibits high activity for methane oxidation under simulated sunlight illumination, and nano silver decoration further enhances the photo-activity via the surface plasmon resonance. The high quantum yield of 8% at wavelengths <400 nm and over 0.1% at wavelengths ∼470 nm achieved on the silver decorated zinc oxide nanostructures shows great promise for atmospheric methane oxidation. Moreover, the nano-particulate composites can efficiently photo-oxidize other small molecular hydrocarbons such as ethane, propane and ethylene, and in particular, can dehydrogenize methane to generate ethane, ethylene and so on. On the basis of the experimental results, a two-step photocatalytic reaction process is suggested to account for the methane photo-oxidation.

  16. Photocatalytic oxidation of methane over silver decorated zinc oxide nanocatalysts

    PubMed Central

    Chen, Xuxing; Li, Yunpeng; Pan, Xiaoyang; Cortie, David; Huang, Xintang; Yi, Zhiguo

    2016-01-01

    The search for active catalysts that efficiently oxidize methane under ambient conditions remains a challenging task for both C1 utilization and atmospheric cleansing. Here, we show that when the particle size of zinc oxide is reduced down to the nanoscale, it exhibits high activity for methane oxidation under simulated sunlight illumination, and nano silver decoration further enhances the photo-activity via the surface plasmon resonance. The high quantum yield of 8% at wavelengths <400 nm and over 0.1% at wavelengths ∼470 nm achieved on the silver decorated zinc oxide nanostructures shows great promise for atmospheric methane oxidation. Moreover, the nano-particulate composites can efficiently photo-oxidize other small molecular hydrocarbons such as ethane, propane and ethylene, and in particular, can dehydrogenize methane to generate ethane, ethylene and so on. On the basis of the experimental results, a two-step photocatalytic reaction process is suggested to account for the methane photo-oxidation. PMID:27435112

  17. Measurements of ethane in Antarctic ice cores

    NASA Astrophysics Data System (ADS)

    Verhulst, K. R.; Fosse, E. K.; Aydin, K. M.; Saltzman, E. S.

    2011-12-01

    Ethane is one of the most abundant hydrocarbons in the atmosphere. The major ethane sources are fossil fuel production and use, biofuel combustion, and biomass-burning emissions and the primary loss pathway is via reaction with OH. A paleoatmospheric ethane record would be useful as a tracer of biomass-burning emissions, providing a constraint on past changes in atmospheric methane and methane isotopes. An independent biomass-burning tracer would improve our understanding of the relationship between biomass burning and climate. The mean annual atmospheric ethane level at high southern latitudes is about 230 parts per trillion (ppt), and Antarctic firn air measurements suggest that atmospheric ethane levels in the early 20th century were considerably lower (Aydin et al., 2011). In this study, we present preliminary measurements of ethane (C2H6) in Antarctic ice core samples with gas ages ranging from 0-1900 C.E. Samples were obtained from dry-drilled ice cores from South Pole and Vostok in East Antarctica, and from the West Antarctic Ice Sheet Divide (WAIS-D). Gases were extracted from the ice by melting under vacuum in a glass vessel sealed by indium wire and were analyzed using high resolution GC/MS with isotope dilution. Ethane levels measured in ice core samples were in the range 100-220 ppt, with a mean of 157 ± 45 ppt (n=12). System blanks contribute roughly half the amount of ethane extracted from a 300 g ice core sample. These preliminary data exhibit a temporal trend, with higher ethane levels from 0-900 C.E., followed by a decline, reaching a minimum between 1600-1700 C.E. These trends are consistent with variations in ice core methane isotopes and carbon monoxide isotopes (Ferretti et al., 2005, Wang et al., 2010), which indicate changes in biomass burning emissions over this time period. These preliminary data suggest that Antarctic ice core bubbles contain paleoatmospheric ethane levels. With further improvement of laboratory techniques it appears

  18. Ethane: A Key to Evaluating Natural Gas Industrial Emissions

    NASA Astrophysics Data System (ADS)

    Yacovitch, T. I.; Herndon, S. C.; Agnese, M.; Roscioli, J. R.; Floerchinger, C. R.; Knighton, W. B.; Pusede, S. E.; Diskin, G. S.; DiGangi, J. P.; Sachse, G. W.; Eichler, P.; Mikoviny, T.; Müller, M.; Wisthaler, A.; Conley, S. A.; Petron, G.

    2014-12-01

    Airborne and mobile-surface measurements of ethane at 1Hz in the Denver-Julesberg oil and gas production basin in NE Colorado reveal a rich set of emission sources and magnitudes. Although ethane has only a mild influence on hemispheric ozone levels, it is often co-emitted with larger hydrocarbons including hazardous air pollutants (HAPs) and ozone precursors that impact local and regional air quality. Ethane/methane enhancement ratios provide a map of expected emission source types in different areas around greater Denver. Links are drawn between the ethane content of isolated methane emission plumes and the prevalence of concomitant HAP and ozone precursor species. The efficacy of using ethane as a dilution tracer specific to the oil & gas footprint will be demonstrated.

  19. Microbial Formation of Ethane in Anoxic Estuarine Sediments

    PubMed Central

    Oremland, Ronald S.

    1981-01-01

    Estuarine sediment slurries produced methane and traces of ethane when incubated under hydrogen. Formation of methane occurred over a broad temperature range with an optimum above 65°C. Ethane formation had a temperature optimum at 40°C. Formation of these two gases was inhibited by air, autoclaving, incubation at 4 and 80°C, and by the methanogenic inhibitor, 2-bromoethanesulfonic acid. Ethane production was stimulated by addition of ethylthioethanesulfonic acid, and production from ethylthioethanesulfonic acid was blocked by 2-bromoethanesulfonic acid. A highly purified enrichment culture of a methanogenic bacterium obtained from sediments produced traces of ethane from ethylthioethanesulfonic acid. These results indicate that the small quantities of ethane found in anaerobic sediments can be formed by certain methanogenic bacteria. PMID:16345805

  20. Microbial formation of ethane in anoxic estuarine sediments

    USGS Publications Warehouse

    Oremland, Ronald S.

    1981-01-01

    Estuarine sediment slurries produced methane and traces of ethane when incubated under hydrogen. Formation of methane occurred over a broad temperature range with an optimum above 65°C. Ethane formation had a temperature optimum at 40°C. Formation of these two gases was inhibited by air, autoclaving, incubation at 4 and 80°C, and by the methanogenic inhibitor, 2-bromoethanesulfonic acid. Ethane production was stimulated by addition of ethylthioethanesulfonic acid, and production from ethylthioethanesulfonic acid was blocked by 2-bromoethanesulfonic acid. A highly purified enrichment culture of a methanogenic bacterium obtained from sediments produced traces of ethane from ethylthioethanesulfonic acid. These results indicate that the small quantities of ethane found in anaerobic sediments can be formed by certain methanogenic bacteria.

  1. Selective dehydrogenation of propane over novel catalytic materials

    SciTech Connect

    Sault, A.G.; Boespflug, E.P.; Martino, A.; Kawola, J.S.

    1998-02-01

    The conversion of small alkanes into alkenes represents an important chemical processing area; ethylene and propylene are the two most important organic chemicals manufactured in the U.S. These chemicals are currently manufactured by steam cracking of ethane and propane, an extremely energy intensive, nonselective process. The development of catalytic technologies (e.g., selective dehydrogenation) that can be used to produce ethylene and propylene from ethane and propane with greater selectivity and lower energy consumption than steam cracking will have a major impact on the chemical processing industry. This report details a study of two novel catalytic materials for the selective dehydrogenation of propane: Cr supported on hydrous titanium oxide ion-exchangers, and Pt nanoparticles encapsulated in silica and alumina aerogel and xerogel matrices.

  2. A two-state computational investigation of methane C--H and ethane C--C oxidative addition to [CpM(PH3)]n+ (M = Co, Rh, Ir; n = 0, 1).

    PubMed

    Petit, Alban; Richard, Philippe; Cacelli, Ivo; Poli, Rinaldo

    2006-01-11

    Reductive elimination of methane from methyl hydride half-sandwich phosphane complexes of the Group 9 metals has been investigated by DFT calculations on the model system [CpM(PH(3))(CH(3))(H)] (M = Co, Rh, Ir). For each metal, the unsaturated product has a triplet ground state; thus, spin crossover occurs during the reaction. All relevant stationary points on the two potential energy surfaces (PES) and the minimum energy crossing point (MECP) were optimized. Spin crossover occurs very near the sigma-CH(4) complex local minimum for the Co system, whereas the heavier Rh and Ir systems remain in the singlet state until the CH(4) molecule is almost completely expelled from the metal coordination sphere. No local sigma-CH(4) minimum was found for the Ir system. The energetic profiles agree with the nonexistence of the Co(III) methyl hydride complex and with the greater thermal stability of the Ir complex relative to the Rh complex. Reductive elimination of methane from the related oxidized complexes [CpM(PH(3))(CH(3))(H)](+) (M = Rh, Ir) proceeds entirely on the spin doublet PES, because the 15-electron [CpM(PH(3))](+) products have a doublet ground state. This process is thermodynamically favored by about 25 kcal mol(-1) relative to the corresponding neutral system. It is essentially barrierless for the Rh system and has a relatively small barrier (ca. 7.5 kcal mol(-1)) for the Ir system. In both cases, the reaction involves a sigma-CH(4) intermediate. Reductive elimination of ethane from [CpM(PH(3))(CH(3))(2)](+) (M = Rh, Ir) shows a similar thermodynamic profile, but is kinetically quite different from methane elimination from [CpM(PH(3))(CH(3))(H)](+): the reductive elimination barrier is much greater and does not involve a sigma-complex intermediate. The large difference in the calculated activation barriers (ca. 12.0 and ca. 30.5 kcal mol(-1) for the Rh and Ir systems, respectively) agrees with the experimental observation, for related systems, of oxidatively

  3. 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.

  4. Evaluation of methyl fluoride and dimethyl ether as inhibitors of aerobic methane oxidation

    USGS Publications Warehouse

    Oremland, R.S.; Culbertson, C.W.

    1992-01-01

    Methyl fluoride (MF) and dimethyl ether (DME) were effective inhibitors of aerobic methanotrophy in a variety of soils. MF and DME blocked consumption of CH4 as well as the oxidation of 14CH4 to 14CO2, but neither MF nor DME affected the oxidation of [14C]methanol or [14C]formate to 14CO2. Cooxidation of ethane and propane by methane-oxidizing soils was also inhibited by MF. Nitrification (ammonia oxidation) in soils was inhibited by both MF and DME. Production of N2O via nitrification was inhibited by MF; however, MF did not affect N2O production associated with denitrification. Methanogenesis was partially inhibited by MF but not by DME. Methane oxidation was ~100-fold more sensitive to MF than was methanogenesis, indicating that an optimum concentration could be employed to selectively block methanotrophy. MF inhibited methane oxidation by cell suspensions of Methylococcus capsulatus; however, DME was a much less effective inhibitor.

  5. Methane, Ethane, And Ethylene Laminar Counterflow Diffusion Flames At Elevated Pressures: Experimental And Computational Investigations Up To 2.0MPa

    DTIC Science & Technology

    2013-08-27

    predicted computationally by Sohn and Chung [2]. In addition, Figura and Gomez [ 3 ] successfully stabi- lized non-premixed methane flames at elevated... Figura and Gomez [ 3 ]. As indicated by the previously stated values of the stoichiome- tric mixture fractions, the peak temperatures are expected to lie on...Niemann, K. Seshadri, F. Williams, Proc. Combust. Inst. 34 (2013) 881–886. [2] C.H. Sohn, S.H. Chung, Combust. Flame 121 (2000) 288–300. [ 3 ] L. Figura , A

  6. An atmospheric history of ethane from South Pole firn air

    NASA Astrophysics Data System (ADS)

    Verhulst, K. R.; Aydin, K. M.; Lang, P.; Saltzman, E. S.

    2009-12-01

    Ethane (C2H6) is the most abundant non-methane hydrocarbon in the atmosphere and is important to tropospheric photochemistry. Sources of ethane include natural gas and oil leaks, automotive emissions and biomass burning, with smaller contributions from oceanic, vegetative, and soil emissions. The primary loss pathway for ethane is via reaction with hydroxyl radical, which controls ethane seasonality and lifetime (1-2 months during summer). There is a relatively limited database of atmospheric ethane measurements, which is insufficient to characterize long-term trends in the sources and sinks of this compound or to determine anthropogenic influence on the ethane budget. In this study, an atmospheric history of ethane over the past century is reconstructed from South Pole firn air measurements, in conjunction with a 1-D firn air diffusion model. Eighty firn air samples were collected in glass flasks from two adjacent holes drilled to 118 m at South Pole, Antarctica during the 2008/2009 season. The flasks were shipped back and analyzed by high resolution GC/MS at UCI. Firn air dating was based on the measured CO2 profile and known atmospheric history of CO2. Ethane levels in the firn increased from about 132 ppt in the deepest sample, to 259 ppt at 106 m, then decreased to 230 ppt at 30 m. Dating based on mean CO2 ages indicates that the ethane levels over Antarctica roughly doubled (from 130 to 260 ppt) between 1930 and the 1980’s. Over this time period, ethane increased at a rate of about 0.7 ppt yr-1 from 1930-1950 and 3.2 ppt yr-1 from 1950-1987. Ethane levels stabilized during the 1980’s and declined by approximately 1.8 ppt yr-1 from 1988-2004. Surface air measurements from several high latitude southern hemisphere sites indicate that the modern mean atmospheric ethane level is approximately 200 ppt.

  7. Bis[1-meth­oxy-2,2,2-tris­(pyrazol-1-yl-κN 2)ethane]­nickel(II) bis­(tri­fluoro­methane­sulfonate) dihydrate

    PubMed Central

    Lyubartseva, Ganna; Parkin, Sean; Mallik, Uma Prasad

    2013-01-01

    In the title salt, [Ni(C12H14N6O)2](CF3SO3)2·2H2O, the NiII cation is located on an inversion centre and is coordinated by six N atoms from two tridentate 1-meth­oxy-2,2,2-tris­(pyrazol-1-yl)ethane ligands in a distorted octa­hedral geometry. The Ni—N distances range from 2.0594 (12) to 2.0664 (12) Å, intra-ligand N—Ni—N angles range from 84.59 (5) to 86.06 (5)°, and adjacent inter-ligand N—Ni—N angles range between 93.94 (5) and 95.41 (5)°. In the crystal, inversion-related pyrazole rings are π–π stacked, with an inter­planar spacing of 3.4494 (18) Å, forming chains that propagate parallel to the a-axis direction. Inter­molecular O—H⋯O hydrogen bonds are present between water mol­ecules and tri­fluoro­methane­sulfonate anions. PMID:24098167

  8. Bis[1-meth­oxy-2,2,2-tris­(pyrazol-1-yl-κN 2)ethane]­nickel(II) bis­(tri­fluoro­methane­sulfonate) methanol disolvate

    PubMed Central

    Lyubartseva, Ganna; Parkin, Sean; Mallik, Uma Prasad

    2013-01-01

    In the title salt, [Ni(C12H14N6O)2](CF3SO3)2·2CH3OH, the NiII ion is coordinated by six N atoms from two tridentate 1-meth­oxy-2,2,2-tris­(pyrazol-1-yl)ethane ligands in a distorted octa­hedral geometry. The NiII ion is situated on an inversion centre. The Ni—N distances range from 2.0589 (19) to 2.0757 (19) Å, intra-ligand N—Ni—N angles range from 84.50 (8) to 85.15 (8)°, and adjacent inter-ligand N—Ni—N angles range between 94.85 (8) and 95.50 (8)°. In the crystal, O—H⋯O hydrogen bonds between methanol solvent mol­ecules and tri­fluoro­methane­sulfonate anions are observed. PMID:24098170

  9. Bis[1-meth-oxy-2,2,2-tris-(pyrazol-1-yl-κN (2))ethane]-nickel(II) bis-(tri-fluoro-methane-sulfonate) methanol disolvate.

    PubMed

    Lyubartseva, Ganna; Parkin, Sean; Mallik, Uma Prasad

    2013-01-01

    In the title salt, [Ni(C12H14N6O)2](CF3SO3)2·2CH3OH, the Ni(II) ion is coordinated by six N atoms from two tridentate 1-meth-oxy-2,2,2-tris-(pyrazol-1-yl)ethane ligands in a distorted octa-hedral geometry. The Ni(II) ion is situated on an inversion centre. The Ni-N distances range from 2.0589 (19) to 2.0757 (19) Å, intra-ligand N-Ni-N angles range from 84.50 (8) to 85.15 (8)°, and adjacent inter-ligand N-Ni-N angles range between 94.85 (8) and 95.50 (8)°. In the crystal, O-H⋯O hydrogen bonds between methanol solvent mol-ecules and tri-fluoro-methane-sulfonate anions are observed.

  10. Detection of (C-13)-ethane in Jupiter's atmosphere

    NASA Technical Reports Server (NTRS)

    Wiedemann, Guenter; Bjoraker, Gordon L.; Jennings, Donald E.

    1991-01-01

    High-resolution (C-12)- and (C-13)-ethane spectra of Jupiter were acquired with the Kitt Peak 4 m Fourier spectrometer and the Goddard postdisperser in June 1987. A relative abundance ratio (C-12/C-13) of 94 +/- 12 was derived from the measurements. This nearly terrestrial value indicates little or no fractionation of carbon isotopes when ethane is produced in the photolysis of methane in Jupiter's atmosphere.

  11. Interannual Variability and Trends of C2-C11 Non-Methane Hydrocarbons in a Subtropical Area close to the Gulf of Mexico

    NASA Astrophysics Data System (ADS)

    Rappenglück, Bernhard

    2016-04-01

    Speciated C2-C11 non-methane hydrocarbons (NMHC) have been measured online on an hourly basis at Lake Jackson/TX close to the Gulf of Mexico. Altogether 48 NMHCs, including the GAW NMHC compounds, along with NO, NO2, NOx, O3 have been collected continuously from January 2004-December 2013 under the auspices of the Texas Commission on Environmental Quality. Data was screened for background conditions representing marine wind sectors. The data set represents a combination of marine air masses mixed with local biogenic emissions. The data analysis addresses photochemical processing of air masses as reflected in the relationship of ln(n-butane/ethane) vs. ln(propane/ethane) and ln(i-butane/ethane) vs. ln(n-butane/ethane). In addition, key NMHC relationships for radical chemistry, e.g. i-butane vs n-butane for OH and Cl chemistry and i-pentane vs. n-pentane for NO3 chemistry, are discussed. Seasonal analysis revealed a clear trend with maximum NMHC mixing ratios in winter time and lowest mixing ratios in summer reflecting the impact of photochemical processes in summer. Propene equivalents were highest during summertime, with significant contributions from alkenes, including isoprene. The relation of propane/ethane vs ethane indicates seasonal variation with lowest values (i.e. most aged air masses) in winter. Contrary to usual GAW NMHC sampling procedures, which at least requires routine daytime samples (e.g. for canister samplings), continuous NMHC data collection allows to analyze nighttime data, which is least impacted by photochemical processes and potentially well-suited for trend analysis. Corresponding trend analysis for the Lake Jackson data suggests an overall slight decrease of selected NMHCs over the 2004-2013 period.

  12. Supercritical extraction of lycopene from tomato industrial wastes with ethane.

    PubMed

    Nobre, Beatriz P; Gouveia, Luisa; Matos, Patricia G S; Cristino, Ana F; Palavra, António F; Mendes, Rui L

    2012-07-11

    Supercritical fluid extraction of all-E-lycopene from tomato industrial wastes (mixture of skins and seeds) was carried out in a semi-continuous flow apparatus using ethane as supercritical solvent. The effect of pressure, temperature, feed particle size, solvent superficial velocity and matrix initial composition was evaluated. Moreover, the yield of the extraction was compared with that obtained with other supercritical solvents (supercritical CO₂ and a near critical mixture of ethane and propane). The recovery of all-E-lycopene increased with pressure, decreased with the increase of the particle size in the initial stages of the extraction and was not practically affected by the solvent superficial velocity. The effect of the temperature was more complex. When the temperature increased from 40 to 60 °C the recovery of all-E-lycopene increased from 80 to 90%. However, for a further increase to 80 °C, the recovery remained almost the same, indicating that some E-Z isomerization could have occurred, as well as some degradation of lycopene. The recovery of all-E-lycopene was almost the same for feed samples with different all-E-lycopene content. Furthermore, when a batch with a higher all-E-lycopene content was used, supercritical ethane and a near critical mixture of ethane and propane showed to be better solvents than supercritical CO₂ leading to a faster extraction with a higher recovery of the carotenoid.

  13. Macroseepage of Methane and Light Alkanes at the La Brea Tar Pits in Los Angeles

    NASA Astrophysics Data System (ADS)

    Doezema, L. A.; Weber, D.; Schuffels, S.; Marquez, A.; Taylor, C.; Raya, P.; Howard, D.; Contreras, P.; Fusco, K.; Morales, F.; Nwachuku, I.

    2015-12-01

    Natural seepage of methane has been theorized to be an underreported source of global methane. Recent studies have also suggested that light alkane flux that is given off in combination with the methane also is underreported in local and global budgets. This study investigated macroseepage, visible seepage, at the La Brea Tar Pits in Los Angeles, CA. More than 100 samples were collected from individual seeps using stainless steel flux chambers and canisters and were analyzed for methane and C2-C5 alkanes using gas chromatography equipped with flame ionization detectors (GC-FID). Maximum hourly fluxes from individual seeps were over 70 g of methane and over 720 mg, 670 mg, 200 mg, 20 mg, 14 mg, and 0.2 mg for ethane, propane, i-butane, n-butane, i-pentane, and n-pentane respectively. In addition to the active seepage sites, a significant amount of methane and light alkanes was also found to come from outgassing from standing tar deposits. Using gas ratios found in this study along with overall methane emission estimates from another recent study, the La Brea Tar Pits were found to be a significant source of light alkanes in the South Coast Air Basin, contributing approximately 2% towards the overall budget.

  14. Titan's carbon budget and the case of the missing ethane.

    PubMed

    Wilson, Eric H; Atreya, Sushil K

    2009-10-22

    The retrieval of data from the Cassini-Huygens mission has revealed much about Titan's atmospheric-surface system and has precipitated more questions. One of these questions involves the lack of large reservoirs of ethane that were predicted by a variety of studies prior to the arrival of the Cassini-Huygens spacecraft. Using an updated and comprehensive photochemical model, we examine the nature of Titan's carbon budget, initiated by the destruction of methane, and the role that ethane condensation plays in this budget. Model results show that 40% of methane destruction results in ethane formation, with a net production rate of 2.7 x 10(9) molecules cm(-2) s(-1), due primarily to acetylenic catalysis in Titan's stratosphere. This corresponds to a liquid ethane layer of several hundred meters over geologic time. However, episodic methane outgassing, subsurface sequestration, and chemical processing of Titan's surface are likely responsible for the limiting of ethane condensate on Titan's surface to less than 10 m globally averaged.

  15. Stability of methane in reduced C-O-H fluid at 6.3 GPa and 1300-1400°C

    NASA Astrophysics Data System (ADS)

    Sokol, A. G.; Tomilenko, A. A.; Bul'bak, T. A.; Palyanova, G. A.; Palyanov, Yu. N.; Sobolev, N. V.

    2017-06-01

    The composition of a reduced C-O-H fluid was studied by the method of chromatography-mass spectrometry under the conditions of 6.3 GPa, 1300-1400°C, and fO2 typical of the base of the subcratonic lithosphere. Fluids containing water (4.4-96.3 rel. %), methane (37.6-0.06 rel. %), and variable concentrations of ethane, propane, and butane were obtained in experiments. With increasing fO2, the proportion of the CH4/C2H6 peak areas on chromatograms first increases and then decreases, whereas the CH4/C3H8 and CH4/C4H10 ratios continually decrease. The new data show that ethane and heavier HCs may be more stable to oxidation, than previously thought. Therefore, when reduced fluids pass the "redox-front," carbon is not completely released from the fluid and may be involved in diamond formation.

  16. Titan's missing ethane: From the atmosphere to the subsurface

    NASA Astrophysics Data System (ADS)

    Gilliam, Ashley E.; Lerman, Abraham

    2016-09-01

    The second most abundant component of the present-day Titan atmosphere, methane (CH4), is known to undergo photolytic conversion to ethane (C2H6) that accumulates as a liquid on Titan's surface. Condensation temperature of ethane is higher than that of methane, so that ethane "rain" may be expected to occur before the liquefaction of methane. At present, the partial pressure of ethane in the atmosphere is 1E-5 bar, much lower than 1E-1 bar of CH4. Estimated 8.46E17 kg or 1.37E6 km3 of C2H6 have been produced on Titan since accretion. The Titan surface reservoirs of ethane are lakes and craters, of estimated volume of 50,000 km3 and 61,000 km3, respectively. As these are smaller than the total volume of liquid ethane produced in the course of Titan's history, the excess may be stored in the subsurface of the crust, made primarily of water ice. The minimum porosity of the crust needed to accommodate all the liquid ethane would be only 0.9% of the uppermost 2 km of the crust. The occurrence of CH4 and liquid C2H6 on Titan has led to much speculation on the possibility of life on that satellite. The aggregation of organic molecules in a "primordial soup or bullion" depends in part on the viscosity of the medium, diffusivity of organic molecules in it, and rates of polymerization reactions. The temperatures on Titan, much lower than on primordial Earth, are less favorable to the "Second Coming of life" on Titan.

  17. Stratospheric ethane on Neptune - Comparison of groundbased and Voyager IRIS retrievals

    NASA Technical Reports Server (NTRS)

    Kostiuk, Theodor; Romani, Paul; Espenak, Fred; Bezard, Bruno

    1992-01-01

    Near-simultaneous ground and spacecraft measurements of 12-micron ethane emission spectra during the Voyager encounter with Neptune have furnished bases for the determination of stratospheric ethane abundance and the testing and constraining of Neptune methane-photochemistry models. The ethane retrievals were sensitive to the thermal profile used. Contribution functions for warm thermal profiles peaked at higher altitudes, as expected, with the heterodyne functions covering lower-pressure regions. Both constant- and nonconstant-with-height profiles remain candidate distributions for Neptune's stratospheric ethane.

  18. Direct measurements of methane emissions from abandoned oil and gas wells in Pennsylvania

    PubMed Central

    Kang, Mary; Kanno, Cynthia M.; Reid, Matthew C.; Zhang, Xin; Mauzerall, Denise L.; Celia, Michael A.; Chen, Yuheng; Onstott, Tullis C.

    2014-01-01

    Abandoned oil and gas wells provide a potential pathway for subsurface migration and emissions of methane and other fluids to the atmosphere. Little is known about methane fluxes from the millions of abandoned wells that exist in the United States. Here, we report direct measurements of methane fluxes from abandoned oil and gas wells in Pennsylvania, using static flux chambers. A total of 42 and 52 direct measurements were made at wells and at locations near the wells (“controls”) in forested, wetland, grassland, and river areas in July, August, October 2013 and January 2014, respectively. The mean methane flow rates at these well locations were 0.27 kg/d/well, and the mean methane flow rate at the control locations was 4.5 × 10−6 kg/d/location. Three out of the 19 measured wells were high emitters that had methane flow rates that were three orders of magnitude larger than the median flow rate of 1.3 × 10−3 kg/d/well. Assuming the mean flow rate found here is representative of all abandoned wells in Pennsylvania, we scaled the methane emissions to be 4–7% of estimated total anthropogenic methane emissions in Pennsylvania. The presence of ethane, propane, and n-butane, along with the methane isotopic composition, indicate that the emitted methane is predominantly of thermogenic origin. These measurements show that methane emissions from abandoned oil and gas wells can be significant. The research required to quantify these emissions nationally should be undertaken so they can be accurately described and included in greenhouse gas emissions inventories. PMID:25489074

  19. Direct measurements of methane emissions from abandoned oil and gas wells in Pennsylvania.

    PubMed

    Kang, Mary; Kanno, Cynthia M; Reid, Matthew C; Zhang, Xin; Mauzerall, Denise L; Celia, Michael A; Chen, Yuheng; Onstott, Tullis C

    2014-12-23

    Abandoned oil and gas wells provide a potential pathway for subsurface migration and emissions of methane and other fluids to the atmosphere. Little is known about methane fluxes from the millions of abandoned wells that exist in the United States. Here, we report direct measurements of methane fluxes from abandoned oil and gas wells in Pennsylvania, using static flux chambers. A total of 42 and 52 direct measurements were made at wells and at locations near the wells ("controls") in forested, wetland, grassland, and river areas in July, August, October 2013 and January 2014, respectively. The mean methane flow rates at these well locations were 0.27 kg/d/well, and the mean methane flow rate at the control locations was 4.5 × 10(-6) kg/d/location. Three out of the 19 measured wells were high emitters that had methane flow rates that were three orders of magnitude larger than the median flow rate of 1.3 × 10(-3) kg/d/well. Assuming the mean flow rate found here is representative of all abandoned wells in Pennsylvania, we scaled the methane emissions to be 4-7% of estimated total anthropogenic methane emissions in Pennsylvania. The presence of ethane, propane, and n-butane, along with the methane isotopic composition, indicate that the emitted methane is predominantly of thermogenic origin. These measurements show that methane emissions from abandoned oil and gas wells can be significant. The research required to quantify these emissions nationally should be undertaken so they can be accurately described and included in greenhouse gas emissions inventories.

  20. Propane Vehicle Demonstration Grant Program

    SciTech Connect

    Jack Mallinger

    2004-08-27

    Project Description: Propane Vehicle Demonstration Grants The Propane Vehicle Demonstration Grants was established to demonstrate the benefits of new propane equipment. The US Department of Energy, the Propane Education & Research Council (PERC) and the Propane Vehicle Council (PVC) partnered in this program. The project impacted ten different states, 179 vehicles, and 15 new propane fueling facilities. Based on estimates provided, this project generated a minimum of 1,441,000 new gallons of propane sold for the vehicle market annually. Additionally, two new off-road engines were brought to the market. Projects originally funded under this project were the City of Portland, Colorado, Kansas City, Impco Technologies, Jasper Engines, Maricopa County, New Jersey State, Port of Houston, Salt Lake City Newspaper, Suburban Propane, Mutual Liquid Propane and Ted Johnson.

  1. 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.

  2. Methane and propane micro-inclusions in olivine in titanoclinohumite-bearing dunites from the Sanbagawa high-P metamorphic belt, Japan: Hydrocarbon activity in a subduction zone and Ti mobility

    NASA Astrophysics Data System (ADS)

    Arai, Shoji; Ishimaru, Satoko; Mizukami, Tomoyuki

    2012-11-01

    Micro-inclusions of methane and propane were examined in olivine and titanoclinohumite in dunite from Fujiwara, Sanbagawa high-P/T metamorphic belt, Japan, in order to understand the behavior of hydrocarbons in the subduction zone and mantle wedge. In the Fujiwara dunite, olivines coexist with magnetite and exhibit a wide range of chemical compositions (Fo88-96 and 0.2-0.6 wt% NiO), possibly indicating a deserpentinization origin for the dunite. The primary chromian spinel shows an intermediate Cr/(Cr+Al) atomic ratio, 0.5-0.6, and 1-3 wt% TiO2, and are enclosed by its alteration phases (ferritechromite and magnetite) that contain less than 0.8 wt% TiO2. Titanoclinohumite is frequently accompanied with the altered spinels, suggesting its Ti was provided by spinel alteration. Thin (<1 cm) titanoclinohumite veinlets are commonly found, indicating Ti was mobile during the metamorphic formation of the Fujiwara meta-dunite. Hydrocarbons are usually associated with serpentine and brucite, almost free of magnetite, in individual micro-inclusions, suggesting initial entrapment of hydrocarbon-rich aqueous fluids and subsequent reaction only between their water component and the wall olivine. The primary dunite of Fujiwara, originally formed as a cumulate from intra-plate magma, and was serpentinized and brecciated to contain carbonaceous matter in the matrix part before incorporation in the subduction zone. The hydrocarbons possibly formed with maturation of the carbonaceous matter in the process of subduction. The continuously formed hydrocarbons mobilized Ti from chromian spinel to leave low-Ti ferritechromite and magnetite in the Fujiwara dunite, and finally stabilized as titanoclinohumite and other Ti-rich minerals during deserpentinization at high pressures. The titanoclinohumite veinlet formation suggests the Ti mobility, although in a short distance in this specific case. Ti is possibly mobile within the mantle wedge if hydrocarbons are available from the slab, but

  3. Low-Latitude Ethane Rain on Titan

    NASA Technical Reports Server (NTRS)

    Dalba, Paul A.; Buratti, Bonnie J.; Brown, R. H.; Barnes, J. W.; Baines, K. H.; Sotin, C.; Clark, R. N.; Lawrence, K. J.; Nicholson, P. D.

    2012-01-01

    Cassini ISS observed multiple widespread changes in surface brightness in Titan's equatorial regions over the past three years. These brightness variations are attributed to rainfall from cloud systems that appear to form seasonally. Determining the composition of this rainfall is an important step in understanding the "methanological" cycle on Titan. I use data from Cassini VIMS to complete a spectroscopic investigation of multiple rain-wetted areas. I compute "before-and-after" spectral ratios of any areas that show either deposition or evaporation of rain. By comparing these spectral ratios to a model of liquid ethane, I find that the rain is most likely composed of liquid ethane. The spectrum of liquid ethane contains multiple absorption features that fall within the 2-micron and 5-micron spectral windows in Titan's atmosphere. I show that these features are visible in the spectra taken of Titan's surface and that they are characteristically different than those in the spectrum of liquid methane. Furthermore, just as ISS saw the surface brightness reverting to its original state after a period of time, I show that VIMS observations of later flybys show the surface composition in different stages of returning to its initial form.

  4. Low-Latitude Ethane Rain on Titan

    NASA Technical Reports Server (NTRS)

    Dalba, Paul A.; Buratti, Bonnie J.; Brown, R. H.; Barnes, J. W.; Baines, K. H.; Sotin, C.; Clark, R. N.; Lawrence, K. J.; Nicholson, P. D.

    2012-01-01

    Cassini ISS observed multiple widespread changes in surface brightness in Titan's equatorial regions over the past three years. These brightness variations are attributed to rainfall from cloud systems that appear to form seasonally. Determining the composition of this rainfall is an important step in understanding the "methanological" cycle on Titan. I use data from Cassini VIMS to complete a spectroscopic investigation of multiple rain-wetted areas. I compute "before-and-after" spectral ratios of any areas that show either deposition or evaporation of rain. By comparing these spectral ratios to a model of liquid ethane, I find that the rain is most likely composed of liquid ethane. The spectrum of liquid ethane contains multiple absorption features that fall within the 2-micron and 5-micron spectral windows in Titan's atmosphere. I show that these features are visible in the spectra taken of Titan's surface and that they are characteristically different than those in the spectrum of liquid methane. Furthermore, just as ISS saw the surface brightness reverting to its original state after a period of time, I show that VIMS observations of later flybys show the surface composition in different stages of returning to its initial form.

  5. First observations of light non-methane hydrocarbons (C2-C5) over a high altitude site in the central Himalayas

    NASA Astrophysics Data System (ADS)

    Sarangi, Tapaswini; Naja, Manish; Lal, S.; Venkataramani, S.; Bhardwaj, Piyush; Ojha, N.; Kumar, R.; Chandola, H. C.

    2016-01-01

    This study presents observations of methane (CH4) and light non-methane hydrocarbons (NMHCs) for the first time from a high altitude site Nainital (29.4°N, 79.5°E, 1958 m amsl) in the central Himalayas. The whole air samples collected with a frequency of 3 samples per week during April 2009-December 2011 are analyzed using a Gas Chromatograph equipped with Flame Ionization Detector (GC-FID). Additionally, samples were collected from two semi-urban sites (Haldwani and Pantnagar) in the adjoining Indo Gangetic plain region. CH4 and NMHCs show a distinct seasonal cycle over this region with more frequent observations of higher levels during winter (DJF) and late autumn (SON) and lower levels during the summer-monsoon (JJA). Different NMHCs exhibit better correlations during autumn/winter as compared to the summer-monsoon season. The annual mean mixing ratios of methane, ethane, ethene, propane, propene, i-butane, n-butane, acetylene, and i-pentane at Nainital are measured to be 1.9 ± 0.1 ppmv, 1.8 ± 1.0, 0.7 ± 0.9, 0.6 ± 0.8, 0.6 ± 0.7, 0.6 ± 0.7, 0.5 ± 0.6, 1.0 ± 0.8, and 0.5 ± 0.6, respectively (all in ppbv). The seasonal cycle of CH4 at Nainital is found to be similar to other global high altitude sites (Jungfraujoch and Mauna Loa) but somewhat different than a high altitude site Mt. Abu in India. NMHCs, other than ethane and propane, are found to be higher over this central Himalayan region than other sites. Additionally, composition of NMHCs is shown to be different over the study region when compared with other sites in the IGP region. A correlation study between ln((n-butane)/(ethane)) and ln((i-butane)/(ethane)) showed that oxidation by the OH radical is the main removal mechanism of these species over the central Himalaya and dilution maintains the ratios of these species. The lowest slope of propane and acetylene with CO during summer and spring are indicating absence of fresh air mass over this region. This study fills a major gap in

  6. Occurrence and origin of methane in groundwater in Alberta (Canada): Gas geochemical and isotopic approaches.

    PubMed

    Humez, P; Mayer, B; Ing, J; Nightingale, M; Becker, V; Kingston, A; Akbilgic, O; Taylor, S

    2016-01-15

    To assess potential future impacts on shallow aquifers by leakage of natural gas from unconventional energy resource development it is essential to establish a reliable baseline. Occurrence of methane in shallow groundwater in Alberta between 2006 and 2014 was assessed and was ubiquitous in 186 sampled monitoring wells. Free and dissolved gas sampling and measurement approaches yielded comparable results with low methane concentrations in shallow groundwater, but in 28 samples from 21 wells methane exceeded 10mg/L in dissolved gas and 300,000 ppmv in free gas. Methane concentrations in free and dissolved gas samples were found to increase with well depth and were especially elevated in groundwater obtained from aquifers containing coal seams and shale units. Carbon isotope ratios of methane averaged -69.7 ± 11.1‰ (n=63) in free gas and -65.6 ± 8.9‰ (n=26) in dissolved gas. δ(13)C values were not found to vary with well depth or lithology indicating that methane in Alberta groundwater was derived from a similar source. The low δ(13)C values in concert with average δ(2)HCH4 values of -289 ± 44‰ (n=45) suggest that most methane was of biogenic origin predominantly generated via CO2 reduction. This interpretation is confirmed by dryness parameters typically >500 due to only small amounts of ethane and a lack of propane in most samples. Comparison with mud gas profile carbon isotope data revealed that methane in the investigated shallow groundwater in Alberta is isotopically similar to hydrocarbon gases found in 100-250 meter depths in the WCSB and is currently not sourced from thermogenic hydrocarbon occurrences in deeper portions of the basin. The chemical and isotopic data for methane gas samples obtained from Alberta groundwater provide an excellent baseline against which potential future impact of deeper stray gases on shallow aquifers can be assessed.

  7. Quantification of Methane Leaks from Abandoned Oil and Gas Wells in California

    NASA Astrophysics Data System (ADS)

    Lebel, E.; Kang, M.; Lu, H.; Jackson, R. B.

    2016-12-01

    Abandoned oil and gas wells can provide a pathway for subterranean methane and other gases to be emitted to the atmosphere. However, abandoned wells are unaccounted for in greenhouse gas emissions inventories. While relatively little is known about abandoned wells, previous studies have shown that emissions from abandoned wells contribute approximately 4-7% of anthropogenic methane emissions in Pennsylvania (Kang et al. 2014) and <1% of regional methane emissions in oil and gas producing regions of Colorado, Utah, Ohio, and Wyoming (Townsend-Small et al. 2015). Another study (Boothroyd et al. 2016) has shown that 30% of abandoned wells in the UK have a positive surface methane flux. California has a long history of oil and gas production, beginning from the 1860s, and currently ranks third in oil production by state. As a result, there are more than 100,000 wells across the state. Our study uses static flux chambers to measure individual abandoned wells in California to estimate state-wide methane emissions from these wells. In addition to measuring methane concentrations, we measure ethane, propane, isobutane, n-butane, and 13-CH4 to understand whether this methane has a biogenic or thermogenic source. We hope that our research will determine whether or not abandoned oil and gas wells are a significant source of anthropogenic methane emissions in California. Our results along with measurements in other parts of the United States can be used to scale up methane emission estimates to the national level, accounting for the millions of abandoned wells in the country.

  8. Characteristics of atmospheric non-methane hydrocarbons during high PM 10 episodes and normal days in Foshan, China

    NASA Astrophysics Data System (ADS)

    Guo, Songjun; Tan, Jihua; Ma, Yongliang; Yang, Fumo; Yu, Yongchan; Wang, Jiewen

    2011-08-01

    Atmospheric non-methane hydrocarbons (NMHCs) were firstly studied during high PM 10 episodes and normal days in December 2008 in Foshan, China. Ethyne, ethene, i-pentane, toluene, ethane and propane are six abundant hydrocarbons, accounting for round 80% of total NMHCs. Both diurnal variations and concentration ratios of morning (evening)/afternoon implied vehicular emission for most hydrocarbons. Correlation coefficients (R 2) of ethene, propene, i-butene, benzene, toluene and i-/n-butanes with ethyne were 0.60-0.88 (they were 0.64-0.88 during high PM 10 episode and 0.60-0.85 in normal days) except for ethene and i-butene in normal days, indicating these hydrocarbons are mainly related to vehicular emission. It suggests liquefied petroleum gas (LPG) and natural gas (NG) leakages are responsible for propane and ethane, respectively. The measured mean benzene/toluene (B/T) ratio (wt/wt) was 0.45 ± 0.29 during total sampling periods together with R 2 analysis, again indicating vehicular emission is main contributor to ambient hydrocarbons. And the lower B/T ratio (0.29 ± 0.11) during high PM 10 episodes than that (0.75 ± 0.29) in normal days is likely caused by air transport containing low B/T value (0.23) from Guangzhou as well as solvent application containing toluene in Foshan.

  9. Geodetic data support trapping of ethane in Titan's polar crust

    NASA Astrophysics Data System (ADS)

    Sotin, Christophe; Rambaux, Nicolas

    2016-04-01

    Titan's surface is characterized by polar depressions that strongly influence interpretations of the gravity data. This study investigates several geodynamical models that can explain these depressions. For each model, the values of the three moments of inertia are computed numerically by discretizing the interior in spherical coordinates. The study shows that a Pratt model where the polar subsurface is made of ethane clathrates can explain the polar depression, the abrupt jump in altitude at about 60 degrees latitude, and the values of the degree 2 gravity coefficients. This model, proposed by Choukroun and Sotin [1], is based on the stability of ethane clathrate hydrates relative to methane clathrate hydrates. In addition to fitting the geodetic data, it explains the absence of ethane in Titan's atmosphere although ethane is the main product of the photolysis of methane. Other geophysical models based on latitudinal variations in the tidal heating production or in the heat flux at the base of the icy crust do not provide such a good match to the gravity and topographic observations. The ethane-clathrate model predicts that all the ethane produced by photolysis of methane at the present rate during the last billion years could be stored in the polar subsurface. It is consistent with the age of Titan's surface and that of Titan's atmospheric methane inferred from geological and geochemical observations by the Cassini/Huygens mission. The present study also emphasizes the role of mass anomalies on the interpretation of the degree 2 gravity coefficients. It shows that for Titan, a slow rotator, the values of the two equatorial moments of inertia (MoI) are largely affected by the polar depressions whereas the value of polar MoI is not. Therefore, as pointed out by previous calculations [2], calculating the moment of inertia (MoI) factor from the value of J2 could lead to major errors. This is not the case for our preferred Titan's model for which the negative polar

  10. Partial oxidation of ethane to oxygenates using Fe- and Cu-containing ZSM-5.

    PubMed

    Forde, Michael M; Armstrong, Robert D; Hammond, Ceri; He, Qian; Jenkins, Robert L; Kondrat, Simon A; Dimitratos, Nikolaos; Lopez-Sanchez, Jose Antonio; Taylor, Stuart H; Willock, David; Kiely, Christopher J; Hutchings, Graham John

    2013-07-31

    Iron and copper containing ZSM-5 catalysts are effective for the partial oxidation of ethane with hydrogen peroxide giving combined oxygenate selectivities and productivities of up to 95.2% and 65 mol kgcat(-1) h(-1), respectively. High conversion of ethane (ca. 56%) to acetic acid (ca. 70% selectivity) can be observed. Detailed studies of this catalytic system reveal a complex reaction network in which the oxidation of ethane gives a range of C2 oxygenates, with sequential C-C bond cleavage generating C1 products. We demonstrate that ethene is also formed and can be subsequently oxidized. Ethanol can be directly produced from ethane, and does not originate from the decomposition of its corresponding alkylperoxy species, ethyl hydroperoxide. In contrast to our previously proposed mechanism for methane oxidation over similar zeolite catalysts, the mechanism of ethane oxidation involves carbon-based radicals, which lead to the high conversions we observe.

  11. Identification and characterization of high methane-emitting abandoned oil and gas wells.

    PubMed

    Kang, Mary; Christian, Shanna; Celia, Michael A; Mauzerall, Denise L; Bill, Markus; Miller, Alana R; Chen, Yuheng; Conrad, Mark E; Darrah, Thomas H; Jackson, Robert B

    2016-11-29

    Recent measurements of methane emissions from abandoned oil/gas wells show that these wells can be a substantial source of methane to the atmosphere, particularly from a small proportion of high-emitting wells. However, identifying high emitters remains a challenge. We couple 163 well measurements of methane flow rates; ethane, propane, and n-butane concentrations; isotopes of methane; and noble gas concentrations from 88 wells in Pennsylvania with synthesized data from historical documents, field investigations, and state databases. Using our databases, we (i) improve estimates of the number of abandoned wells in Pennsylvania; (ii) characterize key attributes that accompany high emitters, including depth, type, plugging status, and coal area designation; and (iii) estimate attribute-specific and overall methane emissions from abandoned wells. High emitters are best predicted as unplugged gas wells and plugged/vented gas wells in coal areas and appear to be unrelated to the presence of underground natural gas storage areas or unconventional oil/gas production. Repeat measurements over 2 years show that flow rates of high emitters are sustained through time. Our attribute-based methane emission data and our comprehensive estimate of 470,000-750,000 abandoned wells in Pennsylvania result in estimated state-wide emissions of 0.04-0.07 Mt (10(12) g) CH4 per year. This estimate represents 5-8% of annual anthropogenic methane emissions in Pennsylvania. Our methodology combining new field measurements with data mining of previously unavailable well attributes and numbers of wells can be used to improve methane emission estimates and prioritize cost-effective mitigation strategies for Pennsylvania and beyond.

  12. Identification and characterization of high methane-emitting abandoned oil and gas wells

    PubMed Central

    Kang, Mary; Christian, Shanna; Celia, Michael A.; Mauzerall, Denise L.; Bill, Markus; Miller, Alana R.; Chen, Yuheng; Conrad, Mark E.; Darrah, Thomas H.; Jackson, Robert B.

    2016-01-01

    Recent measurements of methane emissions from abandoned oil/gas wells show that these wells can be a substantial source of methane to the atmosphere, particularly from a small proportion of high-emitting wells. However, identifying high emitters remains a challenge. We couple 163 well measurements of methane flow rates; ethane, propane, and n-butane concentrations; isotopes of methane; and noble gas concentrations from 88 wells in Pennsylvania with synthesized data from historical documents, field investigations, and state databases. Using our databases, we (i) improve estimates of the number of abandoned wells in Pennsylvania; (ii) characterize key attributes that accompany high emitters, including depth, type, plugging status, and coal area designation; and (iii) estimate attribute-specific and overall methane emissions from abandoned wells. High emitters are best predicted as unplugged gas wells and plugged/vented gas wells in coal areas and appear to be unrelated to the presence of underground natural gas storage areas or unconventional oil/gas production. Repeat measurements over 2 years show that flow rates of high emitters are sustained through time. Our attribute-based methane emission data and our comprehensive estimate of 470,000–750,000 abandoned wells in Pennsylvania result in estimated state-wide emissions of 0.04–0.07 Mt (1012 g) CH4 per year. This estimate represents 5–8% of annual anthropogenic methane emissions in Pennsylvania. Our methodology combining new field measurements with data mining of previously unavailable well attributes and numbers of wells can be used to improve methane emission estimates and prioritize cost-effective mitigation strategies for Pennsylvania and beyond. PMID:27849603

  13. High-pressure/high-temperature gas-solubility study in hydrogen-phenanthrene and methane-phenanthrene systems using static and chromatographic techniques

    SciTech Connect

    Malone, P.V.

    1987-01-01

    The design and discovery of sources for alternative energy such as coal liquefaction has become of major importance over the past two decades. One of the major problems in such design in the lack of available data, particularly, for gas solubility in polycyclic aromatics at high temperature and pressure. Static and gas-liquid partition chromatographic methods were used for the study of hydrogen-phenanthrene and methane-phenanthrene systems. The static data for these two binaries were taken along 398.2, 423.2, 448.2, and 473.2 K isotherms up to 25.23 MPa. Gas-liquid partition chromatography was used to study the infinite dilution behavior of methane, ethane, propane, n-butane, and carbon dioxide in the hydrogen-phenanthrene system as well as hydrogen, ethane, n-butane, and carbon dioxide in the methane-phenanthrene binary. The principle objective was to examine the role of the elution gas. Temperatures were along the same isotherms as the static data and up to 20.77 MPa. With the exception of carbon dioxide, Henry's constants were calculated for all systems. Expressions for the heat of solution as a function of pressure were derived for both binary and chromatographic data. Estimates of delta H/sub i/sup sol/ at high pressure were presented.

  14. The identification of liquid ethane in Titan's Ontario Lacus

    USGS Publications Warehouse

    Brown, R.H.; Soderblom, L.A.; Soderblom, J.M.; Clark, R.N.; Jaumann, R.; Barnes, J.W.; Sotin, Christophe; Buratti, B.; Baines, K.H.; Nicholson, P.D.

    2008-01-01

    Titan was once thought to have global oceans of light hydrocarbons on its surface, but after 40 close flybys of Titan by the Cassini spacecraft, it has become clear that no such oceans exist. There are, however, features similar to terrestrial lakes and seas, and widespread evidence for fluvial erosion, presumably driven by precipitation of liquid methane from Titan's dense, nitrogen-dominated atmosphere. Here we report infrared spectroscopic data, obtained by the Visual and Infrared Mapping Spectrometer (VIMS) on board the Cassini spacecraft, that strongly indicate that ethane, probably in liquid solution with methane, nitrogen and other low-molecular-mass hydrocarbons, is contained within Titan's Ontario Lacus.

  15. The identification of liquid ethane in Titan's Ontario Lacus.

    PubMed

    Brown, R H; Soderblom, L A; Soderblom, J M; Clark, R N; Jaumann, R; Barnes, J W; Sotin, C; Buratti, B; Baines, K H; Nicholson, P D

    2008-07-31

    Titan was once thought to have global oceans of light hydrocarbons on its surface, but after 40 close flybys of Titan by the Cassini spacecraft, it has become clear that no such oceans exist. There are, however, features similar to terrestrial lakes and seas, and widespread evidence for fluvial erosion, presumably driven by precipitation of liquid methane from Titan's dense, nitrogen-dominated atmosphere. Here we report infrared spectroscopic data, obtained by the Visual and Infrared Mapping Spectrometer (VIMS) on board the Cassini spacecraft, that strongly indicate that ethane, probably in liquid solution with methane, nitrogen and other low-molecular-mass hydrocarbons, is contained within Titan's Ontario Lacus.

  16. Ethane ocean on Titan

    NASA Technical Reports Server (NTRS)

    Lunine, J. I.; Stevenson, D. J.; Yung, Y.L.

    1983-01-01

    Voyager I radio occultation data is employed to develop a qualitative model of an ethane ocean on Titan. It is suggested that the ocean contains 25 percent CH4 and that the ocean is in dynamic equilibrium with an N2 atmosphere. Previous models of a CH4 ocean are discounted due to photolysis rates of CH4 gas. Tidal damping of Titan's orbital eccentricity is taken as evidence for an ocean layer approximately 1 km deep, with the ocean floor being covered with a solid C2H2 layer 100 to 200 m thick. The photolytic process disrupting the CH4, if the estimates of the oceanic content of CH4 are correct, could continue for at least one billion years. Verification of the model is dependent on detecting CH4 clouds in the lower atmosphere, finding C2H6 saturation in the lower troposphere, or obtaining evidence of a global ocean.

  17. Methane Emissions from the Arctic Ocean to the Atmosphere

    NASA Astrophysics Data System (ADS)

    Platt, Stephen; Hermansen, Ova; Schmidbauer, Norbert; Pisso, Ignacio; Silyakova, Anna; Ferré, Benedicte; Lowry, Dave; Percival, Carl; Mienert, Jürgen; Myhre, Cathrine Lund

    2015-04-01

    The release of methane (CH4) presently stored in vast hydrate deposits under the seafloor is a potential climate tipping point and a major uncertainty in the global methane budget. Significant methane hydrate deposits are located in shallow waters in the Arctic where they may destabilise, releasing methane to the atmosphere due to ocean warming. To address this issue the Methane Emissions from Arctic Ocean to Atmosphere (MOCA, http://moca.nilu.no/) project was established in cooperation with the CAGE Centre of Excellence (http:cage.uit.no/). State-of-the-art oceanographic and atmospheric measurement techniques were applied over a large area of the Arctic including northern Norway, the Barents Sea, and areas of shallow water around Svalbard during summer 2014. Oceanographic measurements included the deployment of 63 measurement stations (temperature, salinity, density, oxygen, fluorescence, turbidity, etc.), water column sampling (CH4, nitrate, phosphate, silicates), and echo sounding (revealing locations where streams of gas bubbles are vented). Atmospheric on-line measurements were performed aboard the research vessel Helmer Hanssen (CH4, CO2, CO, meteorological parameters) and during a flight campaign (CH4, etc.). Air samples were collected for isotopic analysis (13C, 2H) and quantification of other hydrocarbons (ethane, propane, etc.). Finally, atmospheric measurements are compared with long term data sets from the nearby Zeppelin Mountain monitoring station (Ny Ålesund, Svalbard). Back-trajectory analysis and FLEXPART modelling are used to rule out non-local sources. Here we present an overview of all of these activities and the first results from MOCA in cooperation with CAGE - Centre for Arctic Gas Hydrate, and Climate at UiT, The Arctic University of Norway. We demonstrate that there are hotspots of activity where hydrocarbons are being emitted from the ocean, while in some areas emissions are surprisingly well contained by local biological and hydrological

  18. Low-Latitude Ethane Rain on Titan

    NASA Astrophysics Data System (ADS)

    Dalba, Paul; Buratti, B. J.; Brown, R. H.; Barnes, J. W.; Baines, K. H.; Sotin, C.; Clark, R. N.; Lawrence, K. J.; Nicholson, P. D.

    2012-10-01

    Cassini ISS observed multiple widespread changes in surface brightness in Titan's equatorial regions over the past three years (Barnes, J. W. et al. 2012, Icarus, submitted). These brightness variations are attributed to rainfall from cloud systems that appear to form seasonally (Turtle, E. P. et al. 2011, Science, 331, 1414-1417). Determining the composition of this rainfall is an important step in understanding the “methanological” cycle that dominates Titan's surface and atmosphere. In this study, we use data from Cassini VIMS to complete a thorough spectroscopic investigation of rain-wetted areas near Yalaing Terra, Hetpet Regio and central Adiri on Titan. We compute “before-and-after” spectral ratios of any areas that show either deposition or evaporation of rain at any point in the time span of August 2009 to January 2012. By comparing these spectral ratios to a model of liquid ethane that was calculated to match the resolution and sampling interval of VIMS (Brown, R. H. et al. 2008, Nature, 454, 607-610), we find that the rain is most likely composed of liquid ethane. The spectrum of liquid ethane contains multiple absorption features that fortunately fall within the 2-micron and 5-micron spectral windows in Titan's atmosphere. We show that these features are visible in the spectra taken of Titan's surface and that they are characteristically different than those in the spectrum of liquid methane. Furthermore, just as ISS saw the surface brightness reverting to its original state after a period of time, we show that VIMS observations of later flybys show the surface composition in different stages of returning to its initial form as well. This research was carried out at the Jet Propulsion Laboratory, California Institute of Technology under contract to the National Aeronautics and Space Administration. Copyright 2012. All rights reserved.

  19. Low-latitude ethane rain on Titan

    NASA Astrophysics Data System (ADS)

    Dalba, P. A.; Buratti, B. J.; Brown, R. H.; Barnes, J. W.; Baines, K. H.; Sotin, C.; Clark, R. N.; Lawrence, K. J.; Nicholson, P. D.

    2012-12-01

    Cassini ISS observed multiple widespread changes in surface brightness in Titan's equatorial regions over the past three years (Barnes, J. W. et al. 2012, Icarus, submitted). These brightness variations are attributed to rainfall from cloud systems that appear to form seasonally (Turtle, E. P. et al. 2011, Science, 331, 1414-1417). Determining the composition of this rainfall is an important step in understanding the "methanological" cycle that dominates Titan's surface and atmosphere. In this study, we use data from Cassini VIMS to complete a thorough spectroscopic investigation of rain-wetted areas near Yalaing Terra, Hetpet Regio and central Adiri on Titan. We compute "before-and-after" spectral ratios of any areas that show either deposition or evaporation of rain at any point in the time span of August 2009 to January 2012. By comparing these spectral ratios to a model of liquid ethane that was calculated to match the resolution and sampling interval of VIMS (Brown, R. H. et al. 2008, Nature, 454, 607-610), we find that the rain is most likely composed of liquid ethane. The spectrum of liquid ethane contains multiple absorption features that fortunately fall within the 2-micron and 5-micron spectral windows in Titan's atmosphere. We show that these features are visible in the spectra taken of Titan's surface and that they are characteristically different than those in the spectrum of liquid methane. Furthermore, just as ISS saw the surface brightness reverting to its original state after a period of time, we show that VIMS observations of later flybys show the surface composition in different stages of returning to its initial form as well. Funded by NASA.

  20. Propane Respiration Jump-Starts Microbial Response to a Deep Oil Spill

    NASA Astrophysics Data System (ADS)

    Valentine, David L.; Kessler, John D.; Redmond, Molly C.; Mendes, Stephanie D.; Heintz, Monica B.; Farwell, Christopher; Hu, Lei; Kinnaman, Franklin S.; Yvon-Lewis, Shari; Du, Mengran; Chan, Eric W.; Tigreros, Fenix Garcia; Villanueva, Christie J.

    2010-10-01

    The Deepwater Horizon event resulted in suspension of oil in the Gulf of Mexico water column because the leakage occurred at great depth. The distribution and fate of other abundant hydrocarbon constituents, such as natural gases, are also important in determining the impact of the leakage but are not yet well understood. From 11 to 21 June 2010, we investigated dissolved hydrocarbon gases at depth using chemical and isotopic surveys and on-site biodegradation studies. Propane and ethane were the primary drivers of microbial respiration, accounting for up to 70% of the observed oxygen depletion in fresh plumes. Propane and ethane trapped in the deep water may therefore promote rapid hydrocarbon respiration by low-diversity bacterial blooms, priming bacterial populations for degradation of other hydrocarbons in the aging plume.

  1. Propane respiration jump-starts microbial response to a deep oil spill.

    PubMed

    Valentine, David L; Kessler, John D; Redmond, Molly C; Mendes, Stephanie D; Heintz, Monica B; Farwell, Christopher; Hu, Lei; Kinnaman, Franklin S; Yvon-Lewis, Shari; Du, Mengran; Chan, Eric W; Garcia Tigreros, Fenix; Villanueva, Christie J

    2010-10-08

    The Deepwater Horizon event resulted in suspension of oil in the Gulf of Mexico water column because the leakage occurred at great depth. The distribution and fate of other abundant hydrocarbon constituents, such as natural gases, are also important in determining the impact of the leakage but are not yet well understood. From 11 to 21 June 2010, we investigated dissolved hydrocarbon gases at depth using chemical and isotopic surveys and on-site biodegradation studies. Propane and ethane were the primary drivers of microbial respiration, accounting for up to 70% of the observed oxygen depletion in fresh plumes. Propane and ethane trapped in the deep water may therefore promote rapid hydrocarbon respiration by low-diversity bacterial blooms, priming bacterial populations for degradation of other hydrocarbons in the aging plume.

  2. Measuring In situ Dissolved Methane Concentrations in Gas Hydrate-Rich Systems. Part 2: Investigating Mechanisms Controlling Hydrate Dissolution

    NASA Astrophysics Data System (ADS)

    Wilson, R. M.; Lapham, L.; Riedel, M.; Chanton, J.

    2010-12-01

    Methane is a potent greenhouse gas, twenty times more infrared-active than CO2, and an important energy source. For these reasons, methane hydrate, one of the largest potential reservoirs of methane on earth, is of considerable interest to scientists and industry alike. In particular, questions relating to the stability of methane hydrate are becoming more important as concern about the release of methane into overlying ocean (and eventually the atmosphere) and interest in the recovery of methane from this resource increase. Three primary factors control hydrate stability: pressure (P), temperature (T), and the gas concentration in the surrounding environment. Pressure and temperature govern the stability of the hydrate structure. When hydrate is exposed to P/T regimes outside of the stability zone (HSZ), the hydrate decomposes by dissociation, a relatively fast process resulting in the release of gaseous phase methane (CH4(g)). However, if the P/T regime is within the HSZ, but the concentration of the guest gas (typically CH4) in the surroundings is below saturation, the hydrate will decompose by dissolution resulting in a phase change between hydrate and the dissolved gas phase (CH4(aq)). OsmoSamplers were deployed at a methane hydrate outcrop in Barkley Canyon, Northern Cascadia Margin, collecting porewater samples in a gradient at 1cm increments away from the hydrate surface. Methane, ethane, and propane concentrations in the porewater samples were measured at 6-day resolution over a period of 9 months. At three centimeters from the hydrate face, methane concentrations were significantly lower than predicted saturation for conditions at this site. Curiously, in situ observations of natural hydrate dissolution are up to two orders of magnitude lower than predicted diffusion-controlled dissolution based on surrounding methane concentrations. Since diffusion of methane away from the hydrate surface has been implicated as the dominant control of hydrate dissolution

  3. Methane as a biomarker in the search for extraterrestrial life: Lessons learned from Mars analog hypersaline environments

    NASA Astrophysics Data System (ADS)

    Bebout, B.; Tazaz, A.; Kelley, C. A.; Poole, J. A.; Davila, A.; Chanton, J.

    2010-12-01

    Methane released from discrete regions on Mars, together with previous reports of methane determined with ground-based telescopes, has revived the possibility of past or even extant life near the surface on Mars, since 90% of the methane on Earth has a biological origin. This intriguing possibility is supported by the abundant evidence of large bodies of liquid water, and therefore of conditions conducive to the origin of life, early in the planet's history. The detection and analysis of methane is at the core of NASA’s strategies to search for life in the solar system, and on extrasolar planets. Because methane is also produced abiotically, it is important to generate criteria to unambiguously assess biogenicity. The stable carbon and hydrogen isotopic signature of methane, as well as its ratio to other low molecular weight hydrocarbons (the methane/(ethane + propane) ratio: C1/(C2 + C3)), has been suggested to be diagnostic for biogenic methane. We report measurements of the concentrations and stable isotopic signature of methane from hypersaline environments. We focus on hypersaline environments because spectrometers orbiting Mars have detected widespread chloride bearing deposits resembling salt flats. Other evaporitic minerals, e.g., sulfates, are also abundant in several regions, including those studied by the Mars Exploration Rovers. The presence of evaporitic minerals, together with the known evolution of the Martian climate, from warmer and wetter to cold and hyper-arid, suggest that evaporitic and hypersaline environments were common in the past. Hypersaline environments examined to date include salt ponds located in Baja California, the San Francisco Bay, and the Atacama Desert. Methane was found in gas produced both in the sediments, and in gypsum- and halite-hosted (endolithic) microbial communities. Maximum methane concentrations were as high as 40% by volume. The methane carbon isotopic (δ13C) composition showed a wide range of values, from about

  4. Propane-d6 Heterogeneously Hyperpolarized by Parahydrogen

    PubMed Central

    2015-01-01

    Long-lived spin states of hyperpolarized propane-d6 gas were demonstrated following pairwise addition of parahydrogen gas to propene-d6 using heterogeneous parahydrogen-induced polarization (HET-PHIP). Hyperpolarized molecules were synthesized using Rh/TiO2 solid catalyst with 1.6 nm Rh nanoparticles. Hyperpolarized (PH ∼ 1%) propane-d6 was detected at high magnetic field (9.4 T) spectroscopically and by high-resolution 3D gradient-echo MRI (4.7 T) as the gas flowed through the radiofrequency coil with a spatial and temporal resolution of 0.5 × 0.5 × 0.5 mm3 and 17.7 s, respectively. Stopped-flow hyperpolarized propane-d6 gas was also detected at 0.0475 T with an observed nuclear spin polarization of PH ∼ 0.1% and a relatively long lifetime with T1,eff = 6.0 ± 0.3 s. Importantly, it was shown that the hyperpolarized protons of the deuterated product obtained via pairwise parahydrogen addition could be detected directly at low magnetic field. Importantly, the relatively long low-field T1,eff of HP propane-d6 gas is not susceptible to paramagnetic impurities as tested by exposure to ∼0.2 atm oxygen. This long lifetime and nontoxic nature of propane gas could be useful for bioimaging applications including potentially pulmonary low-field MRI. The feasibility of high-resolution low-field 2D gradient-echo MRI was demonstrated with 0.88 × 0.88 mm2 spatial and ∼0.7 s temporal resolution, respectively, at 0.0475 T. PMID:25506406

  5. Genetic and temporal relations between formation waters and biogenic methane: Upper Devonian Antrim Shale, Michigan Basin, USA

    NASA Astrophysics Data System (ADS)

    Martini, A. M.; Walter, L. M.; Budai, J. M.; Ku, T. C. W.; Kaiser, C. J.; Schoell, M.

    1998-05-01

    Controversy remains regarding how well geochemical criteria can distinguish microbial from thermogenic methane. Natural gas in most conventional deposits has migrated from a source rock to a reservoir, rarely remaining associated with the original or cogenetic formation waters. We investigated an unusual gas reservoir, the Late Devonian Antrim Shale, in which large volumes of variably saline water are coproduced with gas. The Antrim Shale is organic-rich, of relatively low thermal maturity, extensively fractured, and is both source and reservoir for methane that is generated dominantly by microbial activity. This hydrogeologic setting permits integration of chemical and isotopic compositions of coproduced water and gas, providing a unique opportunity to characterize methane generating mechanisms. The well-developed fracture network provides a conduit for gas and water mass transport within the Antrim Shale and allows invasion of meteoric water from overlying aquifers in the glacial drift. Steep regional concentration gradients in chemical and isotopic data are observed for formation waters and gases; dilute waters grade into dense brines (300,000 ppm) over lateral distances of less than 30 km. Radiogenic ( 14C and 3H) and stable isotope ( 18O and D) analyses of shallow Antrim Shale formation waters and glacial drift groundwaters indicate recharge times from modern to 20,000 yr BP. Carbon isotope compositions of methane from Antrim Shale wells are typical of the established range for thermogenic or mixed gas (δ 13C = -47 to -56‰). However, the unusually high δ 13C values of CO 2 coproduced with methane (˜+22‰) and dissolved inorganic carbon (DIC) in formation waters (˜+28‰) require bacterial mediation. The δD values of methane and coproduced formation water provide the strongest evidence of bacterial methanogenesis. Methane/[ethane + propane] ratios and δ 13C values for ethane indicate: (1) the presence of a thermogenic gas component that increases

  6. [1,2-Bis(diphenyl­phosphino)ethane]­chlorido(η5-penta­methyl­cyclo­penta­dien­yl)iron(II) dichloro­methane solvate

    PubMed Central

    Ou, Ya-ping; Feng, Dan; Yuan, Jing-jing

    2010-01-01

    In the title compound, [Fe(C10H15)Cl(C26H24P2)]·CH2Cl2, the FeII atom is coordinated by two P atoms from a 1,2-bis­(diphenyl­phosphino)ethane ligand [Fe—P = 2.2130 (7) and 2.2231 (7) Å], a chloride anion [Fe—Cl = 2.3329 (7) Å] and a penta­methyl­cyclo­penta­dienyl (Cp*) ligand [Fe—centroid(Cp*) = 1.732 (3) Å] in a typical piano-stool geometry. In the crystal structure, the complex and solvent mol­ecules are paired via weak C—H⋯Cl inter­actions. PMID:21588156

  7. The sequestration of ethane on Titan in smog particles.

    PubMed

    Hunten, D M

    2006-10-12

    Saturn's largest satellite, Titan, has a dense atmosphere of nitrogen with a few per cent of methane. At visible wavelengths its surface is hidden by dense orange-brown smog, which is produced in the stratosphere by photochemical reactions following the dissociation of methane by solar ultraviolet light. The most abundant of the products of these reactions is ethane, and enough of it should have been generated over the life of the Solar System to form a satellite-wide ocean one kilometre deep. Radar observations have found specular reflections in 75 per cent of the surface spots observed, but optical searches for a sun-glint off an ocean have been negative. Here I explain the mysterious absence or rarity of liquid ethane: it condenses onto the smog particles, instead of into liquid drops, at the cold temperatures in Titan's atmosphere. This dusty combination of smog and ethane, forming deposits several kilometres thick on the surface, including the observed dunes and dark areas, could be named 'smust'. This satellite-wide deposit replaces the ocean long thought to be an important feature of Titan.

  8. Raman spectra of ethane adn ethylene adsorbed of surface of catalyst Sm 2 O 3/MgO at high temperatures

    NASA Astrophysics Data System (ADS)

    Bobrov, A. V.; Plate, S. E.; Kadushin, A. A.; Kimel'feld, Ya. M.; Seleznev, V. A.; Tulenin, Yu. P.

    1992-03-01

    Raman spectroscopy has been applied for the investigation in situ of catalytic transformations of ethane ethylene and deuterated ethylene on the surface of catalyst Sm 2O 3/MgO at high temperatures (up to 980 K). Ethane and ethylene are the products of the oxidation dehydration of methane. For the understanding of mechanism of this process it is interesting to study of the spectra of ethane and ethylene in the conditions of the real process at high temperature. In the previous paper [1] we have shown that during the flowring of mixture methane with oxygen through the catalyst Sm 2O 3/MgO methane dissociates on CH 3 and CH 2 groups. It has been confirmed by experiment with deuterated methane. The purpose of this work is to study the interaction of ethane and ethylene with Sm 2O 3/MgO in similar conditions by Raman spectroscopy.

  9. Evaluation of Methyl Fluoride and Dimethyl Ether as Inhibitors of Aerobic Methane Oxidation

    PubMed Central

    Oremland, Ronald S.; Culbertson, Charles W.

    1992-01-01

    Methyl fluoride (MF) and dimethyl ether (DME) were effective inhibitors of aerobic methanotrophy in a variety of soils. MF and DME blocked consumption of CH4 as well as the oxidation of 14CH4 to 14CO2, but neither MF nor DME affected the oxidation of [14C]methanol or [14C]formate to 14CO2. Cooxidation of ethane and propane by methane-oxidizing soils was also inhibited by MF. Nitrification (ammonia oxidation) in soils was inhibited by both MF and DME. Production of N2O via nitrification was inhibited by MF; however, MF did not affect N2O production associated with denitrification. Methanogenesis was partially inhibited by MF but not by DME. Methane oxidation was ∼100-fold more sensitive to MF than was methanogenesis, indicating that an optimum concentration could be employed to selectively block methanotrophy. MF inhibited methane oxidation by cell suspensions of Methylococcus capsulatus; however, DME was a much less effective inhibitor. PMID:16348771

  10. Quantifying Methane Emissions from the Arctic Ocean Seabed to the Atmosphere

    NASA Astrophysics Data System (ADS)

    Platt, Stephen; Pisso, Ignacio; Schmidbauer, Norbert; Hermansen, Ove; Silyakova, Anna; Ferré, Benedicte; Vadakkepuliyambatta, Sunil; Myhre, Gunnar; Mienert, Jürgen; Stohl, Andreas; Myhre, Cathrine Lund

    2016-04-01

    Large quantities of methane are stored under the seafloor in the shallow waters of the Arctic Ocean. Some of this is in the form of hydrates which may be vulnerable to deomposition due to surface warming. The Methane Emissions from Arctic Ocean to Atmosphere MOCA, (http://moca.nilu.no/) project was established in collaboration with the Centre for Arctic Gas Hydrate, Environment and Climate (CAGE, https://cage.uit.no/). In summer 2014, and summer and autumn 2015 we deployed oceanographic CTD (Conductivity, Temperature, Depth) stations and performed state-of-the-art atmospheric measurements of CH4, CO2, CO, and other meteorological parameters aboard the research vessel Helmer Hanssen west of Prins Karl's Forland, Svalbard. Air samples were collected for isotopic analysis (13C, 2H) and quantification of other hydrocarbons (ethane, propane, etc.). Atmospheric measurements are also available from the nearby Zeppelin Observatory at a mountain close to Ny-Ålesund, Svalbard. We will present data from these measurements that show an upper constraint of the methane flux in measurement area in 2014 too low to influence the annual CH4 budget. This is further supported by top-down constraints (maximum release consistent with observations at the Helmer Hansen and Zeppelin Observatory) determined using FLEXPART foot print sensitivities and the OsloCTM3 model. The low flux estimates despite the presence of active seeps in the area (numerous gas flares were observed using echo sounding) were apparently due to the presence of a stable ocean pycnocline at ~50 m.

  11. Simulation of ethane steam cracking with severity evaluation

    NASA Astrophysics Data System (ADS)

    Rosli, M. N.; Aziz, N.

    2016-11-01

    Understanding the influence of operating parameters towards cracking severity is paramount in ensuring optimum operation of an ethylene plant. However, changing the parameters in an actual plant for data collection can be dangerous. Thus, a simulation model for ethane steam cracking furnace is developed using ASPEN Plus for the assessment. The process performance is evaluated with cracking severity factors and main product yields. Three severity factors are used for evaluation due to their ease of measurement, which are methane yield (Ymet), Ethylene-Ethane Ratio (EER) and Propylene-Ethylene Ratio (PER). The result shows that cracking severity is primarily influenced by reactor temperature. Operating the furnace with coil outlet temperature ranging between 850°C to 950°C and steam-to-hydrocarbon ratio of 0.3 to 0.5 has led to optimum main product yield.

  12. Speciated non-methane organic compounds emissions from food cooking in Mexico

    NASA Astrophysics Data System (ADS)

    Mugica, V.; Vega, E.; Chow, J.; Reyes, E.; Sánchez, G.; Arriaga, J.; Egami, R.; Watson, J.

    Non-methane organic compound (NMOC) emissions from different sorts of food preparation sites, were quantified for the first time in Mexico, in order to develop emission profiles for further application in the chemical mass balance receptor model (CMB). Restaurants using charcoal grills and LP gas stoves, "tortillerı´as", food frying places and rotisseries were sampled using SUMMA ® stainless-steel canisters to analyse NMOC by high-resolution gas chromatography. The results obtained show that profiles determined from food cooking processes have similarities to those found in LP gas combustion, which is the most common fuel in Mexico used for this purpose, although there were differences in the relative composition of propane and butane in both cases. This suggests that, the rates of combustion of propane and butane are different. It has also been detected that propene, a reactive olefin is produced during the combustion process. The obtained profiles of restaurants, rotisseries and fried food show an important contribution of two carbon compounds (ethane, ethylene and acetylene) that can be attributed to the complex process of grease and meat cooking. The presence of these compounds cannot be attributed to vehicular sources since the concentrations are higher than in ambient air. These were also determined from aromatic compounds such as benzene, toluene and xylene in the combustion of vegetal charcoal. The measured concentrations indicate that NMOC emissions from cooking may become an important indoor source of NMOC under crowded conditions in closed places.

  13. Atmospheric chemistry: The return of ethane

    NASA Astrophysics Data System (ADS)

    Hakola, Hannele; Hellén, Heidi

    2016-07-01

    Ethane emissions can lead to ozone pollution. Measurements at 49 sites show that long-declining atmospheric ethane concentrations started rising in 2010 in the Northern Hemisphere, largely due to greater oil and gas production in the USA.

  14. a Hamiltonian to Obtain a Global Frequency Analysis of all the Vibrational Bands of Ethane

    NASA Astrophysics Data System (ADS)

    Moazzen-Ahmadi, Nasser; Norooz Oliaee, Jalal

    2016-06-01

    The interest in laboratory spectroscopy of ethane stems from the desire to understand the methane cycle in the atmospheres of planets and their moons and from the importance of ethane as a trace species in the terrestrial atmosphere. Solar decomposition of methane in the upper part of these atmospheres followed by a series of reactions leads to a variety of hydrocarbon compounds among which ethane is often the second most abundant species. Because of its high abundance, ethane spectra have been measured by Voyager and Cassini in the regions around 30, 12, 7, and 3 μm. Therefore, a complete knowledge of line parameters of ethane is crucial for spectroscopic remote sensing of planetary atmospheres. Experimental characterization of torsion-vibration states of ethane lying below 1400 cm-1 have been made previously, but extension of the Hamiltonian model for treatment of the strongly perturbed νb{8} fundamental and the complex band system of ethane in the 3 micron region requires careful examination of the operators for many new torsionally mediated vibration-rotation interactions. Following the procedures outlined by Hougen, we have re-examined the transformation properties of the total angular momentum, the translational and vibrational coordinates and momenta of ethane, and for vibration-torsion-rotation interaction terms constructed by taking products of these basic operators. It is found that for certain choices of phase, the doubly degenerate vibrational coordinates with and symmetry can be made to transform under the group elements in such a way as to yield real matrix elements for the torsion-vibration-rotation couplings whereas other choices of phase may require complex algebra. In this talk, I will discuss the construction of a very general torsion-vibration-rotation Hamiltonian for ethane, as well as the prospect for using such a Hamiltonian to obtain a global frequency analysis (based in large part on an extension of earlier programs and ethane fits^a from

  15. Testing different scenarios of emissions from global fossil fuel production using a multi-decadal record of simulated and observed ethane data

    NASA Astrophysics Data System (ADS)

    Chung, L. B.; Butenhoff, C. L.; Rice, A. L.; Kahlil, A.

    2016-12-01

    Ethane is emitted with methane and other trace gases in the production of oil and natural gas during drilling, venting, flaring, and from infrastructure leaks during storage and distribution. Fugitive emissions from oil and gas production are one of the largest anthropogenic sources of ethane and methane and contribute significantly to global trends in their atmospheric burdens. The climate advantage of replacing coal with natural gas in energy portfolios depends critically on methane leakage rates. Because gas fluxes vary widely across production fields and distribution networks, efforts to estimate national and global rates of emissions using bottom-up accounting methods face significant challenges. Recent studies of firn and surface observations show a marked decline in global atmospheric ethane in the 1980s and 1990s which have been interpreted as a decline in fossil fuel ethane emissions. However, this conclusion is contradicted by some bottom-up emissions inventories and global inversions of isotopic methane which find fossil fuel emissions have been flat or increased during this time with a decline in biomass burning emissions. To investigate the temporal record of ethane emissions further, we use four decades (1982 - 2015) of surface air observations of ethane from three sampling networks to test competing ethane emissions scenarios evaluated with the three-dimensional atmospheric chemical-transport model GEOS-Chem. Because ethane's main sources (fossil fuel production, biomass and biofuel burning) have different spatial footprints, we hypothesize that temporal trends for each source, if they exist, will leave unique signatures in the latitudinal distribution of ethane over time. We use GEOS-Chem to predict the source latitudinal trend signatures and assess the ability of the observational ethane record to eliminate different emissions scenarios, providing insight into the recent history of fugitive emissions from fossil fuel production.

  16. Oxidation of ethane by an Acremonium species.

    PubMed Central

    Davies, J S; Wellman, A M; Zajic, J E

    1976-01-01

    Ethane oxidation was studied in ethane-grown resting cells (mycelia) of an Acremonium sp. and in cell-free preparations of such mycelia. From resting cell experiments evidence was found for a pathway of ethane oxidation via ethanol, acetaldehyde, and acetic acid. In vitro studies indicated that ethane-oxidizing activity in such mycelia occurred predominantly in the microsomal fraction of crude homogenates. Microsomal preparations were inactive in the absence of added coenzyme. Marked stimulation of activity was obtained in such preparations with reduced nicotinamide adenine dinucleotide phosphate and to a much lesser degree with nicotinamide adenine dinucleotide phosphate. Ethane oxidation was inhibited by sodium azide and carbon monoxide. PMID:9900

  17. Identifying Methane Sources in Groundwater; Quantifying Changes in Compositional and Stable Isotope Values during Multiphase Transport

    NASA Astrophysics Data System (ADS)

    Larson, T.; Sathaye, K.

    2014-12-01

    A dramatic expansion of hydraulic fracturing and horizontal drilling for natural gas in unconventional reserves is underway. This expansion is fueling considerable public concern, however, that extracted natural gas, reservoir brines and associated fracking fluids may infiltrate to and contaminate shallower (< 500m depth) groundwater reservoirs, thereby posing a health threat. Attributing methane found in shallow groundwater to either deep thermogenic 'fracking' operations or locally-derived shallow microbial sources utilizes geochemical methods including alkane wetness and stable carbon and hydrogen isotope ratios of short chain (C1-C5) hydrocarbons. Compared to shallow microbial gas, thermogenic gas is wetter and falls within a different range of δ13C and δD values. What is not clear, however, is how the transport of natural gas through water saturated geological media may affect its compositional and stable isotope values. What is needed is a means to differentiate potential flow paths of natural gas including 'fast paths' along preexisting fractures and drill casings vs. 'slow paths' through low permeability rocks. In this study we attempt quantify transport-related effects using experimental 1-dimensional two-phase column experiments and analytical solutions to multi-phase gas injection equations. Two-phase experimental results for an injection of natural gas into a water saturated column packed with crushed illite show that the natural gas becomes enriched in methane compared to ethane and propane during transport. Carbon isotope measurements are ongoing. Results from the multi-phase gas injection equations that include methane isotopologue solubility and diffusion effects predict the development of a 'bank' of methane depleted in 13C relative to 12C at the front of a plume of fugitive natural gas. These results, therefore, suggest that transport of natural gas through water saturated geological media may complicate attribution methods needed to distinguish

  18. Costs Associated With Propane Vehicle Fueling Infrastructure

    SciTech Connect

    Smith, M.; Gonzales, J.

    2014-08-05

    This document is designed to help fleets understand the cost factors associated with propane vehicle fueling infrastructure. It provides an overview of the equipment and processes necessary to develop a propane fueling station and offers estimated cost ranges.

  19. Costs Associated With Propane Vehicle Fueling Infrastructure

    SciTech Connect

    Smith, M.; Gonzales, J.

    2014-08-01

    This document is designed to help fleets understand the cost factors associated with propane vehicle fueling infrastructure. It provides an overview of the equipment and processes necessary to develop a propane fueling station and offers estimated cost ranges.

  20. 75 FR 14131 - Effect on Propane Consumers of the Propane Education and Research Council's Operations, Market...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-24

    ... International Trade Administration Effect on Propane Consumers of the Propane Education and Research Council's... comment on whether the operation of the Propane Education and Research Council (PERC), in conjunction with... information to fulfill requirements under the Propane Education and Research Act of 1996 that established PERC...

  1. Preliminary scattering kernels for ethane and triphenylmethane at cryogenic temperatures

    NASA Astrophysics Data System (ADS)

    Cantargi, F.; Granada, J. R.; Damián, J. I. Márquez

    2017-09-01

    Two potential cold moderator materials were studied: ethane and triphenylmethane. The first one, ethane (C2H6), is an organic compound which is very interesting from the neutronic point of view, in some respects better than liquid methane to produce subthermal neutrons, not only because it remains in liquid phase through a wider temperature range (Tf = 90.4 K, Tb = 184.6 K), but also because of its high protonic density together with its frequency spectrum with a low rotational energy band. Another material, Triphenylmethane is an hydrocarbon with formula C19H16 which has already been proposed as a good candidate for a cold moderator. Following one of the main research topics of the Neutron Physics Department of Centro Atómico Bariloche, we present here two ways to estimate the frequency spectrum which is needed to feed the NJOY nuclear data processing system in order to generate the scattering law of each desired material. For ethane, computer simulations of molecular dynamics were done, while for triphenylmethane existing experimental and calculated data were used to produce a new scattering kernel. With these models, cross section libraries were generated, and applied to neutron spectra calculation.

  2. 21 CFR 184.1655 - Propane.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Propane. 184.1655 Section 184.1655 Food and Drugs... Substances Affirmed as GRAS § 184.1655 Propane. (a) Propane (empirical formula C3H8, CAS Reg. No. 74-98-6) is... in the liquid state. Propane is obtained from natural gas by fractionation following absorption in...

  3. 21 CFR 184.1655 - Propane.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Propane. 184.1655 Section 184.1655 Food and Drugs... Substances Affirmed as GRAS § 184.1655 Propane. (a) Propane (empirical formula C3H8, CAS Reg. No. 74-98-6) is... in the liquid state. Propane is obtained from natural gas by fractionation following absorption in...

  4. Kinetics of Ethane Clathrate Hydrate Formation under Titan-Like Conditions

    NASA Astrophysics Data System (ADS)

    Vu, T. H.; Munoz Iglesias, V.; Choukroun, M.; Maynard-Casely, H. E.

    2016-12-01

    Clathrate hydrates are inclusion compounds where small guest molecules are trapped inside highly symmetric water cages. These ice-like crystalline solids are an abundant source of hydrocarbons on Earth that primarily exist in the permafrost and marine sediments. Icy celestial bodies whose pressure and temperature conditions are favorable to the formation of gas hydrates are also expected to contain substantial amounts of these materials. One such example is Saturn's moon Titan, where clathrates are conjectured to be a major crustal component. In fact, clathrate dissociation has been suggested to play a significant role in the replenishment of atmospheric methane on this satellite. In addition to having a substantial atmosphere dominated by nitrogen, Titan is the only body in the Solar System aside from Earth that has standing bodies of liquid on its surface. Liquid methane and ethane have been identified as principal components of the hundreds of lakes that have been observed by the Cassini spacecraft on Titan's surface. As lake fluids come into contact with the pre-existing icy crust, stable layers of ethane clathrate hydrates are expected to form. In this work, we provide experimental evidence for the rapid formation of ethane clathrate from direct contact of liquid ethane with water ice at 1 bar using micro-Raman spectroscopy. Conversion of ice into clathrates is confirmed by the emergence of the characteristic peak at 999 cm-1, which represents the C-C stretch of enclathrated ethane. Kinetics experiments in the temperature range 140-173 K yields an activation energy of 6.75 ± 0.88 kJ/mol for the formation of ethane clathrate. Subsequent thermal analysis indicates a clathrate dissociation temperature of 240 K, consistent with extrapolated literature data. Preliminary synchrotron powder X-ray diffraction experiments have also been carried out to examine the formation kinetics of ethane clathrate from ice/gas mixture at 1 bar. The relatively fast timescale and

  5. Remote Sensing and Sea-Truth Measurements of Methane Flux to the Atmosphere (HYFLUX project)

    SciTech Connect

    Ian MacDonald

    2011-05-31

    A multi-disciplinary investigation of distribution and magnitude of methane fluxes from seafloor gas hydrate deposits in the Gulf of Mexico was conducted based on results obtained from satellite synthetic aperture radar (SAR) remote sensing and from sampling conducted during a research expedition to three sites where gas hydrate occurs (MC118, GC600, and GC185). Samples of sediments, water, and air were collected from the ship and from an ROV submersible using sediments cores, niskin bottles attached to the ROV and to a rosette, and an automated sea-air interface collector. The SAR images were used to quantify the magnitude and distribution of natural oil and gas seeps that produced perennial oil slicks on the ocean surface. A total of 176 SAR images were processed using a texture classifying neural network algorithm, which segmented the ocean surface into oil-free and oil-covered water. Geostatistical analysis indicates that there are a total of 1081 seep formations distributed over the entire Gulf of Mexico basin. Oil-covered water comprised an average of 780.0 sq. km (sd 86.03) distributed with an area of 147,370 sq. km. Persistent oil and gas seeps were also detected with SAR sampling on other ocean margins located in the Black Sea, western coast of Africa, and offshore Pakistan. Analysis of sediment cores from all three sites show profiles of sulfate, sulfide, calcium and alkalinity that indicated anaerobic oxidation of methane with precipitation of authigenic carbonates. Difference among the three sampling sites may reflect the relative magnitude of methane flux. Methane concentrations in water column samples collected by ROV and rosette deployments from MC118 ranged from {approx}33,000 nM at the seafloor to {approx}12 nM in the mixed layer with isolated peaks up to {approx}13,670 nM coincident with the top of the gas hydrate stability field. Average plume methane, ethane, and propane concentrations in the mixed layer are 7, 630, and 9,540 times saturation

  6. Comparison of combustion characteristics of ASTM A-1, propane, and natural-gas fuels in an annular turbojet combustor

    NASA Technical Reports Server (NTRS)

    Wear, J. D.; Jones, R. E.

    1973-01-01

    The performance of an annular turbojet combustor using natural-gas fuel is compared with that obtained using ASTM A-1 and propane fuels. Propane gas was used to simulate operation with vaporized kerosene fuels. The results obtained at severe operating conditions and altitude relight conditions show that natural gas is inferior to both ASTM A-1 and propane fuels. Combustion efficiencies were significantly lower and combustor pressures for relight were higher with natural-gas fuel than with the other fuels. The inferior performance of natural gas is shown to be caused by the chemical stability of the methane molecule.

  7. The identification of liquid ethane in Titan's Ontario Lacus

    USGS Publications Warehouse

    Brown, R.H.; Soderblom, L.A.; Soderblom, J.M.; Clark, R.N.; Jaumann, R.; Barnes, J.W.; Sotin, Christophe; Buratti, B.; Baines, K.H.; Nicholson, P.D.

    2008-01-01

    Titan was once thought to have global oceans of light hydrocarbons on its surface, but after 40 close flybys of Titan by the Cassini spacecraft, it has become clear that no such oceans exist. There are, however, features similar to terrestrial lakes and seas, and widespread evidence for fluvial erosion, presumably driven by precipitation of liquid methane from Titan's dense, nitrogen-dominated atmosphere. Here we report infrared spectroscopic data, obtained by the Visual and Infrared Mapping Spectrometer (VIMS) on board the Cassini spacecraft, that strongly indicate that ethane, probably in liquid solution with methane, nitrogen and other low-molecular-mass hydrocarbons, is contained within Titan's Ontario Lacus. ??2008 Macmillan Publishers Limited. All rights reserved.

  8. Developing receptor-oriented methods for non-methane hydrocarbon characterisation in urban air. Part II: source apportionment

    NASA Astrophysics Data System (ADS)

    Borbon, Agnès; Fontaine, Hervé; Locoge, Nadine; Veillerot, Marc; Galloo, J. C.

    The methods and the results of non-methane hydrocarbon (NMHC) source apportionment are described at urban scale on a spatial and temporal basis. Here, hourly ambient concentrations of nearly 40 C 2-C 9 NMHC are used. Methods are based on the knowledge of the wintertime NMHC vehicle-exhaust emission ratio generally determined by simple regression analysis taking acetylene, ethylene, propene and 1,3-butadiene as auto-exhaust tracers. The RSD of the estimated source contributions is lower than 20%; the developed receptor-oriented methods are flexible and easily transposable to other areas. In winter, vehicle-exhaust emissions explain 100% of the NMHC majority levels and even isoprene. From May to November, our models revealed the temperature-dependent contribution of additional sources (0.71< r<0.90). On the one hand, the evaporation of fuel and solvent affects the whole C 4-C 9 NMHC fraction, and fluctuates between 20% and 50%, even for a northern France urban area. On the other hand, both vehicle-exhaust and biogenic emissions control the highly photoreactive isoprene distribution whatever the site; the traffic is responsible for a third of its levels in summer. Finally, the particular behaviour of the C 2-C 4 compounds pointed out dominant contributions, generally other than traffic. Suspected sources are numerous: natural gas leakage for ethane and propane, wintertime fuel evaporation for butanes and butenes, non-automotive combustion for ethylene and acetylene. Ethane and propane also showed that long-range advective transport, responsible for background concentrations, could significantly contribute to the hydrocarbon levels with a high atmospheric residence time (from 20% to 50%).

  9. Natural flux of greenhouse methane from the Timor Sea to the atmosphere

    NASA Astrophysics Data System (ADS)

    Brunskill, G. J.; Burns, K. A.; Zagorskis, I.

    2011-06-01

    Methane gas bubbles from the Cornea Seep were sampled at the sea surface in the Timor Sea continental shelf area in June 2005. Total bubble gas flux was 0.076 to 0.76 L m-2 h-1 during the 6 h d-1 periods of low neap tides in June 2005. This bubble gas contained an average of 26 mmol CH4 L-1 and about 0.16 and 0.006 mmol L-1 of ethane and propane. We estimate the daily flux from the sea surface to the atmosphere to be 0.012 to 0.12 mol CH4 m-2 d-1 or 0.13 to 1.3 t CH4 d-1 from an area of about 0.7 km2. This methane flux came from a 500 × 1400 m carbonate pavement dome on the seafloor at 84 m water depth. The seep hard ground was swath mapped, and 3.5 kHz subbottom profile data indicate that the seep dome was strongly reflective with poor penetration into the subsurface, consistent with the presence of a carbonate hard ground. Carbon and deuterium isotope ratios (δ13C = -41 to -42‰, δD = -157 to -158‰) of the seep bubble gas indicate that this methane had a thermogenic origin and was in the same isotopic range as gas within the Late Cretaceous Cornea oil and gas field. We could not detect inputs of fluids containing nutrients or short-lived radium isotopes at this site, commonly associated with other cold seeps. Tens to a hundred of kilometers seaward from the Cornea seep site, water column dissolved methane concentrations in this sector of the Timor Sea shelf and slope were 100-500 times supersaturated with respect to the atmosphere, and thus the water column is expected to be degassing additional methane to the atmosphere. Perhaps there are thousands of other methane seeps (of similar magnitude to the Cornea Seep) on this shelf and slope to account for all the excess dissolved methane (˜86,000 t) measured in the water column. These measured and calculated fluxes provide evidence for the hypothesis that shallow sea seeps may be a significant source of atmospheric methane, in contrast to deep sea vents, where most of the methane is dissolved and oxidized in

  10. Assessing the Efficacy of the Aerobic Methanotrophic Biofilter in Methane Hydrate Environments

    SciTech Connect

    Valentine, David

    2012-09-30

    process as a biofilter by studying the distribution of methane oxidation and disposition of methanotrophic populations in the Pacific Ocean. We investigated several environments including the basins offshore California, the continental margin off Central America, and the shallow waters around gas seeps. We succeeded in identifying the distributions of activity in these environments, identified potential physical and chemical controls on methanotrophic activity, we further revealed details about the methanotrophic communities active in these settings, and we developed new approaches to study methanotrophic communities. These findings should improve our capacity to predict the methanotrophic response in ocean waters, and further our ability to generate specific hypotheses as to the ecology and efficacy of pelagic methanotrophic communites. The discharge of methane and other hydrocarbons to Gulf of Mexico that followed the sinking of the Deepwater Horizon provided a unique opportunity to study the methanotorphic biofilter in the deep ocean environment. We set out to understand the consumption of methane and the bloom of methanotrophs resulting from this event, as a window into the regional scale release of gas hydrate under rapid warming scenarios. We found that other hydrocarbon gases, notably propane and ethane, were preferred for consumption over methane, but that methane consumption accelerated rapidly and drove the depletion of methane within a matter of months after initial release. These results revealed the identity of the responsible community, and point to the importance of the seed population in determining the rate at which a methanotrophic community is able to respond to an input of methane. Collectively, these results provide a significant advance in our understanding of the marine methanotrohic biofilter, and further provide direction and context for future investigations of this important phenomenon. This project has resulted in fourteen publications to date

  11. Observation of propane cluster size distributions during nucleation and growth in a Laval expansion

    NASA Astrophysics Data System (ADS)

    Ferreiro, Jorge J.; Chakrabarty, Satrajit; Schläppi, Bernhard; Signorell, Ruth

    2016-12-01

    We report on molecular-level studies of the condensation of propane gas and propane/ethane gas mixtures in the uniform (constant pressure and temperature) postnozzle flow of Laval expansions using soft single-photon ionization by vacuum ultraviolet light and mass spectrometric detection. The whole process, from the nucleation to the growth to molecular aggregates of sizes of several nanometers (˜5 nm), can be monitored at the molecular level with high time-resolution (˜3 μs) for a broad range of pressures and temperatures. For each time, pressure, and temperature, a whole mass spectrum is recorded, which allows one to determine the critical cluster size range for nucleation as well as the kinetics and mechanisms of cluster-size specific growth. The detailed information about the size, composition, and population of individual molecular clusters upon condensation provides unique experimental data for comparison with future molecular-level simulations.

  12. Surface Termination of M1 Phase and Rational Design of Propane Ammoxidation Catalysts

    SciTech Connect

    Guliants, Vadim

    2015-02-16

    This final report describes major accomplishments in this research project which has demonstrated that the M1 phase is the only crystalline phase required for propane ammoxidation to acrylonitrile and that a surface monolayer terminating the ab planes of the M1 phase is responsible for their activity and selectivity in this reaction. Fundamental studies of the topmost surface chemistry and mechanism of propane ammoxidation over the Mo-V-(Te,Sb)-(Nb,Ta)-O M1 and M2 phases resulted in the development of quantitative understanding of the surface molecular structure – reactivity relationships for this unique catalytic system. These oxides possess unique catalytic properties among mixed metal oxides, because they selectively catalyze three alkane transformation reactions, namely propane ammoxidation to acrylonitrile, propane oxidation to acrylic acid and ethane oxidative dehydrogenation, all of considerable economic significance. Therefore, the larger goal of this research was to expand this catalysis to other alkanes of commercial interest, and more broadly, demonstrate successful approaches to rational design of improved catalysts that can be applied to other selective (amm)oxidation processes.

  13. Development of vanadium-phosphate catalysts for methanol production by selective oxidation of methane. Quarterly technical progress report No. 13, April 1996--June 1996

    SciTech Connect

    McCormick, R.L.; Alptekin, G.O.

    1996-07-30

    This document is the thirteenth quarterly technical progress report under Contract No. DE-AC22-92PC92110 {open_quotes}Development of Vanadium-Phosphate Catalysts for Methanol Production by Selective Oxidation of Methane{close_quotes} and covers the period April-June 1996. The basic premise of this project is that vanadyl pyrophosphate (VPO), a catalyst used commercially in the selective oxidation of butane to maleic anhydride, can be developed as a catalyst for selective methane oxidation. Data supporting this idea include published reports indicating moderate to high selectivity in oxidation of ethane, propane, and pentane, as well as butane. Methane oxidation is a much more difficult reaction to catalyze than that of other alkanes and it is expected that considerable modification of vanadyl pyrophosphate will be required for this application. It is well known that VPO can be modified extensively with a large number of different promoters and in particular that promoters can enhance selectivity and lower the temperature required for butane conversion.

  14. Silane-propane ignitor/burner

    DOEpatents

    Hill, Richard W.; Skinner, Dewey F.; Thorsness, Charles B.

    1985-01-01

    A silane propane burner for an underground coal gasification process which is used to ignite the coal and to controllably retract the injection point by cutting the injection pipe. A narrow tube with a burner tip is positioned in the injection pipe through which an oxidant (oxygen or air) is flowed. A charge of silane followed by a supply of fuel, such as propane, is flowed through the tube. The silane spontaneously ignites on contact with oxygen and burns the propane fuel.

  15. Silane-propane ignitor/burner

    DOEpatents

    Hill, R.W.; Skinner, D.F. Jr.; Thorsness, C.B.

    1983-05-26

    A silane propane burner for an underground coal gasification process which is used to ignite the coal and to controllably retract the injection point by cutting the injection pipe. A narrow tube with a burner tip is positioned in the injection pipe through which an oxidant (oxygen or air) is flowed. A charge of silane followed by a supply of fuel, such as propane, is flowed through the tube. The silane spontaneously ignites on contact with oxygen and burns the propane fuel.

  16. Catalysis of propane oxidation and premixed propane-air flames

    NASA Astrophysics Data System (ADS)

    Wiswall, James T.

    Improvements in deriving energy from hydrocarbon fuels will have a large impact on our efforts to transition to sustainable and renewable energy resources. The hypothesis for this work is that catalysis can extend the useful operating conditions for hydrocarbon oxidation and combustion, improve device efficiencies, and reduce pollutants. Catalysis of propane oxidation and premixed propane-air flames are examined experimentally, using a stagnation-flow reactor to identify the important physical and chemical mechanisms over a range of flow catalyst, and temperature conditions. The propane oxidation studies consider five catalyst materials: platinum, palladium, SnO2, 90% SnO2 -- 10% Pt (by mass), and quartz. The volume fractions of CO2, O2, C 3H8, CO, NO and the electric power required to control the catalyst temperature quantify the activity of each catalyst for the equivalence ratios of φ = 0.67, 1.00, and 1.50, and over the catalyst temperature range 23-800°C. Quartz is used as a baseline and confirmed to be non-reactive at all conditions. 100% SnO2 has minimal reactivity. Platinum, palladium, and 90% SnO2 -- 10% Pt show similar trends and have the highest catalytic activity at φ = 1.50. Palladium and 90% SnO 2 -- 10% Pt show an increasing catalyst-activation temperature (Tsa) for decreasing φ, and platinum shows an approximately constant catalyst-activation temperature for decreasing φ (Tsa = 310°C). Of these the 90% SnO2 -- 10% Pt catalyst shows the lowest Tsa, occurring for the φ = 1.5 mixture (Tsa = 250°C). The studies of premixed propane-air flames consider platinum and quartz stagnation surfaces for fuel-mixture velocities from 0.6-1.6 m/s. Five flame structures are observed: cool core envelope, cone, envelope, disk and ring flames. The lean-extinction limit, disk-to-ring flame transition φ, and the disk-flame to stagnation-plane distance are reported. Platinum inhibits the ring flame structure. The lean-extinction limit and disk-flame to stagnation

  17. Phase equilibria and thermodynamic modeling of ethane and propane hydrates in porous silica gels.

    PubMed

    Seo, Yongwon; Lee, Seungmin; Cha, Inuk; Lee, Ju Dong; Lee, Huen

    2009-04-23

    In the present study, we examined the active role of porous silica gels when used as natural gas storage and transportation media. We adopted the dispersed water in silica gel pores to substantially enhance active surface for contacting and encaging gas molecules. We measured the three-phase hydrate (H)-water-rich liquid (L(W))-vapor (V) equilibria of C(2)H(6) and C(3)H(8) hydrates in 6.0, 15.0, 30.0, and 100.0 nm silica gel pores to investigate the effect of geometrical constraints on gas hydrate phase equilibria. At specified temperatures, the hydrate stability region is shifted to a higher pressure region depending on pore size when compared with those of bulk hydrates. Through application of the Gibbs-Thomson relationship to the experimental data, we determined the values for the C(2)H(6) hydrate-water and C(3)H(8) hydrate-water interfacial tensions to be 39 +/- 2 and 45 +/- 1 mJ/m(2), respectively. By using these values, the calculation values were in good agreement with the experimental ones. The overall results given in this study could also be quite useful in various fields, such as exploitation of natural gas hydrate in marine sediments and sequestration of carbon dioxide into the deep ocean.

  18. SUPPRESSION OF COKE FORMATION IN THE STEAM CRACKING OF ALKANES: ETHANE AND PROPANE. (R825412)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  19. SUPPRESSION OF COKE FORMATION IN THE STEAM CRACKING OF ALKANES: ETHANE AND PROPANE. (R825412)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  20. Tunable Diode Laser Absorption Spectroscopy Sensor for Calibration Free Humidity Measurements in Pure Methane and Low CO2 Natural Gas.

    PubMed

    Nwaboh, Javis Anyangwe; Pratzler, Sonja; Werhahn, Olav; Ebert, Volker

    2017-05-01

    We report a new direct tunable diode laser absorption spectroscopy (dTDLAS) sensor for absolute measurements of H2O in methane, ethane, propane, and low CO2 natural gas. The sensor is operated with a 2.7 µm DFB laser, equipped with a high pressure single pass gas cell, and used to measure H2O amount of substance fractions in the range of 0.31-25 000 µmol/mol. Operating total gas pressures are up to 5000 hPa. The sensor has been characterized, addressing the traceability of the spectrometric results to the SI and the evaluation of the combined uncertainty, following the guide to the expression of uncertainty in measurement (GUM). The relative reproducibility of H2O amount of substance fraction measurements at 87 µmol/mol is 0.26% (0.23 µmol/mol). The maximum precision of the sensor was determined using a H2O in methane mixture, and found to be 40 nmol/mol for a time resolution of 100 s. This corresponds to a normalized detection limit of 330 nmol mol(-1)·m Hz(-1/2). The relative combined uncertainty of H2O amount fraction measurements delivered by the sensor is 1.2%.

  1. LABORATORY STUDIES ON THE IRRADIATION OF SOLID ETHANE ANALOG ICES AND IMPLICATIONS TO TITAN'S CHEMISTRY

    SciTech Connect

    Kim, Y. S.; Bennett, C. J.; Chen, L-H; Kaiser, R. I.; O'Brien, K.

    2010-03-10

    Pure ethane ices (C{sub 2}H{sub 6}) were irradiated at 10, 30, and 50 K under contamination-free, ultrahigh vacuum conditions with energetic electrons generated in the track of galactic cosmic-ray (GCR) particles to simulate the interaction of GCRs with ethane ices in the outer solar system. The chemical processing of the samples was monitored by a Fourier transform infrared spectrometer and a quadrupole mass spectrometer during the irradiation phase and subsequent warm-up phases on line and in situ in order to extract qualitative (products) and quantitative (rate constants and yields) information on the newly synthesized molecules. Six hydrocarbons, methane (CH{sub 4}), acetylene (C{sub 2}H{sub 2}), ethylene (C{sub 2}H{sub 4}), and the ethyl radical (C{sub 2}H{sub 5}), together with n-butane (C{sub 4}H{sub 10}) and butene (C{sub 4}H{sub 8}), were found to form at the radiation dose reaching 1.4 eV per molecule. The column densities of these species were quantified in the irradiated ices at each temperature, permitting us to elucidate the temperature and phase-dependent production rates of individual molecules. A kinetic reaction scheme was developed to fit column densities of those species produced during irradiation of amorphous/crystalline ethane held at 10, 30, or 50 K. In general, the yield of the newly formed molecules dropped consistently for all species as the temperature was raised from 10 K to 50 K. Second, the yield in the amorphous samples was found to be systematically higher than in the crystalline samples at constant temperature. A closer look at the branching ratios indicates that ethane decomposes predominantly to ethylene and molecular hydrogen, which may compete with the formation of n-butane inside the ethane matrix. Among the higher molecular products, n-butane dominates. Of particular relevance to the atmosphere of Saturn's moon Titan is the radiation-induced methane production from ethane-an alternative source of replenishing methane into the

  2. Identifying sources, formation pathways and geological controls of methane in shallow groundwater above unconventional natural gas plays in Alberta, Canada

    NASA Astrophysics Data System (ADS)

    Mayer, B.; Humez, P.; Nightingale, M.; Ing, J.; Kingston, A. W.; Clarkson, C.; Cahill, A.; Parker, B. L.; Cherry, J. A.; Millot, R.; Kloppmann, W.; Osadetz, K.; Lawton, D.

    2015-12-01

    With the advent of shale gas development facilitated by hydraulic fracturing it has become increasingly important to develop tracer tools to scientifically determine potential impacts of stray gases on shallow aquifers. To assess potential future impacts on shallow aquifers by leakage of natural gas from unconventional energy resource development, it is essential to establish a reliable baseline. Occurrence of methane in shallow groundwater in Alberta (Canada) between 2006 and 2014 was assessed and was ubiquitous in 186 sampled monitoring wells. Free and dissolved gas sampling and measurement approaches yielded comparable results with often low methane concentrations in shallow groundwater, but in 28 samples methane exceeded 10 mg/L in dissolved gas and 300,000 ppmv in free gas. Methane concentrations in free and dissolved gas samples were found to increase with well depth and were especially elevated in groundwater obtained from aquifers containing coal seams and shale units. Carbon isotope ratios of methane averaged -69.7 ± 11.1 ‰ in free gas and -65.6 ± 8.9 ‰ in dissolved gas. δ13C values were not found to vary with well depth or lithology indicating that the methane in Alberta groundwater was formed via a similar mechanism. The low δ13C values in concert with average δ2H values of -289 ± 44 ‰ suggest that most methane was of biogenic origin predominantly generated via CO2 reduction. This interpretation is confirmed by gas dryness parameters typically >500 due to only small amounts of ethane and a lack of propane in most samples. Novel approaches of in-situ concentration and isotope measurements for methane during drilling of a 530 m deep well yielded a mud-gas profile characterizing natural gas occurrences in the intermediate zone. Comparison with mudgas profile carbon isotope data revealed that methane in the investigated shallow groundwater in Alberta is isotopically similar to hydrocarbon gases found in 100-250 meter depths in the Western

  3. Transformation of γ-Ray-Formed Methyl Radicals in Methane Hydrate at 10 MPa

    NASA Astrophysics Data System (ADS)

    Ishikawa, Kenji; Tani, Atsushi; Otsuka, Takahiro; Nakashima, Satoru

    2007-01-01

    The stability of methyl radicals formed in synthetic methane hydrate by γ-ray irradiation at 77 K was studied at 200-273 K and 10 MPa. The methyl radicals decayed under these conditions, despite the stability of methane hydrate, and changed into other molecules that could not be detected by electron spin resonance (ESR). Decay products were investigated by gas cell infrared (IR) spectroscopy by measuring the decomposed gas from the γ-irradiated methane hydrate. Only ethane molecules were detected from the irradiated sample, while these were absent in an unirradiated sample. The molar ratio of ethane to methane (C2H6/CH4) was 12± 1 ppm, which did not contradict with that of methyl radical to methane (CH3{}\\bullet/CH4) in the literature. Hence, most of the methyl radicals generated by irradiation were supposed to be transformed to ethane in methane hydrate.

  4. High-Resolution Tunable Diode Laser Spectroscopy of Methane

    DTIC Science & Technology

    1986-03-01

    quantitative data from test 14. This table shows that ethylene is by far the most abundant species, with propane and acetylene also being major species. The...Test 14 1. Ethane 2.21 2. Ethylene 77.80 3. Propane 0.75 4. Acetylene 18.61 5. Propene 26.52 6. Acetaldehyde 1.83 7. 1-Butene 5.83 8. 1,3...21. Benzene 9.07 22. l-Heptene 3.16 23. N-Heptane 0.44 24. Toluene 3.33 25. Hexanal 1.09 26. 1- Octene 2.13 27. N-Octane 0.63 28. Ethylbenzene

  5. Sources and turnover of organic carbon and methane in fjord and shelf sediments off northern Norway

    NASA Astrophysics Data System (ADS)

    Sauer, Simone; Hong, Wei-Li; Knies, Jochen; Lepland, Aivo; Forwick, Matthias; Klug, Martin; Eichinger, Florian; Baranwal, Soma; Crémière, Antoine; Chand, Shyam; Schubert, Carsten J.

    2016-10-01

    To better understand the present and past carbon cycling and transformation processes in methane-influenced fjord and shelf areas of northern Norway, we compared two sediment cores from the Hola trough and from Ullsfjorden. We investigated (1) the organic matter composition and sedimentological characteristics to study the sources of organic carbon (Corg) and the factors influencing Corg burial, (2) pore water geochemistry to determine the contribution of organoclastic sulfate reduction and methanogenesis to total organic carbon turnover, and (3) the carbon isotopic signature of hydrocarbons to identify the carbon transformation processes and gas sources. High sedimentation and Corg accumulation rates in Ullsfjorden support the notion that fjords are important Corg sinks. The depth of the sulfate-methane-transition (SMT) in the fjord is controlled by the supply of predominantly marine organic matter to the sediment. Organoclastic sulfate reduction accounts for 60% of the total depth-integrated sulfate reduction in the fjord. In spite of the presence of ethane, propane, and butane, we suggest a purely microbial origin of light hydrocarbons in the sediments based on their low δ13C values. In the Hola trough, sedimentation and Corg accumulation rates changed during the deglacial-to-post-glacial transition from approximately 80 cm ka-1 to erosion at present. Thus, Corg burial in this part of the shelf is presently absent. Low organic matter content in the sediment and low rates of organoclastic sulfate reduction (only 3% of total depth-integrated sulfate reduction) entail that the shallow depth of the SMT is controlled mostly by ascending thermogenic methane from deeper sources.

  6. Ambient air/near-field measurements of methane and Volatile Organic Compounds (VOCs) from a natural gas facility in Northern Europe

    NASA Astrophysics Data System (ADS)

    Baudic, Alexia; Gros, Valérie; Bonsang, Bernard; Baisnee, Dominique; Vogel, Félix; Yver Kwok, Camille; Ars, Sébastien; Finlayson, Andrew; Innocenti, Fabrizio; Robinson, Rod

    2015-04-01

    Since the 1970's, the natural gas consumption saw a rapid growth in large urban centers, thus becoming an important energy resource to meet continuous needs of factories and inhabitants. Nevertheless, it can be a substantial source of methane (CH4) and pollutants in urban areas. For instance, we have determined that about 20% of Volatile Organic Compounds (VOCs) in downtown Paris are originating from this emission source (Baudic, Gros et al., in preparation). Within the framework of the "Fugitive Methane Emissions" (FuME) project (Climate-KIC, EIT); 2-weeks gas measurements were conducted at a gas compressor station in Northern Europe. Continuous ambient air measurements of methane and VOCs concentrations were performed using a cavity ring-down spectrometer (model G2201, Picarro Inc., Santa Clara, USA) and two portable GC-FID (Chromatotec, Saint-Antoine, France), respectively. On-site near-field samplings were also carried out at the source of two pipelines using stainless steel flasks (later analyzed with a laboratory GC-FID). The objective of this study aims to use VOCs as additional tracers in order to better characterize the fugitive methane emissions in a complex environment, which can be affected by several urban sources (road-traffic, others industries, etc.). Moreover, these measurements have allowed determining the chemical composition of this specific source. Our results revealed that the variability of methane and some VOCs was (rather) well correlated, especially for alkanes (ethane, propane, etc.). An analysis of selected events with strong concentrations enhancement was performed using ambient air measurements; thus allowing the preliminary identification of different emission sources. In addition, some flasks were also sampled in Paris to determine the local natural gas composition. A comparison between both was then performed. Preliminary results from these experiments will be presented here.

  7. High-Resolution Spectroscopy of Stratospheric Ethane Following the Jupiter Impact of 2009

    NASA Technical Reports Server (NTRS)

    Fast, Kelly; Kostiuk, Theodor; Livengood, Timothy A.; Hewagama, Tilak; Amen, John

    2010-01-01

    We report on high-resolution infrared spectroscopy of ethane (C2H6) performed at the latitude of an impact site on Jupiter discovered on 19 July 2009 by A. Wesley from a location in Murrumbateman, Australia. The observations used the NASA Goddard Space Flight Center's Heterodyne Instrument for Planetary Wind and Composition (HIPWAC) at the NASA Infrared Telescope Facility (IRTF) on Mauna Kea, Hawaii. HIPWAC is a mid-infrared (9-12 microns) heterodyne spectrometer operating at the highest limit of spectral resolving power (lambda\\Delta\\lambda > l06), providing information on atmospheric constituent abundance and temperature through fully resolved tine shapes. Ethane is a stable trace product of methane photochemistry that is nearly uniformly mixed in Jupiter's stratosphere, providing an effective probe of that altitude region. Ethane emission line profiles near 11,74 microns in the Ug band were measured in Jupiter's stratosphere at 25 MHz (11.00083/cm) resolution. A sequence of spectra of ethane acquired over a range of longitude at the impact latitude (56S planetocentric) probes constituent abundance and temperature profile, both on and off the impact region. Near the site of the impact, ethane emission increased above levels measured well outside the impact region. Radiative transfer analysis indicates increased ethane mole fraction (30% greater). Variation in the measured continuum level and line intensities within 75deg of the impact longitude indicate the presence of an opacity source (haze) at altitudes near and above the tropopause and as high as the 10-mbar level near the impact site. The indication of possible haze opacity up to the 10-mbar level in the atmosphere is consistent with measurements made by HIPWAC's predecessor as part of the IRTF Shoemaker Levy-9 campaign in 1994.

  8. Benzene-Ethane Co-Crystals on the Surface of Titan

    NASA Astrophysics Data System (ADS)

    Vu, T. H.; Hodyss, R. P.; Cable, M. L.; Maynard-Casely, H. E.; Malaska, M. J.; Beauchamp, P. M.

    2014-12-01

    Benzene is found at high abundance in Titan's atmosphere and is a likely constituent of evaporite deposits formed around the hydrocarbon lakes. This work aims to understand the composition and nature of the surface evaporites by focusing on the interaction between benzene and ethane, a principal component of the lake fluids. We have discovered a new benzene-ethane co-crystalline structure which forms under Titan-like conditions (90-150 K and 1 bar), resulting in recrystallization of the benzene lattice that can be detected via micro-Raman spectroscopy. Evidence for ethane incorporation includes two new distinctive ethane features at 2873 and 1455 cm-1 and marked red shifts of the benzene peaks in the Raman spectra. Vibrational analysis reveals a C-H…π interaction between the aromatic ring of benzene and the hydrogen atoms of ethane through a monodentate contact. The kinetics of co-crystal formation is also determined, giving a relatively mild activation energy of 10.2 kJ/mol. It is shown that the formation process would reach completion in ~18 hours, and that benzene precipitates selectively as the co-crystal from a mixture of liquid ethane and methane. Synchrotron powder X-ray diffraction data confirms the crystalline nature of the new material. These results imply that benzene and similar organics may act as potential hydrocarbon reservoirs due to this incorporation mechanism. These novel structures represent a new class of materials for Titan's surface that may influence evaporite characteristics, such as particle size and infrared spectral properties.

  9. Redox controls on methane formation, migration and fate in shallow aquifers

    NASA Astrophysics Data System (ADS)

    Humez, Pauline; Mayer, Bernhard; Nightingale, Michael; Becker, Veith; Kingston, Andrew; Taylor, Stephen; Bayegnak, Guy; Millot, Romain; Kloppmann, Wolfram

    2016-07-01

    geochemistry data revealed that the elevated δ13CCH4 values were caused by microbial oxidation of biogenic methane or post-sampling degradation of low CH4 content samples rather than migration of deep thermogenic gas. A significant number of samples (39.2 %) contained methane with predominantly biogenic C isotope ratios (δ13CCH4 < -55 ‰) accompanied by elevated concentrations of ethane and sometimes trace concentrations of propane. These gases, observed in 28.1 % of the samples, bearing both biogenic (δ13C) and thermogenic (presence of C3) characteristics, are most likely derived from shallow coal seams that are prevalent in the Cretaceous Horseshoe Canyon and neighboring formations in which some of the groundwater wells are completed. The remaining 3.7 % of samples were not assigned because of conflicting parameters in the data sets or between replicates samples. Hence, despite quite variable gas concentrations and a wide range of δ13CCH4 values in baseline groundwater samples, we found no conclusive evidence for deep thermogenic gas migration into shallow aquifers either naturally or via anthropogenically induced pathways in this baseline groundwater survey. This study shows that the combined interpretation of aqueous geochemistry data in concert with chemical and isotopic compositions of dissolved and/or free gas can yield unprecedented insights into formation and potential migration of methane in shallow groundwater. This enables the assessment of cross-formational methane migration and provides an understanding of alkane gas sources and pathways necessary for a stringent baseline definition in the context of current and future unconventional hydrocarbon exploration and exploitation.

  10. Propane decomposition and conversion into other hydrocarbons using metal target assisted laser induced plasma

    NASA Astrophysics Data System (ADS)

    Moosakhani, A.; Parvin, P.; Reyhani, A.; Mortazavi, S. Z.

    2017-01-01

    It is shown that the propane molecules are strongly decomposed in the metal assisted laser induced plasma based on the nano-catalytic adsorption. A Q-Switched Nd:YAG laser is employed to irradiate the propane gas filled in the control chamber in the presence of the reactive metals such as Ni, Fe, Pd, and Cu in order to study the effect of catalysts during the decomposition. The catalytic targets simultaneously facilitate the plasma formation and the decomposition events leading to generate a wide distribution of the light and heavy hydrocarbon molecules, mainly due to the recombination processes. Fourier transform infrared spectroscopy and gas chromatography instruments support the findings by detecting the synthetic components. Furthermore, the optical emission spectroscopy of the laser induced plasma emissions realizes the real time monitoring of the reactions taking place during each laser shot. The subsequent recombination events give rise to the generation of a variety of the hydrocarbon molecules. The dissociation rate, conversion ratio, selectivity, and yield as well as the performance factor arise mainly from the catalytic effects of the metal species. Moreover, the ablation rate of the targets of interest is taken into account as a measure of the catalytic reactivity due to the abundance of the metal species ablated from the target. This leads to assess the better performance factor for Pd among four metal catalysts of interest during propane decomposition. Finally, the molecules such as ethane and ethylene are identified as the stable abundant species created during the successive molecular recombination processes.

  11. Propane vehicles : status, challenges, and opportunities.

    SciTech Connect

    Rood Werpy, M.; Burnham, A.; Bertram, K.; Energy Systems

    2010-06-17

    Propane as an auto fuel has a high octane value and has key properties required for spark-ignited internal combustion engines. To operate a vehicle on propane as either a dedicated fuel or bi-fuel (i.e., switching between gasoline and propane) vehicle, only a few modifications must be made to the engine. Until recently propane vehicles have commonly used a vapor pressure system that was somewhat similar to a carburetion system, wherein the propane would be vaporized and mixed with combustion air in the intake plenum of the engine. This leads to lower efficiency as more air, rather than fuel, is inducted into the cylinder for combustion (Myers 2009). A newer liquid injection system has become available that injects propane directly into the cylinder, resulting in no mixing penalty because air is not diluted with the gaseous fuel in the intake manifold. Use of a direct propane injection system will improve engine efficiency (Gupta 2009). Other systems include the sequential multi-port fuel injection system and a bi-fuel 'hybrid' sequential propane injection system. Carbureted systems remain in use but mostly for non-road applications. In the United States a closed-loop system is used in after-market conversions. This system incorporates an electronic sensor that provides constant feedback to the fuel controller to allow it to measure precisely the proper air/fuel ratio. A complete conversion system includes a fuel controller, pressure regulator valves, fuel injectors, electronics, fuel tank, and software. A slight power loss is expected in conversion to a vapor pressure system, but power can still be optimized with vehicle modifications of such items as the air/fuel mixture and compression ratios. Cold start issues are eliminated for vapor pressure systems since the air/fuel mixture is gaseous. In light-duty propane vehicles, the fuel tank is typically mounted in the trunk; for medium- and heavy-duty vans and trucks, the tank is located under the body of the vehicle

  12. Exhaust gas measurements in a propane fueled swirl stabilized combustor

    NASA Technical Reports Server (NTRS)

    Aanad, M. S.

    1982-01-01

    Exhaust gas temperature, velocity, and composition are measured and combustor efficiencies are calculated in a lean premixed swirl stabilized laboratory combustor. The radial profiles of the data between the co- and the counter swirl cases show significant differences. Co-swirl cases show evidence of poor turbulent mixing across the combustor in comparison to the counter-swirl cases. NO sub x levels are low in the combustor but substantial amounts of CO are present. Combustion efficiencies are low and surprisingly constant with varying outer swirl in contradiction to previous results under a slightly different inner swirl condition. This difference in the efficiency trends is expected to be a result of the high sensitivity of the combustor to changes in the inner swirl. Combustor operation is found to be the same for propane and methane fuels. A mechanism is proposed to explain the combustor operation and a few important characteristics determining combustor efficiency are identified.

  13. Dermal and pulmonary absorption of propan-1-ol and propan-2-ol from hand rubs.

    PubMed

    Below, Harald; Partecke, Ivo; Huebner, Nils-Olaf; Bieber, Nora; Nicolai, Thomas; Usche, Alexander; Assadian, Ojan; Below, Elke; Kampf, Günter; Parzefall, Wolfram; Heidecke, Claus-Dieter; Zuba, Dariusz; Bessonneau, Vincent; Kohlmann, Thomas; Kramer, Axel

    2012-04-01

    It has been shown that nontoxic concentrations of ethanol are absorbed after hand hygiene using ethanol-based hand rubs. This study investigated whether absorption of propan-1-ol and propan-2-ol from commercially available hand rubs results in measurable concentrations after use. The pulmonary and dermal absorption of propanol during hand rubs was investigated. Rubs contained 70% (w/w) propan-1-ol, 63.14% (w/w) propan-2-ol, or 45% (w/w) propan-2-ol in combination with 30% (w/w) propan-1-ol. Peak median blood levels were 9.15 mg/L for propan-1-ol and 5.3 mg/L for propan-2-ol after hygienic hand rubs and 18.0 mg/L and 10.0 mg/L, respectively, after surgical hand rubs. Under actual surgical conditions, the highest median blood levels were 4.08 mg/L for propan-1-ol and 2.56 mg/L for propan-2-ol. The same procedure performed with prevention of pulmonary exposure through the use of a gas-tight mask resulted in peak median blood levels of 1.16 mg/L of propan-1-ol and 1.74 mg/L of propan-2-ol. Only minimal amounts of propanols are absorbed through the use of hand rubs. Based on our experimental data, the risk of chronic systemic toxic effects caused by hand rubs is likely negligible. However, our study did not evaluate the consequences of long-term daily and frequent use of hygienic hand rubs. Copyright © 2012 Association for Professionals in Infection Control and Epidemiology, Inc. Published by Mosby, Inc. All rights reserved.

  14. The Millimeter-Wave Spectrum of Propanal

    NASA Astrophysics Data System (ADS)

    Zingsheim, Oliver; Müller, Holger S. P.; Lewen, Frank; Schlemmer, Stephan

    2017-06-01

    The microwave spectrum of propanal, also known as propionaldehyde, CH_3CH_2CHO, has been investigated in the laboratory already since 1964^1 and has also been detected in space^2. Recently, propanal was detected with the Atacama Large Millimeter/submillimeter Array (ALMA), Protostellar Interferometric Line Survey (PILS)^3. The high sensitivity and resolution of ALMA indicated small discrepancies between observed and predicted rotational spectra of propanal. As higher accuracies are desired the spectrum of propanal was measured up to 500 GHz with the Cologne (Sub-)Millimeter spectrometer. Propanal has two stable conformers, syn and gauche, which differ mainly in the rotation of the aldehyd group with respect to the rigid C-atom framework of the molecule. We extensively studied both of them. The lower syn-conformer shows small splittings caused by the internal rotation of the methyl group, whereas the spectrum of gauche-propanal is complicated due to the tunneling rotation interaction from two stable degenerate conformers. Additionally, we analyzed vibrationally excited states. ^1 Butcher et al., J. Chem. Phys. 40 6 (1964) ^2 Hollis et al., Astrophys. J. 610 L21 (2004) ^3 Lykke et al., A&A 597 A53 (2017)

  15. Does the vertical profile of ethane contain more insight into mixing layer height than carbon monoxide?

    NASA Astrophysics Data System (ADS)

    Herndon, Scott; Yacovitch, Tara; Pusede, Sally; Diskin, Glenn; DiGangi, Joshua; Sachse, Glenn; Crawford, James

    2015-04-01

    To improve the interpretation of satellite data measurements near the surface, the DISCOVER-AQ project embarked on a four year campaign to produce an integrated dataset of airborne and surface based measurements at various locations in North America. One of the key metrics when pursuing the the goal of measuring the surface air quality from space is the mixing layer height. The measurement phase in 2014 included the novel 1-Hz Aerodyne Research, Inc. fast Ethane Spectrometer to distinguish the methane emissions from thermogenic (oil&gas) and biogenic sources in the Denver-Julesberg basin. A second potential use of ethane as a determinant of mixing layer height is revealed in the analysis of 213 vertical profiles collected at 7 points during 21 flights. The findings are evaluated relative to other in-situ metrics, such as carbon monoxide and remote sensing attributions of mixing layer height.

  16. An unnatural death by propan-1-ol and propan-2-ol.

    PubMed

    Skopp, Gisela; Gutmann, Isabelle; Schwarz, Clara-Sophie; Schmitt, Georg

    2016-07-01

    A fatality of an inpatient ingesting a disinfectant containing ethanol, propan-1-ol, and propan-2-ol is reported. The alleged survival time was about 1 h. Major findings at autopsy were an extended hemorrhagic lung edema, an edematous brain, and shock kidneys. Concentrations of alcohols and acetone, a major metabolite of propan-2-ol, were determined from body fluids (blood from the heart and the femoral vein, urine, gastric contents) and tissues (brain, muscle, liver, kidneys, lungs) by headspace/gas chromatography using 2-methylpropan-2-ol as the internal standard. All samples investigated were positive for propan-1-ol, propan-2-ol, ethanol, and acetone except stomach contents, where acetone was not detectable. The low concentration of acetone compared to propan-2-ol likely supports the short survival time. The concentration ratios estimated from the results are in accordance with the physico-chemical properties of the particular alcohols, their different affinities towards alcohol dehydrogenase as well as their interdependence during biotransformation. Autopsy did not reveal the cause of death. According to the few published data, blood concentrations of 1.44 and 1.70 mg/g of propan-2-ol and propan-1-ol, respectively, are considered sufficient to have caused the death. This case also points to the need to restrict access to antiseptic solutions containing alcohols in wards with patients at risk.

  17. Is Optical Gas Imaging Effective for Detecting Fugitive Methane Emissions? - A Technological and Policy Perspective

    NASA Astrophysics Data System (ADS)

    Ravikumar, A. P.; Wang, J.; Brandt, A. R.

    2016-12-01

    Mitigating fugitive methane emissions from the oil and gas industry has become an important concern for both businesses and regulators. While recent studies have improved our understanding of emissions from all sectors of the natural gas supply chain, cost-effectively identifying leaks over expansive natural gas infrastructure remains a significant challenge. Recently, the Environmental Protection Agency (EPA) has recommended the use of optical gas imaging (OGI) technologies to be used in industry-wide leak detection and repair (LDAR) programs. However, there has been little to no systematic study of the effectiveness of infrared-camera-based OGI technology for leak detection applications. Here, we develop a physics-based model that simulates a passive infrared camera imaging a methane leak against varying background and ambient conditions. We verify the simulation tool through a series of large-volume controlled release field experiments wherein known quantities of methane were released and imaged from a range of distances. After simulator verification, we analyze the effects of environmental conditions like temperature, wind, and imaging background on the amount of methane detected from a statistically representative survey program. We also examine the effects of LDAR design parameters like imaging distance, leak size distribution, and gas composition. We show that imaging distance strongly affects leak detection - EPA's expectation of a 60% reduction in fugitive emissions based on a semi-annual LDAR survey will be realized only if leaks are imaged at a distance less than 10 m from the source under ideal environmental conditions. Local wind speed is also shown to be important. We show that minimum detection limits are 3 to 4 times higher for wet-gas compositions that contain a significant fraction of ethane and propane, resulting a significantly large leakage rate. We also explore the importance of `super-emitters' on the performance of an OGI-based leak

  18. Ethane C-C clumping in natural gas : a proxy for cracking processes ?

    NASA Astrophysics Data System (ADS)

    Clog, M. D.; Ferreira, A. A.; Santos Neto, E. V.; Eiler, J. M.

    2014-12-01

    Ethane (C2H6) is the second-most abundant alkane in most natural gas reservoirs, and is used to produce ethylene for petrochemical industries. It is arguably the simplest molecule that can manifest multiple 13C substitutions. There are several plausible controls on ∆13C2H6in natural gas: thermodynamically controlled homogeneous isotope exchange reactions analogous to those behind carbonate clumped isotope thermometry; inheritance from larger biomolecules that undergo thermal degradation to produce natural gas; mixing of natural gases that differ markedly in bulk isotopic composition; diffusive fractionation; or combinations of these and/or other, less expected fractionations. There is little basis for predicting which of these will control isotopic variations among natural ethanes, but we think it likely that addition of this new isotopic proxy will reveal new insights into the natural chemistry of ethane. We have developed a method to measure the abundance of 13C2H6 in natural samples, using high-resolution mass spectrometry. We define ∆13C2H6 as 1000 . ((13C2H6/12C2H6)measured/(13C2H6/12C2H6)stochastic -1). We studied several suites of natural gas samples and experimentally produced or modified ethane. Natural ethanes, including closely related samples from a single natural gas field, exhibit surprisingly large ranges in ∆13C2H6 (4 ‰ overall; up to 3 ‰ in one gas field). Such ranges cannot be explained by thermodynamic equilibrium at a range of different temperatures, or by diffusive fractionation. Kinetic isotope effects associated with 'cracking' reactions, and/or inheritance of non-equilibrium carbon isotope structures from source organics are more likely causes. We observe a correlation between ∆13C2H6 and the concentration of alkanes other than methane in several suites of natural gases, suggesting the causes of clumped isotope variations are tied to the controls on gas wetness. An experiment examining ethane residual to high

  19. Characterization of non-methane hydrocarbons in Asian summer monsoon outflow observed by the CARIBIC aircraft

    NASA Astrophysics Data System (ADS)

    Baker, A. K.; Schuck, T. J.; Slemr, F.; van Velthoven, P.; Zahn, A.; Brenninkmeijer, C. A. M.

    2010-07-01

    Between April and December 2008 the CARIBIC commercial aircraft conducted monthly measurement flights between Frankfurt, Germany and Chennai, India. These flights covered the period of the Asian summer monsoon (June-September), during which enhancements in a number of atmospheric species were observed in monsoon outflow. In addition to in situ measurements of trace gases and aerosols, whole air samples were collected during the flights, and these were subsequently analyzed for a suite of trace gases that included the non-methane hydrocarbons. Non-methane hydrocarbons are relatively short-lived compounds and the large enhancements in their mixing ratios in the upper troposphere over Southwest Asia between June and September, sometimes more than double their spring and fall means, provides qualitative evidence for the influence of convectively uplifted boundary layer air. The particularly large enhancements of the combustion tracers benzene and ethyne, along with the similarity of their ratios to carbon monoxide and emission ratios from the burning of household biofuels, indicate a strong influence of biofuel burning to NMHC emissions in this region. Conversely, the ratios of ethane and propane to carbon monoxide, along with the ratio between i-butane and n-butane, indicate a significant source of these compounds from the use of LPG and natural gas, and comparison to previous campaigns suggests that this source could be increasing. Photochemical aging patterns of NMHCs showed that the CARIBIC samples were collected in two distinctly different regions of the monsoon circulation: a southern region where air masses had been recently influenced by low level contact and a northern region, where air parcels had spent substantial time in transit in the upper troposphere before being probed. Estimates of age using ratios of individual NMHCs have ranges of 3-6 d in the south and 9-12 d in the north.

  20. Characterization of non-methane hydrocarbons in Asian summer monsoon outflow observed by the CARIBIC aircraft

    NASA Astrophysics Data System (ADS)

    Baker, A. K.; Schuck, T. J.; Slemr, F.; van Velthoven, P.; Zahn, A.; Brenninkmeijer, C. A. M.

    2011-01-01

    Between April and December 2008 the CARIBIC commercial aircraft conducted monthly measurement flights between Frankfurt, Germany and Chennai, India. These flights covered the period of the Asian summer monsoon (June-September), during which enhancements in a number of atmospheric species were observed in the upper troposphere over southwestern Asia. In addition to in situ measurements of trace gases and aerosols, whole air samples were collected during the flights, and these were subsequently analyzed for a suite of trace gases that included a number of C2-C8 non-methane hydrocarbons. Non-methane hydrocarbons are relatively short-lived compounds and the large enhancements in their mixing ratios in the upper troposphere over southwestern Asia during the monsoon, sometimes more than double their spring and fall means, provides qualitative evidence for the influence of convectively uplifted boundary layer air. The particularly large enhancements of the combustion tracers benzene and ethyne, along with the similarity of their ratios with carbon monoxide and emission ratios from the burning of household biofuels, indicate a strong influence of biofuel burning to NMHC emissions in this region. Conversely, the ratios of ethane and propane to carbon monoxide, along with the ratio between i-butane and n-butane, indicate a significant source of these compounds from the use of fossil fuels, and comparison to previous campaigns suggests that this source could be increasing. Photochemical aging patterns of NMHCs showed that the CARIBIC samples were collected in two distinctly different regions of the monsoon circulation: a southern region where air masses had been recently influenced by low level contact and a northern region, where air parcels had spent substantial time in transit in the upper troposphere before being probed. Estimates of age using ratios of individual NMHCs have ranges of 3-6 days in the south and 9-12 days in the north.

  1. Ethane-xenon mixtures under shock conditions

    NASA Astrophysics Data System (ADS)

    Flicker, Dawn; Magyar, Rudolph; Root, Seth; Cochrane, Kyle; Mattsson, Thomas

    2015-06-01

    Mixtures of light and heavy elements arise in inertial confinement fusion and planetary science. We present results on the physics of molecular scale mixing through a validation study of equation of state (EOS) properties. Density functional theory molecular dynamics (DFT/QMD) at elevated-temperature and pressure is used to obtain the properties of pure xenon, ethane, and various compressed mixture compositions along their principal Hugoniots. To validate the QMD simulations, we performed high-precision shock compression experiments using Sandia's Z-Machine. A bond tracking analysis of the simulations correlates the sharp rise in the Hugoniot curve with completion of dissociation in ethane. DFT-based simulation results compare well with experimental data and are used to provide insight into the dissociation as a function of mixture composition. Interestingly, we find that the compression ratio for complete dissociation is similar for ethane, Xe-ethane, polymethyl-pentene, and polystyrene, suggesting that a limiting compression exists for C-C bonded systems. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, Security Administration under contract DE-AC04-94AL85000.

  2. The Energy of Substituted Ethanes. Asymmetry Orbitals

    PubMed Central

    Salem, Lionel; Hoffmann, Roald; Otto, Peter

    1973-01-01

    The leading terms in the energy of a general substituted ethane are derived in explicit form as a function of the torsional angle θ, the substituent electronegativities, and their mutual overlaps. The energy is found to be the sum of all four overlaps between pairs of asymmetry orbitals, and satisfies the requisite symmetry properties. PMID:16592060

  3. Emission of methane, carbon monoxide, carbon dioxide and short‐chain hydrocarbons from vegetation foliage under ultraviolet irradiation

    PubMed Central

    FRASER, WESLEY T.; BLEI, EMANUEL; FRY, STEPHEN C.; NEWMAN, MARK F.; REAY, DAVID S.; SMITH, KEITH A.

    2015-01-01

    Abstract The original report that plants emit methane (CH 4) under aerobic conditions caused much debate and controversy. Critics questioned experimental techniques, possible mechanisms for CH 4 production and the nature of estimating global emissions. Several studies have now confirmed that aerobic CH 4 emissions can be detected from plant foliage but the extent of the phenomenon in plants and the precise mechanisms and precursors involved remain uncertain. In this study, we investigated the role of environmentally realistic levels of ultraviolet (UV) radiation in causing the emission of CH 4 and other gases from foliage obtained from a wide variety of plant types. We related our measured emissions to the foliar content of methyl esters and lignin and to the epidermal UV absorbance of the species investigated. Our data demonstrate that the terrestrial vegetation foliage sampled did emit CH 4, with a range in emissions of 0.6–31.8 ng CH 4 g−1 leaf DW h−1, which compares favourably with the original reports of experimental work. In addition to CH 4 emissions, our data show that carbon monoxide, ethene and propane are also emitted under UV stress but we detected no significant emissions of carbon dioxide or ethane. PMID:25443986

  4. Emission of methane, carbon monoxide, carbon dioxide and short-chain hydrocarbons from vegetation foliage under ultraviolet irradiation.

    PubMed

    Fraser, Wesley T; Blei, Emanuel; Fry, Stephen C; Newman, Mark F; Reay, David S; Smith, Keith A; McLeod, Andy R

    2015-05-01

    The original report that plants emit methane (CH4 ) under aerobic conditions caused much debate and controversy. Critics questioned experimental techniques, possible mechanisms for CH4 production and the nature of estimating global emissions. Several studies have now confirmed that aerobic CH4 emissions can be detected from plant foliage but the extent of the phenomenon in plants and the precise mechanisms and precursors involved remain uncertain. In this study, we investigated the role of environmentally realistic levels of ultraviolet (UV) radiation in causing the emission of CH4 and other gases from foliage obtained from a wide variety of plant types. We related our measured emissions to the foliar content of methyl esters and lignin and to the epidermal UV absorbance of the species investigated. Our data demonstrate that the terrestrial vegetation foliage sampled did emit CH4 , with a range in emissions of 0.6-31.8 ng CH4  g(-1) leaf DW h(-1) , which compares favourably with the original reports of experimental work. In addition to CH4 emissions, our data show that carbon monoxide, ethene and propane are also emitted under UV stress but we detected no significant emissions of carbon dioxide or ethane. © 2014 The Authors. Plant, Cell & Environment published by John Wiley & Sons Ltd.

  5. Enhanced ethylene and ethane production with free-radical cracking catalysts.

    PubMed

    Kolts, J H; Delzer, G A

    1986-05-09

    A series of free-radical catalysts have been discovered that increase the yield of highly valuable olefins from the cracking of low molecular weight paraffins. For example, catalytic cracking of n-butane, isobutane, and propane over manganese or iron supported on magnesium oxide (MgO) gave product distributions different from those given by thermal (free-radical) cracking or cracking over traditional acid catalysts. With n-butane and propane feeds, the products from catalytic cracking included large amounts of ethylene and ethane; with isobutane feed, propylene was the major product. Physical characterization of the MgO-supported catalyst showed the manganese to be in a 2+ oxidation state in the reduced catalyst and a 4+ oxidation state in the fully oxidized catalyst. Manganese was also shown to be uniformly distributed in the support material with very little enrichment at the surface. Matrix isolation of the gasphase radicals from n-butane feed showed that ethyl and methyl radicals were produced over the active catalysts. In the thermal process, only methyl radicals were produced. The mechanism of the catalytic reaction appears to be selective formation of primary carbanions at the catalyst surface followed by electron transfer and release of primary hydrocarbon radicals to the gas phase.

  6. Features of propane conversion in the presence of SmVO3 and SmVO4

    NASA Astrophysics Data System (ADS)

    Markova, E. B.; Lyadov, A. S.; Kurilkin, V. V.

    2016-09-01

    Features of propane conversion in the presence of samarium vanadite and samarium vanadate, both produced via solid-phase synthesis, are studied. It is shown that SmVO3 catalyzes mainly the propane cracking process to form methane and ethylene, while SmVO4 equally accelerates both cracking and the dehydrogenation of propane. Based on the results from catalytic experiments, energies of activation are calculated for the thermal cracking of propane (104 kJ/mol) and the conversion of propane in the presence of SmVO3 (39 kJ/mol) and SmVO4 (42 kJ/mol). The thermal stability of SmVO4 in a hydrogen atmosphere is studied via temperature-programmed reduction, while SmVO3 stability in an oxidizing environment is studied by DTA. Energies of activation for the reduction of SmVO4 (75 kJ/mol) and the oxidation of SmVO3 (244 kJ/mol) are calculated using the Kissinger method.

  7. RMP Guidance for Propane Storage Facilities - Main Text

    EPA Pesticide Factsheets

    This document is intended as comprehensive Risk Management Program guidance for larger propane storage or distribution facilities who already comply with propane industry standards. Includes sample RMP, and release calculations.

  8. Low-Temperature Vapor Pressures of Ethylene and Propane

    NASA Astrophysics Data System (ADS)

    Nelson, R. N.; Allen, J. E., Jr.; Harris, B., Sr.

    1997-07-01

    Mass spectra from the Galileo probe exhibit a cluster of peaks associated with two- and three-carbon hydrocarbons and two have been identified as ethylene and propane (Niemann et al. 1996). These molecules are important in the photochemical cycle of methane and are expected to be present in the atmospheres of the outer planets and Titan. To properly model related physical and chemical processes, e.g., cloud formation, it is important to have accurate thermodynamic data for these and other light hydrocarbons over the appropriate temperature and pressure range. The apparatus developed to determine the vapor pressures of gases and gas mixtures (Allen, Nelson, and Harris 1996) has been modified to provide a greater temperature range. Using this new system we have measured the vapor pressure of propane which, besides its role as a constituent in outer-planet atmospheres, is also a good calibration source since its vapor pressure is well determined over the temperature range of interest. The vapor pressure of ethylene was then determined. Little data are available for ethylene below its triple point (104 K); however we were able to extend our measurements past that point into the solid-phase region. The results of our vapor pressure measurements for these gases are presented along with comparisons with existing data sets. Allen, J.E., Jr., Nelson, R.N., Harris, B.C, Sr. 1996, B.A.A.S. underline {28}, 1157. Niemann, H.B. et al. 1996, Science 272, underline {842} and P.R. Mahaffy (private communication).

  9. Photoinduced ethane formation from reaction of ethene with matrix-isolated Ti, V, or Nb atoms.

    PubMed

    Thompson, Matthew G K; Parnis, J Mark

    2005-10-27

    The reactions of matrix-isolated Ti, V, or Nb atoms with ethene (C(2)H(4)) have been studied by FTIR absorption spectroscopy. Under conditions where the ethene dimer forms, metal atoms react with the ethene dimer to yield matrix-isolated ethane (C(2)H(6)) and methane. Under lower ethene concentration conditions ( approximately 1:70 ethene/Ar), hydridic intermediates of the types HMC(2)H(3) and H(2)MC(2)H(2) are also observed, and the relative yield of hydrocarbons is diminished. Reactions of these metals with perdeuterioethene, and equimolar mixtures of C(2)H(4) and C(2)D(4), yield products that are consistent with the production of ethane via a metal atom reaction involving at least two C(2)H(4) molecules. The absence of any other observed products suggests the mechanism also involves production of small, highly symmetric species such as molecular hydrogen and metal carbides. Evidence is presented suggesting that ethane production from the ethene dimer is a general photochemical process for the reaction of excited-state transition-metal atoms with ethene at high concentrations of ethene.

  10. . . . While Others Conserve Cash by Converting from Gasoline to Propane.

    ERIC Educational Resources Information Center

    Rasmussen, Scott A.

    1988-01-01

    Since 1983, when the David Douglas Public Schools (Portland, Oregon) converted 30 buses to propane fuel, the district has saved $75,000 in fuel and maintenance costs. Propane is priced consistently lower than gasoline and burns cleaner. Since propane engines do not require a carburetor, there are fewer maintenance problems. (MLH)

  11. . . . While Others Conserve Cash by Converting from Gasoline to Propane.

    ERIC Educational Resources Information Center

    Rasmussen, Scott A.

    1988-01-01

    Since 1983, when the David Douglas Public Schools (Portland, Oregon) converted 30 buses to propane fuel, the district has saved $75,000 in fuel and maintenance costs. Propane is priced consistently lower than gasoline and burns cleaner. Since propane engines do not require a carburetor, there are fewer maintenance problems. (MLH)

  12. Investigations on the "Extreme" Microbial Methane Cycle within the Sediments of an Acidic Impoundment of the Inactive Sulfur Bank Mercury Mine: Herman Pit, Clear Lake, California.

    NASA Astrophysics Data System (ADS)

    Oremland, R. S.; Baesman, S. M.; Miller, L. G.; Wei, J. H. C.; Welander, P. V.

    2014-12-01

    The inactive Sulfur Bank Mercury Mine is located in a volcanic region having geothermal flow and gas inputs into the Herman Pit impoundment. The acidic (pH 2 - 4) waters of the Herman Pit are permeated by hundreds of continuous flow gas seeps that contain CO2, H2S and CH4. We sampled one seep and found it to be composed of 95 % CO2 and 5 % CH4, in agreement with earlier measurements. Only a trace of ethane (10 - 20 ppm) was found and propane was below detection, resulting in a high CH4/C2H6 + C3H8 ratio of > 5,000, while the δ13CH4 and the δ13CO2 were respectively - 24 and - 11 per mil. Collectively, these results suggested a complex origin for the methane, being made up of a thermogenic component resulting from pyrolysis of buried organics, along with an active methanogenic portion. The relatively 12C-enriched value for the CO2 suggested a reworking of the ebullitive methane by methanotrophic bacteria. We found that dissolved methane in the collected water from 2-4 m depth was high (~ 400 µM), which would support methanotrophy in the lake's aerobic biomes. We therefore tested the ability of bottom sediments to consume methane by conducting aerobic incubations of slurried bottom sediments. Methane was removed from the headspace of live slurries, and subsequent additions of methane to the headspace over the course of 2-3 months resulted in faster removal rates suggesting a buildup of the population of methanotrophs. This activity could be transferred to an artificial medium originally devised for the cultivation of acidophilic iron oxidizing bacteria (Silverman and Lundgren, 1959; J. Bacteriol. 77: 642 - 647), suggesting the possibility of future cultivation of acidophilic methanotrophs. A successful extraction of some hopanoid compounds from the sediments was achieved, although the results were too preliminary at the time of this writing to identify any hopanoids specifically linked to methanotrophic bacteria. Further efforts to amplify functional genes for

  13. Portland Public School Children Move with Propane

    SciTech Connect

    Not Available

    2004-04-01

    This 2-page Clean Cities fact sheet describes the use of propane as a fuel source for Portland Public Schools' fleet of buses. It includes information on the history of the program, along with contact information for the local Clean Cities Coordinator and Portland Public Schools.

  14. Case Study - Propane Bakery Delivery Step Vans

    SciTech Connect

    Laughlin, M.; Burnham, A.

    2016-04-01

    A switch to propane from diesel by a major Midwest bakery fleet showed promising results, including a significant displacement of petroleum, a drop in greenhouse gases and a fuel cost savings of seven cents per mile, according to a study recently completed by the U.S. Department of Energy's Argonne National Laboratory for the Clean Cities program.

  15. Case Study - Propane School Bus Fleets

    SciTech Connect

    Laughlin, M; Burnham, A.

    2014-08-31

    As part of the U.S. Department of Energy’s (DOE’s) effort to deploy transportation technologies that reduce U.S. dependence on imported petroleum, this study examines five school districts, one in Virginia and four in Texas, successful use of propane school buses. These school districts used school buses equipped with the newly developed liquid propane injection system that improves vehicle performance. Some of the school districts in this study saved nearly 50% on a cost per mile basis for fuel and maintenance relative to diesel. Using Argonne National Laboratory’s Alternative Fuel Life-Cycle Environmental and Economic Transportation (AFLEET) Tool developed for the DOE’s Clean Cities program to help Clean Cities stakeholders estimate petroleum use, greenhouse gas (GHG) emissions, air pollutant emissions and cost of ownership of light-duty and heavy-duty vehicles, the results showed payback period ranges from 3—8 years, recouping the incremental cost of the vehicles and infrastructure. Overall, fuel economy for these propane vehicles is close to that of displaced diesel vehicles, on an energy-equivalent basis. In addition, the 110 propane buses examined demonstrated petroleum displacement, 212,000 diesel gallon equivalents per year, and GHG benefits of 770 tons per year.

  16. CASSINI VIMS OBSERVATIONS SHOW ETHANE IS PRESENT IN TITAN'S RAINFALL

    SciTech Connect

    Dalba, Paul A.; Buratti, Bonnie J.; Baines, Kevin H.; Sotin, Christophe; Lawrence, Kenneth J.; Brown, Robert H.; Barnes, Jason W.; Clark, Roger N.; Nicholson, Philip D.

    2012-12-20

    Observations obtained over two years by the Cassini Imaging Science Subsystem suggest that rain showers fall on the surface. Using measurements obtained by the Visual Infrared Mapping Spectrometer, we identify the main component of the rain to be ethane, with methane as an additional component. We observe five or six probable rainfall events, at least one of which follows a brief equatorial cloud appearance, suggesting that frequent rainstorms occur on Titan. The rainfall evaporates, sublimates, or infiltrates on timescales of months, and in some cases it is associated with fluvial features but not with their creation or alteration. Thus, Titan exhibits frequent 'gentle rainfall' instead of, or in addition to, more catastrophic events that cut rivers and lay down large fluvial deposits. Freezing rain may also be present, and the standing liquid may exist as puddles interspersed with patches of frost. The extensive dune deposits found in the equatorial regions of Titan imply multi-season arid conditions there, which are consistent with small, but possibly frequent, amounts of rain, in analogy to terrestrial deserts.

  17. Reduction of halogenated ethanes by green rust.

    SciTech Connect

    O'Loughlin, E. J.; Burris, D. R.; Environmental Research; Air Force Research Lab.; Integrated Science and Technology, Inc.

    2004-01-01

    Green rusts, mixed Fe{sup II}/Fe{sup III} hydroxide minerals present in many suboxic environments, have been shown to reduce a number of organic and inorganic contaminants. The reduction of halogenated ethanes was examined in aqueous suspensions of green rust, both alone and with the addition of Ag{sup I} (AgGR) and Cu{sup II} (CuGR). Hexachloroethane (HCA), pentachloroethane (PCA), 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA), 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA), 1,1,1-trichloroethane (1,1,1-TCA), 1,1,2-trichloroethane (1,1,2-TCA), 1,1-dichloroethane (1,1-DCA), and 1,2-dibromoethane were reduced in the presence of green rust alone, AgGR, or CuGR; only 1,2-dichloroethane and chloroethane were nonreactive. The reduction was generally more rapid for more highly substituted ethanes than for ethanes having fewer halogen groups (HCA > PCA > 1,1,1,2-TeCA > 1,1,1-TCA > 1,1,2,2-TeCA > 1,1,2-TCA > 1,1-DCA), and isomers with the more asymmetric distributions of halogen groups were more rapidly reduced than the isomer with greater symmetry (e.g., 1,1,1-TCA > 1,1,2-TCA). The addition of Ag{sup I} or Cu{sup II} to green rust suspensions resulted in a substantial increase in the rate of halogenated ethane reduction as well as significant differences in the product distributions with respect to green rust alone.

  18. Photochemical Carbonylation of Ethane Under Supercritical Conditions

    SciTech Connect

    Bitterwolf, Thomas E.; Klein, Dinara L.; Linehan, John C. ); Yonker, Clement R. ); Addleman, Raymond S. )

    2001-01-01

    The photochemical carbonylation of hydrocarbons and aromatic compounds[Eq. (1)] by rhodium catalysts of the general formula[Rh(CO)L2 Cl] (where L? PMe3 , PPh3 ) is well known,[1] and the mechanism of these reactions has been examined by several groups.[2] This reaction has been extended to liquid propane[3] and recently the carbonylation of benzene to benzaldehyde and benzyl alcohol in supercritical CO2 (scCO2 ), has been reported in the patent literature.[4

  19. Identifying different types of catalysts for CO2 reduction by ethane through dry reforming and oxidative dehydrogenation

    DOE PAGES

    Marc D. Porosoff; Chen, Jingguang G.; Myint, Myat Noe Zin; ...

    2015-11-10

    In this study, the recent shale gas boom combined with the requirement to reduce atmospheric CO2 have created an opportunity for using both raw materials (shale gas and CO2) in a single process. Shale gas is primarily made up of methane, but ethane comprises about 10 % and reserves are underutilized. Two routes have been investigated by combining ethane decomposition with CO2 reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H2). The second route is oxidative dehydrogenation which produces ethylene using CO2 as a soft oxidant. The results of thismore » study indicate that the Pt/CeO2 catalyst shows promise for the production of synthesis gas, while Mo2C-based materials preserve the C—C bond of ethane to produce ethylene. These findings are supported by density functional theory (DFT) calculations and X-ray absorption near-edge spectroscopy (XANES) characterization of the catalysts under in situ reaction conditions.« less

  20. Identifying different types of catalysts for CO2 reduction by ethane through dry reforming and oxidative dehydrogenation

    SciTech Connect

    Marc D. Porosoff; Chen, Jingguang G.; Myint, Myat Noe Zin; Kattel, Shyam; Xie, Zhenhua; Gomez, Elaine; Liu, Ping

    2015-11-10

    In this study, the recent shale gas boom combined with the requirement to reduce atmospheric CO2 have created an opportunity for using both raw materials (shale gas and CO2) in a single process. Shale gas is primarily made up of methane, but ethane comprises about 10 % and reserves are underutilized. Two routes have been investigated by combining ethane decomposition with CO2 reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H2). The second route is oxidative dehydrogenation which produces ethylene using CO2 as a soft oxidant. The results of this study indicate that the Pt/CeO2 catalyst shows promise for the production of synthesis gas, while Mo2C-based materials preserve the C—C bond of ethane to produce ethylene. These findings are supported by density functional theory (DFT) calculations and X-ray absorption near-edge spectroscopy (XANES) characterization of the catalysts under in situ reaction conditions.

  1. Mobile Laboratory Observations of Methane Emissions in the Barnett Shale Region.

    PubMed

    Yacovitch, Tara I; Herndon, Scott C; Pétron, Gabrielle; Kofler, Jonathan; Lyon, David; Zahniser, Mark S; Kolb, Charles E

    2015-07-07

    Results of mobile ground-based atmospheric measurements conducted during the Barnett Shale Coordinated Campaign in spring and fall of 2013 are presented. Methane and ethane are continuously measured downwind of facilities such as natural gas processing plants, compressor stations, and production well pads. Gaussian dispersion simulations of these methane plumes, using an iterative forward plume dispersion algorithm, are used to estimate both the source location and the emission magnitude. The distribution of emitters is peaked in the 0-5 kg/h range, with a significant tail. The ethane/methane molar enhancement ratio for this same distribution is investigated, showing a peak at ∼1.5% and a broad distribution between ∼4% and ∼17%. The regional distributions of source emissions and ethane/methane enhancement ratios are examined: the largest methane emissions appear between Fort Worth and Dallas, while the highest ethane/methane enhancement ratios occur for plumes observed in the northwestern potion of the region. Individual facilities, focusing on large emitters, are further analyzed by constraining the source location.

  2. Absolute molecular sieve separation of ethylene/ethane mixtures with silver zeolite A.

    PubMed

    Aguado, Sonia; Bergeret, Gérard; Daniel, Cecile; Farrusseng, David

    2012-09-12

    Absolute ethylene/ethane separation is achieved by ethane exclusion on silver-exchanged zeolite A adsorbent. This molecular sieving type separation is attributed to the pore size of the adsorbent, which falls between ethylene and ethane kinetic diameters.

  3. High-pressure oxidation of ethane

    DOE PAGES

    Hashemi, Hamid; Jacobsen, Jon G.; Rasmussen, Christian T.; ...

    2017-05-02

    Here, ethane oxidation at intermediate temperatures and high pressures has been investigated in both a laminar flow reactor and a rapid compression machine (RCM). The flow-reactor measurements at 600–900 K and 20–100 bar showed an onset temperature for oxidation of ethane between 700 and 825 K, depending on pressure, stoichiometry, and residence time. Measured ignition delay times in the RCM at pressures of 10–80 bar and temperatures of 900–1025 K decreased with increasing pressure and/or temperature. A detailed chemical kinetic model was developed with particular attention to the peroxide chemistry. Rate constants for reactions on the C2H5O2 potential energy surfacemore » were adopted from the recent theoretical work of Klippenstein. In the present work, the internal H-abstraction in CH3CH2OO to form CH2CH2OOH was treated in detail. Modeling predictions were in good agreement with data from the present work as well as results at elevated pressure from literature. The experimental results and the modeling predictions do not support occurrence of NTC behavior in ethane oxidation. Even at the high-pressure conditions of the present work where the C2H5 + O2 reaction yields ethylperoxyl rather than C2H4 + HO2, the chain branching sequence CH3CH2OO → CH2CH2OOH → +O2 OOCH2CH2OOH → branching is not competitive, because the internal H-atom transfer in CH3CH2OO to CH2CH2OOH is too slow compared to thermal dissociation to C2H4 and HO2.« less

  4. Adsorptive separation of propylene-propane mixtures

    SciTech Connect

    Jaervelin, H.; Fair, J.R. )

    1993-10-01

    The separation of propylene-propane mixtures is of great commercial importance and is carried out by fractional distillation. It is claimed to be the most energy-intensive distillation practiced in the United States. The purpose of this paper is to describe experimental work that suggests a practical alternative to distillation for separating the C[sub 3] hydrocarbons: adsorption. As studied, the process involves three adsorptive steps: initial separation with molecular sieves with heavy dilution with an inert gas; separation of propylene and propane separately from the inert gas, using activated carbon; and drying of the product streams with any of several available desiccants. The research information presented here deals with the initial step and includes both equilibrium and kinetic data. Isotherms are provided for propylene and propane adsorbed on three zeolites, activated alumina, silica gel, and coconut-based activated carbon. Breakthrough data are provided for both adsorption and regeneration steps for the zeolites, which were found to be superior to the other adsorbents for breakthrough separations. A flow diagram for the complete proposed process is included.

  5. Gas carburizing of steel with furnace atmospheres formed in situ from methane and air and from butane and air

    NASA Astrophysics Data System (ADS)

    Stickels, C. A.; Mack, C. M.; Pieprzak, J. A.

    1992-01-01

    Carburizing experiments were conducted at 927 °C (1700 °F) and 843 °C (1550 °F) using furnace atmospheres formed from methane and air and from butane and air introduced directly into the carburizing furnace. Gas flow rates were low to promote equilibration of the reaction products within the furnace. The air flow rate was held constant while the methane or butane flow was automatically regulated to maintain a constant oxygen potential, as measured by a zirconia oxygen sensor, within the furnace. In comparing the results of these experiments with earlier results obtained using propane and air, several differences were noted: (a) The methane content of the furnace atmosphere, measured by infrared analysis, was about twice as great when methane was the feed gas rather than propane or butane. This was true despite the fact that the mean residence time of the gas within the furnace was greater in the methane experiments. Methane appears to be less effective than propane or butane in reducing the CO2 and H2O contents to the levels required for carburizing. (b) There was a greater tendency for the CO content of the furnace atmosphere to decrease at high carbon potentials when methane is used instead of propane or butane. The decrease in CO content is due to hydrogen dilution caused by sooting in the furnace vestibule. These differences in behavior make propane or butane better suited than methane for in situ generation of carburizing atmospheres. However, there is no difference in the amount of carburizing occurring at a specified carbon potential when methane, propane, or butane are used as the feed gas in this process.

  6. Photolysis of methane and the ionosphere of Uranus

    NASA Astrophysics Data System (ADS)

    Atreya, S. K.; Ponthieu, J. J.

    1983-08-01

    Photochemical calculations for Uranus predict an extensive region of condensation of acetylene, ethane and methane in the vicinity of the temperature inversion layer. This could explain why ethane was not detected on Uranus, unlike Neptune which has a much warmer inversion layer. Subsequent snow-out of the condensibles is expected to result in reduced visibility in the troposphere. Ionospheric calculations for the equatorial region to be probed by Voyager, indicate peak electron concentrations on the order of 5×103 cm-3, if dynamical effects are important. Upper limit to the electron peak is 3×104 cm-3. Exospheric temperatures as high as 200-250K are conceivable.

  7. Attributing Atmospheric Methane to Anthropogenic Emission Sources.

    PubMed

    Allen, David

    2016-07-19

    Methane is a greenhouse gas, and increases in atmospheric methane concentration over the past 250 years have driven increased radiative forcing of the atmosphere. Increases in atmospheric methane concentration since 1750 account for approximately 17% of increases in radiative forcing of the atmosphere, and that percentage increases by approximately a factor of 2 if the effects of the greenhouse gases produced by the atmospheric reactions of methane are included in the assessment. Because of the role of methane emissions in radiative forcing of the atmosphere, the identification and quantification of sources of methane emissions is receiving increased scientific attention. Methane emission sources include biogenic, geogenic, and anthropogenic sources; the largest anthropogenic sources are natural gas and petroleum systems, enteric fermentation (livestock), landfills, coal mining, and manure management. While these source categories are well-known, there is significant uncertainty in the relative magnitudes of methane emissions from the various source categories. Further, the overall magnitude of methane emissions from all anthropogenic sources is actively debated, with estimates based on source sampling extrapolated to regional or national scale ("bottom-up analyses") differing from estimates that infer emissions based on ambient data ("top-down analyses") by 50% or more. To address the important problem of attribution of methane to specific sources, a variety of new analytical methods are being employed, including high time resolution and highly sensitive measurements of methane, methane isotopes, and other chemical species frequently associated with methane emissions, such as ethane. This Account describes the use of some of these emerging measurements, in both top-down and bottom-up methane emission studies. In addition, this Account describes how data from these new analytical methods can be used in conjunction with chemical mass balance (CMB) methods for source

  8. Anaerobic degradation of propane and butane by sulfate-reducing bacteria enriched from marine hydrocarbon cold seeps

    PubMed Central

    Jaekel, Ulrike; Musat, Niculina; Adam, Birgit; Kuypers, Marcel; Grundmann, Olav; Musat, Florin

    2013-01-01

    The short-chain, non-methane hydrocarbons propane and butane can contribute significantly to the carbon and sulfur cycles in marine environments affected by oil or natural gas seepage. In the present study, we enriched and identified novel propane and butane-degrading sulfate reducers from marine oil and gas cold seeps in the Gulf of Mexico and Hydrate Ridge. The enrichment cultures obtained were able to degrade simultaneously propane and butane, but not other gaseous alkanes. They were cold-adapted, showing highest sulfate-reduction rates between 16 and 20 °C. Analysis of 16S rRNA gene libraries, followed by whole-cell hybridizations with sequence-specific oligonucleotide probes showed that each enrichment culture was dominated by a unique phylotype affiliated with the Desulfosarcina-Desulfococcus cluster within the Deltaproteobacteria. These phylotypes formed a distinct phylogenetic cluster of propane and butane degraders, including sequences from environments associated with hydrocarbon seeps. Incubations with 13C-labeled substrates, hybridizations with sequence-specific probes and nanoSIMS analyses showed that cells of the dominant phylotypes were the first to become enriched in 13C, demonstrating that they were directly involved in hydrocarbon degradation. Furthermore, using the nanoSIMS data, carbon assimilation rates were calculated for the dominant cells in each enrichment culture. PMID:23254512

  9. Anaerobic degradation of propane and butane by sulfate-reducing bacteria enriched from marine hydrocarbon cold seeps.

    PubMed

    Jaekel, Ulrike; Musat, Niculina; Adam, Birgit; Kuypers, Marcel; Grundmann, Olav; Musat, Florin

    2013-05-01

    The short-chain, non-methane hydrocarbons propane and butane can contribute significantly to the carbon and sulfur cycles in marine environments affected by oil or natural gas seepage. In the present study, we enriched and identified novel propane and butane-degrading sulfate reducers from marine oil and gas cold seeps in the Gulf of Mexico and Hydrate Ridge. The enrichment cultures obtained were able to degrade simultaneously propane and butane, but not other gaseous alkanes. They were cold-adapted, showing highest sulfate-reduction rates between 16 and 20 °C. Analysis of 16S rRNA gene libraries, followed by whole-cell hybridizations with sequence-specific oligonucleotide probes showed that each enrichment culture was dominated by a unique phylotype affiliated with the Desulfosarcina-Desulfococcus cluster within the Deltaproteobacteria. These phylotypes formed a distinct phylogenetic cluster of propane and butane degraders, including sequences from environments associated with hydrocarbon seeps. Incubations with (13)C-labeled substrates, hybridizations with sequence-specific probes and nanoSIMS analyses showed that cells of the dominant phylotypes were the first to become enriched in (13)C, demonstrating that they were directly involved in hydrocarbon degradation. Furthermore, using the nanoSIMS data, carbon assimilation rates were calculated for the dominant cells in each enrichment culture.

  10. Ethane Ices in the Outer Solar System: Spectroscopy and Chemistry

    NASA Technical Reports Server (NTRS)

    Hudson, R. L.; Moore, M. H.; Raines, L. L.

    2009-01-01

    We report recent experiments on ethane ices made at temperatures applicable to the outer Solar System. New near- and mid-infrared data for crystalline and amorphous ethane, including new spectra for a seldom-studied solid phase that exists at 35-55 K, are presented along with radiation-chemical experiments showing the formation of more-complex hydrocarbons,

  11. 10 CFR 221.11 - Natural gas and ethane.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 3 2012-01-01 2012-01-01 false Natural gas and ethane. 221.11 Section 221.11 Energy DEPARTMENT OF ENERGY OIL PRIORITY SUPPLY OF CRUDE OIL AND PETROLEUM PRODUCTS TO THE DEPARTMENT OF DEFENSE UNDER THE DEFENSE PRODUCTION ACT Exclusions § 221.11 Natural gas and ethane. The supply of natural gas...

  12. 10 CFR 221.11 - Natural gas and ethane.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 10 Energy 3 2014-01-01 2014-01-01 false Natural gas and ethane. 221.11 Section 221.11 Energy DEPARTMENT OF ENERGY OIL PRIORITY SUPPLY OF CRUDE OIL AND PETROLEUM PRODUCTS TO THE DEPARTMENT OF DEFENSE UNDER THE DEFENSE PRODUCTION ACT Exclusions § 221.11 Natural gas and ethane. The supply of natural gas...

  13. 10 CFR 221.11 - Natural gas and ethane.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 3 2013-01-01 2013-01-01 false Natural gas and ethane. 221.11 Section 221.11 Energy DEPARTMENT OF ENERGY OIL PRIORITY SUPPLY OF CRUDE OIL AND PETROLEUM PRODUCTS TO THE DEPARTMENT OF DEFENSE UNDER THE DEFENSE PRODUCTION ACT Exclusions § 221.11 Natural gas and ethane. The supply of natural gas...

  14. 10 CFR 221.11 - Natural gas and ethane.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 3 2010-01-01 2010-01-01 false Natural gas and ethane. 221.11 Section 221.11 Energy DEPARTMENT OF ENERGY OIL PRIORITY SUPPLY OF CRUDE OIL AND PETROLEUM PRODUCTS TO THE DEPARTMENT OF DEFENSE UNDER THE DEFENSE PRODUCTION ACT Exclusions § 221.11 Natural gas and ethane. The supply of natural gas...

  15. 10 CFR 221.11 - Natural gas and ethane.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 10 Energy 3 2011-01-01 2011-01-01 false Natural gas and ethane. 221.11 Section 221.11 Energy DEPARTMENT OF ENERGY OIL PRIORITY SUPPLY OF CRUDE OIL AND PETROLEUM PRODUCTS TO THE DEPARTMENT OF DEFENSE UNDER THE DEFENSE PRODUCTION ACT Exclusions § 221.11 Natural gas and ethane. The supply of natural gas...

  16. Ethane Ices in the Outer Solar System: Spectroscopy and Chemistry

    NASA Technical Reports Server (NTRS)

    Hudson, R. L.; Moore, M. H.; Raines, L. L.

    2009-01-01

    We report recent experiments on ethane ices made at temperatures applicable to the outer Solar System. New near- and mid-infrared data for crystalline and amorphous ethane, including new spectra for a seldom-studied solid phase that exists at 35-55 K, are presented along with radiation-chemical experiments showing the formation of more-complex hydrocarbons

  17. Mechanism of Oxidation of Ethane to Ethanol at Iron(IV)-Oxo Sites in Magnesium-Diluted Fe2(dobdc).

    PubMed

    Verma, Pragya; Vogiatzis, Konstantinos D; Planas, Nora; Borycz, Joshua; Xiao, Dianne J; Long, Jeffrey R; Gagliardi, Laura; Truhlar, Donald G

    2015-05-06

    The catalytic properties of the metal-organic framework Fe2(dobdc), containing open Fe(II) sites, include hydroxylation of phenol by pure Fe2(dobdc) and hydroxylation of ethane by its magnesium-diluted analogue, Fe0.1Mg1.9(dobdc). In earlier work, the latter reaction was proposed to occur through a redox mechanism involving the generation of an iron(IV)-oxo species, which is an intermediate that is also observed or postulated (depending on the case) in some heme and nonheme enzymes and their model complexes. In the present work, we present a detailed mechanism by which the catalytic material, Fe0.1Mg1.9(dobdc), activates the strong C-H bonds of ethane. Kohn-Sham density functional and multireference wave function calculations have been performed to characterize the electronic structure of key species. We show that the catalytic nonheme-Fe hydroxylation of the strong C-H bond of ethane proceeds by a quintet single-state σ-attack pathway after the formation of highly reactive iron-oxo intermediate. The mechanistic pathway involves three key transition states, with the highest activation barrier for the transfer of oxygen from N2O to the Fe(II) center. The uncatalyzed reaction, where nitrous oxide directly oxidizes ethane to ethanol is found to have an activation barrier of 280 kJ/mol, in contrast to 82 kJ/mol for the slowest step in the iron(IV)-oxo catalytic mechanism. The energetics of the C-H bond activation steps of ethane and methane are also compared. Dehydrogenation and dissociation pathways that can compete with the formation of ethanol were shown to involve higher barriers than the hydroxylation pathway.

  18. Ethane-xenon mixtures under shock conditions

    SciTech Connect

    Magyar, Rudolph J.; Root, Seth; Mattsson, Thomas; Cochrane, Kyle Robert; Flicker, Dawn G.

    2015-04-22

    Mixtures of light elements with heavy elements are important in inertial confinement fusion. We explore the physics of molecular scale mixing through a validation study of equation of state (EOS) properties. Density functional theory molecular dynamics (DFT-MD) at elevated temperature and pressure is used to obtain the thermodynamic state properties of pure xenon, ethane, and various compressed mixture compositions along their principal Hugoniots. In order to validate these simulations, we have performed shock compression experiments using the Sandia Z-Machine. A bond tracking analysis correlates the sharp rise in the Hugoniot curve with the completion of dissociation in ethane. Furthermore, the DFT-based simulation results compare well with the experimental data along the principal Hugoniots and are used to provide insight into the dissociation and temperature along the Hugoniots as a function of mixture composition. Interestingly, we find that the compression ratio for complete dissociation is similar for several compositions suggesting a limiting compression for C-C bonded systems.

  19. Ethane-xenon mixtures under shock conditions

    DOE PAGES

    Magyar, Rudolph J.; Root, Seth; Mattsson, Thomas; ...

    2015-04-22

    Mixtures of light elements with heavy elements are important in inertial confinement fusion. We explore the physics of molecular scale mixing through a validation study of equation of state (EOS) properties. Density functional theory molecular dynamics (DFT-MD) at elevated temperature and pressure is used to obtain the thermodynamic state properties of pure xenon, ethane, and various compressed mixture compositions along their principal Hugoniots. In order to validate these simulations, we have performed shock compression experiments using the Sandia Z-Machine. A bond tracking analysis correlates the sharp rise in the Hugoniot curve with the completion of dissociation in ethane. Furthermore, themore » DFT-based simulation results compare well with the experimental data along the principal Hugoniots and are used to provide insight into the dissociation and temperature along the Hugoniots as a function of mixture composition. Interestingly, we find that the compression ratio for complete dissociation is similar for several compositions suggesting a limiting compression for C-C bonded systems.« less

  20. New directions for the catalytic conversion of methane. Final report, November 1987-October 1993

    SciTech Connect

    Lunsford, J.H.

    1994-11-01

    Three classes of catalysts have been studied for the oxidative coupling of methane to form ethane and ethylene. These include (1) molten lithium carbonate that was modified to improve activity and selectivity; (2) lithium-promoted magnesium oxide that contained chloride ions, and (3) selected transition metal ions on magnesium oxide or silicon oxide. Some of the most highly selective catalysts for producing ethane and ethylene from methane may be formed by the addition of manganese ions and sodium tungstate to either magnesium oxide or silica gel. These catalysts are effective at reagent pressures up to 5 atm.

  1. The effect of sulphur on the nonsteady state reaction of propane over a platinum/alumina catalyst at 873 K

    SciTech Connect

    Jackson, S.D.; Leeming, P.; Grenfell, J.

    1994-11-01

    The addition of sulphur to Pt/alumina catalysts, both in the preparation stage and in the gas phase during reaction, has been investigated as to the effect on catalyst activity and selectivity for propane dehydrogenation. The sole hydrocarbon product produced from pulses of propane over a freshly reduced Pt/alumina catalyst at 873 K in the absence of sulphur was methane, with concomitant carbon laydown. The effect on activity and selectivity of predosing the catalyst with hydrogen sulphide at 293 and 873 K was examined, as was the effect of cofeeding at ratios of 1:10 and 10:1 H{sub 2}S:C{sub 3}H{sub 8}. Predosing at 873 K had the largest effect on selectivity, allowing the formation of propene from the first pulse of propane, whereas cofeeding required the build-up of sulphur on the surface before selectivity was achieved. Adding sulphur into the catalyst preparation was more effective than subsequent addition from the gas phase. The results also indicated that the selectivity observed was not directly related to the amount of sulphur on the surface. The presence of a hydrogen reservoir on the catalyst, which was available for reaction, was detected using catalysts reduced in deuterium. The results also indicated that hydrogen from adsorbed hydrogen sulphide could react with hydrocarbon fragments on the catalyst surface to produce methane. 31 refs., 7 tabs.

  2. Characteristics of atmospheric non-methane hydrocarbons during haze episode in Beijing, China.

    PubMed

    Guo, Songjun; Tan, Jihua; Duan, Jingchun; Ma, Yongliang; Yang, Fumo; He, Kebin; Hao, Jimin

    2012-12-01

    This study firstly focused on non-methane hydrocarbons (NMHCs) during three successive days with haze episode (16-18 August 2006) in Beijing. Concentrations of alkanes, alkenes, aromatic hydrocarbons, and ethyne all peaked at traffic rush hour, implying vehicular emission; and alkanes also peaked at non-traffic rush hour in the daytime, implying additional source. Especially, alkanes and aromatics clearly showed higher levels in the nighttime than that in the daytime, implying their active photochemical reactions in the daytime. Correlation coefficients (R (2)) showed that propane, n-butane, i-butane, ethene, propene, and benzene correlated with ethyne (R (2) = 0.61-0.66), suggesting that their main source is vehicular emission; 2-methylpentane and n-hexane correlated with i-pentane (R (2) = 0.61-0.64), suggesting that gasoline evaporation is their main source; and ethylbezene, m-/p-xylene, and o-xylene correlated with toluene (R (2) = 0.60-0.79), suggesting that their main source is similar to that of toluene (e.g., solvent usage). The R (2) of ethyne, i-pentane, and toluene with total NMHCs were 0.58, 0.76, and 0.60, respectively, indicating that ambient hydrocarbons are associated with vehicular emission, gasoline evaporation, and solvent usage. The sources of other hydrocarbons (e.g., ethane) might be natural gas leakage, biogenic emission, or long-range transport of air pollutants. Measured higher mean B/T ratio (0.78 ± 0.27) was caused by the more intensive photochemical activity of toluene than benzene, still indicating the dominant emission from vehicles.

  3. Source attribution of methane emissions from global oil and gas production: results of bottom-up simulations over three decades

    NASA Astrophysics Data System (ADS)

    Höglund-Isaksson, Lena

    2016-04-01

    Existing bottom-up emission inventories of historical methane and ethane emissions from global oil and gas systems do not well explain year-on-year variations estimated by top-down models from atmospheric measurements. This paper develops a bottom-up methodology which allows for country- and year specific source attribution of methane and ethane emissions from global oil and natural gas production for the period 1980 to 2012. The analysis rests on country-specific simulations of associated gas flows which are converted into methane and ethane emissions. The associated gas flows are constructed from country-specific information on oil and gas production and associated gas generation and recovery, and coupled with generic assumptions to bridge regional information gaps on the fractions of unrecovered associated gas that is vented instead of flared. Summing up emissions from associated gas flows with global estimates of emissions from unintended leakage and natural gas transmission and distribution, the resulting global emissions of methane and ethane from oil and gas systems are reasonably consistent with corresponding estimates from top-down models. Also revealed is that the fall of the Soviet Union in 1990 had a significant impact on methane and ethane emissions from global oil and gas systems.

  4. The geochemistry of naturally occurring methane and saline groundwater in an area of unconventional shale gas development

    NASA Astrophysics Data System (ADS)

    Harkness, Jennifer S.; Darrah, Thomas H.; Warner, Nathaniel R.; Whyte, Colin J.; Moore, Myles T.; Millot, Romain; Kloppmann, Wolfram; Jackson, Robert B.; Vengosh, Avner

    2017-07-01

    Since naturally occurring methane and saline groundwater are nearly ubiquitous in many sedimentary basins, delineating the effects of anthropogenic contamination sources is a major challenge for evaluating the impact of unconventional shale gas development on water quality. This study investigates the geochemical variations of groundwater and surface water before, during, and after hydraulic fracturing and in relation to various geospatial parameters in an area of shale gas development in northwestern West Virginia, United States. To our knowledge, we are the first to report a broadly integrated study of various geochemical techniques designed to distinguish natural from anthropogenic sources of natural gas and salt contaminants both before and after drilling. These measurements include inorganic geochemistry (major cations and anions), stable isotopes of select inorganic constituents including strontium (87Sr/86Sr), boron (δ11B), lithium (δ7Li), and carbon (δ13C-DIC), select hydrocarbon molecular (methane, ethane, propane, butane, and pentane) and isotopic tracers (δ13C-CH4, δ13C-C2H6), tritium (3H), and noble gas elemental and isotopic composition (helium, neon, argon) in 105 drinking-water wells, with repeat testing in 33 of the wells (total samples = 145). In a subset of wells (n = 20), we investigated the variations in water quality before and after the installation of nearby (<1 km) shale-gas wells. Methane occurred above 1 ccSTP/L in 37% of the groundwater samples and in 79% of the samples with elevated salinity (chloride > 50 mg/L). The integrated geochemical data indicate that the saline groundwater originated via naturally occurring processes, presumably from the migration of deeper methane-rich brines that have interacted extensively with coal lithologies. These observations were consistent with the lack of changes in water quality observed in drinking-water wells following the installation of nearby shale-gas wells. In contrast to groundwater

  5. Titan's Propane from Cassini Infrared Spectroscopy

    NASA Astrophysics Data System (ADS)

    Nixon, C. A.; Jennings, D. E.; Flaud, J.-M.; Bezard, B.; Teanby, N. A.; Irwin, P. G. J.; Ansty, T. M.; Coustenis, A.; Flasar, F. M.

    2009-04-01

    Propane gas (C3H8) was first detected in the atmosphere of Titan by the Voyager 1 IRIS spectrometer, during the 1980 encounter (Maguire et al., 1981), and remains the heaviest saturated hydrocarbon (alkane) found there to date. Although the identification was based on the detection of several bands (including 748, 922, 1054, 1158 cm-1), only the ν26 band at 748 cm-1 has been subsequently modeled to retrieve the abundance, due to the unique availability of its line parameters in the GEISA database (Husson et al. 1992). Subsequent measurements from the ground (Roe et al., 2003) and Earth-orbit (ISO - Coustenis et al. 2003) have also focused on this one band, deriving an abundance of ~0.5 ppm, although it remains compromised by coincidence with the R-branch of the much stronger acetylene (C2H2) gas. The Composite Infrared Spectrometer (CIRS) instrument carried on-board the Cassini spacecraft in Saturn orbit has now been observing Titan during more than 50 flybys over 5 years, and offers a fresh perspective on the prevalence of propane. With much improved spectral and spatial resolution and sensitivity over IRIS, CIRS is also able to perform repeated limb sounding (viewing through the atmosphere above the surface) to increase signal-to-noise still further. Modeling and removal of the emissions of other gases now shows clearly for the first time a multitude of propane bands: including the four seen by IRIS and at least four others (869, 1338, 1376, 1472 cm-1). In addition, a new line atlas for three bands of propane at shorter wavelengths (1300-1500 cm-1) has now been compiled, based on the work of Flaud et al. (2001). With this, we now have the potential to model these weaker bands, and to check the measurements made by CIRS using the 748 cm-1 band alone. Preliminary analysis has shown that the retrievals are very sensitive to the spectral baseline (haze model) assumed, and that existing lab tholin spectral properties (Khare et al. 1984) do not well match the opacity

  6. Molecular dynamics simulations on gate opening in ZIF-8: identification of factors for ethane and propane separation.

    PubMed

    Zheng, Bin; Pan, Yichang; Lai, Zhiping; Huang, Kuo-Wei

    2013-07-16

    Gate opening of zeolitic imidazolate frameworks (ZIFs) is an important microscopic phenomenon in explaining the adsorption, diffusion, and separation processes for large guest molecules. We present a force field, with input from density functional theory (DFT) calculations, for the molecular dynamics simulation on the gate opening in ZIF-8. The computed self-diffusivities for sorbed C1 to C3 hydrocarbons were in good agreement with the experimental values. The observed sharp diffusion separation from C2H6 to C3H8 was elucidated by investigating the conformations of the guest molecules integrated with the flexibility of the host framework.

  7. 77 FR 2293 - AmeriGas Propane, L.P., AmeriGas Propane, Inc., Energy Transfer Partners, L.P., and Energy...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-01-17

    ... AmeriGas Propane, L.P., AmeriGas Propane, Inc., Energy Transfer Partners, L.P., and Energy Transfer...'') with AmeriGas Propane, L.P. (``AmeriGas''), AmeriGas Propane, Inc., Energy Transfer Partners, L.P. (``ETP''), and Energy Transfer Partners GP, L.P. (``ETP GP''), which is designed to guard...

  8. Solubility of crude oil in methane as a function of pressure and temperature

    USGS Publications Warehouse

    Price, L.C.; Wenger, L.M.; Ging, T.; Blount, C.W.

    1983-01-01

    The solubility of a 44?? API (0.806 sp. gr.) whole crude oil has been measured in methane with water present at temperatures of 50 to 250??C and pressures of 740 to 14,852 psi, as have the solubilities of two high molecular weight petroleum distillation fractions at temperatures of 50 to 250??C and pressures of 4482 to 25,266 psi. Both increases in pressure and temperature increase the solubility of crude oil and petroleum distillation fractions in methane, the effect of pressure being greater than that of temperature. Unexpectedly high solubility levels (0.5-1.5 grams of oil per liter of methane-at laboratory temperature and pressure) were measured at moderate conditions (50-200??C and 5076-14504 psi). Similar results were found for the petroleum distillation fractions, one of which was the highest molecular weight material of petroleum (material boiling above 266??C at 6 microns pressure). Unexpectedly mild conditions (100??C and 15,200 psi; 200??C and 7513 psi) resulted in cosolubility of crude oil and methane. Under these conditions, samples of the gas-rich phase gave solubility values of 4 to 5 g/l, or greater. Qualitative analyses of the crude-oil solute samples showed that at low pressure and temperature equilibration conditions, the solute condensate would be enriched in C5-C15 range hydrocarbons and in saturated hydrocarbons in the C15+ fraction. With increases in temperature and especially pressure, these tendencies were reversed, and the solute condensate became identical to the starting crude oil. The data of this study, compared to that of previous studies, shows that methane, with water present, has a much greater carrying capacity for crude oil than in dry systems. The presence of water also drastically lowers the temperature and pressure conditions required for cosolubility. The data of this and/or previous studies demonstrate that the addition of carbon dioxide, ethane, propane, or butane to methane also has a strong positive effect on crude oil

  9. Reference Correlation for the Viscosity of Ethane

    NASA Astrophysics Data System (ADS)

    Vogel, Eckhard; Span, Roland; Herrmann, Sebastian

    2015-12-01

    A new representation of the viscosity for the fluid phase of ethane includes a zero-density correlation and a contribution for the critical enhancement, initially both developed separately, but based on experimental data. The higher-density contributions are correlated as a function of the reduced density δ = ρ/ρc and of the reciprocal reduced temperature τ = Tc/T (ρc—critical density and Tc—critical temperature). The final formulation contains 14 coefficients obtained using a state-of-the-art linear optimization algorithm. The evaluation and choice of the selected primary data sets is reviewed, in particular with respect to the assessment used in earlier viscosity correlations. The new viscosity surface correlation makes use of the reference equation of state for the thermodynamic properties of ethane by Bücker and Wagner [J. Phys. Chem. Ref. Data 35, 205 (2006)] and is valid in the fluid region from the melting line to temperatures of 675 K and pressures of 100 MPa. The viscosity in the limit of zero density is described with an expanded uncertainty of 0.5% (coverage factor k = 2) for temperatures 290 < T/K < 625, increasing to 1.0% at temperatures down to 212 K. The uncertainty of the correlated values is 1.5% in the range 290 < T/K < 430 at pressures up to 30 MPa on the basis of recent measurements judged to be very reliable as well as 4.0% and 6.0% in further regions. The uncertainty in the near-critical region (1.001 < 1/τ < 1.010 and 0.8 < δ < 1.2) increases with decreasing temperature up to 3.0% considering the available reliable data. Tables of the viscosity calculated from the correlation are listed in an appendix for the single-phase region, for the vapor-liquid phase boundary, and for the near-critical region.

  10. The biological fate of decabromodiphenyl ethane following ...

    EPA Pesticide Factsheets

    1. The disposition of decabromodiphenyl ethane (DBDPE) was investigated based on concerns over its structural similarities to decaBDE, high potential for environmental persistence & bioaccumulation, and high production volume. 2. In the present study, female Sprague Dawley rats were administered a single dose of [14C]-DBDPE by oral, topical, or IV routes. Another set of rats were administered 10 daily oral doses of 14C]-DBDPE. Male B6C3F1/Tac mice were administered a single oral dose.3. DBDPE was poorly absorbed following oral dosing, with 95% of administered [14C]-radioactivity recovered in the feces, 1% recovered in the urine and less than 3% in the tissues at 72 h. DBDPE excretion was similar in male mice and female rats. Accumulation of [14C]-DBDPE was observed in liver and the adrenal gland after 10 daily oral doses.4. The dermis acted as a depot for dermally applied DBDPE; conservative estimates predict approx. 14 ± 8% of DBDPE may be absorbed into human skin in vivo; approx. 7 ± 4% of the parent chemical is expected to reach systemic circulation following continuous exposure (24 h). 5. Following intravenous administration, 6% of the dose was recovered in urine and 28% in the feces, while ~70% of the dose remained in tissues after 72 hours, with the highest concentrations found in the liver (42%) and lung (17%). Decabromodiphenyl ethane (DBDPE) is an additive brominated flame retardant used in a variety commercial products. It has been detected in indo

  11. Simultaneous monitoring of atmospheric methane and speciated non-methane hydrocarbon concentrations using Peltier effect sub-ambient pre-concentration and gas chromatography.

    PubMed

    Harrison, D; Seakins, P W; Lewis, A C

    2000-02-01

    Sub-ambient trapping, used to pre-concentrate atmospheric samples for non-methane hydrocarbon (NMHC) analysis by gas chromatography, can also be used to measure ambient methane concentrations. Above a sample volume of 40 ml, a dynamic equilibrium is established between ambient and trapped methane allowing for simultaneous quantitative determinations of methane and NMHC. The temperature stability of the trap is critical for quantitative methane analysis and this can be achieved by Peltier effect cooling. Simultaneous measurements of methane and NMHC reduce the equipment required for field trips and can ease the interpretation and modelling of atmospheric data. The feasibility for deployment of the system in remote locations was demonstrated by running the apparatus virtually unattended for a 5-day period. The correlations between the concentrations of methane, ethane and ethene measured during this period are discussed.

  12. A Search for Ethane on Pluto and Triton

    NASA Astrophysics Data System (ADS)

    DeMeo, Francesca E.; Dumas, C.; de Bergh, C.; Protopapa, S.; Cruikshank, D. P.; Geballe, T. R.; Alvarez-Candal, A.; Merlin, F.; Barucci, M. A.

    2009-09-01

    We present near-infrared spectral observations in the H and K bands (1.4-2.45 microns) of Pluto over four regions of the surface and Triton for one observation using the VLT and UKIRT. On both Pluto and Triton, a weak 2.405-micron feature is present in our spectra, which was previously detected on Pluto by Cruikshank et al. (DPS meeting abstract, 38, 21.03, 2006) and Verbiscer et al. (Lunar and Planetary Science Abstract XXXVIII - 2007) and on Triton by Cruikshank et al. (Science, 261, 742-745, 1993), Quirico et al. (Icarus, 139, 159-178, 1999) and Cruikshank et al. (Icarus, 147, 309-316, 2000). On Triton, the depth and position of this feature varies but is seen in all high-resolution, published spectra. Both ethane (C2H6) and 13CO display features at this wavelength. To assess whether unexplained absorption bands such as the 2.405 micron feature could be due to ethane, we interpret the spectral behavior if each surface using a modeling algorithm (Protopapa et al., A&A, 490, 365-375, 2008) based on the radiative transfer model of Hapke (Hapke, 1993) with three basic models: a general model without ethane, with ethane, and with ethane diluted in nitrogen. While ethane diluted in nitrogen could potentially explain the 1.69- and 1.75-micron features on Triton and pure ethane could explain the 2.405-micron feature seen on Pluto, the lack of features in the 2.27- to 2.32-micron region limits the abundance of ethane to only a few percent on each body. It is likely that 13CO contributes significantly to the 2.405-micron band, which explains why this band is stronger in spectra of both bodies than other characteristic ethane features.

  13. Reduced chemical kinetics for propane combustion

    NASA Technical Reports Server (NTRS)

    Ying, Shuh-Jing; Nguyen, Hung Lee

    1990-01-01

    It is pointed out that a detailed chemical kinetics mechanism for the combustion of propane consists of 40 chemical species and 118 elementary chemical reactions. An attempt is made to reduce the number of chemical species and elementary chemical reactions so that the computer run times and storage requirements may be greatly reduced in three-dimensional gas turbine combustion flow calculations, while maintaining accurate predictions of the propane combustion and exhaust emissions. By way of a sensitivity analysis, the species of interest and chemical reactions are classified in descending order of importance. Nineteen species are chosen, and their pressure, temperature, and concentration profiles are presented for the reduced mechanisms, which are then compared with those from the full 118 reactions. It is found that 45 reactions involving 27 species have to be kept for comparable agreement. A comparison of the results obtained from the 45 reactions to that of the full 118 shows that the pressure and temperature profiles and concentrations of C3H8, O2, N2, H2O, CO, and CO2 are within 10 percent of maximum change.

  14. TEPC gas gain measurements in propane.

    PubMed

    Moro, D; Chiriotti, S; Colautti, P; Conte, V

    2014-10-01

    Knowledge of the gas gain is important to optimise the design and the operating characteristics of tissue-equivalent proportional counters (TEPCs), especially for simulated sites smaller than 1 µm. TEPC area monitors of the order of centimetres must operate at very low gas pressure to simulate micrometric volumes, consequently the Townsend theory cannot be applied: effects related to the presence of an electric-field gradient become important and must be considered. A detailed description of the electron avalanche formation is complex, but in most practical cases an analytical formula can be used. The so-called gradient-field model includes three characteristic constants of the counting gas, which were already experimentally determined for propane-tissue equivalent (TE) and dimethyl ether (DME) gases. The aim of this work is to measure the gas-dependent parameters for propane gas. Preliminary results obtained with a spherical TEPC are presented. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  15. Extending the Lifetime of Hyperpolarized Propane Gas through Reversible Dissolution.

    PubMed

    Burueva, Dudari B; Romanov, Alexey S; Salnikov, Oleg G; Zhivonitko, Vladimir V; Chen, Yu-Wen; Barskiy, Danila A; Chekmenev, Eduard Y; Hwang, Dennis W; Kovtunov, Kirill V; Koptyug, Igor V

    2017-03-02

    Hyperpolarized (HP) propane produced by the parahydrogen-induced polarization (PHIP) technique has been recently introduced as a promising contrast agent for functional lung magnetic resonance (MR) imaging. However, its short lifetime due to a spin-lattice relaxation time T1 of less than 1 s in the gas phase is a significant translational challenge for its potential biomedical applications. The previously demonstrated approach for extending the lifetime of the HP propane state through long-lived spin states allows the HP propane lifetime to be increased by a factor of ∼3. Here, we demonstrate that a remarkable increase in the propane hyperpolarization decay time at high magnetic field (7.1 T) can be achieved by its dissolution in deuterated organic solvents (acetone-d6 or methanol-d4). The approximate values of the HP decay time for propane dissolved in acetone-d6 are 35.1 and 28.6 s for the CH2 group and the CH3 group, respectively (similar values were obtained for propane dissolved in methanol-d4), which are ∼50 times larger than the gaseous propane T1 value. Furthermore, we show that it is possible to retrieve HP propane from solution to the gas phase with the preservation of hyperpolarization.

  16. Evidence for a polar ethane cloud on Titan

    USGS Publications Warehouse

    Griffith, C.A.; Penteado, P.; Rannou, P.; Brown, R.; Boudon, V.; Baines, K.H.; Clark, R.; Drossart, P.; Buratti, B.; Nicholson, P.; McKay, C.P.; Coustenis, A.; Negrao, A.; Jaumann, R.

    2006-01-01

    Spectra from Cassini's Visual and Infrared Mapping Spectrometer reveal the presence of a vast tropospheric cloud on Titan at latitudes 51?? to 68?? north and all longitudes observed (10?? to 190?? west). The derived characteristics indicate that this cloud is composed of ethane and forms as a result of stratospheric subsidence and the particularly cool conditions near the moon's north pole. Preferential condensation of ethane, perhaps as ice, at Titan's poles during the winters may partially explain the lack of liquid ethane oceans on Titan's surface at middle and lower latitudes.

  17. bdGas carburizing of steel with furnace atmospheres formed in situ from methane and air and from butane and air

    NASA Astrophysics Data System (ADS)

    Stickels, C. A.; Mack, C. M.; Pieprzak, J. A.

    1982-12-01

    Carburizing experiments were conducted at 927°C (1700°F) and 843°C (1550°F) using furnace atmospheres formed from methane and air and from butane and air introduced directly into the carburizing furnace. Gas flow rates were low to promote equilibration of the reaction products within the furnace. The air flow rate was held constant while the methane or butane flow was automatically regulated to maintain a constant oxygen potential, as measured by a zirconia oxygen sensor, within the furnace. In comparing the results of these experiments with earlier results obtained using propane and air, several differences were noted: (a) The methane content of the furnace atmosphere, measured by infrared analysis, was about twice as great when methane was the feed gas rather than propane or butane. This was true despite the fact that the mean residence time of the gas within the furnace was greater in the methane experiments. Methane appears to be less effective than propane or butane in reducing the CO2 and H2O contents to the levels required for carburizing. (b) There was a greater tendency for the CO content of the furnace atmosphere to decrease at high carbon potentials when methane is used instead of propane or butane. The decrease in CO content is due to hydrogen dilution caused by sooting in the furnace vestibule. These differences in behavior make propane or butane better suited than methane for in situ generation of carburizing atmospheres. However, there is no difference in the amount of carburizing occurring at a specified carbon potential when methane, propane, or butane are used as the feed gas in this process.

  18. Following The Carbon: Structure, Chemistry, And Spectroscopy Of Frozen Ethane

    NASA Astrophysics Data System (ADS)

    Raines, Lily; Hudson, R. L.; Moore, M. H.

    2008-09-01

    Oort Cloud comets, as well as TNOs 2005 FY9, Quaoar, and Pluto, are known to contain ethane. Even though this molecule is found in several outer solar system objects, relatively little information is available about its amorphous, metastable, and crystalline phases. In new experiments, we have prepared ethane ices at various temperatures, and heated and ion-irradiated these ices to study phase changes and ethane's radiation chemistry with near- and mid-IR spectroscopy. Recent results will be presented at this meeting. An improved understanding of solid-phase ethane may contribute to future searches for this and other hydrocarbons in the outer solar system. This work was conducted by LLR while a summer research intern at the Goddard Center for Astrobiology, Goddard Space Flight Center. Additional support from NASA's Outer Planets, Planetary Atmospheres, and Planetary Geology and Geophysics programs is acknowledged by all of the authors.

  19. Reference Correlation for the Viscosity of Ethane

    SciTech Connect

    Vogel, Eckhard; Span, Roland; Herrmann, Sebastian

    2015-12-15

    A new representation of the viscosity for the fluid phase of ethane includes a zero-density correlation and a contribution for the critical enhancement, initially both developed separately, but based on experimental data. The higher-density contributions are correlated as a function of the reduced density δ = ρ/ρ{sub c} and of the reciprocal reduced temperature τ = T{sub c}/T (ρ{sub c}—critical density and T{sub c}—critical temperature). The final formulation contains 14 coefficients obtained using a state-of-the-art linear optimization algorithm. The evaluation and choice of the selected primary data sets is reviewed, in particular with respect to the assessment used in earlier viscosity correlations. The new viscosity surface correlation makes use of the reference equation of state for the thermodynamic properties of ethane by Bücker and Wagner [J. Phys. Chem. Ref. Data 35, 205 (2006)] and is valid in the fluid region from the melting line to temperatures of 675 K and pressures of 100 MPa. The viscosity in the limit of zero density is described with an expanded uncertainty of 0.5% (coverage factor k = 2) for temperatures 290 < T/K < 625, increasing to 1.0% at temperatures down to 212 K. The uncertainty of the correlated values is 1.5% in the range 290 < T/K < 430 at pressures up to 30 MPa on the basis of recent measurements judged to be very reliable as well as 4.0% and 6.0% in further regions. The uncertainty in the near-critical region (1.001 < 1/τ < 1.010 and 0.8 < δ < 1.2) increases with decreasing temperature up to 3.0% considering the available reliable data. Tables of the viscosity calculated from the correlation are listed in an appendix for the single-phase region, for the vapor–liquid phase boundary, and for the near-critical region.

  20. Titan's Methane Cycle is Closed

    NASA Astrophysics Data System (ADS)

    Hofgartner, J. D.; Lunine, J. I.

    2013-12-01

    Doppler tracking of the Cassini spacecraft determined a polar moment of inertia for Titan of 0.34 (Iess et al., 2010, Science, 327, 1367). Assuming hydrostatic equilibrium, one interpretation is that Titan's silicate core is partially hydrated (Castillo-Rogez and Lunine, 2010, Geophys. Res. Lett., 37, L20205). These authors point out that for the core to have avoided complete thermal dehydration to the present day, at least 30% of the potassium content of Titan must have leached into an overlying water ocean by the end of the core overturn. We calculate that for probable ammonia compositions of Titan's ocean (compositions with greater than 1% ammonia by weight), that this amount of potassium leaching is achievable via the substitution of ammonium for potassium during the hydration epoch. Formation of a hydrous core early in Titan's history by serpentinization results in the loss of one hydrogen molecule for every hydrating water molecule. We calculate that complete serpentinization of Titan's core corresponds to the release of more than enough hydrogen to reconstitute all of the methane atoms photolyzed throughout Titan's history. Insertion of molecular hydrogen by double occupancy into crustal clathrates provides a storage medium and an opportunity for ethane to be converted back to methane slowly over time--potentially completing a cycle that extends the lifetime of methane in Titan's surface atmosphere system by factors of several to an order of magnitude over the photochemically-calculated lifetime.

  1. Cryptic stereospecificity of methane monooxygenase

    SciTech Connect

    Priestley, N.D.; Floss, H.G.; Lipscomb, J.D.

    1992-09-09

    Methane moonooxygenase (MMO, EC 1.14.13.25) catalyzes the NAD(P)H- and O{sub 2}-dependent hydroxylation of methane to methanol. Soluble MMO from the methanotrophic bacterium, Methylosinus trichosporium OB3b, consists of a 245 kDa hydroxylase component containing a {mu}-(R/H)-oxo bridged binuclear iron cluster, a 40 kDa NAD(P)H-dependent oxidoreductase component, and a 15.8 kDa protein, component B, which has no associated cofactors. The hydroxylase component alone can carry out the same oxidations as the reconstituted three-component system when H{sub 2}O{sub 2} is used as the source of oxygen and reducing equivalents. Several mechanisms have been proposed for MMO-catalyzed alkane oxidation; these invoke an intermediate substrate radical, an additional substrate carbocation intermediate, or a concerted oxygen insertion into a substrate carbon-iron bond. Recent studies support the formation of a substrate intermediate not bound to the iron, however, they utilized diagnostic substrates that may not be representative of the natural substrate, methane. The experiments described here address this question more directly by determining the steric course of the oxidation of (S)- or (R)-[1-{sup 2}H{sub 1}, 1-{sup 3}H{sub 1}] ethane to ethanol catalyzed by MMO. 22 refs., 1 fig., 1 tab.

  2. Emissions results for dedicated propane Chrysler minivans: the 1996 propane vehicle challenge

    SciTech Connect

    Buitrago, C.; Sluder, S.; Larsen, R.

    1997-02-01

    The U.S. Department of Energy (US DOE), through Argonne National Laboratory, and in cooperation with Natural Resources-Canada and Chrysler Canada, sponsored and organized the 1996 Propane Vehicle Challenge (PVC). For this competition , 13 university teams from North America each received a stock Chrysler minivan to be converted to dedicated propane operation while maintaining maximum production feasibility. The converted vehicles were tested for performance (driveability, cold- and hot-start, acceleration, range, and fuel economy) and exhaust emissions. Of the 13 entries for the 1996 PVC, 10 completed all of the events scheduled, including the emissions test. The schools used a variety of fuel-management, fuel-phase and engine-control strategies, but their strategies can be summarized as three main types: liquid fuel-injection, gaseous fuel-injection, and gaseous carburetor. The converted vehicles performed similarly to the gasoline minivan. The University of Windsor`s minivan had the lowest emissions attaining ULEV levels with a gaseous-injected engine. The Texas A&M vehicle, which had a gaseous-fuel injection system, and the GMI Engineering and Management Institute`s vehicle, which had a liquid-injection system both reached LEV levels. Vehicles with an injection fuel system (liquid or gaseous) performed better in terms of emissions than carbureted systems. Liquid injection appeared to be the best option for fuel metering and control for propane, but more research and calibration are necessary to improve the reliability and performance of this design.

  3. Sinking methane.

    PubMed

    Reay, David S

    2003-02-01

    Concentrations of the powerful greenhouse gas, methane, in our atmosphere have doubled since the beginning of the industrial age. Reducing these levels is a vital part of global efforts to combat global warming. Could we make use of the Earth's own methane sinks?

  4. A Quantification of Methane Emissions from Oil and Natural Gas Extraction Regions in the Central/Western U.S. and a Comparison to Previous Studies

    NASA Astrophysics Data System (ADS)

    Peischl, J.; Aikin, K. C.; Eilerman, S. J.; Gilman, J.; De Gouw, J. A.; Herndon, S. C.; Lerner, B. M.; Neuman, J. A.; Tokarek, T. W.; Trainer, M.; Warneke, C.; Ryerson, T. B.

    2015-12-01

    We present airborne measurements of methane and ethane taken aboard a NOAA WP-3D research aircraft over five regions of oil and natural gas extraction in March and April, 2015, as part of the Shale Oil and Natural Gas Nexus (SONGNEX) field study. The five regions are the (1) Haynesville, (2) Barnett, and (3) Eagle Ford regions in Texas, (4) the Denver-Julesburg region of Colorado, and (5) the Bakken region of North Dakota. From these measurements, we derive methane emission rates from these regions using the mass balance method. Next, we attribute the methane emissions to oil and natural gas extraction, livestock operations, and other source sectors based on correlations of methane with ethane and ammonia. We then compare these emissions to those reported from previous studies, where applicable. Finally, we compare reported methane emissions from multiple regional-scale studies with inventory estimates of methane emissions from U.S. oil and natural gas production.

  5. Multi-year levels and trends of non-methane hydrocarbon concentrations observed in ambient air in France

    NASA Astrophysics Data System (ADS)

    Waked, Antoine; Sauvage, Stéphane; Borbon, Agnès; Gauduin, Julie; Pallares, Cyril; Vagnot, Marie-Pierre; Léonardis, Thierry; Locoge, Nadine

    2016-09-01

    Measurements of 31 non-methane hydrocarbons (NMHCs) were carried out at three urban (Paris, 2003-2014, Strasbourg, 2002-2014 and Lyon, 2007-2014) sites in France over the period of a decade. A trend analysis was applied by means of the Mann-Kendall non-parametric test to annual and seasonal mean concentrations in order to point out changes in specific emission sources and to assess the impact of emission controls and reduction strategies. The trends were compared to those from three rural sites (Peyrusse-Vieille, 2002-2013, Tardière, 2003-2013 and Donon, 1997-2007). The results obtained showed a significant yearly decrease in pollutant concentrations over the study period and for the majority of species in the range of -1 to -7% in accordance with the decrease of NMHC emissions in France (-5 to -9%). Concentrations of long-lived species such as ethane and propane which are recognized as tracers of distant sources and natural gas remained constant. Compounds associated with combustion processes such as acetylene, propene, ethylene and benzene showed a significant decline in the range of -2% to -5% yr-1. These trends are consistent with those recently described at urban and background sites in the northern mid-latitudes and with emission inventories. C7-C9 aromatics such as toluene and xylenes as well as C4-C5 alkanes such as isopentane and isobutane also showed a significant decrease in the range of -3% to -7% yr-1. The decreasing trends in terms of % yr-1 observed at these French urban sites were typically higher for acetylene, ethylene and benzene than those reported for French rural sites of the national observatory of Measurement and Evaluation in Rural areas of trans-boundary Air pollution (MERA). The study also highlighted the difficult choice of a long term sampling site representative of the general trends of pollutant concentrations.

  6. The Stable Carbon Isotope Ratio Analysis of Atmospheric Non-Methane Hydrocarbons in Los Angeles, California

    NASA Astrophysics Data System (ADS)

    Gotoh, A. A.; Tyler, S. C.; Meinardi, S.; Gervais, K.; Blake, D. R.

    2003-12-01

    Los Angeles type photochemical air pollution is caused by non-methane hydrocarbons (NMHCs) reacting with hydroxyl radicals and nitrous oxides in the presence of light. To create more effective control strategies in reducing such air pollution, it is essential to have both a better understanding of the complex photochemical processes of NMHCs and the sources of these compounds. From the past successful studies of other atmospheric trace gases such as methane and carbon monoxide, we expect that the stable carbon ratio (13C/12C, reported as a δ 13C value) of each of these hydrocarbons will also reflect the δ 13C value of the source material and/or provide formation on chemical loss processes that fractionate C isotopes. We have developed a NMHC preconcentrator system which enables us to measure δ 13C values using a continuous-flow gas chromatography combustion isotope ratio mass spectrometer (cf-GC/C/IRMS). Our system is similar to the successful design pioneered in Rudolph et al. (1997), but is custom designed by our laboratory. Stable carbon isotope measurements of any of the C2-C5 NMHCs in field and/or lab studies are scarce to date. Our system allows us to report on δ 13C measurements of ethane, ethene, ethyne, propane, propene, n-butane, i-butane, 1-butene, n-pentane, i-pentane, and methyl chloride. To see if we can learn the specific sources contributing to the emissions of a given NMHC within a region by comparing isotopic signatures of its potential sources to δ 13C measurements of it within the local air mass, urban air samples were collected in 3 different cities of Los Angeles County, California, USA, during the summer of 2003 and analyzed for the concentrations and δ 13C values of NMHCs. To our knowledge, this is the first δ 13C analysis of ambient NMHCs conducted in the United States. We report the results of the δ 13C analyses and concentration measurements for selected NMHC species from the urban air samples, and their implications for the local

  7. Non-methane hydrocarbons (NMHCs) and their contribution to ozone formation potential in a petrochemical industrialized city, Northwest China

    NASA Astrophysics Data System (ADS)

    Jia, Chenhui; Mao, Xiaoxuan; Huang, Tao; Liang, Xiaoxue; Wang, Yanan; Shen, Yanjie; Jiang, Wanyanhan; Wang, Huiqin; Bai, Zhilin; Ma, Minquan; Yu, Zhousuo; Ma, Jianmin; Gao, Hong

    2016-03-01

    Hourly air concentrations of fifty-three non-methane hydrocarbons (NMHCs) were measured at downtown and suburb of Lanzhou, a petrochemical industrialized city, Northwest China in 2013. The measured data were used to investigate the seasonal characteristics of NMHCs air pollution and their contributions to the ozone formation in Lanzhou. Annually averaged NMHCs concentration was 38.29 ppbv in downtown Lanzhou. Among 53 NMHCs, alkanes, alkenes, and aromatics accounted for 57%, 23% and 20% of the total NMHCs air concentration, respectively. The atmospheric levels of toluene and propane with mean values of 4.62 and 4.56 ppbv were higher than other NMHCs, respectively. The ambient levels of NMHCs in downtown Lanzhou were compared with measured NMHCs data collected at a suburban site of Lanzhou, located near a large-scale petrochemical industry. Results show that the levels of alkanes, alkenes, and aromatics in downtown Lanzhou were lower by factors of 3-11 than that in west suburb of the city. O3-isopleth plots show that ozone was formed in VOCs control area in downtown Lanzhou and NOx control area at the west suburban site during the summertime. Propylene-equivalent (Prop-Equiv) concentration and the maximum incremental reactivity (MIR) in downtown Lanzhou indicate that cis-2-butene, propylene, and m/p-xylene were the first three compounds contributing to ozone formation potentials whereas in the petrochemical industrialized west suburb, ethane, propene, and trans-2-Butene played more important role in the summertime ozone formation. Principal component analysis (PCA) and multiple linear regression (MLR) were further applied to identify the dominant emission sources and examine their fractions in total NMHCs. Results suggest that vehicle emission, solvent usage, and industrial activities were major sources of NMHCs in the city, accounting for 58.34%, 22.19%, and 19.47% of the total monitored NMHCs in downtown Lanzhou, respectively. In the west suburb of the city

  8. Infrared absorption cross sections of propane broadened by hydrogen

    NASA Astrophysics Data System (ADS)

    Wong, A.; Hargreaves, R. J.; Billinghurst, B.; Bernath, P. F.

    2017-09-01

    Fourier transform infrared absorption cross-sections of pure propane (C3H8) and propane broadened with H2 have been calculated from transmittance spectra recorded at temperatures from 292 K to 205 K. Transmittance spectra were recorded at the Canadian Light Source (CLS) Far-Infrared beamline, utilizing both the synchrotron source and the internal glowbar source. The absorption cross-sections have been calibrated to Pacific Northwest National Laboratory (PNNL) reference cross-sections of propane and can be used to interpret astronomical observations of giant planets such as Jupiter and Saturn as well as exoplanets.

  9. Study on propane-butane gas storage by hydrate technology

    NASA Astrophysics Data System (ADS)

    Hamidi, Nurkholis; Wijayanti, Widya; Widhiyanuriyawan, Denny

    2016-03-01

    Different technology has been applied to store and transport gas fuel. In this work the storage of gas mixture of propane-butane by hydrate technology was studied. The investigation was done on the effect of crystallizer rotation speed on the formation of propane-butane hydrate. The hydrates were formed using crystallizer with rotation speed of 100, 200, and 300 rpm. The formation of gas hydrates was done at initial pressure of 3 bar and temperature of 274K. The results indicated that the higher rotation speed was found to increase the formation rate of propane-butane hydrate and improve the hydrates stability.

  10. Temperature-dependent high resolution absorption cross sections of propane

    NASA Astrophysics Data System (ADS)

    Beale, Christopher A.; Hargreaves, Robert J.; Bernath, Peter F.

    2016-10-01

    High resolution (0.005 cm-1) absorption cross sections have been measured for pure propane (C3H8). These cross sections cover the 2550-3500 cm-1 region at five temperatures (from 296 to 700 K) and were measured using a Fourier transform spectrometer and a quartz cell heated by a tube furnace. Calibrations were made by comparison to the integrated cross sections of propane from the Pacific Northwest National Laboratory. These are the first high resolution absorption cross sections of propane for the 3 μm region at elevated temperatures. The cross sections provided may be used to monitor propane in combustion environments and in astronomical sources such as the auroral regions of Jupiter, brown dwarfs and exoplanets.

  11. 2. View of Liquified Propane Air Plant (New), former Exhaust ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    2. View of Liquified Propane Air Plant (New), former Exhaust and Compressor Building and former Purifying Plant in background. - Concord Gas Light Company, South Main Street, Concord, Merrimack County, NH

  12. Solubility of methane in water under natural conditions: a laboratory study. Final report, April 1, 1978-June 30, 1982

    SciTech Connect

    Blount, C.W.; Price, L.C.

    1982-06-01

    The solubility of methane in aqueous solutions has been determined over a broad range of temperature, pressure and salinities. The effect of dissolved carbon dioxide and ethane on methane solubility has been determined at 302{sup 0}F. Also the solubility of crude oil and water in methane has been determined over a broad range of temperatures and pressures. The solubility of methane is raised by increasing pressure and temperature (above about 170{sup 0}F). There is a solubility minimum near 170{sup 0}F at constant pressure and salinity. Ionic salts effectively salt methane out of solution at all concentrations investigated. The effect of the addition of small amounts of carbon dioxide or ethane to the gas dissolved in aqueous solutions is to enhance methane solubility compared to solutions without other gases. Higher concentrations of dissolved gases, depending upon the salinity and the gas involved, decrease aqueous methane solubility. The addition of carbon dioxide always increased total gas content even when reducing the concentration of methane. With increasing concentration of ethane in the dissolved gases the total gas content reaches a maximum and then both methane and total gas content decrease. Comparison of experimental methane solubilities with gas/water ratios, salinities, bottom hole temperatures and pressures of geopressure test wells suggests that some formation fluids may be near saturation, while many others seem to be undersaturated. Petroleum is soluble in methane. Increasing pressure increases the solubility of crude oil in methane gas. At an elevated pressure, which depends upon the temperature, oil and gas form a single fluid phase.

  13. Breaking methane

    PubMed Central

    Rosenzweig, Amy C.

    2015-01-01

    The most powerful oxidant found in nature is compound Q, an enzymatic intermediate that oxidizes methane. New spectroscopic data have resolved the long-running controversy about Q’s chemical structure. PMID:25607367

  14. Crystal structures of two mononuclear complexes of terbium(III) nitrate with the tripodal alcohol 1,1,1-tris-(hy-droxy-meth-yl)propane.

    PubMed

    Gregório, Thaiane; Giese, Siddhartha O K; Nunes, Giovana G; Soares, Jaísa F; Hughes, David L

    2017-02-01

    Two new mononuclear cationic complexes in which the Tb(III) ion is bis-chelated by the tripodal alcohol 1,1,1-tris-(hy-droxy-meth-yl)propane (H3L(Et), C6H14O3) were prepared from Tb(NO3)3·5H2O and had their crystal and mol-ecular structures solved by single-crystal X-ray diffraction analysis after data collection at 100 K. Both products were isolated in reasonable yields from the same reaction mixture by using different crystallization conditions. The higher-symmetry complex dinitratobis[1,1,1-tris-(hy-droxy-meth-yl)propane]-terbium(III) nitrate di-meth-oxy-ethane hemisolvate, [Tb(NO3)2(H3L(Et))2]NO3·0.5C4H10O2, 1, in which the lanthanide ion is 10-coordinate and adopts an s-bicapped square-anti-prismatic coordination geometry, contains two bidentate nitrate ions bound to the metal atom; another nitrate ion functions as a counter-ion and a half-mol-ecule of di-meth-oxy-ethane (completed by a crystallographic twofold rotation axis) is also present. In product aqua-nitratobis[1,1,1-tris-(hy-droxy-meth-yl)propane]-terbium(III) dinitrate, [Tb(NO3)(H3L(Et))2(H2O)](NO3)2, 2, one bidentate nitrate ion and one water mol-ecule are bound to the nine-coordinate terbium(III) centre, while two free nitrate ions contribute to charge balance outside the tricapped trigonal-prismatic coordination polyhedron. No free water mol-ecule was found in either of the crystal structures and, only in the case of 1, di-meth-oxy-ethane acts as a crystallizing solvent. In both mol-ecular structures, the two tripodal ligands are bent to one side of the coordination sphere, leaving room for the anionic and water ligands. In complex 2, the methyl group of one of the H3L(Et) ligands is disordered over two alternative orientations. Strong hydrogen bonds, both intra- and inter-molecular, are found in the crystal structures due to the number of different donor and acceptor groups present.

  15. Priori calculations of pK/sub a/'s for organic compounds in water. The pK/sub a/ of ethane

    SciTech Connect

    Jorgensen, W.L.; Briggs, J.M.; Gao, J.

    1987-10-28

    The enduring fascination of organic chemists with acidities and basicities reflects the fundamental importance of these concepts in understanding organic reactivity. Developing scales of aqueous acidities for weak organic acids is challenging in view of the need for extrapolations from organic solvents to water, ion-pairing and aggregation effects for organometallic compounds, and the derivation of thermodynamic quantities from kinetic measurements. The problems are reflected in the experimental ranges for the pK/sub a/'s of the simplest alkanes, methane and ethane, which cover from 40 to 60. In the present communication, they demonstrate how simulation methodology can be used to obtain a priori predictions for the relative pK/sub a/'s of organic compounds in water. The first applications are for the pK/sub a/'s of acetonitrile and ethane relative to methanethiol.

  16. Methane in Crystalline Bedrock: the Outokumpu Deep Drill Hole, Finland

    NASA Astrophysics Data System (ADS)

    Kietäväinen, R.; Ahonen, L.; Niinikoski, P.; Itävaara, M.; Kukkonen, I. T.

    2014-12-01

    Carbon is a key element for life. One of the most interesting forms of carbon is methane, as it is both consumed and produced by microorganisms. Methane has also several possible ways of abiotic origin, some of which could provide understanding of the origin of life itself. The study of methane is thus important in order to understand deep subsurface ecosystems such as those found in the 2516 m deep Outokumpu Deep Drill Hole within the Precambrian Fennoscandian Shield in eastern Finland. There rock types differ from graphite-bearing mica schist and black schist to serpentinite and pegmatitic granodiorite and saline, gas-rich water, with up to 32 mmol l-1 of methane, and residence times of tens of millions of years occupies the fracture zones which host diverse microbial life, including methanogenic archaea. In order to understand methane systematics in crystalline bedrock, we analysed several forms of carbon, including dissolved inorganic carbon (DIC), methane and ethane from the Outokumpu Deep Drill Hole for their isotopic composition. In addition, isotopic compositions of water and hydrogen were determined. The results show that hydrogen is in isotopic equilibrium in the system H2O-H2-CH4 at ambient temperatures, which could either indicate equilibration due to long residence time or relatively recent production of methane in situ. Therefore hydrogen is not a very useful indicator for the origin of methane in this case. Carbon isotope analysis shows that both methane and DIC becomes generally more enriched in 13C with depth, which could indicate higher amounts of microbial methane in the upper part of the bedrock. Based on carbon isotope composition, two types of ethane can be discerned. Taken all the evidence together, this leads us to suggest that at least two mechanisms are responsible for the methane production in Outokumpu: 1) Biotic which comprise most of methane and 2) abiotic which dominates in the deeper parts of the bedrock. The former type may include

  17. Methyl Radicals in Oxidative Coupling of Methane Directly Confirmed by Synchrotron VUV Photoionization Mass Spectroscopy

    PubMed Central

    Luo, Liangfeng; Tang, Xiaofeng; Wang, Wendong; Wang, Yu; Sun, Shaobo; Qi, Fei; Huang, Weixin

    2013-01-01

    Gas-phase methyl radicals have been long proposed as the key intermediate in catalytic oxidative coupling of methane, but the direct experimental evidence still lacks. Here, employing synchrotron VUV photoionization mass spectroscopy, we have directly observed the formation of gas-phase methyl radicals during oxidative coupling of methane catalyzed by Li/MgO catalysts. The concentration of gas-phase methyl radicals correlates well with the yield of ethylene and ethane products. These results lead to an enhanced fundamental understanding of oxidative coupling of methane that will facilitate the exploration of new catalysts with improved performance. PMID:23567985

  18. Use of stable isotopes to identify sources of methane in Appalachian Basin shallow groundwaters: a review.

    PubMed

    Hakala, J Alexandra

    2014-09-20

    Development of unconventional shale gas reservoirs in the Appalachian Basin has raised questions regarding the potential for these activities to affect shallow groundwater resources. Geochemical indicators, such as stable carbon and hydrogen isotopes of methane, stable carbon isotopes of ethane, and hydrocarbon ratios, have been used to evaluate methane sources however their utility is complicated by influences from multiple physical (e.g., mixing) and geochemical (e.g., redox) processes. Baseline sampling of shallow aquifers prior to development, and measurement of additional geochemical indicators within samples from across the Appalachian Basin, may aid in identifying natural causes for dissolved methane in shallow groundwater versus development-induced pathways.

  19. New Formulation for the Viscosity of Propane

    NASA Astrophysics Data System (ADS)

    Vogel, Eckhard; Herrmann, Sebastian

    2016-12-01

    A new viscosity formulation for propane, using the reference equation of state for its thermodynamic properties by Lemmon et al. [J. Chem. Eng. Data 54, 3141 (2009)] and valid in the fluid region from the triple-point temperature to 650 K and pressures up to 100 MPa, is presented. At the beginning, a zero-density contribution and one for the critical enhancement, each based on the experimental data, were independently generated in parts. The higher-density contributions are correlated as a function of the reciprocal reduced temperature τ = Tc/T and of the reduced density δ = ρ/ρc (Tc—critical temperature, ρc—critical density). The final formulation includes 17 coefficients inferred by applying a state-of-the-art linear optimization algorithm. The evaluation and choice of the primary data sets are detailed due to its importance. The viscosity at low pressures p ≤ 0.2 MPa is represented with an expanded uncertainty of 0.5% (coverage factor k = 2) for temperatures 273 ≤ T/K ≤ 625. The expanded uncertainty in the vapor phase at subcritical temperatures T ≥ 273 K as well as in the supercritical thermodynamic region T ≤ 423 K at pressures p ≤ 30 MPa is assumed to be 1.5%. In the near-critical region (1.001 < 1/τ < 1.010 and 0.8 < δ < 1.2), the expanded uncertainty increases with decreasing temperature up to 3.0%. It is further increased to 4.0% in regions of less reliable primary data sets and to 6.0% in ranges in which no primary data are available but the equation of state is valid. Tables of viscosity computed for the new formulation are given in an Appendix for the single-phase region, for the vapor-liquid phase boundary, and for the near-critical region.

  20. A Detailed Modeling Study of Propane Oxidation

    SciTech Connect

    Westbrook, C K; Jayaweera, T M; Pitz, W J; Curran, H J

    2004-03-19

    A detailed chemical kinetic mechanism has been used to simulate ignition delay times recorded by a number of experimental shock tube studies over the temperature range 900 {le} T {le} 1800 K, in the pressure range 0.75-40 atm and in the equivalence ratio range 0.5 {le} {phi} {le} 2.0. Flame speed measurements at 1 atm in the equivalence ratio range 0.4 {le} {phi} {le} 1.8 have also been simulated. Both of these data sets, particularly those recorded at high pressure, are of particular importance in validating a kinetic mechanism, as internal combustion engines operate at elevated pressures and temperatures and rates of fuel oxidation are critical to efficient system operation. Experiments in which reactant, intermediate and product species were quantitatively recorded, versus temperature in a jet-stirred reactor (JSR) and versus time in a flow reactor are also simulated. This data provide a stringent test of the kinetic mechanism as it must reproduce accurate quantitative profiles for all reactant, intermediate and product species. The JSR experiments were performed in the temperature range 1000-1110 K, in the equivalence ratio range 0.5 {le} {phi} {le} 4.0, at a pressure of 5 atm. These experiments are complemented by those carried out in a flow reactor in the temperature range 660-820 K, at 10 atm and at an equivalence ratio of 0.4. In addition, burner stabilized flames were simulated, where chemical species profiles were measured at atmospheric pressure for two propane-air flat flames. Overall, reasonably good agreement is observed between the model simulations and the experimental results.

  1. 40 CFR 721.10474 - Substituted amino ethane sulfonic acid salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Substituted amino ethane sulfonic acid... Specific Chemical Substances § 721.10474 Substituted amino ethane sulfonic acid salt (generic). (a... generically as substituted amino ethane sulfonic acid salt (PMN P-04-107) is subject to reporting under this...

  2. 40 CFR 721.10474 - Substituted amino ethane sulfonic acid salt (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Substituted amino ethane sulfonic acid... Specific Chemical Substances § 721.10474 Substituted amino ethane sulfonic acid salt (generic). (a... generically as substituted amino ethane sulfonic acid salt (PMN P-04-107) is subject to reporting under this...

  3. 40 CFR 721.10086 - Ethane, 2-(difluoromethoxy)-1,1,1-trifluoro-.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Ethane, 2-(difluoromethoxy)-1,1,1... Specific Chemical Substances § 721.10086 Ethane, 2-(difluoromethoxy)-1,1,1-trifluoro-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethane,...

  4. 40 CFR 721.3248 - Ethane, 1,2,2- trichlorodifluoro-.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ethane, 1,2,2- trichlorodifluoro-. 721... Substances § 721.3248 Ethane, 1,2,2- trichlorodifluoro-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethane, 1,2,2-trichlorodifluoro- (CAS...

  5. 40 CFR 721.3248 - Ethane, 1,2,2- trichlorodifluoro-.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Ethane, 1,2,2- trichlorodifluoro-. 721... Substances § 721.3248 Ethane, 1,2,2- trichlorodifluoro-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethane, 1,2,2-trichlorodifluoro- (CAS...

  6. 40 CFR 721.10086 - Ethane, 2-(difluoromethoxy)-1,1,1-trifluoro-.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ethane, 2-(difluoromethoxy)-1,1,1... Specific Chemical Substances § 721.10086 Ethane, 2-(difluoromethoxy)-1,1,1-trifluoro-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethane,...

  7. An Atmosphere-based Method for Detection and Quantification of Methane Emisions from Natural Gas Infrastructure in an Urban Environment

    NASA Astrophysics Data System (ADS)

    McKain, K.; Down, A.; Raciti, S. M.; Budney, J.; Hutyra, L.; Floerchinger, C. R.; Herndon, S. C.; Nehrkorn, T.; Zahniser, M. S.; Sargent, M. R.; Jackson, R. B.; Phillips, N. G.; Wofsy, S. C.

    2015-12-01

    Methane emissions from the natural gas supply-chain are highly uncertain and can vary widely among components and processes. We present an atmosphere-based method for detecting and quantifying the area and time-averaged surface flux of methane from natural gas infrastructure, and its application to the case-study of Boston, Massachusetts. Continuous measurements of atmospheric methane at a network of stations, inside and outside the city, are used to quantify the atmospheric methane gradient due to emissions from the urban area. Simultaneous observations of atmospheric ethane, and data on the ethane and methane content of the pipeline gas flowing through the region, are used to trace the atmospheric methane enhancement to the natural gas source. An atmospheric transport model is used to quantitatively relate the observed methane enhancement to a surface flux from the whole urban region. We find that methane emissions from natural gas in the urban region over one year was equal to 2.7 ± 0.6 % of the natural gas delivered to the region. Our findings for Boston suggest natural-gas-consuming regions, generally, may be larger sources of methane to the atmosphere than is current estimated and represent areas of significant resource loss.

  8. The TNT equivalence of an optimum propane oxygen mixture

    NASA Astrophysics Data System (ADS)

    Dewey, J. M.

    2005-12-01

    Measurements of the times of arrival of the primary shock produced by the explosion of a nominal 20 tn propane-oxygen mixture have been analysed to provide the variation of the peak hydrostatic overpressure as a function of distance. The results have been scaled to those for a charge of unit mass at normal temperature and pressure, based on the masses of the propane and oxygen and of the propane alone. The scaled results are compared with those produced by the explosion of a hemispherical unit mass of TNT to provide the TNT equivalence factor as a function of overpressure and distance. For overpressures greater than 1 atm there is a strong dependence on the distance from the centre of the explosion, but at lower overpressures the equivalence factors have almost constant values of 0.55 for the propane-oxygen mixture and 1.95 for the propane alone. The significance of these findings, in relationship to vapour cloud explosions and boiling liquid expanding vapour explosions, is discussed.

  9. Non Methane Hydrocarbons (NMHCs) at the centre of Athens: variability and relative contribution of traffic and wood burning

    NASA Astrophysics Data System (ADS)

    Panopoulou, Anastasia; Liakakou, Eleni; Psiloglou, Basil; Gros, Valerie; Bonsang, Bernard; Sauvage, Stephane; Locoge, Nadine; Lianou, Maria; Gerasopoulos, Evangelos; Mihalopoulos, Nikolaos

    2016-04-01

    Non-methane hydrocarbons (NMHC) can be found in significant concentrations in urban areas. They are emitted by biogenic and anthropogenic sources like vehicle exhaust, gasoline evaporation and solvent use. Once emitted they mainly react with hydroxyl radicals (OH) and in the presence of nitrogen oxides (NOx) lead to the formation of secondary pollutants such as ozone (O3), peroxy acetyl nitrate (PAN) and secondary organic aerosols. In Great Athens Area (GAA) despite the numerous air quality issues especially with exceedances in ozone and particulate matter (PM), continuous monitoring of NMHCs is absent. This work presents the first results of a ChArMEX/TRANSEMED project dealing with VOC source apportionment and emission inventory evaluation in megacities around the Mediterranean basin. A representative site in the centre of Athens is progressively equipped with high performance instruments in order to measure continuously NMHCs (time resolution of 30 min) over a long period. The main objective of this presentation is the determination of the ambient level and temporal variability of C2-C6 NMHCs, as well as the impact of the sources controlling their variability. The importance of this work is attributed to the high time resolution measurements providing a detailed light hydrocarbons profile of the area for first time in the GAA. An automatic gas chromatograph (airmoVOC C2-C6 Chromatrap GC, Chromatotec, France) equipped with a flame ionization detector (FID) has been used for the in-situ measurements of NMHCS with two to six carbon atoms (C2-C6 NMHCs) during the period from the 16 of October to end of December 2015. In addition, meteorological and auxiliary data for major gases (CO, O3, NOx) and particulates (PM and Black Carbon (BC) are also available. Atmospheric concentrations of NMHCs range from below the detection limit to a few ppbs, for example almost 14 ppb, 20 ppb and 25 ppb for ethane, propane and acetylene respectively. Between the NMHCs being monitored

  10. Sampling, storage, and analysis of C2-C7 non-methane hydrocarbons from the US National Oceanic and Atmospheric Administration Cooperative Air Sampling Network glass flasks.

    PubMed

    Pollmann, Jan; Helmig, Detlev; Hueber, Jacques; Plass-Dülmer, Christian; Tans, Pieter

    2008-04-25

    An analytical technique was developed to analyze light non-methane hydrocarbons (NMHC), including ethane, propane, iso-butane, n-butane, iso-pentane, n-pentane, n-hexane, isoprene, benzene and toluene from whole air samples collected in 2.5l-glass flasks used by the National Oceanic and Atmospheric Administration, Earth System Research Laboratory, Global Monitoring Division (NOAA ESRL GMD, Boulder, CO, USA) Cooperative Air Sampling Network. This method relies on utilizing the remaining air in these flasks (which is at below-ambient pressure at this stage) after the completion of all routine greenhouse gas measurements from these samples. NMHC in sample aliquots extracted from the flasks were preconcentrated with a custom-made, cryogen-free inlet system and analyzed by gas chromatography (GC) with flame ionization detection (FID). C2-C7 NMHC, depending on their ambient air mixing ratios, could be measured with accuracy and repeatability errors of generally < or =10-20%. Larger deviations were found for ethene and propene. Hexane was systematically overestimated due to a chromatographic co-elution problem. Saturated NMHC showed less than 5% changes in their mixing ratios in glass flask samples that were stored for up to 1 year. In the same experiment ethene and propene increased at approximately 30% yr(-1). A series of blank experiments showed negligible contamination from the sampling process and from storage (<10 pptv yr(-1)) of samples in these glass flasks. Results from flask NMHC analyses were compared to in-situ NMHC measurements at the Global Atmospheric Watch station in Hohenpeissenberg, Germany. This 9-months side-by-side comparison showed good agreement between both methods. More than 94% of all data comparisons for C2-C5 alkanes, isoprene, benzene and toluene fell within the combined accuracy and precision objectives of the World Meteorological Organization Global Atmosphere Watch (WMO-GAW) for NMHC measurements.

  11. High ethylene to ethane processes for oxidative coupling

    DOEpatents

    Chafin, Richard B.; Warren, Barbara K.

    1991-01-01

    Oxidative coupling of lower alkane to higher hydrocarbon is conducted using catalyst comprising barium and/or strontium component and a metal oxide combustion promoter in the presence of vapor phase halogen component. High ethylene to ethane mole ratios in the product can be obtained over extended operating periods.

  12. Determination of Ethane-1,2-diamine in Inert Complexes.

    ERIC Educational Resources Information Center

    Searle, Graeme H.

    1985-01-01

    Describes a procedure for determining ethane-1,2-diamine (EN) which is generally applicable for inert or labile complexes or for EN in its salts, although it cannot be used directly with ammonium or coordinated ammonia. It gives results with five percent accuracy or better and requires less than one hour laboratory time. (JN)

  13. Determination of Ethane-1,2-diamine in Inert Complexes.

    ERIC Educational Resources Information Center

    Searle, Graeme H.

    1985-01-01

    Describes a procedure for determining ethane-1,2-diamine (EN) which is generally applicable for inert or labile complexes or for EN in its salts, although it cannot be used directly with ammonium or coordinated ammonia. It gives results with five percent accuracy or better and requires less than one hour laboratory time. (JN)

  14. Theoretical CI study of the vertical electronic spectrum of ethane

    SciTech Connect

    Chantranupong, L.; Hirsch, G.; Buenker, R.J.; Dillon, M.A.

    1994-06-01

    Ab initio multireference single- and double-excitation configuration interaction (MRD-CI) calculations are reported for the ground and 32 excited electronic states of ethane, as well as its two lowest ionic states, {sup 2}E{sub g} and {sup 2}A{sub 1g}. The transition energy results indicate that the 3a{sub 1g} molecular orbital is 0.3--0.6 eV more stable than the 1e{sub g} LUMO for the ethane D{sub 3d} equilibrium conformation. The strongest transition is computed to occur for the 3a{sub 1g} {yields} 3p{sigma} {sup 1}A{sub 2u}--{sup 1}A{sub 1g} excitation at 9.933 eV, with an optical f value of 0.1152. The n = 4 Rydberg transitions are also calculated and are found to occur with roughly 40% of their n = 3 counterparts. The observed broadness of the ethane UV spectrum is believed to be caused primarily by the high density of Rydberg upper states, as well as significant relaxation effects which occur upon excitation from the ethane electronic ground state.

  15. High ethylene to ethane processes for oxidative coupling

    DOEpatents

    Chafin, R.B.; Warren, B.K.

    1991-12-17

    Oxidative coupling of lower alkane to higher hydrocarbon is conducted using a catalyst comprising barium and/or strontium component and a metal oxide combustion promoter in the presence of vapor phase halogen component. High ethylene to ethane mole ratios in the product can be obtained over extended operating periods.

  16. Little evidence for significant increases of methane emissions from oil and gas operations in the U.S.

    NASA Astrophysics Data System (ADS)

    Lan, X.; Tans, P. P.; Sweeney, C.; Andrews, A. E.; Dlugokencky, E. J.; Lang, P. M.; Crotwell, M.; Miller, B.; Kofler, J.; Newberger, T.; McKain, K.; Wolter, S.; Montzka, S. A.

    2016-12-01

    Recent studies on whether methane (CH4) emissions from oil and natural gas (ONG) operations in the U.S. have increased are still inconclusive. To provide observational evidence we carefully analyzed the in-situ CH4 measurements from the NOAA/ESRL Global Greenhouse Gas Reference Network (GGGRN) for the best estimates of CH4 trends for 2006-2016. Methane data from more than 20 surface and aircraft sites across the U.S. were included in this study. Variations of sampling frequencies in different seasons were taken into account for accurate trend detection. Correlations among measurements within short sampling intervals were also considered for uncertainty estimates. We found that most of our sites had similar CH4 trends of 6 ppb/yr, which was comparable with the recent global background CH4 trend. Substantially higher growth rates were found at the Southern Great Plain site in Oklahoma (SGP, downwind of the Eagle Ford, Barnett Shale and Woodford ONG fields) and the Dahlen sites in North Dakota (DND, downwind of the Bakken ONG field), which indicated influences from regional ONG activities. Ethane (C2H6) measurements from SGP (C2H6 measurements were not available from DND) and propane (C3H8) measurements from both SPG and DND exhibited significant increasing trends, while trends at other sites were either non-significant (trend < 2*S.D.) or only marginally significant. Linear correlations were well identified for surface C3H8 and CH4 enhancements at these two sites, relative to observations at higher altitudes. However, by applying the observed enhancement ratios of surface C3H8 /CH4 and the C3H8 trends (as indicator for ONG emissions) on CH4 trend estimates, we would infer much larger surface CH4 trends than what we actually observed at these two sites. This discrepancy suggests that using enhancement ratios of C3H8 /CH4 is not likely a reliable approach to compute CH4 emission trends.

  17. Reconciling divergent estimates of oil and gas methane emissions.

    PubMed

    Zavala-Araiza, Daniel; Lyon, David R; Alvarez, Ramón A; Davis, Kenneth J; Harriss, Robert; Herndon, Scott C; Karion, Anna; Kort, Eric Adam; Lamb, Brian K; Lan, Xin; Marchese, Anthony J; Pacala, Stephen W; Robinson, Allen L; Shepson, Paul B; Sweeney, Colm; Talbot, Robert; Townsend-Small, Amy; Yacovitch, Tara I; Zimmerle, Daniel J; Hamburg, Steven P

    2015-12-22

    Published estimates of methane emissions from atmospheric data (top-down approaches) exceed those from source-based inventories (bottom-up approaches), leading to conflicting claims about the climate implications of fuel switching from coal or petroleum to natural gas. Based on data from a coordinated campaign in the Barnett Shale oil and gas-producing region of Texas, we find that top-down and bottom-up estimates of both total and fossil methane emissions agree within statistical confidence intervals (relative differences are 10% for fossil methane and 0.1% for total methane). We reduced uncertainty in top-down estimates by using repeated mass balance measurements, as well as ethane as a fingerprint for source attribution. Similarly, our bottom-up estimate incorporates a more complete count of facilities than past inventories, which omitted a significant number of major sources, and more effectively accounts for the influence of large emission sources using a statistical estimator that integrates observations from multiple ground-based measurement datasets. Two percent of oil and gas facilities in the Barnett accounts for half of methane emissions at any given time, and high-emitting facilities appear to be spatiotemporally variable. Measured oil and gas methane emissions are 90% larger than estimates based on the US Environmental Protection Agency's Greenhouse Gas Inventory and correspond to 1.5% of natural gas production. This rate of methane loss increases the 20-y climate impacts of natural gas consumed in the region by roughly 50%.

  18. Reconciling divergent estimates of oil and gas methane emissions

    PubMed Central

    Zavala-Araiza, Daniel; Lyon, David R.; Alvarez, Ramón A.; Davis, Kenneth J.; Harriss, Robert; Herndon, Scott C.; Karion, Anna; Kort, Eric Adam; Lamb, Brian K.; Lan, Xin; Marchese, Anthony J.; Pacala, Stephen W.; Robinson, Allen L.; Shepson, Paul B.; Sweeney, Colm; Talbot, Robert; Townsend-Small, Amy; Yacovitch, Tara I.; Zimmerle, Daniel J.; Hamburg, Steven P.

    2015-01-01

    Published estimates of methane emissions from atmospheric data (top-down approaches) exceed those from source-based inventories (bottom-up approaches), leading to conflicting claims about the climate implications of fuel switching from coal or petroleum to natural gas. Based on data from a coordinated campaign in the Barnett Shale oil and gas-producing region of Texas, we find that top-down and bottom-up estimates of both total and fossil methane emissions agree within statistical confidence intervals (relative differences are 10% for fossil methane and 0.1% for total methane). We reduced uncertainty in top-down estimates by using repeated mass balance measurements, as well as ethane as a fingerprint for source attribution. Similarly, our bottom-up estimate incorporates a more complete count of facilities than past inventories, which omitted a significant number of major sources, and more effectively accounts for the influence of large emission sources using a statistical estimator that integrates observations from multiple ground-based measurement datasets. Two percent of oil and gas facilities in the Barnett accounts for half of methane emissions at any given time, and high-emitting facilities appear to be spatiotemporally variable. Measured oil and gas methane emissions are 90% larger than estimates based on the US Environmental Protection Agency’s Greenhouse Gas Inventory and correspond to 1.5% of natural gas production. This rate of methane loss increases the 20-y climate impacts of natural gas consumed in the region by roughly 50%. PMID:26644584

  19. An engineered pathway for the biosynthesis of renewable propane

    PubMed Central

    Kallio, Pauli; Pásztor, András; Thiel, Kati; Akhtar, M. Kalim; Jones, Patrik R.

    2014-01-01

    The deployment of next-generation renewable biofuels can be enhanced by improving their compatibility with the current infrastructure for transportation, storage and utilization. Propane, the bulk component of liquid petroleum gas, is an appealing target as it already has a global market. In addition, it is a gas under standard conditions, but can easily be liquefied. This allows the fuel to immediately separate from the biocatalytic process after synthesis, yet does not preclude energy-dense storage as a liquid. Here we report, for the first time, a synthetic metabolic pathway for producing renewable propane. The pathway is based on a thioesterase specific for butyryl-acyl carrier protein (ACP), which allows native fatty acid biosynthesis of the Escherichia coli host to be redirected towards a synthetic alkane pathway. Propane biosynthesis is markedly stimulated by the introduction of an electron-donating module, optimizing the balance of O2 supply and removal of native aldehyde reductases. PMID:25181600

  20. An engineered pathway for the biosynthesis of renewable propane.

    PubMed

    Kallio, Pauli; Pásztor, András; Thiel, Kati; Akhtar, M Kalim; Jones, Patrik R

    2014-09-02

    The deployment of next-generation renewable biofuels can be enhanced by improving their compatibility with the current infrastructure for transportation, storage and utilization. Propane, the bulk component of liquid petroleum gas, is an appealing target as it already has a global market. In addition, it is a gas under standard conditions, but can easily be liquefied. This allows the fuel to immediately separate from the biocatalytic process after synthesis, yet does not preclude energy-dense storage as a liquid. Here we report, for the first time, a synthetic metabolic pathway for producing renewable propane. The pathway is based on a thioesterase specific for butyryl-acyl carrier protein (ACP), which allows native fatty acid biosynthesis of the Escherichia coli host to be redirected towards a synthetic alkane pathway. Propane biosynthesis is markedly stimulated by the introduction of an electron-donating module, optimizing the balance of O2 supply and removal of native aldehyde reductases.

  1. Methane Painting

    NASA Image and Video Library

    2015-09-07

    Why does Saturn look like it's been painted with a dark brush in this infrared image, but Dione looks untouched? Perhaps an artist with very specific tastes in palettes? The answer is methane. This image was taken in a wavelength that is absorbed by methane. Dark areas seen here on Saturn are regions with thicker clouds, where light has to travel through more methane on its way into and back out of the atmosphere. Since Dione (698 miles or 1,123 kilometers across) doesn't have an atmosphere rich in methane the way Saturn does, it does not experience similar absorption -- the sunlight simply bounces off its icy surface. Shadows of the rings are seen cast onto the planet at lower right. This view looks toward Saturn from the unilluminated side of the rings, about 0.3 degrees below the ring plane. The image was taken with the Cassini spacecraft wide-angle camera on May 27, 2015 using a spectral filter which preferentially admits wavelengths of near-infrared light centered at 728 nanometers. http://photojournal.jpl.nasa.gov/catalog/PIA18336

  2. Landfill Methane

    USDA-ARS?s Scientific Manuscript database

    Landfill methane (CH4) accounts for approximately 1.3% (0.6 Gt) of global anthropogenic greenhouse gas emissions relative to total emissions from all sectors of about 49 Gt CO2-eq yr-1. For countries with a history of controlled landfilling, landfills can be one of the larger national sources of ant...

  3. Retrievals of ethane from ground-based high-resolution FTIR solar observations with updated line parameters: determination of the optimum strategy for the Jungfraujoch station.

    NASA Astrophysics Data System (ADS)

    Bader, W.; Perrin, A.; Jacquemart, D.; Sudo, K.; Yashiro, H.; Gauss, M.; Demoulin, P.; Servais, C.; Mahieu, E.

    2012-04-01

    Ethane (C2H6) is the most abundant Non-Methane HydroCarbon (NMHC) in the Earth's atmosphere, with a lifetime of approximately 2 months. C2H6 has both anthropogenic and natural emission sources such as biomass burning, natural gas loss and biofuel consumption. Oxidation by the hydroxyl radical is by far the major C2H6 sink as the seasonally changing OH concentration controls the strong modulation of the ethane abundance throughout the year. Ethane lowers Cl atom concentrations in the lower stratosphere and is a major source of peroxyacetyl nitrate (PAN) and carbon monoxide (by reaction with OH). Involved in the formation of tropospheric ozone and in the destruction of atmospheric methane through changes in OH, C2H6 is a non-direct greenhouse gas with a net-global warming potential (100-yr horizon) of 5.5. The retrieval of ethane from ground-based infrared (IR) spectra is challenging. Indeed, the fitting of the ethane features is complicated by numerous interferences by strong water vapor, ozone and methane absorptions. Moreover, ethane has a complicated spectrum with many interacting vibrational modes and the current state of ethane parameters in HITRAN (e.g. : Rothman et al., 2009, see http://www.hitran.com) was rather unsatisfactory in the 3 μm region. In fact, PQ branches outside the 2973-3001 cm-1 range are not included in HITRAN, and most P and R structures are missing. New ethane absorption cross sections recorded at the Molecular Spectroscopy Facility of the Rutherford Appleton Laboratory (Harrison et al., 2010) are used in our retrievals. They were calibrated in intensity by using reference low-resolution spectra from the Pacific Northwest National Laboratory (PNNL) IR database. Pseudoline parameters fitted to these ethane spectra have been combined with HITRAN 2004 line parameters (including all the 2006 updates) for all other species encompassed in the selected microwindows. Also, the improvement brought by the update of the line positions and intensities

  4. Diacetonitrile[N,N′-bis(2,6-diisopropyl­phenyl)ethane-1,2-diimine]dichloridochromium(II) acetonitrile solvate

    PubMed Central

    Peitz, Stephan; Peulecke, Normen; Müller, Bernd H.; Spannenberg, Anke; Rosenthal, Uwe

    2009-01-01

    The title compound, [CrCl2(CH3CN)2(C26H36N2)]·CH3CN, was synthesized by the reaction of CrCl2(THF)2 with N,N′-bis­(2,6-diisopropyl­phen­yl)ethane-1,2-diimine in dichloro­methane/acetonitrile. The chromium center is coordinated by two N atoms of the chelating diimine ligand, two chloride ions in a trans configuration with respect to each other, and by two N atoms of two acetonitrile mol­ecules in a distorted octa­hedral geometry. PMID:21578093

  5. Oxidative dehydrogenation of propane over Mg-Mo-O catalysts

    SciTech Connect

    Cadus, L.E.; Abello, M.C.; Gomez, M.F.; Rivarola, J.B.

    1996-01-01

    Mg-Mo-O catalysts have been investigated with different techniques (XRD, XPS, IR, and EPR spectroscopies) in order to explain the difference in catalytic behavior in the oxidative dehydrogenation of propane to propene. The active site would be a coordinatively unsaturated form of Mo{sup 5+}. The active Mo{sup 5+} could be generated on the surface by propane reduction. The slight excess of MoO{sub 3} which is necessary for the catalyst to become an active one probably contributes to the formation of Mo{sup 5+}.

  6. Laboratory measurements of cross sections of propane in the 7 - 15 μm using FT-IR at cold temperatures

    NASA Astrophysics Data System (ADS)

    Sung, K.; Toon, G. C.; Brown, L. R.; Mantz, A. W.; Smith, M. A.

    2012-12-01

    Propane (C3H8) is one of the most abundant non-methane hydrocarbons (NMHC) in the natural environment of the Earth. In addition to biogenic and anthropogenic emissions, the natural degassing from geological processes is also reported to be a significant source (Etiope and Ciccioli, Science, 323, 478, 1999). At Titan, propane is an important component of the photochemistry and may provide insights into pre-biotic chemistry. To support atmospheric remote sensing of propane, absorption cross sections of N2-broadened C3H8 were obtained at temperatures between 145 and 296 K at the Jet Propulsion Laboratory. For this, 17 spectra of pure- and N2-broadened propane were recorded in the 690 to 1550 cm-1 region using a Fourier transform spectrometer (Bruker IFS-125HR) configured with a 20.38 cm long temperature-stabilized cryogenic absorption cell, developed at Connecticut College (Mantz, et al., Mol.Spectrosc. Symposium at OSU, 2010; Sung et al. JMS, 262, 122, 2010). We report the absorption cross sections at the various cold temperatures for several strong propane bands in the region. In addition, we present empirical positions, intensities, and lower state energies' determined by fitting "pseudo-lines" to the high-resolution laboratory spectra, (see http://mark4sun.jpl.nasa.gov/data/ spec/Pseudo/Readme). The resulting compilation will be compared to earlier work, including the C3H8+N2 spectra recorded at PNNL (Sharpe, et al. Appl Spectrosc 58, 1452, 2004) and available line-by-line predictions (Flaud et al., J Chem Phys 114, 9361, 2001; Flaud et al. Mol Phys 108, 699, 2010). [ Research described in this paper was performed at the Jet Propulsion Laboratory, California Institute of Technology, Connecticut College, and NASA Langley Research Center, under contracts and cooperative agreements with the National Aeronautics and Space Administration.

  7. Anthropogenic emissions of methane in the United States

    PubMed Central

    Miller, Scot M.; Wofsy, Steven C.; Michalak, Anna M.; Kort, Eric A.; Andrews, Arlyn E.; Biraud, Sebastien C.; Dlugokencky, Edward J.; Eluszkiewicz, Janusz; Fischer, Marc L.; Janssens-Maenhout, Greet; Miller, Ben R.; Miller, John B.; Montzka, Stephen A.; Nehrkorn, Thomas; Sweeney, Colm

    2013-01-01

    This study quantitatively estimates the spatial distribution of anthropogenic methane sources in the United States by combining comprehensive atmospheric methane observations, extensive spatial datasets, and a high-resolution atmospheric transport model. Results show that current inventories from the US Environmental Protection Agency (EPA) and the Emissions Database for Global Atmospheric Research underestimate methane emissions nationally by a factor of ∼1.5 and ∼1.7, respectively. Our study indicates that emissions due to ruminants and manure are up to twice the magnitude of existing inventories. In addition, the discrepancy in methane source estimates is particularly pronounced in the south-central United States, where we find total emissions are ∼2.7 times greater than in most inventories and account for 24 ± 3% of national emissions. The spatial patterns of our emission fluxes and observed methane–propane correlations indicate that fossil fuel extraction and refining are major contributors (45 ± 13%) in the south-central United States. This result suggests that regional methane emissions due to fossil fuel extraction and processing could be 4.9 ± 2.6 times larger than in EDGAR, the most comprehensive global methane inventory. These results cast doubt on the US EPA’s recent decision to downscale its estimate of national natural gas emissions by 25–30%. Overall, we conclude that methane emissions associated with both the animal husbandry and fossil fuel industries have larger greenhouse gas impacts than indicated by existing inventories. PMID:24277804

  8. 78 FR 62323 - MarkWest Liberty Ethane Pipeline L.L.C.; Notice of Petition for Declaratory Order

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-10-16

    ... Energy Regulatory Commission MarkWest Liberty Ethane Pipeline L.L.C.; Notice of Petition for Declaratory... Practices and Procedure, 18 CFR 385.207(a)(2)(2013), MarkWest Liberty Ethane Pipeline L.L.C. (MarkWest... new ethane pipeline system that will transport ethane from the vicinity of Majorsville, West...

  9. Bis[N,N′-bis­(2,6-diisopropyl­phen­yl)ethane-1,2-diimine]-1κ2 N,N′;2κ2 N,N′-tri-μ-trichlorido-1:2κ6 Cl:Cl-chlorido-1κCl-tetra­hydro­furan-2κO-dichromium(II) dichloro­methane 4.5-solvate

    PubMed Central

    Peitz, Stephan; Peulecke, Normen; Müller, Bernd H.; Spannenberg, Anke; Rosenthal, Uwe

    2009-01-01

    In the mol­ecular structure of the title compound, [Cr2Cl4(C26H36N2)2(C4H8O)]·4.5CH2Cl2, the two CrII centers are bridged by three Cl atoms, forming a dinuclear complex. Each CrII center is coordinated by one chelating bis­(2,6-diisopropyl­phen­yl)ethane-1,2-diimine ligand via both N atoms. An additional chloride ion binds to one chromium center, whereas an additional tetra­hydro­furan mol­ecule coordinates to the second CrII center. The coordination geometry at each CrII center can be best described as distorted octa­hedral. PMID:21578607

  10. Three new olanzapine structures: the acetic acid monosolvate, and the propan-2-ol and propan-2-one hemisolvate monohydrates.

    PubMed

    Bojarska, Joanna; Maniukiewicz, Waldemar; Sieroń, Lesław

    2013-07-01

    The crystal structures of three new solvates of olanzapine [systematic name: 2-methyl-4-(4-methylpiperazin-1-yl)-10H-thieno[2,3-b][1,5]benzodiazepine], namely olanzapine acetic acid monosolvate, C17H20N4S·C2H4O2, (I), olanzapine propan-2-ol hemisolvate monohydrate, C17H20N4S·0.5C3H8O·H2O, (II), and olanzapine propan-2-one hemisolvate monohydrate, C17H20N4S·0.5C3H6O·H2O, (III), are presented and compared with other known olanzapine forms. There is a fairly close resemblance of the molecular conformation for all studied analogues. The crystal structures are built up through olanzapine dimers, which are characterized via C-H...π interactions between the aliphatic fragment (1-methylpiperazin-4-yl) and the aromatic fragment (benzene system). All solvent (guest) molecules participate in hydrogen-bonding networks. The crystal packing is sustained via intermolecular N(host)-H···O(guest), O(guest)-H···N(host), O(guest)-H···O(guest) and C(host)-H···O(guest) hydrogen bonds. It should be noted that the solvent propan-2-ol in (II) and propan-2-one in (III) show orientational disorder. The propan-2-ol molecule lies close to a twofold axis, while the propan-2-one molecule resides strictly on a twofold axis through the carbonyl C atom. In both cases, the water molecules present positional disorder of the H atoms.

  11. Complex Hydrocarbon Chemistry in Interstellar and Solar System Ices Revealed: A Combined Infrared Spectroscopy and Reflectron Time-of-flight Mass Spectrometry Analysis of Ethane (C2H6) and D6-Ethane (C2D6) Ices Exposed to Ionizing Radiation

    NASA Astrophysics Data System (ADS)

    Abplanalp, Matthew J.; Kaiser, Ralf I.

    2016-08-01

    The irradiation of pure ethane (C2H6/C2D6) ices at 5.5 K, under ultrahigh vacuum conditions was conducted to investigate the formation of complex hydrocarbons via interaction with energetic electrons simulating the secondary electrons produced in the track of galactic cosmic rays. The chemical modifications of the ices were monitored in situ using Fourier transform infrared spectroscopy (FTIR) and during temperature-programmed desorption via mass spectrometry exploiting a quadrupole mass spectrometer with electron impact ionization (EI-QMS) as well as a reflectron time-of-flight mass spectrometer coupled to a photoionization source (PI-ReTOF-MS). FTIR confirmed previous ethane studies by detecting six molecules: methane (CH4), acetylene (C2H2), ethylene (C2H4), the ethyl radical (C2H5), 1-butene (C4H8), and n-butane (C4H10). However, the TPD phase, along with EI-QMS, and most importantly, PI-ReTOF-MS, revealed the formation of at least 23 hydrocarbons, many for the first time in ethane ice, which can be arranged in four groups with an increasing carbon-to-hydrogen ratio: C n H2n+2 (n = 3, 4, 6, 8, 10), C n H2n (n = 3-10), {{{C}}}n{{{H}}}2n-2 (n = 3-10), and {{{C}}}n{{{H}}}2n-4 (n = 4-6). The processing of simple ethane ices is relevant to the hydrocarbon chemistry in the interstellar medium, as ethane has been shown to be a major product of methane, as well as in the outer solar system. These data reveal that the processing of ethane ices can synthesize several key hydrocarbons such as C3H4 and C4H6 isomers, which ha­ve been found to synthesize polycyclic aromatic hydrocarbons like indene (C9H8) and naphtha­lene (C10H8) in the ISM and in hydrocarbon-rich atmospheres of planets and their moons such as Titan.

  12. Recent increase of ethane detected in the remote atmosphere of the Northern Hemisphere

    NASA Astrophysics Data System (ADS)

    Franco, Bruno; Bader, Whitney; Bovy, Benoît; Mahieu, Emmanuel; Fischer, Emily V.; Strong, Kimberly; Conway, Stephanie; Hannigan, James W.; Nussbaumer, Eric; Bernath, Peter F.; Boone, Chris D.; Walker, Kaley A.

    2015-04-01

    Ethane (C2H6) has a large impact on tropospheric composition and air quality because of its involvement in the global VOC (volatile organic compound) - HOx - NOx chemistry responsible for generating and destroying tropospheric ozone. By acting as a major sink for tropospheric OH radicals, the abundance of C2H6 influences the atmospheric content of carbon monoxide and impacts the lifetime of methane. Moreover, it is an important source of PAN, a thermally unstable reservoir for NOx radicals. On a global scale, the main sources of C2H6 are leakage from the production, transport of natural gas loss, biofuel consumption and biomass burning, mainly located in the Northern Hemisphere. Due to its relatively long lifetime of approximately two months, C2H6 is a sensitive indicator of tropospheric pollution and transport. Using an optimized retrieval strategy (see Franco et al., 2014), we present here a 20-year long-term time series of C2H6 column abundance retrieved from ground-based Fourier Transform InfraRed (FTIR) solar spectra recorded from 1994 onwards at the high-altitude station of Jungfraujoch (Swiss Alps, 46.5° N, 3580 m a.s.l.), part of the Network for the Detection of Atmospheric Composition Change (NDACC, see http://www.ndacc.org). After a regular 1994 - 2008 decrease of the C2H6 amounts, which is very consistent with prior major studies (e.g., Aydin et al., 2011; Simpson et al., 2012) and our understanding of global C2H6 emissions, trend analysis using a bootstrap resampling tool reveals a C2H6 upturn and a statistically-significant sharp burden increase from 2009 onwards (Franco et al., 2014). We hypothesize that this observed recent increase in C2H6 could affect the whole Northern Hemisphere and may be related to the recent massive growth in the exploitation of shale gas and tight oil reservoirs. This hypothesis is supported by measurements derived from solar occultation observations performed since 2004 by the Atmospheric Chemistry Experiment - Fourier

  13. 40 CFR 721.10339 - Adipic acid, substituted propane, alkyldiol, acrylate (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Adipic acid, substituted propane... Significant New Uses for Specific Chemical Substances § 721.10339 Adipic acid, substituted propane, alkyldiol... substance identified generically as adipic acid, substituted propane, alkyldiol, acrylate (PMN P-04-113)...

  14. 40 CFR 721.10339 - Adipic acid, substituted propane, alkyldiol, acrylate (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Adipic acid, substituted propane... Significant New Uses for Specific Chemical Substances § 721.10339 Adipic acid, substituted propane, alkyldiol... substance identified generically as adipic acid, substituted propane, alkyldiol, acrylate (PMN P-04-113)...

  15. 40 CFR 721.10339 - Adipic acid, substituted propane, alkyldiol, acrylate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Adipic acid, substituted propane... Significant New Uses for Specific Chemical Substances § 721.10339 Adipic acid, substituted propane, alkyldiol... substance identified generically as adipic acid, substituted propane, alkyldiol, acrylate (PMN P-04-113)...

  16. Use of the HadGEM2 climate-chemistry model to investigate interannual variability in methane sources

    NASA Astrophysics Data System (ADS)

    Hayman, Garry; O'Connor, Fiona; Clark, Douglas; Huntingford, Chris; Gedney, Nicola

    2013-04-01

    The global mean atmospheric concentration of methane (CH4) has more than doubled during the industrial era [1] and now constitutes ? 20% of the anthropogenic climate forcing by greenhouse gases [2]. The globally-averaged CH4 growth rate, derived from surface measurements, has fallen significantly from a high of 16 ppb yr-1 in the late 1970s/early 1980s and was close to zero between 1999 and 2006 [1]. This overall period of declining or low growth was however interspersed with years of positive growth-rate anomalies (e.g., in 1991-1992, 1998-1999 and 2002-2003). Since 2007, renewed growth has been evident [1, 3], with the largest increases observed over polar northern latitudes and the Southern Hemisphere in 2007 and in the tropics in 2008. The observed inter-annual variability in atmospheric methane concentrations and the associated changes in growth rates have variously been attributed to changes in different methane sources and sinks [1, 4]. In this paper, we report results from runs of the HadGEM2 climate-chemistry model [5] using year- and month-specific emission datasets. The HadGEM2 model includes the comprehensive atmospheric chemistry and aerosol package, the UK Chemistry Aerosol community model (UKCA, http://www.ukca.ac.uk/wiki/index.php). The Standard Tropospheric Chemistry scheme was selected for this work. This chemistry scheme simulates the Ox, HOx and NOx chemical cycles and the oxidation of CO, methane, ethane and propane. Year- and month-specific emission datasets were generated for the period from 1997 to 2009 for the emitted species in the chemistry scheme (CH4, CO, NOx, HCHO, C2H6, C3H8, CH3CHO, CH3CHOCH3). The approach adopted varied depending on the source sector: Anthropogenic: The emissions from anthropogenic sources were based on decadal-averaged emission inventories compiled by [6] for the Coupled Carbon Cycle Climate Model Intercomparison Project (C4MIP). These were then used to derive year-specific emission datasets by scaling the

  17. Zeolitic imidazolate frameworks for kinetic separation of propane and propene

    DOEpatents

    Li, Jing; Li, Kunhao; Olson, David H.

    2014-08-05

    Zeolitic Imidazolate Frameworks (ZIFs) characterized by organic ligands consisting of imidazole ligands that are either essentially all 2-chloroimidazole ligands or essentially all 2-bromoimidazole ligands are disclosed. Methods for separating propane and propene with the ZIFs of the present invention, as well as other ZIFs, are also disclosed.

  18. Stability and dynamic processes in 16VE iridium(III) ethyl hydride and rhodium(I) σ-ethane complexes: experimental and computational studies.

    PubMed

    Walter, Marc D; White, Peter S; Schauer, Cynthia K; Brookhart, Maurice

    2013-10-23

    Iridium(I) and rhodium(I) ethyl complexes, (PONOP)M(C2H5) (M = Ir (1-Et), Rh (2-Et)) and the iridium(I) propyl complex (PONOP)Ir(C3H7) (1-Pr), where PONOP is 2,6-(tBu2PO)2C5H3N, have been prepared. Low-temperature protonation of the Ir complexes yields the alkyl hydrides, (PONOP)Ir(H)(R) (1-(H)(Et)(+) and 1-(H)(Pr)(+)), respectively. Dynamic (1)H NMR characterization of 1-(H)(Et)(+) establishes site exchange between the Ir-H and Ir-CH2 protons (ΔG(exH)(‡)(-110 °C) = 7.2(1) kcal/mol), pointing to a σ-ethane intermediate. By dynamic (13)C NMR spectroscopy, the exchange barrier between the α and β carbons ("chain-walking") was measured (ΔG(exC)(‡)(-110 °C) = 8.1(1) kcal/mol). The barrier for ethane loss is 17.4(1) kcal/mol (-40 °C), to be compared with the reported barrier to methane loss in 1-(H)(Me)(+) of 22.4 kcal/mol (22 °C). A rhodium σ-ethane complex, (PONOP)Rh(EtH) (2-(EtH)(+)), was prepared by protonation of 2-Et at -150 °C. The barrier for ethane loss (ΔG(dec)(‡)(-132 °C) = 10.9(2) kcal/mol) is lower than for the methane complex, 2-(MeH)(+), (ΔG(dec)(‡)(-87 °C) = 14.5(4) kcal/mol). Full spectroscopic characterization of 2-(EtH)(+) is reported, a key feature of which is the upfield signal at -31.2 ppm for the coordinated CH3 group in the (13)C NMR spectrum. The exchange barrier of the hydrogens of the coordinated methyl group is too low to be measured, but the chain-walking barrier of 7.2(1) kcal/mol (-132 °C) is observable by (13)C NMR. The coordination mode of the alkane ligand and the exchange pathways for the Rh and Ir complexes are evaluated by DFT studies. On the basis of the computational studies, it is proposed that chain-walking occurs by different mechanisms: for Rh, the lowest energy path involves a η(2)-ethane transition state, while for Ir, the lowest energy exchange pathway proceeds through the symmetrical ethylene dihydride complex.

  19. Thermal Vacuum Testing of Swift XRT Ethane Heat Pipes

    NASA Technical Reports Server (NTRS)

    Kobel, Mark; Ku, Jentung

    2003-01-01

    This paper presents the results obtained from a recent ethane heat pipe program. Three identical ethane heat pipes were tested individually, and then two selected heat pipes were tested collectively in their system configuration. Heat transport, thermal conductance, and non-condensable gas tests were performed on each heat pipe. To gain insight into the reflux operation as seen at spacecraft level ground testing, the test fixture was oriented in a vertical configuration. The system level test included a computer-controlled heater designed to emulate the heat load generated at the thermoelectric cooler interface. The system performance was successfully characterized for a wide range of environmental conditions while staying within the operating limits.

  20. Microfluidic Separation of Ethylene and Ethane Using Frustrated Lewis Pairs.

    PubMed

    Voicu, Dan; Stephan, Douglas W; Kumacheva, Eugenia

    2015-12-21

    Separation of gaseous olefins and paraffins is one of the most important separation processes in the industry. Development of new cost-effective technologies aims at reducing the high energy consumption during the separation process. Here, we took advantage of the reaction of frustrated Lewis pairs (FLPs) with ethylene to achieve reactive extraction of ethylene from ethylene-ethane mixtures. The extraction was studied using a microfluidic platform, which enabled a rapid, high-throughput assessment of reaction conditions to optimize gas separation efficiency. A separation factor of 7.3 was achieved for ethylene from a 1:1 volume ratio mixture of ethylene and ethane, which corresponded to an extracted ethylene purity of 88 %. The results obtained in the microfluidic studies were validated using infrared spectroscopy. This work paves the way for further development of the FLPs and optimization of reaction conditions, thereby maximizing the separation efficiency of olefins from their mixtures with paraffins.

  1. Measuring Concentrations of Dissolved Methane and Ethane and the (13) C of Methane in Shale and Till.

    PubMed

    Hendry, M Jim; Barbour, S Lee; Schmeling, Erin E; Mundle, Scott O C

    2017-01-01

    Baseline characterization of concentrations and isotopic values of dissolved natural gases is needed to identify contamination caused by the leakage of fugitive gases from oil and gas activities. Methods to collect and analyze baseline concentration-depth profiles of dissolved CH4 and C2 H6 and δ(13) C-CH4 in shales and Quaternary clayey tills were assessed at two sites in the Williston Basin, Canada. Core and cuttings samples were stored in Isojars(®) in a low O2 headspace prior to analysis. Measurements and multiphase diffusion modeling show that the gas concentrations in core samples yield well-defined and reproducible depth profiles after 31-d equilibration. No measurable oxidative loss or production during core sample storage was observed. Concentrations from cuttings and mud gas logging (including IsoTubes(®) ) were much lower than from cores, but correlated well. Simulations suggest the lower concentrations from cuttings can be attributed to drilling time, and therefore their use to define gas concentration profiles may have inherent limitations. Calculations based on mud gas logging show the method can provide estimates of core concentrations if operational parameters for the mud gas capture cylinder are quantified. The δ(13) C-CH4 measured from mud gas, IsoTubes(®) , cuttings, and core samples are consistent, exhibiting slight variations that should not alter the implications of the results in identifying the sources of the gases. This study shows core and mud gas techniques and, to a lesser extent, cuttings, can generate high-resolution depth profiles of dissolved hydrocarbon gas concentrations and their isotopes. © 2016, National Ground Water Association.

  2. Extraction of Peace River bitumen using supercritical ethane

    NASA Astrophysics Data System (ADS)

    Rose, Jeffrey Lawrence

    2000-10-01

    As the supply of conventional crude oil continues to decline, petroleum companies are looking for alternative hydrocarbon sources. The vast reserves of heavy oil and bitumen located in northern Alberta are among the alternatives. The challenge facing engineers is to develop a process for recovering this oil which is economic, efficient and environmentally acceptable. Supercritical fluid extraction is one method being investigated which could potentially meet all of these criteria. In this study, Peace River bitumen was extracted using supercritical ethane. The bitumen was mixed with sand and packed into a semi-batch extractor. Ethane contacted the bitumen/sand mixture and the fraction of the bitumen soluble in the ethane was removed and subsequently collected in a two phase separator. The flow of ethane was such that the experiments were governed by equilibrium and not mass transfer. Experimental temperatures and pressures were varied in order to observe the effect of these parameters on the mass and composition of the extracted material. The extraction yields increased as the temperature decreased and pressure increased. Samples were collected at various time intervals to measure changes in the properties of the extracted bitumen over the duration of the process. As the extraction proceeded, the samples became heavier and more viscous. The bitumen feed was characterised and the experimental data was then modelled using the Peng-Robinson equation of state. The characterisation process involved the distillation of the bitumen into five fractions. The distillation curve and density of each fraction was measured and this data was used in conjunction with correlations to determine the critical properties of the bitumen. Interaction parameters in the equation of state were then optimised until the predicted composition of extracted bitumen matched the experimental results.

  3. Coalbed Methane Outreach Program

    EPA Pesticide Factsheets

    Coalbed Methane Outreach Program, voluntary program seeking to reduce methane emissions from coal mining activities. CMOP promotes profitable recovery/use of coal mine methane (CMM), addressing barriers to using CMM instead of emitting it to atmosphere.

  4. METHANE: INDUSTRIAL SOURCES

    EPA Science Inventory

    The chapter provides qualitative information on the magnitude of industrial sources of methane and, where possible, provides information to allow the reader to quantify methane emissions. One difficulty in quantifying methane emissions from industry is the inconsistent treatment ...

  5. Activation energy of methyl radical decay in methane hydrate.

    PubMed

    Takeya, Kei; Nango, Kouhei; Sugahara, Takeshi; Ohgaki, Kazunari; Tani, Atsushi

    2005-11-10

    The thermal stability of gamma-ray-induced methyl radicals in methane hydrate was studied using the ESR method at atmospheric pressure and 210-260 K. The methyl radical decay proceeded with the second-order reaction, and ethane molecules were generated from the dimerization process. The methyl radical decay proceeds by two different temperature-dependent processes, that is, the respective activation energies of these processes are 20.0 +/- 1.6 kJ/mol for the lower temperature region of 210-230 K and 54.8 +/- 5.7 kJ/mol for the higher temperature region of 235-260 K. The former agrees well with the enthalpy change of methane hydrate dissociation into ice and gaseous methane, while the latter agrees well with the enthalpy change into liquid water and gaseous methane. The present findings reveal that methane hydrates dissociate into liquid (supercooled) water and gaseous methane in the temperature range of 235-260 K.

  6. Relative effects on global warming of halogenated methanes and ethanes of social and industrial interest

    NASA Technical Reports Server (NTRS)

    Fisher, Donald A.; Hales, Charles H.; Wang, Wei-Chyung; Ko, Malcolm K. W.; Sze, N. Dak

    1990-01-01

    The relative potential global warming effects for several halocarbons (chlorofluorocarbons (CFC's)-11, 12, 113, 114, and 115; hydrochlorofluorocarbons (HCFC's) 22, 123, 124, 141b, and 142b; and hydrofluorocarbons (HFC's) 125, 134a, 143a, and 152a; carbon tetrachloride; and methyl chloroform) were calculated by two atmospheric modeling groups. These calculations were based on atmospheric chemistry and radiative convective models to determine the chemical profiles and the radiative processes. The resulting relative greenhouse warming when normalized to the effect of CFC-11 agree reasonably well as long as we account for differences between modeled lifetimes. Differences among results are discussed. Sensitivity of relative warming values is determined with respect to trace gas levels assumed. Transient relative global warming effects are analyzed.

  7. Relative effects on stratospheric ozone of halogenated methanes and ethanes of social and industrial interest

    NASA Technical Reports Server (NTRS)

    Fisher, Donald A.; Hales, Charles H.; Filkin, David L.; Ko, Malcolm K. W.; Sze, N. Dak; Connell, Peter S.; Wuebbles, Donald J.; Isaksen, Ivar S. A.; Stordal, Frode

    1990-01-01

    Four atmospheric modeling groups have calculated relative effects of several halocarbons (chlorofluorocarbons (CFC's)-11, 12, 113, 114, and 115; hydrochlorofluorocarbons (HCFC's) 22, 123, 124, 141b, and 142b; hydrofluorocarbons (HFC's) 125, 134a, 143a, and 152a, carbon tetrachloride; and methyl chloroform) on stratospheric ozone. Effects on stratospheric ozone were calculated for each compound and normalized relative to the effect of CFC-11. These models include the representations for homogeneous physical and chemical processes in the middle atmosphere but do no account for either heterogeneous chemistry or polar dynamics which are important in the spring time loss of ozone over Antarctica. Relative calculated effects using a range of models compare reasonably well. Within the limits of the uncertainties of these model results, compounds now under consideration as functional replacements for fully halogenated compounds have modeled stratospheric ozone reductions of 10 percent or less of that of CFC-11. Sensitivity analyses examined the sensitivity of relative calculated effects to levels of other trace gases, assumed transport in the models, and latitudinal and seasonal local dependencies. Relative effects on polar ozone are discussed in the context of evolving information on the special processes affecting ozone, especially during polar winter-springtime. Lastly, the time dependency of relative effects were calculated.

  8. MODELING AROMATIC AND POLYCYCLIC AROMATIC HYDROCARBON FORMATION IN PREMIXED METHANE AND ETHANE FLAMES. (R825412)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  9. Concerted mechanism for ethane hydroxylation by the particulate methane monooxygenase from Methylococcus capsulatus (Bath)

    SciTech Connect

    Wilkinson, B.; Priestly, N.D.; Floss, H.G.; Zhu, M.; Nguyen, H.H.T.; Chan, S.I.; Morimoto, Hiromi; Williams, P.G.

    1996-01-31

    The ethanol samples in the isolated alcohol/water mixtures were converted into their (2R)-2-acetoxy-2-phenylethanoate derivatives (2-34 mCi). Examination of the well-resolved {sup 3}H NMR spectra for these derivatives produced an exceptionally consistent set of stereochemical data. When corrected for the enantiomeric purity of the ethyl tosylate starting materials, the data clearly show that the reaction occurs with complete retention of configuration, i.e., with 100% stereoselection. Barring substantial slowing of the carbon-carbon bond rotation of the ethyl radical when bound to the enzyme, this result rules out mechanisms proceeding via alkyl radical (and/or cation) structures, even very short-lived ones, as such intermediates would have to have a lifetime of < 1 x 10{sup -14} s in order not to undergo any detectable C-C bond rotation, i.e., the capture reaction would have to be much faster than the decay of a transition state. The data instead point to a mechanism in which C-H bond cleavage is preceded by bond formation at the alkyl carbon, i.e., one proceeding through a pentacoordinated carbon species. 29 refs., 1 fig., 1 tab.

  10. Methyl-coenzyme M reductase from methanogenic archaea: isotope effects on label exchange and ethane formation with the homologous substrate ethyl-coenzyme M.

    PubMed

    Scheller, Silvan; Goenrich, Meike; Thauer, Rudolf K; Jaun, Bernhard

    2013-10-09

    Ethyl-coenzyme M (CH3CH2-S-CH2CH2-SO3(-), Et-S-CoM) serves as a homologous substrate for the enzyme methyl-coenzyme M reductase (MCR) resulting in the product ethane instead of methane. The catalytic reaction proceeds via an intermediate that already contains all six C-H bonds of the product. Because product release occurs after a second, rate-limiting step, many cycles of intermediate formation and reconversion to substrate occur before a substantial amount of ethane is released. In deuterated buffer, the intermediate becomes labeled, and C-H activation in the back reaction rapidly leads to labeled Et-S-CoM, which enables intermediate formation to be detected. Here, we present a comprehensive analysis of this pre-equilibrium. (2)H- and (13)C-labeled isotopologues of Et-S-CoM were used as the substrates, and the time course of each isotopologue was followed by NMR spectroscopy. A kinetic simulation including kinetic isotope effects allowed determination of the primary and α- and β-secondary isotope effects for intermediate formation and for the C-H/C-D bond activation in the ethane-containing intermediate. The values obtained are in accordance with those found for the native substrate Me-S-CoM (see preceding publication, Scheller, S.; Goenrich, M.; Thauer, R. K.; Jaun, B. J. Am. Chem. Soc. 2013, 135, DOI: 10.1021/ja406485z) and thus imply the same catalytic mechanism for both substrates. The experiment by Floss and co-workers, demonstrating a net inversion of configuration to chiral ethane with CH3CDT-S-CoM as the substrate, is compatible with the observed rapid isotope exchange if the isotope effects measured here are taken into account.

  11. Non-oxidative coupling of methane catalysed by supported tungsten hydride onto alumina and silica-alumina in classical and H2 permeable membrane fixed-bed reactors.

    PubMed

    Szeto, K C; Norsic, S; Hardou, L; Le Roux, E; Chakka, S; Thivolle-Cazat, J; Baudouin, A; Papaioannou, C; Basset, J-M; Taoufik, M

    2010-06-14

    Non-oxidative coupling of methane with high selectivity into ethane (>99% among hydrocarbon) in a classical fixed-bed reactor catalysed by SiO(2)-Al(2)O(3) or gamma-Al(2)O(3) supported tungsten hydride is presented. Continuous hydrogen separation, using a Pd-Ag membrane in a fixed-bed reactor, led to methane coupling far beyond the thermodynamic equilibrium conversion.

  12. Dynamics of Alkane Hydroxylation at the Non-Heme Diiron Center in Methane Monooxygenase

    SciTech Connect

    Guallar, Victor; Gherman, Benjamin F.; Lippard, Stephen J.; Friesner, Richard A.

    2002-03-12

    Semiclassical molecular dynamics simulations have been combined with quantum chemistry calculations to provide detailed modeling of the methane and ethane hydroxylation reactions catalyzed by the hydroxylase enzymes of the soluble methane monooxygenase system. The experimental distribution of enantiomeric alcohols in the reaction of ethanes made chiral by the use of hydrogen isotopes is quantitatively reproduced and explained. The reaction dynamics involve a mixture of concerted and bound radical trajectories, and we characterize each of these reactive channels in detail. Diffusion of the bound radical intermediate at the active site core determines the global rate constant. The results also provide a qualitative rationale for the lack of ring-opened products derived from certain radical clock substrate probes and for the relative rate constants and kinetic isotope effects exhibited by a variety of substrates.

  13. Ethane oxidative dehydrogenation pathways on vanadium oxide catalysts

    SciTech Connect

    Argyle, Morris; Chen, Kaidong; Bell, Alexis T.; Iglesia, Enrique

    2001-12-10

    Kinetic and isotopic tracer and exchange measurements were used to determine the identity and reversibility of elementary steps involved in ethane oxidative dehydrogenation (ODH) on VOx/Al2O3 and VOx/ZrO2. C2H6-C2D6-O2 and C2H6-D2O-O2 react to form alkenes and COx without concurrent formation of C2H6-xDx orC2H4-xDx isotopomers, suggesting that C-H bond cleavage in ethane and ethene is an irreversible and kinetically relevant step in ODH and combustion reactions. Primary ethane ODH reactions show normal kinetic isotopic effects (kC-H/kC-D 2.4); similar values were measured for ethane and ethene combustion(1.9 and 2.8, respectively). 16O2-18O2-C2H6 reactions on supported V16Ox domains led to the initial appearance of 16O from the lattice in H2O, CO, and CO2, consistent with the involvement of lattice oxygen in C-H bond activation steps. Isotopic contents are similar in H2O, CO, and CO2, suggesting that ODH and combustion reactions use similar lattice oxygen sites. No 16O-18O isotopomer s were detected during reactions of 16O2-18O2-C2H6 mixtures, as expected if dissociative O2 chemisorption steps were irreversible. The alkyl species formed in these steps desorb irreversibly as ethene and the resulting O-H groups recombine to form H2O and reduced V centers in reversible desorption steps. These reduced V centers reoxidize by irreversible dissociative chemisorption of O2. A pseudo-steady state analysis of these elementary steps together with these reversibility assumptions led to a rate expression that accurately describes the observed inhibition of ODH rates by water and the measured kinetic dependence of ODH rates on C2H6 and O2 pressures. This kinetic analysis suggests that surface oxygen, OH groups, and oxygen vacancies are the most abundant reactive intermediates during ethane ODH on active VOx domains.

  14. Ethane oxidative dehydrogenation pathways on vanadium oxide catalysts

    SciTech Connect

    Argyle, Morris; Chen, Kaidong; Bell, Alexis T.; Iglesia, Enrique

    2001-12-10

    Kinetic and isotopic tracer and exchange measurements were used to determine the identity and reversibility of elementary steps involved in ethane oxidative dehydrogenation (ODH) on VOx/Al2O3 and VOx/ZrO2. C2H6-C2D6-O2 and C2H6-D2O-O2 react to form alkenes and COx without concurrent formation of C2H6-xDx orC2H4-xDx isotopomers, suggesting that C-H bond cleavage in ethane and ethene is an irreversible and kinetically relevant step in ODH and combustion reactions. Primary ethane ODH reactions show normal kinetic isotopic effects (kC-H/kC-D) 2.4; similar values were measured for ethane and ethene combustion(1.9 and 2.8, respectively). 16O2-18O2-C2H6 reactions on supported V16Ox domains led to the initial appearance of 16O from the lattice in H2O, CO, and CO2, consistent with the involvement of lattice oxygen in C-H bond activation steps. Isotopic contents are similar in H2O, CO, and CO2, suggesting that ODH and combustion reactions use similar lattice oxygen sites. No 16O-18O isotopomer s were detected during reactions of 16O2-18O2-C2H6 mixtures, as expected if dissociative O2 chemisorption steps were irreversible. The alkyl species formed in these steps desorb irreversibly as ethene and the resulting O-H groups recombine to form H2O and reduced V centers in reversible desorption steps. These reduced V centers reoxidize by irreversible dissociative chemisorption of O2. A pseudo-steady state analysis of these elementary steps together with these reversibility assumptions led to a rate expression that accurately describes the observed inhibition of ODH rates by water and the measured kinetic dependence of ODH rates on C2H6 and O2 pressures. This kinetic analysis suggests that surface oxygen, OH groups, and oxygen vacancies are the most abundant reactive intermediates during ethane ODH on active VOx domains.

  15. Dissociation of methane under high pressure.

    PubMed

    Gao, Guoying; Oganov, Artem R; Ma, Yanming; Wang, Hui; Li, Peifang; Li, Yinwei; Iitaka, Toshiaki; Zou, Guangtian

    2010-10-14

    Methane is an extremely important energy source with a great abundance in nature and plays a significant role in planetary physics, being one of the major constituents of giant planets Uranus and Neptune. The stable crystal forms of methane under extreme conditions are of great fundamental interest. Using the ab initio evolutionary algorithm for crystal structure prediction, we found three novel insulating molecular structures with P2(1)2(1)2(1), Pnma, and Cmcm space groups. Remarkably, under high pressure, methane becomes unstable and dissociates into ethane (C(2)H(6)) at 95 GPa, butane (C(4)H(10)) at 158 GPa, and further, carbon (diamond) and hydrogen above 287 GPa at zero temperature. We have computed the pressure-temperature phase diagram, which sheds light into the seemingly conflicting observations of the unusually low formation pressure of diamond at high temperature and the failure of experimental observation of dissociation at room temperature. Our results support the idea of diamond formation in the interiors of giant planets such as Neptune.

  16. Electric Field-Enhanced Catalytic Conversion of Methane: AN Experimental Study on the Effects of Corona Discharge on Methane Reactions

    NASA Astrophysics Data System (ADS)

    Marafee, Abdulathim M. J.

    The oxidative coupling of methane (OCM) is currently being actively studied for the production of higher hydrocarbons from natural gas. The present study concentrates on the oxidative conversion of methane in a high-pressure (one atmosphere), nonthermal plasma formed by corona discharge. Here, methyl radicals are formed by the reaction of methane with negatively-charged oxygen species created in the corona discharge. The results of methane conversion in the presence of both AC and DC corona discharges revealed that ethane and ethylene product selectivity is affected by electrode polarity, frequency, and oxygen partial pressure in the feed. Higher C_2 yields were obtained with the AC corona. All of the AC corona discharges specified here were initiated at room temperature (i.e., no oven or other heat source used), with temperature increases from 300 to 500^circC due to the exothermic gas discharge and exothermic reaction. A reaction mechanism is presented to explain the observed phenomena. The results suggest that AC and/or DC gas discharge techniques should be further studied for improved economics of methane conversion. The oxidative dehydrogenation of ethane in DC corona discharges was investigated. The atomic oxygen radicals initiated by corona discharges are thought to be active for the OXD of ethane. The selectivity to ethylene is affected by the reaction temperature, the DC applied voltage, voltage polarity, and the C_2H _6/O_2 ratio. The results of this study suggest the corona discharge process to be very efficient and selective in the oxidative dehydrogenation of ethane. The effects of DC corona discharge were examined in the presence of a typical OCM catalyst, Sr/La _2O_3. Experimental investigations have correspondingly been conducted, in which all reactive gases passed through a catalyst bed situated within the corona-induced plasma zone. The methane conversion and C_2 yield increased (with O_2 partial pressure) during the corona-enhanced catalytic

  17. Processing of polyolefin blends in supercritical propane solution

    NASA Astrophysics Data System (ADS)

    Han, Suh Joon

    New polymer blending methods are developed and studied by processing polyolefins in supercritical propane in this research. Polypropylene and ethylene copolymers were dissolved in supercritical propane, and processed via various paths and reactions, i.e., RESS (rapid expansion of supercritical solution), ICSS (isobaric crystallization from supercritical solution), and thermoplastic vulcanizate (TPV) formation. Each process resulted in a unique morphology of polyolefin blends. The effect of polyolefin microstructure on the solution behavior in supercritical propane was investigated, and the relationship between the morphology of the polyolefin blends and processing paths in supercritical propane solutions was established. To understand the thermodynamic properties of polyolefins in bulk and solutions, the solubility parameter was estimated by measurement of the internal pressure from the experimental P-V-T data for polyolefins in the melt state. As the short chain branch content in the ethylene copolymers increased, the internal pressure decreased. The cloud-point pressures of binary polymer solutions in propane decreased as the extent of short chain branching increased in the ethylene copolymers. At the same degree of branching, the cloud-point pressure decreased slightly with increasing branch length. The cloud-point pressures of a ternary polymer solution in the pressure-temperature phase diagrams were higher than those of binary polymer solutions at the same composition (indicating poorer solubility). Microfibers and microparticles (10 ˜ 50 mum diameter) were precipitated from the RESS process while microcellular foams were obtained from the ICSS process. The phase domains of the ethylene-butene (EB) copolymer in the polypropylene from the RESS process were smaller for highly branched EB copolymer. The surface morphology of ethylene copolymers in the microcelluar foams was also changed by increasing the branch content from microparticles to a viscous layer. New

  18. SmoXYB1C1Z of Mycobacterium sp. strain NBB4: a soluble methane monooxygenase (sMMO)-like enzyme, active on C2 to C4 alkanes and alkenes.

    PubMed

    Martin, Kiri E; Ozsvar, Jazmin; Coleman, Nicholas V

    2014-09-01

    Monooxygenase (MO) enzymes initiate the aerobic oxidation of alkanes and alkenes in bacteria. A cluster of MO genes (smoXYB1C1Z) of thus-far-unknown function was found previously in the genomes of two Mycobacterium strains (NBB3 and NBB4) which grow on hydrocarbons. The predicted Smo enzymes have only moderate amino acid identity (30 to 60%) to their closest homologs, the soluble methane and butane MOs (sMMO and sBMO), and the smo gene cluster has a different organization from those of sMMO and sBMO. The smoXYB1C1Z genes of NBB4 were cloned into pMycoFos to make pSmo, which was transformed into Mycobacterium smegmatis mc(2)-155. Cells of mc(2)-155(pSmo) metabolized C2 to C4 alkanes, alkenes, and chlorinated hydrocarbons. The activities of mc(2)-155(pSmo) cells were 0.94, 0.57, 0.12, and 0.04 nmol/min/mg of protein with ethene, ethane, propane, and butane as substrates, respectively. The mc(2)-155(pSmo) cells made epoxides from ethene, propene, and 1-butene, confirming that Smo was an oxygenase. Epoxides were not produced from larger alkenes (1-octene and styrene). Vinyl chloride and 1,2-dichloroethane were biodegraded by cells expressing Smo, with production of inorganic chloride. This study shows that Smo is a functional oxygenase which is active against small hydrocarbons. M. smegmatis mc(2)-155(pSmo) provides a new model for studying sMMO-like monooxygenases.

  19. SmoXYB1C1Z of Mycobacterium sp. Strain NBB4: a Soluble Methane Monooxygenase (sMMO)-Like Enzyme, Active on C2 to C4 Alkanes and Alkenes

    PubMed Central

    Martin, Kiri E.; Ozsvar, Jazmin

    2014-01-01

    Monooxygenase (MO) enzymes initiate the aerobic oxidation of alkanes and alkenes in bacteria. A cluster of MO genes (smoXYB1C1Z) of thus-far-unknown function was found previously in the genomes of two Mycobacterium strains (NBB3 and NBB4) which grow on hydrocarbons. The predicted Smo enzymes have only moderate amino acid identity (30 to 60%) to their closest homologs, the soluble methane and butane MOs (sMMO and sBMO), and the smo gene cluster has a different organization from those of sMMO and sBMO. The smoXYB1C1Z genes of NBB4 were cloned into pMycoFos to make pSmo, which was transformed into Mycobacterium smegmatis mc2-155. Cells of mc2-155(pSmo) metabolized C2 to C4 alkanes, alkenes, and chlorinated hydrocarbons. The activities of mc2-155(pSmo) cells were 0.94, 0.57, 0.12, and 0.04 nmol/min/mg of protein with ethene, ethane, propane, and butane as substrates, respectively. The mc2-155(pSmo) cells made epoxides from ethene, propene, and 1-butene, confirming that Smo was an oxygenase. Epoxides were not produced from larger alkenes (1-octene and styrene). Vinyl chloride and 1,2-dichloroethane were biodegraded by cells expressing Smo, with production of inorganic chloride. This study shows that Smo is a functional oxygenase which is active against small hydrocarbons. M. smegmatis mc2-155(pSmo) provides a new model for studying sMMO-like monooxygenases. PMID:25015887

  20. Development of a 100 nmol mol(-1) propane-in-air SRM for automobile-exhaust testing for new low-emission requirements.

    PubMed

    Rhoderick, George C

    2007-04-01

    New US federal low-level automobile emission requirements, for example zero-level-emission vehicle (ZLEV), for hydrocarbons and other species, have resulted in the need by manufacturers for new certified reference materials. The new emission requirement for hydrocarbons requires the use, by automobile manufacturing testing facilities, of a 100 nmol mol(-1) propane in air gas standard. Emission-measurement instruments are required, by federal law, to be calibrated with National Institute of Standards and Technology (NIST) traceable reference materials. Because a NIST standard reference material (SRM) containing 100 nmol mol(-1) propane was not available, the US Environmental Protection Agency (EPA) and the Automobile Industry/Government Emissions Research Consortium (AIGER) requested that NIST develop such an SRM. A cylinder lot of 30 gas mixtures containing 100 nmol mol(-1) propane in air was prepared in 6-L aluminium gas cylinders by a specialty gas company and delivered to the Gas Metrology Group at NIST. Another mixture, contained in a 30-L aluminium cylinder and included in the lot, was used as a lot standard (LS). Using gas chromatography with flame-ionization detection all 30 samples were compared to the LS to obtain the average of six peak-area ratios to the LS for each sample with standard deviations of <0.31%. The average sample-to-LS ratio determinations resulted in a range of 0.9828 to 0.9888, a spread of 0.0060, which corresponds to a relative standard deviation of 0.15% of the average for all 30 samples. NIST developed its first set of five propane in air primary gravimetric standards covering a concentration range 91 to 103 nmol mol(-1) with relative uncertainties of 0.15%. This new suite of propane gravimetric standards was used to analyze and assign a concentration value to the SRM LS. On the basis of these data each SRM sample was individually certified, furnishing the desired relative expanded uncertainty of +/-0.5%. Because automobile companies

  1. Use of Onion Extract as a Dairy Cattle Feed Supplement: Monitoring Propyl Propane Thiosulfonate as a Marker of Its Effect on Milk Attributes.

    PubMed

    Abad, Paloma; Arroyo-Manzanares, Natalia; Gil, Lidia; García-Campaña, Ana M

    2017-02-01

    Onion extract is used as a feed supplement for the diet of dairy cows, acting as inhibitor of methane production; however, its properties could alter sensory attributes of milk. In this work, we propose a method to evaluate the influence of this extract on milk properties, using propyl propane thiosulfonate (PTSO) as a marker. PTSO is extracted using a quick, easy, cheap, effective, rugged, and safe procedure and monitored by high-performance liquid chromatography with ultraviolet detection. The method was applied to milk samples obtained from 100 dairy cows fed during 2 months with enriched feed. In addition, a milk tasting panel was established to evaluate the PTSO residue that should not be exceeded to guarantee milk sensory attributes. It was established that a value of PTSO lower than 2 mg kg(-1) does not alter milk organoleptic properties. This fact makes onion extract an interesting alternative as a feed supplement to control the methane emissions without any influence on milk attributes.

  2. Two cases of acute propane/butane poisoning in prison.

    PubMed

    Rossi, Riccardo; Suadoni, Fabio; Pieroni, Ludovica; De-Giorgio, Fabio; Lancia, Massimo

    2012-05-01

    Hydrocarbon inhalation is seldom chosen as a means to commit suicide. This practice is exclusively a prerogative of the prison population; it is, however, only exceptionally found in this environment. The two cases of lethal inhalation of propane/butane gas observed by us over a very short time occurred in this context. Toxicologic analyses were performed by means of gas chromatography (head space) and revealed a propane/butane mixture in all specimens (heart blood, bile, and urine) except vitreous humor. Although fatal arrhythmia posthydrocarbon gas abuse is well known, the concentrations of the two hydrocarbons were sufficient to induce death by asphyxiation and were distributed (fairly) homogeneously in all biological fluids and organs examined, a parameter permitting one to assume that death occurred within a relatively short period of time. The absence of finding in vitreous humor and the trace amount in urine suggests that both men died very quickly. © 2011 American Academy of Forensic Sciences.

  3. Intermolecular potential energy surface and thermophysical properties of propane

    NASA Astrophysics Data System (ADS)

    Hellmann, Robert

    2017-03-01

    A six-dimensional potential energy surface (PES) for the interaction of two rigid propane molecules was determined from supermolecular ab initio calculations up to the coupled cluster with single, double, and perturbative triple excitations level of theory for 9452 configurations. An analytical site-site potential function with 14 sites per molecule was fitted to the calculated interaction energies. To validate the analytical PES, the second virial coefficient and the dilute gas shear viscosity and thermal conductivity of propane were computed. The dispersion part of the potential function was slightly adjusted such that quantitative agreement with the most accurate experimental data for the second virial coefficient at room temperature was achieved. The adjusted PES yields values for the three properties that are in very good agreement with the best experimental data at all temperatures.

  4. Dissociation heat transfer characteristics of methane hydrates

    SciTech Connect

    Kamath, V.A.; Holder, G.D.

    1987-02-01

    Knowledge of the interfacial heat transfer phenomenon during the dissociation of gas hydrates is essential in modeling the hydrate dissociation process. Such knowledge has applications in natural gas processing, storage, or transportation; in the drilling and recovery of oil and gas in the presence of gas hydrates; in the desalination of sea water; and in the production of natural gas from hydrate reservoirs. The process of hydrate dissociation is a unique phenomenon in which gas and water are simultaneously produced at the dissociated hydrate surface and play an important role in the mechanism of heat transfer to hydrates. An earlier study of propane hydrate dissociation showed that hydrate dissociation is a heat-transfer-limited process and somewhat similar to the nucleate boiling of liquids. In the present study, heat transfer limitations for methane hydrate dissociation were studied for two reasons. First, a comparison of the results of this study with propane hydrate was desired. Second, the effect of hydrate structure and gas molecule type on the rate of heat transfer during hydrate dissociation was sought.

  5. Evolutionary history of a specialized P450 propane monooxygenase

    PubMed Central

    Fasan, Rudi; Meharenna, Yergalem T.; Snow, Christopher D.; Poulos, Thomas L.; Arnold, Frances H.

    2008-01-01

    Summary The evolutionary pressures that shaped the specificity and catalytic efficiency of enzymes can only be speculated. While directed evolution experiments show that new functions can be acquired under positive selection with few mutations, the role of negative selection in eliminating undesired activities and achieving high specificity remains unclear. Here we examine intermediates along the ‘lineage’ from a naturally-occurring C12–C20 fatty acid hydroxylase (P450BM3) to a laboratory-evolved P450 propane monooxygenase (P450PMO) having 20 heme domain substitutions compared to P450BM3. Biochemical, crystallographic and computational analyses show that a minimal perturbation of the P450BM3 fold and substrate binding pocket accompanies a significant broadening of enzyme substrate range and the emergence of propane activity. In contrast, refinement of the enzyme catalytic efficiency for propane oxidation (~9,000-fold increase in kcat/Km) involves profound reshaping and partitioning of the substrate access pathway. Remodeling of the substrate recognition mechanisms ultimately results in remarkable narrowing of the substrate profile around propane and enables the acquisition of a basal iodomethane dehalogenase activity as yet unknown in natural alkane monooxygenases. A highly destabilizing L188P substitution in a region of the enzyme that undergoes a large conformational change during catalysis plays an important role in adaptation to the gaseous alkane. This work demonstrates that positive selection alone is sufficient to completely re-specialize the cytochrome P450 for function on a non-native substrate. PMID:18619466

  6. Differential microbial transformation of nitrosamines by an inducible propane monooxygenase.

    PubMed

    Homme, Carissa L; Sharp, Jonathan O

    2013-07-02

    The toxicity of N-nitrosamines, their presence in drinking and environmental water supplies, and poorly understood recalcitrance collectively necessitate a better understanding of their potential for bioattenuation. Here, we show that the bacterial strain Rhodococcus jostii RHA1 can biotransform N-nitrosodiethylamine (NDEA), N-nitrosodi-n-propylamine (NDPA), N-nitrosopyrrolidine (NPYR), and possibly N-nitrosomorpholine (NMOR) in addition to N-nitrosodimethylamine (NDMA). Growth of cells on propane as the sole carbon source greatly enhanced degradation rates when contrasted with cells grown on complex organics. Propane-induced rates in order of fastest to slowest were NDMA > NDEA > NDPA > NPYR > NMOR at concentrations <2000 μg/L. Removal rates for linear functional groups scaled inversely with mass and cyclic nitrosamines were more recalcitrant than linear nitrosamines. Controls demonstrated significant NDEA and NDPA losses independent of biomass, suggesting abiotic processes may play a role in attenuation of these two compounds under experimental conditions tested here. In contrast to NDMA, a transition from first to zero order kinetics was not observed for the other nitrosamines included in this study over a concentration range of 20-2000 μg/L. A genetic knockout for the propane monooxygenase enzyme (PrMO) confirmed the role of this enzyme in the biotransformation of NDEA and NPYR. This study furthers our understanding of environmental nitrosamine attenuation by revealing an enzymatic mechanism for the biotransformation of multiple nitrosamines, their relative recalcitrance to transformation, and potential for abiotic loss.

  7. Gas Phase UTE MRI of Propane and Propene

    PubMed Central

    Kovtunov, Kirill V.; Romanov, Alexey S.; Salnikov, Oleg G.; Barskiy, Danila A.; Chekmenev, Eduard Y.; Koptyug, Igor V.

    2016-01-01

    1H MRI of gases can potentially enable functional lung imaging to probe gas ventilation and other functions. In this work, 1H MR images of hyperpolarized and thermally polarized propane gas were obtained using UTE (ultrashort echo time) pulse sequence. A 2D image of thermally polarized propane gas with ~0.9×0.9 mm2 spatial resolution was obtained in less than 2 seconds, demonstrating that even non-hyperpolarized hydrocarbon gases can be successfully utilized for conventional proton MRI. The experiments were also performed with hyperpolarized propane gas and demonstrated acquisition of high-resolution multi-slice FLASH 2D images in ca. 510 s and non slice-selective 2D UTE MRI images in ca. 2 s. The UTE approach adopted in this study can be potentially used for medical lung imaging. Furthermore, the possibility to combine UTE with selective suppression of 1H signals from one of the two gases in a mixture is demonstrated in this MRI study. The latter can be useful for visualizing industrially important processes where several gases may be present, e.g., gas-solid catalytic reactions. PMID:27478870

  8. Crystal structures of two mononuclear complexes of terbium(III) nitrate with the tripodal alcohol 1,1,1-tris­(hy­droxy­meth­yl)propane

    PubMed Central

    Gregório, Thaiane; Giese, Siddhartha O. K.; Nunes, Giovana G.; Soares, Jaísa F.; Hughes, David L.

    2017-01-01

    Two new mononuclear cationic complexes in which the TbIII ion is bis-chelated by the tripodal alcohol 1,1,1-tris­(hy­droxy­meth­yl)propane (H3 L Et, C6H14O3) were prepared from Tb(NO3)3·5H2O and had their crystal and mol­ecular structures solved by single-crystal X-ray diffraction analysis after data collection at 100 K. Both products were isolated in reasonable yields from the same reaction mixture by using different crystallization conditions. The higher-symmetry complex dinitratobis[1,1,1-tris­(hy­droxy­meth­yl)propane]­terbium(III) nitrate di­meth­oxy­ethane hemisolvate, [Tb(NO3)2(H3 L Et)2]NO3·0.5C4H10O2, 1, in which the lanthanide ion is 10-coordinate and adopts an s-bicapped square-anti­prismatic coordination geometry, contains two bidentate nitrate ions bound to the metal atom; another nitrate ion functions as a counter-ion and a half-mol­ecule of di­meth­oxy­ethane (completed by a crystallographic twofold rotation axis) is also present. In product aqua­nitratobis[1,1,1-tris­(hy­droxy­meth­yl)propane]­terbium(III) dinitrate, [Tb(NO3)(H3 L Et)2(H2O)](NO3)2, 2, one bidentate nitrate ion and one water mol­ecule are bound to the nine-coordinate terbium(III) centre, while two free nitrate ions contribute to charge balance outside the tricapped trigonal-prismatic coordination polyhedron. No free water mol­ecule was found in either of the crystal structures and, only in the case of 1, di­meth­oxy­ethane acts as a crystallizing solvent. In both mol­ecular structures, the two tripodal ligands are bent to one side of the coordination sphere, leaving room for the anionic and water ligands. In complex 2, the methyl group of one of the H3 L Et ligands is disordered over two alternative orientations. Strong hydrogen bonds, both intra- and inter­molecular, are found in the crystal structures due to the number of different donor and acceptor groups present. PMID:28217359

  9. Studies of site selective hydrogen atom abstractions by Cl atoms from isobutane and propane by laser flash photolysis/IR diode laser spectroscopy.

    PubMed

    Choi, N; Pilling, M J; Seakins, P W; Wang, L

    2006-05-14

    The kinetics of chlorine atom abstractions from normal and selectively deuterated propane and isobutane have been measured at room temperature and 195 K using a laser flash photolysis system, and following the course of the reaction via IR diode laser absorption measurements of HCl product. In conjunction with the kinetic measurements, a comparison of the HCl signal heights from pairs of measurements on normal and selectively deuterated systems has allowed the determination of the branching fractions of the reactions at the primary, secondary (propane) and tertiary (isobutane) positions. The kinetic data (all in units of cm(3) molecule(-1) s(-1)) for the reaction of Cl atoms with propane ((1.22 +/- 0.02) x10(-10), 195 K; (1.22 +/- 0.03) x10(-10) 298 K) and isobutane ((1.52 +/- 0.02) x10(-10), 195 K; (1.25 +/- 0.04) x10(-10), 298 K) are generally in good agreement with literature data. No data are available for comparison with our measurements for the reactions of Cl atoms with CH(3)CD(2)CH(3) ((1.02 +/- 0.03) x10(-10), 195 K; (1.09 +/- 0.02) x10(-10), 298 K) or (CH(3))(3)CD ((1.32 +/- 0.03) x10(-10), 195 K; (1.12 +/- 0.04) x10(-10), 298 K). Rate coefficients at 195 K for the reactions of Cl atoms with ethane ((5.04 +/- 0.08) x10(-11) and n-butane ((2.19 +/- 0.03) x10(-10)) were also measured. The branching fractions for abstraction at the primary position increased with temperature for both propane ((40 +/- 3)% at 195 K to (48 +/- 3)% at 298 K) and isobutane ((49 +/- 4)% at 195 K to (62 +/- 5)% at 298 K). The direct measurements from this study are in good agreement with most calculations based on structure activity relationships.

  10. A quantification of methane emissions from the Bakken shale play region of North Dakota

    NASA Astrophysics Data System (ADS)

    Peischl, J.; Ryerson, T. B.; Karion, A.; Aikin, K. C.; Kort, E. A.; Newberger, T.; Smith, M. L.; Sweeney, C.; Trainer, M.; Wolter, S.

    2014-12-01

    Natural gas extracted from shale formations accounts for 40% of the domestic U.S. natural gas supply. Although natural gas combustion emits less carbon dioxide per energy produced than other fossil fuels, this climate benefit may be offset by the methane emitted to the atmosphere through leaks in the natural gas production and distribution infrastructure. To better understand the climate impacts of the oil and natural gas extracted from the Bakken shale play in North Dakota, we present airborne measurements of methane taken over this region aboard a NOAA Twin Otter aircraft during Spring 2014. Using the mass balance technique, we estimate methane emissions from the region with four flights intended for this purpose in May 2014. We further attribute these methane emissions to the oil and gas industry using measurements of ethane and other hydrocarbons aboard the Twin Otter.

  11. Oxidative Coupling of Methane over Li/MgO: Catalyst and Nanocatalyst Performance

    NASA Astrophysics Data System (ADS)

    Farsi, Ali; Moradi, Ali; Ghader, Sattar; Shadravan, Vahid

    2011-02-01

    The Li/MgO catalyst and nanocatalyst were prepared by the incipient wetness impregnation and sol-gel method, respectively. The catalytic performance of the Li/MgO catalyst and nanocatalyst on oxidative coupling of methane was compared. The catalysts prepared in two ways were characterized by X-ray powder diffraction, Brunauer-Emmett-Teller surface and transmission electron microscope. The catalyst was tested at temperature of 973-1073 K with constant total pressure of 101 kPa. Experimental results showed that Li/MgO nanocatalyst in the oxidative coupling of methane would result in higher conversion of methane, higher selectivity, and higher yield of main products (ethane and ethylene) compared to ordinary catalyst. The results show the improved influence of nanoscale Li/MgO catalyst performance on oxidative coupling of methane.

  12. Environmental analysis of higher brominated diphenyl ethers and decabromodiphenyl ethane.

    PubMed

    Kierkegaard, Amelie; Sellström, Ulla; McLachlan, Michael S

    2009-01-16

    Methods for environmental analysis of higher brominated diphenyl ethers (PBDEs), in particular decabromodiphenyl ether (BDE209), and the recently discovered environmental contaminant decabromodiphenyl ethane (deBDethane) are reviewed. The extensive literature on analysis of BDE209 has identified several critical issues, including contamination of the sample, degradation of the analyte during sample preparation and GC analysis, and the selection of appropriate detection methods and surrogate standards. The limited experience with the analysis of deBDethane suggests that there are many commonalities with BDE209. The experience garnered from the analysis of BDE209 over the last 15 years will greatly facilitate progress in the analysis of deBDethane.

  13. Studies of cosolvent systems in supercritical ethane using solvated electrons.

    SciTech Connect

    Dimitrijevic, N. M.; Bartels, D. M.; Jonah, C. D.; Takahashi, K.

    2000-11-14

    In this paper, pulse-radiolytic studies of the methanol-ethane cosolvent system are carried out. Our results show that at temperatures below approximately 110 C, there are high local concentrations of alcohols (clusters) that are capable of solvating an electron, suggesting a size of approximately 4-5 methanol molecules at approximately 0.15 mole fraction alcohol. Reactions have been carried out between these solvated electrons and silver ions that are (presumably) dissolved in other small clusters of alcohols. These results show that the reaction between species in two different clusters is approximately 2 orders of magnitude slower than diffusion-controlled reactions.

  14. Experimental study on transmission of an overdriven detonation wave from propane/oxygen to propane/air

    SciTech Connect

    Li, J.; Lai, W.H.; Chung, K.; Lu, F.K.

    2008-08-15

    Two sets of experiments were performed to achieve a strong overdriven state in a weaker mixture by propagating an overdriven detonation wave via a deflagration-to-detonation transition (DDT) process. First, preliminary experiments with a propane/oxygen mixture were used to evaluate the attenuation of the overdriven detonation wave in the DDT process. Next, experiments were performed wherein a propane/oxygen mixture was separated from a propane/air mixture by a thin diaphragm to observe the transmission of an overdriven detonation wave. Based on the characteristic relations, a simple wave intersection model was used to calculate the state of the transmitted detonation wave. The results showed that a rarefaction effect must be included to ensure that there is no overestimate of the post-transmission wave properties when the incident detonation wave is overdriven. The strength of the incident overdriven detonation wave plays an important role in the wave transmission process. The experimental results showed that a transmitted overdriven detonation wave occurs instantaneously with a strong incident overdriven detonation wave. The near-CJ state of the incident wave leads to a transmitted shock wave, and then the transition to the overdriven detonation wave occurs downstream. The attenuation process for the overdriven detonation wave decaying to a near-CJ state occurs in all tests. After the attenuation process, an unstable detonation wave was observed in most tests. This may be attributed to the increase in the cell width in the attenuation process that exceeds the detonability cell width limit. (author)

  15. Catalysts for conversion of methane to higher hydrocarbons

    DOEpatents

    Siriwardane, Ranjani V.

    1993-01-01

    Catalysts for converting methane to higher hydrocarbons such as ethane and ethylene in the presence of oxygen at temperatures in the range of about 700.degree. to 900.degree. C. are described. These catalysts comprise calcium oxide or gadolinium oxide respectively promoted with about 0.025-0.4 mole and about 0.1-0.7 mole sodium pyrophosphate. A preferred reaction temperature in a range of about 800.degree. to 850.degree. C. with a preferred oxygen-to-methane ratio of about 2:1 provides an essentially constant C.sub.2 hydrocarbon yield in the range of about 12 to 19 percent over a period of time greater than about 20 hours.

  16. Partial oxidation of methane by pulsed corona discharges

    NASA Astrophysics Data System (ADS)

    Hoeben, W. F. L. M.; Boekhoven, W.; Beckers, F. J. C. M.; van Heesch, E. J. M.; Pemen, A. J. M.

    2014-09-01

    Pulsed corona-induced partial oxidation of methane in humid oxygen or carbon dioxide atmospheres has been investigated for future fuel synthesis applications. The obtained product spectrum is wide, i.e. saturated, unsaturated and oxygen-functional hydrocarbons. The generally observed methane conversion levels are 6-20% at a conversion efficiency of about 100-250 nmol J-1. The main products are ethane, ethylene and acetylene. Higher saturated hydrocarbons up to C6 have been detected. The observed oxygen-functional hydrocarbons are methanol, ethanol and lower concentrations of aldehydes, ketones, dimethylether and methylformate. Methanol seems to be exclusively produced with CH4/O2 mixtures at a maximum production efficiency of 0.35 nmol J-1. CH4/CO2 mixtures appear to yield higher hydrocarbons. Carboxylic acids appear to be mainly present in the aqueous reactor phase, possibly together with higher molecular weight species.

  17. Physicochemical and catalytic properties of Ga and In pentasils in the reaction of propane aromatization

    NASA Astrophysics Data System (ADS)

    Vosmerikova, L. N.; Volynkina, A. N.; Zaikovskii, V. I.; Vosmerikov, A. V.

    2017-05-01

    Ga and In ZSM-5 zeolites are obtained via hydrothermal crystallization from alkali aluminosilicate gels. Their physicochemical and catalytic properties during conversion of propane into aromatic hydrocarbons are studied. These catalysts exhibit different activity and selectivity in propane aromatization process due to their specific physicochemical properties and the localization of promoter atoms in different sites of the zeolite structure. A zeolite containing 1.85 wt % of gallium oxide is the most effective catalyst for propane aromatization.

  18. Identification of the flame retardant decabromodiphenyl ethane in the environment.

    PubMed

    Kierkegaard, Amelie; Björklund, Jonas; Fridén, Ulrika

    2004-06-15

    The brominated flame retardant decabromodiphenyl ethane, DeBDethane, is marketed as an alternative to decabromodiphenyl ether, BDE209. There are currently no data available about the presence of DeBDethane in the environment. In this study, DeBDethane was positively identified by high-resolution mass spectrometry and quantified by low-resolution mass spectrometry with electron capture negative ionization in sewage sludge, sediment, and indoor air. It was found in 25 of the 50 Swedish sewage treatment plants investigated, with estimated levels up to about 100 ng/g dry weight. The concentration of DeBDethane in sediment from Western Scheldt in The Netherlands was 24 ng/g dry weight, and in an air sample from a Swedish electronics dismantling facility it was 0.6 ng/m3. DeBDethane was also found together with nonabromodiphenyl ethanes in water piping insulation. All samples contained BDE209 in higher concentrations as compared to DeBDethane (DeBDethane/BDE209 ratios ranging from 0.02 to 0.7), probably reflecting the higher and longer usage of BDE209. There is an ongoing risk assessment within the European Union regarding BDE209. Since DeBDethane has similar applications, it is important to investigate its environmental behavior before using it to replace BDE209.

  19. Partial ionisation cross-sections of 2-propanol and ethanal

    NASA Astrophysics Data System (ADS)

    Vacher, J. R.; Jorand, F.; Blin-Simiand, N.; Pasquiers, S.

    2006-04-01

    Electron impact ionisation of 2-propanol and ethanal is studied using mass spectrometry. Cross-sections of the formation of molecular ions and ionic fragments are measured between 14 and 86 eV. Free energy changes are evaluated using ab initio calculations. For 2-propanol, two ions, identified as CH 3CHOH + (45 amu) and CH3CHCH3+ (43 amu), contribute more than 75% to the total cross-section over the whole range of electron energies and are produced by simple bond cleavage in the molecular ion. Both processes occur spontaneously, leaving the molecular ion as a minority species. For ethanal, two ions, identified as HCO + (29 amu) and CH 3CO + (43 amu), and the molecular ion (44 amu) contribute more than 80% to the total cross-section. The ions of 29 and 43 amu result from a simple bond cleavage in the molecular ion. These sprocesses are not spontaneous and the contribution of the molecular ion becomes predominant at 15 eV and is therefore significant over the whole range of ionisation energies.

  20. The rotational barrier in ethane: a molecular orbital study.

    PubMed

    Quijano-Quiñones, Ramiro F; Quesadas-Rojas, Mariana; Cuevas, Gabriel; Mena-Rejón, Gonzalo J

    2012-04-20

    The energy change on each Occupied Molecular Orbital as a function of rotation about the C-C bond in ethane was studied using the B3LYP, mPWB95 functional and MP2 methods with different basis sets. Also, the effect of the ZPE on rotational barrier was analyzed. We have found that σ and π energies contribution stabilize a staggered conformation. The σ(s) molecular orbital stabilizes the staggered conformation while the stabilizes the eclipsed conformation and destabilize the staggered conformation. The π(z) and molecular orbitals stabilize both the eclipsed and staggered conformations, which are destabilized by the π(v) and molecular orbitals. The results show that the method of calculation has the effect of changing the behavior of the energy change in each Occupied Molecular Orbital energy as a function of the angle of rotation about the C-C bond in ethane. Finally, we found that if the molecular orbital energy contribution is deleted from the rotational energy, an inversion in conformational preference occurs.

  1. Fugitive emissions from the Bakken shale illustrate role of shale production in global ethane shift

    NASA Astrophysics Data System (ADS)

    Kort, E. A.; Smith, M. L.; Murray, L. T.; Gvakharia, A.; Brandt, A. R.; Peischl, J.; Ryerson, T. B.; Sweeney, C.; Travis, K.

    2016-05-01

    Ethane is the second most abundant atmospheric hydrocarbon, exerts a strong influence on tropospheric ozone, and reduces the atmosphere's oxidative capacity. Global observations showed declining ethane abundances from 1984 to 2010, while a regional measurement indicated increasing levels since 2009, with the reason for this subject to speculation. The Bakken shale is an oil and gas-producing formation centered in North Dakota that experienced a rapid increase in production beginning in 2010. We use airborne data collected over the North Dakota portion of the Bakken shale in 2014 to calculate ethane emissions of 0.23 ± 0.07 (2σ) Tg/yr, equivalent to 1-3% of total global sources. Emissions of this magnitude impact air quality via concurrent increases in tropospheric ozone. This recently developed large ethane source from one location illustrates the key role of shale oil and gas production in rising global ethane levels.

  2. Fugitive Emissions from the Bakken Shale Illustrate Role of Shale Production in Global Ethane Shift

    NASA Technical Reports Server (NTRS)

    Kort, E. A.; Smith, M. L.; Murray, L. T.; Gvakharia, A.; Brandt, A. R.; Peischl, J.; Ryerson, T. B.; Sweeney, C.; Travis, K.

    2016-01-01

    Ethane is the second most abundant atmospheric hydrocarbon, exerts a strong influence on tropospheric ozone, and reduces the atmosphere's oxidative capacity. Global observations showed declining ethane abundances from 1984 to 2010, while a regional measurement indicated increasing levels since 2009, with the reason for this subject to speculation. The Bakken shale is an oil and gas-producing formation centered in North Dakota that experienced a rapid increase in production beginning in 2010. We use airborne data collected over the North Dakota portion of the Bakken shale in 2014 to calculate ethane emissions of 0.23 +/- 0.07 (2 sigma) Tg/yr, equivalent to 1-3% of total global sources. Emissions of this magnitude impact air quality via concurrent increases in tropospheric ozone. This recently developed large ethane source from one location illustrates the key role of shale oil and gas production in rising global ethane levels.

  3. Fugitive Emissions from the Bakken Shale Illustrate Role of Shale Production in Global Ethane Shift

    NASA Technical Reports Server (NTRS)

    Kort, E. A.; Smith, M. L.; Murray, L. T.; Gvakharia, A.; Brandt, A. R.; Peischl, J.; Ryerson, T. B.; Sweeney, C.; Travis, K.

    2016-01-01

    Ethane is the second most abundant atmospheric hydrocarbon, exerts a strong influence on tropospheric ozone, and reduces the atmosphere's oxidative capacity. Global observations showed declining ethane abundances from 1984 to 2010, while a regional measurement indicated increasing levels since 2009, with the reason for this subject to speculation. The Bakken shale is an oil and gas-producing formation centered in North Dakota that experienced a rapid increase in production beginning in 2010. We use airborne data collected over the North Dakota portion of the Bakken shale in 2014 to calculate ethane emissions of 0.23 +/- 0.07 (2 sigma) Tg/yr, equivalent to 1-3% of total global sources. Emissions of this magnitude impact air quality via concurrent increases in tropospheric ozone. This recently developed large ethane source from one location illustrates the key role of shale oil and gas production in rising global ethane levels.

  4. Spatial patterns and source attribution of urban methane in the Los Angeles Basin

    NASA Astrophysics Data System (ADS)

    Hopkins, Francesca M.; Kort, Eric A.; Bush, Susan E.; Ehleringer, James R.; Lai, Chun-Ta; Blake, Donald R.; Randerson, James T.

    2016-03-01

    Urban areas are increasingly recognized as a globally important source of methane to the atmosphere; however, the location of methane sources and relative contributions of source sectors are not well known. Recent atmospheric measurements in Los Angeles, California, USA, show that more than a third of the city's methane emissions are unaccounted for in inventories and suggest that fugitive fossil emissions are the unknown source. We made on-road measurements to quantify fine-scale structure of methane and a suite of complementary trace gases across the Los Angeles Basin in June 2013. Enhanced methane levels were observed across the basin but were unevenly distributed in space. We identified 213 methane hot spots from unknown emission sources. We made direct measurements of ethane to methane (C2H6/CH4) ratios of known methane emission sources in the region, including cattle, geologic seeps, landfills, and compressed natural gas fueling stations, and used these ratios to determine the contribution of biogenic and fossil methane sources to unknown hot spots and to local urban background air. We found that 75% of hot spots were of fossil origin, 20% were biogenic, and 5% of indeterminate source. In regionally integrated air, we observed a wider range of C2H6/CH4 values than observed previously. Fossil fuel sources accounted for 58-65% of methane emissions, with the range depending on the assumed C2H6/CH4 ratio of source end-members and model structure. These surveys demonstrated the prevalence of fugitive methane emissions across the Los Angeles urban landscape and suggested that uninventoried methane sources were widely distributed and primarily of fossil origin.

  5. Ground truthing for methane hotspots at Railroad Valley, NV - application to Mars

    NASA Astrophysics Data System (ADS)

    Detweiler, A. M.; Kelley, C. A.; Bebout, B.; McKay, C. P.; DeMarines, J.; Yates, E. L.; Iraci, L. T.

    2011-12-01

    During the 2010 Greenhouse gas Observing SATellite (GOSAT) calibration and validation campaign at Railroad Valley (RRV) playa, NV, unexpected methane and carbon dioxide fluctuations were observed at the dry lakebed. Possible sources included the presence of natural gas (thermogenic methane) from oil deposits in the surrounding playa, and/or methane production from microbial activity (biogenic) in the subsurface of the playa. In the summer of 2011, measurements were undertaken to identify potential methane sources at RRV. The biogenicity of the methane was determined based on δ13C values and methane/ethane ratios. Soil gas samples and sediments were collected at different sites in the playa and surrounding areas. The soils of the playa consist of a surface crust layer (upper ~ 10 cm) grading to a dense clay below about 25 cm. Soil gas from the playa, sampled at about 20 and 80 cm depths, reflected atmospheric methane concentrations, ranging from 2 to 2.4 ppm, suggesting that no methane was produced within the playa. Natural springs on the northeast and western border of the playa, detected as methane hotspots from a flyover by the Sensor Integrated Environmental Remote Research Aircraft (SIERRA), were also sampled. Bubbles in these springs had methane concentrations that ranged from 69 to 84% by volume. In addition, ethane was detected at very low concentrations, giving methane/ethane ratios in excess of 100,000, indicating biogenic methane in the springs. Soils and sediments collected at the playa and spring sites were incubated in vials over a period of ~23 days. Methane production was observed in the spring sites (avg. 228.6 ± 49.1 nmol/g/d at Kate Springs), but was not evident for the playa sites. The incubation data, therefore, corroborated in situ methane concentration measurements. Particulate organic carbon (POC) was low for all sites samples (0.05-0.38%), with the exception of Kate Springs, which had a much higher POC concentration of 3.4 ± 0

  6. A novel predictive model for formation enthalpies of Si and Ge hydrides with propane- and butane-like structures.

    PubMed

    Weng, C; Kouvetakis, J; Chizmeshya, A V G

    2011-04-15

    erratic predictions. Our approach also provides quantitative bond-additivity rules for the chlorination of these heavier species. Finally, we discuss structure and bonding trends across the entire sequence of butane-, propane-, and ethane-like molecules with a special focus on the isomeric variations.

  7. Computational modeling of a direct propane fuel cell

    NASA Astrophysics Data System (ADS)

    Khakdaman, H.; Bourgault, Y.; Ternan, M.

    2011-03-01

    The first two dimensional mathematical model of a complete direct propane fuel cell (DPFC) is described. The governing equations were solved using FreeFem software that uses finite element methods. Robin boundary conditions were used to couple the anode, membrane, and cathode sub-domains successfully. The model showed that a polytetrafluoroethylene membrane having its pores filled with zirconium phosphate (ZrP-PTFE), in a DPFC at 150 °C performed much the same as other electrolytes; Nafion, aqueous H3PO4, and H2SO4 doped polybenzimidazole, when they were used in DPFCs. One advantage of a ZrP-PTFE at 150 °C is that it operates without liquid phase water. As a result corrosion will be much less severe and it may be possible for non-precious metal catalysts to be used. Computational results showed that the thickness of the catalyst layer could be increased sufficiently so that the pressure drop between the reactant and product channels of the interdigitated flow fields is small. By increasing the width of the land and therefore the reactant's contact time with the catalyst it was possible to approach 100% propane conversion. Therefore fuel cell operation with a minimum concentration of propane in the product stream should be possible. Finally computations of the electrical potential in the ZrP phase, the electron flux in the Pt/C phase, and the overpotential in both the anode and cathode catalyst layers showed that serious errors in the model occurred because proton diffusion, caused by the proton concentration gradient, was neglected in the equation for the conservation of protons.

  8. Supercritical convection, critical heat flux, and coking characteristics of propane

    NASA Technical Reports Server (NTRS)

    Rousar, D. C.; Gross, R. S.; Boyd, W. C.

    1984-01-01

    The heat transfer characteristics of propane at subcritical and supercritical pressure were experimentally evaluated using electrically heated Monel K-500 tubes. A design correlation for supercritical heat transfer coefficient was established using the approach previously applied to supercritical oxygen. Flow oscillations were observed and the onset of these oscillations at supercritical pressures was correlated with wall-to-bulk temperature ratio and velocity. The critical heat flux measured at subcritical pressure was correlated with the product of velocity and subcooling. Long duration tests at fixed heat flux conditions were conducted to evaluate coking on the coolant side tube wall and coking rates comparable to RP-1 were observed.

  9. Supercritical convection, critical heat flux, and coking characteristics of propane

    NASA Technical Reports Server (NTRS)

    Rousar, D. C.; Gross, R. S.; Boyd, W. C.

    1984-01-01

    The heat transfer characteristics of propane at subcritical and supercritical pressure were experimentally evaluated using electrically heated Monel K-500 tubes. A design correlation for supercritical heat transfer coefficient was established using the approach previously applied to supercritical oxygen. Flow oscillations were observed and the onset of these oscillations at supercritical pressures was correlated with wall-to-bulk temperature ratio and velocity. The critical heat flux measured at subcritical pressure was correlated with the product of velocity and subcooling. Long duration tests at fixed heat flux conditions were conducted to evaluate coking on the coolant side tube wall and coking rates comparable to RP-1 were observed.

  10. Assessment of potential for natural attenuation of chlorinated ethenes and ethanes in ground water at a petrochemical reclamation site, Harris County, Texas

    USGS Publications Warehouse

    Huff, Glenn F.; Braun, Christopher L.; Lee, Roger W.

    2000-01-01

    Redox conditions in the Numerous Sand Channels Zone beneath a petrochemical reclamation site in Harris County, Texas, range from sulfate reducing to methanogenic as indicated by the presence of methane in ground water and the range of molecular hydrogen concentrations. Assessment of the potential for reductive dechlorination using BIOCHLOR as a screening tool indicated conditions favoring anaerobic degradation of chlorinated organic compounds in the Numerous Sand Channels Zone. Evidence supporting reductive dechlorination includes apparently biogenic cis-1,2-dichloroethene; an increased ratio of 1,2-dichloroethane to 1,1,2-trichloroethane downgradient from the assumed contaminant source area; ethene and methane concentrations greater than background concentrations within the area of the contaminant plume; and a positive correlation of the ratio of ethene to vinyl chloride as a function of methane concentrations. The body of evidence presented in this report argues for hydrogenolysis of trichloroethene to cis-1,2-dichloroethene; of 1,1,2-trichloroethane to 1,2-dichloroethane; and of vinyl chloride to ethene within the Numerous Sand Channels Zone. Simulations using BIOCHLOR yielded apparent first-order decay constants for reductive dechlorination in the sequence Tetrachloroethene --> trichloroethene --> cis-1,2-dichloroethene --> vinyl chloride --> ethene within the range of literature values reported for each compound and apparent first-order decay constants for reductive dechlorination in the sequence 1,1,2-trichloroethane --> 1,2-dichloroethane slightly greater than literature values reported for each compound along the upgradient segment of a simulated ground-water flowpath. Except for vinyl chloride, apparent rates of reductive dechlorination for all simulated species show a marked decrease along the downgradient segment of the simulated ground-water flowpath. Evidence for reductive dechlorination of chlorinated ethenes within the Numerous Sand Channels Zone

  11. Up with methane

    SciTech Connect

    Barlaz, M.A.; Milke, M.W.; Ham, R.K.

    1986-12-01

    Methane production from municipal refuse represents a rapidly developing source of energy which remains underutilized. Part of the problem is the small amount of methane which is typically collected relative to the refuse's methane generation potential. This study was undertaken to define the parameters which affect the onset of methane production and methane yields in sanitary landfills. Ultimately, we need to develop refuse disposal methods which enhance its methane production potential. Included in the study were tests of how introduction of old refuse, use of sterile cover soil, addition of acetate to refuse, and use of leachate, recycling and neutralization affect methane generation. A more thorough understanding of how the microbes present in refuse react to different variables is the first step in the development of techniques for stimulating methane production in sanitary landfills.

  12. Methane Plumes on Mars

    NASA Image and Video Library

    Spectrometer instruments attached to several telescopes detect plumes of methane emitted from Mars during its summer and spring seasons. High levels of methane are indicated by warmer colors. The m...

  13. Gold(I) chloride adducts of 1,3-bis(di-2-pyridylphosphino)propane: synthesis, structural studies and antitumour activity

    SciTech Connect

    Humphreys, Anthony S.; Filipovska, Aleksandra; Berners-Price, Susan J.; Koutsantonis, George A.; Skelton, Brian W.; White, Allan H.

    2008-06-30

    The novel water soluble bidentate phosphine ligand 1,3-bis(di-2-pyridylphosphino)propane (d2pypp) has been synthesized by a convenient route involving treatment of 2-pyridyllithium with Cl{sub 2}P(CH{sub 2}){sub 3}PCl{sub 2} and isolation in crystalline form as the hydrochloride salt. The synthesis of the precursor Cl{sub 2}P(CH{sub 2}){sub 3}PCl{sub 2} has been optimized by the use of triphosgene as the chlorinating agent. The 2:1 and 1:2 AuCl:d2pypp adducts have been synthesized and characterized by NMR spectroscopy and single crystal X-ray studies, and shown to be of the form (AuCl){sub 2}({mu}-d2pypp-P,P{prime}) and Au(d2pypp-P,P{prime}){sub 2}Cl(-3.75H{sub 2}O), respectively. The latter is more lipophilic than analogous 1:2 adducts of gold(I) chloride with the diphosphine ligands 1,2-bis(di-n-pyridylphosphino)ethane (dnpype) for n = 2, 3 and 4, based on measurement of the n-octanol-water partition coefficient (log P = -0.46). A single crystal structure determination of the 1:2 Au(I) complex of the 3-pyridyl ethane ligand shows it to be of the form [Au(d3pype-P,P{prime}){sub 2}]Cl {center_dot} 5H{sub 2}O. The in vitro cytotoxic activity of [Au(d2pypp){sub 2}]Cl was assessed in human normal and cancer breast cells and selective toxicity to the cancer cells found. The significance of these results to the antitumour properties of chelated 1:2 Au(I) diphosphine complexes is discussed.

  14. Oxidation of C1 Compounds by Particulate fractions from Methylococcus capsulatus: distribution and properties of methane-dependent reduced nicotinamide adenine dinucleotide oxidase (methane hydroxylase).

    PubMed Central

    Ribbons, D W

    1975-01-01

    Cell-free particulate fractions of extracts from the obligate methylotroph Methylococcus capsulatus catalyze the reduced nicotinamide adenine dinucleotide (NADH) and O2-dependent oxidation of methane (methane hydroxylase). The only oxidation product detected was formate. These preparations also catalyze the oxidation of methanol and formaldehyde to formate in the presence or absence of phenazine methosulphate with oxygen as the terminal electron acceptor. Methane hydroxylase activity cannot be reproducibly obtained from disintegrated cell suspensions even though the whole cells actively respired when methane was presented as a substrate. Varying the disintegration method or extraction medium had no significant effect on the activities obtained. When active particles were obtained, hydroxylase activity was stable at 0 C for days. Methane hydroxylase assays were made by measuring the methane-dependent oxidation of NADH by O2. In separate experiments, methane consumption and the accumulation of formate were also demonstrated. Formate is not oxidized by these particulate fractions. The effects of particle concentration, temperature, pH, and phosphate concentration on enzymic activity are described. Ethane is utilized in the presence of NADH and O2. The stoichiometric relationships of the reaction(s) with methane as substrate were not established since (i) the presumed initial product, methanol, is also oxidized to formate, and (ii) the contribution that NADH oxidase activity makes to the observed consumption of reactants could not be assessed in the presence of methane. Studies with known inhibitors of electron transport systems indicate that the path of electron flow from NADH to oxygen is different for the NADH oxidase, methane hydroxylase, and methanol oxidase activities. Images PMID:238946

  15. Methane emissions from natural gas infrastructure and use in the urban region of Boston, Massachusetts

    NASA Astrophysics Data System (ADS)

    McKain, Kathryn; Down, Adrian; Raciti, Steve M.; Budney, John; Hutyra, Lucy R.; Floerchinger, Cody; Herndon, Scott C.; Nehrkorn, Thomas; Zahniser, Mark S.; Jackson, Robert B.; Phillips, Nathan; Wofsy, Steven C.

    2015-02-01

    Methane emissions from natural gas delivery and end use must be quantified to evaluate the environmental impacts of natural gas and to develop and assess the efficacy of emission reduction strategies. We report natural gas emission rates for 1 y in the urban region of Boston, using a comprehensive atmospheric measurement and modeling framework. Continuous methane observations from four stations are combined with a high-resolution transport model to quantify the regional average emission flux, 18.5 ± 3.7 (95% confidence interval) g CH4ṡm-2ṡy-1. Simultaneous observations of atmospheric ethane, compared with the ethane-to-methane ratio in the pipeline gas delivered to the region, demonstrate that natural gas accounted for ∼60-100% of methane emissions, depending on season. Using government statistics and geospatial data on natural gas use, we find the average fractional loss rate to the atmosphere from all downstream components of the natural gas system, including transmission, distribution, and end use, was 2.7 ± 0.6% in the Boston urban region, with little seasonal variability. This fraction is notably higher than the 1.1% implied by the most closely comparable emission inventory.

  16. Methane emissions from natural gas infrastructure and use in the urban region of Boston, Massachusetts.

    PubMed

    McKain, Kathryn; Down, Adrian; Raciti, Steve M; Budney, John; Hutyra, Lucy R; Floerchinger, Cody; Herndon, Scott C; Nehrkorn, Thomas; Zahniser, Mark S; Jackson, Robert B; Phillips, Nathan; Wofsy, Steven C

    2015-02-17

    Methane emissions from natural gas delivery and end use must be quantified to evaluate the environmental impacts of natural gas and to develop and assess the efficacy of emission reduction strategies. We report natural gas emission rates for 1 y in the urban region of Boston, using a comprehensive atmospheric measurement and modeling framework. Continuous methane observations from four stations are combined with a high-resolution transport model to quantify the regional average emission flux, 18.5 ± 3.7 (95% confidence interval) g CH4 ⋅ m(-2) ⋅ y(-1). Simultaneous observations of atmospheric ethane, compared with the ethane-to-methane ratio in the pipeline gas delivered to the region, demonstrate that natural gas accounted for ∼ 60-100% of methane emissions, depending on season. Using government statistics and geospatial data on natural gas use, we find the average fractional loss rate to the atmosphere from all downstream components of the natural gas system, including transmission, distribution, and end use, was 2.7 ± 0.6% in the Boston urban region, with little seasonal variability. This fraction is notably higher than the 1.1% implied by the most closely comparable emission inventory.

  17. Methane emissions from natural gas infrastructure and use in the urban region of Boston, Massachusetts

    PubMed Central

    McKain, Kathryn; Down, Adrian; Raciti, Steve M.; Budney, John; Hutyra, Lucy R.; Floerchinger, Cody; Herndon, Scott C.; Nehrkorn, Thomas; Zahniser, Mark S.; Jackson, Robert B.; Phillips, Nathan; Wofsy, Steven C.

    2015-01-01

    Methane emissions from natural gas delivery and end use must be quantified to evaluate the environmental impacts of natural gas and to develop and assess the efficacy of emission reduction strategies. We report natural gas emission rates for 1 y in the urban region of Boston, using a comprehensive atmospheric measurement and modeling framework. Continuous methane observations from four stations are combined with a high-resolution transport model to quantify the regional average emission flux, 18.5 ± 3.7 (95% confidence interval) g CH4⋅m−2⋅y−1. Simultaneous observations of atmospheric ethane, compared with the ethane-to-methane ratio in the pipeline gas delivered to the region, demonstrate that natural gas accounted for ∼60–100% of methane emissions, depending on season. Using government statistics and geospatial data on natural gas use, we find the average fractional loss rate to the atmosphere from all downstream components of the natural gas system, including transmission, distribution, and end use, was 2.7 ± 0.6% in the Boston urban region, with little seasonal variability. This fraction is notably higher than the 1.1% implied by the most closely comparable emission inventory. PMID:25617375

  18. Mobile Methane Measurements of Natural Gas Distribution and End-use Emissions in Indianapolis

    NASA Astrophysics Data System (ADS)

    Lamb, B. K.; Roscioli, J. R.; Floerchinger, C. R.; Herndon, S. C.; Ferrara, T.

    2015-12-01

    Indianapolis is the site of the INFLUX program to investigate greenhouse gas emissions from a large metropolitan area. A key question in INFLUX is the relative contributions of methane emissions from the local gas distribution system in comparison to biogenic sources, such as the wastewater treatment system and landfills, and of end use emissions from furnaces and other combustion devices downstream of customer gas meters. During February and March, 2015, the Aerodyne van was used to measure methane, ethane, CO2 and other trace gases during mobile sampling traverses through a number of urban and suburban Indianapolis neighborhoods. Signatures of distinct natural gas emissions, biogenic emissions, and combustion emissions were observed in small plumes. In a number of cases, these sources were identified as manhole covers in city streets, where nearby leaks can seep into the local wastewater system. Quantification of ethane and methane from 45 manholes reveal that some had emissions that were clearly biogenic while others had a distinct natural gas signature. This paper describes the results from the analysis of these mobile data in the context of the current Indianapolis methane emission inventory.

  19. Formation of a new benzene-ethane co-crystalline structure under cryogenic conditions.

    PubMed

    Vu, Tuan Hoang; Cable, Morgan L; Choukroun, Mathieu; Hodyss, Robert; Beauchamp, Patricia

    2014-06-12

    We report the first experimental finding of a solid molecular complex between benzene and ethane, two small apolar hydrocarbons, at atmospheric pressure and cryogenic temperatures. Considerable amounts of ethane are found to be incorporated inside the benzene lattice upon the addition of liquid ethane onto solid benzene at 90-150 K, resulting in formation of a distinctive co-crystalline structure that can be detected via micro-Raman spectroscopy. Two new features characteristic of these co-crystals are observed in the Raman spectra at 2873 and 1455 cm(-1), which are red-shifted by 12 cm(-1) from the υ1 (a1g) and υ11 (eg) stretching modes of liquid ethane, respectively. Analysis of benzene and ethane vibrational bands combined with quantum mechanical modeling of isolated molecular dimers reveal an interaction between the aromatic ring of benzene and the hydrogen atoms of ethane in a C-H···π fashion. The most favored configuration for the benzene-ethane dimer is the monodentate-contact structure, with a calculated interaction energy of 9.33 kJ/mol and an equilibrium bonding distance of 2.66 Å. These parameters are comparable to those for a T-shaped co-crystalline complex between benzene and acetylene that has been previously reported in the literature. These results are relevant for understanding the hydrocarbon cycle of Titan, where benzene and similar organics may act as potential hydrocarbon reservoirs due to this incorporation mechanism.

  20. Heat pipe methanator

    DOEpatents

    Ranken, William A.; Kemme, Joseph E.

    1976-07-27

    A heat pipe methanator for converting coal gas to methane. Gravity return heat pipes are employed to remove the heat of reaction from the methanation promoting catalyst, transmitting a portion of this heat to an incoming gas pre-heat section and delivering the remainder to a steam generating heat exchanger.

  1. Documentation for propane fleet conversion cost-effectiveness model

    NASA Astrophysics Data System (ADS)

    Taylor, D.; Euritt, M.; Mahmassani, H.

    1992-10-01

    Increased emphasis on energy efficiency and air quality has resulted in a number of state and federal initiatives examining the use of alternative fuels for motor vehicles. Texas instituted an alternative fuels program for public fleet operations beginning in the 1991-92 fiscal year. Life-cycle cost/benefit models for evaluating the economic implications of the action have been developed at the University of Texas at Austin Center for Transportation Research for both compressed natural gas (CNG) and propane. The report documents the various input data, calculations, and assumptions of the Propane Net Present Value (NPV) model. A similar report (number 983-1) documents the same for the CNG model. Input data with constant values across different fleets and locations are discussed first and include basic parameters for on-board storage capacity, vehicle conversion costs, equipment salvage values, etc. Variable input data, reflecting a given fleet size, composition, and location, include the number and types of vehicles, fuel consumption, etc. The next section presents the formulas for the internal model calculations. The final section discusses the basic assumptions underlying the model.

  2. 40 CFR 1065.341 - CVS and batch sampler verification (propane check).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... engineering judgment and safe practices, this check may be performed using a gas other than propane, such as... § 1065.340. (6) Other problems with the CVS or sampling verification hardware or software.Inspect the CVS system, CVS verification hardware, and software for discrepancies. (b) A propane check uses either a...

  3. In-Situ Remediation of MTBE Contaminated Aquifers Using Propane Biosparging. Revision 1

    DTIC Science & Technology

    2003-01-03

    NOAEL No-Observable-Adverse- Effect -Level OIPs Oxygen injection points ORP Oxidation reduction potential PIPs Propane injection points PMO Propane...most petroleum constituents (BTEX, alkanes, etc), subsurface aeration effectively promotes aerobic contaminant destruction by stimulating the natural...flow rates. Unfortunately, active MTBE degradation in our Control Plot during this demonstration prevents a thorough evaluation of the effectiveness of

  4. Location dependent orientational structure and dynamics of ethane in ZSM5

    NASA Astrophysics Data System (ADS)

    Gautam, Siddharth; Liu, Tingting; Patankar, Sumant; Tomasko, David; Cole, David

    2016-03-01

    Orientational structure and dynamics of ethane confined in ZSM5 zeolite at four different loadings are reported. The effect of pore geometry on ethane is studied by isolating the contribution from ethane molecules in different locations, viz. straight channels, sinusoidal channels and their intersections. Orientational dynamics is found to be hindered in general and exhibits librational motion, with the extant of hindrance being the greatest in sinusoidal channels. Librational motion becomes faster with an increase in loading. This counterintuitive finding is consistent with experiments reported elsewhere and is explained on the basis of a decreased orientational anisotropy at higher loadings.

  5. Freon or propane: new design methods give a choice for small gas-processing plants

    SciTech Connect

    Love, D.L.

    1986-03-10

    Propane, and sometimes ammonia, have been the major refrigerants considered for refrigeration in liquid extraction plants. Freon was considered only for automotive and building air conditioning. With modular plants on skids becoming more popular for small volume applications, less-expensive equipment approaches are required to economically justify these small projects. Commercial and residential design methods can be used for refrigerated liquid extraction. They can significantly reduce the cost, compared to propane, for small volume applications. Although it appears to be a simple substitution of freon for propane, there are many complications in using freon. They include major changes in materials, and in chiller and compressor design. Love Process Engineering Inc. (LPE) has conducted extensive research on freon and propane plants for modular applications. This article will not discuss detailed design requirements, but compare freon and propane in the initial selection of project development for small volume applications.

  6. Prediction of supercritical ethane bulk solvent densities for pyrazine solvation shell average occupancy by 1, 2, 3, and 4 ethanes: combined experimental and ab initio approach.

    PubMed

    Hrnjez, Bruce J; Sultan, Samuel T; Natanov, Georgiy R; Kastner, David B; Rosman, Michael R

    2005-11-17

    We introduce a method that addresses the elusive local density at the solute in the highly compressible regime of a supercritical fluid. Experimentally, the red shift of the pyrazine n-pi electronic transition was measured at infinite dilution in supercritical ethane as a function of pressure from 0 to about 3000 psia at two temperatures, one close (35.0 degrees C) to the critical temperature and the other remote (55.0 degrees C). Computationally, stationary points were located on the potential surfaces for pyrazine and one, two, three, and four ethanes at the MP2/6-311++G(d,p) level. The vertical n-pi ((1)B(3u)) transition energies were computed for each of these geometries with a TDDFT/B3LYP/6-311++G(d,p) method. The combination of experiment and computation allows prediction of supercritical ethane bulk densities at which the pyrazine primary solvation shell contains an average of one, two, three, and four ethane molecules. These density predictions were achieved by graphical superposition of calculated shifts on the experimental shift versus density curves for 35.0 and 55.0 degrees C. Predicted densities are 0.0635, 0.0875, and 0.0915 g cm(-3) for average pyrazine primary solvation shell occupancy by one, two, and three ethanes at both 35.0 and 55.0 degrees C. Predicted densities are 0.129 and 0.150 g cm(-3) for occupancy by four ethanes at 35.0 and 55.0 degrees C, respectively. An alternative approach, designed to "average out" geometry specific shifts, is based on the relationship Deltanu = -23.9n cm(-1), where n = ethane number. Graphical treatment gives alternative predicted densities of 0.0490, 0.0844, and 0.120 g cm(-3) for average pyrazine primary solvation shell occupancy by one, two, and three ethanes at both 35.0 and 55.0 degrees C, and densities of 0.148 and 0.174 g cm(-3) for occupancy by four ethanes at 35.0 and 55.0 degrees C, respectively.

  7. Homicide by methane gas.

    PubMed

    De-Giorgio, Fabio; Grassi, Vincenzo M; Vetrugno, Giuseppe; Rossi, Riccardo; Fucci, Nadia; d'Aloja, Ernesto; Pascali, Vincenzo L

    2012-09-10

    Methane is a suffocating gas, and "methane deaths" are largely the result of suffocation by gas-air displacement after accidental or deliberate exposure. Neither methane gas nor other suffocating gases are a common means of homicide, with the potential exception of the use of gas in chemical weapons or gas chambers. Here, we report the case of a 53-year-old woman who was killed by her husband with methane gas. The man had given his wife a dose of Lorazepam before setting up a hose that conveyed methane from the kitchen into the apartment's bedroom. The man subsequently faked his own suicide, which was later discovered.

  8. Biodegradation of individual and multiple chlorinated aliphatic hydrocarbons by methane-oxidizing cultures.

    PubMed Central

    Chang, H L; Alvarez-Cohen, L

    1996-01-01

    The microbial degradation of chlorinated and nonchlorinated methanes, ethanes, and ethanes by a mixed methane-oxidizing culture grown under chemostat and batch conditions is evaluated and compared with that by two pure methanotrophic strains: CAC1 (isolated from the mixed culture) and Methylosinus trichosporium OB3b. With the exception of 1,1-dichloroethylene, the transformation capacity (Tc) for each chlorinated aliphatic hydrocarbon was generally found to be in inverse proportion to its chlorine content within each aliphatic group (i.e., methanes, ethanes, and ethenes), whereas similar trends were not observed for degradation rate constants. Tc trends were similar for all methane-oxidizing cultures tested. None of the cultures were able to degrade the fully chlorinated aliphatics such as perchloroethylene and carbon tetrachloride. Of the four cultures tested, the chemostat-grown mixed culture exhibited the highest Tc for trichloroethylene, cis-1,2-dichloroethylene, tetrachloroethane, 1,1,1-trichloroethane, and 1,2-dichloroethane, whereas the pure batch-grown OB3b culture exhibited the highest Tc for all other compounds tested. The product toxicity of chlorinated aliphatic hydrocarbons in a mixture containing multiple compounds was cumulative and predictable when using parameters measured from the degradation of individual compounds. The Tc for each chlorinated aliphatic hydrocarbon in a mixture (Tcmix) and the total Tc for the mixture (sigma Tcmix) are functions of the individual Tc, the initial substrate concentration (S0), and the first-order rate constant (k/Ks) of each compound in the mixture, indicating the importance of identifying the properties and compositions of all potentially degradable compounds in a contaminant mixture. PMID:8795228

  9. Crystal structure of naltrexone chloride solvates with ethanol, propan-2-ol, and 2-methyl-propan-2-ol.

    PubMed

    Menze, Aveary R; Sinnott, Jefferson P; Nazarenko, Alexander Y

    2017-07-01

    Naltrexone [systematic name: 17-(cyclo-propyl-meth-yl)-3,14-di-hydroxy-4,5α-epoxymorphinan-6-one] is an opioid receptor competitive antagonist that has been widely used to prevent relapse in opioid- and alcohol-dependent subjects. Its chloride salt forms non-isomorphic solvates with ethanol (C20H24NO4(+)·Cl(-)·C2H5OH) (I), propan-2-ol (C20H24NO4(+)·Cl(-)·C3H7OH) (II), and 2-methyl-propan-2-ol (C20H24NO4(+)·Cl(-)·C4H9OH) (III). The naltrexone cation can be described as a T-shape made out of two ring systems, a tetra-hydro-2H-naphtho-[1,8-bc]furan system and a deca-hydro-isoquinolinium subunit, that are nearly perpendicular to one another. The flexible cyclo-propyl-methyl group can adopt various different conformations in response to its surroundings: an increase of available space around cyclo-propyl-methyl group may allow it to adopt a more favorable conformation. In all these structures, the alcohol mol-ecules occupy infinite solvent-filled channels. All three compounds described are attractive crystalline forms for unambiguous identification of naltrexone chloride after isolation from a pharmaceutical form. Compound (III) was refined as a two-component twin.

  10. Modeling and Measurements of Atmospheric Methane at Four Corners, NM

    NASA Astrophysics Data System (ADS)

    Costigan, K. R.; Lindenmaier, R.; Dubey, M. K.

    2014-12-01

    Methane (CH4) fugitive emissions from fossil energy mining remain highly uncertain and scrutinized with the rapid expansion in domestic production by hydraulic fracturing. Top down observational studies of reported bottom up inventories are limited, but the latter may be biased low. We focus on the Four Corners region of the Southwestern United States, a region with extensive coal bed methane production, to verify its current emissions. At our site we measured methane over a range of scales using ground-based, in-situ instruments and a Fourier Transform Spectrometer (FTS), which is part of the Total Carbon Column Observing Network (TCCON). Measurements of CH4 produced much higher concentrations of methane in this rural area than previously expected. The diurnal variation and wind direction dependence in the CH4 concentrations suggest a source location tied to topographically induced winds and consistent with oil and gas production. This paper presents the results of WRF-Chem simulations that are performed to simulate methane concentrations in this region. Emissions from the Emissions Database for Global Atmospheric Research (EDGAR) indicate large CH4 emissions, associated with the gas production and distribution sector, in one 0.1 x 0.1 degree grid cell within the region and these emissions are employed in the simulations. A series of six simulations are run at two-month intervals during 2012. Each simulates a six-day time series to demonstrate the diurnal and seasonal characteristics of the methane concentrations that would be expected at the FTS location, from the sources reported in the EDGAR data set. The results of these simulations will be presented, along with the implications for interpretation of the FTS measurements. We will also interpret our FTS measurements of ethane (C2H6), which is emitted only from fossil fuel mining, to attribute leaks.

  11. Biogenic methane from abyssal brine seeps at the base of the Florida escarpment

    SciTech Connect

    Martens, C.S.; Chanton, J.P.; Paull, C.K. )

    1991-08-01

    Dissolved methane is present at concentrations exceeding 10mM in the pore waters of sulfidic, salt-brine-enriched sediments underlying chemosynthetic communities at the base of the Florida escarpment. Light hydrocarbon samples were obtained from brine seep sediments by means of an in situ probe and push cores deployed by the deep submersible Alvin. Pore-water methane had a {delta}{sup 13}C value of {minus}83.3 {plus minus}7.0 (Peedee belemnite, N = 17), contained < 1.3% modern carbon, and was enriched over ethane concentrations by 10{sup 3} to 10{sup 5}; these results all indicate a fossil, biogenic carbon source within the Florida platform. Methane-rich brine fluids arriving at seep sites are depleted in dissolved sulfate, although they have been diluted twenty-fold with sulfate-rich seawater during transit. It appears that sulfate reduction and methano-genesis are important processes within the platform.

  12. Surface and bulk properties of stoichiometric and nonstoichiometric strontium hydroxyapatite and the oxidation of methane

    SciTech Connect

    Sugiyama, Shigeru; Minami, Toshimitsu; Hayashi, Hiromu

    1996-11-01

    The oxidation of methane on near-stoichiometric strontium hydroxyapatites pretreated at 873, 1048 and 1123 K in O{sub 2} has been examined in the presence and absence of tetrachloromethane (TCM) as a gas-phase additive at 973 K. Under these conditions, strontium hydroxyapatite, regardless of its stoichiometry, is converted, at least in part, to Sr{sub 3}(PO{sub 4}){sub 2}. On introduction of TCM to the feedstream, the selectivities to carbon monoxide, ethane, and ethylene are increased while the conversion of methane is decreased. Qualitatively similar effects of TCM on the oxidation were observed on Sr{sub 3}(PO{sub 4}){sub 2} prepared by an independent procedure. Strontium chlorapatite, formed from the apatites and phosphate during the oxidation in the presence of TCM, as shown from XRD, contributes to the increased selectivity to CO and decreased conversion of methane.

  13. International comparison CCQM-K66: Impurity analysis of methane

    NASA Astrophysics Data System (ADS)

    Kato, Kenji; Watanabe, Takuro; Heine, Hans-Joachim; Boissiere, C.; Schulz, G.; Woo, Jin-Chun; Seog Kim, Jin; Hyup Oh, Sang; Bae, Hyun Kil; Du Kim, Yong; Qiao, Han; Guenther, Frank R.; Rhoderick, George C.; Miller, Walter; Smeulders, Damian; Botha, Angelique; Janse van Rensburg, Mellisa; Tshilongo, James; Leshabane, Nompumelelo; Ntsasa, Napo; Milton, Martin J. T.; Vargha, Gergely; Harling, Alice; Konopelko, L. A.; Kustikov, Y. A.; Vasserman, I. I.; Zavyalov, S. V.; Popova, T. A.; Pankratov, V. V.; Pir, M. N.; Maltsev, M. A.; Oudwater, Rutger; Persijn, Stefan; van Wijk, Janneke; Wessel, Rob M.

    2012-01-01

    This key comparison was performed to demonstrate the capability of NMIs to analyse the purity of methane for use as a source gas in the preparation of standard gas mixtures. This capability is an essential requirement for the preparation of accurate standards of natural gas and some other fuels. Since it is difficult to carry out a comparison with individual samples of pure gas, the sample for this comparison was a synthetic mixture of high purity methane with selected added impurities of nitrogen, argon, carbon dioxide and ethane. These mixtures were prepared by a gas company as a batch of 10 cylinders and their homogeneity and stability were evaluated by NMIJ. The KCRVs for the four different analytes in this key comparison are based on a consensus of values reported by participants. The uncertainties in the degrees of equivalence were calculated by combining the reported uncertainties with the homogeneity of the samples and the uncertainty of the KCRV. The results submitted are generally consistent with the KCRV within the estimated uncertainties. Finally, this comparison demonstrates that the analysis of nitrogen, argon, carbon dioxide and ethane in methane at amount fractions of 1 µmol/mol to 5 µmol/mol is generally possible with an uncertainty of 5% to 10%. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (MRA).

  14. Methane photochemistry and methane production on Neptune

    SciTech Connect

    Romani, P.N.; Atreya, S.K.

    1988-06-01

    The Neptune stratosphere's methane photochemistry is presently studied by means of a numerical model in which the observed mixing ratio of methane prompts photolysis near the CH4 homopause. Haze generation by methane photochemistry has its basis in the formation of hydrocarbon ices and polyacetylenes; the hazes can furnish the requisite aerosol haze at the appropriate pressure levels required by observations of Neptune in the visible and near-IR. Comparisons of model predictions with Uranus data indicate a lower ratio of polyacetylene production to hydrocarbon ice, as well as a lower likelihood of UV postprocessing of the acetylene ice to polymers on Neptune, compared to Uranus. 65 references.

  15. Methane photochemistry and methane production on Neptune

    NASA Astrophysics Data System (ADS)

    Romani, P. N.; Atreya, S. K.

    1988-06-01

    The Neptune stratosphere's methane photochemistry is presently studied by means of a numerical model in which the observed mixing ratio of methane prompts photolysis near the CH4 homopause. Haze generation by methane photochemistry has its basis in the formation of hydrocarbon ices and polyacetylenes; the hazes can furnish the requisite aerosol haze at the appropriate pressure levels required by observations of Neptune in the visible and near-IR. Comparisons of model predictions with Uranus data indicate a lower ratio of polyacetylene production to hydrocarbon ice, as well as a lower likelihood of UV postprocessing of the acetylene ice to polymers on Neptune, compared to Uranus.

  16. Methane photochemistry and methane production on Neptune

    NASA Technical Reports Server (NTRS)

    Romani, P. N.; Atreya, S. K.

    1988-01-01

    The Neptune stratosphere's methane photochemistry is presently studied by means of a numerical model in which the observed mixing ratio of methane prompts photolysis near the CH4 homopause. Haze generation by methane photochemistry has its basis in the formation of hydrocarbon ices and polyacetylenes; the hazes can furnish the requisite aerosol haze at the appropriate pressure levels required by observations of Neptune in the visible and near-IR. Comparisons of model predictions with Uranus data indicate a lower ratio of polyacetylene production to hydrocarbon ice, as well as a lower likelihood of UV postprocessing of the acetylene ice to polymers on Neptune, compared to Uranus.

  17. Methane photochemistry and methane production on Neptune

    NASA Technical Reports Server (NTRS)

    Romani, P. N.; Atreya, S. K.

    1988-01-01

    The Neptune stratosphere's methane photochemistry is presently studied by means of a numerical model in which the observed mixing ratio of methane prompts photolysis near the CH4 homopause. Haze generation by methane photochemistry has its basis in the formation of hydrocarbon ices and polyacetylenes; the hazes can furnish the requisite aerosol haze at the appropriate pressure levels required by observations of Neptune in the visible and near-IR. Comparisons of model predictions with Uranus data indicate a lower ratio of polyacetylene production to hydrocarbon ice, as well as a lower likelihood of UV postprocessing of the acetylene ice to polymers on Neptune, compared to Uranus.

  18. Clumped Methane Isotopologue Temperatures of Microbial Methane

    NASA Astrophysics Data System (ADS)

    Ono, S.; Wang, D. T.; Gruen, D.; Delwiche, K.; Hemond, H.; Pohlman, J.

    2014-12-01

    We will report the abundance of 13CH3D, a clumped isotopologue of methane, in microbial methane sampled from natural environments. They yield some expected and some unexpected results reflecting both equilibrium and kinetic isotope effects controlling the abundance of 13CH3D in low temperature environments. The four isotopologues of methane (12CH4, 13CH4, 12CH3D and 13CH3D) were measured by a tunable infrared spectroscopy method at a precision of 0.2‰ and accuracy of 0.5‰ (Ono et al., 2014). Similar to carbonate clumped isotope thermometry, clumped isotopologues of methane become more stable at lower temperatures. The equilibrium constant for the isotope exchange reaction 13CH4 + 12CH3D ⇌ 13CH3D + 12CH4 deviates from unity by +6.3 to +3.5 ‰ for methane equilibrated between 4 and 121 °C, a range expected for microbial methanogenesis. This would be measurably-distinct from a thermogenic methane signal, which typically have apparent 13CH3D-based temperatures ranging from 150 to 220 °C (+3.0 to +2.2 ‰ clumped isotope effect; Ono et al., 2014; Stolper et al. 2014). Marine samples, such as methane clathrates and porewater methane from the Cascadia margin, have 13CH3D-based temperatures that appear to be consistent with isotopic equilibration at in situ temperatures that are reasonable for deep sedimentary environments. In contrast, methane from freshwater environments, such as a lake and a swamp, yield apparent temperatures that are much higher than the known or inferred environmental temperature. Mixing of two or more distinct sources of methane could potentially generate this high temperature bias. We suggest, however, that this high-temperature bias likely reflects a kinetic isotope fractionation intrinsic to methanogenesis in fresh water environments. In contrast, the low-temperature signals from marine methane could be related to the slow metabolic rates and reversibility of microbial methanogenesis and methanotrophy in marine sedimentary environments

  19. Ethane and n-pentane in exhaled breath are biomarkers of exposure not effect

    PubMed Central

    Gorham, Katrine A.; Sulbaek Andersen, Mads P.; Meinardi, Simone; Delfino, Ralph J.; Staimer, Norbert; Tjoa, Thomas; Rowland, F. Sherwood; Blake, Donald R.

    2013-01-01

    The relationship of exhaled ethane and n-pentane to exhaled NO, carbonylated proteins, and indoor/outdoor atmospheric pollutants were examined in order to evaluate ethane and n-pentane as potential markers of airway inflammation and/or oxidative stress. Exhaled NO and carbonylated proteins were found to have no significant associations with either ethane (p = 0.96 and p = 0.81, respectively) or n-pentane (p = 0.44 and 0.28, respectively) when outliers were included. In the case where outliers were removed n-pentane was found to be inversely associated with carbonylated proteins. Exhaled hydrocarbons adjusted for indoor hydrocarbon concentrations were instead found to be positively associated with air pollutants (NO, NO2 and CO), suggesting pollutant exposure is driving exhaled hydrocarbon concentrations. Given these find-ings, ethane and n-pentane do not appear to be markers of airway inflammation or oxidative stress. PMID:19283520

  20. Ethane and n-pentane in exhaled breath are biomarkers of exposure not effect.

    PubMed

    Gorham, Katrine A; Sulbaek Andersen, Mads P; Meinardi, Simone; Delfino, Ralph J; Staimer, Norbert; Tjoa, Thomas; Rowland, F Sherwood; Blake, Donald R

    2009-02-01

    The relationship of exhaled ethane and n-pentane to exhaled NO, carbonylated proteins, and indoor/outdoor atmospheric pollutants were examined in order to evaluate ethane and n-pentane as potential markers of airway inflammation and/or oxidative stress. Exhaled NO and carbonylated proteins were found to have no significant associations with either ethane (p = 0.96 and p = 0.81, respectively) or n-pentane (p = 0.44 and 0.28, respectively) when outliers were included. In the case where outliers were removed n-pentane was found to be inversely associated with carbonylated proteins. Exhaled hydrocarbons adjusted for indoor hydrocarbon concentrations were instead found to be positively associated with air pollutants (NO, NO(2) and CO), suggesting pollutant exposure is driving exhaled hydrocarbon concentrations. Given these findings, ethane and n-pentane do not appear to be markers of airway inflammation or oxidative stress.

  1. An integral proton conducting SOFC for simultaneous production of ethylene and power from ethane.

    PubMed

    Fu, Xian-Zhu; Luo, Jing-Li; Sanger, Alan R; Danilovic, Nemanja; Chuang, Karl T

    2010-03-28

    A novel, integral, tri-layered, proton conducting membrane SOFC was readily fabricated for simultaneous conversion of ethane at 650-700 degrees C to electrical power and ethylene with high selectivity.

  2. Ethane adsorption on aggregates of dahlia-like nanohorns: experiments and computer simulations.

    PubMed

    Russell, Brice A; Migone, Aldo D; Petucci, Justin; Mercedes Calbi, M; Yudasaka, Masako; Iijima, Sumio

    2016-06-01

    This is a report on a study of the adsorption characteristics of ethane on aggregates of unopened dahlia-like carbon nanohorns. This sorbent presents two main groups of adsorption sites: the outside surface of individual nanohorns and deep, interstitial spaces between neighbouring nanohorns towards the interior of the aggregates. We have explored the equilibrium properties of the adsorbed ethane films by determining the adsorption isotherms and isosteric heat of adsorption. Computer simulations performed on different model structures indicate that the majority of ethane adsorption occurs on the outer region of the aggregates, near the ends of the nanohorns. We have also measured the kinetics of adsorption of ethane on this sorbent. The measurements and simulations were conducted along several isotherms spanning the range between 120 K and 220 K.

  3. The biological fate of decabromodiphenyl ethane following oral, dermal or intravenous administration

    EPA Science Inventory

    1. The disposition of decabromodiphenyl ethane (DBDPE) was investigated based on concerns over its structural similarities to decaBDE, high potential for environmental persistence & bioaccumulation, and high production volume. 2. In the present study, female Sprague Dawley ra...

  4. Large-Scale Computational Screening of Zeolites for Ethane/Ethene Separation

    SciTech Connect

    Kim, J; Lin, LC; Martin, RL; Swisher, JA; Haranczyk, M; Smit, B

    2012-08-14

    Large-scale computational screening of thirty thousand zeolite structures was conducted to find optimal structures for seperation of ethane/ethene mixtures. Efficient grand canonical Monte Carlo (GCMC) simulations were performed with graphics processing units (GPUs) to obtain pure component adsorption isotherms for both ethane and ethene. We have utilized the ideal adsorbed solution theory (LAST) to obtain the mixture isotherms, which were used to evaluate the performance of each zeolite structure based on its working capacity and selectivity. In our analysis, we have determined that specific arrangements of zeolite framework atoms create sites for the preferential adsorption of ethane over ethene. The majority of optimum separation materials can be identified by utilizing this knowledge and screening structures for the presence of this feature will enable the efficient selection of promising candidate materials for ethane/ethene separation prior to performing molecular simulations.

  5. Protonated ethane. A theoretical investigation of C[sub 2]H[sub 7][sup +] structures and energies

    SciTech Connect

    Carneiro, J.W.M. de; Schleyer, P.R. von ); Saunders, M. ); Remington, R.; Schaefer, H.F. III ); Rauk, A.; Sorensen, T.S. )

    1994-04-20

    The C[sub 2]H[sub 7][sup +] potential energy surface was characterized by high-level ab initio calculations. The effects of electron correlation on geometries and relative energies are substantial. At MP4(SDTQ)/6-311G**//MP2(full)/6-31G**, the global minimum is the C-C protonated structure 1, 4.4 kcal/mol (corrected to 298 K) more stable than the C-H protonated form 3. The proton affinity of ethane to give 1 (142.5 kcal/mol) is 12.5 kcal/mol greater than that of methane (130 kcal/mol). Methane adds to the methyl cation, leading to 1 without activation energy. Barriers for intramolecular hydrogen interchange are lower than the dissociation energy into the ethyl cation and hydrogen, consistent with the experimental observation that deuterium scrambling is faster than dissociation. C[sub 2]H[sub 7][sup +] loses H[sub 2] by 1,1-elimination in an endothermic (10.6 kcal/mol) process. Three frequencies deduced experimentally for C[sub 2]H[sub 7][sup +] correspond to those computed for 1, but neither 2, the H[sub 2]-rotated C-H protonated form, nor 3 can explain the other set of experimental spectral data. Complexes between H[sub 2] and bridged C[sub 2]H[sub 5][sup +] were located, but they are too weakly bonded to be detected experimentally. 45 refs., 3 figs., 9 tabs.

  6. Propane-1,3-diammonium dichromate(VI).

    PubMed

    Trabelsi, Sonia; Marouani, Houda; Al-Deyab, Salem S; Rzaigui, Mohamed

    2012-08-01

    The title compound, (C(3)H(12)N(2))[Cr(2)O(7)], consists of a discrete dichromate anion with an eclipsed conformation and a propane-1,3-diammonium cation. Both kinds of ions have a mirror plane passing through the bridging O atom and the central methyl-ene C atom of the Cr(2)O(7) (2-) and C(3)H(12)N(2) (2+) moieties, respectively. Anions and cations are alternately stacked to form columns parallel to the b axis. Ions are linked by intra- and inter-column hydrogen bonds of types N-H⋯O and C-H⋯O, involving O atoms of the dichromate anions as acceptors, and ammonium or methyl-ene groups as donors.

  7. Chemical kinetic reaction mechanism for the combustion of propane

    NASA Technical Reports Server (NTRS)

    Jachimowski, C. J.

    1984-01-01

    A detailed chemical kinetic reaction mechanism for the combustion of propane is presented and discussed. The mechanism consists of 27 chemical species and 83 elementary chemical reactions. Ignition and combustion data as determined in shock tube studies were used to evaluate the mechanism. Numerical simulation of the shock tube experiments showed that the kinetic behavior predicted by the mechanism for stoichiometric mixtures is in good agrement with the experimental results over the entire temperature range examined (1150-2600K). Sensitivity and theoretical studies carried out using the mechanism revealed that hydrocarbon reactions which are involved in the formation of the HO2 radical and the H2O2 molecule are very important in the mechanism and that the observed nonlinear behavior of ignition delay time with decreasing temperature can be interpreted in terms of the increased importance of the HO2 and H2O2 reactions at the lower temperatures.

  8. An analysis of US propane markets, winter 1996-1997

    SciTech Connect

    1997-06-01

    In late summer 1996, in response to relatively low inventory levels and tight world oil markets, prices for crude oil, natural gas, and products derived from both began to increase rapidly ahead of the winter heating season. Various government and private sector forecasts indicated the potential for supply shortfalls and sharp price increases, especially in the event of unusually severe winter weather. Following a rapid runup in gasoline prices in the spring of 1996, public concerns were mounting about a possibly similar situation in heating fuels, with potentially more serious consequences. In response to these concerns, the Energy Information Administration (EIA) participated in numerous briefings and meetings with Executive Branch officials, Congressional committee members and staff, State Energy Offices, and consumers. EIA instituted a coordinated series of actions to closely monitor the situation and inform the public. This study constitutes one of those actions: an examination of propane supply, demand, and price developments and trends.

  9. Propane spectral resolution enhancement by the maximum entropy method

    NASA Technical Reports Server (NTRS)

    Bonavito, N. L.; Stewart, K. P.; Hurley, E. J.; Yeh, K. C.; Inguva, R.

    1990-01-01

    The Burg algorithm for maximum entropy power spectral density estimation is applied to a time series of data obtained from a Michelson interferometer and compared with a standard FFT estimate for resolution capability. The propane transmittance spectrum was estimated by use of the FFT with a 2 to the 18th data sample interferogram, giving a maximum unapodized resolution of 0.06/cm. This estimate was then interpolated by zero filling an additional 2 to the 18th points, and the final resolution was taken to be 0.06/cm. Comparison of the maximum entropy method (MEM) estimate with the FFT was made over a 45/cm region of the spectrum for several increasing record lengths of interferogram data beginning at 2 to the 10th. It is found that over this region the MEM estimate with 2 to the 16th data samples is in close agreement with the FFT estimate using 2 to the 18th samples.

  10. [1,3-Bis(diphenylphosphino)propane]trichlorooxorhenium(V).

    PubMed

    Suescun, L; Mombrú, A W; Mariezcurrena, R A; Pardo, H; Russi, S; Kremer, C; Rivero, M; Kremer, E

    2000-08-01

    Trichlorooxo[1,3-propanediylbis(diphenylphosphine)-P,P ']rhenium(V), [ReCl(3)O(C(27)H(26)P(2))], crystallizes with four formula units per unit cell. The crystal structure consists of neutral complexes of [ReOCl(3)(dppp)] [dppp is 1,3-bis(diphenylphosphino)propane] packed by H.pi-ring interactions. The Re atom is octahedrally coordinated to the oxo anion, three Cl atoms and two P atoms from the dppp ligand. The six-membered ring formed by the bidentate dppp ligand and the rhenium metal centre is in a chair conformation. The title compound is an intermediate in the synthesis of bis(dppp) complexes of rhenium.

  11. Propane spectral resolution enhancement by the maximum entropy method

    NASA Technical Reports Server (NTRS)

    Bonavito, N. L.; Stewart, K. P.; Hurley, E. J.; Yeh, K. C.; Inguva, R.

    1990-01-01

    The Burg algorithm for maximum entropy power spectral density estimation is applied to a time series of data obtained from a Michelson interferometer and compared with a standard FFT estimate for resolution capability. The propane transmittance spectrum was estimated by use of the FFT with a 2 to the 18th data sample interferogram, giving a maximum unapodized resolution of 0.06/cm. This estimate was then interpolated by zero filling an additional 2 to the 18th points, and the final resolution was taken to be 0.06/cm. Comparison of the maximum entropy method (MEM) estimate with the FFT was made over a 45/cm region of the spectrum for several increasing record lengths of interferogram data beginning at 2 to the 10th. It is found that over this region the MEM estimate with 2 to the 16th data samples is in close agreement with the FFT estimate using 2 to the 18th samples.

  12. On the role of ethenol in equilibrium gas-phase ethanal

    NASA Astrophysics Data System (ADS)

    Slanina, Zdeněk

    1984-03-01

    The ethenol content in gas-phase ethanal has been evaluated under equilibrium conditions within a broad temperature interval, and it has been shown that the content thresholds of 1% and 1% can be crossed at about 650 and 1000 K, respectively. At moderate and higher temperatures the presence of ethenol is manifested by contributions to thermodynamic functions of the equilibrium gas-phase ethanal which can be even higher than the usual anharmonicity and non-rigidity corrections.

  13. Methane emission from sewers.

    PubMed

    Liu, Yiwen; Ni, Bing-Jie; Sharma, Keshab R; Yuan, Zhiguo

    2015-08-15

    Recent studies have shown that sewer systems produce and emit a significant amount of methane. Methanogens produce methane under anaerobic conditions in sewer biofilms and sediments, and the stratification of methanogens and sulfate-reducing bacteria may explain the simultaneous production of methane and sulfide in sewers. No significant methane sinks or methanotrophic activities have been identified in sewers to date. Therefore, most of the methane would be emitted at the interface between sewage and atmosphere in gravity sewers, pumping stations, and inlets of wastewater treatment plants, although oxidation of methane in the aeration basin of a wastewater treatment plant has been reported recently. Online measurements have also revealed highly dynamic temporal and spatial variations in methane production caused by factors such as hydraulic retention time, area-to-volume ratio, temperature, and concentration of organic matter in sewage. Both mechanistic and empirical models have been proposed to predict methane production in sewers. Due to the sensitivity of methanogens to environmental conditions, most of the chemicals effective in controlling sulfide in sewers also suppress or diminish methane production. In this paper, we review the recent studies on methane emission from sewers, including the production mechanisms, quantification, modeling, and mitigation.

  14. Coexistance of two Different Methane Hydrate Phases at Moderate Pressure and Temperature Conditions

    NASA Astrophysics Data System (ADS)

    Erzinger, J.

    2003-12-01

    For a better understanding of the formation and decomposition of natural gas hydrates, detailed data on their thermodynamical properties are an important prerequisite. Until now, it was generally accepted that small guest molecules such as methane and carbondioxid form structure I hydrates whereas large molecules such as propane form structure II hydrates. Expectedly, natural gas hydrates and synthesized methane hydrates grown under natural conditions, prefer structure I. The formation of structure II methane hydrates was only observed at very high pressures ( 100 MPa) by Chou et al. 1 In this contribution, results from Raman spectroscopic investigation on pure methane hydrates are presented. It will be shown, that a coexistence of structure I and structure II methane hydrates at pressures between 3.0 and 9.0 MPa and at temperatures between -15° C and +15° C is possible. However, structure II methane hydrate are present as a metastable phase in a kinetic inhibited equilibrium with the established structure I methane hydrate phase. A slight variation of the T-P-x-conditions initiates the transformation of the structure II methane hydrates into structure I hydrates. This (exothermic) process results in a re crystallization of the complete hydrate phase until a stable state is reached. It turned out, that the instability of the structure II methane hydrate phase is also the driving force for other processes, such as the exchange of CH4 with CO2: A change in the composition of the gaseous phase through the addition of CO2 induces an immediate replacement of methane with carbondioxid in the structure II hydrate. In contrast, the exchange of CH4 with CO2 in structure I hydrates is a very slow process. 1 Chou, I-M.; Sharma, A.; Burrus, R. C.; Shu, J.; Mao, H-k.; Hemley, R. J.; Goncharov, A. F.; Stern, L. A.; Kirby, S. H.; PNAS; vol. 97; no. 25;13484-13487 (2000)

  15. Methane-Powered Vehicles

    NASA Technical Reports Server (NTRS)

    1982-01-01

    Liquid methane is beginning to become an energy alternative to expensive oil as a power source for automotive vehicles. Methane is the principal component of natural gas, costs less than half as much as gasoline, and its emissions are a lot cleaner than from gasoline or diesel engines. Beech Aircraft Corporation's Boulder Division has designed and is producing a system for converting cars and trucks to liquid methane operation. Liquid methane (LM) is a cryogenic fuel which must be stored at a temperature of 260 degrees below zero Fahrenheit. The LM system includes an 18 gallon fuel tank in the trunk and simple "under the hood" carburetor conversion equipment. Optional twin-fuel system allows operator to use either LM or gasoline fuel. Boulder Division has started deliveries for 25 vehicle conversions and is furnishing a liquid methane refueling station. Beech is providing instruction for Northwest Natural Gas, for conversion of methane to liquid state.

  16. Mars methane engine

    NASA Technical Reports Server (NTRS)

    Bui, Hung; Coletta, Chris; Debois, Alain

    1994-01-01

    The feasibility of an internal combustion engine operating on a mixture of methane, carbon dioxide, and oxygen has been verified by previous design groups for the Mars Methane Engine Project. Preliminary stoichiometric calculations examined the theoretical fuel-air ratios needed for the combustion of methane. Installation of a computer data acquisition system along with various ancillary components will enable the performance of the engine, running on the described methane mixture, to be optimized with respect to minimizing excess fuel. Theoretical calculations for stoichiometric combustion of methane-oxygen-carbon dioxide mixtures yielded a ratio of 1:2:4.79 for a methane-oxygen-carbon dioxide mixture. Empirical data shows the values to be closer to 1:2.33:3.69 for optimum operation.

  17. High Resolution Investigation of the Ethane Spectrum at 7 μ

    NASA Astrophysics Data System (ADS)

    Brown, Linda R.; Sung, K.; Di Lauro, C.; Lattanzi, F.; Vander Auwera, J.; Mantz, A. W.; Smith, M. A. H.

    2010-10-01

    A new theoretical analysis of the ethane spectrum between 1330 and 1610 cm-1 has been undertaken in order to create the first line-by-line database of molecular parameters for this spectral region. For this, high resolution spectra were obtained at room and cold (130 K) temperatures with two Bruker Fourier transform spectrometers (at 0.002 cm-1 resolution in Brussels and at 0.003 cm-1 resolution in Pasadena). Over 5000 lines were assigned to five bands in the region: v6, v8, v4+v12 and 2v4+v9 cold bands, and one hot band (v4+v8-v4). This new study employed a much improved theoretical Hamiltonian to reproduce the very complicated spectral structures resulting from numerous interactions between these vibrational modes. This advancement has enabled us to provide a quantum mechanical prediction of line positions and intensities of C2H6 at 7 micron long needed for remote sensing of outer planets and Titan. Two manuscripts are in preparation. Part of the research described in this paper was performed at the Jet Propulsion Laboratory, California Institute of Technology, Connecticut College, and NASA Langley under contract with the National Aeronautics and Space Administration, and with funding from FRS-FNRS in Belgium.

  18. Investigating model deficiencies in the global budget of ethane

    NASA Astrophysics Data System (ADS)

    Tzompa Sosa, Z. A.; Keller, C. A.; Turner, A. J.; Mahieu, E.; Franco, B.; Fischer, E. V.

    2015-12-01

    Many locations in the Northern Hemisphere show a statistically-significant sharp increase in measurements of ethane (C2H6) since 2009. It is hypothesized that the recent massive growth of shale gas exploitation in North America could be the source of this change. However, state-of-the-science chemical transport models are currently unable to reproduce the hemispheric burden of C2H6 or the recent sharp increase, pointing to a potential problem with current emission inventories. To resolve this, we used space-borne CH4 observations from the Greenhouse Gases Observing SATellite (GOSAT) to derive C2H6 emissions. By using known emission ratios to CH4, we estimated emissions of C2H6 from oil and gas activities, biofuels, and biomass burning over North America. The GEOS-Chem global chemical transport model was used to simulate atmospheric abundances of C2H6 with the new emissions estimates. The model is able to reproduce Northern Hemisphere surface concentrations. However, the model significantly under-predicts the amount of C2H6 throughout the column and the observed Northern Hemispheric gradient as diagnosed by comparisons to aircraft observations from the Hiaper Pole-to-Pole (HIPPO) Campaign.

  19. Jovian Northern Ethane Aurora and the Solar Cycle

    NASA Technical Reports Server (NTRS)

    Kostiuk,T.; Livengood, T.; Fast, K.; Buhl, D.; Goldstein, J.; Hewagama, T.

    1999-01-01

    Thermal infrared auroral spectra from Jupiter's North polar region have been collected from 1979 to 1998 in a continuing study of long-term variability in the northern thermal IR aurora, using C2H6 emission lines near 12 microns as a probe. Data from Voyager I and 2 IRIS measurements and ground based spectral measurements were analyzed using the same model atmosphere to provide a consistent relative comparison. A retrieved equivalent mole fraction was used to compare the observed integrated emission. Short term (days), medium term (months) and long term (years) variability in the ethane emission was observed. The variability Of C2H6 emission intensities was compared to Jupiter's seasonal cycle and the solar activity cycle. A positive correlation appears to exist, with significantly greater emission and short term variability during solar maxima. Observations on 60 N latitude during increased solar activity in 1979, 1989, and most recently in 1998 show up to 5 times brighter integrated line emission of C2H6 near the north polar "hot spot" (150-210 latitude) than from the north quiescent region. Significantly lower enhancement was observed during periods of lower solar activity in 1982, 1983, 1993, and 1995. Possible sources and mechanisms for the enhancement and variability will be discussed.

  20. Variation of the pressure limits of flame propagation with tube diameter for propane-air mixtures

    NASA Technical Reports Server (NTRS)

    Belles, Frank E; Simon, Dorothy M

    1951-01-01

    An investigation was made of the variation of the pressure limits of flame propagation with tube diameter for quiescent propane with tube diameter for quiescent propane-air mixtures. Pressure limits were measured in glass tubes of six different inside diameters, with a precise apparatus. Critical diameters for flame propagation were calculated and the effect of pressure was determined. The critical diameters depended on the pressure to the -0.97 power for stoichiometric mixtures. The pressure dependence decreased with decreasing propane concentration. Critical diameters were related to quenching distance, flame speeds, and minimum ignition energy.

  1. Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems

    USGS Publications Warehouse

    Ni, Y.; Ma, Q.; Ellis, G.S.; Dai, J.; Katz, B.; Zhang, S.; Tang, Y.

    2011-01-01

    Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using ??D values in ethane from several basins in the world are in close agreement with similar predictions based on the ??13C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that ??D values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that ??D values in ethane might be more suitable for modeling than comparable values in methane and propane. ?? 2011 Elsevier Ltd.

  2. Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems

    NASA Astrophysics Data System (ADS)

    Ni, Yunyan; Ma, Qisheng; Ellis, Geoffrey S.; Dai, Jinxing; Katz, Barry; Zhang, Shuichang; Tang, Yongchun

    2011-05-01

    Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2 cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using δD values in ethane from several basins in the world are in close agreement with similar predictions based on the δ 13C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that δD values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that δD values in ethane might be more suitable for modeling than comparable values in methane and propane.

  3. Methane emissions from cattle.

    PubMed

    Johnson, K A; Johnson, D E

    1995-08-01

    Increasing atmospheric concentrations of methane have led scientists to examine its sources of origin. Ruminant livestock can produce 250 to 500 L of methane per day. This level of production results in estimates of the contribution by cattle to global warming that may occur in the next 50 to 100 yr to be a little less than 2%. Many factors influence methane emissions from cattle and include the following: level of feed intake, type of carbohydrate in the diet, feed processing, addition of lipids or ionophores to the diet, and alterations in the ruminal microflora. Manipulation of these factors can reduce methane emissions from cattle. Many techniques exist to quantify methane emissions from individual or groups of animals. Enclosure techniques are precise but require trained animals and may limit animal movement. Isotopic and nonisotopic tracer techniques may also be used effectively. Prediction equations based on fermentation balance or feed characteristics have been used to estimate methane production. These equations are useful, but the assumptions and conditions that must be met for each equation limit their ability to accurately predict methane production. Methane production from groups of animals can be measured by mass balance, micrometeorological, or tracer methods. These techniques can measure methane emissions from animals in either indoor or outdoor enclosures. Use of these techniques and knowledge of the factors that impact methane production can result in the development of mitigation strategies to reduce methane losses by cattle. Implementation of these strategies should result in enhanced animal productivity and decreased contributions by cattle to the atmospheric methane budget.

  4. Detecting Methane Leaks

    NASA Technical Reports Server (NTRS)

    Grant, W. B.; Hinkley, E. D.

    1984-01-01

    Remote sensor uses laser radiation backscattered from natural targets. He/Ne Laser System for remote scanning of Methane leaks employs topographic target to scatter light to receiver near laser transmitter. Apparatus powered by 1.5kW generator transported to field sites and pointed at suspected methane leaks. Used for remote detection of natural-gas leaks and locating methane emissions in landfill sites.

  5. Shock-tube and modeling study of methane pyrolysis and oxidation

    SciTech Connect

    Hidaka, Yoshiaki; Sato, Kazutaka; Henmi, Yusuke; Tanaka, Hiroya; Inami, Koji

    1999-08-01

    Methane pyrolysis and oxidation were studied behind reflected shock waves in the temperature range 1350--2400 K at pressures of 1.6 to 4.4 atm. Methane decay in both the pyrolysis and oxidation reactions was measured by using time-resolved infrared (IR) laser absorption at 3.39 {micro}m. CO{sub 2} production was also measured by time-resolved IR emission at 4.24 {micro}m. The production yields were also studied using a single-pulse method. The pyrolysis and oxidation of methane were modeled using a kinetic reaction mechanism including the most recent mechanism for formaldehyde, ketene, acetylene, ethylene, and ethane oxidations. The present and earlier shock tube data is reproduced by the proposed mechanism with 157 reaction steps and 48 species. The reactions and the rate constants, which were important to predict these and earlier shock tube data for methane pyrolysis and the oxidation with mixtures of wide composition from methane-rich to methane-lean, are discussed in detail.

  6. State heating oil and propane program: Final report. Survey of No.2 heating oil and propane prices at the retail level, October 1997 through March 1998

    SciTech Connect

    1998-11-01

    The Energy Efficiency Division of the Vermont Department of Public Service (DPS) monitored the price and inventory of residential heating oil and propane during the 1997--98 heating season under a grant from the US Department of Energy`s Energy Information Administration (EIA). DPS staff collected data biweekly between October 5, 1997 and March 16, 1998 on the retail price of {number_sign}2 home heating oil and propane by telephone survey. Propane price quoted was based on the rate for a residential home heating customer using 1,000+ per year. The survey included a sample of fuel dealers selected by the EIA, plus additional dealers and fuels selected by the DPS. The EIA weighted, analyzed, and reported the data collected from their sample.

  7. The future of methane

    SciTech Connect

    Howell, D.G.

    1995-12-31

    Natural gas, mainly methane, produces lower CO{sub 2}, CO, NO{sub x}, SO{sub 2} and particulate emissions than either oil or coal; thus further substitutions of methane for these fuels could help mitigate air pollution. Methane is, however, a potent greenhouse gas and the domestication of ruminants, cultivation of rice, mining of coal, drilling for oil, and transportation of natural gas have all contributed to a doubling of the amount of atmospheric methane since 1800. Today nearly 300,000 wells yearly produce ca. 21 trillion cubic feet of methane. Known reserves suggest about a 10 year supply at the above rates of recovery; and the potential for undiscovered resources is obscured by uncertainty involving price, new technologies, and environmental restrictions steming from the need to drill an enormous number of wells, many in ecologically sensitive areas. Until all these aspects of methane are better understood, its future role in the world`s energy mix will remain uncertain. The atomic simplicity of methane, composed of one carbon and four hydrogen atoms, may mask the complexity and importance of this, the most basic of organic molecules. Within the Earth, methane is produced through thermochemical alteration of organic materials, and by biochemical reactions mediated by metabolic processes of archaebacteria; some methane may even be primordial, a residue of planetary accretion. Methane also occurs in smaller volumes in landfills, rice paddies, termite complexes, ruminants, and even many humans. As an energy source, its full energy potential is controversial. Methane is touted by some as a viable bridge to future energy systems, fueled by the sun and uranium and carried by electricity and hydrogen.

  8. Methanation assembly using multiple reactors

    DOEpatents

    Jahnke, Fred C.; Parab, Sanjay C.

    2007-07-24

    A methanation assembly for use with a water supply and a gas supply containing gas to be methanated in which a reactor assembly has a plurality of methanation reactors each for methanating gas input to the assembly and a gas delivery and cooling assembly adapted to deliver gas from the gas supply to each of said methanation reactors and to combine water from the water supply with the output of each methanation reactor being conveyed to a next methanation reactor and carry the mixture to such next methanation reactor.

  9. Short-Term Energy Outlook Model Documentation: Regional Residential Propane Price Model

    EIA Publications

    2009-01-01

    The regional residential propane price module of the Short-Term Energy Outlook (STEO) model is designed to provide residential retail price forecasts for the 4 Census regions: Northeast, South, Midwest, and West.

  10. School Districts Move to the Head of the Class with Propane

    SciTech Connect

    2016-01-01

    Propane has been a proven fuel for buses for decades. For the first time in 2007, Blue Bird rolled out a propane school bus using direct liquid injection, which was later followed by Thomas Built Buses and Navistar. Because this new technology is much more reliable than previous designs, it is essentially reintroducing propane buses to many school districts. During this same time period, vehicle emissions standards have tightened. To meet them, diesel engine manufacturers have added diesel particulate filters (DPF) and, more recently, selective catalytic reduction (SCR) systems. As an alternative to diesel buses with these systems, many school districts have looked to other affordable, clean alternatives, and they've found that propane fits the bill.

  11. PHYSICAL PROPERTIES OF FLUORINATED PROPANE AND BUTANE DERIVATIVES AS ALTERNATIVE REFRIGERANTS

    EPA Science Inventory

    Physical property measurements are presented for 24 fluorinated propane and butane derivatives and one fluorinated ether. These measurements include melting point, boiling point, vapor pressure below the boiling point, heat of vaporization at the boiling point, critical propertie...

  12. Burning of the Supersonic Propane-Air Mixture in the Aerodynamic Channel With the Stagnant Zone

    DTIC Science & Technology

    2007-11-02

    V.Chernikov, V.Shibkov, O.Surkont. Mechanisms of transversal electric discharge sustention in supersonic air and propane-air flows. -American Institute of Aeronautics and Astronautics, AIAA Paper, 2003, No.03-0872, p. 1 -6 .

  13. PHYSICAL PROPERTIES OF FLUORINATED PROPANE AND BUTANE DERIVATIVES AS ALTERNATIVE REFRIGERANTS

    EPA Science Inventory

    Physical property measurements are presented for 24 fluorinated propane and butane derivatives and one fluorinated ether. These measurements include melting point, boiling point, vapor pressure below the boiling point, heat of vaporization at the boiling point, critical propertie...

  14. Short-Term Energy Outlook Model Documentation: Regional Residential Propane Price Model

    EIA Publications

    2009-01-01

    The regional residential propane price module of the Short-Term Energy Outlook (STEO) model is designed to provide residential retail price forecasts for the 4 Census regions: Northeast, South, Midwest, and West.

  15. Effect of preprocessing and compressed propane extraction on quality of cilantro (Coriandrum sativum L.).

    PubMed

    Sekhon, Jasreen K; Maness, Niels O; Jones, Carol L

    2015-05-15

    Dehydration leads to quality defects in cilantro such as loss in structure, color, aroma and flavor. Solvent extraction with compressed propane may improve the dehydrated quality. In the present study, effect of drying temperature, particle size, and propane extraction on color, volatile composition, and fatty acid composition of cilantro was evaluated. Cilantro was dehydrated (40°C or 60°C), size reduced and separated into three particles sizes, and extracted with compressed propane at 21-27°C. Major volatile compounds found in dried cilantro were E-2-tetradecenal, dodecanal, E-2-dodecenal, and tetradecanal. Major fatty acids were linoleic acid and α-linolenic acid. Drying at 60°C compared to 40°C resulted in better preservation of color (decrease in browning index values) and volatile compounds. Propane extraction led to a positive change in color values and a decrease in volatile composition, oil content, and fatty acid composition.

  16. Deposit formation in hydrocarbon rocket fuels with an evaluation of a propane heat transfer correlation

    NASA Technical Reports Server (NTRS)

    Masters, P. A.; Aukerman, C. A.

    1982-01-01

    A high pressure fuel coking testing apparatus was designed and developed and was used to evaluate thermal decomposition limits and carbon decomposition rates in heated copper tubes for hydrocarbon fuels. A commercial propane (90% grade) and chemically pure (CP) propane were tested. Heat transfer to supercritical propane was evaluated at 136 atm, bulk fluid velocities of 6 to 30 m/s, and tube wall temperatures in the range of 422 to 811 K. A forced convection heat transfer correlation developed in a previous test effort verified a prediction of most of the experimental data within a + or - 30% range, with good agreement for the CP propane data. No significant differences were apparent in the predictions derived from the correlation when the carbon resistance was included with the film resistance. A post-test scanning electron microprobe analysis indicated occurrences of migration and interdiffusion of copper into the carbon deposit.

  17. Propane dehydrogenation over Pt-Cu bimetallic catalysts: the nature of coke deposition and the role of copper

    NASA Astrophysics Data System (ADS)

    Han, Zhiping; Li, Shuirong; Jiang, Feng; Wang, Tuo; Ma, Xinbin; Gong, Jinlong

    2014-08-01

    This paper describes an investigation of the promotional effect of Cu on the catalytic performance of Pt/Al2O3 catalysts for propane dehydrogenation. We have shown that Pt/Al2O3 catalysts possess higher propylene selectivity and lower deactivation rate as well as enhanced anti-coking ability upon Cu addition. The optimized loading content of Cu is 0.5 wt%, which increases the propylene selectivity to 90.8% with a propylene yield of 36.5%. The origin of the enhanced catalytic performance and anti-coking ability of the Pt-Cu/Al2O3 catalyst is ascribed to the intimate interaction between Pt and Cu, which is confirmed by the change of particle morphology and atomic electronic environment of the catalyst. The Pt-Cu interaction inhibits propylene adsorption and elevates the energy barrier of C-C bond rupture. The inhibited propylene adsorption diminishes the possibility of coke formation and suppresses the cracking reaction towards the formation of lighter hydrocarbons on Pt-Cu/Al2O3, while a higher energy barrier for C-C bond cleavage suppresses the methane formation.

  18. Gaseous abundances and methane supersaturation in Titan's troposphere

    NASA Technical Reports Server (NTRS)

    Samuelson, Robert E.; Nath, Nitya R.; Borysow, Aleksandra

    1997-01-01

    Various properties of Titan's troposphere are inferred from an analysis of Voyager I infrared spectrometer (IRIS) data between 200 and 600/ cm. Two homogeneous spectral averages acquired at widely separated emission angles are chosen for the analysis. Both data sets are associated with northern low latitudes very close to that of the radio science ingress occultation point. Solutions require simultaneous nonlinear least-squares fits to the two IRIS data sets, coupled with iteration of the radio occultation refractivity data. Values and associated 1-sigma uncertainties of several parameters are inferred from our analysis. These include mole fractions for molecular hydrogen (approx. 0.0011), argon (small), and methane near the surface ( approx. 0.057). Solutions are also obtained for the hydrogen parafraction (close to equilibrium, with considerable uncertainty), air temperature near the surface ( approx. 93 K), surface surface temperature discontinuity (approx. 1 K), and maximum degree of methane supersaturation in the upper troposphere (approx. 1.5). Actual values for the above-mentioned parameters depend on the amount of ethane cloud near the tropopause. There is no evidence for methane clouds in the upper troposphere, nor is their presence compatible with large degrees of supersaturation. A wave number dependence for the stratos