Science.gov

Sample records for methane ethane propane

  1. HOMOGENEOUS HYDROLYSIS RATE CONSTANTS FOR SELECTED CHLORINATED METHANES, ETHANES, ETHENES, AND PROPANES

    EPA Science Inventory

    Hydrolysis rate constants of 18 chlorinated methanes, ethanes, ethenes, and propanes have been measured in dilute aqueous solutions within the temperature range of 0 to 180 oC and at pH values of 3 to l4. rrhenius parapmeters were determined for both neutral and alkaline hydrolys...

  2. 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

  3. Main-group compounds selectively oxidize mixtures of methane, ethane, and propane to alcohol esters.

    PubMed

    Hashiguchi, Brian G; Konnick, Michael M; Bischof, Steven M; Gustafson, Samantha J; Devarajan, Deepa; Gunsalus, Niles; Ess, Daniel H; Periana, Roy A

    2014-03-14

    Much of the recent research on homogeneous alkane oxidation has focused on the use of transition metal catalysts. Here, we report that the electrophilic main-group cations thallium(III) and lead(IV) stoichiometrically oxidize methane, ethane, and propane, separately or as a one-pot mixture, to corresponding alcohol esters in trifluoroacetic acid solvent. Esters of methanol, ethanol, ethylene glycol, isopropanol, and propylene glycol are obtained with greater than 95% selectivity in concentrations up to 1.48 molar within 3 hours at 180°C. Experiment and theory support a mechanism involving electrophilic carbon-hydrogen bond activation to generate metal alkyl intermediates. We posit that the comparatively high reactivity of these d(10) main-group cations relative to transition metals stems from facile alkane coordination at vacant sites, enabled by the overall lability of the ligand sphere and the absence of ligand field stabilization energies in systems with filled d-orbitals. PMID:24626925

  4. 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.

  5. 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.

  6. 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. PMID:26745181

  7. 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)

  8. Portable, fast-response gas sensor for measuring methane and ethane and propane in liquefied natural gas spills

    NASA Astrophysics Data System (ADS)

    Bingham, G. E.; Kiefer, R. D.; Gillespie, C. H.; McRae, T. G.; Goldwire, H. C.; Koopman, R. P.

    1983-10-01

    We have developed a four-band, IR radiometer for measuring methane and ethane plus propane in the 1% to 100% gas per volume of air range in liquefied natural gas spills. The instrument is a small and lightweight open-cell, pyroelectric detector-based sensor designed for field use. It compensates for attenuation because of dense fog and is sufficiently hardened to allow continuous operation in the transient flame front of an ignited natural gas cloud. The sensor transmits five determinations of the gas concentration each second to a data-collection station on an interrupt-driven, serial data link. It has an operational power requirement of 15 W at 12 V dc.

  9. Modeling nitrogen and methane with ethane and propane gas hydrates at low temperatures (173-290 K) with applications to Titan

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

    The FREZCHEM model was primarily designed for cold temperatures (173-298 K) and high pressures (1-1000 bars). Nitrogen gas (95.0%) and methane gas (5.0%) are major gases on the surface of Titan. Recently, we added nitrogen and methane gas hydrates to FREZCHEM model on Titan; and nitrogen-methane gas hydrates formed on Titan at 178 K. The other common but less abundant gases on Titan are ethane (C2H6) and propane (C3H8) that can also form gas hydrates with nitrogen and methane. The specific objectives of this study were to (1) add ethane and propane to gas hydrates, including mixtures with nitrogen, methane, and carbon dioxide, and (2) explore the potential roles of gas hydrates on Titan. At 273 K, the Ln(gas hydrates) were 5.095 for N2, 3.217 for CH4, 2.327 for CO2, 1.288 for C2H6, and 0.281 for C3H8. At 173 K, the Ln(gas hydrates) were -4.968 for N2, -6.102 for CH4, -7.803 for CO2, -5.125 for C2H6, and -5.512 for C3H8. Apparently C2H6 and C3H8 gas hydrates change less at lower temperatures than N2, CH4, and CO2 gas hydrates. In previous papers, we added three mixed CH4-CO2, N2-CH4, and N2-CO2 binary gas hydrates. In this paper, we added ethane and propane to include new binary gas hydrate mixtures of N2-C2H6, N2-C3H8, C2H6-C3H8, CH4-C2H6, CH4-C3H8, CO2-C2H6, and CO2-C3H8. Today, there are ten binary gas hydrates in the FREZCHEM model. In the text, how to cope with more than two species is described. Simulations from 273 K to 173 K used a surface Titan pressure of 1.467 bars with a major gas of nitrogen (94.24%), a minor gas of methane (5.65%), and extremely minor gases of ethane (0.0038%), and propane (0.000343%). Eventually at 178 K, N2·6H2O formed with 0.17694 mol, CH4·6H2O formed with 0.04101 mol, C2H6·6H2O formed with 6.48e-6 mol, and C3H8·6H2O formed with 9.36e-7 mol. Based on the atmospheric conditions of Titan, the trace gases of ethane and propane led to low gas hydrate precipitations of ethane and propane with nitrogen and methane. However, the gas

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

    PubMed

    Smith, R Scott; May, R Alan; Kay, Bruce D

    2016-03-01

    The desorption kinetics for Ar, Kr, Xe, N2, O2, CO, methane, ethane, and propane from graphene-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 multilayer 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 nonalignment 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. PMID:26595145

  11. A geochemical model of non-ideal solutions in the methane-ethane-propane-nitrogen-acetylene system on Titan

    NASA Astrophysics Data System (ADS)

    Glein, Christopher R.; Shock, Everett L.

    2013-08-01

    Saturn's largest moon, Titan, has an atmosphere and surface that are rich in organic compounds. Liquid hydrocarbons exist on the surface, most famously as lakes. Photochemical reactions produce solid organics in Titan's atmosphere, and these materials settle or snow onto the surface. At the surface, liquids can interact with solids, and geochemical processes can occur. The consequences of these processes can be explored using a thermodynamic model to calculate the solubilities of gases and solids in liquid hydrocarbons at cryogenic temperatures. The van Laar model developed in this study was parameterized using experimental phase equilibrium data, and accurately represents the data for the CH4-C2H6-C3H8-N2-C2H2 chemical system from 90 to 110 K. The model generally gives more accurate results than existing models. The model also features a suitable balance between accuracy and simplicity, and can serve as a foundation for studies of fluvial geochemistry on Titan because it can be extended to any number of components while maintaining thermodynamic consistency. Application of the model to Titan reveals that the equilibrium composition of surface liquids depends on the abundance of methane gas in the local atmosphere, consistent with prior studies. The concentration of molecular nitrogen in Titan's lakes varies inversely with the ethane content of the lakes. The model indicates that solid acetylene should be quite soluble in surface liquids, which implies that acetylene-rich sedimentary rocks would be susceptible to chemical erosion, and acetylene evaporites may form on Titan. The geochemical character of acetylene in liquid hydrocarbons on Titan appears to be intermediate to those of calcite and gypsum in surface waters on Earth. Specific recommendations are given of observational, experimental, and theoretical work that will lead to significant advancements in our knowledge of geochemical processes on Titan. This paper represents the beginning of a new kind of

  12. 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

  13. PREDICTIONS OF AZEOTROPES FORMED FROM FLUORINATED ETHERS, ETHANES, AND PROPANES

    EPA Science Inventory

    The paper discusses an evaluation of the potential for azeotrope formation and performance for fluorinated ethers, ethanes, and propanes. (NOTE: The synthesis of new non-chlorinated refrigerants expands the base of alternatives for replacing ozone-depleting chlorofluorocarbons (O...

  14. 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.

  15. THERMODYNAMIC EVALUATION OF PREDICTED FLUORINATED ETHER, ETHANE, AND PROPANE AZEOTROPES

    EPA Science Inventory

    The paper gives results of thermodynamic analyses, using basic thermophysical property data, to evaluate seven predicted fluorinated ether, ethane, and propane azeotropes: E125/RC270, E125/R134a, E143a/R134, R134a/E143a, E143a/ R152a, R134/R245cb, and R245cb/R227ea. he performanc...

  16. 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.

  17. Isolation and Characterization of Ethane, Propane, and Butane Consuming Bacteria from Marine Hydrocarbon Seeps

    NASA Astrophysics Data System (ADS)

    Redmond, M. C.; Valentine, D. L.

    2005-12-01

    Three strains of ethane, propane, or butane consuming bacteria were isolated from marine hydrocarbon seep sediments at Coal Oil Point, off shore Santa Barbara, CA. These three isolates (MR1, MR2 and MR3) were capable of growth at natural environmental temperatures and salinity. Isolate MR2 was capable of growth on ethane or propane as the sole carbon source, isolate MR4 on propane or butane, and isolate MR3 on ethane, propane, or butane. All three isolates were also able to grow on other carbon-containing molecules, including ethanol, 1-propanol, 2-propanol, acetate, butyrate, sucrose, and dextrose, and isolates MR3 and MR4 were able to grow on 1-butanol and 2-butanol. None showed significant growth with methane, methanol, or formate as the sole carbon source. 16S rDNA sequencing indicated that isolate MR2 was most closely related to the gamma-Proteobacterium Pseudomonas stutzeri, while isolates MR3 and MR4 were both Gram-positive and most similar to Rhodococcus wratislaviensis and Rhodococcus opacus, respectively. Compared to methanotrophs, relatively little is known about the organisms that consume the C2-C4 alkanes, but both our isolates and the previously described species appear to be capable of metabolizing a wide variety of carbon compounds, including several common pollutants. The growth of these hydrocarbon-oxidizing bacteria on other organic compounds raises the possibility that the abundance and distribution of organic matter might be expected to impact the oxidation of C2-C4 hydrocarbons. Additional studies will further characterize the range of metabolism, and will investigate the importance of these organisms in natural hydrocarbon seep environments.

  18. 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. PMID:24945706

  19. THERMODYNAMIC EVALUATION OF FLUORINATED ETHERS, ETHANES, AND PROPANES AS ALTERNATIVE REFRIGERANTS

    EPA Science Inventory

    The visuals, part of a thermodynamic evaluation of fluorinated ethers, ethanes, and propanes as alternative refrigerants, are a useful tool in comparing new chemicals to existing refrigerants in vapor compression cycles. hey present the required suction superheat and the performa...

  20. Hydrogen and Nitrogen Broadened Ethane and Propane Absorption Cross Sections

    NASA Astrophysics Data System (ADS)

    Hargreaves, Robert J.; Appadoo, Dominique; Billinghurst, Brant E.; Bernath, Peter F.

    2015-06-01

    High-resolution infrared absorption cross sections are presented for the ν9 band of ethane (C2H6) at 823 cm-1. These cross sections make use of spectra recorded at the Australian Synchrotron using a Fourier transform infrared spectrometer with maximum resolution of 0.00096 cm-1. The spectra have been recorded at 150, 120 and 90 K for hydrogen and nitrogen broadened C2H6. They cover appropriate temperatures, pressures and broadening gases associated with the atmospheres of the Outer Planets and Titan, and will improve atmospheric retrievals. The THz/Far-IR beamline at the Australian Synchrotron is unique in combining a high-resolution Fourier transform spectrometer with an 'enclosive flow cooling' (EFC) cell designed to study molecules at low temperatures. The EFC cell is advantageous at temperatures for which the vapor pressure is very low, such as C2H6 at 90 K. Hydrogen broadened absorption cross sections of propane between 700 and 1200 cm-1 will also be presented based on spectra obtained at the Canadian Light Source.

  1. METHANE GAS STABILIZES SUPERCOOLED ETHANE DROPLETS IN TITAN'S CLOUDS

    SciTech Connect

    Wang, Chia C.; Lang, E. Kathrin; Signorell, Ruth

    2010-03-20

    Strong evidence for ethane clouds in various regions of Titan's atmosphere has recently been found. Ethane is usually assumed to exist as ice particles in these clouds, although the possible role of liquid and supercooled liquid ethane droplets has been recognized. Here, we report on infrared spectroscopic measurements of ethane aerosols performed in the laboratory under conditions mimicking Titan's lower atmosphere. The results clearly show that liquid ethane droplets are significantly stabilized by methane gas which is ubiquitous in Titan's nitrogen atmosphere-a phenomenon that does not have a counterpart for water droplets in Earth's atmosphere. Our data imply that supercooled ethane droplets are much more abundant in Titan's clouds than previously anticipated. Possibly, these liquid droplets are even more important for cloud processes and the formation of lakes than ethane ice particles.

  2. 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.

  3. Laboratory studies of methane nucleation on ethane: Application to Titan's clouds

    NASA Astrophysics Data System (ADS)

    Curtis, D. B.; Toon, OB; Tolbert, M. A.; McKay, C. P.; Khare, B. N.

    2003-05-01

    Titan's unusually thick atmosphere is composed mainly of nitrogen with a few percent methane and several gas phase species. The most abundant of these gas phase species is ethane, thought to be present at amounts of approximately 20 parts per million, while HCN, ethylene, propane, and many other species are also produced. Complex photochemistry in Titan's upper atmosphere produces a solid haze, which is thought to settle towards the surface. As the haze particles settle, it is likely that they become coated with ethane in Titan's lower stratosphere. Near Titan's tropopause, methane is saturated with respect to nucleation and could condense to form clouds. However, reanalysis of the Voyager I and II data suggests that the methane does not condense, but becomes supersaturated up to a saturation ratio of 1.5. In contrast, recent Earth-based observations indicate that methane clouds are indeed present in Titan's atmosphere. In order to elucidate Titan's cloud formation mechanism, we have made laboratory measurements of methane nucleation onto a film of solid ethane at approximately 45 K using a vacuum chamber apparatus. We find that a saturation ratio of S = 1.10 is required for methane to nucleate onto ethane, indicating that cloud formation onto coated haze particles is relatively easy and that large areas of supersaturation are not likely. Ongoing studies will measure the saturation ratio required for methane nucleation onto laboratory-produced model haze particles and films of various hydrocarbons and nitriles. This work was funded by the NASA Astrobiology Institute. DBC was supported by a NASA GSRP Fellowship through NASA Ames Research Center.

  4. 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

    2015-07-01

    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. PMID:26148554

  5. Molecular jet study of the solvation of toluene by methane, ethane, and propanea)

    NASA Astrophysics Data System (ADS)

    Schauer, Mark; Law, K. S.; Bernstein, E. R.

    1985-01-01

    Two color time of flight mass spectroscopy studies of toluene solvated by methane, ethane, and propane in a supersonic molecular jet have been carried out. This work is quite similar to the studies in the preceding paper on benzene. The conclusions and finding in the benzene investigation are strengthened and elaborated. The comparison of calculations and experiments has yielded information on binding enegy, geometry, and spectral shift. A strong correlation is found between observed cluster transition intensity and cluster nucleation processes and a tentative nucleation scheme for the molecular jet formation of solute-solvent clusters is presented.

  6. Methane and ethane at high pressures: structure and stability

    NASA Astrophysics Data System (ADS)

    Goncharov, A.; Stavrou, E.; Lobanov, S.; Oganov, A. R.; Chanyshev, A.; Litasov, K.; Konopkova, Z.; Prakapenka, V.

    2013-12-01

    Methane is one of the most abundant hydrocarbon molecules in the universe and is expected to be a significant part of the icy giant planets (Uranus and Neptune) and their satellites. Ethane is one of the most predictable products of chemical reactivity of methane at extreme pressures and temperatures. In spite of numerous experimental and theoretical studies, the structure and relative stability of these materials even at room temperature remains controversial. We have performed a combined experimental, using x-ray diffraction and Raman spectroscopy, and theoretical, using the ab-initio evolutionary algorithm, study of both methane and ethane up at high pressures up to 120 GPa at 300 K. In the case of methane we have successfully solved the structure of phase B by determining the space group and the positional parameters of carbon atoms, and by completing these results for the hydrogen positions using the theoretical calculations. The general structural behavior under pressure and the relation between phase B and phases A and pre-B will be also discussed. For ethane we have determined the crystallization point, for room temperature, at 1.7 GPa and also the low pressure crystal structure (Phase I). This crystal structure is orientationally disordered (plastic phase) and deviates from the known crystal structures for ethane at low temperatures. Moreover, a pressure induced phase transition has been indentified, for the first time, at 18 GPa to a monoclinic phase II, the structure of which is solved based on a good agreement of the experimental results and theoretical predictions. We have determined the equations of state of methane and ethane, which provides a solid basis for the discussion of their relative stability at high pressures.

  7. Analysis of solvation structure and thermodynamics of ethane and propane in water by reference interaction site model theory using all-atom models

    NASA Astrophysics Data System (ADS)

    Cui, Qizhi; Smith, Vedene H.

    2001-08-01

    Following our previous paper on methane [Cui and Smith, J. Chem. Phys. 113, 10240 (2000)], we study the solvation structures and thermodynamics of ethane and propane in water at the infinite dilution limit by using the hypernetted chain closure reference interaction site model (HNC-RISM) theory with all-atom representations for solute molecules. At four thermodynamic states: temperature T=283.15, 298.15, 313.15, 328.15 K and the corresponding bulk water density ρ=0.9997, 0.9970, 0.9922, 0.9875 g cm-3, all the atomic solute-solvent radial distribution functions are obtained, and the corresponding running coordination numbers and the hydration free energies, energies, enthalpies, and entropies are calculated with the radial distribution functions as input. The hydration structures of ethane and propane are presented and analyzed at the atomic level in terms of the atomic solute-solvent radial distribution functions. With the optimized nonbonded potential parameters based on the CHARMM96 all-atom model for alkanes [Yin and Mackerell, J. Comput. Chem. 19, 334 (1998)], the ethane and propane hydration thermodynamic properties predicted by the HNC-RISM theory are improved in the specified temperature range (10-55 °C).

  8. Elastic properties of methane-propane mixed gas hydrate under high pressure

    NASA Astrophysics Data System (ADS)

    Miwa, Shinya; Kanou, Masaki; Kume, Tetsuji; Sasaki, Shigeo

    2013-06-01

    Methane hydrate (MH) is widely observed in Earth's environment such as permafrost and deep sea floors. At low temperature and low pressure conditions, pure MH crystallizes a cubic structure I (sI) which consists of hydrogen-bonded two small and six medium water cages which enclathrate methane molecules as guests. However, actual MH in deep sea deposits contains not only methane molecules but also ethane and propane molecules. Therefore, the estimation of elastic properties and mechanical stability for both sI and structure II (sII) are required for the safe extraction of methane gas from the deep sea floors. The purpose of this study is to determine the elastic properties of methane-propane mixed gas hydrate (MPH) with sII by applying the high-pressure Brillouin spectroscopy to a single crystal of MPH-sII grown in a diamond anvil cell. The obtained elastic constant C11 of MPH-sII showing independent of pressure is obviously different from that of pure MH-sI. On the other hand, the C12 and C44 are similar to MH-sI. The present results suggest that a variety of gas hydrates have the individual elastic properties and stability depending on the gas hydrate structures.

  9. Accurate values of some thermodynamic properties for carbon dioxide, ethane, propane, and some binary mixtures.

    PubMed

    Velasco, Inmaculada; Rivas, Clara; Martínez-López, José F; Blanco, Sofía T; Otín, Santos; Artal, Manuela

    2011-06-30

    Quasicontinuous PρT data of CO(2), ethane, propane, and the [CO(2) + ethane] mixture have been determined along subcritical, critical, and supercritical regions. These data have been used to develop the optimal experimental method and to determine the precision of the results obtained when using an Anton Paar DMA HPM vibrating-tube densimeter. A comparison with data from reference EoS and other authors confirm the quality of our experimental setup, its calibration, and testing. For pure compounds, the value of the mean relative deviation is MRD(ρ) = 0.05% for the liquid phase and for the extended critical and supercritical region. For binary mixtures the mean relative deviation is MRD(ρ) = 0.70% in the range up to 20 MPa and MRD(ρ) = 0.20% in the range up to 70 MPa. The number of experimental points measured and their just quality have enable us to determine some derivated properties with satisfactory precision; isothermal compressibilities, κ(T), have been calculated for CO(2) and ethane (MRD(κ(T)) = 1.5%), isobaric expasion coefficients, α(P), and internal pressures, π(i), for CO(2) (MRD(α(P)) = 5% and MRD(π(i)) = 7%) and ethane (MRD(α(P)) = 7.5% and MRD(π(i)) = 8%). An in-depth discussion is presented on the behavior of the properties obtained along subcritical, critical, and supercritical regions. In addition, PuT values have been determined for water and compressed ethane from 273.19 to 463.26 K up to pressures of 190.0 MPa, using a device based on a 5 MHz pulsed ultrasonic system (MRD(u) = 0.1%). With these data we have calibrated the apparatus and have verified the adequacy of the operation with normal liquids as well as with some compressed gases. From density and speed of sound data of ethane, isentropic compressibilities, κ(s), have been obtained, and from these and our values for κ(T) and α(P), isobaric heat capacities, C(p), have been calculated with MRD(C(p)) = 3%, wich is within that of the EoS. PMID:21639086

  10. 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

  11. Solubility of methane and ethane in aqueous solutions of methydiethanolamine

    SciTech Connect

    Jou, F.Y.; Mather, A.E.; Otto, F.D.; Carroll, J.J.

    1998-09-01

    Data are presented for the solubility of methane and of ethane in a 3 kmol/m{sup 3} (34.7 mass %) solution of methyldiethanolamine. Temperatures in this study ranged from 25 to 130 C and pressures to 13 MPa. The data were incorporated into a rigorous thermodynamic model that has been applied to other similar systems. The model is a combined Raoult`s law-Henry`s law approach. The solubilities in the alkanolamine solution are correlated in terms of the salting-in ratio, the ratio of the mole fraction solubility in the amine solution to that in pure water.

  12. Oxidative dehydrogenation of ethane and propane over Ca-Co-P catalysts

    NASA Astrophysics Data System (ADS)

    Aaddane, A.; Kacimi, M.; Ziyad, M.

    2005-03-01

    Different compositions of calcium-cobalt phosphate Ca{3-x}Cox(PO{4})2 (0≤ x≤ 3) were synthesized by the precipitation method. The X-ray diffraction patterns showed that in the range 0 ≤x≤0.3 the solid displays a whitlockite-type structure which belongs to rhombohedral symmetry with the space group R3c (Z = 6). U.V-visible investigations showed that Co2+ ions occupy the M(5) sites of the phosphate. The same technique revealed that all cobalt cations exist under the +II oxidation state. Pure tricalcium phosphate β -Ca{3}(PO{4})2 was found inactive in the ODH reactions of ethane and propane. An increase of Co2+ concentration in the catalysts improved the performances.

  13. 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.

  14. 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.

  15. Long-term trends in global trace gas emissions: CH4, ethane, propane, ethyne, C2Cl4, CHCl3

    NASA Astrophysics Data System (ADS)

    Simpson, I. J.; Meinardi, S.; Sulbaek Andersen, M.; Blake, N. J.; Rowland, F. S.; Blake, D. R.

    2011-12-01

    The University of California, Irvine (UC-Irvine) has monitored global atmospheric trace gas mixing ratios since 1978 using ground-based canister measurements in the remote Pacific basin (71N to 47S). The measured gases include methane (CH4), C2-C4 alkanes, ethyne, C1-C3 alkyl nitrates, CFCs, CH3CCl3, CCl4 and H-1211. Long-term records of several of these gases are unique to the UC-Irvine global monitoring network, and here we present our research highlights and inferred global trace gas emission trends. Despite a long-term decline in its global growth rate, the global CH4 mixing ratio has increased by 9% over the past 25 years, from 1647.7 ± 0.6 ppbv in 1985 to 1792.4 ± 0.7 ppbv in 2010, representing a global emission increase of ~48 Tg yr-1 assuming constant global OH levels. Over the same time, the global mixing ratio of ethane has declined by 21%, from 791 ± 19 pptv in 1986 to 625 ± 12 pptv in 2010, or a global emission decrease of ~3.4 Tg yr-1. The global trends of CH4 growth and ethane mixing ratio have shown a remarkably strong correlation in the past 25 years. The long-term global ethane decline has also been accompanied by simultaneous decreases in global levels of propane and the butanes since 1996. This is consistent with a long-term change in a source common to all four compounds, likely a decline in evaporative emissions from the oil and natural gas industry. The combustion tracer ethyne has also shown an 11% decline between 1996 and 2008, most likely related to improved controls on vehicle emissions despite an expanding global vehicle fleet. Global levels of the anthropogenic tracer and CFC-113 precursor tetrachloroethene (C2Cl4) have declined by 60% since 1989, to 2.5 ± 0.2 pptv (or 185 Gg yr-1) in 2009 (Fig. 1). In contrast, global levels of the industrial solvent chloroform (CHCl3) have increased by almost 20% since the late 1990s, from 9.0 ± 0.3 pptv in 1997 to 10.7 ± 0.4 pptv in 2008 (Fig. 1). These results highlight major temporal shifts

  16. 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.

  17. 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. PMID:22914166

  18. 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

    2011-08-11

    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. PMID:21833087

  19. 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.

  20. 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.

  1. 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.

  2. 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...

  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

  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. 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).

  6. 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.

  7. 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

  8. 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.

  9. 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

  10. 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. PMID:24945600

  11. 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.

  12. 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.

  13. Modeling of methane and ethane hydrate formation kinetics based on non-equilibrium thermodynamics

    NASA Astrophysics Data System (ADS)

    Mottahedin, Mona; Varaminian, Farshad; Mafakheri, Kaveh

    2011-05-01

    In this study, experimental data of the kinetics of methane and ethane hydrate formation at constant volume were collected. The experiments were carried out in a batch reactor at different temperatures and pressures. The property of chemical affinity was used in the modeling of hydrate formation rate in a constant volume process. In this model a macroscopic driving force was defined which only needed the initial (experimental condition, temperature, and pressure) and final conditions (equilibrium conditions); thus, this model did not have the limitations of microscopic models, such as heat and mass transfer coefficients or population of particles, which may differ for each experiment. The experiments were carried out at temperatures 273, 274, 275.5, and 276 K for methane and 272, 273, 274, and 275 K for ethane with different initial pressures. The parameters of the model, Ar and tK , were obtained for each experiment, and the results show that the parameter of for each gas has a constant value. Subsequently, parameters of the model were used to predict experimental data and the variation of pressures with time. The results indicated that this model can well predict constant volume experimental data for crystals I hydrate former.

  14. 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. PMID:25760799

  15. Absorption cross-section measurements of methane, ethane, ethylene and methanol at high temperatures

    NASA Astrophysics Data System (ADS)

    Alrefae, Majed; Es-sebbar, Et-touhami; Farooq, Aamir

    2014-09-01

    Mid-IR absorption cross-sections are measured for methane, ethane, ethylene and methanol over 2800-3400 cm-1 (2.9-3.6 μm) spectral region. Measurements are carried out using a Fourier-Transform-Infrared (FTIR) spectrometer with temperatures ranging 296-1100 K and pressures near atmospheric. As temperature increases, the peak cross-sections decrease but the wings of the bands increase as higher rotational lines appear. Integrated band intensity is also calculated over the measured spectral region and is found to be a very weak function of temperature. The absorption cross-sections of the relatively small fuels studied here show dependence on the bath gas. This effect is investigated by studying the variation of absorption cross-sections at 3.392 μm using a HeNe laser in mixtures of fuel and nitrogen, argon, or helium. Mixtures of fuel with He have the highest value of absorption cross-sections followed by Ar and N2. Molecules with narrow absorption lines, such as methane and methanol, show strong dependence on bath gas than molecules with relatively broader absorption features i.e. ethane and ethylene.

  16. 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.

  17. Hydrate decomposition conditions in the system hydrogen sulfide-methane, and propane

    SciTech Connect

    Schroeter, J.P.; Kobayashi, R.; Hildebrand, H.A.

    1982-12-01

    Experimental hydrate decomposition conditions are presented for 3 different H/sub 2/S-containing mixtures in the temperature region 0 C to 30 C. The 3 mixtures investigated were 4% H/sub 2/S, 7% propane, 89% methane; 12% H/sub 2/S, 7% propane, 81% methane; and 30% H/sub 2/S, 7% propane, 63% methane. Hydrate decomposition pressures and temperatures were obtained for each of these mixtures by observation of the pressure-temperature hysteresis curves associated with formation and decomposition of the hydrate crystals. A repeatable decomposition point was observed in every case, and this was identified as the hydrate point. The results for the 4% H/sub 2/S mixture were used to adjust parameters in a computer model based on the Parrish and Prausnitz statistical thermodynamics method, coupled with the BWRS equation of state. After the parameter adjustment, the computer model predicted the behavior of the 12% H/sub 2/S and the 30% H/sub 2/S mixtures to within 2 C. Experimental data for the 3 mixtures are given.

  18. Adsorption equilibrium of binary methane/ethane mixtures in BPL activated carbon: isotherms and calorimetric heats of adsorption.

    PubMed

    He, Yufeng; Yun, Jeong-Ho; Seaton, Nigel A

    2004-08-01

    The adsorption of pure methane and ethane in BPL activated carbon has been measured at temperatures between 264 and 373 K and at pressures up to 3.3 MPa with a bench-scale high-pressure open-flow apparatus. The same apparatus was used to measure the adsorption of binary methane/ethane mixtures in BPL at 301.4 K and at pressures up to 2.6 MPa. Thermodynamic consistency tests demonstrate that the data are thermodynamically consistent. In contrast to two sets of data previously published, we found that the adsorption of binary methane/ethane in BPL behaves ideally (in the sense of obeying ideal adsorbed solution theory, IAST) throughout the pressure and gas-phase composition range studied. A Tian-Calvet type microcalorimeter was used to measure low-pressure isotherms, the isosteric heats of adsorption of pure methane and ethane in BPL activated carbon, and the individual heats of adsorption in binary mixtures, at 297 K and at pressures up to 100 kPa. The mixture heats of adsorption were consistent with IAST. PMID:15274571

  19. 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...

  20. 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

  1. Remote sensing of propane and methane by means of a differential absorption lidar by topographic reflection

    NASA Astrophysics Data System (ADS)

    Prasad, Narasimha S.; Geiger, Allen R.

    1996-04-01

    The development of a differential absorption lidar (DIAL) system in the mid-IR region for the detection and monitoring of light hydrocarbons is presented. Two lithium niobate optical parametric oscillators provided the signal and reference wavelengths. With the aid of a retroreflector, the system detected 0.63 ppm of propane and 0.05 ppm of methane in the atmosphere at a greater than 1 mile range in the controlled release tests. Subsequently, the system mapped a petroleum deposit in eastern New Mexico.

  2. 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

  3. 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.

  4. 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.

  5. 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.

    2011-10-05

    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 (Ω pilot ∼ 0.2-0.6 and Ω overall ∼ 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 Ω pilot (> 0.5), increasing Ω 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 Ω overall (at constant Ω 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.

  6. A mechanistic change results in 100 times faster CH functionalization for ethane versus methane by a homogeneous Pt catalyst.

    PubMed

    Konnick, Michael M; Bischof, Steven M; Yousufuddin, Muhammed; Hashiguchi, Brian G; Ess, Daniel H; Periana, Roy A

    2014-07-16

    The selective, oxidative functionalization of ethane, a significant component of shale gas, to products such as ethylene or ethanol at low temperatures and pressures remains a significant challenge. Herein we report that ethane is efficiently and selectively functionalized to the ethanol ester of H2SO4, ethyl bisulfate (EtOSO3H) as the initial product, with the Pt(II) "Periana-Catalytica" catalyst in 98% sulfuric acid. A subsequent organic reaction selectively generates isethionic acid bisulfate ester (HO3S-CH2-CH2-OSO3H, ITA). In contrast to the modest 3-5 times faster rate typically observed in electrophilic CH activation of higher alkanes, ethane CH functionalization was found to be ~100 times faster than that of methane. Experiment and quantum-mechanical calculations reveal that this unexpectedly large increase in rate is the result of a fundamentally different catalytic cycle in which ethane CH activation (and not platinum oxidation as for methane) is now turnover limiting. Facile Pt(II)-Et functionalization was determined to occur via a low energy β-hydride elimination pathway (which is not available for methane) to generate ethylene and a Pt(II)-hydride, which is then rapidly oxidized by H2SO4 to regenerate Pt(II)-X2. A rapid, non-Pt-catalyzed reaction of formed ethylene with the hot, concentrated H2SO4 solvent cleanly generate EtOSO3H as the initial product, which further reacts with the H2SO4 solvent to generate ITA. PMID:24925375

  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. 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

  9. 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.

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

    PubMed

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

    2013-09-14

    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 η(2) 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 η(2) and an η(1) 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. PMID:24050357

  11. 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.

  12. Unsaturated hydrocarbons in the lakes of Titan: Benzene solubility in liquid ethane and methane at cryogenic temperatures

    NASA Astrophysics Data System (ADS)

    Diez-y-Riega, Helena; Camejo, David; Rodriguez, Abraham E.; Manzanares, Carlos E.

    2014-09-01

    The solubility of benzene in liquid ethane has been measured using ultraviolet absorption. Spectra were recorded in the 200-1000 nm range. The secondary absorption band (1B2u) of benzene in the region 230-260 nm was recorded to determine the solubility of the sample. Ethane does not absorb in the benzene UV region but absorption bands are observed at 908 nm, 745 nm, and 634 nm corresponding to C-H vibrational overtone transitions of liquid ethane with Δυ=4, 5 and 6, respectively. Spectra were obtained at several concentrations and temperatures. The solubilities are: (26±6) ppm at 94 K, (39±6) ppm at 102 K, (48±8) ppm at 111 K, (72±10) ppm at 132 K, and (170±38) ppm at 162 K. With the solubility obtained at each temperature the enthalpy and entropy of solution were calculated from the experimental data. The spectra of solutions of benzene in liquid methane have been obtained to determine the solubility at 97 K. Thermodynamic parameters and solubility data from experimental measurements are important for more realistic simulations of the chemical composition of the lakes of Titan.

  13. 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.

  14. 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.

  15. Radiolytic oxidation of propane. [Gamma radiation

    SciTech Connect

    Gupta, A.K.

    1983-01-01

    The Co-60 ..gamma.. radiolysis of gaseous propane was studied at 100 torr pressure and 25/sup 0/C, both pure and with 10% added oxygen. In the unscavenged system the major products and their G-values were hydrogen, 4.99; methane, 1.30; ethane, 1.95; iso-butane, 0.61; n-butane, 0.25; i-pentane, 0.42; n-pentane, 0.14; and hexanes, 0.89. Minor products were heptanes, 0.082; octanes, 0.067; nonanes, 0.088, and decanes, 0.033. Small yields of ethylene and propylene were also observed. Yields in the presence of 10% added oxygen were hydrogen, 1.87; methane, 0.83; and ethane, 1.22. Higher saturated hydrocarbons were eliminated. The reaction scheme for formation of major products was examined using computer modeling based on 24 reactions in the unscavenged system and 28 reactions in the propane-oxygen system. Yields could be brought into agreement with the data within experimental error in nearly all cases, but in the pure propane system it was necessary to assume that the molecular hydrogen yield was accompanied by the deposition of polymer on the vessel wall.

  16. 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

  17. MICROBIAL REMOVAL OF HALOGENATED METHANES, ETHANES, AND ETHYLENES IN AN AEROBIC SOIL EXPOSED TO METHANE. (JOURNAL VERSION)

    EPA Science Inventory

    Contamination of ground water with halogenated aliphatic hydrocarbons threatens the source of drinking water. To study microbial processes that may enhance the removal of these compounds, Lincoln fine sand was exposed to an atmosphere containing methane (4%) to enrich microorgani...

  18. 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.

  19. TECHNICAL GUIDANCE FOR THE NATURAL ATTENUATION INDICATORS: METHANE, ETHANE, AND ETHENE

    EPA Science Inventory

    To monitor natural attenuation, the following procedure is used to analyze ground water samples. An inert gas is injected into the VOA or serum vial containing the water sample to create headspace. After equilibrium, the headspace is analyzed for the target gases, methane, eth...

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

    PubMed

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

    2013-10-01

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

  1. Phase behavior and 13C NMR spectroscopic analysis of the mixed methane + ethane + propane hydrates in mesoporous silica gels.

    PubMed

    Lee, Seungmin; Cha, Inuk; Seo, Yongwon

    2010-11-25

    In this study, the phase behavior and quantitative determination of hydrate composition and cage occupancy for the mixed CH(4) + C(2)H(6) + C(3)H(8) hydrates were closely investigated through the experimental measurement of three-phase hydrate (H)-water-rich liquid (L(W))-vapor (V) equilibria and (13)C NMR spectra. To examine the effect of pore size and salinity, we measured hydrate phase equilibria for the quaternary CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) + water mixtures in silica gel pores of nominal diameters of 6.0, 15.0, and 30.0 nm and for the quinary CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) + NaCl + water mixtures of two different NaCl concentrations (3 and 10 wt %) in silica gel pores of a nominal 30.0 nm diameter. The value of hydrate-water interfacial tension for the CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) hydrate was found to be 47 ± 4 mJ/m(2) from the relation of the dissociation temperature depression with the pore size of silica gels at a given pressure. At a specified temperature, three-phase H-L(W)-V equilibrium curves of pore hydrates were shifted to higher pressure regions depending on pore sizes and NaCl concentrations. From the cage-dependent (13)C NMR chemical shifts of enclathrated guest molecules, the mixed CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) gas hydrate was confirmed to be structure II. The cage occupancies of each guest molecule and the hydration number of the mixed gas hydrates were also estimated from the (13)C NMR spectra. PMID:20964277

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  3. Synthesis of ethylene and ethane by partial oxidation of methane over lithium-doped magnesium oxide

    NASA Astrophysics Data System (ADS)

    Ito, Tomoyasu; Lunsford, Jack H.

    1985-04-01

    The partial oxidation of methane into more useful chemicals such as methanol, ethylene and benzene has been investigated extensively, although yields for these products have been poor1-4. Moreover, in several of these processes the required oxidant is N2O rather than O2. Recent work5 in our laboratory has demonstrated that lithium-doped magnesium oxide (Li/MgO) in the presence of O2 has high activity for abstracting H from CH4 to form .CH3 radicals. This suggests that C2H6 and C2H4 (C2 compounds) are produced by a coupling between two gaseous .CH3 radicals formed on this catalyst. We report here our success in converting CH4 to C2 compounds in high yields in conventional catalytic conditions.

  4. 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.

  5. 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.

  6. In Silico Design of Highly Selective Mo-V-Te-Nb-O Mixed Metal Oxide Catalysts for Ammoxidation and Oxidative Dehydrogenation of Propane and Ethane.

    PubMed

    Cheng, Mu-Jeng; Goddard, William A

    2015-10-21

    We used density functional theory quantum mechanics with periodic boundary conditions to determine the atomistic mechanism underlying catalytic activation of propane by the M1 phase of Mo-V-Nb-Te-O mixed metal oxides. We find that propane is activated by Te═O through our recently established reduction-coupled oxo activation mechanism. More importantly, we find that the C-H activation activity of Te═O is controlled by the distribution of nearby V atoms, leading to a range of activation barriers from 34 to 23 kcal/mol. On the basis of the new insight into this mechanism, we propose a synthesis strategy that we expect to form a much more selective single-phase Mo-V-Nb-Te-O catalyst. PMID:26423704

  7. Dynamic light scattering in sooting premixed atmospheric-pressure methane-, propane-, ethene-, and propene-oxygen flames

    SciTech Connect

    Lamprecht, A.; Eimer, W.; Kohse-Hoeinghaus, K.

    1999-07-01

    In a systematic investigation under well-defined flame conditions, dynamic light scattering (DLS) was applied to the determination of soot particle radii with the aim of examining the suitability of this technique for accurate soot particle sizing. In particular, flat premixed methane-, propane-, ethene-, and propene-oxygen flames at atmospheric pressure were investigated, and particle sizes were obtained as a function of stoichiometry and height above the burner surface. In combination with absorption measurements, soot volume fraction and particle number density were determined; also, the temperature was measured at each flame condition. In comparison to absorption techniques, attractive features of DLS are its independence of the particle refractive index and its insensitivity to fluorescence interference; also, it offers spatial resolution. In principle, additional information on the particle size distribution as well as on the global shape of the particles may be obtained from DLS experiments. This study is therefore an evaluation of the potential of DLS as a complement to other soot diagnostic techniques.

  8. Performance and Emissions Characteristics of Bio-Diesel (B100)-Ignited Methane and Propane Combustion in a Four Cylinder Turbocharged Compression Ignition Engine

    DOE PAGESBeta

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

    2011-10-05

    Different combustion strategies and fuel sources are needed to deal with increasing fuel efficiency demands and emission restrictions. One possible strategy is dual fueling using readily available resources. Propane and natural gas are readily available with the current infrastructure and biodiesel is growing in popularity as a renewable fuel. This paper presents experimental results from dual fuel combustion of methane (as a surrogate for natural gas) and propane as primary fuels with biodiesel pilots in a 1.9 liter, turbocharged, 4 cylinder diesel engine at 1800 rev/min. Experiments were performed with different percentage energy substitutions (PES) of propane and methane andmore » at different brake mean effective pressures (BMEP/bmep). Brake thermal efficiency (BTE) and emissions (NOx, HC, CO, CO2, O2 and smoke) were also measured. Maximum PES levels for B100-methane dual fuelling were limited to 70% at 2.5 bar bmep and 48% at 10 bar bmep, and corresponding values for B100-propane dual fuelling were 64% and 43%, respectively. Maximum PES was limited by misfire at 2.5 bar bmep and the onset of engine knock at 10 bar bmep. Dual fuel BTEs approached straight B100 values at 10 bar bmep while they were significantly lower than B100 values at 2.5 bar bmep. In general dual fuelling was beneficial in reducing NOx and smoke emissions by 33% and 50%, respectively from baseline B100 levels; however, both CO and THC emissions were significantly higher than baseline B100 levels at all PES and loads.« less

  9. Performance and Emissions Characteristics of Bio-Diesel (B100)-Ignited Methane and Propane Combustion in a Four Cylinder Turbocharged Compression Ignition Engine

    SciTech Connect

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

    2011-10-05

    Different combustion strategies and fuel sources are needed to deal with increasing fuel efficiency demands and emission restrictions. One possible strategy is dual fueling using readily available resources. Propane and natural gas are readily available with the current infrastructure and biodiesel is growing in popularity as a renewable fuel. This paper presents experimental results from dual fuel combustion of methane (as a surrogate for natural gas) and propane as primary fuels with biodiesel pilots in a 1.9 liter, turbocharged, 4 cylinder diesel engine at 1800 rev/min. Experiments were performed with different percentage energy substitutions (PES) of propane and methane and at different brake mean effective pressures (BMEP/bmep). Brake thermal efficiency (BTE) and emissions (NOx, HC, CO, CO2, O2 and smoke) were also measured. Maximum PES levels for B100-methane dual fuelling were limited to 70% at 2.5 bar bmep and 48% at 10 bar bmep, and corresponding values for B100-propane dual fuelling were 64% and 43%, respectively. Maximum PES was limited by misfire at 2.5 bar bmep and the onset of engine knock at 10 bar bmep. Dual fuel BTEs approached straight B100 values at 10 bar bmep while they were significantly lower than B100 values at 2.5 bar bmep. In general dual fuelling was beneficial in reducing NOx and smoke emissions by 33% and 50%, respectively from baseline B100 levels; however, both CO and THC emissions were significantly higher than baseline B100 levels at all PES and loads.

  10. 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.

  11. Determination of the carbon kinetic isotope effects on propane hydroxylation mediated by the methane monooxygenases from Methylococcus capsulatus (Bath) by using stable carbon isotopic analysis.

    PubMed

    Huang, Ded-Shih; Wu, Suh-Huey; Wang, Yane-Shih; Yu, Steve S-F; Chan, Sunney I

    2002-08-01

    Authentic propane with known position-specific carbon isotope composition at each carbon atom was subjected to hydroxylation by the particulate and soluble methane monooxygenase (pMMO and sMMO) from Methylococcus capsulatus (Bath), and the corresponding position-specific carbon isotope content was redetermined for the product 2-propanol. Neither the reaction mediated by pMMO nor that with sMMO showed an intermolecular (12)C/(13)C kinetic isotope effect effect on the propane hydroxylation at the secondary carbon; this indicates that there is little structural change at the carbon center attacked during formation of the transition state in the rate-determining step. This finding is in line with the concerted mechanism proposed for pMMO (Bath), and suggested for sMMO (Bath), namely, direct side-on insertion of an active "O" species across the C-H bond, as has been previously reported for singlet carbene insertion. PMID:12203974

  12. 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

  13. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1996-01-01

    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.

  15. 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. PMID:8650540

  16. 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.

  17. 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)

  18. 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.

  19. Mid-infrared dual-gas sensor for simultaneous detection of methane and ethane using a single continuous-wave interband cascade laser.

    PubMed

    Ye, Weilin; Li, Chunguang; Zheng, Chuantao; Sanchez, Nancy P; Gluszek, Aleksander K; Hudzikowski, Arkadiusz J; Dong, Lei; Griffin, Robert J; Tittel, Frank K

    2016-07-25

    A continuous-wave (CW) interband cascade laser (ICL) based mid-infrared sensor system was demonstrated for simultaneous detection of atmospheric methane (CH4) and ethane (C2H6). A 3.337 µm CW ICL with an emitting wavenumber range of 2996.0-3001.5 cm-1 was used to simultaneously target two absorption lines, C2H6 at 2996.88 cm-1 and CH4 at 2999.06 cm-1, respectively. The sensor performance was first evaluated for single-gas detection by only targeting the absorption line of one gas species. Allan deviations of 11.2 parts per billion in volume (ppbv) for CH4 and 1.86 ppbv for C2H6 with an averaging time of 3.4 s were achieved for the detection of these two gases. Dual-gas detection was realized by using a long-term scan signal to target both CH4 and C2H6 lines. The Allan deviations increased slightly to 17.4 ppbv for CH4 and 2.4 ppbv for C2H6 with an averaging time of 4.6 s due to laser temperature and power drift caused by long-term wavelength scanning. Measurements for both indoor and outdoor concentration changes of CH4 and C2H6 were conducted. The reported single ICL based dual-gas sensor system has the advantages of reduced size and cost compared to two separate sensor systems. PMID:27464149

  20. 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. PMID:26014851

  1. 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.

  2. 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.

  3. Ionization cross section data of nitrogen, methane, and propane for light ions and electrons and their suitability for use in track structure simulations

    NASA Astrophysics Data System (ADS)

    Bug, Marion U.; Gargioni, Elisabetta; Nettelbeck, Heidi; Baek, Woon Yong; Hilgers, Gerhard; Rosenfeld, Anatoly B.; Rabus, Hans

    2013-10-01

    Track structure Monte Carlo simulations are frequently applied in micro- and nanodosimetry to calculate the radiation transport in detail. The use of a well-validated set of cross section data in such simulation codes ensures accurate calculations of transport parameters, such as ionization yields. These cross section data are, however, scarce and often discrepant when measured by different groups. This work surveys literature data on ionization and charge-transfer cross sections of nitrogen, methane, and propane for electrons, protons, and helium particles, focusing on the energy range between 100 keV and 20 MeV. Based on the evaluated data, different models for the parametrization of the cross section data are implemented in the code ptra, developed for simulating proton and alpha particle transport in an ion-counting nanodosimeter. The suitability of the cross section data is investigated by comparing the calculated mean ionization cluster size and energy loss with experimental results in either nitrogen or propane. For protons, generally good agreement between measured and simulated data is found when the Rudd model is used in ptra. For alpha particles, however, a considerable influence of different parametrizations of cross sections for ionization and charge transfer is observed. The ptra code using the charge-transfer data is, nevertheless, successfully benchmarked by the experimental data for the calculation of nanodosimetric quantities, but remaining discrepancies still have to be further investigated (up to 13% lower energy loss and 19% lower mean ionization cluster size than in the experiment). A continuation of this work should investigate data for the energy loss per interaction as well as differential cross section data of nitrogen and propane. Interpolation models for ionization and charge-transfer data are proposed. The Barkas model, frequently used for a determination of the effective charge in the ionization cross section, significantly

  4. Ionization cross section data of nitrogen, methane, and propane for light ions and electrons and their suitability for use in track structure simulations.

    PubMed

    Bug, Marion U; Gargioni, Elisabetta; Nettelbeck, Heidi; Baek, Woon Yong; Hilgers, Gerhard; Rosenfeld, Anatoly B; Rabus, Hans

    2013-10-01

    Track structure Monte Carlo simulations are frequently applied in micro- and nanodosimetry to calculate the radiation transport in detail. The use of a well-validated set of cross section data in such simulation codes ensures accurate calculations of transport parameters, such as ionization yields. These cross section data are, however, scarce and often discrepant when measured by different groups. This work surveys literature data on ionization and charge-transfer cross sections of nitrogen, methane, and propane for electrons, protons, and helium particles, focusing on the energy range between 100 keV and 20 MeV. Based on the evaluated data, different models for the parametrization of the cross section data are implemented in the code ptra, developed for simulating proton and alpha particle transport in an ion-counting nanodosimeter. The suitability of the cross section data is investigated by comparing the calculated mean ionization cluster size and energy loss with experimental results in either nitrogen or propane. For protons, generally good agreement between measured and simulated data is found when the Rudd model is used in ptra. For alpha particles, however, a considerable influence of different parametrizations of cross sections for ionization and charge transfer is observed. The ptra code using the charge-transfer data is, nevertheless, successfully benchmarked by the experimental data for the calculation of nanodosimetric quantities, but remaining discrepancies still have to be further investigated (up to 13% lower energy loss and 19% lower mean ionization cluster size than in the experiment). A continuation of this work should investigate data for the energy loss per interaction as well as differential cross section data of nitrogen and propane. Interpolation models for ionization and charge-transfer data are proposed. The Barkas model, frequently used for a determination of the effective charge in the ionization cross section, significantly

  5. 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.

  6. 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. PMID:24372450

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. Modification of Encapsulation Pressure of Reverse Micelles in Liquid Ethane

    PubMed Central

    Peterson, Ronald W.; Nucci, Nathaniel V.; Wand, A. Joshua

    2011-01-01

    Encapsulation of within reverse micelles dissolved in low viscosity fluids offers a potential solution to the slow tumbling problem presented by large soluble macromolecules to solution NMR spectroscopy. The reduction in effective macromolecular tumbling is directly dependent upon the viscosity of the solvent. Liquid ethane is of sufficiently low viscosity at pressures below 5,000 p.s.i. to offer a significant advantage. Unfortunately, the viscosity of liquid ethane shows appreciable pressure dependence. Reverse micelle encapsulation in liquid ethane often requires significantly higher pressures, which obviates the potential advantages offered by liquid ethane over liquid propane. Addition of co-surfactants or co-solvents can be used to manipulate the minimum pressure required to obtain stable, well-behaved solutions of reverse micelles prepared in liquid ethane. A library of potential additives is examined and several candidates suitable for use with encapsulated proteins are described. PMID:21764613

  12. Modification of encapsulation pressure of reverse micelles in liquid ethane.

    PubMed

    Peterson, Ronald W; Nucci, Nathaniel V; Wand, A Joshua

    2011-09-01

    Encapsulation within reverse micelles dissolved in low viscosity fluids offers a potential solution to the slow tumbling problem presented by large soluble macromolecules to solution NMR spectroscopy. The reduction in effective macromolecular tumbling is directly dependent upon the viscosity of the solvent. Liquid ethane is of sufficiently low viscosity at pressures below 5000 psi to offer a significant advantage. Unfortunately, the viscosity of liquid ethane shows appreciable pressure dependence. Reverse micelle encapsulation in liquid ethane often requires significantly higher pressures, which obviates the potential advantages offered by liquid ethane over liquid propane. Addition of co-surfactants or co-solvents can be used to manipulate the minimum pressure required to obtain stable, well-behaved solutions of reverse micelles prepared in liquid ethane. A library of potential additives is examined and several candidates suitable for use with encapsulated proteins are described. PMID:21764613

  13. The fate of ethane in Titan's hydrocarbon lakes and seas

    NASA Astrophysics Data System (ADS)

    Mousis, Olivier; Lunine, Jonathan I.; Hayes, Alexander G.; Hofgartner, Jason D.

    2016-05-01

    Ethane is expected to be the dominant photochemical product on Titan's surface and, in the absence of a process that sequesters it from exposed surface reservoirs, a major constituent of its lakes and seas. Absorption of Cassini's 2.2 cm radar by Ligeia Mare however suggests that this north polar sea is dominated by methane. In order to explain this apparent ethane deficiency, we explore the possibility that Ligeia Mare is the visible part of an alkanofer that interacted with an underlying clathrate layer and investigate the influence of this interaction on an assumed initial ethane-methane mixture in the liquid phase. We find that progressive liquid entrapment in clathrate allows the surface liquid reservoir to become methane-dominated for any initial ethane mole fraction below 0.75. If interactions between alkanofers and clathrates are common on Titan, this should lead to the emergence of many methane-dominated seas or lakes.

  14. Interpretation of the ethane deficiency in Ligeia Mare

    NASA Astrophysics Data System (ADS)

    Mousis, O.; Lunine, J. I.; Hayes, A. G.; Hofgartner, J.

    2015-10-01

    Absorption of Cassini's 2.2 cm radar by Ligeia Mare suggests that this north polar sea is dominated by methane. In order to explain this apparent ethane deficiency, we explore the possibility that Ligeia Mare is the visible part of an alkanofer that interacted with an underlying clathrate layer and investigate the influence of this inter action on an assumed initial ethane- methane mixture in the liquid phase.

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

    PubMed

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

    2016-01-01

    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

  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. 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

  18. 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

  19. Trends and Climatology of Northern Hemisphere Non-Methane Hydrocarbon Emissions

    NASA Astrophysics Data System (ADS)

    Helmig, Detlev; Petrenko, Vasilli; Martinerie, Patricia; Witrant, Emmanuel; Roeckmann, Thomas; Hueber, Jacques; Sturges, William; Baker, Angela; Blunier, Thomas; Etheridge, David; Rubino, Mauro; Tans, Pieter; Zuiderweg, Adriaan; Holzinger, Rupert

    2013-04-01

    Atmospheric non-methane hydrocarbon (NMHC) data can yield valuable insight into anthropogenic and biogenic emissions into the atmosphere. For instance, recent research has pointed out a tight linkage of the atmospheric concentration of the NMHC ethane to the atmospheric growth rate of methane, and this relationship has been used to infer global changes in methane emission sources. Furthermore, NMHC play a pivotal role in photochemical production of ozone in the troposphere. We reconstructed the 1950-2010 Northern Hemisphere concentrations of the NMHC ethane, propane, i-butane, n-butane, i-pentane, and n-pentane using 1. measurements of air samples extracted from three boreholes in the firn layer at North Greenland Eemian Ice Drilling (NEEM) project site; 2. a firn air transport model that allows reconstructing atmospheric concentrations of trace gas from borehole measurements; and 3. eight years of data from ambient NMHC monitoring at five Arctic sites within the NOAA Global Monitoring Division Cooperative Air Sampling Network. Results indicate that these C2-C5 NMHC increased by ~ 40-120% after 1950, then peaked between 1965-1985, and have since dramatically decreased to near-1950 levels. Different peak times of ethane versus C3-C5 NMHC suggest that different processes and emission mitigation measures contributed to the decline in these NMHC. NMHC mole fraction trends, observed changes in the ratio of selected NMHC pairs, and NMHC/carbon monoxide ratios are used to infer post-1950 changes in fossil fuel sources and tropospheric ozone production.

  20. 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.

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

    PubMed

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

    2014-08-25

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

  2. Decomposition of ethane and its reaction with CO{sub 2} over Rh/ZSM-5 catalyst

    SciTech Connect

    Solymosi, F.; Szoke, A.; Ovari, L.

    1999-09-10

    The interaction of ethane with Rh/ZSM-5 and its decomposition and reactions with CO{sub 2} on Rh/ZSM-5 have been investigated. Methods used were Fourier-transform infrared spectroscopy and temperature-programmed desorption and reaction (TPD and TPR). The decomposition of ethane and its reaction with CO{sub 2} have been studied in a fixed-bed continuous-flow reactor. IR measurements showed that ethane interacted strongly with the highly dispersed Rh above 206 K and gave rise to the formation of ethylidyne surface species very likely through the transient formation of ethylene. At 523--573 K, the decomposition of ethane produces hydrogen, methane, and propane. Above 623 K ethylene became the main product, but benzene and toluene were also detected. Independent of the temperature, the rate of the decomposition decayed after 5--10 min to a very low level (1--2% conversion), but it did not cease completely even after several hours (673 K). The reactivities of surface carbon formed at different temperatures toward H{sub 2}, O{sub 2}, and CO{sub 2} have been examined. Carbon exhibited the highest reactivity with O{sub 2} and less reactivity with CO{sub 2}. The peak temperatures of its reaction in TPR shifted to a higher temperature with the temperature of its production in all the three cases. Carbon formed at 773 K in the ethane decomposition reacted with CO{sub 2} at maximum rate at 973 K. The reaction between C{sub 2}H{sub 6} and CO{sub 2} occurred rapidly above 700 K to give mainly H{sub 2} and CO with a ratio of 0.3--0.6. In contrast with the CH{sub 4} + CO{sub 2} reaction on the same catalyst, a significant deactivation of the catalyst occurred at the stoichiometric CO{sub 2}/C{sup 2}H{sub 6} ratio. This feature is attributed to the low reactivity of hydrocarbon fragments formed by the decomposition of ethane compared to those produced by CH{sub 4} dissociation. Deactivation can be decreased or almost ceased by using a large excess of CO{sub 2}.

  3. 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.

  4. Laser-induced fluorescence monitoring of higher alkanes production from pure methane using non-oxidative processes.

    PubMed

    Gondal, M A; Dastgeer, A; Yamani, Zain H; Arfaj, A; Ali, M A

    2003-02-01

    A novel method for the study of non-oxidative methane conversion process into higher value hydrocarbon and hydrogen has been invented. The method involves the multiphoton dissociation of methane under the influence of the high power pulsed ultraviolet laser radiation at 355 nm wavelength at room temperature (293 K) and standard pressure (1 atm). The products generated as a result of methane conversion like ethane, ethylene, propane, propylene and isobutane are analyzed using an online gas chromatograph while the other species such as CH, CH(2) and C(2)H(2), atomic and molecular hydrogen are characterized by real-time laser-induced fluorescence technique for the first time. A typical 7% conversion of methane into ethane has been achieved using 80 mJ of laser irradiation at 355 nm. The important features of this method are that it is non-oxidative, does not require any catalyst, high temperatures or pressures, which is normally the case in conventional techniques for methane conversion. PMID:18968911

  5. 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.

  6. 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.

  7. 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

  8. 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. PMID:25489074

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

    PubMed

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

    2013-05-01

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

  10. Quantifying Emissions from the Eagle Ford Shale Using Ethane Enhancement

    NASA Astrophysics Data System (ADS)

    Roest, G. S.; Schade, G. W.

    2014-12-01

    Emissions from unconventional oil and natural gas exploration in the Eagle Ford Shale have been conjectured as a contributing factor to increasing ozone concentrations in the San Antonio Metropolitan Area, which is on track to be designated as a nonattainment area by the EPA. Primary species found in natural gas emissions are alkanes, with C3 and heavier alkanes acting as short-lived VOCs contributing to regional ozone formation. Methane emissions from the industry are also a forcing mechanism for climate change as methane is a potent greenhouse gas. Recent studies have highlighted a high variability and uncertainties in oil and natural gas emissions estimates in emissions inventories. Thus, accurately quantifying oil and natural gas emissions from the Eagle Ford Shale is necessary to assess the industry's impacts on climate forcing and regional air quality. We estimate oil and natural gas emissions in the Eagle Ford Shale using in situ ethane measurements along southwesterly trajectories from the Gulf of Mexico, dominantly during the summertime. Ethane enhancement within the drilling area is estimated by comparing ethane concentrations upwind of the shale, near the Texas coastline, to downwind measurements in the San Antonio Metropolitan Area, Odessa, and Amarillo. Upwind ethane observations indicate low background levels entering Texas in the Gulf of Mexico air masses. Significant ethane enhancement is observed between the coast and San Antonio, and is attributed to oil and natural gas operations due to the concurrent enhancements of heavier alkanes. Using typical boundary layer depths and presuming homogenous emissions across the Eagle Ford shale area, the observed ethane enhancements are used to extrapolate an estimate of oil and natural gas industry emissions in the Eagle Ford. As oil and natural gas production in the area is projected to grow rapidly over the coming years, the impacts of these emissions on regional air quality will need to be thoroughly

  11. 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

  12. 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. PMID:26476065

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. Origin and stability of a permafrost methane hydrate occurrence in the Canadian Shield

    NASA Astrophysics Data System (ADS)

    Stotler, Randy L.; Frape, Shaun K.; Ahonen, Lasse; Clark, Ian; Greene, Shane; Hobbs, Monique; Johnson, Elizabeth; Lemieux, Jean-Michel; Peltier, Richard; Pratt, Lisa; Ruskeeniemi, Timo; Sudicky, Ed; Tarasov, Lev

    2010-08-01

    Relatively little attention has been given to the stability of methane hydrates, formed during periods of past climate change, currently in areas of continuous permafrost. Although a large portion of the Canadian arctic is underlain by crystalline rocks, the occurrence, phase, and origin of alkanes in crystalline rocks under thick permafrost conditions (> 500 m) have not been reported. For the first time, composition and isotopic data for gases from a crystalline shield environment currently under permafrost conditions are presented. Gas and water samples were collected from exploration boreholes and seeps between 890 and 1130 m depths in the Lupin gold mine, Nunavut, Canada. Gases were methane-dominate (64-87%), with nitrogen (10-37%) the next largest component, and smaller amounts of ethane, propane, and carbon dioxide. Pressure and temperature measurements indicated gas hydrates were stable at the site prior to mining operations, a conclusion supported by noble gas and salinity determinations. Gas hydrate stability over the last 120 kyr glacial cycle was demonstrated by calculating transient subsurface pressure and temperature conditions utilizing the Memorial University/University of Toronto Glacial Systems Model (MUN/UofT GSM) and the Hydrogeosphere groundwater flow model. Model results also indicated glacial loading increased subsurface pressures, resulting in increased hydrate stability fields during glacial periods. Subglacial groundwater recharge would be limited by any significant formation of gas hydrates. Gas composition, combined with carbon and hydrogen isotopic determinations on methane (- 56 to - 42‰ VPDB and - 349 to - 181‰ VSMOW), carbon dioxide (- 55 to - 15‰ VPDB), ethane (- 37 to - 27‰ VPDB and - 330 to - 228‰ VSMOW), and propane (- 34 to - 27‰ VPDB and - 196 to - 172‰ VSMOW), indicated formation of natural gases by thermogenic processes, mixed with bacteriogenic gas, reasonable, given site geologic history. Methane hydrate

  18. Isolation of Two Novel Marine Ethylene-Assimilating Bacteria, Haliea Species ETY-M and ETY-NAG, Containing Particulate Methane Monooxygenase-like Genes

    PubMed Central

    Suzuki, Toshihiro; Nakamura, Takamichi; Fuse, Hiroyuki

    2012-01-01

    Two novel ethylene-assimilating bacteria, strains ETY-M and ETY-NAG, were isolated from seawater around Japan. The characteristics of both strains were investigated, and phylogenetic analyses of their 16S rRNA gene sequences showed that they belonged to the genus Haliea. In C1–4 gaseous hydrocarbons, both strains grew only on ethylene, but degraded ethane, propylene, and propane in addition to ethylene. Methane, n-butane, and i-butane were not utilized or degraded by either strain. Soluble methane monooxygenase-type genes, which are ubiquitous in alkene-assimilating bacteria for initial oxidation of alkenes, were not detected in these strains, although genes similar to particulate methane monooxygenases (pMMO)/ammonia monooxygenases (AMO) were observed. The phylogenetic tree of the deduced amino acid sequences formed a new clade near the monooxygenases of ethane-assimilating bacteria similar to other clades of pMMOs in type I, type II, and Verrucomicrobia methanotrophs and AMOs in alpha and beta proteobacteria. PMID:22307463

  19. 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

  20. 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

  1. 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.

  2. 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

    2010-10-01

    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. PMID:20847236

  3. 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.

  4. The ozone formation potential of 1-bromo-propane.

    PubMed

    Whitten, Gary Z; Cohen, Jonathan P; Myers, Thomas C; Carter, William P L

    2003-03-01

    1-Bromo-propane (1-BP) is a replacement for high-end chlorofluorocarbon (HCFC) solvents. Its reaction rate constant with the OH radical is, on a weight basis, significantly less than that of ethane. However, the overall smog formation chemistry of 1-BP appears to be very unusual compared with typical volatile organic compounds (VOCs) and relatively complex because of the presence of bromine. In smog chamber experiments, 1-BP initially shows a faster ozone build-up than what would be expected from ethane, but the secondary products containing bromine tend to destroy ozone such that 1-BP can have a net overall negative reactivity. Alternative sets of reactions are offered to explain this unusual behavior. Follow-up studies are suggested to resolve the chemistry. Using one set of bromine-related reactions in a photochemical grid model shows that 1-BP would be less reactive toward peak ozone formation than ethane with a trend toward even lower ozone impacts in the future. PMID:12661686

  5. 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.

  6. 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

  7. 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

  8. 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

  9. Significant Methane Emissions from Abandoned Oil and Gas wells in Northwest Pennsylvania

    NASA Astrophysics Data System (ADS)

    Kang, M.; Zhang, X.; Reid, M. C.; Kanno, C.; Celia, M. A.; Mauzerall, D. L.; Sun, K.; Miller, D. J.; Zondlo, M. A.; Chen, Y.; Onstott, T. C.

    2013-12-01

    Abandoned (no longer operated), Orphaned (abandoned and responsible party unavailable), and/or Lost (location unknown, cannot be confirmed, or not on record) (AOL) wells provide a potential pathway for subsurface migration, and emissions to the atmosphere, of methane and other volatile hydrocarbons. However, little is known about methane fluxes from AOL wells. Of the 12,000 abandoned and orphaned oil and gas wells on the Pennsylvania Department of Environmental Protection's (PA DEP) list, 36% are in McKean County. McKean County is home to the Bradford Oil Field, the world's first large oil field, which in 1881 produced 83% of America's output. A large fraction of the oil and gas wells in McKean County are AOL and some estimates of the number of AOL wells exceed the number of wells listed by the PA DEP by factors of 20 or more. To characterize AOL wells' potential as a significant methane source, we made first-of-a-kind measurements of methane fluxes from 8 abandoned wells in McKean County using static flux chambers. These wells are on a 40-acre lot, which includes various land cover types. Four of the eight measured wells are in forested areas, while three are in grassland, and one is in wetland areas. Two of the eight wells, one in a forested area and one in the grassland area, are plugged. Fluxes of methane, ethane, propane, and n-butane were measured using flame ionization gas chromatography. To gain insight into the source of methane (biogenic vs. thermogenic), carbon and hydrogen isotopes of methane were analyzed and the ratio of methane to heavier hydrocarbons were computed. In addition, a LI-7700 open path methane analyzer was used to provide on-line methane concentration measurement in the vicinity of AOL wells and in flux chambers. We found methane fluxes from the measured AOL wells to be significantly higher than fluxes observed in similar natural environments. Methane emissions from the two plugged wells were smaller than those from unplugged wells but

  10. EFFECTS OF ETHANE DIMETHANESULFONATE (EDS) ON ADULT AND IMMATURE RABBIT LEYDIG CELLS: COMPARISON WITH EDS-TREATED RAT LEYDIG CELLS

    EPA Science Inventory

    Ethane-dimethanesulfonate (EDS) has been shown to selectively kill Leydig cells and depress testosterone production in adult rats. ecent study has shown that immature rat leydig cells are less sensitive to EDS exposure. here is evidence that the rabbit metabolizes EDS to methane ...

  11. 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

  12. 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

  13. Conversion of methane to higher hydrocarbons in ac nonequilibrium plasmas

    SciTech Connect

    Thanyachotpaiboon, K.; Chavadej; Caldwell, T.A.; Lobban, L.L.; Mallinson, R.G.

    1998-10-01

    The effects of plasma chemistry on the conversion of methane were studied using a dielectric barrier discharge reactor at ambient temperatures. A dielectric barrier discharge reactor generates a nonequilibrium plasma when a sufficiently high voltage is applied across the reactor`s electrodes. Methane molecules are activated at this temperature and coupled to form C{sub 2} hydrocarbons, higher hydrocarbons, and hydrogen. The study on the effect of voltage, residence time and third bodies on methane conversion and product selectivity shows that methane conversion initially increases with increasing voltage and residence time above the breakdown voltage, and product selectivities are essentially independent of the voltage. Production of hydrogen during the reaction limits olefin production. Methane conversion also increases when helium and ethane are in the feed stream. Helium and ethane both appear to be more easily activated than methane and enhance methane activation and conversion.

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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

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

  20. 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.

  1. 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.

  2. 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...

  3. Purification and properties of the methane mono-oxygenase enzyme system from Methylosinus trichosporium OB3b.

    PubMed Central

    Tonge, G M; Harrison, D E; Higgins, I J

    1977-01-01

    1. A three-component enzyme system that catalyses the oxidation of methane to methanol has been highly purified from Methylosinus trichosporium. 2. The components are (i) a soluble CO-binding cytochrome c, (ii) a copper-containing protein and (iii) a small protein; the mol. wts. are 13 000, 47 000 and 9400 respectively. The cytochrome component cannot be replaced by similar cytochrome purified from Pseudomonas extorquens or by horse heart cytochrome c. 3. The stoicheiometry suggests a mono-oxygenase mechanism and the specific activity with methane as substrate is 6 micronmol/min per mg of protein. 4. Other substrates rapidly oxidized are ethane, n-propane, n-butane and CO. Dimethyl ether is not a substrate. 5. The purified enzyme system utilizes ascorbate or, in the presence of partially purified M. trichosporium methanol dehydrogenase, methanol as electron donor but not NADH or NADPH. 6. Activity is highly sensitive to low concentrations of a variety of chelating agents, cyanide, 2-mercaptoethanol and dithiothreitol. 7. Activity is highly pH-dependent (optimum 6.9-7.0) and no component of the enzyme is stable to freezing. 8. The soluble CO-binding cytochrome c shows oxidase acitivity and the relationship between this and the oxygenase activity is discussed. Images Fig. 3. PMID:15544

  4. C-H and C-C clumping in ethane by high-resolution mass spectrometry

    NASA Astrophysics Data System (ADS)

    Clog, M. D.; Eiler, J. M.

    2014-12-01

    Ethane (C2H6) is an important natural compound, and its geochemistry can be studied through 13C-13C, 13C-D and/or D-D clumping. Such measurements are potentially important both as a stepping stone towards the study of more complex organic molecules and, in its own regard, to understand processes controlling the generation, migration and destruction of natural gas. Isotopic clumping on C-C and C-H bonds could be influenced by thermodynamics, chemical kinetics, diffusion or gas mixing. Previous work showed that 13C-D clumping in methane generally reflects equilibrium and provides a measure of formation temperature (Stolper et al 2014a), whereas 13C-13C clumping in ethane is likely most controlled by chemical-kinetic processes and/or inheritance from the isotopic structure of source organic compounds (Clog et al 2014). 13C-D clumping in ethane has the potential to provide a thermometer for its synthesis, as it does for methane. However, the difference in C-H bond dissociation energy for these two compounds may suggest a lower 'blocking temperature' for this phenomenon in ethane (the blocking temperature for methane is ≥~250 C in geological conditions). We present analytical techniques to measure both 13C-13C and 13C-D clumping in ethane, using a novel two-instrument technique, including both the Thermo 253-Ultra and the Thermo DFS. In this method, the Ultra is used to measure the relative abundances of combinations nearly isobaric isotopologues: (13C12CH6 + 12C2DH5)/12C2H6 and (13C2H6 + 12C13CDH5)/12C2H6, free of other isobaric interferences like O2. The DFS, a very high resolution single-collector instrument, is then used to measure the ratios of isotopologues of ethane at a single cardinal mass: 12C2DH5/13C12CH6, and 12C13CDH5/13C2H6, with precisions of ~1 permil. Those 4 measurements allow us to calculate the bulk isotopic composition (D and 13C) as well as the abundance of 13C2H6 and 13C12CDH5. We also present progress on the development of software tools

  5. Laboratory Studies on the Irradiation of Solid Ethane Analog Ices and Implications to Titan's Chemistry

    NASA Astrophysics Data System (ADS)

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

    2010-03-01

    Pure ethane ices (C2H6) 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 (CH4), acetylene (C2H2), ethylene (C2H4), and the ethyl radical (C2H5), together with n-butane (C4H10) and butene (C4H8), 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 atmosphere. Finally, we discuss to what extent the n-butane could be the

  6. 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.

  7. Carbonyls and non-methane hydrocarbons at a rural mountain site in northeastern United States.

    PubMed

    Khwaja, Haider A; Narang, Amarjit

    2008-05-01

    Measurements of carbonyls and C(2)-C(6) non-methane hydrocarbons (NMHCs) were made in ambient air at a rural site at the summit of Whiteface Mountain (WFM) in New York State. Alkanes dominated in the samples, with ethane and propane making up about 55% of the total on a carbon-atom basis. Ethane, the longest-lived of the NMHCs, showed a mixing ratio in the range of 0.86-2.1 ppbv. Photochemical ageing analysis indicated an anthropogenic influence on the NMHC levels. The photochemical reactivity of the hydrocarbons, calculated in terms of propylene-equivalent concentration, was dominated by alkenes (propene and ethene), which accounted for 74% of the total NMHC sum. Air mass back-trajectories have been used to investigate the origin of the observed NMHCs and carbonyls. Higher concentrations were found when air masses arrived from the midwestern US corridor. Acetone was the most abundant species, comprising from 31% to 53% of the total detected carbonyls, followed by MEK (15-53%), HCHO (7-39%), and CH(3)CHO (7-19%). Average concentrations were determined to be 1.61 ppbv for CH(3)C(O)CH(3), 1.40 ppbv for MEK, 1.16 ppbv for HCHO, and 0.49 ppbv for CH(3)CHO. The variations in carbonyl concentrations were observed to follow patterns similar to variations in O(3) concentrations, typical of secondary products. Correlations and statistical analysis of the carbonyls and NMHCs were performed, and showed that most of the compounds derived from mixing and photochemical transformation of long-range transported pollutants from the major source areas. Ranking of the carbonyls with respect to removal of the OH radical showed HCHO to be the most important species, followed by CH(3)CHO, MEK, and CH(3)C(O)CH(3). PMID:18420251

  8. 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.

  9. 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.

  10. Propane Market Model documentation report

    SciTech Connect

    Not Available

    1993-12-01

    The purpose of this report is to define the objectives of the Propane Market Model (PMM), describe its basic approach, and to provide details on model functions. This report is intended as a reference document for model analysts, users, and the general public. Documentation of the model is in accordance with EIA`s legal obligation to provide adequate documentation in support of its models. The PMM performs a short-term (6- to 9-months) forecast of demand and price for consumer-grad propane in the national US market; it also calculates the end-of-month stock level during the term of the forecast. Another part of the model allows for short-term demand forecasts for certain individual Petroleum Administration for Defense (PAD) districts. The model is used to analyze market behavior assumptions or shocks and to determine the effect on market price, demand, and stock level.

  11. 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.

  12. Self- and air-broadened cross sections of ethane (C2H6) determined by frequency-stabilized cavity ring-down spectroscopy near 1.68 μm

    NASA Astrophysics Data System (ADS)

    Reed, Zachary D.; Hodges, Joseph T.

    2015-07-01

    The absorption spectrum of ethane was measured by frequency-stabilized cavity ring-down spectroscopy over the wave number range 5950-5967 cm-1. Spectra are reported for both pure ethane acquired at pressures near 3 Pa and mixtures of ethane in air at pressures ranging from 666 Pa to 101.3 kPa. Absorption cross sections are reported with a spectrum sampling period of 109 MHz and frequency resolution of 200 kHz. Atmospheric pressure cross sections agree fairly well with existing cross sections determined by FTS in nitrogen, but there are significant variations in cross sections at lower pressures. Source identification of fugitive methane emissions using spectroscopic measurements of the atmospheric ethane-to-methane ratio is also discussed.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. Operation of gas electron multiplier (GEM) with propane gas at low pressure and comparison with tissue-equivalent gas mixtures

    NASA Astrophysics Data System (ADS)

    De Nardo, L.; Farahmand, M.

    2016-05-01

    A Tissue-Equivalent Proportional Counter (TEPC), based on a single GEM foil of standard geometry, has been tested with pure propane gas at low pressure, in order to simulate a tissue site of about 1 μm equivalent size. In this work, the performance of GEM with propane gas at a pressure of 21 and 28 kPa will be presented. The effective gas gain was measured in various conditions using a 244Cm alpha source. The dependence of effective gain on the electric field strength along the GEM channel and in the drift and induction region was investigated. A maximum effective gain of about 5×103 has been reached. Results obtained in pure propane gas are compared with gas gain measurements in gas mixtures commonly employed in microdosimetry, that is propane and methane based Tissue-Equivalent gas mixtures.

  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. Ethane-xenon mixtures under shock conditions

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    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. 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. 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.

  20. 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. PMID:16866395

  1. Thermomechanically integrated distillation of ethylene from ethane

    SciTech Connect

    Greene, D.G.; Haddad, H.; Manley, D.B.

    1994-12-31

    The separation of ethylene from ethane by distillation is normally the final step in the production of ethylene. The critical temperature of ethylene is about 50 F, therefore moderately low temperatures and moderately high pressures are typically used to provide optimum economic conditions. The optimum design can require thick walled and heavy pressure vessels which may be constructed of expensive alloy steels depending on the specific operating conditions. The required purity of ethylene usually exceeds 99.9%, and the economic level of recovery is approximately 99%. In addition, the relative volatility of ethylene to ethane is moderately small ranging from about 1.13 for high pressure mixtures rich in ethylene to 2.34 for low pressure mixtures rich in ethane. The relatively high purity and recovery and relatively low relative volatility dictate a large distillation column with more than 100 trays and a large diameter for world scale production levels of over a billion pounds per year of ethylene. The installed capital cost for a unit of this type and size can exceed twenty million dollars, and utility costs can exceed one million dollars per year. Consequently, there is a strong economic incentive to reduce costs through improved process designs for the distillation of ethylene from ethane, and the process is well studied in the literature. Thermomechanically integrated distillation provides an improved design which can reduce both capital and operating costs as compared to the best conventional designs. In this paper, the conventional designs for both vapor and liquid feeds are reviewed, the underlying thermodynamics characterizing the process is discussed, alternative thermomechanically integrated designs are presented, and utility and purchased equipment costs are compared.

  2. 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.

  3. 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.

  4. GLOBAL FLUX OF METHANE FROM SHALLOW SUBMARINE SEDIMENTS

    EPA Science Inventory

    The seepage of methane through the seabed of the world's continental shelves is considered. ethane may be generated by both bacterial and thermogenic processes acting on the complex organic matter stored in the seabed. ecause these processes are ubiquitous, occurrences of gas and...

  5. 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

  6. 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. PMID:25443986

  7. 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

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

    DOE PAGESBeta

    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 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

  9. 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.

  10. Identifying Different Types of Catalysts for CO2 Reduction by Ethane through Dry Reforming and Oxidative Dehydrogenation.

    PubMed

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

    2015-12-14

    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 Mo2 C-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. PMID:26554872

  11. 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

  12. An analysis of high frequency methane measurements in central New England

    NASA Astrophysics Data System (ADS)

    Shipham, Mark Charles

    A unique high resolution ambient air methane data set consisting of approximately 125,000 independently measured data points for the years 1991-1995 has been collected at a site in the northeastern United States. This data base is used to examine the long term trend, seasonal and diurnal cycles, and the frequent pollution events that affect the site on a year round basis. The annual median mixing ratio of methane for all measurements was 1808 ppbv in 1992, increasing at a variable rate to 1837 ppbv in 1995. The lower 10-30% of the data from each month was defined as representative of background air and was compared to the global CMDL data set. The background data exhibit a variable upward trend of 5.5 ± 2 ppbv/year during the 4-year time period, with most of the increase observed during 1993 and 1994. The seasonal cycle for the background data set is similar to what is observed by CMDL stations and varies from 24 to 35 ppbv. The amplitude of the seasonal cycle for the full data set was larger, ranging from 35 to 44 ppbv. Differences between the full and background mixing ratios vary on a seasonal basis and are largest in the winter and smallest in the summer. These differences appear to be controlled by changes in atmospheric stability and changes in emissions from local and regional sources throughout the year. Wind roses of chemical species are examined for annual and seasonal time periods with enhancements in anthropogenic species corresponding to the location of large cities and landfills. Methane is strongly correlated to species that have an anthropogenic component, including acetylene, propane, ethane, and hexane. The southwest quadrant is subjected to the most severe pollution events and is impacted by outflow from large cities in that sector, including Northampton and Springfield, MA. Emissions from cities in other quadrants, including Boston and Worcester, MA., Providence, RI., and the near by town of Petersham, MA, also affect the site, but to a lesser

  13. 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.

  14. Ethane-xenon mixtures under shock conditions

    DOE PAGESBeta

    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, 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

  15. 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...

  16. 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...

  17. 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...

  18. 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...

  19. 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...

  20. 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,

  1. 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. PMID:26712504

  2. Quantum molecular dynamics simulations of thermophysical properties of fluid ethane

    NASA Astrophysics Data System (ADS)

    Zhang, Yujuan; Wang, Cong; Zheng, Fawei; Zhang, Ping

    2012-12-01

    We have performed first-principles molecular-dynamics simulations based on density-functional theory to study the thermophysical properties of ethane under extreme conditions. We present results for the equation of state of fluid ethane in the warm dense region. The optical conductivity is calculated via the Kubo-Greenwood formula from which the dc conductivity and optical reflectivity are derived. The close correlation between the nonmetal-metal transition of ethane and its decomposition, that ethane dissociates significantly into molecular and/or atomic hydrogen and some long alkane chains, has been systematically studied by analyzing the optical conductivity spectra, pair correlation functions, electronic density of states, and charge density distribution of fluid ethane.

  3. 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

    2015-07-01

    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. PMID:25751617

  4. 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

    2015-05-01

    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. PMID:25882096

  5. Methane emissions from the 2015 Aliso Canyon blowout in Los Angeles, CA.

    PubMed

    Conley, S; Franco, G; Faloona, I; Blake, D R; Peischl, J; Ryerson, T B

    2016-03-18

    Single-point failures of natural gas infrastructure can hamper methane emission control strategies designed to mitigate climate change. The 23 October 2015 blowout of a well connected to the Aliso Canyon underground storage facility in California resulted in a massive release of natural gas. Analysis of methane and ethane data from dozens of plume transects, collected during 13 research-aircraft flights between 7 November 2015 and 13 February 2016, shows atmospheric leak rates of up to 60 metric tons of methane and 4.5 metric tons of ethane per hour. At its peak, this blowout effectively doubled the methane emission rate of the entire Los Angeles basin and, in total, released 97,100 metric tons of methane to the atmosphere. PMID:26917596

  6. 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

  7. 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.

  8. No. 2 heating oil/propane program

    SciTech Connect

    McBrien, J.

    1991-06-01

    During the 1990/91 heating season, the Massachusetts Division of Energy Resources (DOER) participated in a joint data collection program between several state energy offices and the federal Department of Energy's (DOE) Energy Information Administration (EIA). The purpose of the program was to collect and monitor retail and wholesale heating oil and propane prices and inventories from October 1990 through March 1991. This final report begins with an overview of the unique events which had an impact on the reporting period. Next, the report summarizes the results from the residential heating oil and propane price surveys conducted by DOER over the 1990/91 heating season. The report also incorporates the wholesale heating oil and propane prices and inventories collected by the EIA and distributed to the states.

  9. Propane Clathrate Hydrate Formation Accelerated by Methanol.

    PubMed

    Amtawong, Jaruwan; Guo, Jin; Hale, Jared S; Sengupta, Suvrajit; Fleischer, Everly B; Martin, Rachel W; Janda, Kenneth C

    2016-07-01

    The role of methanol as both an inhibitor and a catalyst for the formation of clathrate hydrates (CHs) has been a topic of intense study. We report a new quantitative study of the kinetics of propane CH formation at 253 K from the reaction of propane gas with <75 μm ice particles that have been doped with varying amounts of methanol. We find that methanol significantly accelerates the formation reaction with quite small doping quantities. Even for only 1 methanol molecule per 10 000 water molecules, the maximum uptake rate of propane into CHs is enhanced and the initiation pressure is reduced. These results enable more efficient production of CHs for gas storage. This remarkable acceleration of the CH formation reaction by small quantities of methanol may place constraints on the mechanism of the inhibition effect observed under other conditions, usually employing much larger quantities of methanol. PMID:27275862

  10. 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.

  11. 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.

  12. Co-cracking of ethane and naphtha in millisecond furnaces

    SciTech Connect

    Nowowiejski, G.B.; Petterson, W.C.; Kii, T.; Suwa, A.

    1982-05-01

    This paper presents results of an experimental program in which the process of short contact pyrolysis of mixtures of ethane and naphthas has been investigated as an economic alternative way to the production of olefins. The benefits of co-cracking of ethane recycle with naphtha feed in millisecond furnace are demonstrated. There is a directional improvement is selectivity to ethylene product which would result in about 2% less naphtha consumption at constant ethylene production. There is greater operating flexibility in terms of processing additional fresh ethane or LPG, when the furnace area is designed with the co-cracking concept.

  13. . . . 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)

  14. Correlation of refrigerant mass flow rate through adiabatic capillary tubes using mixture refrigerant carbondioxide and ethane for low temperature applications

    NASA Astrophysics Data System (ADS)

    Nasruddin, Syaka, Darwin R. B.; Alhamid, M. Idrus

    2012-06-01

    Various binary mixtures of carbon dioxide and hydrocarbons, especially propane or ethane, as alternative natural refrigerants to Chlorofluorocarbons (CFCs) or Hydro fluorocarbons (HFCs) are presented in this paper. Their environmental performance is friendly, with an ozone depletion potential (ODP) of zero and Global-warming potential (GWP) smaller than 20. The capillary tube performance for the alternative refrigerant HFC HCand mixed refrigerants have been widely studied. However, studies that discuss the performance of the capillary tube to a mixture of natural refrigerants, in particular a mixture of azeotrope carbon dioxide and ethane is still undeveloped. A method of empirical correlation to determine the mass flow rate and pipe length has an important role in the design of the capillary tube for industrial refrigeration. Based on the variables that effect the rate of mass flow of refrigerant in the capillary tube, the Buckingham Pi theorem formulated eight non-dimensional parameters to be developed into an empirical equations correlation. Furthermore, non-linear regression analysis used to determine the co-efficiency and exponent of this empirical correlation based on experimental verification of the results database.

  15. Rapid catalytic processes in reforming of methane and successive synthesis of methanol and its derivatives

    NASA Astrophysics Data System (ADS)

    Inui, Tomoyuki

    1997-11-01

    In order to obtain high quality fuels and basic raw materials for petrochemical industries, novel catalysts which enable the realization of new synthetic routes have been investigated. First, a highly active Rh-modified Ni-based composite catalyst, NiCe 2O 3PtRh, supported on a ceramic fiber in a plate shape was developed, which reformed methane into the syngas having an appropriate ratio of H2/CO. Furthermore, more combustible ethane or propane was added into the reaction gas and its catalytic combustion was allowed to occur on the same catalyst. The combustion heat compensated the reforming heat resulting in an extraordinarily high space-time yield of hydrogen, as high as 10,000 mol/1·h, even under the condition of a very short contact time, 5 ms, and a very low furnace temperature at around 400°C. Next, a highly active catalyst for methanol synthesis from CO 2-rich or CO-rich syngases was developed. A Cu-based CuZnCrAlGa mixed oxide catalyst was prepared by the uniform gelation method and it was mixed with Pd supported on χ-alumina. The composite catalyst exhibited a much higher activity than the conventional catalyst prepared by the precipitation method and a space-time yield of methanol of 1,300 and 6,730 g/l·h was amounted, respectively, from CO 2-rich and CO-rich syngases under 80 atm and at 270°C. Finally, the products obtained as mentioned above were introduced into the reactor, which was connected in series and the methanol was totally converted into hydrocarbons. In the case of a HGa-silicate catalyst, gasoline was obtained at as high a value as 1,860 g/l·h in space-time yield, and in the case of SAPO-34, ethylene and propylene were obtained with an equivalent selectivity.

  16. 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.

  17. 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.

  18. 21 CFR 582.1655 - Propane.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Propane. 582.1655 Section 582.1655 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE General Purpose Food Additives §...

  19. 21 CFR 582.1655 - Propane.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Propane. 582.1655 Section 582.1655 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE General Purpose Food Additives §...

  20. 21 CFR 184.1655 - Propane.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... in the liquid state. Propane is obtained from natural gas by fractionation following absorption in... also known as dimethylmethane or propyl hydrid. It is a colorless, odorless, flammable gas at normal... manufacturing practice conditions of use: (1) The ingredient is used as a propellant, aerating agent, and gas...

  1. 21 CFR 184.1655 - Propane.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... in the liquid state. Propane is obtained from natural gas by fractionation following absorption in... also known as dimethylmethane or propyl hydrid. It is a colorless, odorless, flammable gas at normal... manufacturing practice conditions of use: (1) The ingredient is used as a propellant, aerating agent, and gas...

  2. 21 CFR 184.1655 - Propane.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... state. Propane is obtained from natural gas by fractionation following absorption in oil, adsorption to... dimethylmethane or propyl hydrid. It is a colorless, odorless, flammable gas at normal temperatures and pressures... practice conditions of use: (1) The ingredient is used as a propellant, aerating agent, and gas as...

  3. 21 CFR 184.1655 - Propane.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... in the liquid state. Propane is obtained from natural gas by fractionation following absorption in... also known as dimethylmethane or propyl hydrid. It is a colorless, odorless, flammable gas at normal... manufacturing practice conditions of use: (1) The ingredient is used as a propellant, aerating agent, and gas...

  4. 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.

  5. The stereospecific hydroxylation of [2,2-2H2]butane and chiral dideuteriobutanes by the particulate methane monooxygenase from Methylococcus capsulatus (Bath).

    PubMed

    Yu, Steve S-F; Wu, Lo-Ying; Chen, Kelvin H-C; Luo, Wen-I; Huang, Ded-Shih; Chan, Sunney I

    2003-10-17

    Experiments on cryptically chiral ethanes have indicated that the particulate methane monooxygenase (pMMO) from Methylococcus capsulatus (Bath) catalyzes the hydroxylation of ethane with total retention of configuration at the carbon center attacked. This result would seem to rule out a radical mechanism for the hydroxylation chemistry, at least as mediated by this enzyme. The interpretation of subsequent experiments on n-propane, n-butane, and n-pentane has been complicated by hydroxylation at both the pro-R and pro-S secondary C-H bonds, where the hydroxylation takes place. It has been suggested that these results merely reflect presentation of both the pro-R and pro-S C-H bonds to the hot "oxygen atom" species generated at the active site, and that the oxo-transfer chemistry, in fact, proceeds concertedly with retention of configuration. In the present work, we have augmented these earlier studies with experiments on [2,2-2H2]butane and designed d,l form chiral dideuteriobutanes. Essentially equal amounts of (2R)-[3,3-2H2]butan-2-ol and (2R)-[2-2H1]butan-2-ol are produced upon hydroxylation of [2,2-2H2]butane. The chemistry is stereospecific with full retention of configuration at the secondary carbon oxidized. In the case of the various chiral deuterated butanes, the extent of configurational inversion has been shown to be negligible for all the chiral butanes examined. Thus, the hydroxylation of butane takes place with full retention of configuration in butane as well as in the case of ethane. These results are interpreted in terms of an oxo-transfer mechanism based on side-on singlet oxene insertion across the C-H bond similar to that previously noted for singlet carbene insertion (Kirmse, W., and Ozkir, I. S. (1992) J. Am. Chem. Soc. 114, 7590-7591). Finally, we discuss how even the oxene insertion mechanism, with "spin crossover" in the transition state, could lead to small amounts of radical rearrangement products, if and when such products are observed. A

  6. Electron attenuation in free, neutral ethane clusters.

    PubMed

    Winkler, M; Myrseth, V; Harnes, J; Børve, K J

    2014-10-28

    The electron effective attenuation length (EAL) in free, neutral ethane clusters has been determined at 40 eV kinetic energy by combining carbon 1s x-ray photoelectron spectroscopy and theoretical lineshape modeling. More specifically, theory is employed to form model spectra on a grid in cluster size (N) and EAL (λ), allowing N and λ to be determined by optimizing the goodness-of-fit χ(2)(N, λ) between model and observed spectra. Experimentally, the clusters were produced in an adiabatic-expansion setup using helium as the driving gas, spanning a range of 100-600 molecules in mean cluster size. The effective attenuation length was determined to be 8.4 ± 1.9 Å, in good agreement with an independent estimate of 10 Å formed on the basis of molecular electron-scattering data and Monte Carlo simulations. The aggregation state of the clusters as well as the cluster temperature and its importance to the derived EAL value are discussed in some depth. PMID:25362297

  7. Electron attenuation in free, neutral ethane clusters

    SciTech Connect

    Winkler, M.; Harnes, J.; Børve, K. J.; Myrseth, V.

    2014-10-28

    The electron effective attenuation length (EAL) in free, neutral ethane clusters has been determined at 40 eV kinetic energy by combining carbon 1s x-ray photoelectron spectroscopy and theoretical lineshape modeling. More specifically, theory is employed to form model spectra on a grid in cluster size (N) and EAL (λ), allowing N and λ to be determined by optimizing the goodness-of-fit χ{sup 2}(N, λ) between model and observed spectra. Experimentally, the clusters were produced in an adiabatic-expansion setup using helium as the driving gas, spanning a range of 100–600 molecules in mean cluster size. The effective attenuation length was determined to be 8.4 ± 1.9 Å, in good agreement with an independent estimate of 10 Å formed on the basis of molecular electron-scattering data and Monte Carlo simulations. The aggregation state of the clusters as well as the cluster temperature and its importance to the derived EAL value are discussed in some depth.

  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. A search for ethane on Pluto and Triton

    NASA Astrophysics Data System (ADS)

    DeMeo, Francesca E.; Dumas, Christophe; de Bergh, Catherine; Protopapa, Silvia; Cruikshank, Dale P.; Geballe, Thomas R.; Alvarez-Candal, Alvaro; Merlin, Frédéric; Barucci, Maria A.

    2010-07-01

    We present here a search for solid ethane, C 2H 6, on the surfaces of Pluto and Triton, based on near-infrared spectral observations in the H and K bands (1.4-2.45 μm) using the Very Large Telescope (VLT) and the United Kingdom Infrared Telescope (UKIRT). We model each surface using a radiative transfer model based on Hapke theory (Hapke, B. [1993]. Theory of Reflectance and Emittance Spectroscopy. Cambridge University Press, Cambridge, UK) with three basic models: without ethane, with pure ethane, and with ethane diluted in nitrogen. On Pluto we detect weak features near 2.27, 2.405, 2.457, and 2.461 μm that match the strongest features of pure ethane. An additional feature seen at 2.317 μm is shifted to longer wavelengths than ethane by at least 0.002 μm. The strength of the features seen in the models suggests that pure ethane is limited to no more than a few percent of the surface of Pluto. On Triton, features in the H band could potentially be explained by ethane diluted in N, however, the lack of corresponding features in the K band makes this unlikely (also noted by Quirico et al. (Quirico, E., Doute, S., Schmitt, B., de Bergh, C., Cruikshank, D.P., Owen, T.C., Geballe, T.R., Roush, T.L. [1999]. Icarus 139, 159-178)). While Cruikshank et al. (Cruikshank, D.P., Mason, R.E., Dalle Ore, C.M., Bernstein, M.P., Quirico, E., Mastrapa, R.M., Emery, J.P., Owen, T.C. [2006]. Bull. Am. Astron. Soc. 38, 518) find that the 2.406-μm feature on Triton could not be completely due to 13CO, our models show that it could not be accounted for entirely by ethane either. The multiple origin of this feature complicates constraints on the contribution of ethane for both bodies.

  10. Evidence from firn air for recent decreases in non-methane hydrocarbons and a 20th century increase in nitrogen oxides in the northern hemisphere

    NASA Astrophysics Data System (ADS)

    Worton, David R.; Sturges, William T.; Reeves, Claire E.; Newland, Mike J.; Penkett, Stuart A.; Atlas, Elliot; Stroud, Verity; Johnson, Kristen; Schmidbauer, Norbert; Solberg, Sverre; Schwander, Jakob; Barnola, Jean-Marc

    2012-07-01

    The atmospheric evolution of eight non-methane hydrocarbons (ethane, acetylene, propane, n-butane, isobutane, n-pentane, isopentane and benzene) and five alkyl nitrates (2-propyl, 2-butyl, 3-methyl-2-butyl and the sum of 2+3-pentyl nitrates) are reconstructed for the latter half of the 20th century based on Arctic firn air measurements. The reconstructed trends of the non-methane hydrocarbons (NMHCs) show increasing concentrations from 1950 to a maximum in 1980 before declining towards the end of last century. These observations provide direct evidence that NMHCs in the northern hemisphere have declined substantially during the period 1980-2001. Benzene concentrations show a smaller increase between 1950 and 1980 than the other NMHCs indicating that additional sources of benzene, other than fossil fuel combustion, were likely important contributors to the benzene budget prior to and during this period. The declining benzene concentrations from 1980 to 2001 would suggest that biomass burning is unlikely to be important in the benzene budget as biomass burning emissions were reportedly increasing over the same period. Methyl and ethyl nitrate show growth patterns in the firn that suggested perturbation by in-situ production from an unidentified mechanism. However, the higher alkyl nitrates show evidence for increasing concentrations from 1950 to maxima in the mid 1990s before decreasing slightly toward the end of the last century. The differing atmospheric evolution of the alkyl nitrates relative to their parent hydrocarbons indicate an increase in their production efficiency per hydrocarbon molecule. Using a steady state analysis of hydrocarbon oxidation and alkyl nitrate production and loss we show that reactive nitrogen oxide (NOx) concentrations in the northern hemisphere have likely increased considerably between 1950 and 2001.

  11. Direct conversion of methane to C sub 2 's and liquid fuels

    SciTech Connect

    Warren, B.K.; Campbell, K.D.; Matherne, J.L.

    1990-02-14

    Research on promoted metal oxide catalysts has continued with the study of alkaline earth/metal oxide halide catalysts. A barium bromide/alumina catalyst was comparable in methane conversion and selectivity to C{sub 2}'s to barium chloride/alumina catalysts. The effects of varying methane to oxygen feed ratios were explored for one of the best alkaline earth catalysts and one of the best literature catalysts (Li/MgO). A significant decrease in the selectivity to C{sub 2}'s is observed upon addition of ethane to the feed gas (feed gas methane/ethane ratio of 3). This observation demonstrates that a significant amount of ethane should not be recycled during methane oxidation over these types of catalysts under process conditions used. Methane oxidation over barium carbonate alone results in high enough selectivities and methane conversions to suggest an oxidized barium species may be responsible for methane oxidation on barium/metal oxide catalysts. Methane coupling studies have continued using layered perovskite catalysts in the cofeed mode and double perovskite catalysts in the sequential mode. Addition of sodium to the double perovskite LaCaMnCoO{sub 6} resulted in a catalyst with improved selectivity over the one without sodium. A reactor system containing two reactors in under construction. These reactors will be used to study different feed diluents, including steam. One reactor will be used to study the effects of pressure on the reaction. Process economics were explored for a hypothetical methane coupling scheme employing a feed mixture of 7/2/1 nitrogen/methane/oxygen. Economic evaluations of the first two of a series of cases based on extrapolations of Union Carbide methane coupling results have been completed. 33 refs., 17 figs., 2 tabs.

  12. 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.

  13. METHANE PRODUCTION FROM ANAEROBIC SOIL AMENDED WITH RICE STRAW AND NITROGEN FERTILIZERS

    EPA Science Inventory

    Laboratory experiments were conducted on the effects of rice straw application and inorganic N fertilization on methane (CH4) production from a flooded Louisiana, USA, rice soil. ignificant increase of CH4 production was observed following rice straw application. ethane productio...

  14. CURRENT AND FUTURE ENVIRONMENTAL ROLE OF ATMOSPHERIC METHANE: MODEL STUDIES AND UNCERTAINTIES

    EPA Science Inventory

    Concern over increasing levels of methane in the atmosphere centers on its radiative and chemical properties. ethane absorbs terrestrial infrared radiation and contributes to the greenhouse effect. ffects on other greenhouse absorbers (e.g., O3, H2O, and CO2) as the result of its...

  15. 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.

  16. 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.

  17. Aging tests of ethylene contaminated argon/ethane

    SciTech Connect

    Atac, M.; Bauer, G.

    1994-09-22

    We report on aging tests of argon/ethane gas with a minor (1800 ppM) component of ethylene. The measurements were first conducted with the addition of alcohol to test the suppression of aging by this additive, with exposure up to {approx}1.5 C/cm. Tests have included: a proportional tube with ethanol, another with isopropyl alcohol, and for comparison a tube has also been run with ethanol and argon/ethane from CDF`s old (ethylene-free) ethane supply. The aging test with ethanol showed no difference between the ethylene-free and the ethylene tube. Furthermore, raw aging rates of argon/ethane and argon/ethane/ethylene were measured by exposing tubes without the addition of alcohol to about 0.1 C/cm. Again, no significant difference was observed. In conclusion, we see no evidence that ethylene contamination up to 1800 ppM has any adverse effect on wire aging. However, this level of ethylene does seem to significantly suppress the gas gain.

  18. 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

  19. OH and halogen atom influence on the variability of non-methane hydrocarbons in the Antarctic Boundary Layer

    NASA Astrophysics Data System (ADS)

    Read, Katie A.; Lewis, Alastair C.; Salmon, Rhian A.; Jones, Anna E.; Bauguitte, Stéphane

    2007-02-01

    Measurements of C2-C8 non-methane hydrocarbons (NMHCs) have been made in situ at Halley Base, Antarctica (75°35'S, 26°19'W) from February 2004 to February 2005 as part of the Chemistry of the Antarctic Boundary Layer and the Interface with Snow (CHABLIS) experiment. The data show long- and short-term variabilities in NMHCs controlled by the seasonal and geographic dependence of emissions and variation in atmospheric removal rates and pathways. Ethane, propane, iso-butane, n-butane and acetylene abundances followed a general OH-dependent sinusoidal seasonal cycle. The yearly averages were 186, 31, 3.2, 4.9 and 19 pptV, respectively, lower than those which were reported in some previous studies. Superimposed on a seasonal cycle was shorter-term variability that could be attributed to both synoptic airmass variability and localized loss processes due to other radical species. Hydrocarbon variability during periods of hour-to-day-long surface O3 depletion in late winter/early spring indicated active halogen atom chemistry estimated to be in the range 1.7 × 103-3.4 × 104 atom cm-3 for Cl and 4.8 × 106-9.6 × 107 atom cm-3 for Br. Longer-term negative deviations from sinusoidal behaviour in the late August were indicative of NMHC reaction with a persistent [Cl] of 2.3 × 103 atom cm-3. Maximum ethene and propene of 157 and 179 pptV, respectively, were observed in the late February/early March, consistent with increased oceanic biogenic emissions; however, their presence was significant year-round (June-August concentrations of 17.1 +/- 18.3 and 7.9 +/- 20.0 pptV, respectively).

  20. 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.

  1. 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.

  2. 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

  3. 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

  4. Alkane Activation Initiated by Hydride Transfer: Co-conversion of Propane and Methanol over H-ZSM-5 Zeolite.

    PubMed

    Yu, Si-Min; Wu, Jian-Feng; Liu, Chong; Liu, Wei; Bai, Shi; Huang, Jun; Wang, Wei

    2015-06-15

    Co-conversion of alkane with another reactant over zeolite catalysts has emerged as a new approach to the long-standing challenge of alkane transformation. With the aid of solid-state NMR spectroscopy and GC-MS analysis, it was found that the co-conversion of propane and methanol can be readily initiated by hydride transfer at temperatures of ≥449 K over the acidic zeolite H-ZSM-5. The formation of (13)C-labeled methane and singly (13)C-labeled n-butanes in selective labeling experiments provided the first evidence for the initial hydride transfer from propane to surface methoxy intermediates. The results not only provide new insight into carbocation chemistry of solid acids, but also shed light on the low-temperature transformation of alkanes for industrial applications. PMID:25959356

  5. An intensity study of the torsional bands of ethane at 35 μm

    NASA Astrophysics Data System (ADS)

    Moazzen-Ahmadi, N.; Norooz Oliaee, J.; Ozier, I.; Wishnow, E. H.; Sung, K.; Crawford, T. J.; Brown, L. R.; Devi, V. M.

    2015-01-01

    Ethane is the second most abundant hydrocarbon detected in the outer planets. Although the torsional mode is not infrared active in the lowest order, the strongest feature in this band can be seen near 289 cm-1 in the CASSINI CIRS spectrum of Titan. Prior laboratory studies have characterized the torsional frequencies to high accuracy and measured the intensities to temperatures as low as 208 K. However, for the interpretation of the far-infrared observations of Titan, further investigation was needed to determine the intensities at lower temperatures and to higher accuracy. The spectrum of C2H6 was investigated from 220 to 330 cm-1 to obtain the band strengths of the torsional fundamental ν4 (near 289 cm-1) and the first torsional hot band (2ν4 -ν4). Seven laboratory spectra were obtained at resolutions of 0.01 and 0.02 cm-1 using a Bruker IFS-125 Fourier transform spectrometer at the Jet Propulsion Laboratory. The interferometer was coupled to a coolable multi-pass absorption cell set to an optical path length of 52 m. The range of temperatures was 166-292 K with the lower temperatures being most relevant to the stratosphere of Titan. The ethane sample pressures ranged from 35 to 254 Torr. The modeling of the transition intensities required the expansion of the dipole moment operator to higher order; this introduced Herman-Wallis like terms. The fitting process involved five independent dipole constants and a single self-broadening parameter. The results presented should lead to an improved understanding of the methane cycle in planetary atmospheres and permit other molecular features in the CIRS spectra to be identified.

  6. Equivalence of pure propane and propane TE gases for microdosimetric measurements.

    PubMed

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

    2015-09-01

    A tissue-equivalent proportional counter (TEPC) simulates micrometric volumes of tissue if the energy deposited in the counter cavity is the same as that in the tissue volume. Nevertheless, a TEPC measures only the ionisations created in the gas, which are later converted into imparted energy. Therefore, the equivalence of the simulated diameter (Dρ) in two gases should be based on the equality of the mean number of ions pairs in the gas rather than on the imparted energy. Propane-based tissue-equivalent gas is the most commonly used gas mixture at present, but it has the drawback that its composition may change with time. From this point of view, the use of pure propane offers practical advantages: higher gas gain and longer stability. In this work, microdosimetric measurements performed with pure propane, at site sizes 0.05 mg cm(-2) ≤ Dρ ≤ 0.3 mg cm(-2), demonstrate that the response of a propane-filled detector in gamma and in neutron fields is almost the same if an appropriate gas density is used. PMID:25944956

  7. 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...

  8. 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...

  9. 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...

  10. 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)

  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. 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.

  13. Diffusion of iodo-ethane (1); helium (2)

    NASA Astrophysics Data System (ADS)

    Winkelmann, J.

    This document is part of Subvolume A `Gases in Gases, Liquids and their Mixtures' of Volume 15 `Diffusion in Gases, Liquids and Electrolytes' of Landolt-Börnstein Group IV `Physical Chemistry'. It is part of the chapter of the chapter `Diffusion in Pure Gases' and contains data on diffusion of (1) iodo-ethane; (2) helium

  14. 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

  15. Enhanced c2 yields from methane oxidative coupling by means of a separative chemical reactor.

    PubMed

    Tonkovich, A L; Carr, R W; Aris, R

    1993-10-01

    Of the processes for converting natural gas into a more useful chemical feedstock, the oxidative coupling of methane to form ethane and ethylene (C(2)) has perhaps been the most intensively investigated in recent years, but it has proved extremely difficult to obtain C(2) yields in excess of 20 to 25%. Methane oxidative coupling was carried out in a separative chemical reactor that simulated a countercurrent chromatographic moving-bed. This reaction gives 65% methane conversion, 80% C(2) selectivity, and a C(2) yield slightly better than 50% with Sm(2)O(3) catalyst at approximately 1000 K. PMID:17841868

  16. 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. PMID:25033440

  17. Oxidative coupling of methane with ac and dc corona discharges

    SciTech Connect

    Liu, C.; Marafee, A.; Hill, B.; Xu, G.; Mallinson, R.; Lobban, L.

    1996-10-01

    The oxidative coupling of methane (OCM) is being actively studied for the production of higher hydrocarbons from natural gas. The present study concentrated on the oxidative conversion of methane in an atmospheric pressure, nonthermal plasma formed by ac or dc corona discharges. Methyl radicals are formed by reaction with negatively-charged oxygen species created in the corona discharge. The selectivity to products ethane and ethylene is affected by electrode polarity, frequency, and oxygen partial pressure in the feed. Higher C{sub 2} yields were obtained with the ac corona. All the ac corona discharges are initiated at room temperature (i.e., no oven or other heat source is used), and the temperature increases to 300--500 C due to the exothermic reactions and the discharge itself. The largest C{sub 2} yield is 21% with 43.3% methane conversion and 48.3% C{sub 2} selectivity at a flowrate of 100 cm{sup 3}/min when the ac corona is at 30 Hz, 5 kV (rms) input power was used. The methane conversion may be improved to more than 50% by increasing the residence time, but the C{sub 2} selectivity decreases. A reaction mechanism including the oxidative dehydrogenation (OXD) of ethane to ethylene is presented to explain the observed phenomena. The results suggest that ac and/or dc gas discharge techniques have significant promise for improving the economics of OCM processes.

  18. 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.

  19. Catalytic combustion of ethane over palladium foil in the 300--450 C range: Kinetics and surface composition studies

    SciTech Connect

    Descorme, C.; Jacobs, P.W.; Somorjai, G.A.

    1998-09-10

    Catalytic oxidation of ethane over palladium foils was studied and the kinetic parameters were determined for the reaction. The studies were carried out at 800 Torr total pressure over a wide range of reaction conditions in the temperature range of 300--425 C. The catalyst surface composition was characterized before and after reaction by Auger electron spectroscopy (AES). While the authors detected only metallic palladium before reaction, the postreaction analysis showed significant formation of PdO{sub x}, a surface oxide, at all temperatures and under all ethane/oxygen ratios. The catalyst that exhibits optimum combustion activity is the one covered with 0.3 to 0.5 monolayer of oxygen. Carbon monoxide temperature-programmed desorption (CO-TPD) was used to evaluate the surface area of the metallic and oxidized palladium in order to normalize the measured catalytic reaction rates. Apparent activation energies of 104, 116, and 189 kJ/mol under fuel lean, stoichiometric, and fuel-rick conditions, respectively, were observed. While CO{sub 2} is the main carbonaceous product, unoxidized and partially oxidized species, methane and ethylene, are produced in small amounts. The product distribution is typically 98.6 mol% CO{sub 2}, 0.9 mol% C{sub 2}H{sub 4}, and 0.5 mol% CH{sub 4} at 10% conversion during a reaction at 350 C under stoichiometric conditions.

  20. Anthropogenic emissions of methane in the United States.

    PubMed

    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

    2013-12-10

    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

  1. 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

  2. Landfill Methane

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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. 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.

  4. 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

  5. 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%. PMID:26644584

  6. 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.

  7. Mid-Infrared Ethane Emission on Neptune and Uranus

    NASA Astrophysics Data System (ADS)

    Hammel, H. B.; Sitko, M. L.; Lynch, D. K.; Russell, R. W.; Hewagama, T.; Bernstein, L.

    2005-08-01

    We report spectroscopy of Neptune at 8-13 microns using the NASA Infrared Telescope Facility spanning 19 years. The data showed an increase in Neptune's atmospheric 12-micron ethane emission through 2003. The simplest explanation is an increase in stratospheric effective temperature from 155 K (1985) to 178 K (2003), followed by a slight decrease in 2004; the temperatures represent a combination of cold background and warm regions. The ethane band shape also exhibited variation that could not be reproduced by temperature changes alone. We interpret this variation as evidence for stratospheric ethane ice particulates, which were sensed by emission that propagated downward before reflecting off a lower layer to re-emerge. No ice was required to fit the 1985 and 1991 spectra, but after 2002 an ice column abundance of order 0.23 cm-atm was required. In 2002, the ice absorption fell at a short-wavelength position. From 2002 to 2003, the ice absorption shifted to a long-wavelength position as the effective temperature increased. From 2003 to 2004, the only difference was a drop in effective temperature. The long-term mid-IR variations may be correlated with increasing visible-wavelength brightness, possibly indicating hydrocarbon creation associated with cloud activity. We plan coordinated mid-IR spectroscopy and adaptive-optics imaging with Gemini and Keck in July 2005 to explore this. We also report a possible detection of ethane emission on Uranus in 2002, but the signal levels are more than two orders of magnitude lower than those of Neptune. The deduced mole fraction and temperature are consistent with past upper limits. Additional observations are warranted to confirm this. This work was supported in part by NASA grants NAG5-10451 and NAG5-11961. DKL and RWR acknowledge The Aerospace Corporation's Independent Research and Development program. HBH, DLK, and RWR were visiting astronomers at the IRTF, operated by U. Hawaii under contract from NASA.

  8. 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.

  9. 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

  10. 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

  11. Oxidative dehydrogenation of ethane on dynamically rearranging supported chloride catalysts.

    PubMed

    Gärtner, Christian A; van Veen, André C; Lercher, Johannes A

    2014-09-10

    Ethane is oxidatively dehydrogenated with a selectivity up to 95% on catalysts comprising a mixed molten alkali chloride supported on a mildly redox-active Dy2O3-doped MgO. The reactive oxyanionic OCl(-) species acting as active sites are catalytically formed by oxidation of Cl(-) at the MgO surface. Under reaction conditions this site is regenerated by O2, dissolving first in the alkali chloride melt, and in the second step dissociating and replenishing the oxygen vacancies on MgO. The oxyanion reactively dehydrogenates ethane at the melt-gas phase interface with nearly ideal selectivity. Thus, the reaction is concluded to proceed via two coupled steps following a Mars-van-Krevelen-mechanism at the solid-liquid and gas-liquid interface. The dissociation of O2 and/or the oxidation of Cl(-) at the melt-solid interface is concluded to have the lowest forward rate constants. The compositions of the oxide core and the molten chloride shell control the catalytic activity via the redox potential of the metal oxide and of the OCl(-). Traces of water may be present in the molten chloride under reaction conditions, but the specific impact of this water is not obvious at present. The spatial separation of oxygen and ethane activation sites and the dynamic rearrangement of the surface anions and cations, preventing the exposure of coordinatively unsaturated cations, are concluded to be the origin of the surprisingly high olefin selectivity. PMID:25118821

  12. 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.

  13. 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. PMID:18355832

  14. Mechanistic studies of the reaction of reduced methane monooxygenase hydroxylase with dioxygen and substrates

    SciTech Connect

    Valentine, A.M.; Stahl, S.S.; Lippard, S.J.

    1999-04-28

    species. Intermediate Q exhibits photosensitivity when monitored by diode array methodology, a property that may arise from enhanced reactivity of a transient charge-transfer species. The photoreaction can be avoided by using a monochromator to obtain kinetics data at single wavelengths. The reactions of substrates with intermediate species were studied by single- and double-mixing stopped-flow spectroscopy. The Q decay rate exhibits an approximate first-order dependence on substrate concentration for a wide range of hydrocarbons, the relative reactivity varying according to the sequence acetylene > ethylene > ethane > methane > propylene > propane. In addition, the data indicate that H{sub peroxo} can oxidize olefins but not acetylene or saturated hydrocarbons.

  15. 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.

  16. Fully Borylated Methane and Ethane by Ruthenium-Mediated Cleavage and Coupling of CO.

    PubMed

    Batsanov, Andrei S; Cabeza, Javier A; Crestani, Marco G; Fructos, Manuel R; García-Álvarez, Pablo; Gille, Marie; Lin, Zhenyang; Marder, Todd B

    2016-04-01

    Many transition-metal complexes and some metal-free compounds are able to bind carbon monoxide, a molecule which has the strongest chemical bond in nature. However, very few of them have been shown to induce the cleavage of its C-O bond and even fewer are those that are able to transform CO into organic reagents with potential in organic synthesis. This work shows that bis(pinacolato)diboron, B2pin2, reacts with ruthenium carbonyl to give metallic complexes containing borylmethylidyne (CBpin) and diborylethyne (pinBC≡CBpin) ligands and also metal-free perborylated C1 and C2 products, such as C(Bpin)4 and C2 (Bpin)6, respectively, which have great potential as building blocks for Suzuki-Miyaura cross-coupling and other reactions. The use of (13)CO-enriched ruthenium carbonyl has demonstrated that the boron-bound carbon atoms of all of these reaction products arise from CO ligands. PMID:26953905

  17. 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.

  18. 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.

  19. Optical constants of solid methane and ethane from 10,000 to 450 cm-1

    NASA Astrophysics Data System (ADS)

    Pearl, J.; Ngoh, M.; Ospina, M.; Khanna, R.

    1991-09-01

    We made thin film transmission measurements of solid CH4 (phases I and II) and C2H6 (phase II). From these, the complex indices of refraction at near- and mid-infrared wavelengths were determined by using a combined least squares and Kramers-Kronig analysis.

  20. 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.

  1. 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

  2. Direct aromatization of methane. Quarterly technical progress report No. 9, October 1, 1994--December 31, 1994

    SciTech Connect

    1995-05-30

    Further experiments have been performed on the assisted pyrolysis by the addition of a free-radical initiator, as well as on the initiation of pyrolysis by a solid surface using a variety of catalysts. The reaction has been studied in the temperature range of 850-1100{degrees}C, methane flow rates of 475-1000 Scc/min, and ethane flow rates of 21-42 Scc/min. Significant reduction in the pyrolysis temperature was observed in both cases, with measurable amounts of methane being converted at temperatures as low as 850{degrees}C. When ethane was added as a free-radical initiator, the major pyrolysis products were ethylene and propylene at temperatures below 950{degrees}C. At higher pyrolysis temperatures, the selectivity shifted toward benzene and acetylene which became the main analyzable products at 1050{degrees}C and 1100{degrees}C.

  3. Structure and molecular interactions in {ethanol + (propan-1-ol/propan-2-ol)} mixtures at 303.15 K

    NASA Astrophysics Data System (ADS)

    Deosarkar, S. D.; Puyad, A. L.

    2014-06-01

    In view of industrial importance of binary {ethyl alcohol + (propan-1-ol/propan-2-ol)} mixtures, the densities (ρ) and refractive indices ( n D ) of these alkanols mixtures were measured for different compositions at 303.15 K. Molar volumes ( V m) and excess molar volumes ( V E) of these binary mixtures were calculated from experimental density data of pure solvents and solvents mixtures. The measured refractive index and density data was used to calculate specific refractions ( R D ), molar refractions ( R M) and apparent molar refractions ( R φ, i ) of binary mixtures. From mole fraction dependence of apparent molar refractions, the limiting apparent molar refractions ( R {φ,/i ○}) of propan-1-ol and propan-2-ol have been determined. The graphical values of R {φ,/i ○} for propan-1-ol and propan-2-ol were found to be 9.5664 and 7.405 cm3 mol-1 respectively. Structural changes, geometrical fittings and molecular interactions in binary mixtures of these alkanols have been discussed.

  4. 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. PMID:20950018

  5. Low temperature production and exhalation of methane from serpentinized rocks on Earth: A potential analog for methane production on Mars

    NASA Astrophysics Data System (ADS)

    Etiope, Giuseppe; Ehlmann, Bethany L.; Schoell, Martin

    2013-06-01

    We evaluate, based on terrestrial analogs, the potential flux, origin and isotopic signature of methane (CH4) from serpentinized or serpentinizing rocks on Mars. The Tekirova ophiolites, in Turkey, have been shown to release, either via focused vents or through diffuse microseepage, substantial amounts of CH4 which could be produced via catalyzed abiotic methanation (Sabatier reaction) at low temperatures (<50 °C). Serpentinized ultramafic rocks on Mars are likely to have necessary chemical constituents for methane production and fractures for release of gas to the atmosphere, similar to those on Earth. A simple, first-order estimation gas-advection model suggests that methane fluxes on the order of several mg m-2 d-1, similar to microseepage observed in terrestrial ophiolites, could occur in martian rocks. High temperature, hydrothermal conditions may not be necessary for abiotic CH4 synthesis on Mars: low temperature (<50 °C) methanation is possible in the presence of catalysts like ruthenium, rhodium or, more commonly, chromium minerals, which occur in terrestrial ophiolites as in martian mantle meteorites. The terrestrial analog environment of abiotic microseepage may thus explain production of methane on Mars in the ancient past or at present. The wide range of martian 12C/13C and D/H ratios and the potential secondary alteration of CH4 by abiotic oxidation, as observed on Earth, could result in large isotope variations of methane on Mars. CH4 isotopic composition alone may not allow definitive determination of biotic vs. abiotic gas origin. Using our terrestrial vs. martian analysis as guide to future Mars exploration we propose that direct methane and ethane gas detection and isotopic measurements on the ground over serpentinized/serpentinizing rocks should be considered in developing future strategies for unraveling the source and origin of methane on Mars.

  6. Swelling Behavior of Ultrathin Polymer Films in Supercritical Ethane

    NASA Astrophysics Data System (ADS)

    Ji, Yuan; Koga, Tadanori; Seo, Young-Soo; Rafailovich, Miriam; Sokolov, Jonathan; Satija, Sushil

    2003-03-01

    Swelling behavior of ultrathin polymer films in supercritical ethane (T_c=32^oC, P_c=4.86MPa) was investigated by using in situ neutron reflectivity (NR). The polymers used in this study were deuterated polystyrene(dPS), deuterated styrene-butadiene copolymer(dSBR), deuterated polymethylmethacrylate(dPMMA), deuterated polybutadiene(dPB) and the films were spun cast on the HF etched cleaned silicon wafers. NR experiments were conducted with the pressure range of 0.1-15 MPa at T=37^oC by using NG7 reflectometer at NIST. As a result, we found that all the polymers used showed anomalous peak in the linear dilation (S_f) curve at P=5.5MPa, i.e., the density fluctuation ridge of ethane while the Sf values for the rubbery polymers were significantly larger (0.8) than those of glassy polymers (0.3). In this presentation, we will also discuss about the universality in the swelling behavior of the polymer thin films in the presence of the supercritical fluids.

  7. Evaluation of various models of propane-powered mosquito traps.

    PubMed

    Kline, Daniel L

    2002-06-01

    Large cage and field studies were conducted to determine the efficacy of various models of propane-powered mosquito traps. These traps utilized counterflow technology in conjunction with catalytic combustion to produce attractants (carbon dioxide, water vapor, and heat) and a thermoelectric generator that converted excess heat into electricity for stand-alone operation. The cage studies showed that large numbers of Aedes aegypti and Ochlerotatus taeniorhynchus were captured and that each progressive model resulted in increased trapping efficiency. In several field studies against natural populations of mosquitoes two different propane traps were compared against two other trap systems, the professional (PRO) and counterflow geometry (CFG) traps. In these studies the propane traps consistently caught more mosquitoes than the PRO trap and significantly fewer mosquitoes than the CFG traps. The difference in collection size between the CFG and propane traps was due mostly to Anopheles crucians. In spring 1997 the CFG trap captured 3.6X more An. crucians than the Portable Propane (PP) model and in spring 1998 it captured 6.3X more An. crucians than the Mosquito Magnet Beta-1 (MMB-1) trap. Both the PP and MMB-1 captured slightly more Culex spp. than the CFG trap. PMID:12125861

  8. Adsorptive separation of ethylene/ethane mixtures using carbon nanotubes: a molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Tian, Xingling; Wang, Zhigang; Yang, Zaixing; Xiu, Peng; Zhou, Bo

    2013-10-01

    Ethylene/ethane separation is a very important process in the chemical industry. Traditionally, this process is achieved by cryodistillation, which is extremely energy-intensive. The adsorptive separation is an energy-saving and environmentally benign alternative. In this study, we employ molecular dynamics simulations to study the competitive adsorption of an equimolar mixture of gaseous ethane and ethylene inside single-walled carbon nanotubes (SWNTs) of different diameters at room temperature. We find that for narrow SWNTs, i.e. the (6, 6) and (7, 7) SWNTs, the selectivities towards ethane, fselec, can reach values of 3.1 and 3.7, respectively. Such high selectivities are contrary to the opinion of many researchers that the adsorptive separation of an ethylene/ethane mixture by means of dispersion interaction is difficult due to the same carbon number of ethane and ethylene. The key for our observation is that the role of dispersion interaction of ethane's additional two hydrogen atoms with the SWNT becomes significant under extreme confinement. Interestingly, the (8, 8) SWNT prefers ethylene to ethane with fselec = 0.6. For wider SWNTs, fselec converges to ∼1. The mechanisms behind these observations, as well as the kinetics of single-file nanopore filling and kinetics of confined gas molecules are discussed. Our findings suggest that efficient ethane/ethylene separation can be achieved by using bundles/membranes of SWNTs with appropriate diameters.

  9. Solubilities of ethane in aqueous solutions of sodium dodecyl sulfate at elevated pressures

    SciTech Connect

    Li, P.; Han, B.; Yan, H.; Liu, R.

    1995-10-01

    The solubilities of ethane in aqueous solutions of sodium dodecyl sulfate (SDS) were measured at 313.15 K and at pressures up to 3 MPa. The molalities of SDS (m{sub SDS}) in the aqueous solution were 0.0000, 0.0020, 0.0040, 0.0060, 0.0070, 0.0080, 0.0090, 0.0100, 0.0126, 0.0150, 0.0200, and 0.0300. The effect of SDS on the gas solubility in both concentration regions below and above the critical micelle concentration (cmc) was studied. The existence of the micelles of SDS in the solution is favorable to the dissolution of ethane due to the hydrocarbon-like interior of the micelles. The solubilities of ethane in each micelle at different pressures were evaluated based on some assumptions. It was found that the intramicellar solubility of ethane is less than that of the gas in n-dodecane. It was also found that the solubility of ethane in the micelles increases linearly with the partial pressure of ethane. The cmc of SDS was evaluated based on the solubility vs m{sub SDS} curves and the effect of dissolved ethane on the cmc was studied. It was observed that the cmc shifts toward a higher value with the increase in dissolved ethane.

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. An engineered pathway for the biosynthesis of renewable propane.

    PubMed

    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

  16. 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.

  17. 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. PMID:25015887

  18. 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

  19. Methane flux in gas hydrate potential area offshore Southwestern Taiwan

    NASA Astrophysics Data System (ADS)

    Yang, T. F.; Hu, C.; Chuang, P.; Chen, N.; Chen, C.; Lin, S.; Wang, Y.; Chung, S.; Chen, P.

    2012-12-01

    The widely distributed BSRs imply the existence of potential gas hydrates in offshore southwestern Taiwan. To better constrain the gas sources in this area, in total 22 cores have been collected from different tectonic environments in offshore SW Taiwan during the r/v Marion Dufresne 178 cruise, including 17 giant piston cores, 4 CASQ box cores, and 1 gravity core. The results show that the major gas is methane with very few ethane and carbon dioxide. It indicates they are mostly biogenic source in origin. However, some gas samples from active margin do also exhibit heavier carbon isotopic compositions, which range from -40 to -60 permil and are similar with the gas composition of inland mud volcanoes of SW Taiwan. It implies that there is also thermogenic gas source in this region. Total changes of the dissolved inorganic carbon (DIC) fluxes (ΔDIC-Prod ) can be used to estimate the methane flux quantitatively, and we confirm that the sulfate depletion is mainly controlled by the anaerobic oxidation of methane (AOM) reaction and/or the sedimentary organic matter. Although BSRs are widely distributed both in the active margin and in the passive margin, the methane fluxes in active margin are greater than in passive margin of the coring sites. All the estimated methane fluxes in offshore SW Taiwan are higher than other gas hydrate and upwelling area.

  20. Gaseous abundances and methane supersaturation in Titan's troposphere

    NASA Astrophysics Data System (ADS)

    Samuelson, Robert E.; Nath, Nitya R.; Borysow, Aleksandra

    1997-08-01

    Various properties of Titan's troposphere are inferred from an analysis of Voyager 1 infrared spectrometer (IRIS) data between 200 and 600 cm -1. 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-σ uncertainties of several parameters are inferred from our analysis. These include mole fractions for molecular hydrogen (˜0.0011), argon (small), and methane near the surface (˜0.057). Solutions are also obtained for the hydrogen para-fraction (close to equilibrium, with considerable uncertainty), air temperature near the surface (˜93 K), surface temperature discontinuity (˜1 K), and maximum degree of methane supersaturation in the upper troposphere (˜ 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 stratospheric haze opacity is inferred similar to that found for a polymeric residue created in laboratory discharge experiments. This haze appears to be uniformly distributed with latitude between altitudes of 40 and 160 km, provided those nighttime data at southern high latitudes that are subject to possible systematic calibration errors are discounted. Assuming uniform haze distribution, both the air temperature and methane vapor mole fraction near the surface are symmetrically distributed about the equator, with lower values at higher latitudes. Either the tropopause temperature or the maximum degree of methane supersaturation is asymmetrically distributed about the equator. In

  1. Interest in propane futures appears to be growing

    SciTech Connect

    Not Available

    1992-12-01

    The last couple of decades have seen significant and sometimes abrupt change sin world energy markets and prices. In addition to regional politics, war, and changing economic patterns, the energy industry has undergone structural changes that have increased price and supply stability. This paper reports that these changes have filtered through the energy industry to the LPG market giving many in the industry a reason to use the propane futures market. The current operative market is run by the New York Mercantile Exchange (NYMEX). Started up in 1987, this propane futures market is much more successful than its predecessors.

  2. [Frostbite injuries causing compromised airway after inhalation of propane].

    PubMed

    Straarup, Therese Simonsen; Fink, Anders Olsen; Larsen, Jens Kjærgaard Rolighed

    2015-01-01

    We describe a case report of a 23-year-old man with acute pharyngeal injuries due to frostbite subsequent to inhalation of propane. He was fiber-optically intubated on admission to hospital since his airways were considered acutely compromised. He was subsequently kept intubated for 11 days due to persistent pharyngeal oedema and frostbite injuries. The latter is caused by low temperature of propane upon release from a pressurized container. Injuries caused by frostbite often gradually progress and thus caution should be exerted in regards to airway management. PMID:25557449

  3. 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.

  4. 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.

  5. Mid-Infrared Ethane Emission on Neptune: 2005-2009

    NASA Astrophysics Data System (ADS)

    Hammel, Heidi B.; Sitko, M. L.; Russell, R. W.; Lynch, D. K.; Bernstein, L. S.; Perry, R. B.

    2009-09-01

    Hammel et al. (2006, ApJ 644, 1326) reported 8- to 13-micron spectral observations of Neptune spanning more than a decade. Those data indicated a steady increase in Neptune's 12-micron atmospheric ethane emission from 1985 to 2003, followed by a slight decrease in 2004. The simplest explanation for the intensity variation was an increase in stratospheric effective temperature from 155 K in 1985 to 176 K in 2003 (an average rate of 1.2 K/year), and subsequent decrease to 165 K in 2004 (uncertainties +/- 3 K). Later disk-resolved 12-micron images (Hammel et al. 2007, AJ 134, 637; Orton et al. 2007, AA 473, L5) showed Neptune's ethane emission arose mainly from two regions: emission distributed nearly uniformly around the planet's limb and emission near the south pole. Because much of the non-limb emission was confined to the near-polar region, seasonal variation may play some role in the long-term mid-infrared brightness variations: i.e., more of that region was revealed as Neptune neared solstice in 2005. We will report the results of an additional half decade of mid-infrared spectroscopic observations, from 2005 through 2009, using the Broadband Array Spectrograph System on the NASA Infrared Telescope Facility (IRTF). These post-solstice data should elucidate whether the variations are intrinsic, or due to changes in viewing angle. HBH acknowledges support from NASA grants NNX06AD12G and NNA07CN65A. This work was supported at The Aerospace Corporation by the Independent Research and Development Program. LSB acknowledges the support of Spectral Sciences, Inc. IR and D funding. We also gratefully acknowledge D. Kim (The Aerospace Corporation) for BASS technical support, as well as the support of IRTF staff and telescope operators. We recognize the significant cultural role of Mauna Kea within the indigenous Hawaiian community, and we appreciate the opportunity to conduct observations from this revered site.

  6. 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

  7. 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. PMID:24809894

  8. 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.

  9. Diffusion of 2-iodo-propane (1); helium (2)

    NASA Astrophysics Data System (ADS)

    Winkelmann, J.

    This document is part of Subvolume A `Gases in Gases, Liquids and their Mixtures' of Volume 15 `Diffusion in Gases, Liquids and Electrolytes' of Landolt-Börnstein Group IV `Physical Chemistry'. It is part of the chapter of the chapter `Diffusion in Pure Gases' and contains data on diffusion of (1) 2-iodo-propane; (2) helium

  10. Diffusion of 1-iodo-propane (1); air (2)

    NASA Astrophysics Data System (ADS)

    Winkelmann, J.

    This document is part of Subvolume A `Gases in Gases, Liquids and their Mixtures' of Volume 15 `Diffusion in Gases, Liquids and Electrolytes' of Landolt-Börnstein Group IV `Physical Chemistry'. It is part of the chapter of the chapter `Diffusion in Pure Gases' and contains data on diffusion of (1) 1-iodo-propane; (2) air

  11. Diffusion of 2-iodo-propane (1); air (2)

    NASA Astrophysics Data System (ADS)

    Winkelmann, J.

    This document is part of Subvolume A `Gases in Gases, Liquids and their Mixtures' of Volume 15 `Diffusion in Gases, Liquids and Electrolytes' of Landolt-Börnstein Group IV `Physical Chemistry'. It is part of the chapter of the chapter `Diffusion in Pure Gases' and contains data on diffusion of (1) 2-iodo-propane; (2) air

  12. Diffusion of 1-iodo-propane (1); helium (2)

    NASA Astrophysics Data System (ADS)

    Winkelmann, J.

    This document is part of Subvolume A `Gases in Gases, Liquids and their Mixtures' of Volume 15 `Diffusion in Gases, Liquids and Electrolytes' of Landolt-Börnstein Group IV `Physical Chemistry'. It is part of the chapter of the chapter `Diffusion in Pure Gases' and contains data on diffusion of (1) 1-iodo-propane; (2) helium

  13. Ordered mesoporous carbon catalyst for dehydrogenation of propane to propylene.

    PubMed

    Liu, Lei; Deng, Qing-Fang; Agula, Bao; Zhao, Xu; Ren, Tie-Zhen; Yuan, Zhong-Yong

    2011-08-01

    Metal-free ordered mesoporous carbons were demonstrated to be robust catalysts for direct dehydrogenation of propane to propylene, in the absence of any auxiliary steam, exhibiting high activity and selectivity, as well as long catalytic stability, in comparison with nanostructured carbons. PMID:21687889

  14. 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.

  15. 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

  16. 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.

  17. Dynamic light scattering measurements of reverse micelle phases in liquid and supercritical ethane

    SciTech Connect

    Blitz, J.P.; Fulton, J.L.; Smith, R.D.

    1988-05-19

    Dynamic light scattering of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) in liquid and supercritical ethane provides the first direct evidence of reverse micelles in a supercritical fluid (dense gas). Micellar hydrodynamic diameters are only slightly larger in ethane than in liquid isooctane at the same concentrations and temperature, but diffusion coefficients are more than 10 times greater. Measurements of micelle diffusion coefficient and hydrodynamic diameter versus pressure in liquid and supercritical ethane show that density has a strong effect on hydrodynamic size and suggest that micelle clustering may be significant and highly sensitive to pressure. The utility of dynamic light scattering for studying reverse micelle phases in a dense gas is demonstrated.

  18. Methane Plumes on Mars

    NASA Video Gallery

    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...

  19. 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.

  20. 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

  1. Methane Emissions from Natural Gas in the Urban Region of Boston, Massachusetts

    NASA Astrophysics Data System (ADS)

    McKain, K.; Down, A.; Raciti, S. M.; Budney, J.; Hutyra, L.; Floerchinger, C. R.; Herndon, S. C.; Zahniser, M. S.; Nehrkorn, T.; Jackson, R. B.; Phillips, N. G.; Wofsy, S. C.

    2014-12-01

    Methane emissions from the natural gas supply chain must be quantified to assess environmental impacts of natural gas and to develop emission reduction strategies. We report natural gas emission rates for one year in the urban region of Boston, MA, using an 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 rate, 20.6 ± 1.7 (95 % CI) g CH4 m-2 yr-1. Simultaneous observations of atmospheric ethane, compared with the ethane to methane ratio in pipeline gas, demonstrate that natural gas accounted for 58 - 100 % of methane emissions, depending on season. Using government statistics and geospatial data on energy consumption, we estimate the fractional loss rate to the atmosphere from all downstream components of the natural gas system, including transmission, distribution, and end-use, was 2.9 ± 0.3 % in the Boston urban region, compared to 1.1 % inferred by the Massachusetts greenhouse gas inventory.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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. PMID:27218414

  7. Preparation, characterization, and sequential transformation of dicarbide cluster compounds with permetalated ethyne, ethene, and ethane structures

    SciTech Connect

    Akita, Munetaka; Sugimoto, Shuichiro; Tanaka, Masako; Moro-oka, Yoshihiko

    1992-09-09

    The preparation, characterization and sequential transformation of dicarbide cluster compounds with permetalated ethyne, ethene and ethane structures is discussed. The group reporting has developed a preparative method for ethynediyldimetal complexes via deprotonation. 10 refs., 3 figs.

  8. Laboratory Studies of Ethane Ice Relevant to Outer Solar System Surfaces

    NASA Technical Reports Server (NTRS)

    Moore, Marla H.; Hudson, Reggie; Raines, Lily

    2009-01-01

    Oort Cloud comets, as well as TNOs Makemake (2045 FYg), Quaoar, and Pluto, are known to contain ethane. However, even though this molecule is found on several outer Solar System objects relatively little information is available about its amorphous and crystalline phases. In new experiments, we have prepared ethane ices at temperatures applicable to the outer Solar System, and have heated and ion-irradiated these ices to study phase changes and ethane's radiation chemistry using mid-IR spectroscopy (2.2 - 16.6 microns). Included in our work is the meta-stable phase that exists at 35 - 55 K. These results, including newly obtained optical constants, are relevant to ground-based observational campaigns, the New Horizons mission, and supporting laboratory work. An improved understanding of solid-phase ethane may contribute to future searches for this and other hydrocarbons in the outer Solar System.

  9. Attenuation of methane and volatile organic compounds in landfill soil covers.

    PubMed

    Scheutz, Charlotte; Mosbaek, Hans; Kjeldsen, Peter

    2004-01-01

    The potential for natural attenuation of volatile organic compounds (VOCs) in landfill covers was investigated in soil microcosms incubated with methane and air, simulating the gas composition in landfill soil covers. Soil was sampled at Skellingsted Landfill at a location emitting methane. In total, 26 VOCs were investigated, including chlorinated methanes, ethanes, ethenes, fluorinated hydrocarbons, and aromatic hydrocarbons. The soil showed a high capacity for methane oxidation resulting in very high oxidation rates of between 24 and 112 microg CH4 g(-1) h(-1). All lower chlorinated compounds were shown degradable, and the degradation occurred in parallel with the oxidation of methane. In general, the degradation rates of the chlorinated aliphatics were inversely related to the chlorine to carbon ratios. For example, in batch experiments with chlorinated ethylenes, the highest rates were observed for vinyl chloride (VC) and lowest rates for trichloroethylene (TCE), while tetrachloroethylene (PCE) was not degraded. Maximal oxidation rates for the halogenated aliphatic compounds varied between 0.03 and 1.7 microg g(-1) h(-1). Fully halogenated hydrocarbons (PCE, tetrachloromethane [TeCM], chlorofluorocarbon [CFC]-11, CFC-12, and CFC-113) were not degraded in the presence of methane and oxygen. Aromatic hydrocarbons were rapidly degraded giving high maximal oxidation rates (0.17-1.4 microg g(-1) h(-1)). The capacity for methane oxidation was related to the depth of oxygen penetration. The methane oxidizers were very active in oxidizing methane and the selected trace components down to a depth of 50 cm below the surface. Maximal oxidation activity occurred in a zone between 15 and 20 cm below the surface, as this depth allowed sufficient supply of both methane and oxygen. Mass balance calculations using the maximal oxidation rates obtained demonstrated that landfill soil covers have a significant potential for not only methane oxidation but also cometabolic

  10. 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

  11. 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.

  12. Studies and evaluation of the potential toxicity of decabromodiphenyl ethane to five aquatic and sediment organisms.

    PubMed

    Hardy, M L; Krueger, H O; Blankinship, A S; Thomas, S; Kendall, T Z; Desjardins, D

    2012-01-01

    The potential toxicity of decabromodiphenyl ethane (DBDP-Ethane) was explored in 5 types of organisms residing in the water column and/or sediment, e.g. Oncorhynchus mykiss, Pseudokirchneriella subcapitata, Daphnia magna, Chironmus riparius, and Lumbriculus variegates. Fish, algae or Daphnia were unaffected by acute exposures to water accommodated fractions of 110mg DBDP-Ethane/L. Chronic exposure to DBDP-Ethane at the highest dose tested, 5000mg/kg dry sediment, did not affect midge mean development times, emergence or development rates or oligochaete survival, reproduction or dry weight. The chronic EC50, LOEC and NOEC were ≥5000mg/kg in the two sediment species. Applying an assessment factor of 50, the unbounded predicted no effect concentration (PNEC(sediment)) was 100mg/kg dry sediment. The calculated PNEC indicates DBDPE-Ethane presents little risk to sediment organisms. These results add to DBDP-Ethane's existing database in the terrestrial compartment and mammals. PMID:21862128

  13. Selective oxidation of ethane using the Au|YSZ|Ag electrochemical membrane system

    SciTech Connect

    Hamakawa, Satoshi; Sato, Koichi; Hayakawa, Takashi; York, A.P.E.; Tsunoda, Tatsuo; Suzuki, Kunio; Shimizu, Masao; Takehira, Katsuomi

    1997-01-01

    The catalytic conversion of ethane to acetaldehyde on an inert gold electrode has been studied using the electrochemical membrane reactor with yttria-stabilized zirconia (YSZ) solid electrolyte at 475 C. On applying a direct current to the reaction cell, 5% ethane in N{sub 2}, Au|YSZ|Ag, 100% O{sub 2}, acetaldehyde was formed and the formation rate increased linearly with increasing current. Selectivities to acetaldehyde and carbon dioxide were 45 and 55%, respectively. The addition of oxygen to the ethane-mixed gas in the anode space did not affect the acetaldehyde formation. The use of YSZ powder as a fixed bed catalyst under the mixed gas flow of ethane and oxygen at 450 to 600 C resulted in the formation of carbon monoxide, carbon dioxide, and ethene. Even the use of N{sub 2}O instead of oxygen resulted in no formation of acetaldehyde. Hence, it is likely that partial oxidation of ethane to acetaldehyde was carried out by the oxygen species transferred electrochemically through the YSZ which appeared at the gold-YSZ-gas triple-phase boundary. From the results of ethanol oxidation over the Au|YSZ|Ag system, the following mechanism was proposed: ethane is dehydrogenated to an ethyl radical, then converted to ethoxide, and finally to acetaldehyde by the oxygen species transferred through the YSZ.

  14. 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. PMID:22721935

  15. 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

  16. Novel catalysts for methane activation. Quarterly report No. 9, October 1, 1994--December 31, 1994

    SciTech Connect

    Hirschon, A.S.; Wu, H.J.; Malhotra, R.; Wilson, R.B.

    1995-04-20

    Fullerenes are a recently discovered allotrope of carbon that have been found to possess unusual properties, some of which may be ideal for methane activation. This project is designed to evaluate these carbon-based materials for conversion of methane into higher hydrocarbons. The project is divided into three technical tasks. Task 1 deals with synthesis and characterization of the fullerenes and fullerene soots, Task 2 with testing of the catalysts, and Task 3 with evaluation of the results and technical reporting. The results and accomplishments for this quarter are as follows: Reconstituted fullerene soot was prepared by adding C{sub 60} to a toluene-extracted Terrasimco fullerene soot; K-doped fullerene soots of different potassium concentrations were prepared; Fullerene soot doped with cesium was prepared by addition of cesium carbonate; The reconstituted fullerene soot was tested for methane activation. K-doped soots at different K concentrations were tested for methane activation. K-doped soot was examined for methane activation in the presence of co-feeds of either ethane or ethylene; a higher selectivity to C{sub 3} and C{sub 4} hydrocarbons was observed for the K-soot than when these reactions were conducted using soot as a catalyst, or when thermally induced. The Cs-doped soot was tested for methane activation; the selectivity for hydrocarbons from the methane conversion catalyzed by this soot was found to be higher than catalyzed by fullerene soot but lower than by K-soot.

  17. 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.

  18. Symmetry classification of the degenerate vibrational normal modes of ethane

    NASA Astrophysics Data System (ADS)

    Lattanzi, F.; di Lauro, C.; Legay-Sommaire, N.

    1992-11-01

    We determine the G36(EM) (usually called G 36†) symmetry species of all the degenerate vibrational normal modes of ethane unambiguously. We are able to do this as a result of observing the K-dependence of the sign of the energy separation between the torsionally split levels of ν4 + νy combination states, where ν4 is the torsion and νy ⊂ Eg of D3 d, and by observing the lack of any intrinsic torsional splitting or broadening in the νx fundamentals and hot ( ν4 + νx) - ν4 transitions ( νx ⊂ Eu of D3 d). It is found that in C 2H 6 all the Eu normal modes of D3 d correlate with E1 d of G36(EM) (and hence E' of D3 h), and all the Eg normal modes of D3 d correlate with E1 d of G36(EM) (and hence E″ of D3 h). High-resolution Q branches of ν8, ν4 + ν12, and ( ν4 + ν8) - ν4 of C 2H 6 are shown as illustrations.

  19. Vitiated ethane oxidation in a high-pressure flow reactor

    SciTech Connect

    Walters, K.M.; Bowman, C.T.

    2009-10-15

    Vitiated combustion processes offer the potential to improve the thermodynamic efficiency in hydrocarbon-fueled combustion systems, providing a subsequent decrease in energy-specific CO{sub 2} emissions along with a decrease in the emission levels of nitrogen oxides (NO{sub x}) and particulate matter. The present work comprises an experimental and modeling study of vitiated ethane oxidation in a high-pressure flow reactor, with pressures of 1-6 bar, O{sub 2} mole fractions of 3.5-7.0%, temperatures of 1075-1100 K and 15-18 mole.% H{sub 2}O. Time-history measurements of species are used to characterize the overall rate of reaction and track the fuel-carbon through intermediate and product species. A one-dimensional mixing-reacting model that accounts for partial oxidation during reactant mixing is used in conjunction with a detailed kinetic mechanism. Changes in competing pathways due to variations in pressure and O{sub 2} mole fraction give rise to the complex pressure dependence seen in the experiments. (author)

  20. 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.

  1. 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. PMID:22150071

  2. Atomic-Scale Determination of Active Facets on the MoVTeNb Oxide M1 Phase and Their Intrinsic Catalytic Activity for Ethane Oxidative Dehydrogenation.

    PubMed

    Melzer, Daniel; Xu, Pinghong; Hartmann, Daniela; Zhu, Yuanyuan; Browning, Nigel D; Sanchez-Sanchez, Maricruz; Lercher, Johannes A

    2016-07-25

    Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) has been used to image the basal {001} plane of the catalytically relevant M1 phase in MoVTeNb complex oxides. Facets {010}, {120}, and {210} are identified as the most frequent lateral termination planes of the crystals. Combination of STEM with He ion microscopy (HIM) images, Rietveld analysis, and kinetic tests reveals that the activation of ethane is correlated to the availability of facets {001}, {120}, and {210} at the surface of M1 crystals. The lateral facets {120} and {210} expose crystalline positions related to the typical active centers described for propane oxidation. Conversely, the low activity of the facet {010} is attributed to its configuration, consisting of only stable M6 O21 units connected by a single octahedron. Thus, we quantitatively demonstrated that differences in catalytic activity among M1 samples of equal chemical composition depend primarily on the morphology of the particles, which determines the predominant terminating facets. PMID:26990594

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. 3-Oxo-3-(piperidin-1-yl)propane­nitrile

    PubMed Central

    Fun, Hoong-Kun; Quah, Ching Kheng; Abdel-Aziz, Hatem A.; Ghabbour, Hazem A.

    2012-01-01

    In the title compound, C8H12N2O, the piperidine ring exhibits a chair conformation and its least-squares plane (all atoms) makes a dihedral angle of 32.88 (12)° with the propane­nitrile unit (r.m.s. deviation = 0.001 Å). In the crystal, mol­ecules are linked by C—H⋯O hydrogen bonds, forming chains along [001]. PMID:22969610

  10. 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

  11. The viscosity of gaseous propane and its initial density dependence

    NASA Astrophysics Data System (ADS)

    Vogel, E.

    1995-11-01

    Results of five series of high-precision viscosity measurements on gaseous propane, each differing in density, are reported. The measurements were performed in a quartz oscillating-disk viscometer with small gaps from room temperature up to about 625 K and for densities between 0.01 and 0.05 mol · L-1. The experimental data were evaluated with a first-order expansion, in terms of density, for the viscosity. Reduced values of the second viscosity virial coefficients deduced from the zero-density and initial-density viscosity coefficients for propane and for further n-alkanes are in close agreement with the theoretical representation of the Rainwater-Friend theory for the potential parameter ratios by Bich and Vogel. A new representation of the viscosity of propane in the limit of zero density is provided using the new experimental data and some data sets from literature. The universal correlation based on the extended principle of corresponding states extends over the temperature range 293 to 625 K with an uncertainty of ±0.5 % and deviates from earlier representations by about 1 % at the upper temperature limit.

  12. The viscosity of gaseous propane and its initial density dependence

    SciTech Connect

    Vogel, E.

    1995-11-01

    Results of five series of high-precision viscosity measurements on gaseous propane, each differing in density, are reported. The measurements were performed in a quartz oscillating-disk viscometer with small gaps from room temperature up to about 625 K and for densities between 0.01 and 0.05 mol {center_dot} L{sup -1}. The experimental data were evaluated with a first-order expansion, in terms of density, for the viscosity. Reduced values of the second viscosity virial coefficients deduced from the zero-density and initial-density viscosity coefficients for propane and for further n-alkanes are in close agreement with the theoretical representation of the Rainwater-Friend theory for the potential parameter ratios by Bich and Vogel. A new representation of the viscosity of propane in the limit of zero density is provided using the new experimental data and some data sets from literature. The universal correlation based on the extended principle of corresponding states extends over the temperature range 293 to 625 K with an uncertainty of {plus_minus}0.5% and deviates from earlier representations by about 1% at the upper temperature limit.

  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. PMID:25889543

  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. Infrared Spectra and Optical Constants of Acetylene and Ethane Ices

    NASA Astrophysics Data System (ADS)

    Moore, Marla H.; Ferrante, R. F.; Hudson, R. L.; Moore, W. J.

    2012-10-01

    Hydrocarbon-containing ices have characteristic absorption bands in both the mid- and near-infrared spectral regions, yet accurate optical constants are not available for most of these molecules. Ices with a hydrocarbon component have been identified on several TNOs (1) and the presence of volatiles, such as hydrocarbons, is inferred for intermediate or large TNOs based on sublimation models (2, 3). In our laboratory we recently have undertaken low-temperature spectroscopic studies of C2 hydrocarbons. We report IR spectra for acetylene (C2H2) and ethane (C2H6) ice in both the amorphous and crystalline phases at multiple temperatures. We include measurements of the refractive index at 670 nm for both the amorphous and crystalline phases of each ice. The optical constants, the real (n) and imaginary (k) components of the complex index of refraction, were determined from 7000 - 400 cm-1 (1.4 - 25 microns) at multiple temperatures using a Kramers-Kronig analysis. A goal of the present work is to provide a data base of optical constants of C2 molecules similar to that of Hudgins et al. (4) and Moore et al. (5). These values, as well as our calculated individual band strengths, will have great practical importance for the ongoing analysis of TNO spectra. (1) Brown, M.E. et al., Astron J., 133, 284, 2007. (2) Delsanti, A. et al., A&A, 52, A40, 2010. (3) Schaller, E. L. & Brown, M. E., ApJ, 659, L61, 2007. (4) Hudgins, D. M. et al., ApJS, 86, 713, 1993. (5) Moore, M. H. et al., ApJS, 191, 96, 2010. This work is supported by NASA’s Planetary Atmospheres, Outer Planets, and Cassini Data Analysis programs, and The Goddard Center for Astrobiology.

  16. 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.

  17. Methane Hydrate Field Program

    SciTech Connect

    2013-12-31

    This final report document summarizes the activities undertaken and the output from three primary deliverables generated during this project. This fifteen month effort comprised numerous key steps including the creation of an international methane hydrate science team, determining and reporting the current state of marine methane hydrate research, convening an international workshop to collect the ideas needed to write a comprehensive Marine Methane Hydrate Field Research Plan and the development and publication of that plan. The following documents represent the primary deliverables of this project and are discussed in summary level detail in this final report. • Historical Methane Hydrate Project Review Report • Methane Hydrate Workshop Report • Topical Report: Marine Methane Hydrate Field Research Plan • Final Scientific/Technical Report

  18. 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.

  19. 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. PMID:20949518

  20. 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.

  1. 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.

  2. CFD Modeling of a Laser-Induced Ethane Pyrolysis in a Wall-less Reactor

    NASA Astrophysics Data System (ADS)

    Stadnichenko, Olga; Snytnikov, Valeriy; Yang, Junfeng; Matar, Omar

    2014-11-01

    Ethylene, as the most important feedstock, is widely used in chemical industry to produce various rubbers, plastics and synthetics. A recent study found the IR-laser irradiation induced ethane pyrolysis yields 25% higher ethylene production rates compared to the conventional steam cracking method. Laser induced pyrolysis is initiated by the generation of radicals upon heating of the ethane, then, followed by ethane/ethylene autocatalytic reaction in which ethane is converted into ethylene and other light hydrocarbons. This procedure is governed by micro-mixing of reactants and the feedstock residence time in reactor. Under mild turbulent conditions, the turbulence enhances the micro-mixing process and allows a high yield of ethylene. On the other hand, the high flow rate only allows a short residence time in the reactor which causes incomplete pyrolysis. This work attempts to investigate the interaction between turbulence and ethane pyrolysis process using large eddy simulation method. The modelling results could be applied to optimize the reactor design and operating conditions. Skolkovo Foundation through the UNIHEAT Project.

  3. Ethane pollution in the UTLS observed with the imaging infrared limb sounder GLORIA

    NASA Astrophysics Data System (ADS)

    Sumińska-Ebersoldt, Olga

    2015-04-01

    Ethane (C2H6) in the atmosphere results from the production and transmission of fossil fuels, biofuel use and biomass burning. Due to its lifetime of 2 - 3 months, ethane is a significant indicator and tracer of industrial pollution and enables investigation of transport and mixing in the UTLS region. During the TACTS/ESMVal flight over Arabian Sea and Arabian Peninsula in summer 2012, GLORIA (Gimballed Limb Observer for Radiance Imaging of the Atmosphere) detected two layers (at 10-12 km and 12-14 km altitude) and two vertical plums of enhanced ethane with mixing ratios of about 1000 ppt. The spatial distribution cross sections of ethane retrieved from GLORIA chemistry mode measurements show good correlation with numerous trace gases sampled with in-situ instruments during the flight. Based on the data and the climatology, we evaluate here the sources of the ethane mixing ratio enhancements with backward trajectory calculations and investigate an impact of outflow of pollutants from the Asian summer monsoon on the composition of the UTLS in the flight region.

  4. Diurnal variability of atmospheric methane, nonmethane hydrocarbons, and carbon monoxide at Mauna Loa

    NASA Astrophysics Data System (ADS)

    Greenberg, J. P.; Zimmerman, P. R.; Pollock, W. F.; Lueb, R. A.; Heidt, L. E.

    1992-06-01

    Results are presented on measurements of atmospheric CH4, nonmethane hydrocarbons, and CO, made in May-June 1988 at Mauna Loa Observatory (MLO). The results pointed to marine sources for ethylene and propylene and island sources for isoprene. The mixing ratio of ethylene and propylene measured at the MLO location (3.4 km elevation) were consistent with previously reported boundary layer values and flux estimates. It is suggested that oxidation of ethylene and propylene may represent a significant source of CO in the marine boundary layer. Isoprene fluxes from major flora on Hawaii were low compared to continental emissions from several species of oak reported by Zimmerman (1979). A comparison of in situ sampling and canister sampling techniques for measurements of CH4, CO, ethane, and propane yielded good agreement.

  5. 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.

  6. 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.

  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. 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 stratospheric haze opacity is inferred similar to that found for a polymeric residue created in laboratory discharge experiments. This haze appears to be uniformly distributed with latitude between altitudes of 40 and 160 km, provided those nighttime data at southern high latitudes that are discounted.

  9. Highly active composite catalysts for reforming of methane into syngas

    SciTech Connect

    Inui, T.; Saigo, K.; Ichino, K.

    1997-12-31

    Development in highly active catalysts for the reforming of methane with H{sub 2}O, CO{sub 2}, H{sub 2}O + CO{sub 2}, and partial oxidation of methane was conducted to produce hydrogen with high reaction rates. A Ni-based four component catalyst, Ni-Ce{sub 2}O{sub 3}-Pt-Rh supported on an alumina wash-coated ceramic fiber in a plate shape was suitable for the objective reaction. By combining the catalytic combustion reaction, methane conversion was markedly enhanced. Furthermore, by combining the combustion of ethane or ethylene, significantly high space-time yields of hydrogen such as 6,731 mol/1-h or 6,907 mol/l{center_dot}h, respectively at 700{degrees}C. In a reaction of CH{sub 4}-CO{sub 2}-H{sub 2}O-O{sub 2} on the four component catalyst, an extraordinary high space-time yield of hydrogen, 12,190 mol/l{center_dot}h was realized even under the very rapid operation conditions as 3 m-sec short contact time.

  10. An ab initio study of three (ethane-1,2 diol/water) complexes

    NASA Astrophysics Data System (ADS)

    Manivet, Philippe; Masella, Michel

    1998-05-01

    Three (ethane-1,2 diol/water) complexes have been studied using ab initio calculations at the MP2 level. In two complexes, the ethane-1,2 diol structure is close to its gas phase experimental structure (presence of an intramolecular hydrogen bond HB and the O-C-C-O dihedral angle is gauche) while the intramolecular HB is disrupted by the presence of a water molecule in the third ( tGg'a). Computations have shown that most of the experimental observations regarding the solvation of ethane-1,2 diol in water may be reproduced only by considering the tGg'a complex (absence of intramolecular HB, O-C-C-O dihedral angle of 72-74°), which is also more stable than the other two by 2 kcal mol -1.

  11. 1,3-Bis[(4-methylbenzylidene)amino-oxy]propane.

    PubMed

    Wu, Jian-Chao; Gao, Su-Xia; Dong, Wen-Kui; Tong, Jun-Feng; Li, Li

    2009-01-01

    The title bis-oxime compound, C(19)H(22)N(2)O(2), synthesized by the reaction of 4-methyl-2-hydroxy-benzaldehyde with 1,3-bis-(amino-oxy)propane in ethanol, adopts a V-shaped conformation. The dihedral angle between the rings is 84.59 (3)°. The mol-ecule is disposed about a crystallographic twofold rotation axis, with one C atom lying on the axis. In the crystal, mol-ecules are packed by C-H⋯π(Ph) inter-actions, forming chains. PMID:21578377

  12. Novel adsorption distillation hybrid scheme for propane/propylene separation

    SciTech Connect

    Kumar, R.; Golden, T.C.; White, T.R.; Rokicki, A. )

    1992-12-01

    A novel adsorption-distillation hybrid scheme is proposed for propane/propylene separation. The suggested scheme has potential for saving up to [approximately]50% energy and [approximately]15-30% in capital costs as compared with current technology. The key concept of the proposed scheme is to separate olefins from alkanes by adsorption and then separate individual olefins and alkanes by simple distillation, thereby eliminating energy intensive and expensive olefin-alkane distillation. A conceptual flow schematic for the proposed hybrid scheme and potential savings are outlined.s

  13. 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.

  14. Geoengineering treatment of methane

    NASA Astrophysics Data System (ADS)

    Lockley, Andrew; Gardian, Alan

    2010-05-01

    Methane is a significant GHG, and substantial reservoirs are vulnerable to instability due to AGW. Excursions, from permafrost and clathrates especially, act a positive feedback to AGW. Existing concentrations of well-mixed atmospheric methane substantially exceed pre-industrial levels. Various geoengineering methods are herein proposed for containment of methane, and/or accelerated oxidation to CO2 (a gas with a lower GWP over all timescales). A basic qualitative analysis of each technique is undertaken, to direct further study. Consideration is also given to the potential capacity of each technique to treat the total likely excursions of methane expected as a result of AGW. Proposed techniques: Section 0 SRM (comparison option) Section 1 Pre-emptive treatment of methane reservoirs Soil heating (polytunnels, heat pumps); Soil aeration; Mining of clathrates; Burning of clathrates Section 2 Remediation of aquatic methane excursions Lake sealing; Mixing of aquatic strata; Bubble capture; Lake aeration; Biological oxidation in aquatic environments Section 3 Remediation of concentrated atmospheric methane Regenerative thermal oxidation; Electrical ignition; Thermal ignition; Using incendiary munitions Section 4 Remediation of diffuse atmospheric methane Thermal oxidation by concentrated solar power; Compression ignition; Chemical degradation Assessment criteria: Infrastructure/implementation cost; Energy cost; Expected efficacy; Complexity/development path; Environmental impacts; Potential for CCS

  15. Efficient methane conversion to hydrogen and hydrocarbons by combination of corona and glow discharge

    NASA Astrophysics Data System (ADS)

    Ghorbanzadeh, A. M.; Matin, N. S.

    2004-03-01

    In this study we offer a new type of plasma which consists of double, corona and glow, discharge to convert natural gas, the main part of which is methane. The most important future of this type of plasma is the steady increase of overall chemical energy efficiency by enhancement of repetition rate. At repetition rate of R=80 Hz, the energy efficiency of 5.5% was increased to 10% at R=330 Hz and more improvement was yet expected at higher repetition rates. Easy control of selectivity of products that were hydrogen, acetylene, ethylene, ethane and hydrocarbons with up to 5 carbons, was also possible by repetition rate.

  16. 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.

  17. 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.

  18. Cassini/Huygens Investigations of Titan's Methane Cycle

    NASA Astrophysics Data System (ADS)

    Griffith, C. A.; Penteado, P.

    2008-12-01

    the Methane Cycle in Titan's Atmosphere. Phil. Trans. Royal Society A. In Press (2008). Penteado, P.F. & C.A. Griffith Ground-based measurements of the methane distribution on Titan. In Preparation for submission to Icarus Griffith C.A. et al. Evidence for a Polar Ethane Cloud on Titan, Science, 313, 1620 (2006). Griffith C.A. et al. The Evolution of Titan's Mid-Latitude Clouds, Science, 310, 474 (2005).

  19. 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

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Federal 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....

  20. Breath ethane as a marker of reactive oxygen species during manipulation of diet and oxygen tension in rats.

    PubMed

    Risby, T H; Jiang, L; Stoll, S; Ingram, D; Spangler, E; Heim, J; Cutler, R; Roth, G S; Rifkind, J M

    1999-02-01

    Breath ethane, O2 consumption, and CO2 production were analyzed in 24-mo-old female Fischer 344 rats that had been fed continuously ad libitum (AL) or restricted 30% of AL level (DR) diets since 6 wk of age. Rats were placed in a glass chamber that was first flushed with air, then with a gas mixture containing 12% O2. After equilibration, a sample of the outflow was collected in gas sampling bags for subsequent analyses of ethane and CO2. The O2 and CO2 levels were also directly monitored in the outflow of the chamber. O2 consumption and CO2 production increased for DR rats. Hypoxia decreased O2 consumption and CO2 production for the AL-fed and DR rats. These changes reflect changes in metabolic rate due to diet and PO2. A significant decrease in ethane generation was found in DR rats compared with AL-fed rats. Under normoxic conditions, breath ethane decreased from 2.20 to 1.61 pmol ethane/ml CO2. During hypoxia the levels of ethane generation increased, resulting in a DR-associated decrease in ethane from 2.60 to 1.90 pmol ethane/ml CO2. These results support the hypothesis that DR reduces the level of oxidative stress. PMID:9931199

  1. Methane on Mars

    NASA Astrophysics Data System (ADS)

    Krasnopolsky, V. A.

    Detection of methane on Mars has been claimed by Krasnopolsky Maillard Owen 2004 using FTS CFHT Formisano et al 2004 using PFS MEX and Mumma et al in preparation using CSHELL IRTF and Phoenix Gemini The measured abundances are 10 pm 3 ppb in Krasnopolsky et al 10 pm 5 ppb varying from 0 to 40 ppb in Formisano et al and 80 ppb varying from 30 to 300 ppb in Mumma et al The methane lifetime is sim 300 yr and its production loss is 300 tons yr -1 based on gas-phase chemistry Two basic questions are 1 why are the mean abundances so different and 2 how can methane vary if its lifetime is so long Variations of methane on Mars require a very effective heterogeneous loss of methane which is higher than that on Earth by a factor of ge 1000 although the expected efficiency on Earth is stronger than that on Mars because of the liquid ocean and the abundant oxygen Thermodynamic and kinetic data on the catalysis of methane do not also support variations of methane on Mars Production of methane on Mars by impacts of comets meteorites and interplanetary dust is sim 15 t yr -1 A probability that the observed methane on Mars came from impact of a single comet is 0 001 The lack of current volcanism hydrothermal activity hot spots and very low seepage of gases from the interior are not favorable for geologic methane Some weak points in the suggested geologic sources are discussed Though the geologic sources are not completely ruled out methanogenesis by living subterranean organisms is a plausible

  2. Coal-transformation chemistry. Ninth quarterly progress report. [1,2-di(1-naphthyl)ethane and 1,2-di(9-anthryl)ethane

    SciTech Connect

    Stock, L.M.

    1982-01-01

    The effort on donor solvent coal chemistry during this quarter concerned the factors that govern the cleavage of ethylene linkages in several representative compounds. The behavior of the resulting radicals were also studied. Bibenzyl, 1,2-di(1-naphthyl)ethane and 1,2-di(9-anthryl)ethane were selected as the reaction substrates. The latter two compounds have been synthesized and the catalytic effect of these compounds on the exchange reaction of diphenylmethane with tetralin-d/sub 12/ at 400/sup 0/C was examined. The results showed that the catalytic effect was in the order: 1,2-di(1-naphthyl)ethane ..-->.. 1,2-di(9-anthryl)ethane ..-->.. bibenzyl. Nuclear Overhauser effect (NOE) suppression in carbon nmr spectra of reductively alkylated coals is discussed. Suppression of NOE in /sup 13/C-enriched alkylated coal samples does not result in a difference in carbon to oxygen alkylation ratios. However, for unenriched reductively alkylated coal samples, suppression of NOE is essential for accurate quantitative analysis. With NOE suppression, the carbon to oxygen alkylation ratios of reductively ethylated coal are consistent with previous results for reductively methylated and butylated Illinois No. 6 coal. The EPR spectra of Illinois No. 6 coal and several of its reductive alkylation products were studied. The EPR spectra of the hydrofuran soluble reaction products and the insoluble reaction products were each studied. There is a large decrease in the spin concentration in the reductive alkylation products in both the soluble and insoluble products. However, the insoluble materials which are, of course, relatively rich in inorganic compounds exhibit broad resonance bands extending to zero field. The substances responsible for these broad absorptions are readily removed by treatment with dilute hydrochloric acid. The materials treated in this way exhibit only a weak resonance at g = 2. 7 figures, 7 tables.

  3. 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.

  4. On the Sources of Methane to the Los Angeles Atmosphere

    NASA Technical Reports Server (NTRS)

    Wennberg, Paul O.; Mui, Wilton; Fischer, Marc L.; Wunch, Debra; Kort, Eric A.; Blake, Donald R.; Atlas, Elliot L.; Santoni, Gregory W.; Wofsy, Steven C.; Diskin, Glenn S.; Jeong, Seongeun

    2012-01-01

    We use historical and new atmospheric trace gas observations to refine the estimated source of methane (CH4) emitted into California's South Coast Air Basin (the larger Los Angeles metropolitan region). Referenced to the California Air Resources Board (CARB) CO emissions inventory, total CH4 emissions are 0.44 +/- 0.15 Tg each year. To investigate the possible contribution of fossil fuel emissions, we use ambient air observations of methane (CH4), ethane (C2H6), and carbon monoxide (CO), together with measured C2H6 to CH4 enhancement ratios in the Los Angeles natural gas supply. The observed atmospheric C2H6 to CH4 ratio during the ARCTAS (2008) and CalNex (2010) aircraft campaigns is similar to the ratio of these gases in the natural gas supplied to the basin during both these campaigns. Thus, at the upper limit (assuming that the only major source of atmospheric C2H6 is fugitive emissions from the natural gas infrastructure) these data are consistent with the attribution of most (0.39 +/- 0.15 Tg yr-1) of the excess CH4 in the basin to uncombusted losses from the natural gas system (approximately 2.5-6% of natural gas delivered to basin customers). However, there are other sources of C2H6 in the region. In particular, emissions of C2H6 (and CH4) from natural gas seeps as well as those associated with petroleum production, both of which are poorly known, will reduce the inferred contribution of the natural gas infrastructure to the total CH4 emissions, potentially significantly. This study highlights both the value and challenges associated with the use of ethane as a tracer for fugitive emissions from the natural gas production and distribution system.

  5. 40 CFR 1065.341 - CVS and batch sampler verification (propane check).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 34 2013-07-01 2013-07-01 false CVS and batch sampler verification... Measurements § 1065.341 CVS and batch sampler verification (propane check). (a) A propane check serves as a CVS... system that extracts a sample from a CVS, as described in paragraph (g) of this section. Using...

  6. 40 CFR 721.533 - Propane, 1,1,1,3,3-pentachloro-.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.533 Propane, 1,1,1,3,3-pentachloro-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as propane, 1,1,1,3,3-pentachloro- (PMN...

  7. 40 CFR 721.533 - Propane, 1,1,1,3,3-pentachloro-.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.533 Propane, 1,1,1,3,3-pentachloro-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as propane, 1,1,1,3,3-pentachloro- (PMN...

  8. Aromatization of Propane over Element-Alumosilicate Catalysts with ZSM-5 Structure

    NASA Astrophysics Data System (ADS)

    Vosmerikova, L. N.; Volynkina, A. N.; Vosmerikov, A. V.

    2014-08-01

    A method of hydrothermal crystallization of alkaline alumosilicagels is used to manufacture element-alumosilicates with ZSM-5 structure. Their physicochemical and acid properties are investigated and their catalytic activity in the course of propane conversion to aromatic hydrocarbons is determined. The Ga-alumosilicate is found to be the most efficient zeolite catalyst for propane aromatization.

  9. PROGRAM TO DETERMINE PERFORMANCE OF FLUORINATED ETHERS AND FLUORINATED PROPANES IN A COMPRESSOR CALORIMETER

    EPA Science Inventory

    The paper discusses a program to determine the performance of fluorinated ethers and fluorinated propanes in a compressor calorimeter. These chlorine free ethers and propanes are being considered as potential long-term replacements for CFC-11, -12, -114, and -115. A standard comp...

  10. Measuring doubly 13C-substituted ethane by mass spectrometry

    NASA Astrophysics Data System (ADS)

    Clog, M.; Ling, C.; Eiler, J. M.

    2012-12-01

    Ethane (C2H6) is present in non-negligible amounts in most natural gas reservoirs and is used to produce ethylene for petrochemical industries. It is one of the by-products of lipid metabolism and is the arguably simplest molecule that can manifest multiple 13C substitutions. There are several plausible controls on the relative abundances of 13C2H6 in natural gases: thermodynamically controlled homogeneous isotope exchange reactions analogous to those behind carbonate clumped isotope thermometry; inheritance from larger biomolecules that under thermal degradation to produce natural gas; mixing of natural gases that differ markedly in bulk isotopic composition; or combinations of these and/or other, less expected fractionations. There is little basis for predicting which of these will dominate in natural samples. Here, we focus on an analytical techniques that will provide the avenue for exploring these phenomena. The method is based on high-resolution gas source isotope ratio mass spectrometry, using the Thermo 253-Ultra (a new prototype mass spectrometer). This instrument achieves the mass resolution (M/Δ M) up to 27,000, permitting separation of the isobaric interferences of potential contaminants and isotopologues of an analtye or its fragments which share a cardinal mass. We present techniques to analyze several isotopologues of molecular and fragment ions of C2H6. The critical isobaric separations for our purposes include: discrimination of 13C2H6 from 13C12CDH5 at mass 32 and separation of the 13CH3 fragment from 12CH4 at mass 16, both requiring at least a mass resolution of 20000 to make an adequate measurement. Other obvious interferences are either cleanly separated (e.g., O2, O) or accounted for by peak-stripping (CH3OH on mass 32 and NH2 on mass 16). We focus on a set of measurements which constrain: the doubly-substituted isotopologue, 13C2H6, and the 13CH3/12CH3 ratio of the methyl fragment, which constrains the bulk δ 13C. Similar methods can be

  11. Methane Emission by Camelids

    PubMed Central

    Dittmann, Marie T.; Runge, Ullrich; Lang, Richard A.; Moser, Dario; Galeffi, Cordula; Kreuzer, Michael; Clauss, Marcus

    2014-01-01

    Methane emissions from ruminant livestock have been intensively studied in order to reduce contribution to the greenhouse effect. Ruminants were found to produce more enteric methane than other mammalian herbivores. As camelids share some features of their digestive anatomy and physiology with ruminants, it has been proposed that they produce similar amounts of methane per unit of body mass. This is of special relevance for countrywide greenhouse gas budgets of countries that harbor large populations of camelids like Australia. However, hardly any quantitative methane emission measurements have been performed in camelids. In order to fill this gap, we carried out respiration chamber measurements with three camelid species (Vicugna pacos, Lama glama, Camelus bactrianus; n = 16 in total), all kept on a diet consisting of food produced from alfalfa only. The camelids produced less methane expressed on the basis of body mass (0.32±0.11 L kg−1 d−1) when compared to literature data on domestic ruminants fed on roughage diets (0.58±0.16 L kg−1 d−1). However, there was no significant difference between the two suborders when methane emission was expressed on the basis of digestible neutral detergent fiber intake (92.7±33.9 L kg−1 in camelids vs. 86.2±12.1 L kg−1 in ruminants). This implies that the pathways of methanogenesis forming part of the microbial digestion of fiber in the foregut are similar between the groups, and that the lower methane emission of camelids can be explained by their generally lower relative food intake. Our results suggest that the methane emission of Australia's feral camels corresponds only to 1 to 2% of the methane amount produced by the countries' domestic ruminants and that calculations of greenhouse gas budgets of countries with large camelid populations based on equations developed for ruminants are generally overestimating the actual levels. PMID:24718604

  12. Methane emission by camelids.

    PubMed

    Dittmann, Marie T; Runge, Ullrich; Lang, Richard A; Moser, Dario; Galeffi, Cordula; Kreuzer, Michael; Clauss, Marcus

    2014-01-01

    Methane emissions from ruminant livestock have been intensively studied in order to reduce contribution to the greenhouse effect. Ruminants were found to produce more enteric methane than other mammalian herbivores. As camelids share some features of their digestive anatomy and physiology with ruminants, it has been proposed that they produce similar amounts of methane per unit of body mass. This is of special relevance for countrywide greenhouse gas budgets of countries that harbor large populations of camelids like Australia. However, hardly any quantitative methane emission measurements have been performed in camelids. In order to fill this gap, we carried out respiration chamber measurements with three camelid species (Vicugna pacos, Lama glama, Camelus bactrianus; n = 16 in total), all kept on a diet consisting of food produced from alfalfa only. The camelids produced less methane expressed on the basis of body mass (0.32±0.11 L kg⁻¹ d⁻¹) when compared to literature data on domestic ruminants fed on roughage diets (0.58±0.16 L kg⁻¹ d⁻¹). However, there was no significant difference between the two suborders when methane emission was expressed on the basis of digestible neutral detergent fiber intake (92.7±33.9 L kg⁻¹ in camelids vs. 86.2±12.1 L kg⁻¹ in ruminants). This implies that the pathways of methanogenesis forming part of the microbial digestion of fiber in the foregut are similar between the groups, and that the lower methane emission of camelids can be explained by their generally lower relative food intake. Our results suggest that the methane emission of Australia's feral camels corresponds only to 1 to 2% of the methane amount produced by the countries' domestic ruminants and that calculations of greenhouse gas budgets of countries with large camelid populations based on equations developed for ruminants are generally overestimating the actual levels. PMID:24718604

  13. Theoretical Study of the Reactions of Methane and Ethane with Electronically Excited N2(A(3)Σu(+)).

    PubMed

    Sharipov, Alexander S; Loukhovitski, Boris I; Starik, Alexander M

    2016-06-30

    Comprehensive quantum chemical analysis with the usage of density functional theory and post-Hartree-Fock approaches were carried out to study the processes in the N2(A(3)Σu(+)) + CH4 and N2(A(3)Σu(+)) + C2H6 systems. The energetically favorable reaction pathways have been revealed on the basis of the examination of potential energy surfaces. It has been shown that the reactions N2(A(3)Σu(+)) + CH4 and N2(A(3)Σu(+)) + C2H6 occur with very small or even zero activation barriers and, primarily, lead to the formation of N2H + CH3 and N2H + C2H5 products, respectively. Further, the interaction of these species can give rise the ground state N2(X(1)Σg(+)) and CH4 (or C2H6) products, i.e., quenching of N2(A(3)Σu(+)) by CH4 and C2H6 molecules is the complex two-step process. The possibility of dissociative quenching in the course of the interaction of N2(A(3)Σu(+)) with CH4 and C2H6 molecules has been analyzed on the basis of RRKM theory. It has been revealed that, for the reaction of N2(A(3)Σu(+)) with CH4, the dissociative quenching channel could occur with rather high probability, whereas in the N2(A(3)Σu(+)) + C2H6 reacting system, an analogous process was little probable. Appropriate rate constants for revealed reaction channels have been estimated by using a canonical variational theory and capture approximation. The estimations showed that the rate constant of the N2(A(3)Σu(+)) + C2H6 reaction path is considerably greater than that for the N2(A(3)Σu(+)) + CH4 one. PMID:27266481

  14. N,N′-(Ethane-1,2-di­yl)bis­(methane­sulfon­amide)

    PubMed Central

    Chan, Wesley Ting Kwok; Kung, Ka Yan Karen; Wong, Man-kin

    2014-01-01

    The mol­ecular structure of the title compound, C4H12N2O4S2, has crystallographic inversion symmetry. The central N—C—C—N moiety was refined as disordered over two sets of sites with an approximate occupancy ratio of 3:1 [0.742 (15):0.258 (15). In the crystal, N—H⋯O hydrogen bonds link adjacent mol­ecules into a thick sheet structure parallel to the b-axis direction. PMID:24764874

  15. CHEMICAL ENHANCEMENT OF VIRAL TRANSFORMATION IN SYRIAN HAMSTER EMBRYO CELLS BY GASEOUS AND VOLATILE CHLORINATED METHANES AND ETHANES

    EPA Science Inventory

    Methods were developed for exposing cells in vitro to gases or vapors of volatilized organic liquids. Compounds were selected for their industrial importance, environmental impact, and suspected role in the etilogy of some human cancers. Exposure chambers were designed for easy i...

  16. Optical constants of solid methane and ethane from 10,000 to 450/cm. [in outer planets atmospheres

    NASA Technical Reports Server (NTRS)

    Pearl, J.; Ngoh, M.; Ospina, M.; Khanna, R.

    1991-01-01

    Near- and mid-IR spectra of thin films of crystalling phase I and phase II C2H6 are presented using a combined least squares and Kramers-Kronig analysis. Complex refractive indices derived from these data are also presented. To obtain material in phase I, samples are annealed at 33 K for about 30 min; phase II is obtained by recooling below the transition temperature of 20.4 K. The derived optical parameters are shown. The infrared spectrum of phase I CH4 exhibits broad structureless absorptions at about 1300 and 2600/cm. On cooling the sample below 20.4 K (phase II), the absorptions are sharpened, and each band develops fine structure. The present results and those of Roux et al. (1979) are compared. The agreement with the real parts is found to be excellent; given the difference in resolution, the agreement with the imaginary parts is also good.

  17. Effect of Propellant Flowrate and Purity on Carbon Deposition in LO2/Methane Gas Generators

    NASA Technical Reports Server (NTRS)

    Bossard, J. A.; Burkhardt, W. M.; Niiya, K. Y.; Braam, F.

    1989-01-01

    The generation and deposition of carbon was studied in the Carbon Deposition Program using subscale hardware with LO2/Liquid Natural Gas (LNG) and LO2/Methane propellants at low mixture ratios. The purpose of the testing was to evaluate the effect of methane purity and full scale injection density on carbon deposition. The LO2/LNG gas generator/preburner testing was performed at mixture ratios between 0.24 and 0.58 and chamber pressures from 5.8 to 9.4 MPa (840 to 1370 psia). A total of seven 200 second duration tests were performed. The LNG testing occurred at low injection densities, similar to the previous LO2/RP-1, LO2/propane, and LO2/methane testing performed on the carbon deposition program. The current LO2/methane test series occurred at an injection density factor of approximately 10 times higher than the previous testing. The high injection density LO2/methane testing was performed at mixture ratios between from 0.23 to 0.81 and chamber pressures from 6.4 to 15.2 MPa (925 to 2210 psia). A total of nine high injection density tests were performed. The testing performed demonstrated that low purity methane (LNG) did not produce any detectable change in carbon deposition when compared to pure methane. In addition, the C* performance and the combustion gas temperatures measured were similar to those obtained for pure methane. Similar results were obtained testing pure methane at higher propellant injection densities with coarse injector elements.

  18. Laboratory Studies of Ethane Ice Relevant to Outer Solar System Surfaces

    NASA Astrophysics Data System (ADS)

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

    2009-09-01

    Oort Cloud comets, as well as TNOs Makemake (2005 FY9), Quaoar, and Pluto, are known to contain ethane. However, even though this molecule is found on several outer Solar System objects relatively little information is available about its amorphous and crystalline phases. In new experiments, we have prepared ethane ices at temperatures applicable to the outer Solar System, and have heated and ion-irradiated these ices to study phase changes and ethane's radiation chemistry using mid-IR spectroscopy (2.2 - 16.6 microns). Included in our work is the meta-stable phase that exists at 35 - 55 K. These results, including newly obtained optical constants, are relevant to ground-based observational campaigns, the New Horizons mission, and supporting laboratory work. 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 funded by NASA's Planetary Geology and Geophysics, Planetary Atmospheres, and Outer Planets programs. LR was supported by a summer research internship at the NASA Astrobiology Institute's Goddard Center for Astrobiology.

  19. EFFECTS OF GESTATIONAL EXPOSURE TO ETHANE DIMETHANESULFONATE IN CD-1 MICE: MICROTIA AND PRELIMINARY HEARING TESTS

    EPA Science Inventory

    Microtia is a reduction in pinna size, usually seen in humans in conjunction with other medical conditions. Here we report microtia in CD-1 mice following gestational exposure to ethane dimethanesulfonate (EDS), an alkylating agent and adult rat Leydig cell toxicant. Methods...

  20. Turboexpander plant designs can provide high ethane recovery without inlet CO/sub 2/ removal

    SciTech Connect

    Wilkinson, J.D.; Hudson, H.M.

    1982-05-03

    New turboexpander plant designs can process natural gas streams containing moderate amounts of carbon dioxide (CO/sub 2/) for high ethane recovery without inlet gas treating. The designs will handle a wide range of inlet ethane-plus fractions. They also offer reduced horsepower requirements compared to other processes. CO/sub 2/ is a typical component of most natural gas streams. In many cases, processing of these gas streams in a turboexpander plant for high ethane recovery requires pre-treatment of the gas for CO/sub 2/ removal. This is required to avoid the formation of solid CO/sub 2/ (freezing) in the cold sections of the process and/or to meet necessary residue gas and liquid product CO/sub 2/ specifications. Depending on the quantities involved, the CO/sub 2/ removal systems is generally a significant portion of both the installed cost and operating cost for the ethane recovery facility. Therefore, turboexpander plant designs that are capable of handling increased quantities of CO/sub 2/ in the feed gas without freezing can offer the gas processor substantial economic benefits.

  1. DEGRATION OF SELECTED HALOGENATED ETHANES IN ANOXIC SEDIMENT-WATER SYSTEMS

    EPA Science Inventory

    The degradation of selected halogenated ethanes was studied in anoxic sediment-water suspensions at 1 to 20% sediment concentrations. Batch kinetic experiments were used to quantify decay. Eh measurements of all suspensions were below -100mV (vs SHE), indicating reduced environme...

  2. A Convenient Synthetic Protocol to 1,2-Bis(dialkylphosphino)ethanes

    PubMed Central

    Doyle, Laurence R; Heath, Alex; Low, Choon Heng; Ashley, Andrew E

    2014-01-01

    1,2-Bis(dialkylphosphino)ethanes are readily prepared from the parent phosphine oxides, via a novel sodium aluminium hydride/sodium hydride reduction protocol of intermediate chlorophosphonium chlorides. This approach is amenable to multi-gram syntheses, utilises readily available and inexpensive reagents, and benefits from a facile non-aqueous work-up in the final reductive step. PMID:26190960

  3. Chiral separation of metolachlor ethane sulfonic acid as a groundwater dating tool

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We have studied the hydrologic fate of metolachlor and its two predominant metabolites, metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid, in groundwater and base flows of streams for several years. These two metabolites are excellent markers for groundwater processes related to...

  4. Using chiral identification of metolachlor ethane sulfonic acid as a groundwater dating tool

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We have studied the hydrologic fate of metolachlor and its two predominant metabolites, metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid, in groundwater and base flows of streams for several years. These two metabolites are excellent markers for groundwater processes related to...

  5. MULTIPLE EFFECTS OF ETHANE DIMENTHANESULFONATE ON THE EPIDIDYMIS OF ADULT RATS

    EPA Science Inventory

    Ethane dimethanesulphonate (EDS), a compound cytotoxic to Leydig cells which causes transient infertility, was used in a 4 d post-exposure experimental protocol designed to identify any effects this compound might exert on the epididymis. he techniques efferent duct ligation and ...

  6. Oxidative dehydrogenation of ethane at millisecond contact times: Effect of H{sub 2} addition

    SciTech Connect

    Bodke, A.S.; Henning, D.; Schmidt, L.D.; Bharadwaj, S.S.; Maj, J.J.; Siddall, J.

    2000-04-01

    The oxidative dehydrogenation of ethane using Pt/{alpha}-Al{sub 2}O{sub 3} and various bimetallic catalysts operating at {approximately}1,000 C and very short contact times is examined with H{sub 2} addition to the feed. When H{sub 2} is added with a Pt catalyst, the ethylene selectivity rises from 65 to 72% but ethane conversion drops from 70 to 52%. However, using a Pt-Sn/{alpha}-Al{sub 2}O{sub 3} catalyst, the C{sub 2}H{sub 4} selectivity increases from 70 to greater than 85%, while the conversion remains {approximately}70%. The process also produces approximately as much H{sub 2} as is added to the feed. Effects of other metal promoters, sphere bed and fibermat supports, preheat, pressure, nitrogen dilution, and flow rate are examined in an effort to further elucidate the mechanism. Deactivation of the Pt-Sn catalyst is examined, and a simple method of regenerating the activity on-line is demonstrated. Possible mechanisms to explain high selectivities to ethylene are discussed. Although the process can be regarded as a simple two-step reaction sequence with the exothermic oxidation of hydrogen or ethane driving the endothermic dehydrogenation of ethane to ethylene, the exact contributions of heterogeneous or gas-phase reactions and their spatial variations within the catalyst are yet to be determined.

  7. IN VITRO/IN VIVO EFFECTS OF ETHANE DIMETHANESULPHONATE ON LEYDIG CELLS OF ADULT RATS

    EPA Science Inventory

    Ethane dimethanesulphonate (EDS) is studied extensively to date, certain toxicological criteria have not been met. or instance, the does-responsiveness of Leydig cells to EDS, both in vitro and in vivo, is not well established. n addition, the date regarding the cellular site of ...

  8. IMMATURE RAT LEYDIG CELLS ARE INTRINSICALLY LESS SENSITIVE THAN ADULT LEYDIG CELLS TO ETHANE DIMETHANESULFONATE

    EPA Science Inventory

    Leydig cells from immature rat tests appear to be insensitive to doses of ethane-1,2-dimethanesulfonate (EDS) which eliminate Leydig cells from adult rat testes. e sought to determine whether this differential response to EDS is intrinsic to the Leydig cell or mediated by other i...

  9. A co-crystal between benzene and ethane: a potential evaporite material for Saturn's moon Titan.

    PubMed

    Maynard-Casely, Helen E; Hodyss, Robert; Cable, Morgan L; Vu, Tuan Hoang; Rahm, Martin

    2016-05-01

    Using synchrotron X-ray powder diffraction, the structure of a co-crystal between benzene and ethane formed in situ at cryogenic conditions has been determined, and validated using dispersion-corrected density functional theory calculations. The structure comprises a lattice of benzene molecules hosting ethane molecules within channels. Similarity between the intermolecular interactions found in the co-crystal and in pure benzene indicate that the C-H⋯π network of benzene is maintained in the co-crystal, however, this expands to accommodate the guest ethane molecules. The co-crystal has a 3:1 benzene:ethane stoichiometry and is described in the space group [Formula: see text] with a = 15.977 (1) Å and c = 5.581 (1) Å at 90 K, with a density of 1.067 g cm(-3). The conditions under which this co-crystal forms identify it is a potential that forms from evaporation of Saturn's moon Titan's lakes, an evaporite material. PMID:27158505

  10. Determination of the Rotational Barrier in Ethane by Vibrational Spectroscopy and Statistical Thermodynamics

    ERIC Educational Resources Information Center

    Ercolani, Gianfranco

    2005-01-01

    The finite-difference boundary-value method is a numerical method suited for the solution of the one-dimensional Schrodinger equation encountered in problems of hindered rotation. Further, the application of the method, in combination with experimental results for the evaluation of the rotational energy barrier in ethane is presented.

  11. GESTATIONAL EXPOSURE TO ETHANE DIMETHANESULFONATE PERMANENTLY ALTERS REPRODUCTIVE COMPETENCE IN THE CD-1 MOUSE

    EPA Science Inventory

    While the adult mouse Leydig cell (LC) has been considered refractory to cytotoxic destruction by ethane dimethanesulfonate (EDS), the potential consequences of exposure during reproductive development in this species are unknown. Herein pregnant CD-1 mice were treated with 160 m...

  12. GESTATIONAL EXPOSURE TO ETHANE DIMETHANESULFONATE (EDS) ALTERS DEVELOPMENT OF THE MOUSE TESTIS

    EPA Science Inventory

    GESTATIONAL EXPOSURE TO ETHANE DIMETHANESULFONATE (EDS) ALTERS DEVELOPMENT OF THE MOUSE TESTIS. D.K. Tarka*1,2, J.D. Suarez*2, N.L. Roberts*2, J.M. Rogers*1,2, M.P. Hardy3, and G.R. Klinefelter1,2. 1University of North Carolina, Curriculum in Toxicology, Chapel Hill, NC; 2USEPA,...

  13. Direct conversion of methane to C sub 2 's and liquid fuels

    SciTech Connect

    Warren, B.K.; Campbell, K.D.

    1989-11-22

    Objectives of the project are to discover and evaluate novel catalytic systems for the conversion of methane or by-product light hydrocarbon gases either indirectly (through intermediate light gases rich in C{sub 2}'s) or directly to liquid hydrocarbon fuels, and to evaluate, from an engineering perspective, different conceptualized schemes. The approach is to carry out catalyst testing on several specific classes of potential catalysts for the conversion of methane selectively to C{sub 2} products. Promoted metal oxide catalysts were tested. Several of these exhibited similar high ethylene to ethane ratios and low carbon dioxide to carbon monoxide ratios observed for the NaCl/{alpha}-alumina catalyst system reported earlier. Research on catalysts containing potentially activated metals began with testing of metal molecular sieves. Silver catalysts were shown to be promising as low temperature catalysts. Perovskites were tested as potential methane coupling catalysts. A layered perovskite (K{sub 2}La{sub 2}Ti{sub 3}O{sub 10}) gave the highest C{sub 2} yield. Work continued on the economic evaluation of a hypothetical process converting methane to ethylene. An engineering model of the methane coupling system has been prepared. 47 refs., 17 figs., 57 tabs.

  14. Seasonal Variations of Temperature, Acetylene and Ethane in Saturn's Stratosphere from 2005 to 2010

    NASA Astrophysics Data System (ADS)

    Sinclair, James; Irwin, P. G. J.; Fletcher, L. N.; Moses, J. I.; Greathouse, T. K.; Friedson, A. J.; Hesman, B.; Hurley, J.; Merlet, C.

    2012-10-01

    Acetylene (C2H2) and ethane (C2H6) exemplify by-products of complex photochemistry in Saturn’s stratosphere. Their relative stability together with their strong vertical gradients in concentration allow for their use as tracers of vertical motion in Saturn’s lower stratosphere. Earlier studies of Saturn's hydrocarbons have provided only a snapshot of their behaviour with temporal variations remaining to be determined. In this study, we investigate how the thermal structure and concentrations of acetylene and ethane have evolved on Saturn with the changing season. We use FIRMAP (15.5 cm-1 spectral resolution) Cassini-CIRS observations, initially retrieve temperature and subsequently retrieve the abundances of acetylene and ethane. In comparing 2005, 2009 and 2010 results, we observe the disappearance of Saturn's southern warm polar hood with cooling of up to 18.6 K ± 0.9 K at 1.1 mbar south of 75°S (planetographic). This suggests dissipation of Saturn's south polar vortex in addition to an autumnal cooling. We observe a 20% ± 9% enrichment of acetylene and a 30% ± 10% enrichment of ethane at 2.1 mbar at 25°N, together with a 14% ± 9% depletion of acetylene and an 18% ± 7% depletion of ethane at the same altitude at 15°S. This suggests the presence of localised downwelling and upwelling at these latitudes, respectively. These vertical motions are consistent with a recently-developed GCM (global circulation model) of Saturn's tropopause and stratosphere, which predicts this pattern of upwelling and downwelling as a result of seasonally-reversing Hadley circulation.

  15. Enzymatic Oxidation of Methane

    SciTech Connect

    Sirajuddin, S; Rosenzweig, AC

    2015-04-14

    Methane monooxygenases (MMOs) are enzymes that catalyze the oxidation of methane to methanol in methanotrophic bacteria. As potential targets for new gas-to-liquid methane bioconversion processes, MMOs have attracted intense attention in recent years. There are two distinct types of MMO, a soluble, cytoplasmic MMO (sMMO) and a membrane-bound, particulate MMO (pMMO). Both oxidize methane at metal centers within a complex, multisubunit scaffold, but the structures, active sites, and chemical mechanisms are completely different. This Current Topic review article focuses on the overall architectures, active site structures, substrate reactivities, proteinprotein interactions, and chemical mechanisms of both MMOs, with an emphasis on fundamental aspects. In addition, recent advances, including new details of interactions between the sMMO components, characterization of sMMO intermediates, and progress toward understanding the pMMO metal centers are highlighted. The work summarized here provides a guide for those interested in exploiting MMOs for biotechnological applications.

  16. Venus methane and water

    NASA Astrophysics Data System (ADS)

    Donahue, T. M.; Hodges, R. R.

    1993-04-01

    Data collected by the Pioneer Venus Large Probe Neutral Mass Spectrometer are presented and discussed. Results indicate the presence of a large amount of methane in the Venus atmosphere from 60 km to the surface. Deuterium transfer from atmospheric HDO to poorly deuterated methane may account for the puzzling apparent gradient in the water vapor mixing ration below 10 km. Deuterium transfer within the mass spectrometer may cause reduction in the apparent ratio of HDO to H2O. Accounting for the deuterium atoms leads to a revised water vapor mixing ratio of 28 ppm. Arguments against the methane detected being purely atmospheric are overwhelming. The methane may have been generated by a reaction between a highly deuterated atmospheric constituent and a poorly deuterated instrumental contaminant.

  17. Methane heat transfer investigation

    NASA Technical Reports Server (NTRS)

    1984-01-01

    Future high chamber pressure LOX/hydrocarbon booster engines require copper base alloy main combustion chamber coolant channels similar to the SSME to provide adequate cooling and reusable engine life. Therefore, it is of vital importance to evaluate the heat transfer characteristics and coking thresholds for LNG (94% methane) cooling, with a copper base alloy material adjacent to he fuel coolant. High pressure methane cooling and coking characteristics recently evaluated at Rocketdyne using stainless steel heated tubes at methane bulk temperatures and coolant wall temperatures typical of advanced engine operation except at lower heat fluxes as limited by the tube material. As expected, there was no coking observed. However, coking evaluations need be conducted with a copper base surface exposed to the methane coolant at higher heat fluxes approaching those of future high chamber pressure engines.

  18. Methane heat transfer investigation

    NASA Technical Reports Server (NTRS)

    Cook, R. T.

    1984-01-01

    Future high chamber pressure LOX/hydrocarbon booster engines require copper-base alloy main combustion chamber coolant channels similar to the SSME to provide adequate cooling and resuable engine life. Therefore, it is of vital importance to evaluate the heat transfer characteristics and coking thresholds for LNG (94% methane) cooling, with a copper-base alloy material adjacent to the fuel coolant. High-pressure methane cooling and coking characteristics were recently evaluated using stainless-steel heated tubes at methane bulk temperatures and coolant wall temperatures typical of advanced engine operation except at lower heat fluxes as limited by the tube material. As expected, there was no coking observed. However, coking evaluations need be conducted with a copper-base surface exposed to the methane coolant at higher heat fluxes approaching those of future high chamber pressure engines.

  19. Electrochemical methane sensor

    DOEpatents

    Zaromb, S.; Otagawa, T.; Stetter, J.R.

    1984-08-27

    A method and instrument including an electrochemical cell for the detection and measurement of methane in a gas by the oxidation of methane electrochemically at a working electrode in a nonaqueous electrolyte at a voltage about 1.4 volts vs R.H.E. (the reversible hydrogen electrode potential in the same electrolyte), and the measurement of the electrical signal resulting from the electrochemical oxidation.

  20. Laser beam methane detector

    NASA Technical Reports Server (NTRS)

    Hinkley, E. D., Jr.

    1981-01-01

    Instrument uses infrared absorption to determine methane concentration in liquid natural gas vapor. Two sensors measure intensity of 3.39 mm laser beam after it passes through gas; absorption is proportional to concentration of methane. Instrument is used in modeling spread of LNG clouds and as leak detector on LNG carriers and installations. Unit includes wheels for mobility and is both vertically and horizontally operable.

  1. Role of Confinement on Adsorption and Dynamics of Ethane and an Ethane–CO 2 Mixture in Mesoporous CPG Silica

    DOE PAGESBeta

    Patankar, Sumant; Gautam, Siddharth; Rother, Gernot; Podlesnyak, Andrey; Ehlers, Georg; Liu, Tingting; Cole, David R.; Tomasko, David L.

    2016-02-10

    It was found that ethane is confined to mineral and organic pores in certain shale formations. Effects of confinement on structural and dynamic properties of ethane in mesoporous controlled pore glass (CPG) were studied by gravimetric adsorption and quasi-elastic neutron scattering (QENS) measurements. The obtained isotherms and scattering data complement each other by quantifying the relative strength of the solid–fluid interactions and the transport properties of the fluid under confinement, respectively. We used a magnetic suspension balance to measure the adsorption isotherms at two temperatures and over a range of pressures corresponding to a bulk density range of 0.01–0.35 g/cm3.more » Key confinement effects were highlighted through differences between isotherms for the two pore sizes. A comparison was made with previously published isotherms for CO2 on the same CPG materials. Behavior of ethane in the smaller pore size was probed further using quasi-elastic neutron scattering. By extracting the self-diffusivity and residence time, we were able to study the effect of pressure and transition from gaseous to supercritical densities on the dynamics of confined ethane. Moreover, a temperature variation QENS study was also completed with pure ethane and a CO2–ethane mixture. Activation energies extracted from the Arrhenius plots show the effects of CO2 addition on ethane mobility.« less

  2. 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.

  3. 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.

  4. 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.

  5. Chemical kinetic modeling of propane oxidation behind shock waves

    NASA Technical Reports Server (NTRS)

    Mclain, A. G.; Jachimowski, C. J.

    1977-01-01

    The stoichiometric combustion of propane behind incident shock waves was studied experimentally and analytically over a temperature range from 1700 K to 2600 K and a pressure range from 1.2 to 1.9 atm. Measurements of the concentrations of carbon monoxide (CO) and carbon dioxide (CO2) and the product of the oxygen atom and carbon dioxide concentrations (O)(CO) were made after passage of the incident shock wave. A kinetic mechanism was developed which, when used in a computer program for a flowing, reacting gas behind an incident shock wave predicted experimentally measured results quite well. Ignition delay times from the literature were also predicted quite well. The kinetic mechanism consisted of 59 individual kinetic steps.

  6. Effect of hydrogen injection stability and emissions of an experimental premixed prevaporized propane burner

    NASA Technical Reports Server (NTRS)

    Anderson, D. N.

    1975-01-01

    Hydrogen in quantities up to 5 percent by weight of the total fuel flow was injected into a premixed propane burner. The hydrogen was either premixed with the propane and air upstream of the burner or introduced as a torch at the flameholder. Emissions of total nitrogen oxides, carbon monoxide, and unburned hydrocarbon are reported as are combustion efficiencies and lean blowout limits. To maintain at least 99 percent combustion efficiency at a 700 K inlet mixture temperature with no hydrogen added, it was necessary to burn with a propane equivalence ratio of 0.525. When 4 percent hydrogen was premixed with the propane and air, a combustion efficiency greater than 99 percent was recorded at a propane equivalence ratio of 0.425. The total nitrogen oxides (NOx) emissions corresponding to these two conditions were 0.8 g NO2/kg equivalent propane and 0.44 g NO2/kg equivalent propane, respectively. The hydrogen torch did not reduce NOx emissions.

  7. Irradiation chemistry in the outer solar system

    NASA Astrophysics Data System (ADS)

    Brown, Michael E.

    2014-11-01

    The dark, reddish tinged surfaces of icy bodies in the outer solar are usually attributed to the long term irradiation of simple hydrocarbons such as methane leading to the loss of hydrogen and the production of long carbon chains. While methane is stable and detected on the most massive bodies in the Kuiper belt, evidence of active irradiation chemistry is scant except for the presence of ethane on methane-rich Makemake and possible detections of ethane on more methane-poor Pluto and Quaoar. We have obtained deep high signal-to-noise spectra of Makemake from 1.5 to 2.5 microns in an attempt to trace the radiation chemistry in the outer solar system beyond the initial ethane formation. We present the first astrophysical detections of solid ethylene, acetylene, and possibly propane -- all expected products of the continued irradiation of methane, and use these species to map the chemical pathway from methane to long-chain hydrocarbons.

  8. Methane Emissions from Upland Forests

    NASA Astrophysics Data System (ADS)

    Megonigal, Patrick; Pitz, Scott; Wang, Zhi-Ping

    2016-04-01

    Global budgets ascribe 4-10% of atmospheric methane sinks to upland soils and assume that soils are the sole surface for methane exchange between upland forests and the atmosphere. The dogma that upland forests are uniformly atmospheric methane sinks was challenged a decade ago by the discovery of abiotic methane production from plant tissue. Subsequently a variety of relatively cryptic microbial and non-microbial methane sources have been proposed that have the potential to emit methane in upland forests. Despite the accumulating evidence of potential methane sources, there are few data demonstrating actual emissions of methane from a plant surface in an upland forest. We report direct observations of methane emissions from upland tree stems in two temperate forests. Stem methane emissions were observed from several tree species that dominate a forest located on the mid-Atlantic coast of North America (Maryland, USA). Stem emissions occurred throughout the growing season while soils adjacent to the trees simultaneously consumed methane. Scaling fluxes by stem surface area suggested the forest was a net methane source during a wet period in June, and that stem emissions offset 5% of the soil methane sink on an annual basis. High frequency measurements revealed diurnal cycles in stem methane emission rates, pointing to soils as the methane source and transpiration as the most likely pathway for gas transport. Similar observations were made in an upland forest in Beijing, China. However, in this case the evidence suggested the methane was not produced in soils, but in the heartwood by microbial or non-microbial processes. These data challenge the concept that forests are uniform sinks of methane, and suggest that upland forests are smaller methane sinks than previously estimated due to stem emissions. Tree emissions may be particularly important in upland tropical forests characterized by high rainfall and transpiration.

  9. Effect of temperature and pressure on the dynamics of nanoconfined propane

    SciTech Connect

    Gautam, Siddharth Liu, Tingting Welch, Susan; Cole, David; Rother, Gernot; Jalarvo, Niina; Mamontov, Eugene

    2014-04-24

    We report the effect of temperature and pressure on the dynamical properties of propane confined in nanoporous silica aerogel studied using quasielastic neutron scattering (QENS). Our results demonstrate that the effect of a change in the pressure dominates over the effect of temperature variation on the dynamics of propane nano-confined in silica aerogel. At low pressures, most of the propane molecules are strongly bound to the pore walls, only a small fraction is mobile. As the pressure is increased, the fraction of mobile molecules increases. A change in the mechanism of motion, from continuous diffusion at low pressures to jump diffusion at higher pressures has also been observed.

  10. Hydrocarbon emissions and characterization of methane sources in the Barnett Shale

    NASA Astrophysics Data System (ADS)

    Marrero, J. E.; Townsend-Small, A.; Meinardi, S.; Blake, D. R.

    2014-12-01

    As energy demand and costs continue to rise worldwide, so does the development of energy from natural gas. The United States in particular has expanded its natural gas industry, becoming one of the world's top gas producing countries. The Barnett Shale of northern Texas is one of the most developed and productive natural gas shale plays in the United States. However, emissions from the many oil and gas system components in the region have not been fully characterized. An extensive list of volatile organic compounds (VOCs) was measured from 120 whole air canisters collected throughout the Barnett shale in October 2013. Known methane sources were targeted and included oil and natural gas well pads, compressor stations, distribution pipelines and city gates, cattle feedlots and landfills. C1-C5 alkanes were elevated throughout the region and were similar to or greater than concentrations in major U.S. cities. The VOC source signature for oil and gas operations was distinguished from biogenic sources. Average ethane content relative to methane was calculated for each of the source types, and ranged from 0.7 to 12.8%. For the whole region, the ethane content was 7.2±6.1%, illustrating the high variability and effect of the various hydrocarbon sources on the local air.

  11. Effects of natural gas composition on ignition delay under diesel conditions

    SciTech Connect

    Naber, J.D.; Siebers, D.L.; Di Julio, S.S.; Westbrook, C.K.

    1993-12-03

    Effects of variations in natural gas composition on autoignition of natural gas under direct-injection (DI) diesel engine conditions were studied experimentally in a constant-volume combustion vessel and computationally using a chemical kinetic model. Four fuel blends were investigated: pure methane, a capacity weighted mean natural gas, a high ethane content natural gas, and a natural gas with added propane typical of peak shaving conditions. Experimentally measured ignition delays were longest for pure methane and became progressively shorter as ethane and propane concentrations increased. At conditions characteristic of a DI compression ignition natural gas engine at Top Dead Center (CR=23:1, p = 6.8 MPa, T = 1150K), measured ignition delays for the four fuels varied from 1.8 ms for the peak shaving and high ethane gases to 2.7 ms for pure methane. Numerically predicted variations in ignition delay as a function of natural gas composition agreed with these measurements.

  12. 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.

  13. Propane dehydrogenation over Pt-Cu bimetallic catalysts: the nature of coke deposition and the role of copper.

    PubMed

    Han, Zhiping; Li, Shuirong; Jiang, Feng; Wang, Tuo; Ma, Xinbin; Gong, Jinlong

    2014-09-01

    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. PMID:24933477

  14. Combustion of Methane Hydrate

    NASA Astrophysics Data System (ADS)

    Roshandell, Melika

    A significant methane storehouse is in the form of methane hydrates on the sea floor and in the arctic permafrost. Methane hydrates are ice-like structures composed of water cages housing a guest methane molecule. This caged methane represents a resource of energy and a potential source of strong greenhouse gas. Most research related to methane hydrates has been focused on their formation and dissociation because they can form solid plugs that complicate transport of oil and gas in pipelines. This dissertation explores the direct burning of these methane hydrates where heat from the combustion process dissociates the hydrate into water and methane, and the released methane fuels the methane/air diffusion flame heat source. In contrast to the pipeline applications, very little research has been done on the combustion and burning characteristics of methane hydrates. This is the first dissertation on this subject. In this study, energy release and combustion characteristics of methane hydrates were investigated both theoretically and experimentally. The experimental study involved collaboration with another research group, particularly in the creation of methane hydrate samples. The experiments were difficult because hydrates form at high pressure within a narrow temperature range. The process can be slow and the resulting hydrate can have somewhat variable properties (e.g., extent of clathration, shape, compactness). The experimental study examined broad characteristics of hydrate combustion, including flame appearance, burning time, conditions leading to flame extinguishment, the amount of hydrate water melted versus evaporated, and flame temperature. These properties were observed for samples of different physical size. Hydrate formation is a very slow process with pure water and methane. The addition of small amounts of surfactant increased substantially the hydrate formation rate. The effects of surfactant on burning characteristics were also studied. One finding

  15. Development of vanadium-phosphate catalysts for methanol production by selective oxidation of methane

    SciTech Connect

    McCormick, R.L.; Jha, M.C.

    1993-03-04

    Amax R D will perform laboratory scale development of a promising, practical catalyst for the selective oxidation of methane to methanol. The primary component of this catalyst is vanadium-phosphate (VPO) which has shown good activity and selectivity in the partial oxidation of n-butane and propane but has not been studied in detail for methane oxidation. The goal of the project is to develop a catalyst which allows methane oxidation to methanol to be conducted at high conversion and selectivity. A low CH[sub 4]/O[sub 2] ratio will be employed with air as the source of oxygen. Temperatures below 600[degrees]C and pressures up to 20 atm are to be investigated. The use of steam in the feed gas will also be investigated. The catalyst development strategy will be to utilize promoters and supports to improve the activity and selectivity of the unmodified VPO catalyst. The catalyst testing reactor system was used to perform blank (empty) reactor runs over a wide range of temperatures, pressure, and flow rates. No methane conversion was observed at temperatures of 500[degrees]C or lower in any of the tests. At higher temperatures, significant methane conversion to carbon dioxide was observed. At 550[degrees]C, 300 psig, and the highest flow rate studied, reactor ignition was observed. Based on the results of these blank runs, we conclude that catalyst testing should be performed at temperatures not to exceed 500[degrees]C.

  16. Real-time monitoring of ethane in human breath using mid-infrared cavity leak-out spectroscopy

    NASA Astrophysics Data System (ADS)

    Dahnke, H.; Kleine, D.; Hering, P.; Mürtz, M.

    2001-06-01

    We report on spectroscopic real-time analysis of ethane traces in exhaled human breath. Ethane is considered the most important volatile marker of free-radical induced lipid peroxidation and cell damage in the human body. Our measurements were carried out by means of mid-infrared cavity leak-out spectroscopy in the 3 μm region, a cw variant of cavity ring-down spectroscopy. The spectrometer is based on a CO overtone laser with tunable microwave sidebands. The resulting system proved to be an unique tool with high sensitivity and selectivity for rapid and precise breath testing. With a 5 s integration time, we achieved a detection limit on the order of 100 parts per trillion ethane in human breath. Thus, sample preconcentration is unnecessary. Time-resolved monitoring of the decaying ethane fraction in breath after smoking a cigarette is demonstrated.

  17. DISTRIBUTION OF [14C]ETHANE DIMENTHANESULFONATE IN IMMATURE AND ADULT MALE RATS FOLLOWING AN ACUTE EXPOSURE

    EPA Science Inventory

    In the adult rat, ethane dimethanesulphonate (EDS) reduces testosterone (T) production by killing Leydig cells. Studies have also shown that acute EDS administration produces transient infertility and epididymal effects. Although these later effects were believed to be indirect r...

  18. Methane formation and methane oxidation by methanogenic bacteria.

    PubMed Central

    Zehnder, A J; Brock, T D

    1979-01-01

    Methanogenic bacteria were found to form and oxidize methane at the same time. As compared to the quantity of methane formed, the amount of methane simultaneously oxidized varied between 0.3 and 0.001%, depending on the strain used. All the nine tested strains of methane producers (Methanobacterium ruminantium, Methanobacterium strain M.o.H., M. formicicum, M. thermoautotrophicum, M. arbophilicum, Methanobacterium strain AZ, Methanosarcina barkeri, Methanospirillum hungatii, and the "acetate organism") reoxidized methane to carbon dioxide. In addition, they assimilated a small part of the methane supplied into cell material. Methanol and acetate also occurred as oxidation products in M. barkeri cultures. Acetate was also formed by the "acetate organism," a methane bacterium unable to use methanogenic substrates other than acetate. Methane was the precursor of the methyl group of the acetate synthesized in the course of methane oxidation. Methane formation and its oxidation were inhibited equally by 2-bromoethanesulfonic acid. Short-term labeling experiments with M. thermoautotrophicum and M. hungatii clearly suggest that the pathway of methane oxidation is not identical with a simple back reaction of the methane formation process. Images PMID:762019

  19. 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.

  20. Direct catalytic conversion of methane and light hydrocarbon gases. Final report, October 1, 1986--July 31, 1989

    SciTech Connect

    Wilson, R.B. Jr.; Posin, B.M.; Chan, Yee-Wai

    1995-06-01

    This project explored conversion of methane to useful products by two techniques that do not involve oxidative coupling. The first approach was direct catalytic dehydrocoupling of methane to give hydrocarbons and hydrogen. The second approach was oxidation of methane to methanol by using heterogenized versions of catalysts that were developed as homogeneous models of cytochrome-P450, an enzyme that actively hydroxylates hydrocarbons by using molecular oxygen. Two possibilities exist for dehydrocoupling of methane to higher hydrocarbons: The first, oxidative coupling to ethane/ethylene and water, is the subject of intense current interest. Nonoxidative coupling to higher hydrocarbons and hydrogen is endothermic, but in the absence of coke formation the theoretical thermodynamic equilibrium yield of hydrocarbons varies from 25% at 827{degrees}C to 65% at 1100{degrees}C (at atmospheric pressure). In this project we synthesized novel, highly dispersed metal catalysts by attaching metal clusters to inorganic supports. The second approach mimics microbial metabolism of methane to produce methanol. The methane mono-oxygenase enzyme responsible for the oxidation of methane to methanol in biological systems has exceptional selectivity and very good rates. Enzyme mimics are systems that function as the enzymes do but overcome the problems of slow rates and poor stability. Most of that effort has focused on mimics of cytochrome P-450, which is a very active selective oxidation enzyme and has a metalloporphyrin at the active site. The interest in nonporphyrin mimics coincides with the interest in methane mono-oxygenase, whose active site has been identified as a {mu}-oxo dinuclear iron complex.We employed mimics of cytochrome P-450, heterogenized to provide additional stability. The oxidation of methane with molecular oxygen was investigated in a fixed-bed, down-flow reactor with various anchored metal phthalocyanines (PC) and porphyrins (TPP) as the catalysts.

  1. 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...

  2. Highly efficient VOx/SBA-15 mesoporous catalysts for oxidative dehydrogenation of propane.

    PubMed

    Liu, Yong-Mie; Cao, Yong; Zhu, Ka-Ke; Yan, Shi-Run; Dai, Wei-Lin; He, He-Yong; Fan, Kang-Nian

    2002-12-01

    Highly dispersed vanadia species on SBA-15 mesoporous silica have been found to exhibit a highly efficient catalytic performance for the oxidative dehydrogenation (ODH) of propane to light olefins (propene + ethylene). PMID:12478769

  3. 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. PMID:25577087

  4. 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.

  5. 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.

  6. 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.

  7. The basics of coalbed methane

    SciTech Connect

    2006-12-15

    The report is an overview of coalbed methane (CBM), also known as coal seam gas. It provides an overview of what coalbed methane is and the current status of global coalbed methane exploration and production. Topics covered in the report include: An analysis of the natural gas industry, including current and future production, consumption, and reserves; A detailed description of coalbed methane, its characteristics, and future potential; An analysis of the key business factors that are driving the increased interest in coalbed methane; An analysis of the barriers that are hindering the development of coalbed methane; An overview of the technologies used for coalbed methane production and water treatment; and Profiles of key coalbed methane producing countries. 25 figs., 5 tabs., 1 app.

  8. Atmospheric pressure ionization of chlorinated ethanes in ion mobility spectrometry and mass spectrometry

    SciTech Connect

    Ewing, Robert G.; Atkinson, David A.; Benson, Michael T.

    2015-05-16

    This study investigates the APCI mechanisms associated with chlorinated ethanes in an attempt to define conditions under which unique pseudo-molecular adducts, in addition to chloride ion, can be produced for analytical measurements using IMS and MS. The ionization chemistry of chlorinated compounds typically leads to the detection of only the halide ions. Using molecular modeling, which provides insights into the ion formation and relative binding energies, predictions for the formation of pseudo-molecular adducts are postulated. Predicted structures of the chloride ion with multiple hydrogens on the ethane backbone was supported by the observation of specific pseudo-molecular adducts in IMS and MS spectra. With the proper instrumental conditions, such as short reaction times and low temp.

  9. Radiolytically induced formation and optical absorption spectra of colloidal silver nanoparticles in supercritical ethane.

    SciTech Connect

    Dimitrijevic, N. M.; Bartels, D. M.; Jonah, C. D.; Takahashi, K.; Rajh, T.; Chemistry

    2001-02-08

    Colloidal silver nanoparticles were synthesized in supercritical ethane at 80 {sup o}C and 80-120 bar, with methanol as cosolvent. Solvated electrons, produced by a pulse of 20 MeV electrons, reduced the silver ions. The time-resolved technique of pulse radiolysis was employed to characterize the reduction products and colloidal metallic particles. The absorption spectra of small silver clusters (Ag{sub 2}{sup +}, Ag{sub 3}{sup +}, Ag{sub 4}{sup 2+}, etc.) were detected at short times after the pulse. Colloidal metallic silver particles were identified by their characteristic plasmon absorption at 1-10 s after the pulse. Colloidal particles are stable for hours in supercritical ethane. The particles are less than 10 nm in diameter. Their size was determined using transmission electron microscope after precipitation from the solution.

  10. Vibration-Torsion Dynamics of Ethane-like Molecules in Degenerate Vibrational States

    NASA Astrophysics Data System (ADS)

    Dilauro, C.; Lattanzi, F.; Avellino, R.

    1994-10-01

    We examine the mechanisms of interaction between the deformations of the two identical halves of ethane-like molecules in degenerate vibrational states, in order to determine the most convenient symmetries of the degenerate vibrational wavefunctions, in the molecular symmetry group G36( EM). In moderate barrier molecules this is related to the problem of the vibration-torsion symmetry labeling of the tunneling split components, in the order of increasing energies, in given rotational states. Numerical calculations have been performed as a guide to explore several different situations. It has been proved that the torsional splittings in degenerate vibrational states of molecules with a moderate barrier depend dramatically on the value of the γ-Coriolis coefficient and, unlike the splittings in nondegenerate vibrational states, are not determined only by the effective torsional potential function. Theory and numerical predictions support the experimental result that all normal modes of ethane behave as E1 d, E2 d pairs.

  11. Comparison of experimental and theoretical electron-impact-ionization triple-differential cross sections for ethane

    NASA Astrophysics Data System (ADS)

    Ali, Esam; Nixon, Kate; Murray, Andrew; Ning, Chuangang; Colgan, James; Madison, Don

    2015-10-01

    We have recently examined electron-impact ionization of molecules that have one large atom at the center, surrounded by H nuclei (H2O , N H3 , C H4 ). All of these molecules have ten electrons; however, they vary in their molecular symmetry. We found that the triple-differential cross sections (TDCSs) for the highest occupied molecular orbitals (HOMOs) were similar, as was the character of the HOMO orbitals which had a p -type "peanut" shape. In this work, we examine ethane (C2H6 ) which is a molecule that has two large atoms surrounded by H nuclei, so that its HOMO has a double-peanut shape. The experiment was performed using a coplanar symmetric geometry (equal final-state energies and angles). We find the TDCS for ethane is similar to the single-center molecules at higher energies, and is similar to a diatomic molecule at lower energies.

  12. Transformations in methane hydrates

    PubMed Central

    Chou, I-Ming; Sharma, Anurag; Burruss, Robert C.; Shu, Jinfu; Mao, Ho-kwang; Hemley, Russell J.; Goncharov, Alexander F.; Stern, Laura A.; Kirby, Stephen H.

    2000-01-01

    Detailed study of pure methane hydrate in a diamond cell with in situ optical, Raman, and x-ray microprobe techniques reveals two previously unknown structures, structure II and structure H, at high pressures. The structure II methane hydrate at 250 MPa has a cubic unit cell of a = 17.158(2) Å and volume V = 5051.3(13) Å3; structure H at 600 MPa has a hexagonal unit cell of a = 11.980(2) Å, c = 9.992(3) Å, and V = 1241.9(5) Å3. The compositions of these two investigated phases are still not known. With the effects of pressure and the presence of other gases in the structure, the structure II phase is likely to dominate over the known structure I methane hydrate within deep hydrate-bearing sediments underlying continental margins. PMID:11087836

  13. 1,2-Bis(2-meth­oxy-6-formyl­phen­oxy)ethane

    PubMed Central

    Li, Hongqi; Cai, Li; Chen, Dongling; Li, Jinxing; Chen, Yijun

    2011-01-01

    In the title compound [systematic name: 3,3′-dimethoxy-2,2′-(ethane-1,2-diyldioxy)dibenzaldehyde], C18H18O6, prepared from 1,2-dibromo­ethane and ortho-vanillin in the presence of sodium carbonate, the two vanillin units are linked via a CH2–CH2 bridge. The two benzene rings are inclined at a dihedral angle of 41.6 (5)°. PMID:21522995

  14. Highly Selective Adsorption of Ethylene over Ethane in a MOF Featuring the Combination of Open Metal Site and -Complexation

    DOE PAGESBeta

    Zhang, Yiming; Li, Baiyan; Wu, Zili; Ma, Shengqian

    2015-01-09

    The introduction of the combination of open metal site (OMS) and -complexation into MOF has led to very high ethylene/ethane adsorption selectivity at 318K, as illustrated in the context of MIL-101-Cr-SO3Ag. The interactions with ethylene from both OMS and -complexation in MIL-101-Cr-SO3Ag have been investigated by in situ IR spectroscopic studies and computational calculations, which suggest -complexation contributes dominantly to the high ethylene/ethane adsorption selectivity.

  15. Temperature dependence of the hydrogen-broadening coefficient for the nu 9 fundamental of ethane

    NASA Technical Reports Server (NTRS)

    Halsey, G. W.; Hillman, J. J.; Nadler, Shacher; Jennings, D. E.

    1988-01-01

    Experimental results for the temperature dependence of the H2-broadening coefficient for the nu 9 fundamental of ethane are reported. Measurements were made over the temperature range 95-300 K using a novel low-temperature absorption cell. These spectra were recorded with the Doppler-limited diode laser spectrometer at NASA Goddard. The results are compared with recent measurements and model predictions.

  16. Niobium phosphates as new highly selective catalysts for the oxidative dehydrogenation of ethane.

    PubMed

    Weng, Weihao; Davies, Mathew; Whiting, Gareth; Solsona, Benjamin; Kiely, Christopher J; Carley, Albert F; Taylor, Stuart H

    2011-10-14

    Several niobium phosphate phases have been prepared, fully characterized and tested as catalysts for the selective oxidation of ethane to ethylene. Three distinct niobium phosphate catalysts were prepared, and each was comprised predominantly of a different bulk phase, namely Nb(2)P(4)O(15), NbOPO(4) and Nb(1.91)P(2.82)O(12). All of the niobium phosphate catalysts showed high selectivity towards ethylene, but the best catalyst was Nb(1.91)P(2.82)O(12), which was produced from the reduction of niobium oxide phosphate (NbOPO(4)) by hydrogen. It was particularly selective for ethylene, giving ca. 95% selectivity at 5% conversion, decreasing to ca. 90% at 15% conversion, and only produced low levels of carbon oxides. It was also determined that the only primary product from ethane oxidation over this catalyst was ethylene. Catalyst activity also increased with time-on-line, and this behaviour was ascribed to an increase of the concentration of the Nb(1.91)P(2.82)O(12) phase, as partially transformed NbOPO(4), formed during preparation, was converted to Nb(1.91)P(2.82)O(12) during use. Catalysts with predominant phases of Nb(2)P(4)O(15) and NbOPO(4) also showed appreciable activity and selectivities to ethylene with values around 75% and 85% respectively at 5% ethane conversion. The presence of phosphorous is required to achieve high ethylene selectivity, as orthorhombic and monoclinic Nb(2)O(5) catalysts showed similar activity, but displayed selectivities to ethylene that were <20% under the same reaction conditions. To the best of our knowledge, this is the first time that niobium phosphates have been shown to be highly selective catalysts for the oxidation of ethane to ethylene, and demonstrates that they are worthy candidates for further study. PMID:21881631

  17. Methane: Small molecule, big impact

    SciTech Connect

    Ferry, J.G.

    1997-11-21

    Methanogenesis occures in anaerobic conditions in vast natural and human made environments. The estimated 1% annual increase in global methane is mainly attributed to human activities. This article gives an overall perspective on methane-producing microbes, which are phylogenetically distinct from all other prokaryotes and eukaryotes, the food chain which produces atmospheric methane, and biochemical pathways leading to methane production in these microbes. 12 refs., 12 figs.

  18. Calculating Thermophysical Properties Of 12 Fluids

    NASA Technical Reports Server (NTRS)

    Cleghorn, T. F.; Mccarty, R. D.

    1991-01-01

    MIPROPS is set of computer programs giving thermophysical and transport properties of selected fluids. Calculates properties of fluids in both liquid and vapor states over wide range of temperatures and pressures. Fluids included: helium, hydrogen, nitrogen, oxygen, argon, nitrogen trifluoride, methane, ethylene, ethane, propane, isobutane, and normal butane. All programs except helium program incorporate same equation of state. Written in FORTRAN 77.

  19. Mutagenic activity of halogenated propanes and propenes: effect of bromine and chlorine positioning.

    PubMed

    Låg, M; Omichinski, J G; Dybing, E; Nelson, S D; Søderlund, E J

    1994-10-01

    A series of halogenated propanes and propenes were studied for mutagenic effects in Salmonella typhimurium TA100 in the absence or presence of NADPH plus liver microsomes from phenobarbital-induced rats as an exogenous metabolism system. The cytotoxic and mutagenic effects of the halogenated propane 1,2-dibromo-3-chloropropane (DBCP) has previously been studied in our laboratories. These studies showed that metabolic activation of DBCP was required to exert its detrimental effects. All of the trihalogenated propane analogues were mutagenic when the microsomal activation system was included. The highest mutagenic activity was obtained with 1,2,3-tribromopropane, with approximately 50-fold higher activity than the least mutagenic trihalogenated propane, 1,2,3-trichloropropane. The order of mutagenicity was as follows: 1,2,3-tribromopropane > or = 1,2-dibromo- 3-chloropropane > 1,3-dibromo-2-chloropropane > or = 1,3-dichloro-2-bromopropane > 1-bromo-2,3-dichloropropane > 1,2,3-trichloropropane. Compared to DBCP, the dihalogenated propanes were substantially less mutagenic. Only 1,2-dibromopropane was mutagenic and its mutagenic potential was approximately 1/30 of that of DBCP. In contrast to DBCP, 1,2-dibromopropane showed similar mutagenic activity with and without the addition of an activation system. The halogenated propenes 2,3-dibromopropene and 2-bromo-3-chloropropene were mutagenic to the bacteria both in the absence and presence of the activation system, whereas 2,3-dichloropropene did not show any mutagenic effect. The large differences in mutagenic potential between the various halogenated propanes and propenes are proposed to be due to the formation of different possible proximate and ultimate mutagenic metabolites resulting from the microsomal metabolism of the various halogenated propanes and propenes, and to differences in the rate of formation of the metabolites. Pathways are proposed for the formation of genotoxic metabolites of di- and trihalogenated

  20. Kinetic isotopic effects in oxidative dehydrogenation of propane on vanadium oxide catalysts

    SciTech Connect

    Chen, K.; Iglesia, E.; Bell, A.T.

    2000-05-15

    Kinetic isotopic effects (KIEs) for oxidative dehydrogenation of propane were measured on 10 wt% V{sub 2}O{sub 5}/ZrO{sub 2}. Normal KIEs were obtained using CH{sub 3}CH{sub 2}CH{sub 3} and CD{sub 3}CD{sub 2}CD{sub 3} as reactants for primary dehydrogenation (2.8) and combustion (1.9) of propane and for secondary combustion of propene (2.6), suggesting that in all cases C-H bond dissociation is a kinetically relevant step. CH{sub 3}CH{sub 2}CH{sub 3} and CH{sub 3}CD{sub 2}CH{sub 3} reactants led to normal KIEs for dehydrogenation (2.7) and combustion (1.8) of propane, but to a very small KIE (1.1) for propene combustion. These results show that the methylene C-H bond is activated in the rate-determining steps for propane dehydrogenation and combustion reactions. The rate-determining step in secondary propene combustion involves the allylic C-H bond. In each reaction, the weakest C-H bond in the reactant is cleaved in the initial C-H bond activation step. The measured propane oxidative dehydrogenation KIEs are in agreement with theoretical estimates using a sequence of elementary steps, reaction rate expression, and transition state theory. The much smaller KIE for propane oxidative dehydrogenation (2.8) than the maximum KIE (6) expected for propane thermal dehydrogenation indicates the participation of lattice oxygen. The different KIE values for propane primary dehydrogenation and combustion suggest that these two reactions involve different lattice oxygen sites.

  1. 40 CFR 1065.341 - CVS and batch sampler verification (propane check).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... reference mass or a reference flow rate of C3H8 as a tracer gas in a CVS. Note that if you use a reference... gas assumptions in § 1065.640 and § 1065.642. The propane check compares the calculated mass of... for the propane check as follows: (1) If you use a reference mass of C3H8 instead of a reference...

  2. Methane-Powered Airplane

    NASA Technical Reports Server (NTRS)

    1984-01-01

    Beech Aircraft's Corporation's Boulder Division developed expertise in producing superinsulated virtually leak-proof cryogenic equipment for storing liquid oxygen and hydrogen fuels in NASA's Apollo, Skylab and Space Shuttle programs. Boulder Division used this experience in designing a fuel storage tank for liquid methane, a "cryogenic" fuel that must be supercooled to keep it liquid. Beech Aircraft is producing a four-place lightplane powered by liquid methane (LM) which is stored in two of these specially designed cryogenic storage tanks holding 18 gallons each.

  3. Biomimetic methane oxidation

    NASA Astrophysics Data System (ADS)

    Watkins, B. E.; Droege, M. W.; Taylor, R. T.; Satcher, J. H.

    1992-06-01

    Methane monooxygenase (MMO) is an enzyme found in methanotrophs that catalyses the selective oxidation of methane to methanol. MMO is protein complex one component of which is a binuclear metal center containing oxygenase. We have completed one round of a design/synthesis/evaluation cycle in the development of coordination complexes that mimic the structure/function of the MMO active site. One of these, a binuclear, coordinately-asymmetric copper complex, is capable of oxidizing cyclohexane to a mixture of cyclohexanol and cyclohexanone in the presence of hydrogen peroxide.

  4. Stable carbon isotope ratios of ethane over the North Pacific: Atmospheric measurements and global chemical transport modeling

    NASA Astrophysics Data System (ADS)

    Saito, Takuya; Stein, Olaf; Tsunogai, Urumu; Kawamura, Kimitaka; Nakatsuka, Takeshi; Gamo, Toshitaka; Yoshida, Naohiro

    2011-01-01

    The atmospheric mixing ratios of ethane and its stable carbon isotope ratios (δ13C) were measured over the North Pacific (2°N to 38°N, 140°E to 90°W) during oceanographic cruises in summer and autumn. The measured mixing ratios were relatively low (mostly <1 ppbv) over the North Pacific, whereas elevated ethane levels (>1 ppbv) were observed over the western North Pacific near Japan, with lower δ13C values (approximately -25‰), suggesting recent emissions from neighboring source regions. The most 13C-enriched values of ethane (approximately -16‰) were observed over the western equatorial Pacific rather than the central and eastern equatorial Pacific. This is likely caused by the kinetic isotope effect (KIE) for the removal of ethane during the atmospheric transport from potential upwind source regions to the most remote region under the prevailing trade easterly winds. The measurements were compared with the results of a global chemical transport model including two ethane isotopologues (12C2H6 and 13C2H6). The model-estimated δ13C values were too high compared with the observations. It is likely that this discrepancy is partly due to an approximately 40% overestimation of the reported KIE for the reaction between ethane and OH radicals.

  5. The Infrared Optical Constants of Ethane and Ethylene Ices: Relevance to Pluto and Triton

    NASA Astrophysics Data System (ADS)

    Gerakines, Perry A.; Hudson, Reggie L.; Moore, Marla H.

    2014-11-01

    As New Horizons approaches the Pluto system, our research group is carrying out new infrared optical-constants measurements of hydrocarbons with an emphasis on temperatures below ~70 K. Our goal is to add to the relatively meager literature on this subject and to provide electronic versions of state-of-the-art data, since the abundances of such molecules cannot be deduced without accurate optical constants (n, k) and reference spectra. Ethane (C2H6) and ethylene (C2H4) are the subject of the present work. Photochemical models of the atmospheres of Pluto and Triton predict both of these molecules as abundant precipitating products (Krasnopolsky and Cruikshank, 1995, JGR 100, 21271-21286; Krasnopolsky and Cruikshank,1999, JGR 104, 21979-21996), and the infrared reflectance features of both Pluto and Triton are well fit by laboratory spectra when pure, solid ethane is included as a component (Cruikshank et al., 2006, Bulletin of the AAS 38, 518). Here we present our recent measurements of near- and mid-infrared optical constants for ethane and ethylene in multiple ice phases and at multiple temperatures. We also report new measurements of the index of refraction of each ice at 670 nm. Comparisons are made to earlier work where possible. Electronic versions of our new results are available at http://science.gsfc.nasa.gov/691/cosmicice/constants.html.

  6. Benzophenone as a probe of local cosolvent effects in supercritical ethane

    SciTech Connect

    Knutson, B.L.; Sherman, S.R.; Bennett, K.L.; Liotta, C.L.; Eckert, C.A.

    1997-03-01

    The n {yields} {pi}* shift of benzophenone has been used to quantify solute-cosolvent interactions in supercritical ethane. Dilute solutions of benzophenone in cosolvent/supercritical ethane mixtures were studied at 35 C from 50 to 100 bar over a range of cosolvent concentrations. The following cosolvents were chosen for investigation on the basis of their varying abilities to interact with benzophenone: 2,2,2-trifluoroethanol, ethanol, chloroform, propionitrile, 1,2-dibromoethane, and 1,1,1-trichloroethane. In the supercritical systems investigated here, hydrogen bonding of protic cosolvents to the carbonyl oxygen of benzophenone is the primary mechanism of the n {yields} {pi}* shift. The results of this investigation are consistent with a chemical-physical interpretation of cosolvent effects in supercritical fluids in the presence of strong specific solute-cosolvent interactions. The experimental results for the ethane/TFE/benzophenone system were analyzed by using integral equations in order to study the assumptions of the chemical-physical model. This combination of spectroscopic data with radial distribution function models provides a powerful tool for understanding cosolvent effects.

  7. ACTION CONCENTRATION FOR MIXTURES OF VOLATILE ORGANIC COMPOUNDS (VOC) & METHANE & HYDROGEN

    SciTech Connect

    MARUSICH, R.M.

    2006-07-10

    Waste containers may contain volatile organic compounds (VOCs), methane, hydrogen and possibly propane. These constituents may occur individually or in mixtures. Determining if a waste container contains a flammable concentration of flammable gases and vapors (from VOCs) is important to the safety of the handling, repackaging and shipping activities. This report provides the basis for determining the flammability of mixtures of flammable gases and vapors. The concentration of a mixture that is at the lowest flammability limit for that mixture is called the action concentration. The action concentration can be determined using total VOC concentrations or actual concentration of each individual VOC. The concentrations of hydrogen and methane are included with the total VOC or individual VOC concentration to determine the action concentration. Concentrations below this point are not flammable. Waste containers with gas/vapor concentrations at or above the action concentration are considered flammable.

  8. Study of the Low Temperature Oxidation of Propane

    PubMed Central

    Cord, Maximilien; Husson, Benoit; Huerta, Juan Carlos Lizardo; Herbinet, Olivier; Glaude, Pierre-Alexandre; Fournet, René; Sirjean, Baptiste; Battin-Leclerc, Frédérique; Ruiz-Lopez, Manuel; Wang, Zhandong; Xie, Mingfeng; Cheng, Zhanjun; Qi, Fei

    2013-01-01

    The low-temperature oxidation of propane was investigated using a jet-stirred reactor at atmospheric pressure and two methods of analysis: gas chromatography and synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) with direct sampling through a molecular jet. The second method allowed the identification of products, such as molecules with hydroperoxy functions, which are not stable enough to be detected by gas chromatography. Mole fractions of the reactants and reaction products were measured as a function of the temperature (530-730 K), with a particular attention to reaction products involved in the low temperature oxidation, such as cyclic ethers, aldehydes, alcohols, ketones, and hydroperoxides. A new model has been obtained from an automatically generated one, which was used as a starting point, with a large number of re-estimated thermochemical and kinetic data. The kinetic data of the most sensitive reactions, i.e., isomerizations of alkylperoxy radicals and the subsequent decompositions, have been calculated at the CBS-QB3 level of theory. The model allows a satisfactory prediction of the experimental data. A flow rate analysis has allowed highlighting the important reaction channels. PMID:23181456

  9. Preparation of platinum nanoparticle catalyst for propane dehydrogenation.

    PubMed

    Li, Jun; Wang, Jun; Ma, Zhanhua; Sun, Lanyi; Hu, Yangdong

    2014-09-01

    Supported Pt nanoparticle catalysts were prepared by combing a chemical reduction method with an ultrasonic sonication loading method. Several techniques including transmission electron microscopy (TEM), nitrogen sorption technique and pyridine adsorption Fourier-transform infrared (Py-IR) were applied to characterize the physicochemical properties of these catalysts. The catalytic performance of catalysts was evaluated in the dehydrogenation of propane. The influence of the preparation method of Pt nanoparticles, the ratio of Polyvinyl Pyrrolidone (PVP) to Pt, loading method and different supports on the catalytic performance was investigated. PVP is useful for controlling the size of Pt nanoparticles and a PVP/Pt ratio of 15 is favorable to achieve a good catalytic performance. NaBH4 reduction is better than ethanol refluxing in preparing Pt nanoparticles. The ultrasonic sonication is effective to load the Pt nanoparticles onto the support channels. The mesoporous alumina proved to be a good catalyst support due to its high surface area and unique pore structure. PMID:25924358

  10. Autothermal reforming of propane over Ni-based hydrotalcite catalysts.

    PubMed

    Park, Sun-Young; Kim, Jong-Ho; Moon, Dong-Ju; Park, Nam-Cook; Kim, Young-Chul

    2010-05-01

    Ni-based hydrotalcite catalysts were investigated for ATR of propane in a fixed-bed flow reactor. The reactions were carried out with a H2O/C/O2 stream ratio of 3/1/0.73 at temperatures ranging from 300 to 700 degrees C. The solvents used in the manufacture of Ni-based catalysts noble metal/Ni/MgAl catalysts or substituted active material were changed in order to decrease the level of catalyst deactivation. The use of a mixture of ethanol and water during the formation of the Pd-Ni/MgAl catalyst produced a higher hydrogen yield than that using water only. In addition, the use of acetone in the synthesis of Ru-Ni/MgAl catalyst produced a higher hydrogen yield than using water only. This shows that the solvents used for the noble metals affect the degree of dispersion and particle size of the nickel and prevented carbon deposition resulting in the enhanced hydrogen selectivity and catalyst activity. Active metals were substituted during the preparation of hydrotalcite catalysts. Among the catalysts prepared with various ratio (Ni:Fe) tested at high temperature, the ratio, Ni:Fe = 75:25, showed best performance. There was less sintering of Ni particles due to substitution of the active metal at the optimal ratio. PMID:20358916

  11. Polymerization of methane molecules and phase transition of san carlos olivine under the Earth's mantle conditions

    NASA Astrophysics Data System (ADS)

    Shinozaki, A.; Hirai, H.; Kagi, H.; Kondo, T.; Yagi, T.

    2010-03-01

    High-pressure and high-temperature experiments of the olivine-methane-water system were performed using a laser-heated diamond anvil cell at pressure range from 5.8 GPa to 29.4 GPa and temperatures up to 2000K. The samples were examined by X-ray diffractometry and Raman spectroscopy under high pressures and room temperature. The heated areas of the samples changed to black color. Raman spectroscopy revealed the existence of ethane, heavier hydrocarbons, graphite and glassy carbon besides methane molecules. X-ray diffractometry showed that olivine was remained in the sample heated at 5. 8 GPa, 2000K. Wadsleyite and ringwoodite were observed in the samples heated at 14.5 GPa and 19.5 GPa, respectively. At 29.4 GPa, the diffraction line of Mg-perovskite and magnesiowustite were observed. The observed phase changes were similar to those observed in anhydrous and hydrous conditions. The present results suggest that polymerization of methane molecules occurred and that phase transition of olivine occurred even under the existence of methane-water fluid in the deeper part of the mantle.

  12. Physical Chemical Controls of Methane and other Hydrocarbon gases in Outer Solar System Water-Ice Systems

    NASA Astrophysics Data System (ADS)

    Osegovic, J. P.; Max, M. D.

    2012-12-01

    transferred. The model is constrained by the molecular diffusion rate of gas approaching the hydrate phase boundary. The heat produced or consumed by the hydrate system will affect the ice system and phase boundary. Fick's law can be used to model steady state diffusion. Flux is related to the diffusivity of the component and as a function of concentration and the distance over which the reactions take place. Initial model calculations indicate that in some cases, methane (ΔH = -56 kJ/mol for small molecules (CH4, N2, CO2, H2S) may affect the water-ice energy balance sufficiently to contribute to the maintenance of a deep ocean below ice. The effect of the presence of higher density hydrocarbons (ΔH = -72 kJ/mol for ethane and -126 kJ/mol for propane) accentuate the thermal transfer effect but may diffuse too slowly to be a thermal forcing agent in the hydrate system.

  13. Direct Aromaization of Methane

    SciTech Connect

    George Marcelin

    1997-01-15

    The thermal decomposition of methane offers significant potential as a means of producing higher unsaturated and aromatic hydrocarbons when the extent of reaction is limited. Work in the literature previous to this project had shown that cooling the product and reacting gases as the reaction proceeds would significantly reduce or eliminate the formation of solid carbon or heavier (Clo+) materials. This project studied the effect and optimization of the quenching process as a means of increasing the amount of value added products during the pyrolysis of methane. A reactor was designed to rapidly quench the free-radical combustion reaction so as to maximize the yield of aromatics. The use of free-radical generators and catalysts were studied as a means of lowering the reaction temperature. A lower reaction temperature would have the benefits of more rapid quenching as well as a more feasible commercial process due to savings realized in energy and material of construction costs. It was the goal of the project to identify promising routes from methane to higher hydrocarbons based on the pyrolysis of methane.

  14. Methane Clathrate Hydrate Prospecting

    NASA Technical Reports Server (NTRS)

    Duxbury, N.; Romanovsky, V.

    2003-01-01

    A method of prospecting for methane has been devised. The impetus for this method lies in the abundance of CH4 and the growing shortages of other fuels. The method is intended especially to enable identification of subpermafrost locations where significant amounts of methane are trapped in the form of methane gas hydrate (CH4(raised dot)6H2O). It has been estimated by the U.S. Geological Survey that the total CH4 resource in CH4(raised dot) 6H2O exceeds the energy content of all other fossil fuels (oil, coal, and natural gas from non-hydrate sources). Also, CH4(raised dot)6H2O is among the cleanest-burning fuels, and CH4 is the most efficient fuel because the carbon in CH4 is in its most reduced state. The method involves looking for a proxy for methane gas hydrate, by means of the combination of a thermal-analysis submethod and a field submethod that does not involve drilling. The absence of drilling makes this method easier and less expensive, in comparison with prior methods of prospecting for oil and natural gas. The proposed method would include thermoprospecting in combination with one more of the other non-drilling measurement techniques, which could include magneto-telluric sounding and/or a subsurface-electrical-resistivity technique. The method would exploit the fact that the electrical conductivity in the underlying thawed region is greater than that in the overlying permafrost.

  15. Enzymatic oxidation of methane.

    PubMed

    Sirajuddin, Sarah; Rosenzweig, Amy C

    2015-04-14

    Methane monooxygenases (MMOs) are enzymes that catalyze the oxidation of methane to methanol in methanotrophic bacteria. As potential targets for new gas-to-liquid methane bioconversion processes, MMOs have attracted intense attention in recent years. There are two distinct types of MMO, a soluble, cytoplasmic MMO (sMMO) and a membrane-bound, particulate MMO (pMMO). Both oxidize methane at metal centers within a complex, multisubunit scaffold, but the structures, active sites, and chemical mechanisms are completely different. This Current Topic review article focuses on the overall architectures, active site structures, substrate reactivities, protein-protein interactions, and chemical mechanisms of both MMOs, with an emphasis on fundamental aspects. In addition, recent advances, including new details of interactions between the sMMO components, characterization of sMMO intermediates, and progress toward understanding the pMMO metal centers are highlighted. The work summarized here provides a guide for those interested in exploiting MMOs for biotechnological applications. PMID:25806595

  16. Methane emissions from natural wetlands

    SciTech Connect

    Meyer, J.L.; Burke, R.A. Jr.

    1993-09-01

    Analyses of air trapped in polar ice cores in conjunction with recent atmospheric measurements, indicate that the atmospheric methane concentration increased by about 250% during the past two or three hundred years (Rasmussen and Khalil, 1984). Because methane is a potent ``greenhouse`` gas, the increasing concentrations are expected to contribute to global warning (Dickinson and Cicerone, 1986). The timing of the methane increase suggests that it is related to the rapid growth of the human population and associated industrialization and agricultural development. The specific causes of the atmospheric methane concentration increase are not well known, but may relate to either increases in methane sources, decreases in the strengths of the sinks, or both.

  17. Future methane emissions from animals

    SciTech Connect

    Anastasi, C.; Simpson, V.J. )

    1993-04-20

    The authors project future methane emissions from animals to the year 2025. They review the present estimated sources of methane from enteric fermentation in animals. Ruminant animals produce the highest concentrations of methane. Methane is a byproduct of anaerobic breakdown of carbohydrates by microbes in the digestive tract of herbatious animals. In general the methane production depends on the variety of animal, the quality of the feed, and the feeding level. Since cattle, sheep, and buffalo account for roughly 91% of all animal methane emission, they only study these animals in detail. Results suggest a rise in methane production of roughly 1% per year averaged through 2025. Increasing levels are found to originate from developed countries even though the feedstock levels are lower.

  18. The landfill methane balance: Model and practical applications

    SciTech Connect

    Bogner, J.; Spokas, K.

    1995-10-01

    A rational mass-balance framework is described for improved quantification of landfill methane processes at a given site. The methane balance model examines the partitioning of methane generated into methane recovered (via extraction systems), methane emitted, methane oxidized, methane migrated, and methane storage. This model encourages use of field-based data to better quantify rates of methane recovery and emissions.

  19. Methane Leakage from Oil & Gas Operations. What have we learned from recent studies in the U.S.?

    NASA Astrophysics Data System (ADS)

    Zavala-Araiza, Daniel; Hamburg, Steven

    2016-04-01

    Methane, the principal component of natural gas, is a powerful greenhouse gas. Methane losses from the natural gas supply chain erode the climate benefits of fuel switching to natural gas from other fossil fuels, reducing or eliminating them for several decades or longer. Global data on methane emissions from the oil and gas sector is uncertain and as a consequence, measuring and characterizing methane emissions is critical to the design of effective mitigation strategies. In this work, we synthesize lessons learned from dozens of U.S. studies that characterized methane emissions along each stage of the natural gas supply chain. These results are relevant to the design of methane measurement campaigns outside the U.S. A recurring theme in the research conducted in the U.S. is that public emissions inventories (e.g., The U.S. Environmental Protection Agency's National Greenhouse gas Inventory) tend to underestimate emissions for two key reasons: (1) use of non-representative emission factors and (2) inaccurate activity data (incomplete counts of facilities and equipment). Similarly, the accuracy of emission factors and the effectiveness of mitigation strategies are heavily affected by the existence of low-probability, unpredictable high emitters-which have been observed all along the supply chain- and are spatiotemporally variable. We conducted a coordinated campaign to measure methane emissions in a major gas producing region of the U.S. (Barnett Shale region of Texas) using a diversity of approaches. As part of this study we identified methods for effective quantification of regional fossil methane emissions using atmospheric data (through replicate mass balance flights and source apportionment using methane to ethane ratios) as well as how to build an accurate inventory that includes a statistical estimator that more rigorously captures the magnitude and frequency of high emitters. We found agreement between large-scale atmospheric sampling estimates and source

  20. The relationship between methane migration and shale-gas well operations near Dimock, Pennsylvania, USA

    NASA Astrophysics Data System (ADS)

    Hammond, Patrick A.

    2016-03-01

    Migration of stray methane gas near the town of Dimock, Pennsylvania, has been at the center of the debate on the safety of shale gas drilling and hydraulic fracturing in the United States. The presented study relates temporal variations in molecular concentrations and stable isotope compositions of methane and ethane to shale-gas well activity (i.e., vertical/horizontal drilling, hydraulic fracturing and remedial actions). This was accomplished by analyzing data collected, between 2008 and 2012, by state and federal agencies and the gas well operator. In some cases, methane migration started prior to hydraulic fracturing. Methane levels of contaminated water wells sampled were one to several orders of magnitude greater than the concentrations due to natural variation in water wells of the local area. Isotope analyses indicate that all samples had a thermogenic origin at varying maturity levels, but from formations above the hydraulically fractured Marcellus Shale. The results from the initial water well samples were similar to annular gas values, but not those of production gases. This indicates that leakage by casing cement seals most likely caused the impacts, not breaks in the production casing walls. Remediation by squeeze cementing was partially effective in mitigating impacts of gas migration. In several cases where remediation caused a substantial reduction in methane levels, there were also substantial changes in the isotope values, providing evidence of two sources, one natural and the other man-induced. Sampling water wells while venting gas wells appears to be a cost-effective method for determining if methane migration has occurred.

  1. DEVELOPMENT OF A CATALYST/SORBENT FOR METHANE REFORMING

    SciTech Connect

    B.H. Shanks; T.D. Wheelock; Justinus A. Satrio; Timothy Diehl; Brigitte Vollmer

    2004-09-27

    This work has led to the initial development of a very promising material that has the potential to greatly simplify hydrocarbon reforming for the production of hydrogen and to improve the overall efficiency and economics of the process. This material, which was derived from an advanced calcium-based sorbent, was composed of core-in-shell pellets such that each pellet consisted of a CaO core and an alumina-based shell. By incorporating a nickel catalyst in the shell, a combined catalyst and sorbent was prepared to facilitate the reaction of hydrocarbons with steam. It was shown that this material not only catalyzes the reactions of methane and propane with steam, it also absorbs CO{sub 2} simultaneously, and thereby separates the principal reaction products, H{sub 2} and CO{sub 2}. Furthermore, the absorption of CO{sub 2} permits the water gas shift reaction to proceed much further towards completion at temperatures where otherwise it would be limited severely by thermodynamic equilibrium. Therefore, an additional water gas shift reaction step would not be required to achieve low concentrations of CO. In a laboratory test of methane reforming at 600 C and 1 atm it was possible to produce a gaseous product containing 96 mole% H{sub 2} (dry basis) while also achieving a H{sub 2} yield of 95%. Methane reforming under these conditions without CO{sub 2} absorption provided a H{sub 2} concentration of 75 mole% and yield of 82%. Similar results were achieved in a test of propane reforming at 560 C and 1 atm which produced a product containing 96 mole% H{sub 2} while CO{sub 2} was being absorbed but which contained only 69 mole% H{sub 2} while CO{sub 2} was not being absorbed. These results were achieved with an improved catalyst support that was developed by replacing a portion of the {alpha}-alumina in the original shell material with {gamma}-alumina having a much greater surface area. This replacement had the unfortunate consequence of reducing the overall compressive

  2. Detection of CO and Ethane in Comet 21P/Giacobini-Zinner: Evidence for Variable Chemistry in the Outer Solar Nebula

    NASA Technical Reports Server (NTRS)

    Mumma, M. J.; DiSanti, M. A.; DelloRusso, N.; Magee-Sauer, K.; Rettig, T. W.

    1999-01-01

    Ethane and carbon monoxide were detected in a short-period comet of probable Kuiper belt origin. Ethane is substantially less abundant compared with Hyakutake and Hale-Bopp, two comets from the giant-planets region of the solar nebula, suggesting a heliocentric gradient in ethane in pre-cometary ices. It is argued that processing by X-rays from the young sun may be responsible.

  3. Detection of CO and Ethane in Comet 21P/Giacobini-Zinner: Evidence for Variable Chemistry in the Outer Solar Nebula.

    PubMed

    Mumma; DiSanti; Dello Russo N; Magee-Sauer; Rettig

    2000-03-10

    Ethane and carbon monoxide were detected in a short-period comet of probable Kuiper Belt origin. Ethane is substantially less abundant compared with Hyakutake and Hale-Bopp, two comets from the giant-planet region of the solar nebula, suggesting a heliocentric gradient in ethane in precometary ices. It is argued that processing by X-rays from the young Sun may be responsible. PMID:10688776

  4. Assessment of the risk of transporting propane by truck and train

    SciTech Connect

    Geffen, C.A.

    1980-03-01

    The risk of shipping propane is discussed and the risk assessment methodology is summarized. The risk assessment model has been constructed as a series of separate analysis steps to allow the risk to be readily reevaluated as additional data becomes available or as postulated system characteristics change. The transportation system and accident environment, the responses of the shipping system to forces in transportation accidents, and release sequences are evaluated to determine both the likelihood and possible consequences of a release. Supportive data and analyses are given in the appendices. The risk assessment results are related to the year 1985 to allow a comparison with other reports in this series. Based on the information presented, accidents involving tank truck shipments of propane will be expected to occur at a rate of 320 every year; accidents involving bobtails would be expected at a rate of 250 every year. Train accidents involving propane shipments would be expected to occur at a rate of about 60 every year. A release of any amount of material from propane trucks, under both normal transportation and transport accident conditions, is to be expected at a rate of about 110 per year. Releases from propane rail tank cars would occur about 40 times a year. However, only those releases that occur during a transportation accident or involve a major tank defect will include sufficient propane to present the potential for danger to the public. These significant releases can be expected at the lower rate of about fourteen events per year for truck transport and about one event every two years for rail tank car transport. The estimated number of public fatalities resulting from these significant releases in 1985 is fifteen. About eleven fatalities per year result from tank truck operation, and approximately half a death per year stems from the movement of propane in rail tank cars.

  5. Dehydrogenation of propane over chromia-pillared zirconium phosphate catalysts

    SciTech Connect

    Perez-Reina, F.J.; Rodriguez-Castellon, E.; Jimenez-Lopez, A.

    1999-11-23

    Two series of porous chromia-pillared {alpha}-zirconium phosphate materials, prepared using two different methods of colloidization of the initial phase and with variable chromium contents (CrZrP-Xa and CrZrP-Xb) have been tested in the oxidative and nonoxidative dehydrogenation of propane in a flow reactor at atmospheric pressure. All catalysts are highly selective to propene under nonoxidative conditions at 823 K. In both series of catalysts, the initial activity increases with the chromium content, but generally CrZrP-Xb catalysts are more active than those of series CrZrP-Xa, which is in good agreement with their higher chromium contents and greater dispersions. In all cases, deactivation was detected due to coke formed from undesired reactions. When the reactions were carried out under oxidative conditions at 673 K, the activities were enhanced and the observed deactivation was minimum. The activities found vary between 0.47 and 1.31 {micro}mol of propene g{sup {minus}1} s{sup {minus}1} and are maintained after 200 min of reaction. These activity values were also related to the chromium content, being slightly higher for CrZrP-Xb materials. A parallel study to evaluate the influence of acidity in the obtained results has been carried out. The activities found of these catalysts seem to be related to the presence of Cr(III) centers with vacancies in their coordination sphere. These vacancies, in nonoxidative conditions, can activate the reactive molecules originating propene and hydrogen. On the other hand, in an oxidative atmosphere, Cr(III) species can activate oxygen molecules, through an electronic transference process, yielding propene and water.

  6. Counterflow diffusion flames of hydrogen, and hydrogen plus methane, ethylene, propane, and silane vs. air - Strain rates at extinction

    NASA Technical Reports Server (NTRS)

    Pellett, G. L.; Northam, G. Burton; Wilson, L. G.

    1991-01-01

    Five coaxial tubular opposed jet burners (OJBs) with tube diameter D(T) of 1.8-10 mm and 5 mm conical nozzles were used to form dish-shaped counterflow diffusion flames centered by opposing laminar jets of nitrogen and hydrocarbon-diluted H2 versus air in an argon-purged chamber at 1 atm. Area-averaged air jet velocities at blowoff of the central flame, U(air), characterized extinction of the airside flame as functions of input H2 concentration on the fuelside. A master plot of extensive U(air) data at blowoff versus D(T) shows that U(air) varies linearly with D(T). This and other data sets are used to find that nozzle OJB results for U(air)/diameter average 4.24 + or - 0.28 times larger than tubular OJB results for the same fuel compositions. Critical radial velocity gradients consistent with one-dimensional stagnation point boundary theory and with plug flow inputs are estimated. The results compare favorably with published numerical results based only on potential flow.

  7. 10-Methyl-9-[2-(propan-2-yl)phenoxy­carbonyl]­acridinium trifluoro­methane­sulfonate

    PubMed Central

    Trzybiński, Damian; Krzymiński, Karol; Błażejowski, Jerzy

    2010-01-01

    In the crystal of the title compound, C24H22NO2 +·CF3SO3 −, adjacent cations and anions are connected through C—H⋯O, C—H⋯F and S–O⋯π inter­actions, while neighboring cations via π–π inter­actions [centroid–centroid distance = 3.962 (2) Å]. The acridine and benzene ring systems are oriented at a dihedral angle of 14.6 (1)°. The carboxyl group is twisted at an angle of 87.6 (1)° relative to the acridine skeleton. The mean planes of adjacent acridine units are parallel or inclined at an angle of 13.4 (1)° in the crystal structure. PMID:21588973

  8. Methane cycling. Nonequilibrium clumped isotope signals in microbial methane.

    PubMed

    Wang, David T; Gruen, Danielle S; Lollar, Barbara Sherwood; Hinrichs, Kai-Uwe; Stewart, Lucy C; Holden, James F; Hristov, Alexander N; Pohlman, John W; Morrill, Penny L; Könneke, Martin; Delwiche, Kyle B; Reeves, Eoghan P; Sutcliffe, Chelsea N; Ritter, Daniel J; Seewald, Jeffrey S; McIntosh, Jennifer C; Hemond, Harold F; Kubo, Michael D; Cardace, Dawn; Hoehler, Tori M; Ono, Shuhei

    2015-04-24

    Methane is a key component in the global carbon cycle, with a wide range of anthropogenic and natural sources. Although isotopic compositions of methane have traditionally aided source identification, the abundance of its multiply substituted "clumped" isotopologues (for example, (13)CH3D) has recently emerged as a proxy for determining methane-formation temperatures. However, the effect of biological processes on methane's clumped isotopologue signature is poorly constrained. We show that methanogenesis proceeding at relatively high rates in cattle, surface environments, and laboratory cultures exerts kinetic control on (13)CH3D abundances and results in anomalously elevated formation-temperature estimates. We demonstrate quantitatively that H2 availability accounts for this effect. Clumped methane thermometry can therefore provide constraints on the generation of methane in diverse settings, including continental serpentinization sites and ancient, deep groundwaters. PMID:25745067

  9. Wintertime Methane and Non-Methane Hydrocarbon Measurements Utah's Uintah Basin

    NASA Astrophysics Data System (ADS)

    Martin, R. S.

    2012-12-01

    As a part of the winter 2011/2012 Uintah Basin Winter Ozone Study, ambient methane (CH4) and total non-methane hydrocarbons (TNMHC) were measured at a population center (Roosevelt) and within the oil/gas field (Horse Pool). At Horse Pool, near real-time CH4/TNMHC were monitored using a GC-FID analyzer. Samples were collected for 30 seconds once every five minutes. The TNMHC concentrations were reported in ppb-C3, or parts per billion in C3 (propane) equivalents. At Roosevelt, discrete volatile organic carbon (VOC) samples were collected for two weeks beginning on Feb. 14, 2012 using evacuated stainless steel Summa canisters. The samples were collected over four 1-hr time periods spaced throughout the day. After collection, the canisters were shipped to a commercial laboratory for GC-MS quantification. Methane samples were obtained at Roosevelt by whole vial collection and subsequently analyzed via GC-FID. Nominally, the CH4 vials were collected at the start and end of each canister collection period, as well as intermittently throughout the daily periods. Furthermore, CH4 grab samples were collected at several other locations throughout the Basin when possible. For the full wintertime study period (Jan. 19 - Mar. 15, 2012), the CH4 and TNMHC at Horse Pool averaged 3.47±1.8 ppm and 243±253 ppb-C3 (± 1σ), respectively. A very strong diurnal behavior was seen for both classes of compounds, with CH4 maximums approaching 30 ppm in the early morning hours. During the comparative February time period, CH4 concentrations at Horse Pool averaged 3.25±0.07 ppm (± 95% CI), while CH4 at Roosevelt averaged 2.52±0.08 ppm. No strong diurnal behavior was observed at Roosevelt and the maximum CH4 levels only reached 4.08 ppm. Grab samples from the other locations found similar or slightly lower CH4 concentrations, with the exception of Ouray (3.91±1.27 ppm) which was also located in the production/exploration area, but was among the lowest elevation of the sampling sites. It

  10. Comparison of facility-level methane emission rates from natural gas production well pads in the Marcellus, Denver-Julesburg, and Uintah Basins

    NASA Astrophysics Data System (ADS)

    Omara, M.; Li, X.; Sullivan, M.; Subramanian, R.; Robinson, A. L.; Presto, A. A.

    2015-12-01

    The boom in shale natural gas (NG) production, brought about by advances in horizontal drilling and hydraulic fracturing, has yielded both economic benefits and concerns about environmental and climate impacts. In particular, leakages of methane from the NG supply chain could substantially increase the carbon footprint of NG, diminishing its potential role as a transition fuel between carbon intensive fossil fuels and renewable energy systems. Recent research has demonstrated significant variability in measured methane emission rates from NG production facilities within a given shale gas basin. This variability often reflect facility-specific differences in NG production capacity, facility age, utilization of emissions capture and control, and/or the level of facility inspection and maintenance. Across NG production basins, these differences in facility-level methane emission rates are likely amplified, especially if significant variability in NG composition and state emissions regulations are present. In this study, we measured methane emission rates from the NG production sector in the Marcellus Shale Basin (Pennsylvania and West Virginia), currently the largest NG production basin in the U.S., and contrast these results with those of the Denver-Julesburg (Colorado) and Uintah (Utah) shale basins. Facility-level methane emission rates were measured at 106 NG production facilities using the dual tracer flux (nitrous oxide and acetylene), Gaussian dispersion simulations, and the OTM 33A techniques. The distribution of facility-level average methane emission rate for each NG basin will be discussed, with emphasis on how variability in NG composition (i.e., ethane-to-methane ratios) and state emissions regulations impact measured methane leak rates. While the focus of this presentation will be on the comparison of methane leak rates among NG basins, the use of three complimentary top-down methane measurement techniques provides a unique opportunity to explore the

  11. Project identification for methane reduction options

    SciTech Connect

    Kerr, T.

    1996-12-31

    This paper discusses efforts directed at reduction in emission of methane to the atmosphere. Methane is a potent greenhouse gas, which on a 20 year timeframe may present a similar problem to carbon dioxide. In addition, methane causes additional problems in the form of smog and its longer atmospheric lifetime. The author discusses strategies for reducing methane emission from several major sources. This includes landfill methane recovery, coalbed methane recovery, livestock methane reduction - in the form of ruminant methane reduction and manure methane recovery. The author presents examples of projects which have implemented these ideas, the economics of the projects, and additional gains which come from the projects.

  12. Methane Clouds on Titan

    NASA Astrophysics Data System (ADS)

    Griffith, Caitlin A.

    Following the Voyager encounter with Titan in 1981 Saturn's largest moon was hypothesized sport a liquid cycle similar that on Earth with clouds rain and seas. On Titan methane is the condensible playing the role that water plays on Earth. Although the presence of seas is difficult to establish from ground methane clouds have been detected on Titan. Ground-based observations reveal that Titan's clouds differ remarkedly from their terrestrial counterparts. Titan's clouds are sparse reside primarily at particular altitude and concentrate presently in the south pole. That Titan's clouds are exotic is not surprising. Titan receives ~100 times less sunlight than Earth to drive weather. In addition Titan's radiative time constant is 180 years large compared to the 3 month terrestrial value. With little power and sluggish conditions it is not clear how clouds form on Titan. This talk will compare Titan to Earth to explore the nature of clouds under Titan's foreign conditions.

  13. Heteroepitaxially grown zeolitic imidazolate framework membranes with unprecedented propylene/propane separation performances.

    PubMed

    Kwon, Hyuk Taek; Jeong, Hae-Kwon; Lee, Albert S; An, He Seong; Lee, Jong Suk

    2015-09-30

    Propylene/propane separation is one of the most challenging separations, currently achieved by energy-intensive cryogenic distillation. Despite the great potential for energy-efficient membrane-based separations, no commercial membranes are currently available due to the limitations of current polymeric materials. Zeolitic imidazolate framework, ZIF-8, with the effective aperture size of ∼4.0 Å, has been shown to be very promising for propylene/propane separation. Despite the extensive research on ZIF-8 membranes, only a few reported ZIF-8 membranes have displayed good propylene/propane separation performances presumably due to the challenges of controlling the microstructures of polycrystalline membranes. Here we report the first well-intergrown membranes of ZIF-67 (Co-substituted ZIF-8) by heteroepitaxially growing ZIF-67 on ZIF-8 seed layers. The ZIF-67 membranes exhibited impressively high propylene/propane separation capabilities. Furthermore, when a tertiary growth of ZIF-8 layers was applied to heteroepitaxially grown ZIF-67 membranes, the membranes exhibited unprecedentedly high propylene/propane separation factors of ∼200 possibly due to enhanced grain boundary structure. PMID:26364888

  14. No. 2 heating oil/propane program 1994--1995. Final report

    SciTech Connect

    McBrien, J.

    1995-05-01

    During the 1994--95 heating season, the Massachusetts Division of Energy Resources (DOER) participated in a joint data collection program between several state energy offices and the federal Department of Energy`s (DOE) Energy Information Administration (EIA). The purpose of the program was to collect and monitor retail and wholesale heating oil and propane prices and inventories from October 1994 through March 1995. This program augmented the existing Massachusetts data collection system and served several important functions. The information helped the federal and state governments respond to consumer, congressional and media inquiries regarding No. 2 oil and propane. The information also provided policy decision-makers with timely, accurate and consistent data to monitor current heating oil and propane markets and develop appropriate state responses when necessary. In addition, the communication network between states and the DOE was strengthened through this program. This final report begins with an overview of the unique events that had an impact on the petroleum markets prior to and during the reporting period. Next, the report summarizes the results from residential heating oil and propane price surveys conducted by DOER over the 1994--95 heating season. The report also incorporates the wholesale heating oil and propane prices and inventories collected by EIA and distributed to the states. Finally, the report outlines DOER`s use of the data.

  15. State Heating Oil & Propane Program. Final report 1997/98 heating season

    SciTech Connect

    Hunton, G.

    1998-06-01

    The following is a summary report of the New Hampshire Governor`s Office of Energy and Community Services (ECS) participation in the State Heating Oil and Propane Program (SHOPP) for the 1997/98 heating season. SHOPP is a cooperative effort, linking energy offices in East Coast and Midwest states, with the Department of Energy (DOE), Energy Information Administration (EIA) for the purpose of collecting retail price data for heating oil and propane. The program is funded by the participating state with a matching grant from DOE. SHOPP was initiated in response to congressional inquires into supply difficulties and price spikes of heating oil and propane associated with the winter of 1989/90. This is important to New Hampshire because heating oil controls over 55% of the residential heating market statewide. Propane controls 10% of the heating market statewide and is widely used for water heating and cooking in areas of the state where natural gas is not available. Lower installation cost, convenience, lower operating costs compared to electricity, and its perception as a clean heating fuel have all worked to increase the popularity of propane in New Hampshire and should continue to do so in the future. Any disruption in supply of these heating fuels to New Hampshire could cause prices to skyrocket and leave many residents in the cold.

  16. Coal Bed Methane Primer

    SciTech Connect

    Dan Arthur; Bruce Langhus; Jon Seekins

    2005-05-25

    During the second half of the 1990's Coal Bed Methane (CBM) production increased dramatically nationwide to represent a significant new source of income and natural gas for many independent and established producers. Matching these soaring production rates during this period was a heightened public awareness of environmental concerns. These concerns left unexplained and under-addressed have created a significant growth in public involvement generating literally thousands of unfocused project comments for various regional NEPA efforts resulting in the delayed development of public and fee lands. The accelerating interest in CBM development coupled to the growth in public involvement has prompted the conceptualization of this project for the development of a CBM Primer. The Primer is designed to serve as a summary document, which introduces and encapsulates information pertinent to the development of Coal Bed Methane (CBM), including focused discussions of coal deposits, methane as a natural formed gas, split mineral estates, development techniques, operational issues, producing methods, applicable regulatory frameworks, land and resource management, mitigation measures, preparation of project plans, data availability, Indian Trust issues and relevant environmental technologies. An important aspect of gaining access to federal, state, tribal, or fee lands involves education of a broad array of stakeholders, including land and mineral owners, regulators, conservationists, tribal governments, special interest groups, and numerous others that could be impacted by the development of coal bed methane. Perhaps the most crucial aspect of successfully developing CBM resources is stakeholder education. Currently, an inconsistent picture of CBM exists. There is a significant lack of understanding on the parts of nearly all stakeholders, including industry, government, special interest groups, and land owners. It is envisioned the Primer would being used by a variety of

  17. Decomposition of chlorinated ethylenes and ethanes in an electron beam generated plasma reactor

    SciTech Connect

    Vitale, S.A.

    1996-02-01

    An electron beam generated plasma reactor (EBGPR) is used to determine the plasma chemistry kinetics, energetics and decomposition pathways of six chlorinated ethylenes and ethanes: 1,1,1-trichloroethane, 1,1-dichloroethane, ethyl chloride, trichloroethylene, 1,1-dichloroethylene, and vinyl chloride. A traditional chemical kinetic and chemical engineering analysis of the data from the EBGPR is performed, and the following hypothesis was verified: The specific energy required for chlorinated VOC decomposition in the electron beam generated plasma reactor is determined by the electron attachment coefficient of the VOC and the susceptibility of the molecule to radical attack. The technology was demonstrated at the Hanford Reservation to remove VOCs from soils.

  18. Formation of gas hydrate during crystallization of ethane-saturated amorphous ice

    NASA Astrophysics Data System (ADS)

    Faizullin, M. Z.; Vinogradov, A. V.; Skokov, V. N.; Koverda, V. P.

    2014-10-01

    Layers of ethane-saturated amorphous ice were prepared by depositing molecular beams of water and gas on a substrate cooled with liquid nitrogen. The heating of the layers was accompanied by vitrification (softening) followed by spontaneous crystallization. Crystallization of condensates under the conditions of deep metastability proceeded with gas hydrate formation. The vitrification and crystallization temperatures of the condensates were determined from the changes in their dielectric properties on heating. The thermal effects of transformations were recorded by differential thermal analysis. The crystallization of the amorphous water layers was studied by electron diffraction. Formation of a metastable packing with elements of a cubic diamond-like structure was noted.

  19. Estimates of methane emissions from India using CH4-CO-C2H6 relationships from CARIBIC observations in monsoon convective outflow

    NASA Astrophysics Data System (ADS)

    Baker, A. K.; Rauthe-Schöch, A.; Schuck, T. J.; van Velthoven, P. F.; Slemr, F.; Brenninkmeijer, C. A.

    2010-12-01

    A large fraction of methane sources are anthropogenic, and include fossil fuel use, biomass/biofuel burning, agriculture and waste treatment. Recently, much attention regarding emissions of greenhouse gases has focused on large, developing nations, as their emissions are expected to rise rapidly over the coming decades. As the second most populous country in the world, and one of the fastest growing economies, India has been of particular interest. Arguably the most important feature of meteorology in India is the Asian summer monsoon. During the monsoon period there exists persistent deep convection over Southern Asia, and the composition of convected air masses is strongly influenced by emissions from India. This ultimately results in a well-mixed air parcel containing air from India being transported to the upper troposphere. Over the course of the 2008 monsoon period the CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) passenger aircraft conducted monthly measurement flights which probed this outflow. Data collected during these flights provides a unique opportunity to examine sources of atmospheric species in India. Here we use measurements of methane (CH4), carbon monoxide (CO) and ethane (C2H6) from whole air samples collected during CARIBIC flights to estimate emissions of methane and to quantify those emissions related to flooding during the monsoon. Methane data from the monsoon period show enhancements inside the monsoon plume, which increase as the monsoon progresses. Using emission data for CO and ΔCH4/ΔCO derived from CARIBIC measurements, we estimate total methane emissions to be ~40 Tg yr-1. Relationships of methane to ethane, which shares the bulk of its sources with methane but lacks a biological component, are further used to estimate the fraction of “extra” emissions from biological activity related to increased monsoon rains. This additional methane is a considerable fraction of

  20. No. 2 heating oil/propane program. Final report, 1990/91

    SciTech Connect

    McBrien, J.

    1991-06-01

    During the 1990/91 heating season, the Massachusetts Division of Energy Resources (DOER) participated in a joint data collection program between several state energy offices and the federal Department of Energy`s (DOE) Energy Information Administration (EIA). The purpose of the program was to collect and monitor retail and wholesale heating oil and propane prices and inventories from October 1990 through March 1991. This final report begins with an overview of the unique events which had an impact on the reporting period. Next, the report summarizes the results from the residential heating oil and propane price surveys conducted by DOER over the 1990/91 heating season. The report also incorporates the wholesale heating oil and propane prices and inventories collected by the EIA and distributed to the states.