Temperature and abundances in the Jovian auroral stratosphere. 1: Ethane as a probe of the millibar region

NASA Technical Reports Server (NTRS)

Livengood, Timothy A.; Kostiuk, Theodor; Espenak, Fred

1993-01-01

We report infrared heterodyne spectroscopy (lambda/delta lambda is approximately 10(exp 6)) of C2H6 emission at 11.9 microns from the northern Jovian auroral region, in observations conducted over December 2-7, 1989. Accurately measured line shapes provide information on C2H6 abundance as well as temperature and permit retrieval of the source pressure region. Enhanced emission was observed in the longitude range approximately 150-180 deg at approximately 60 deg north latitude, approximately corresponding to the CH4 7.8 micron hot spot and the region of brightest UV aurora. Significant brightness variations were observed in the hot spot emissions on a time scale of approximately 20 hours. Analysis of the brightest hot spot spectra indicates C2H6 mole fractions of approximately (6.3-6.8) x 10(exp -6) at temperatures of approximately 182-184 K at 1 mbar, compared to mole fractions of (3.8 +/- 1.4) x 10(exp -6) averaged over spectra outside the hot spot at a temperature of approximately 172 K at the same pressure. Fixing the mole fraction to the lower limit retrieved in the quiescent (non-hot spot) region allows the temperature at 1 mbar to be as high as approximately 200 K within the hot spot. These results provide upper limits to the temperature increase near the source of the C2H6 thermal infrared emission. Combined with results from similar measurements of ethylene emission probing the approximately 10-microbar region (Kostiuk et al., this issue), altitude information on the thermal structure of the Jovian auroral stratosphere can be obtained for the first time.

Non-monotonic dynamics of water in its binary mixture with 1,2-dimethoxy ethane: A combined THz spectroscopic and MD simulation study.

PubMed

Das Mahanta, Debasish; Patra, Animesh; Samanta, Nirnay; Luong, Trung Quan; Mukherjee, Biswaroop; Mitra, Rajib Kumar

2016-10-28

A combined experimental (mid- and far-infrared FTIR spectroscopy and THz time domain spectroscopy (TTDS) (0.3-1.6 THz)) and molecular dynamics (MD) simulation technique are used to understand the evolution of the structure and dynamics of water in its binary mixture with 1,2-dimethoxy ethane (DME) over the entire concentration range. The cooperative hydrogen bond dynamics of water obtained from Debye relaxation of TTDS data reveals a non-monotonous behaviour in which the collective dynamics is much faster in the low X w region (where X w is the mole fraction of water in the mixture), whereas in X w ∼ 0.8 region, the dynamics gets slower than that of pure water. The concentration dependence of the reorientation times of water, calculated from the MD simulations, also captures this non-monotonous character. The MD simulation trajectories reveal presence of large amplitude angular jumps, which dominate the orientational relaxation. We rationalize the non-monotonous, concentration dependent orientational dynamics by identifying two different physical mechanisms which operate at high and low water concentration regimes.

Rapid and Simple Capillary-Rise/Vanishing Interfacial Tension Method To Determine Crude Oil Minimum Miscibility Pressure: Pure and Mixed CO 2 , Methane, and Ethane

DOE PAGES

Hawthorne, Steven B.; Miller, David J.; Jin, Lu; ...

2016-07-20

We report here a simplification of the capillary-rise/vanishing interfacial tension (IFT) method to measure minimum miscibility pressure (MMP) based on only requiring knowledge of when the interfacial tension approaches zero. Simply measuring the height of the crude oil in a capillary at several pressures from ambient to near the MMP pressure and extrapolating the oil height versus pressure plot to zero oil height yields the MMP without the need of the additional instrumentation and labor required to perform actual IFT measurements. A total of 2−4 MMP values can be determined per day with only one experimental apparatus, and the methodmore » greatly reduces the initial cost and complexity of the required instrumentation. The use of three capillaries having different inner diameters allows for triplicate determinations of MMP from each experiment. Because the actual MMP pressure need not be reached during the experiment, MMP values that exceed the pressure ratings of the equipment can be reasonably estimated (e.g., MMPs using pure nitrogen). The method was used to determine the MMP pressure for crude oil samples from a conventional Muddy Formation reservoir in the Powder River Basin [American Petroleum Institute (API) gravity of 35.8°] and an unconventional Bakken Formation reservoir in the Williston Basin (API gravity of 38.7°). The method is reproducible [typically <4% relative standard deviation (RSD)], and the method gave good agreement for a “live” Bakken oil with the results from a slim tube test of a commercial laboratory. Approximately 80 MMP values were measured using pure CO2, methane, and ethane as well as 0−100% mole ratios of methane/CO2 and methane/ethane. For both oil samples, ethane MMPs were ca. one-half those with CO2, while methane MMPs were ca. double or triple those with CO2. MMPs with mixed methane/CO2 showed a linear increase with mole percent methane for both crude oils, while both oils showed an exponential increase in MMP with mole percent methane in ethane, with a little increase in MMP until ca. 20 mol % methane in ethane.« less

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 ethane emissions in the region. Flight track colored by methane (CH4, left) and ethane (C2H6, right) mole fraction. A three-hour back trajectory (red line) constructed from lidar wind measurements passes over the Barnett natural gas well locations (gray points) prior to reaching the location on the flight path indicated by the red star.

Excited state intramolecular charge transfer reaction in binary mixtures of water and tertiary butanol (TBA): alcohol mole fraction dependence.

PubMed

Pradhan, Tuhin; Ghoshal, Piue; Biswas, Ranjit

2008-02-07

The excited state intramolecular charge transfer reaction of 4-(1-azetidinyl)benzonitrile (P4C) has been studied in water-tertiary butanol (TBA) mixtures at different alcohol mole fractions by using steady state and time-resolved fluorescence spectroscopy. The ratio between the areas under the locally excited (LE) and charge transferred (CT) emission bands is found to exhibit a sharp rise at alcohol mole fraction approximately 0.04, a value at which several thermodynamic properties of this mixture is known to show anomalous change due to the enhancement of H-bonding network. The radiative rate associated with the LE emission also shows a maximum at this TBA mole fraction. Although the structural transition from the water-like tetrahedral network to the alcohol-like chain is reflected in the red shift of the absorption spectrum up to TBA mole fraction approximately 0.10, the emission bands (both LE and CT) show the typical nonideal alcohol mole fraction dependence at all TBA mole fractions. Quantum yield, CT radiative rate as well as transition moments also exhibit a nonideal alcohol mole fraction dependence. The time-resolved emission decay of P4C has been found to be biexponential at all TBA mole fractions, regardless of emission collection around either the LE or the CT bands. The time constant associated with the slow component (tau(slow)) shows a minimum at TBA mole fraction approximately 0.04, whereas such a minimum for the fast time constant, tau(fast) (representing the rate of LE --> CT conversion reaction) is not observed. The nonobservation of the minimum in tau(fast) might be due to the limited time resolution employed in our experiments.

Jovian Northern Ethane Aurora and the Solar Cycle

NASA Technical Reports Server (NTRS)

Kostiuk,T.; Livengood, T.; Fast, K.; Buhl, D.; Goldstein, J.; Hewagama, T.

1999-01-01

Thermal infrared auroral spectra from Jupiter's North polar region have been collected from 1979 to 1998 in a continuing study of long-term variability in the northern thermal IR aurora, using C2H6 emission lines near 12 microns as a probe. Data from Voyager I and 2 IRIS measurements and ground based spectral measurements were analyzed using the same model atmosphere to provide a consistent relative comparison. A retrieved equivalent mole fraction was used to compare the observed integrated emission. Short term (days), medium term (months) and long term (years) variability in the ethane emission was observed. The variability Of C2H6 emission intensities was compared to Jupiter's seasonal cycle and the solar activity cycle. A positive correlation appears to exist, with significantly greater emission and short term variability during solar maxima. Observations on 60 N latitude during increased solar activity in 1979, 1989, and most recently in 1998 show up to 5 times brighter integrated line emission of C2H6 near the north polar "hot spot" (150-210 latitude) than from the north quiescent region. Significantly lower enhancement was observed during periods of lower solar activity in 1982, 1983, 1993, and 1995. Possible sources and mechanisms for the enhancement and variability will be discussed.

Reinterpreting the Anomalous Mole Fraction Effect: The Ryanodine Receptor Case Study

PubMed Central

Gillespie, Dirk; Giri, Janhavi; Fill, Michael

2009-01-01

Abstract The origin of the anomalous mole fraction effect (AMFE) in calcium channels is explored with a model of the ryanodine receptor. This model predicted and experiments verified new AMFEs in the cardiac isoform. In mole fraction experiments, conductance is measured in mixtures of ion species X and Y as their relative amounts (mole fractions) vary. This curve can have a minimum (an AMFE). The traditional interpretation of the AMFE is that multiple interacting ions move through the pore in a single file. Mole fraction curves without minima (no AMFEs) are generally interpreted as X displacing Y from the pore in a proportion larger than its bath mole fraction (preferential selectivity). We find that the AMFE is also caused by preferential selectivity of X over Y, if X and Y have similar conductances. This is a prediction applicable to any channel and provides a fundamentally different explanation of the AMFE that does not require single filing or multiple occupancy: preferential selectivity causes the resistances to current flow in the baths, channel vestibules, and selectivity filter to change differently with mole fraction, and produce the AMFE. PMID:19843453

Results from the Gas Chromatograph Mass Spectrometer (GCMS) Experiment on the Cassini-Huygens Probe

NASA Technical Reports Server (NTRS)

Niemann, Hasso B.

2006-01-01

The GCMS was part of the instrument complement on the Cassini-Huygens Probe to measure in situ the chemical composition of the atmosphere during the probe descent and coupled with the Aerosol Collector Pyrolyser (ACP) experiment by serving as detector for the pyrolization products to determine the composition of the aerosol particles. The GCMS employed a quadrupole mass filter with a secondary electron multiplier detection system and a gas sampling system providing continuous direct atmospheric composition measurements and batch sampling through three gas chromatographic (GC) columns, a chemical scrubber and a hydrocarbon enrichment cell. The GCMS gas inlet was heated to prevent condensation, and to evaporate volatiles from the surface after impact. The GCMS collected data from an altitude of 146 km to ground impact. The Probe and the GCMS survived impact and collected data for 1 hour and 9 minutes on the surface. Mass spectra were collected during descent and on the ground over a range of m/z from 2 to 141. The major constituents of the lower atmosphere were confirmed to be NP and CH4. The methane mole fraction was uniform in the stratosphere. It increased below the tropopause, at about 32 km altitude, monotonically toward the surface, reaching a plateau at about 8 km at a level near saturation. After surface impact a steep increase of the methane signal was observed, suggesting evaporation of surface condensed methane due to heating by the GCMS sample inlet heater. The measured mole fraction of Ar-40 is 4.3 x 10(exp-5) and of Ar-36 is 2.8 x 10(exp -7). The other primordial noble gases were below mole fraction. The isotope ratios of C-12/C-13 determined from methane measurements are 82.3 and of N-14/N-15 determined from molecular nitrogen are 183. The D/H isotope ratio determined from the H2 and HD measurements is 2.3 x l0(exp -4). Carbon dioxide, ethane, acetylene and cyanogen were detected evaporating from the surface in addition to methane.

Results from the Gas Chromatograph Mass Spectrometer (GCMS) Experiment on the Cassini-Huygens Probe

NASA Technical Reports Server (NTRS)

Niemann, Hasso; Atreya, S.; Demick-Monelara, J.; Haberman, J.; Harpold, D.; Kasprzak, W.; Owen, T.; Raaen, E.; Way, S.

2006-01-01

The Gas Chromatograph Mass Spectrometer was one of six instruments on the Cassini-Huygens Probe mission to Titan. The GCMS measured in situ the chemical composition of the atmosphere during the probe descent and served as the detector for the pyrolization products for the Aerosol Collector Pyrolyser (ACP) experiment to determine the composition of the aerosol particles. The GCMS collected data from an altitude of 146 km to ground impact. The Probe and the GCMS survived impact and collected data for 1 hour and 9 minutes on the surface. Mass spectra were collected during descent and on the ground over a range of mlz from 2 to 141. The major constituents of the lower atmosphere were confirmed to be N2 and CH4. The methane mole fraction was uniform in the stratosphere. It increased below the tropopause, at about 32 km altitude, monotonically toward the surface, reaching a plateau at about 8 km at a level near saturation. After surface impact a steep increase of the methane signal was observed, suggesting evaporation of surface condensed methane due to heating by the GCMS sample inlet heater. The measured mole fraction of Ar-40 is 4.3x10(exp -5) and of Ar-36 is 2.8x10(exp -7). The other primordial noble gases were below 10(exp -8) mole fraction. The isotope ratios of C-12/C-13 determined from methane measurements are 82.3 and of N-14/N-15 determined from molecular nitrogen are 183. The D/H isotope ratio determined from the H2 and HD measurements is 2.3x10(exp -4). Carbon dioxide, ethane, acetylene and cyanogen were detected evaporating from the surface in addition to methane. The GCMS employed a quadrupole mass filter with a secondary electron multiplier detection system and a gas sampling system providing continuous direct atmospheric composition measurements and batch sampling through three gas chromatographic (GC) columns, a chemical scrubber and a hydrocarbon enrichment cell. The GCMS gas inlet was heated to prevent condensation, and to evaporate volatiles from the surface after impact.

Chemical structure influence on NAPL mixture nonideality evolution, rate-limited dissolution, and contaminant mass flux.

PubMed

Padgett, Mark C; Tick, Geoffrey R; Carroll, Kenneth C; Burke, William R

2017-03-01

The influence of chemical structure on NAPL mixture nonideality evolution, rate-limited dissolution, and contaminant mass flux was examined. The variability of measured and UNIFAC modeled NAPL activity coefficients as a function of mole fraction was compared for two NAPL mixtures containing structurally-different contaminants of concern including toluene (TOL) or trichloroethene (TCE) within a hexadecane (HEXDEC) matrix. The results showed that dissolution from the NAPL mixtures transitioned from ideality for mole fractions >0.05 to nonideality as mole fractions decreased. In particular, the TCE generally exhibited more ideal dissolution behavior except at lower mole fractions, and may indicate greater structural/polarity similarity between the two compounds. Raoult's Law and UNIFAC generally under-predicted the batch experiment results for TOL:HEXDEC mixtures especially for mole fractions ≤0.05. The dissolution rate coefficients were similar for both TOL and TCE over all mole fractions tested. Mass flux reduction (MFR) analysis showed that more efficient removal behavior occurred for TOL and TCE with larger mole fractions compared to the lower initial mole fraction mixtures (i.e. <0.2). However, compared to TOL, TCE generally exhibited more efficient removal behavior over all mole fractions tested and may have been the result of structural and molecular property differences between the compounds. Activity coefficient variability as a function of mole fraction was quantified through regression analysis and incorporated into dissolution modeling analyses for the dynamic flushing experiments. TOL elution concentrations were modeled (predicted) reasonable well using ideal and equilibrium assumptions, but the TCE elution concentrations could not be predicted using the ideal model. Rather, the dissolution modeling demonstrated that TCE elution was better described by the nonideal model whereby NAPL-phase activity coefficient varied as a function of COC mole fraction. For dynamic column flushing experiments, dissolution rate kinetics can vary significantly with changes in NAPL volume and surface area. However, under conditions whereby NAPL volume and area are not significantly altered during dissolution, mixture nonideality effects may have a greater relative control on dissolution (elution) and MFR behavior compared to kinetic rate limitations. Copyright © 2017 Elsevier B.V. All rights reserved.

Chemical structure influence on NAPL mixture nonideality evolution, rate-limited dissolution, and contaminant mass flux

NASA Astrophysics Data System (ADS)

Padgett, Mark C.; Tick, Geoffrey R.; Carroll, Kenneth C.; Burke, William R.

2017-03-01

The influence of chemical structure on NAPL mixture nonideality evolution, rate-limited dissolution, and contaminant mass flux was examined. The variability of measured and UNIFAC modeled NAPL activity coefficients as a function of mole fraction was compared for two NAPL mixtures containing structurally-different contaminants of concern including toluene (TOL) or trichloroethene (TCE) within a hexadecane (HEXDEC) matrix. The results showed that dissolution from the NAPL mixtures transitioned from ideality for mole fractions > 0.05 to nonideality as mole fractions decreased. In particular, the TCE generally exhibited more ideal dissolution behavior except at lower mole fractions, and may indicate greater structural/polarity similarity between the two compounds. Raoult's Law and UNIFAC generally under-predicted the batch experiment results for TOL:HEXDEC mixtures especially for mole fractions ≤ 0.05. The dissolution rate coefficients were similar for both TOL and TCE over all mole fractions tested. Mass flux reduction (MFR) analysis showed that more efficient removal behavior occurred for TOL and TCE with larger mole fractions compared to the lower initial mole fraction mixtures (i.e. < 0.2). However, compared to TOL, TCE generally exhibited more efficient removal behavior over all mole fractions tested and may have been the result of structural and molecular property differences between the compounds. Activity coefficient variability as a function of mole fraction was quantified through regression analysis and incorporated into dissolution modeling analyses for the dynamic flushing experiments. TOL elution concentrations were modeled (predicted) reasonable well using ideal and equilibrium assumptions, but the TCE elution concentrations could not be predicted using the ideal model. Rather, the dissolution modeling demonstrated that TCE elution was better described by the nonideal model whereby NAPL-phase activity coefficient varied as a function of COC mole fraction. For dynamic column flushing experiments, dissolution rate kinetics can vary significantly with changes in NAPL volume and surface area. However, under conditions whereby NAPL volume and area are not significantly altered during dissolution, mixture nonideality effects may have a greater relative control on dissolution (elution) and MFR behavior compared to kinetic rate limitations.

Huygens Gas Chromatograph Mass Spectrometer Results from Titan

NASA Technical Reports Server (NTRS)

Niemann, Hasso

2008-01-01

The Huygens Probe executed a successful entry, descent and impact on the Saturnian moon of Titan on January 14, 2005. Gas Chromatograph Mass Spectrometer (GCMS) instrument conducted isotopic and compositional measurements throughout the two and one half hour descent from 146 km altitude, and on the surface for 69 minutes until loss of signal from the orbiting Cassini spacecraft. The GCMS incorporated a quadrupole mass filter with a secondary electron multiplier detection system. The gas sampling system provided continuous direct atmospheric composition measurements and batch sampling through three gas chromatographic (GC) columns, a chemical scrubber and a hydrocarbon enrichment cell. The GCMS gas inlet was heated to prevent condensation, and to evaporate volatiles from the surface after impact. Data products from the GCMS included altitude profiles of the major atmospheric constituents dinitrogen (N2) and methane (CH4), isotope ratios of N-14/N-15, C-12/C-13, and D/H, mole fractions of radiogenic argon (Ar-40)and primordial argon Ar-36), and upper limits on the mole fractions of neon, krypton and xenon, which were found to be below the detection limit of the instrument or absent. Surface measurements confirmed the presence of ethane (C2H6) and cyanogen (C2N2). Later data products include the instrument response to surface outgassing of C2N2, C2H6, acetylene (C2H2),and carbon dioxide (CO2). More recent results include the detection of benzene (C6H6) and height profiles of molecular hydrogen (H2). Numerous other trace species evaporating from the surface were also identified using the GCMS data.

Huygens GCMS Results from Titan

NASA Technical Reports Server (NTRS)

Niemann, Hasso B.; Demick, Jaime; Kasprzak, Wayne; Atreya, Sushil; Owen, Tobias

2007-01-01

The Huygens Probe executed a successful entry, descent and impact on the Saturnian moon of Titan on January 14, 2005. The Gas Chromatograph Mass Spectrometer (GCMS) instrument conducted isotopic and compositional measurements throughout the two and one half hour descent from 146 km altitude, and on the surface for 69 minutes until loss of signal from the orbiting Cassini spacecraft. The GCMS incorporated a quadrupole mass filter with a secondary electron multiplier detection system. The gas sampling system provided continuous direct atmospheric composition measurements and batch sampling through three gas chromatographic (GC) columns, a chemical scrubber and a hydrocarbon enrichment cell. The GCMS gas inlet was heated to prevent condensation, and to evaporate volatiles from the surface after impact. Data products from the GCMS included altitude profiles of the major atmospheric constituents dinitrogen (N2) and methane (CH4), isotope ratios of 14N/15N, 12C/13C, and D/H, mole fractions of radiogenic argon (40Ar) and primordial argon (36Ar), and upper limits on the mole fractions of neon, krypton and xenon, which were found to be absent. Surface measurements confirmed the presence of ethane (C2H6) and cyanogen (C2N2). Later data products expanded atmospheric profiles to include the surface response of C2N2. C2H6, acetylene (C2H2), and carbon dioxide (CO2). More recent results include the profiles of benzene (C6H6) and molecular hydrogen (H2). The GCMS data are being further analyzed to obtain higher precision results and to identify other trace species ion the atmosphere and evaporating from the surface.

Fluxes of Greenhouse Gases from the Baltimore-Washington Area: Results from WINTER 2015 Aircraft Observations

NASA Astrophysics Data System (ADS)

Dickerson, R. R.; Ren, X.; Shepson, P. B.; Salmon, O. E.; Brown, S. S.; Thornton, J. A.; Whetstone, J. R.; Salawitch, R. J.; Sahu, S.; Hall, D.; Grimes, C.; Wong, T. M.

2015-12-01

Urban areas are responsible for a major component of the anthropogenic greenhouse gas (GHG) emissions. Quantification of urban GHG fluxes is important for establishing scientifically sound and cost-effective policies for mitigating GHGs. Discrepancies between observations and model simulations of GHGs suggest uncharacterized sources in urban environments. In this work, we analyze and quantify fluxes of CO2, CH4, CO (and other trace species) from the Baltimore-Washington area based on the mass balance approach using the two-aircraft observations conducted in February-March 2015. Estimated fluxes from this area were 110,000±20,000 moles s-1 for CO2, 700±330 moles s-1 for CH4, and 535±188 moles s-1 for CO. This implies that methane is responsible for ~20% of the climate forcing from these cities. Point sources of CO2 from four regional power plants and one point source of CH4 from a landfill were identified and the emissions from these point sources were quantified based on the aircraft observation and compared to the emission inventory data. Methane fluxes from the Washington area were larger than from the Baltimore area, indicating a larger leakage rate in the Washington area. The ethane-to-methane ratios, with a mean of 3.3%, in the limited canister samples collected during the flights indicate that natural gas leaks and the upwind oil and natural gas operations are responsible for a substantial fraction of the CH4 flux. These observations will be compared to models using Ensemble Kalman Filter Assimilation techniques.

The presence of functional groups key for biodegradation in ionic liquids: effect on gas solubility.

PubMed

Deng, Yun; Morrissey, Saibh; Gathergood, Nicholas; Delort, Anne-Marie; Husson, Pascale; Costa Gomes, Margarida F

2010-03-22

The effect of the incorporation of either ester or ester and ether functions into the side chain of an 1-alkyl-3-methylimidazolium cation on the physico-chemical properties of ionic liquids containing bis(trifluoromethylsulfonyl)imide or octylsulfate anions is studied. It is believed that the introduction of an ester function into the cation of the ionic liquids greatly increases their biodegradability. The density of three such ionic liquids is measured as a function of temperature, and the solubility of four gases-carbon dioxide, ethane, methane, and hydrogen-is determined between 303 K and 343 K and at pressures close to atmospheric level. Carbon dioxide is the most soluble gas, followed by ethane and methane; the mole fraction solubilities vary from 1.8 x 10(-3) to 3.7 x 10(-2). These solubilities are of the same order of magnitude as those determined for alkylimidazolium-based ionic liquids. The chemical modification of the alkyl side chain does not result in a significant change of the solvation properties of the ionic liquid. All of the solubilities decrease with increasing temperature, corresponding to an exothermal solvation process. From the variation of this property with temperature, the thermodynamic functions of solvation (Gibbs energy, enthalpy, and entropy) are calculated and provide information about the solute-solvent interactions and the molecular structure of the solutions.

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.

Muon radiolysis affected by density inhomogeneity in near-critical fluids.

PubMed

Cormier, P J; Alcorn, C; Legate, G; Ghandi, K

2014-04-01

In this article we show the significant tunability of radiation chemistry in supercritical ethane and to a lesser extent in near critical CO2. The information was obtained by studies of muonium (Mu = μ(+)e(-)), which is formed by the thermalization of positive muons in different materials. The studies of the proportions of three fractions of muon polarization, PMu, diamagnetic PD and lost fraction, PL provided the information on radiolysis processes involved in muon thermalization. Our studies include three different supercritical fluids, water, ethane and carbon dioxide. A combination of mobile electrons and other radiolysis products such as (•)C2H5 contribute to interesting behavior at densities ∼40% above the critical point in ethane. In carbon dioxide, an increase in electron mobility contributes to the lost fraction. The hydrated electron in water is responsible for the lost fraction and decreases the muonium fraction.

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.

Current transport mechanism in graphene/AlGaN/GaN heterostructures with various Al mole fractions

NASA Astrophysics Data System (ADS)

Pandit, Bhishma; Seo, Tae Hoon; Ryu, Beo Deul; Cho, Jaehee

2016-06-01

The current transport mechanism of graphene formed on AlxGa1-xN/GaN heterostructures with various Al mole fractions (x = 0.15, 0.20, 0.30, and 0.40) is investigated. The current-voltage measurement from graphene to AlGaN/GaN shows an excellent rectifying property. The extracted Schottky barrier height of the graphene/AlGaN/GaN contacts increases with the Al mole fraction in AlGaN. However, the current transport mechanism deviates from the Schottky-Mott theory owing to the deterioration of AlGaN crystal quality at high Al mole fractions confirmed by reverse leakage current measurement.

Oxidation of ethane by an Acremonium species.

PubMed Central

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

1976-01-01

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

Cloudy with a Chance of Ice: The Stratification of Titan's Vernal Ponds and Formation of Ethane Ice

NASA Astrophysics Data System (ADS)

Soderblom, J. M.; Steckloff, J. K.

2017-12-01

Cassini ISS observations revealed regions on Saturn's moon Titan that become significantly darker (lower albedo) following storm events [1]. These regions are observed to be topographically low [2], indicating that liquid (predominantly methane-ethane-nitrogen) is pooling on Titan after these storm events. These dark ponds, however, are then observed to significantly brighten (higher albedo relative to pre-storm albedo), before fading to their pre-storm albedos [2-3]. We interpret these data to indicate ethane ice formation, which cools from evaporation of methane. The formation of ethane ices results from a unique sequence of thermophysical and thermochemical phenomena. Initially, the methane in the mixture evaporates, cooling the pond. Nitrogen, dissolved primarily in the methane, exsolves, further cooling the liquid. However, because nitrogen is significantly more soluble in cooler methane-hydrocarbon mixtures, relatively more methane than nitrogen leaves the fluid, increasing the relative fraction of nitrogen. This increased nitrogen fraction increases the density of the liquid, as nitrogen is significantly denser than methane or ethane (pure ethane's density is intermediate to that of methane and nitrogen). At around 85 K the mixture is as dense as pure liquid ethane. Thus, further evaporative methane loss and cooling at the pond's surface leads to a chemical stratification, with an increasingly ethane rich epilimnion (surface layer) overlying a methane rich hypolimnion (subsurface layer). Further evaporation of methane from the ethane-rich epilimnion drives its temperature and composition toward the methane-ethane-nitrogen liquidus curve, causing pure ethane ice to precipitate out of solution and settle to the bottom of the pool. This settling would obscure the ethane ice from Cassini VIMS and ISS, which would instead continue to appear as a dark pond on the surface. As the ethane precipitates out completely, a binary methane-nitrogen liquid mixture remains. Eventually, this residual liquid evaporates away, exposing the submerged ethane ice, which Cassini VIMS and ISS would observe as a dramatic brightening of the surface, consistent with observations. [1] Turtle et al. 2009, GRL; 2011, Science; [2] Soderblom et al. 2014, DPS; [3] Barnes et al. 2013 Planet. Sci

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

NASA Technical Reports Server (NTRS)

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

1991-01-01

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

Analytical Phase Equilibrium Function for Mixtures Obeying Raoult's and Henry's Laws

NASA Astrophysics Data System (ADS)

Hayes, Robert

When a mixture of two substances exists in both the liquid and gas phase at equilibrium, Raoults and Henry's laws (ideal solution and ideal dilute solution approximations) can be used to estimate the gas and liquid mole fractions at the extremes of either very little solute or solvent. By assuming that a cubic polynomial can reasonably approximate the intermediate values to these extremes as a function of mole fraction, the cubic polynomial is solved and presented. A closed form equation approximating the pressure dependence on mole fraction of the constituents is thereby obtained. As a first approximation, this is a very simple and potentially useful means to estimate gas and liquid mole fractions of equilibrium mixtures. Mixtures with an azeotrope require additional attention if this type of approach is to be utilized. This work supported in part by federal Grant NRC-HQ-84-14-G-0059.

Comparison of atmospheric CO2 mole fractions and source-sink characteristics at four WMO/GAW stations in China

NASA Astrophysics Data System (ADS)

Cheng, Siyang; Zhou, Lingxi; Tans, Pieter P.; An, Xingqin; Liu, Yunsong

2018-05-01

As CO2 is a primary driving factor of climate change, the mole fraction and source-sink characteristics of atmospheric CO2 over China are constantly inferred from multi-source and multi-site data. In this paper, we compared ground-based CO2 measurements with satellite retrievals and investigated the source-sink regional representativeness at China's four WMO/GAW stations. The results indicate that, firstly, atmospheric CO2 mole fractions from ground-based sampling measurement and Greenhouse Gases Observing Satellite (GOSAT) products reveal similar seasonal variation. The seasonal amplitude of the column-averaged CO2 mole fractions is smaller than that of the ground-based CO2 at all stations. The extrema of the seasonal cycle of ground-based and column CO2 mole fractions are basically synchronous except a slight phase delay at Lin'an (LAN) station. For the two-year average, the column CO2 is lower than ground-based CO2, and both of them reveal the lowest CO2 mole fraction at Waliguan (WLG) station. The lowest (∼4 ppm) and largest (∼8 ppm) differences between the column and ground-based CO2 appear at WLG and Longfengshan (LFS) stations, respectively. The CO2 mole fraction and its difference between GOSAT and ground-based measurement are smaller in summer than in winter. The differences of summer column CO2 among these stations are also much smaller than their ground-based counterparts. In winter, the maximum of ground-based CO2 mole fractions and the greatest difference between the two (ground-based and column) datasets appear at the LFS station. Secondly, the representative areas of the monthly CO2 background mole fractions at each station were found by employing footprints and emissions. Smaller representative areas appeared at Shangdianzi (SDZ) and LFS, whereas larger ones were seen at WLG and LAN. The representative areas in summer are larger than those in winter at WLG and SDZ, but the situation is opposite at LAN and LFS. The representative areas for the stations are different in summer and winter, distributed in four typical regions. The CO2 net fluxes in these representative areas show obvious seasonal cycles with similar trends but different varying ranges and different time of the strongest sink. The intensities and uncertainties of the CO2 fluxes are different at different stations in different months and source-sink sectors. Overall, the WLG station is almost a carbon sink, but the other three stations present stronger carbon sources for most of the year. These findings could be conducive to the application of multi-source CO2 data and the understanding of regional CO2 source-sink characteristics and patterns over China.

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 Δ13C2H6in 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 Δ13C2H6 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 Δ13C2H6 (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 Δ13C2H6 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-temperature pyrolysis confirms this trend could be an isotopic fingerprint for ethane destruction.

Analysis of laser-induced-fluorescence carbon monoxide measurements in turbulent nonpremixed flames

NASA Astrophysics Data System (ADS)

Mokhov, A. V.; Levinsky, H. B.; van der Meij, C. E.; Jacobs, R. A. A. M.

1995-10-01

The influence of fluctuating concentrations and temperature on the laser-induced-fluorescence (LIF) measurement of CO in turbulent flames is described, under conditions in which the fluorescence and the temperature are measured independently. The analysis shows that correlations between CO concentration and temperature can bias the averaged mole fraction extracted from LIF measurements. The magnitude of the bias can exceed the order of the average CO mole fraction. Further, LIF measurements of CO concentrations in a turbulent, nonpremixed, natural gas flame are described. The averaged CO mole fractions are derived from the fluorescence measurements by the use of flame temperatures independently measured by coherent anti-Stokes Raman spectroscopy. Analysis of the fluctuations in measured temperature and fluorescence indicates that temperature and CO concentrations in flame regions with intensive mixing are indeed correlated. In the flame regions where burnout of CO has ceased, the LIF measurements of the CO mole fraction correspond to the probe measurements in exhaust.

Mixtures of tense and relaxed state polymerized human hemoglobin regulate oxygen affinity and tissue construct oxygenation

PubMed Central

Belcher, Donald Andrew; Banerjee, Uddyalok; Baehr, Christopher Michael; Richardson, Kristopher Emil; Cabrales, Pedro; Berthiaume, François

2017-01-01

Pure tense (T) and relaxed (R) quaternary state polymerized human hemoglobins (PolyhHbs) were synthesized and their biophysical properties characterized, along with mixtures of T- and R-state PolyhHbs. It was observed that the oxygen affinity of PolyhHb mixtures varied linearly with T-state mole fraction. Computational analysis of PolyhHb facilitated oxygenation of a single fiber in a hepatic hollow fiber (HF) bioreactor was performed to evaluate the oxygenation potential of T- and R-state PolyhHb mixtures. PolyhHb mixtures with T-state mole fractions greater than 50% resulted in hypoxic and hyperoxic zones occupying less than 5% of the total extra capillary space (ECS). Under these conditions, the ratio of the pericentral volume to the perivenous volume in the ECS doubled as the T-state mole fraction increased from 50 to 100%. These results show the effect of varying the T/R-state PolyhHb mole fraction on oxygenation of tissue-engineered constructs and their potential to oxygenate tissues. PMID:29020036

Mid-infrared laser-absorption diagnostic for vapor-phase fuel mole fraction and liquid fuel film thickness

NASA Astrophysics Data System (ADS)

Porter, J. M.; Jeffries, J. B.; Hanson, R. K.

2011-02-01

A novel two-wavelength mid-infrared laser-absorption diagnostic has been developed for simultaneous measurements of vapor-phase fuel mole fraction and liquid fuel film thickness. The diagnostic was demonstrated for time-resolved measurements of n-dodecane liquid films in the absence and presence of n-decane vapor at 25°C and 1 atm. Laser wavelengths were selected from FTIR measurements of the C-H stretching band of vapor n-decane and liquid n-dodecane near 3.4 μm (3000 cm-1). n-Dodecane film thicknesses <20 μm were accurately measured in the absence of vapor, and simultaneous measurements of n-dodecane liquid film thickness and n-decane vapor mole fraction (300 ppm) were measured with <10% uncertainty for film thicknesses <10 μm. A potential application of the measurement technique is to provide accurate values of vapor mole fraction in combustion environments where strong absorption by liquid fuel or oil films on windows make conventional direct absorption measurements of the gas problematic.

Opposed Jet Burner Extinction Limits: Simple Mixed Hydrocarbon Scramjet Fuels vs Air

NASA Technical Reports Server (NTRS)

Pellett, Gerald L.; Vaden, Sarah N.; Wilson, Lloyd G.

2007-01-01

Opposed Jet Burner tools have been used extensively by the authors to measure Flame Strength (FS) of laminar non-premixed H2 air and simple hydrocarbon (HC) air counterflow diffusion flames at 1-atm. FS represents a strain-induced extinction limit based on air jet velocity. This paper follows AIAA-2006-5223, and provides new HC air FSs for global testing of chemical kinetics, and for characterizing idealized flameholding potentials during early scramjet-like combustion. Previous FS data included six HCs, pure and N2-diluted; and three HC-diluted H2 fuels, where FS decayed very nonlinearly as HC was added to H2, due to H-atom scavenging. This study presents FSs on mixtures of (candidate surrogate) HCs, some with very high FS ethylene. Included are four binary gaseous systems at 300 K, and a hot ternary system at approx. 600 K. The binaries are methane + ethylene, ethane + ethylene, methane + ethane, and methane + propylene. The first three also form two ternary systems. The hot ternary includes both 10.8 and 21.3 mole % vaporized n-heptane and full ranges of methane + ethylene. Normalized FS data provide accurate means of (1) validating, globally, chemical kinetics for extinction of non-premixed flames, and (2) estimating (scaling by HC) the loss of incipient flameholding in scramjet combustors. The n-heptane is part of a proposed baseline simulant (10 mole % with 30% methane + 60% ethylene) that mimics the ignition of endothermically cracked JP-7 like kerosene fuel, as suggested by Colket and Spadaccini in 2001 in their shock tube Scramjet Fuels Autoignition Study. Presently, we use FS to gauge idealized flameholding, and define HC surrogates. First, FS was characterized for hot nheptane + methane + ethylene; then a hot 36 mole % methane + 64% ethylene surrogate was defined that mimics FS of the baseline simulant system. A similar hot ethane + ethylene surrogate can also be defined, but it has lower vapor pressure at 300 K, and thus exhibits reduced gaseous capacity. The new FS results refine our earlier idealized reactivity scale that shows wide ranging (50 x) diameter-normalized FSs for various HCs. These range from JP-10 and methane to H2 air, which produces an exceptionally strong flame that agrees within approx. 1% of recent 2-D numerically simulations. Finally, we continue advocating the FS approach as more direct and fundamental, for assessing idealized scramjet flameholding potentials, than measurements of unstrained laminar burning velocity or blowout in a Perfectly Stirred Reactor.

Raman line imaging for spatially and temporally resolved mole fraction measurements in internal combustion engines.

PubMed

Miles, P C

1999-03-20

An optical diagnostic system based on line imaging of Raman-scattered light has been developed to study the mixing processes in internal combustion engines. The system permits multipoint, single laser-shot measurements of CO(2), O(2), N(2), C(3)H(8), and H(2)O mole fractions with submillimeter spatial resolution. Selection of appropriate system hardware is discussed, as are subsequent data reduction and analysis procedures. Results are reported for data obtained at multiple crank angles and in two different engine flow fields. Measurements are made at 12 locations simultaneously, each location having measurement volume dimensions of 0.5 mm x 0.5 mm x 0.9 mm. The data are analyzed to obtain statistics of species mole fractions: mean, rms, histograms, and both spatial and cross-species covariance functions. The covariance functions are used to quantify the accuracy of the measured rms mole fraction fluctuations, to determine the integral length scales of the mixture inhomogeneities, and to quantify the cycle-to-cycle fluctuations in bulk mixture composition under well-mixed conditions.

Reports of investigations on: Derivation of an infinite-dilution activity coefficient model and application to two-component vapor/liquid equilibria data: Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roper, V.P.; Kobayashi, R.

1988-02-01

Infinite-dilution fugacity coefficients were obtained for the system fluorene/phenanthrene at thirteen temperatures by fitting total pressure across the entire mole fraction range by a computer routine. A thermodynamically consistent routine, that allowed for both positive and negative pressure deviations from the ideal values, was used to correlate data over the full mole fraction range from 0 to 1. The four-suffix Margules activity coefficient model without modification essentially served this purpose since total pressures and total pressure derivatives with respect to mole fraction were negligible compared to pressure measurement precision. The water/ethanol system and binary systems comprised of aniline, chlorobenzene, acetonitrilemore » and other polar compounds were fit for total pressure across the entire mole fraction range for binary Vapor-Liquid-Equilbria (VLE) using the rigorous, thermodynamically consistent Gibbs-Duhem Relation derived by Ibl and Dodge. Data correlation was performed using a computer least squares procedure. Infinite-dilution fugacity coefficients were obtained using a modified Margules activity coefficient model.« less

Experimental study on steam condensation with non-condensable gas in horizontal microchannels

NASA Astrophysics Data System (ADS)

Ma, Xuehu; Fan, Xiaoguang; Lan, Zhong; Jiang, Rui; Tao, Bai

2013-07-01

This paper experimentally studied steam condensation with non-condensable gas in trapezoidal microchannels. The effect of noncondensable gas on condensation two-phase flow patterns and the characteristics of heat transfer and frictional pressure drop were investigated. The visualization study results showed that the special intermittent annular flow was found in the microchannel under the condition of larger mole fraction of noncondensable gas and lower steam mass flux; the apical area of injection was much larger and the neck of injection was longer for mixture gas with lower mole fraction of noncondensable gas in comparison with pure steam condensation; meanwhile, the noncondensable gas resulted in the decrease of flow patterns transitional steam mass flux and quality. The experimental results also indicated that the frictional pressure drop increased with the increasing mole fraction of noncondensable gas when the steam mass flux was fixed. Unlike nature convective condensation heat transfer, the mole fraction of noncondensable gas had little effect on Nusselt number. Based on experimental data, the predictive correlation of Nusselt number for mixture gas condensation in microchannels was established showed good agreement with experimental data.

Thermodynamic equilibrium calculations of dimethyl ether steam reforming and dimethyl ether hydrolysis

NASA Astrophysics Data System (ADS)

Semelsberger, Troy A.; Borup, Rodney L.

The production of a hydrogen-rich fuel-cell feed by dimethyl ether (DME) steam reforming was investigated using calculations of thermodynamic equilibrium as a function of steam-to-carbon ratio (0.00-4.00), temperature (100-600 °C), pressure (1-5 atm), and product species. Species considered were acetone, acetylene, carbon dioxide, carbon monoxide, dimethyl ether, ethane, ethanol, ethylene, formaldehyde, formic acid, hydrogen, isopropanol, methane, methanol, methyl-ethyl ether, n-propanol and water. Thermodynamic equilibrium calculations of DME steam reforming indicate complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide at temperatures greater than 200 °C and steam-to-carbon ratios greater than 1.25 at atmospheric pressure ( P = 1 atm). Increasing the operating pressure shifts the equilibrium toward the reactants; increasing the pressure from 1 to 5 atm decreases the conversion of dimethyl ether from 99.5 to 76.2%. The trend of thermodynamically stable products in decreasing mole fraction is methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol, methyl-ethyl ether and methanol-formaldehyde, formic acid, and acetylene were not observed. Based on the equilibrium calculations, the optimal processing conditions for dimethyl ether steam reforming occur at a steam-to-carbon ratio of 1.50, a pressure of 1 atm, and a temperature of 200 °C. These thermodynamic equilibrium calculations show dimethyl ether processed with steam will produce hydrogen-rich fuel-cell feeds—with hydrogen concentrations exceeding 70%. The conversion of dimethyl ether via hydrolysis (considering methanol as the only product) is limited by thermodynamic equilibrium. Equilibrium conversion increases with temperature and steam-to-carbon ratio. A maximum dimethyl ether conversion of 62% is achieved at a steam-to-carbon ratio of 5.00 and a processing temperature of 600 °C.

Intercomparison of infrared cavity leak-out spectroscopy and gas chromatography-flame ionization for trace analysis of ethane.

PubMed

Thelen, Sven; Miekisch, Wolfram; Halmer, Daniel; Schubert, Jochen; Hering, Peter; Mürtz, Manfred

2008-04-15

Comparison of two different methods for the measurement of ethane at the parts-per-billion (ppb) level is reported. We used cavity leak-out spectroscopy (CALOS) in the 3 microm wavelength region and gas chromatography-flame ionization detection (GC-FID) for the analysis of various gas samples containing ethane fractions in synthetic air. Intraday and interday reproducibilities were studied. Intercomparing the results of two series involving seven samples with ethane mixing ratios ranging from 0.5 to 100 ppb, we found a reasonable agreement between both methods. The scatter plot of GC-FID data versus CALOS data yields a linear regression slope of 1.07 +/- 0.03. Furthermore, some of the ethane mixtures were checked over the course of 1 year, which proved the long-term stability of the ethane mixing ratio. We conclude that CALOS shows equivalent ethane analysis precision compared to GC-FID, with the significant advantage of a much higher time resolution (<1 s) since there is no requirement for sample preconcentration. This opens new analytical possibilities, e.g., for real-time monitoring of ethane traces in exhaled human breath.

Background Mole Fractions of Hydrocarbons in North America Determined from NOAA Global Reference Network Data

NASA Astrophysics Data System (ADS)

Mielke-Maday, I.

2015-12-01

The National Oceanic and Atmospheric Administration (NOAA) Global Monitoring Division (GMD) maintains a global reference network for over 50 trace gas species and analyzes discrete air samples collected by this network throughout the world at the Earth System Research Laboratory in Boulder, Colorado. In particular, flask samples are analyzed for a number of hydrocarbons with policy and health relevance such as ozone precursors, greenhouse gases, and hazardous air pollutants. Because this global network's sites are remote and therefore minimally influenced by local anthropogenic emissions, these data yield information about background ambient mole fractions and can provide a context for observations collected in intensive field campaigns, such as the Front Range Air Pollution and Photochemistry Experiment (FRAPPE), the Southeast Nexus (SENEX) study, and the DISCOVER-AQ deployments. Information about background mole fractions during field campaigns is critical for calculating hydrocarbon enhancements in the region of study and for assessing the extent to which a particular region's local emissions sources contribute to these enhancements. Understanding the geographic variability of the background and its contribution to regional ambient mole fractions is also crucial for the development of realistic regulations. We present background hydrocarbon mole fractions and their ratios in North America using data from air samples collected in the planetary boundary layer at tall towers and aboard aircraft from 2008 to 2014. We discuss the spatial and seasonal variability in these data. We present trends over the time period of measurements and propose possible explanations for these trends.

Two-dimensional simulation of GaAsSb/GaAs quantum dot solar cells

NASA Astrophysics Data System (ADS)

Kunrugsa, Maetee

2018-06-01

Two-dimensional (2D) simulation of GaAsSb/GaAs quantum dot (QD) solar cells is presented. The effects of As mole fraction in GaAsSb QDs on the performance of the solar cell are investigated. The solar cell is designed as a p-i-n GaAs structure where a single layer of GaAsSb QDs is introduced into the intrinsic region. The current density–voltage characteristics of QD solar cells are derived from Poisson’s equation, continuity equations, and the drift-diffusion transport equations, which are numerically solved by a finite element method. Furthermore, the transition energy of a single GaAsSb QD and its corresponding wavelength for each As mole fraction are calculated by a six-band k · p model to validate the position of the absorption edge in the external quantum efficiency curve. A GaAsSb/GaAs QD solar cell with an As mole fraction of 0.4 provides the best power conversion efficiency. The overlap between electron and hole wave functions becomes larger as the As mole fraction increases, leading to a higher optical absorption probability which is confirmed by the enhanced photogeneration rates within and around the QDs. However, further increasing the As mole fraction results in a reduction in the efficiency because the absorption edge moves towards shorter wavelengths, lowering the short-circuit current density. The influences of the QD size and density on the efficiency are also examined. For the GaAsSb/GaAs QD solar cell with an As mole fraction of 0.4, the efficiency can be improved to 26.2% by utilizing the optimum QD size and density. A decrease in the efficiency is observed at high QD densities, which is attributed to the increased carrier recombination and strain-modified band structures affecting the absorption edges.

Accurate measurements of carbon monoxide in humid air using the cavity ring-down spectroscopy (CRDS) technique

NASA Astrophysics Data System (ADS)

Chen, H.; Karion, A.; Rella, C. W.; Winderlich, J.; Gerbig, C.; Filges, A.; Newberger, T.; Sweeney, C.; Tans, P. P.

2013-04-01

Accurate measurements of carbon monoxide (CO) in humid air have been made using the cavity ring-down spectroscopy (CRDS) technique. The measurements of CO mole fractions are determined from the strength of its spectral absorption in the near-infrared region (~1.57 μm) after removing interferences from adjacent carbon dioxide (CO2) and water vapor (H2O) absorption lines. Water correction functions that account for the dilution and pressure-broadening effects as well as absorption line interferences from adjacent CO2 and H2O lines have been derived for CO2 mole fractions between 360-390 ppm and for reported H2O mole fractions between 0-4%. The line interference corrections are independent of CO mole fractions. The dependence of the line interference correction on CO2 abundance is estimated to be approximately -0.3 ppb/100 ppm CO2 for dry mole fractions of CO. Comparisons of water correction functions from different analyzers of the same type show significant differences, making it necessary to perform instrument-specific water tests for each individual analyzer. The CRDS analyzer was flown on an aircraft in Alaska from April to November in 2011, and the accuracy of the CO measurements by the CRDS analyzer has been validated against discrete NOAA/ESRL flask sample measurements made on board the same aircraft, with a mean difference between integrated in situ and flask measurements of -0.6 ppb and a standard deviation of 2.8 ppb. Preliminary testing of CRDS instrumentation that employs improved spectroscopic model functions for CO2, H2O, and CO to fit the raw spectral data (available since the beginning of 2012) indicates a smaller water vapor dependence than the models discussed here, but more work is necessary to fully validate the performance. The CRDS technique provides an accurate and low-maintenance method of monitoring the atmospheric dry mole fractions of CO in humid air streams.

Calibration and field testing of cavity ring-down laser spectrometers measuring CH4, CO2, and δ13CH4 deployed on towers in the Marcellus Shale region

NASA Astrophysics Data System (ADS)

Miles, Natasha L.; Martins, Douglas K.; Richardson, Scott J.; Rella, Christopher W.; Arata, Caleb; Lauvaux, Thomas; Davis, Kenneth J.; Barkley, Zachary R.; McKain, Kathryn; Sweeney, Colm

2018-03-01

Four in situ cavity ring-down spectrometers (G2132-i, Picarro, Inc.) measuring methane dry mole fraction (CH4), carbon dioxide dry mole fraction (CO2), and the isotopic ratio of methane (δ13CH4) were deployed at four towers in the Marcellus Shale natural gas extraction region of Pennsylvania. In this paper, we describe laboratory and field calibration of the analyzers for tower-based applications and characterize their performance in the field for the period January-December 2016. Prior to deployment, each analyzer was tested using bottles with various isotopic ratios, from biogenic to thermogenic source values, which were diluted to varying degrees in zero air, and an initial calibration was performed. Furthermore, at each tower location, three field tanks were employed, from ambient to high mole fractions, with various isotopic ratios. Two of these tanks were used to adjust the calibration of the analyzers on a daily basis. We also corrected for the cross-interference from ethane on the isotopic ratio of methane. Using an independent field tank for evaluation, the standard deviation of 4 h means of the isotopic ratio of methane difference from the known value was found to be 0.26 ‰ δ13CH4. Following improvements in the field tank testing scheme, the standard deviation of 4 h means was 0.11 ‰, well within the target compatibility of 0.2 ‰. Round-robin style testing using tanks with near-ambient isotopic ratios indicated mean errors of -0.14 to 0.03 ‰ for each of the analyzers. Flask to in situ comparisons showed mean differences over the year of 0.02 and 0.08 ‰, for the east and south towers, respectively. Regional sources in this region were difficult to differentiate from strong perturbations in the background. During the afternoon hours, the median differences of the isotopic ratio measured at three of the towers, compared to the background tower, were &minus0.15 to 0.12 ‰ with standard deviations of the 10 min isotopic ratio differences of 0.8 ‰. In terms of source attribution, analyzer compatibility of 0.2 ‰ δ13CH4 affords the ability to distinguish a 50 ppb CH4 peak from a biogenic source (at -60 ‰, for example) from one originating from a thermogenic source (-35 ‰), with the exact value dependent upon the source isotopic ratios. Using a Keeling plot approach for the non-afternoon data at a tower in the center of the study region, we determined the source isotopic signature to be -31.2 ± 1.9 ‰, within the wide range of values consistent with a deep-layer Marcellus natural gas source.

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.

Ignition and Combustion of Pulverized Coal and Biomass under Different Oxy-fuel O2/N2 and O2/CO2 Environments

NASA Astrophysics Data System (ADS)

Khatami Firoozabadi, Seyed Reza

This work studied the ignition and combustion of burning pulverized coals and biomasses particles under either conventional combustion in air or oxy-fuel combustion conditions. Oxy-fuel combustion is a 'clean-coal' process that takes place in O2/CO2 environments, which are achieved by removing nitrogen from the intake gases and recirculating large amounts of flue gases to the boiler. Removal of nitrogen from the combustion gases generates a high CO2-content, sequestration-ready gas at the boiler effluent. Flue gas recirculation moderates the high temperatures caused by the elevated oxygen partial pressure in the boiler. In this study, combustion of the fuels took place in a laboratory laminar-flow drop-tube furnace (DTF), electrically-heated to 1400 K, in environments containing various mole fractions of oxygen in either nitrogen or carbon-dioxide background gases. The experiments were conducted at two different gas conditions inside the furnace: (a) quiescent gas condition (i.e., no flow or inactive flow) and, (b) an active gas flow condition in both the injector and furnace. Eight coals from different ranks (anthracite, semi-snthracite, three bituminous, subbituminous and two lignites) and four biomasses from different sources were utilized in this work to study the ignition and combustion characteristics of solid fuels in O2/N2 or O2/CO2 environments. The main objective is to study the effect of replacing background N2 with CO2, increasing O2 mole fraction and fuel type and rank on a number of qualitative and quantitative parameters such as ignition/combustion mode, ignition temperature, ignition delay time, combustion temperatures, burnout times and envelope flame soot volume fractions. Regarding ignition, in the quiescent gas condition, bituminous and sub-bituminous coal particles experienced homogeneous ignition in both O2/N 2 and O2/CO2 atmospheres, while in the active gas flow condition, heterogeneous ignition was evident in O2/CO 2. Anthracite, semi-anthracite and lignites mostly experienced heterogeneous ignition in either O2/N2 or O2/CO2 atmospheres in both flow conditions. Replacing the N2 by CO 2 slightly increased the ignition temperature (30--40K). Ignition temperatures increased with the enhancement of coal rank in either air or oxy-fuel combustion conditions. However, increasing oxygen mole fraction decreased the ignition temperature for all coals. The ignition delay of coal particles was prolonged in the slow-heating O2/CO2 atmospheres, relative to the faster-heating O2/N2 atmospheres, particularly at high-diluent mole fractions. At higher O2 mole fractions, ignition delays decreased in both environments. Higher rank fuels such as anthracite and semi-anthracite experienced higher ignition delays while lower rank fuels such as lignite and biomasses experienced lower igniton delay times. In combustion, fuel particles were observed to burn in different modes, such as two-mode, or in one-mode combustion, depending on their rank and the furnace conditions. Strong tendencies were observed for all fuels to burn in one-mode when N2 was replaced by CO2, and when O 2 mole fraction increased in both environments. Moreover, increasing the coal rank, from lignite to bituminous, enhanced the tendency of coal particles to exhibit a two-mode combustion behavior. Particle luminosity, fragmentation and deduced temperatures were higher in O2/N2 than in O2/CO2 atmospheres, and corresponding burnout times were shorter, at the same O2 mole fractions. Particle luminosity and temperatures increased with increasing O2 mole fractions in both N2 and in CO2 background gases, and corresponding burnout times decreased with increasing O2 mole fractions. Bituminous coal particles swelled, whereas sub-bituminous coal particles exhibited limited fragmentation prior to and during the early stages of combustion. Lignite coal particles fragmented extensively and burned in one-mode regardless of the O2 mole fraction and the background gas. The timing of fragmentation (prior or after ignition) and the number of fragments depended on the type of the lignite and on the particle shape. Temperatures and burnout times of particles were also affected by the combustion mode. In nearly all bituminous and biomass particles combustion, sooty envelope flames were formed around the particles. Replacement of background N 2 by CO2 gas decreased the average soot volume fraction, fv, whereas increasing O2 from 20% to 30--40% increased the fv and then further increasing O2 to 100% decreased the soot volume fraction drastically. bituminous coal particle flames generated lower soot volume fractions in the range 2x10 -5--9x10-5, depending on O2 mole fraction. Moreover, biomass particle flames were optically thin and of equal-sized at all O2 mole fractions. (Abstract shortened by UMI.).

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.

The solubility of ethane in aqueous solutions of sodium 1-pentanesulfonate, sodium 1-hexanesulfonate, sodium 1-heptanesulfonate, and sodium 1-octanesulfonate at 25 degrees C.

PubMed

Calhoun, A R; King, A D

2007-05-15

Measurements have been made to determine the solubility of ethane, C2H6, in aqueous solutions of four different surfactants of the linear alkanesulfonate class at 25 degrees C. The surfactants, sodium 1-pentanesulfonate, sodium 1-hexanesulfonate, sodium 1-heptanesulfonate, and sodium 1-octanesulfonate, all share a common head group (-SO-3) and counter ion (Na+), and differ only in the length of the alkyl chain attached to the head group. The solubility of ethane has been determined as a function of surfactant concentration for each surfactant. At surfactant concentrations below the critical micelle concentration (CMC), the solubility of ethane is quite low and differs only slightly from the solubility of ethane in pure water. At concentrations greater than the CMC, the solubility of ethane exhibits a gradual increase with surfactant concentration. At high surfactant concentrations, well in excess of the CMC, the solubility of ethane is found to increase as a linear function of surfactant concentration. From this data it becomes possible to determine the fractional population of the surfactant in the free and micellized states. The solubility data measured for ethane is interpreted in terms of the mass-action model for micelle formation.

Preliminary study of atmospheric carbon dioxide in a glacial area of the Qilian Mountains, west China

NASA Astrophysics Data System (ADS)

Li, Chuanjin; Zhou, Lingxi; Qin, Dahe; Liu, Lixin; Qin, Xiang; Wang, Zebin; Ren, Jiawen

2014-12-01

Carbon dioxide represents the most important contribution to increased radiative forcing. The preliminary results of the atmospheric carbon dioxide mole fraction from the glacial region in the Qilian Mountains area, in the northeast of the Qinghai-Xizang (Tibetan) Plateau during July, 2009 to October, 2012 are presented. The annual mean CO2 mole fractions in 2010 and 2011 were 388.4 ± 2.7 ppm and 392.7 ± 2.6 ppm, respectively. These values were consistent with the CO2 mole fractions from the WMO/GAW stations located at high altitudes. However, both the concentration and seasonal variation were significantly lower than stations located adjacent to megacities or economic centers at low latitudes in eastern China. Shorter durations of photosynthesis of the alpine vegetation system that exceeded respiration were detected at the Qilian Mountains glacial area. The annual mean increase during the sampling period was 2.9 ppm yr-1 and this value was higher than the global mean values. Anthropogenic activities in the cities adjacent to the Qilian Mountains may have important influences on the CO2 mole fractions, especially in summer, when north and north-north-west winds are typical.

CCQM Pilot Study CCQM-P140: Quantitative surface analysis of multi-element alloy films

NASA Astrophysics Data System (ADS)

Kim, Kyung Joong; Jang, Jong Shik; Kim, An Soon; Suh, Jung Ki; Chung, Yong-Duck; Hodoroaba, Vasile-Dan; Wirth, Thomas; Unger, Wolfgang; Kang, Hee Jae; Popov, Oleg; Popov, Inna; Kuselman, Ilya; Lee, Yeon Hee; Sykes, David E.; Wang, Meiling; Wang, Hai; Ogiwara, Toshiya; Nishio, Mitsuaki; Tanuma, Shigeo; Simons, David; Szakal, Christopher; Osborn, William; Terauchi, Shinya; Ito, Mika; Kurokawa, Akira; Fujimoto, Toshiyuki; Jordaan, Werner; Jeong, Chil Seong; Havelund, Rasmus; Spencer, Steve; Shard, Alex; Streeck, Cornelia; Beckhoff, Burkhard; Eicke, Axel; Terborg, Ralf

2015-01-01

A pilot study for a quantitative surface analysis of multi-element alloy films has been performed by the Surface Analysis Working Group (SAWG) of the Consultative Committee for Amount of Substance (CCQM). The aim of this pilot study is to evaluate a protocol for a key comparison to demonstrate the equivalence of measures by National Metrology Institutes (NMIs) and Designated Institutes (DI) for the mole fractions of multi-element alloy films. A Cu(In,Ga)Se2 (CIGS) film with non-uniform depth distribution was chosen as a representative multi-element alloy film. The mole fractions of the reference and the test CIGS films were certified by isotope dilution—inductively coupled plasma/mass spectrometry. A total number counting (TNC) method was used as a method to determine the signal intensities of the constituent elements acquired in SIMS, XPS and AES depth profiling. TNC method is comparable with the certification process because the certified mole fractions are the average values of the films. The mole fractions of the CIGS films were measured by Secondary Ion Mass Spectrometry (SIMS), Auger Electron Spectroscopy (AES), X-ray Photoelectron Spectroscopy (XPS), X-Ray Fluorescence (XRF) Analysis and Electron Probe Micro Analysis (EPMA) with Energy Dispersive X-ray Spectrometry (EDX). Fifteen laboratories from eight NMIs, one DI, and six non-NMIs participated in this pilot study. The average mole fractions of the reported data showed relative standard deviations from 5.5 % to 6.8 % and average relative expanded uncertainties in the range from 4.52 % to 4.86 % for the four test CIGS specimens. These values are smaller than those in the key comparison CCQM-K67 for the measurement of mole fractions of Fe-Ni alloy films. As one result it can be stated that SIMS, XPS and AES protocols relying on the quantification of CIGS films using the TNC method are mature to be used in a CCQM key comparison. Main text. To reach the main text of this paper, click on Final Report. The final report has been peer-reviewed and approved for publication by CCQM.

Tunable diode laser absorption spectroscopy-based tomography system for on-line monitoring of two-dimensional distributions of temperature and H2O mole fraction.

PubMed

Xu, Lijun; Liu, Chang; Jing, Wenyang; Cao, Zhang; Xue, Xin; Lin, Yuzhen

2016-01-01

To monitor two-dimensional (2D) distributions of temperature and H2O mole fraction, an on-line tomography system based on tunable diode laser absorption spectroscopy (TDLAS) was developed. To the best of the authors' knowledge, this is the first report on a multi-view TDLAS-based system for simultaneous tomographic visualization of temperature and H2O mole fraction in real time. The system consists of two distributed feedback (DFB) laser diodes, a tomographic sensor, electronic circuits, and a computer. The central frequencies of the two DFB laser diodes are at 7444.36 cm(-1) (1343.3 nm) and 7185.6 cm(-1) (1391.67 nm), respectively. The tomographic sensor is used to generate fan-beam illumination from five views and to produce 60 ray measurements. The electronic circuits not only provide stable temperature and precise current controlling signals for the laser diodes but also can accurately sample the transmitted laser intensities and extract integrated absorbances in real time. Finally, the integrated absorbances are transferred to the computer, in which the 2D distributions of temperature and H2O mole fraction are reconstructed by using a modified Landweber algorithm. In the experiments, the TDLAS-based tomography system was validated by using asymmetric premixed flames with fixed and time-varying equivalent ratios, respectively. The results demonstrate that the system is able to reconstruct the profiles of the 2D distributions of temperature and H2O mole fraction of the flame and effectively capture the dynamics of the combustion process, which exhibits good potential for flame monitoring and on-line combustion diagnosis.

Tunable diode laser absorption spectroscopy-based tomography system for on-line monitoring of two-dimensional distributions of temperature and H2O mole fraction

NASA Astrophysics Data System (ADS)

Xu, Lijun; Liu, Chang; Jing, Wenyang; Cao, Zhang; Xue, Xin; Lin, Yuzhen

2016-01-01

To monitor two-dimensional (2D) distributions of temperature and H2O mole fraction, an on-line tomography system based on tunable diode laser absorption spectroscopy (TDLAS) was developed. To the best of the authors' knowledge, this is the first report on a multi-view TDLAS-based system for simultaneous tomographic visualization of temperature and H2O mole fraction in real time. The system consists of two distributed feedback (DFB) laser diodes, a tomographic sensor, electronic circuits, and a computer. The central frequencies of the two DFB laser diodes are at 7444.36 cm-1 (1343.3 nm) and 7185.6 cm-1 (1391.67 nm), respectively. The tomographic sensor is used to generate fan-beam illumination from five views and to produce 60 ray measurements. The electronic circuits not only provide stable temperature and precise current controlling signals for the laser diodes but also can accurately sample the transmitted laser intensities and extract integrated absorbances in real time. Finally, the integrated absorbances are transferred to the computer, in which the 2D distributions of temperature and H2O mole fraction are reconstructed by using a modified Landweber algorithm. In the experiments, the TDLAS-based tomography system was validated by using asymmetric premixed flames with fixed and time-varying equivalent ratios, respectively. The results demonstrate that the system is able to reconstruct the profiles of the 2D distributions of temperature and H2O mole fraction of the flame and effectively capture the dynamics of the combustion process, which exhibits good potential for flame monitoring and on-line combustion diagnosis.

Tunable diode laser absorption spectroscopy-based tomography system for on-line monitoring of two-dimensional distributions of temperature and H{sub 2}O mole fraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Lijun, E-mail: lijunxu@buaa.edu.cn; Liu, Chang; Jing, Wenyang

2016-01-15

To monitor two-dimensional (2D) distributions of temperature and H{sub 2}O mole fraction, an on-line tomography system based on tunable diode laser absorption spectroscopy (TDLAS) was developed. To the best of the authors’ knowledge, this is the first report on a multi-view TDLAS-based system for simultaneous tomographic visualization of temperature and H{sub 2}O mole fraction in real time. The system consists of two distributed feedback (DFB) laser diodes, a tomographic sensor, electronic circuits, and a computer. The central frequencies of the two DFB laser diodes are at 7444.36 cm{sup −1} (1343.3 nm) and 7185.6 cm{sup −1} (1391.67 nm), respectively. The tomographicmore » sensor is used to generate fan-beam illumination from five views and to produce 60 ray measurements. The electronic circuits not only provide stable temperature and precise current controlling signals for the laser diodes but also can accurately sample the transmitted laser intensities and extract integrated absorbances in real time. Finally, the integrated absorbances are transferred to the computer, in which the 2D distributions of temperature and H{sub 2}O mole fraction are reconstructed by using a modified Landweber algorithm. In the experiments, the TDLAS-based tomography system was validated by using asymmetric premixed flames with fixed and time-varying equivalent ratios, respectively. The results demonstrate that the system is able to reconstruct the profiles of the 2D distributions of temperature and H{sub 2}O mole fraction of the flame and effectively capture the dynamics of the combustion process, which exhibits good potential for flame monitoring and on-line combustion diagnosis.« less

Accurate measurements of carbon monoxide in humid air using the cavity ring-down spectroscopy (CRDS) technique

NASA Astrophysics Data System (ADS)

Chen, H.; Karion, A.; Rella, C. W.; Winderlich, J.; Gerbig, C.; Filges, A.; Newberger, T.; Sweeney, C.; Tans, P. P.

2012-09-01

Accurate measurements of carbon monoxide (CO) in humid air have been made using the cavity ring-down spectroscopy (CRDS) technique. The measurements of CO mole fractions are determined from the strength of its spectral absorption in the near infrared region (∼1.57 μm) after removing interferences from adjacent carbon dioxide (CO2) and water vapor (H2O) absorption lines. Water correction functions that account for the dilution and pressure-broadening effects as well as absorption line interferences from adjacent CO2 and H2O lines have been derived for CO2 mole fractions between 360-390 ppm. The line interference corrections are independent of CO mole fractions. The dependence of the line interference correction on CO2 abundance is estimated to be approximately -0.3 ppb/100 ppm CO2 for dry mole fractions of CO. Comparisons of water correction functions from different analyzers of the same type show significant differences, making it necessary to perform instrument-specific water tests for each individual analyzer. The CRDS analyzer was flown on an aircraft in Alaska from April to November in 2011, and the accuracy of the CO measurements by the CRDS analyzer has been validated against discrete NOAA/ESRL flask sample measurements made on board the same aircraft, with a mean difference between integrated in situ and flask measurements of -0.6 ppb and a standard deviation of 2.8 ppb. Preliminary testing of CRDS instrumentation that employs new spectroscopic analysis (available since the beginning of 2012) indicates a smaller water vapor dependence than the models discussed here, but more work is necessary to fully validate the performance. The CRDS technique provides an accurate and low-maintenance method of monitoring the atmospheric dry mole fractions of CO in humid air streams.

Facile Dehydrogenation of Ethane on the IrO2(110) Surface.

PubMed

Bian, Yingxue; Kim, Minkyu; Li, Tao; Asthagiri, Aravind; Weaver, Jason F

2018-02-21

Realizing the efficient and selective conversion of ethane to ethylene is important for improving the utilization of hydrocarbon resources, yet remains a major challenge in catalysis. Herein, ethane dehydrogenation on the IrO 2 (110) surface is investigated using temperature-programmed reaction spectroscopy (TPRS) and density functional theory (DFT) calculations. The results show that ethane forms strongly bound σ-complexes on IrO 2 (110) and that a large fraction of the complexes undergo C-H bond cleavage during TPRS at temperatures below 200 K. Continued heating causes as much as 40% of the dissociated ethane to dehydrogenate and desorb as ethylene near 350 K, with the remainder oxidizing to CO x species. Both TPRS and DFT show that ethylene desorption is the rate-controlling step in the conversion of ethane to ethylene on IrO 2 (110) during TPRS. Partial hydrogenation of the IrO 2 (110) surface is found to enhance ethylene production from ethane while suppressing oxidation to CO x species. DFT predicts that hydrogenation of reactive oxygen atoms of the IrO 2 (110) surface effectively deactivates these sites as H atom acceptors, and causes ethylene desorption to become favored over further dehydrogenation and oxidation of ethane-derived species. The study reveals that IrO 2 (110) exhibits an exceptional ability to promote ethane dehydrogenation to ethylene near room temperature, and provides molecular-level insights for understanding how surface properties influence selectivity toward ethylene production.

Impact of underlap and mole-fraction on RF performance of strained-Si/Si1-xGex/strained-Si DG MOSFETs

NASA Astrophysics Data System (ADS)

Dutta, Arka; Koley, Kalyan; Sarkar, Chandan K.

2014-11-01

In this paper, a systematic RF performance analysis of double-gate strained silicon (DGSS) nMOSFETs is presented. The analysis is focused upon impact of Germanium mole-fraction variation on RF performance of underlap engineered DGSS nMOSFET. The RF performance of the device is analysed as a function of intrinsic RF figure of merits (FOMs) including non-quasi static effects (NQS). The RF FOMs are represented by the intrinsic gate to source/drain capacitance (Cgs and Cgd) and resistance (Rgs and Rgd), the transport delay (τm), the intrinsic inductance (Lsd), the cut-off frequency (fT), and the maximum oscillation frequency (fMAX). The results of the study suggested a significant improvement in the device performance, up to 40% increase in Germanium mole fraction (χ).

Isentropic expansion and related thermodynamic properties of non-ionic amphiphile-water mixtures.

PubMed

Reis, João Carlos R; Douhéret, Gérard; Davis, Michael I; Fjellanger, Inger Johanne; Høiland, Harald

2008-01-28

A concise thermodynamic formalism is developed for the molar isentropic thermal expansion, ES,m = ( partial differential Vm/ partial differential T)(Sm,x), and the ideal and excess quantities for the molar, apparent molar and partial molar isentropic expansions of binary liquid mixtures. Ultrasound speeds were determined by means of the pulse-echo-overlap method in aqueous mixtures of 2-methylpropan-2-ol at 298.15 K over the entire composition range. These data complement selected extensive literature data on density, isobaric heat capacity and ultrasound speed for 9 amphiphile (methanol, ethanol, propan-1-ol, propan-2-ol, 2-methylpropan-2-ol, ethane-1,2-diol, 2-methoxyethanol, 2-ethoxyethanol or 2-butoxyethanol)-water binary systems, which form the basis of tables listing molar and excess molar isobaric expansions and heat capacities, and molar and excess molar isentropic compressions and expansions at 298.15 K and at 65 fixed mole fractions spanning the entire composition range and fine-grained in the water-rich region. The dependence on composition of these 9 systems is graphically depicted for the excess molar isobaric and isentropic expansions and for the excess partial molar isobaric and isentropic expansions of the amphiphile. The analysis shows that isentropic thermal expansion properties give a much stronger response to amphiphile-water molecular interactions than do their isobaric counterparts. Depending on the pair property-system, the maximum excess molar isentropic value is generally twenty- to a hundred-fold greater than the corresponding maximum isobaric value, and occurs at a lower mole fraction of the amphiphile. Values at infinite dilution of the 9 amphiphiles in water are given for the excess partial molar isobaric heat capacity, isentropic compression, isobaric expansion and isentropic expansion. These values are interpreted in terms of the changes occurring when amphiphile molecules cluster into an oligomeric form. Present results are discussed from theoretical and experimental thermodynamic viewpoints. It is concluded that isentropic thermal expansion properties constitute a new distinct resource for revealing particular features and trends in complex mixing processes, and that analyses using these new properties compare favourably with conventional approaches.

Temperature and abundances in the Jovian auroral stratosphere. 2: Ethylene as a probe of the microbar region

NASA Technical Reports Server (NTRS)

Kostiuk, Theodor; Romani, Paul; Espenak, Fred; Livengood, Timothy A.

1993-01-01

Individual emission lines of ethylene (C2H4) near 10.5 micron were measured from the equatorial and north polar regions of Jupiter. Observations were made at a spectral resolution of 0.00083/cm using infrared heterodyne spectroscopy at the NASA Infrared Telescope Facility of Mauna Kea, Hawaii. The line shape information possible with this resolving power permitted the retrieval of quiescent ethylene abundances and the investigation of abundance and thermal structure variability in the polar auroral region. A rough distribution of the north polar emission as a function of longitude was obtained with an instantaneous field of view (full width at half maximum) of approximately 1 arc sec on the planet. The greatest C2H4 emission was observed near the nominal north polar methane hot spot (60 deg N, 180 deg longitude, System III, 1965). It was found to be confined to less than 10 deg longitude on the planet. Using a Voyager-derived thermal profile, retrieved ethylene mole fractions for equatorial and north polar quiescent (non-hot spot) regions were consistent with results from existing photochemical models. At the hot spot an 18-fold increase in abundance was required near the 10-microbar level to reproduce the data. Alternatively varying the stratospheric thermal profile, a 67-137 K increase in temperature was required at the approximately 10-microbar level to satisfy the observed emission, if the C2H4 mole fraction is fixed to the quiescent value. These results provide the first direct probe of the upper stratosphere of Jupiter and give upper limits to the temperature increase near the source of the north polar thermal infrared aurora. Combined with results from similar measurements of auroral ethane emission (Livengood et al., this issue) probing the 1-mbar region, altitude information on the thermal structure can be obtained for the first time. The ethylene line emission region extends to the few microbar pressure level and may overlap the region where the H2 ultraviolet aurora is formed; thus it can be used as a probe of the coupling between the ultraviolet and thermal infrared phenomena.

A correlation between structural distortion and variation of TC in Ba1-x/2LaxBi4-x/2Ti4O15

NASA Astrophysics Data System (ADS)

Asha, M. Arul; Gajendra Babu, M. Veera; Abdul Kader, S. M.; Sundarakannan, B.; Srihari, V.; Sridharan, V.

2012-06-01

Ba and Bi ions were simultaneously substituted by La ion up to 0.3 mole fraction and studied by powder XRD and temperature dependent dielectric measurements. Perovskite slab thickness reduces due to octahedral tilting and the cell volume decreases. Low mole fraction of simultaneous substitution of La is preferred as it increases physical properties.

[In-situ measurement of background atmospheric HCFC-142b using GC-MS and GC-ECD method].

PubMed

Guo, Li-feng; Yao, Bo; Zhou, Ling-xi; Li, Pei-chang; Xu, Lin

2013-05-01

Custom-made GC-MS and GC-ECD in-situ measurement systems were established at the Shangdianzi GAW Regional station. From May 2010 to May 2011, the precisions for GC-MS and GC-ECD systems were 0.23% and 0.88%, respectively, and the HCFC-142b mole fraction during the observation period ranged from 21 x 10(-12) to 355 x 10(-12). The result of the independent-sample T test was P > 0.05, and there was no significant difference in HCFC-142b mole fraction measured by the two systems. The small difference of HCFC-142b mole fraction measured by GC-MS and GC-ECD might be associated with the different sampling time and precision of the two systems. A statistical filter of "robust local regression" was applied to separate HCFC-142b background and pollution data. The mean difference, median difference, 25 and 75 percent difference of background data measured by GC-MS and GC-ECD were all within the precisions. The pollution events captured by the two systems showed similar characters. Results from both systems showed a higher HCFC-142b level in summer and autumn than in winter. The pollution mole fraction of the two systems showed similar seasonal changes.

Simulation and optimization of deep violet InGaN double quantum well laser

NASA Astrophysics Data System (ADS)

Alahyarizadeh, Gh.; Ghazai, A. J.; Rahmani, R.; Mahmodi, H.; Hassan, Z.

2012-03-01

The performance characteristics of a deep violet InGaN double quantum well laser diode (LD) such as threshold current ( Ith), external differential quantum efficiency (DQE) and output power have been investigated using the Integrated System Engineering Technical Computer Aided Design (ISE-TCAD) software. As well as its operating parameters such as internal quantum efficiency ( ηi), internal loss ( αi) and transparency threshold current density ( J0) have been studied. Since, we are interested to investigate the mentioned characteristics and parameters independent of well and barrier thickness, therefore to reach a desired output wavelength, the indium mole fraction of wells and barriers has been varied consequently. The indium mole fractions of well and barrier layers have been considered 0.08 and 0.0, respectively. Some important parameters such as Al mole fraction of the electronic blocking layer (EBL) and cavity length which affect performance characteristics were also investigated. The optimum values of the Al mole fraction and cavity length in this study are 0.15 and 400 μm, respectively. The lowest threshold current, the highest DQE and output power which obtained at the emission wavelength of 391.5 nm are 43.199 mA, 44.99% and 10.334 mW, respectively.

Vanadium-based Ohmic contacts to n-AlGaN in the entire alloy composition

NASA Astrophysics Data System (ADS)

France, Ryan; Xu, Tao; Chen, Papo; Chandrasekaran, R.; Moustakas, T. D.

2007-02-01

The authors report on the formation and evaluation of V-based Ohmic contacts to n-AlGaN films in the entire alloy composition. The films were produced by plasma assisted molecular beam epitaxy and doped n-type with Si. The conductivity of the films was determined to vary from 103to10-2(Ωcm )-1 as the AlN mole fraction increases from 0% to 100%. Ohmic contacts were formed by e-beam evaporation of V(15nm )/Al(80nm)/V(20nm)/Au(100nm). These contacts were rapid thermal annealed in N2 for 30s at various temperatures. The optimum annealing temperature for this contact scheme to n-GaN is about 650°C and increases monotonically to about 1000°C for 95%-100% AlN mole fraction. The specific contact resistivity was found to be about 10-6Ωcm2 for all films up to 70% AlN mole fraction and then increases to 0.1-1Ωcm2 for films from 95%-100% AlN mole fraction. These results were accounted for by hypothesizing that vanadium, upon annealing, interacts with the nitride film and forms vanadium nitride, which is consistent with reports that it is a metal with low work function.

Synthesis, microstructure and dielectric properties of zirconium doped barium titanate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Rohtash; School of Physical Sciences, Jawaharlal Nehru University, New Delhi; Asokan, K.

2016-05-23

We report on synthesis, microstructural and relaxor ferroelectric properties of Zirconium(Zr) doped Barium Titanate (BT) samples with general formula Ba(Ti{sub 1-x}Zr{sub x})O{sub 3} (x=0.20, 0.35). These lead-free ceramics were prepared by solid state reaction route. The phase transition behavior and temperature dependent dielectric properties and composition dependent ferroelectric properties were investigated. XRD analysis at room temperature confirms phase purity of the samples. SEM observations revealed retarded grain growth with increasing Zr mole fraction. Dielectric properties of BZT ceramics is influenced significantly by small addition of Zr mole fraction. With increasing Zr mole fraction, dielectric constant decreases while FWHM and frequencymore » dispersion increases. Polarization vs electric field hysteresis measurements reveal ferroelectric relaxor phase at room temperature. The advantages of such substitution maneuvering towards optimizing ferroelectric properties of BaTiO{sub 3} are discussed.« less

Determination of ethane, pentane and isoprene in exhaled air--effects of breath-holding, flow rate and purified air.

PubMed

Lärstad, M A E; Torén, K; Bake, B; Olin, A-C

2007-01-01

Exhaled ethane, pentane and isoprene have been proposed as biomarkers of oxidative stress. The objectives were to explore whether ethane, pentane and isoprene are produced within the airways and to explore the effect of different sampling parameters on analyte concentrations. The flow dependency of the analyte concentrations, the concentrations in dead-space and alveolar air after breath-holding and the influence of inhaling purified air on analyte concentrations were investigated. The analytical method involved thermal desorption from sorbent tubes and gas chromatography. The studied group comprised 13 subjects with clinically stable asthma and 14 healthy controls. Ethane concentrations decreased slightly, but significantly, at higher flow rates in subjects with asthma (P = 0.0063) but not in healthy controls. Pentane levels were increased at higher flow rates both in healthy and asthmatic subjects (P = 0.022 and 0.0063 respectively). Isoprene levels were increased at higher flow rates, but only significantly in healthy subjects (P = 0.0034). After breath-holding, no significant changes in ethane levels were observed. Pentane and isoprene levels increased significantly after 20 s of breath-holding. Inhalation of purified air before exhalation resulted in a substantial decrease in ethane levels, a moderate decrease in pentane levels and an increase in isoprene levels. The major fractions of exhaled ethane, pentane and isoprene seem to be of systemic origin. There was, however, a tendency for ethane to be flow rate dependent in asthmatic subjects, although to a very limited extent, suggesting that small amounts of ethane may be formed in the airways.

Geochemical mole-balance modeling with uncertain data

USGS Publications Warehouse

Parkhurst, David L.

1997-01-01

Geochemical mole-balance models are sets of chemical reactions that quantitatively account for changes in the chemical and isotopic composition of water along a flow path. A revised mole-balance formulation that includes an uncertainty term for each chemical and isotopic datum is derived. The revised formulation is comprised of mole-balance equations for each element or element redox state, alkalinity, electrons, solvent water, and each isotope; a charge-balance equation and an equation that relates the uncertainty terms for pH, alkalinity, and total dissolved inorganic carbon for each aqueous solution; inequality constraints on the size of the uncertainty terms; and inequality constraints on the sign of the mole transfer of reactants. The equations and inequality constraints are solved by a modification of the simplex algorithm combined with an exhaustive search for unique combinations of aqueous solutions and reactants for which the equations and inequality constraints can be solved and the uncertainty terms minimized. Additional algorithms find only the simplest mole-balance models and determine the ranges of mixing fractions for each solution and mole transfers for each reactant that are consistent with specified limits on the uncertainty terms. The revised formulation produces simpler and more robust mole-balance models and allows the significance of mixing fractions and mole transfers to be evaluated. In an example from the central Oklahoma aquifer, inclusion of up to 5% uncertainty in the chemical data can reduce the number of reactants in mole-balance models from seven or more to as few as three, these being cation exchange, dolomite dissolution, and silica precipitation. In another example from the Madison aquifer, inclusion of the charge-balance constraint requires significant increases in the mole transfers of calcite, dolomite, and organic matter, which reduce the estimated maximum carbon 14 age of the sample by about 10,000 years, from 22,700 years to 12,600 years.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 themore » 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.« less

Pond Hockey on Whitmore Lacus: the Formation of Ponds and Ethane Ice Deposits Following Storm Events on Titan

NASA Astrophysics Data System (ADS)

Steckloff, Jordan; Soderblom, Jason M.

2017-10-01

Cassini ISS observations reveled regions, later identified as topographic low spots (Soderblom et al. 2014, DPS) on Saturn’s moon Titan become significantly darker (lower albedo) following storm events (Turtle et al. 2009, GRL; 2011, Science), suggesting pools of liquid hydrocarbon mixtures (predominantly methane-ethane-nitrogen). However, these dark ponds then significantly brighten (higher albedo relative to pre-storm albedo), before fading to their pre-storm albedos (Barnes et al. 2013 Planet. Sci; Soderblom et al. 2014, DPS). We interpret these data to be the result of ethane ice formation, which cools from evaporation of methane. The formation of ethane ices results from a unique sequence of thermophysical processes. Initially, the methane in the ternary mixture evaporates, cooling the pond. Nitrogen, dissolved primarily in the methane, exsolves, further cooling the liquid. However, because nitrogen is significantly more soluble in cooler methane-hydrocarbon mixtures, the relative concentration of nitrogen in the solution increases as it cools. This increased nitrogen fraction increases the density of the pond, as nitrogen is significantly more dense thane methane or ethane (pure ethane’s density is intermediate to that of methane and nitrogen). At around ~85 K the mixture is as dense as pure liquid ethane. Thus, further evaporative methane loss and cooling at the pond’s surface leads to a chemical stratification, with an increasingly ethane rich epilimnion (surface layer) overlying a methane rich hypolimnion (subsurface layer). Further evaporation of methane from the ethane-rich epilimnion drives its temperature and composition toward the methane-ethane-nitrogen liquidus curve, causing pure ethane ice to precipitate out of solution and settle to the bottom of the pool. This settling would obscure the ethane ice from Cassini VIMS and ISS, which would instead continue to appear as a dark pond on the surface. As the ethane precipitates out completely, a binary methane-nitrogen liquid mixture remains. Eventually, this residual liquid evaporates away, exposing the submerged ethane ice, which Cassini VIMS and ISS would observe as a dramatic brightening of the surface, consistent with observations.

The Component Slope Linear Model for Calculating Intensive Partial Molar Properties: Application to Waste Glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reynolds, Jacob G.

2013-01-11

Partial molar properties are the changes occurring when the fraction of one component is varied while the fractions of all other component mole fractions change proportionally. They have many practical and theoretical applications in chemical thermodynamics. Partial molar properties of chemical mixtures are difficult to measure because the component mole fractions must sum to one, so a change in fraction of one component must be offset with a change in one or more other components. Given that more than one component fraction is changing at a time, it is difficult to assign a change in measured response to a changemore » in a single component. In this study, the Component Slope Linear Model (CSLM), a model previously published in the statistics literature, is shown to have coefficients that correspond to the intensive partial molar properties. If a measured property is plotted against the mole fraction of a component while keeping the proportions of all other components constant, the slope at any given point on a graph of this curve is the partial molar property for that constituent. Actually plotting this graph has been used to determine partial molar properties for many years. The CSLM directly includes this slope in a model that predicts properties as a function of the component mole fractions. This model is demonstrated by applying it to the constant pressure heat capacity data from the NaOH-NaAl(OH{sub 4}H{sub 2}O system, a system that simplifies Hanford nuclear waste. The partial molar properties of H{sub 2}O, NaOH, and NaAl(OH){sub 4} are determined. The equivalence of the CSLM and the graphical method is verified by comparing results detennined by the two methods. The CSLM model has been previously used to predict the liquidus temperature of spinel crystals precipitated from Hanford waste glass. Those model coefficients are re-interpreted here as the partial molar spinel liquidus temperature of the glass components.« less

Injectant mole-fraction imaging in compressible mixing flows using planar laser-induced iodine fluorescence

NASA Technical Reports Server (NTRS)

Hartfield, Roy J., Jr.; Abbitt, John D., III; Mcdaniel, James C.

1989-01-01

A technique is described for imaging the injectant mole-fraction distribution in nonreacting compressible mixing flow fields. Planar fluorescence from iodine, seeded into air, is induced by a broadband argon-ion laser and collected using an intensified charge-injection-device array camera. The technique eliminates the thermodynamic dependence of the iodine fluorescence in the compressible flow field by taking the ratio of two images collected with identical thermodynamic flow conditions but different iodine seeding conditions.

Online recording of ethane traces in human breath via infrared laser spectroscopy.

PubMed

von Basum, Golo; Dahnke, Hannes; Halmer, Daniel; Hering, Peter; Mürtz, Manfred

2003-12-01

A method is described for rapidly measuring the ethane concentration in exhaled human breath. Ethane is considered a volatile marker for lipid peroxidation. The breath samples are analyzed in real time during single exhalations by means of infrared cavity leak-out spectroscopy. This is an ultrasensitive laser-based method for the analysis of trace gases on the sub-parts per billion level. We demonstrate that this technique is capable of online quantifying of ethane traces in exhaled human breath down to 500 parts per trillion with a time resolution of better than 800 ms. This study includes what we believe to be the first measured expirograms for trace fractions of ethane. The expirograms were recorded after a controlled inhalation exposure to 1 part per million of ethane. The normalized slope of the alveolar plateau was determined, which shows a linear increase over the first breathing cycles and ends in a mean value between 0.21 and 0.39 liter-1. The washout process was observed for a time period of 30 min and was modelled by a threefold exponential decay function, with decay times ranging from 12 to 24, 341 to 481, and 370 to 1770 s. Our analyzer provides a promising noninvasive tool for online monitoring of the oxidative stress status.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

The largest emissions sources of methane, a potent greenhouse gas and the primary component of natural gas, are the fossil fuel sector and microbial processes that occur in agricultural settings, landfills, and wetlands. Attribution of methane to these different source sectors has proven difficult, as evidenced by persistent disagreement between the annual emissions estimated from atmospheric observations (top-down) and from inventories (bottom-up). Given the rapidly changing natural gas infrastructure in North America, and the implications of associated rapid changes in emissions of methane for climate, it is crucial we improve our ability to quantify and understand current and future methane emissions. Here, we present evidence that continuous in-situ airborne observations of ethane, which is a tracer for fossil fuel emissions, are a new and useful tool for attribution of methane emissions to specific source sectors. Additionally, with these new airborne observations we present the first tightly constrained ethane emissions estimates of oil and gas production fields using the well-known mass balance method. The ratios of ethane-to-methane (C2H6:CH4) of specific methane emissions sources were studied over regions of high oil and gas production from the Barnett, TX and Bakken, ND shale plays, using continuous (1Hz frequency) airborne ethane measurements paired with simultaneous methane measurements. Despite the complex mixture of sources in the Barnett region, the methane emissions were well-characterized by distinct C2H6:CH4 relationships indicative of a high-ethane fossil fuel source (e.g., "wet" gas), a low-ethane fossil fuel source (e.g., "dry" gas), and an ethane-free, or microbial source. The defined set of C2H6:CH4 that characterized the emissions input to the atmosphere was used in conjunction with the total ethane and methane fluxes to place bounds on the fraction of methane emissions attributable to each source. Additionally, substantial ethane fluxes from the Barnett and Bakken regions were observed (1% to 10% of estimated national ethane emissions), and emissions of these magnitudes may significantly impact regional atmospheric chemistry and air quality by influencing production of tropospheric ozone.

Heat Effect of the Protonation of Glycine and the Enthalpies of Resolvation of Participating Chemical Species in Water-Dimethylsulfoxide Solvent Mixtures

NASA Astrophysics Data System (ADS)

Isaeva, V. A.; Sharnin, V. A.

2018-02-01

Enthalpies of the protonation of glycine in water‒dimethylsulfoxide (DMSO) mixed solvents are determined calorimetrically in the range of DMSO mole fractions of 0.0 to 0.9, at T = 298.15 K and an ionic strength μ = 0.3 (NaClO4). It is established that the protonation of glycine becomes more exothermic with an increasing mole fraction of DMSO, and the enthalpies of resolvation of glycine and glycinium ions in water‒DMSO solvent mixtures are calculated. It is shown that the small changes in the enthalpy of protonation observed at low mole fractions of DMSO are caused by the contributions from the solvation of proton and protonated glycine cancelling each other out. The enthalpy term of the Gibbs energy of the reaction leading to the formation of glycinium ion is estimated along with the enthalpy of resolvation of the reacting species in the water‒DMSO mixed solvent.

Empirical Correlations for the Solubility of Pressurant Gases in Cryogenic Propellants

NASA Technical Reports Server (NTRS)

Zimmerli, Gregory A.; Asipauskas, Marius; VanDresar, Neil T.

2010-01-01

We have analyzed data published by others reporting the solubility of helium in liquid hydrogen, oxygen, and methane, and of nitrogen in liquid oxygen, to develop empirical correlations for the mole fraction of these pressurant gases in the liquid phase as a function of temperature and pressure. The data, compiled and provided by NIST, are from a variety of sources and covers a large range of liquid temperatures and pressures. The correlations were developed to yield accurate estimates of the mole fraction of the pressurant gas in the cryogenic liquid at temperature and pressures of interest to the propulsion community, yet the correlations developed are applicable over a much wider range. The mole fraction solubility of helium in all these liquids is less than 0.3% at the temperatures and pressures used in propulsion systems. When nitrogen is used as a pressurant for liquid oxygen, substantial contamination can result, though the diffusion into the liquid is slow.

Ab initio study of the structural properties of acetonitrile-water mixtures

NASA Astrophysics Data System (ADS)

Chen, Jinfan; Sit, Patrick H.-L.

2015-08-01

Structural properties of acetonitrile and acetonitrile-water mixtures are studied using Density Functional Theory (DFT) and ab initio molecular dynamics simulations. Stable molecular clusters consisted of several water and acetonitrile molecules are identified to provide microscopic understanding of the interaction among water and acetonitrile molecules. Ab initio molecular dynamics simulations are performed to study the liquid structure at the finite temperature. Three mixing compositions in which the mole fraction of acetonitrile equals 0.109, 0.5 and 0.891 are studied. These compositions correspond to three distinct structural regimes. At the 0.109 and 0.891 mole fraction of acetonitrile, the majority species are mostly connected among themselves and the minority species are either isolated or forming small clusters without disrupting the network of the majority species. At the 0.5 mole fraction of acetonitrile, large water and acetonitrile clusters persist throughout the simulation, exhibiting the microheterogeneous behavior in acetonitrile-water mixtures in the mid-range mixing ratio.

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

PubMed

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

2015-07-07

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

Crystallization of aqueous inorganic-malonic acid particles: nucleation rates, dependence on size, and dependence on the ammonium-to-sulfate ratio.

PubMed

Parsons, Matthew T; Riffell, Jenna L; Bertram, Allan K

2006-07-06

Using an electrodynamic balance, we determined the relative humidity (RH) at which aqueous inorganic-malonic acid particles crystallized, with ammonium sulfate ((NH(4))(2)SO(4)), letovicite ((NH(4))(3)H(SO(4))(2)), or ammonium bisulfate (NH(4)HSO(4)) as the inorganic component. The results for (NH(4))(2)SO(4)-malonic acid particles and (NH(4))(3)H(SO(4))(2)-malonic acid particles show that malonic acid decreases the crystallization RH of the inorganic particles by less than 7% RH when the dry malonic acid mole fraction is less than 0.25. At a dry malonic acid mole fraction of about 0.5, the presence of malonic acid can decrease the crystallization RH of the inorganic particles by up to 35% RH. For the NH(4)HSO(4)-malonic acid particles, the presence of malonic acid does not significantly modify the crystallization RH of the inorganic particles for the entire range of dry malonic acid mole fractions studied; in all cases, either the particles did not crystallize or the crystallization RH was close to 0% RH. Size dependent measurements show that the crystallization RH of aqueous (NH(4))(2)SO(4) particles is not a strong function of particle volume. However, for aqueous (NH(4))(2)SO(4)-malonic acid particles (with dry malonic acid mole fraction = 0.36), the crystallization RH is a stronger function of particle volume, with the crystallization RH decreasing by 6 +/- 3% RH when the particle volume decreases by an order of magnitude. To our knowledge, these are the first size dependent measurements of the crystallization RH of atmospherically relevant inorganic-organic particles. These results suggest that for certain organic mole fractions the particle size and observation time need to be considered when extrapolating laboratory crystallization results to atmospheric scenarios. For aqueous (NH(4))(2)SO(4) particles, the homogeneous nucleation rate data are a strong function of RH, but for aqueous (NH(4))(2)SO(4)-malonic acid particles (with dry organic mole fraction = 0.36), the rates are not as dependent on RH. The homogeneous nucleation rates for aqueous (NH(4))(2)SO(4) particles were parametrized using classical nucleation theory, and from this analysis we determined that the interfacial surface tension between the crystalline ammonium sulfate critical nucleus and an aqueous ammonium sulfate solution is between 0.053 and 0.070 J m(-2).

Single Droplet Combustion of Decane in Microgravity: Experiments and Numerical Modeling

NASA Technical Reports Server (NTRS)

Dietrich, D. L.; Struk, P. M.; Ikegam, M.; Xu, G.

2004-01-01

This paper presents experimental data on single droplet combustion of decane in microgravity and compares the results to a numerical model. The primary independent experiment variables are the ambient pressure and oxygen mole fraction, pressure, droplet size (over a relatively small range) and ignition energy. The droplet history (D(sup 2) history) is non-linear with the burning rate constant increasing throughout the test. The average burning rate constant, consistent with classical theory, increased with increasing ambient oxygen mole fraction and was nearly independent of pressure, initial droplet size and ignition energy. The flame typically increased in size initially, and then decreased in size, in response to the shrinking droplet. The flame standoff increased linearly for the majority of the droplet lifetime. The flame surrounding the droplet extinguished at a finite droplet size at lower ambient pressures and an oxygen mole fraction of 0.15. The extinction droplet size increased with decreasing pressure. The model is transient and assumes spherical symmetry, constant thermo-physical properties (specific heat, thermal conductivity and species Lewis number) and single step chemistry. The model includes gas-phase radiative loss and a spherically symmetric, transient liquid phase. The model accurately predicts the droplet and flame histories of the experiments. Good agreement requires that the ignition in the experiment be reasonably approximated in the model and that the model accurately predict the pre-ignition vaporization of the droplet. The model does not accurately predict the dependence of extinction droplet diameter on pressure, a result of the simplified chemistry in the model. The transient flame behavior suggests the potential importance of fuel vapor accumulation. The model results, however, show that the fractional mass consumption rate of fuel in the flame relative to fuel vaporized is close to 1.0 for all but the lowest ambient oxygen mole fractions.

Dependence of Strain Distribution on In Content in InGaN/GaN Quantum Wires and Spherical Quantum Dots

NASA Astrophysics Data System (ADS)

Sharma, Akant Sagar; Dhar, S.

2018-02-01

The distribution of strain, developed in zero-dimensional quantum spherical dots and one-dimensional cylindrical quantum wires of an InGaN/GaN system is calculated as functions of radius of the structure and indium mole fraction. The strain shows strong dependence on indium mole fraction at small distances from the center. The strain associated with both the structures is found to decrease exponentially with the increase in dot or cylinder radius and increases linearly with indium content.

Near azeotropic mixture substitute for dichlorodifluoromethane

NASA Technical Reports Server (NTRS)

Jones, Jack A. (Inventor)

1998-01-01

A refrigerant and a process of formulating thereof that consists of a mixture of a first mole fraction of CH.sub.2 FCF.sub.3 and a second mole fraction of a component selected from the group consisting of a mixture of CHClFCF.sub.3 and CH.sub.3 CClF.sub.2 ; a mixture of CHF.sub.2 CH.sub.3 and CH.sub.3 CClF.sub.2 ; and a mixture of CHClFCF.sub.3, CH.sub.3 CClF.sub.2 and CHF.sub.2 CH.sub.3.

The component slope linear model for calculating intensive partial molar properties /application to waste glasses and aluminate solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reynolds, Jacob G.

2013-01-11

Partial molar properties are the changes occurring when the fraction of one component is varied while the fractions of all other component mole fractions change proportionally. They have many practical and theoretical applications in chemical thermodynamics. Partial molar properties of chemical mixtures are difficult to measure because the component mole fractions must sum to one, so a change in fraction of one component must be offset with a change in one or more other components. Given that more than one component fraction is changing at a time, it is difficult to assign a change in measured response to a changemore » in a single component. In this study, the Component Slope Linear Model (CSLM), a model previously published in the statistics literature, is shown to have coefficients that correspond to the intensive partial molar properties. If a measured property is plotted against the mole fraction of a component while keeping the proportions of all other components constant, the slope at any given point on a graph of this curve is the partial molar property for that constituent. Actually plotting this graph has been used to determine partial molar properties for many years. The CSLM directly includes this slope in a model that predicts properties as a function of the component mole fractions. This model is demonstrated by applying it to the constant pressure heat capacity data from the NaOH-NaAl(OH){sub 4}-H{sub 2}O system, a system that simplifies Hanford nuclear waste. The partial molar properties of H{sub 2}O, NaOH, and NaAl(OH){sub 4} are determined. The equivalence of the CSLM and the graphical method is verified by comparing results determined by the two methods. The CSLM model has been previously used to predict the liquidus temperature of spinel crystals precipitated from Hanford waste glass. Those model coefficients are re-interpreted here as the partial molar spinel liquidus temperature of the glass components.« less

The Component Slope Linear Model for Calculating Intensive Partial Molar Properties: Application to Waste Glasses and Aluminate Solutions - 13099

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reynolds, Jacob G.

2013-07-01

Partial molar properties are the changes occurring when the fraction of one component is varied while the fractions of all other component mole fractions change proportionally. They have many practical and theoretical applications in chemical thermodynamics. Partial molar properties of chemical mixtures are difficult to measure because the component mole fractions must sum to one, so a change in fraction of one component must be offset with a change in one or more other components. Given that more than one component fraction is changing at a time, it is difficult to assign a change in measured response to a changemore » in a single component. In this study, the Component Slope Linear Model (CSLM), a model previously published in the statistics literature, is shown to have coefficients that correspond to the intensive partial molar properties. If a measured property is plotted against the mole fraction of a component while keeping the proportions of all other components constant, the slope at any given point on a graph of this curve is the partial molar property for that constituent. Actually plotting this graph has been used to determine partial molar properties for many years. The CSLM directly includes this slope in a model that predicts properties as a function of the component mole fractions. This model is demonstrated by applying it to the constant pressure heat capacity data from the NaOHNaAl(OH){sub 4}-H{sub 2}O system, a system that simplifies Hanford nuclear waste. The partial molar properties of H{sub 2}O, NaOH, and NaAl(OH){sub 4} are determined. The equivalence of the CSLM and the graphical method is verified by comparing results determined by the two methods. The CSLM model has been previously used to predict the liquidus temperature of spinel crystals precipitated from Hanford waste glass. Those model coefficients are re-interpreted here as the partial molar spinel liquidus temperature of the glass components. (authors)« less

Local structure of dilute aqueous DMSO solutions, as seen from molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Idrissi, Abdenacer; Marekha, Bogdan A.; Barj, Mohammed; Miannay, François Alexandre; Takamuku, Toshiyuki; Raptis, Vasilios; Samios, Jannis; Jedlovszky, Pál

2017-06-01

The information about the structure of dimethyl sulfoxide (DMSO)-water mixtures at relatively low DMSO mole fractions is an important step in order to understand their cryoprotective properties as well as the solvation process of proteins and amino acids. Classical MD simulations, using the potential model combination that best reproduces the free energy of mixing of these compounds, are used to analyze the local structure of DMSO-water mixtures at DMSO mole fractions below 0.2. Significant changes in the local structure of DMSO are observed around the DMSO mole fraction of 0.1. The array of evidence, based on the cluster and the metric and topological parameters of the Voronoi polyhedra distributions, indicates that these changes are associated with the simultaneous increase of the number of DMSO-water and decrease of water-water hydrogen bonds with increasing DMSO concentration. The inversion between the dominance of these two types of H-bonds occurs around XDMSO = 0.1, above which the DMSO-DMSO interactions also start playing an important role. In other words, below the DMSO mole fraction of 0.1, DMSO molecules are mainly solvated by water molecules, while above it, their solvation shell consists of a mixture of water and DMSO. The trigonal, tetrahedral, and trigonal bipyramidal distributions of water shift to lower corresponding order parameter values indicating the loosening of these orientations. Adding DMSO does not affect the hydrogen bonding between a reference water molecule and its first neighbor hydrogen bonded water molecules, while it increases the bent hydrogen bond geometry involving the second ones. The close-packed local structure of the third, fourth, and fifth water neighbors also is reinforced. In accordance with previous theoretical and experimental data, the hydrogen bonding between water and the first, the second, and the third DMSO neighbors is stronger than that with its corresponding water neighbors. At a given DMSO mole fraction, the behavior of the intensity of the high orientational order parameter values indicates that water molecules are more ordered in the vicinity of the hydrophilic group while their structure is close-packed near the hydrophobic group of DMSO.

Liquidus Diagram of the Ba-Y-Cu-O System in the Vicinity of the Ba2YCu3O6+x Phase Field

PubMed Central

Wong-Ng, Winnie; Cook, Lawrence P.

1998-01-01

This paper describes the melting equilibria in the vicinity of the high Tc phase Ba2YCu3O6+x, including evidence for two Ba-Y-Cu-O immiscible liquids. Melting equilibria have been investigated in purified air using a combination of differential thermal analysis (DTA), thermogravimetric analysis (TGA), powder x-ray diffraction (XRD), MgO wick entrapment of liquid for analysis, scanning electron microscopy (SEM) coupled with energy dispersive x-ray analysis (EDS), and hydrogen reduction for determination of copper oxidation state. For relatively barium-rich compositions, it was necessary to prepare the starting materials under controlled atmosphere conditions using BaO. A liquidus diagram was derived from quantitative data for the melts involved in various melting reactions. In general the 1/2(Y2O3) contents of the melts participating in these equilibria were low (mole fraction <4 %). The primary phase field of Ba2YCu3O6+x occurs at a mole fraction of <2.0 % 1/2Y2O3 and lies very close along the BaO-CuOx edge, extending from a mole fraction of ≈43 % CuO to a mole fraction of ≈76 % CuO. It is divided by a liquid miscibility gap and extends on either side about this gap. The topological sequence of melting reactions associated with the liquidus is presented as a function of temperature. Implications for the growth of Ba2YCu3O6+x crystals are discussed. PMID:28009382

Atmospheric CO2 Record from In Situ Measurements at Amsterdam Island (1980-1995)

DOE Data Explorer

Gaudry, A. [Centre des Faibles Radioactivites, Laboratoire de Modelisation du Climat et de l'Environnement, Centre d'Etudes de Saclay, France; Kazan, V. [Centre des Faibles Radioactivites, Laboratoire de Modelisation du Climat et de l'Environnement, Centre d'Etudes de Saclay, France; Monfray, P. [Centre des Faibles Radioactivites, Laboratoire de Modelisation du Climat et de l'Environnement, Centre d'Etudes de Saclay, France

1996-09-01

Until 1993 air samples were collected continuously through an air intake located at the top of a tower, 9 m above ground and 65 m above mean sea level. Since 1994, the intake has been situated 20 m above ground and 76 m above mean sea level. The tower is located at the north-northwest end of the island on the edge of a 55 m cliff. The air is dried by means of a cryogenic water trap at -60°C. Until 1990, determinations of CO2 were made by using successively two Hartmann-Braun URAS 2T nondispersive infrared (NDIR) analyzers. Since 1991, CO2 determinations have been made using a Siemens ULTRAMAT 5F NDIR. Standard gases in use from October 1980 to December of 1984 were CO2-in-N2 mixtures certified by Scripps Institution of Oceanography (SIO). The N2 scale was corrected for the carrier gas effect to obtain the air scale (WMO mole fraction scale). In 1985, CO2-in-air mixtures expressed in the 1985 WMO mole fraction in air scale were introduced. In 1990, a new series of 12 primary standard gases were gravimetrically prepared, then linearly adjusted at the laboratory and checked several times (i.e., 1990, 1992, and 1993) through intercalibrations with DSIR in New Zealand and NOAA/CMDL, which both used the 1985 mole fraction scale. The agreement was always better than 0.1 ppm (Monfray et al. 1992). Since 1993, the 1993 mole fraction scale has been used thanks to a new series of 10 cylinders provided by SIO.

Mid-infrared laser-absorption diagnostic for vapor-phase measurements in an evaporating n-decane aerosol

NASA Astrophysics Data System (ADS)

Porter, J. M.; Jeffries, J. B.; Hanson, R. K.

2009-09-01

A novel three-wavelength mid-infrared laser-based absorption/extinction diagnostic has been developed for simultaneous measurement of temperature and vapor-phase mole fraction in an evaporating hydrocarbon fuel aerosol (vapor and liquid droplets). The measurement technique was demonstrated for an n-decane aerosol with D 50˜3 μ m in steady and shock-heated flows with a measurement bandwidth of 125 kHz. Laser wavelengths were selected from FTIR measurements of the C-H stretching band of vapor and liquid n-decane near 3.4 μm (3000 cm -1), and from modeled light scattering from droplets. Measurements were made for vapor mole fractions below 2.3 percent with errors less than 10 percent, and simultaneous temperature measurements over the range 300 K< T<900 K were made with errors less than 3 percent. The measurement technique is designed to provide accurate values of temperature and vapor mole fraction in evaporating polydispersed aerosols with small mean diameters ( D 50<10 μ m), where near-infrared laser-based scattering corrections are prone to error.

The interaction of triethyltin with components of animal tissues

PubMed Central

Rose, M. S.; Aldridge, W. N.

1968-01-01

1. The distribution of triethyl[113Sn]tin chloride in the rat, guinea pig and hamster is not uniform, the highest concentrations being in rat blood and the liver of all three species. 2. Subcellular fractionation of rat liver, brain and kidney shows that triethyltin binds to all fractions to different extents. In the liver of the rat and guinea pig the supernatant fraction contains the largest amount and the highest specific concentration; this triethyltin is bound to a non-diffusible component. 3. Rat haemoglobin is responsible for the binding of triethyltin in rat blood (2 moles of triethyltin/mole of haemoglobin). Haemoglobins from other species have much less affinity for triethyltin. 4. A variety of other proteins do not bind triethyltin. PMID:5637365

Development of TDLAS sensor for diagnostics of CO, H2O and soot concentrations in reactor core of pilot-scale gasifier

NASA Astrophysics Data System (ADS)

Sepman, A.; Ögren, Y.; Gullberg, M.; Wiinikka, H.

2016-02-01

This paper reports on the development of the tunable diode laser absorption spectroscopy sensor near 4350 cm-1 (2298 nm) for measurements of CO and H2O mole fractions and soot volume fraction under gasification conditions. Due to careful selection of the molecular transitions [CO ( υ″ = 0 → υ' = 2) R34-R36 and H2O at 4349.337 cm-1], a very weak (negligible) sensitivity of the measured species mole fractions to the temperature distribution inside the high-temperature zone (1000 K < T < 1900 K) of the gasification process is achieved. The selected transitions are covered by the tuning range of single diode laser. The CO and H2O concentrations measured in flat flames generally agree better than 10 % with the results of 1-D flame simulations. Calibration-free absorption measurements of studied species in the reactor core of atmospheric pilot-scale entrained-flow gasifier operated at 0.1 MW power are reported. Soot concentration is determined from the measured broadband transmittance. The estimated uncertainties in the reactor core CO and H2O measurements are 15 and 20 %, respectively. The reactor core average path CO mole fractions are in quantitative agreement with the µGC CO concentrations sampled at the gasifier output.

Simulations of normal and inverse laminar diffusion flames under oxygen enhancement and gravity variation

NASA Astrophysics Data System (ADS)

Bhatia, P.; Katta, V. R.; Krishnan, S. S.; Zheng, Y.; Sunderland, P. B.; Gore, J. P.

2012-10-01

Steady-state global chemistry calculations for 20 different flames were carried out using an axisymmetric Computational Fluid Dynamics (CFD) code. Computational results for 16 flames were compared with flame images obtained at the NASA Glenn Research Center. The experimental flame data for these 16 flames were taken from Sunderland et al. [4] which included normal and inverse diffusion flames of ethane with varying oxidiser compositions (21, 30, 50, 100% O2 mole fraction in N2) stabilised on a 5.5 mm diameter burner. The test conditions of this reference resulted in highly convective inverse diffusion flames (Froude numbers of the order of 10) and buoyant normal diffusion flames (Froude numbers ∼0.1). Additionally, six flames were simulated to study the effect of oxygen enhancement on normal diffusion flames. The enhancement in oxygen resulted in increased flame temperatures and the presence of gravity led to increased gas velocities. The effect of gravity-variation and oxygen enhancement on flame shape and size of normal diffusion flames was far more pronounced than for inverse diffusion flames. For normal-diffusion flames, their flame-lengths decreased (1 to 2 times) and flames-widths increased (2 to 3 times) when going from earth-gravity to microgravity, and flame height decreased by five times when going from air to a pure oxygen environment.

A high ozone episode in winter 2013 in the Uinta Basin oil and gas region characterized by aircraft measurements

NASA Astrophysics Data System (ADS)

Oltmans, S. J.; Karion, A.; Schnell, R. C.; Pétron, G.; Sweeney, C.; Wolter, S.; Neff, D.; Montzka, S. A.; Miller, B. R.; Helmig, D.; Johnson, B. J.; Hueber, J.

2014-08-01

During the winter of 2012-2013 atmospheric surface ozone mole fractions exceeded the US 8 h standard of 75 ppb on 39 days in the Uinta Basin of Utah. As part of the Uinta Basin Winter Ozone Study (UBWOS) aircraft flights were conducted throughout the basin with continuous measurements of ozone (O3), methane (CH4), carbon dioxide (CO2), carbon monoxide (CO), nitrogen dioxide (NO2), and discrete whole air flask samples for determination of ∼50 trace gases including a number of non-methane hydrocarbons (NMHCs). During the course of seven flights conducted between 31 January and 7 February 2013, coinciding with strong, multi-day temperature inversions, O3 levels gradually built up in the shallow boundary layer from ∼45 ppb to ∼140 ppb. Near-surface CH4 mole fractions increased during the episode from near background levels of ∼2 ppm to over 10 ppm. Based on elevated levels of CH4 across the basin and high correlations of CH4 with NMHCs from the discrete air samples, O3 precursor NMHCs were also inferred to be elevated throughout the basin. Discrete plumes of high NO2 were observed in the gas production region of the basin suggesting that gas processing plants and compressor facilities were important point sources of reactive nitrogen oxides (NOx). Vertical profiles obtained during the flights showed that the high O3 mole fractions (as well as other elevated constituents) were confined to a shallow layer from near the ground to 300-400 m above ground level (m a.g.l.) capped by a strong temperature inversion. The highest mole fractions of the measured constituents during the study period were in an isothermal cold layer that varied from ∼300 m depth on 4 February to ∼150 m on 5 February. A gradient layer with declining mole fractions with altitude extended above the isothermal layer to ∼1900 m a.s.l. (300-400 m a.g.l.) indicative of some mixing of air out of the boundary layer. O3 mole fractions continued to increase within the basin as the high O3 episode developed over the course of a week. CH4 mole fractions, on the other hand, leveled off after several days. On several flights, the aircraft sampled the plume of a coal-fired power plant (located east of the main gas field) flowing above the inversion layer. These measurements ruled out the effluents of the power plant as a significant source of NOx for O3 production beneath the temperature inversion in the basin. The presence of elevated O3 precursors within the basin and the rapid daytime production of O3 in the atmosphere beneath the temperature inversion both indicated that O3 was being produced from precursors emitted within the basin beneath the temperature inversion. Although observations show that horizontal winds in the surface layer were relatively light during the high ozone event, they were sufficient to disperse precursors up to 80 km from primary sources in the main gas field in the southeast quadrant to the balance of the Uinta Basin.

Is Solute Rotation in an Ionic Liquid Influenced by the Addition of Glucose?

PubMed

Maurya, Rajan; Naithani, Sudhanshu; Bandyopadhyay, Dibyendu; Choudhury, Niharendu; Dutt, G B

2017-12-07

Fluorescence anisotropy measurements and molecular dynamics (MD) simulations have been performed to understand the specific interactions of two structurally similar nondipolar solutes, 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and 1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP), with neat 1-butyl-3-methylimidazolium dicyanamide ([BMIM][N(CN) 2 ]) and also in the presence of glucose. It has been observed that the measured reorientation times of DMDPP in neat [BMIM][N(CN) 2 ] follow the predictions of the Stokes-Einstein-Debye hydrodynamic theory with slip boundary condition. Addition of glucose (0.075 and 0.15 mole fraction) has no bearing on the rotational diffusion of the solute apart from the viscosity related effects. In contrast, the reorientation times of DPP in neat [BMIM][N(CN) 2 ] obey stick boundary condition as the hydrogen bond donating solute experiences specific interactions with the dicyanamide anion. No influence of the additive can be noticed on the rotational diffusion of DPP at 0.075 mole fraction of glucose. However, at 0.15 mole fraction of glucose, the reorientation times of the solute at a given viscosity and temperature decrease by 15-40% compared to those obtained in the neat ionic liquid. MD simulations indicate that each DPP molecule hydrogen bonds with two dicyanamide anions in neat ionic liquid. The simulations also reveal that, at 0.15 mole fraction of glucose, the concentration of anions hydrogen bonded to glucose increases significantly; therefore, the percentage of solute molecules that can form hydrogen bonds with two dicyanamide anions decreases to 84, which leads to faster rotation of DPP.

Study of atmospheric CH4 mole fractions at three WMO/GAW stations in China

NASA Astrophysics Data System (ADS)

Fang, Shuang-Xi; Zhou, Ling-Xi; Masarie, Kenneth A.; Xu, Lin; Rella, Chris W.

2013-05-01

CH4 mole fractions were continuously measured from 2009 to 2011 at three WMO/GAW stations in China (Lin'an, LAN; Longfengshan, LFS; and Waliguan, WLG) using three Cavity Ring Down Spectroscopy instruments. LAN and LFS are GAW regional measurement stations. LAN is located in China's most economically developed region, and LFS is in a rice production area (planting area > 40,000 km2). WLG is a global measurement station in remote northwest China. At LAN, high methane mole fractions are observed in all seasons. Surface winds from the northeast enhance CH4 values, with a maximum increase of 32 ± 15 ppb in summer. The peak to peak amplitude of the seasonal cycle is 77 ± 35 ppb. At LFS, the diurnal cycle amplitude is approximately constant throughout the year except summer, when a value of 196 ± 65 ppb is observed. CH4 values at LFS reach their peak in July, which is different from seasonal variations typically observed in the northern hemisphere. CH4 mole fractions at WLG show both the smallest values and the lowest variability. Maximum values occur during summer, which is different from other northern hemisphere WMO/GAW global stations. The seasonal cycle amplitude is 17 ± 11 ppb. The linear growth rates at LAN, LFS, and WLG are 8.0 ± 1.2, 7.9 ± 0.9, and 9.4 ± 0.2 ppb yr-1, respectively, which are all larger than the global mean over the same 3 year period. Results from this study attempt to improve our basic understanding of observed atmospheric CH4 in China.

Cavity Enhanced Spectrometer performance assessment for greenhouse gas dry mole fraction measurement in humid air.

NASA Astrophysics Data System (ADS)

Laurent, Olivier; Yver Kwok, Camille; Guemri, Ali; Philippon, Carole; Rivier, Leonard; Ramonet, Michel

2017-04-01

Due to the high variability of the water vapor content in the atmosphere, the mole fraction of trace gas such as greenhouse gas (GHG) in the atmosphere is usually presented as mole fraction in dry air. In consequence, the first technology used for GHG measurement, gas chromatography or non-dispersive infra-red spectroscopy, required to dry the air sample prior to analysis at a dew point lower than -50°C. The emergence of new GHG analyzers using infrared Enhanced Cavity Spectroscopy which measure the water vapor content in the air sample, allows providing the dry mole fraction of GHG without any drying system upstream by applying appropriate correction of the water vapor effects (dilution, pressure broadening…). In the framework of ICOS, a European research infrastructure aiming to provide harmonized high precision data for advanced research on carbon cycle and GHG budgets over Europe, the Metrology Lab of the Atmosphere Thematic Centre (ATC), located at LSCE in France, is mainly dedicated to elaborating measurement protocols and evaluating performance of GHG analyzers. Among the different tests conducted to characterize the metrological performance, the Metrology Lab focuses on the water vapor correction to apply on the GHG measurement. Most of the analyzers tested at the Metrology Lab are based on Cavity Enhanced Spectroscopy measuring the ICOS mandatory species, CO2, CH4 and CO. This presentation presents the results of the performance assessment of the manufacturer built-in water vapor correction and the possible improvement. Thanks to the large number of instrument tested, the presentation provides a performance overview of the GHG analyzers deployed in the ICOS atmospheric station network. Finally the performance of the water vapor correction will be discussed in regard of the performance obtained by using a drying system.

Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C2H4F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)

NASA Astrophysics Data System (ADS)

Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C2H4F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)' providing data from direct measurement of pressure and mole fraction in vapor phase at variable mole fraction in liquid phase and constant temperature.

Study of Injection of Helium into Supersonic Air Flow Using Rayleigh Scattering

NASA Technical Reports Server (NTRS)

Seaholtz, Richard G.; Buggele, Alvin E.

1997-01-01

A study of the transverse injection of helium into a Mach 3 crossflow is presented. Filtered Rayleigh scattering is used to measure penetration and helium mole fraction in the mixing region. The method is based on planar molecular Rayleigh scattering using an injection-seeded, frequency-doubled ND:YAG pulsed laser and a cooled CCD camera. The scattered light is filtered with an iodine absorption cell to suppress stray laser light. Preliminary data are presented for helium mole fraction and penetration. Flow visualization images obtained with a shadowgraph and wall static pressure data in the vicinity of the injection are also presented.

Development of a Dual-Pump CARS System for Measurements in a Supersonic Combusting Free Jet

NASA Technical Reports Server (NTRS)

Magnotti, Gaetano; Cutler, Andrew D.; Danehy, Paul

2012-01-01

This work describes the development of a dual-pump CARS system for simultaneous measurements of temperature and absolute mole fraction of N2, O2 and H2 in a laboratory scale supersonic combusting free jet. Changes to the experimental set-up and the data analysis to improve the quality of the measurements in this turbulent, high-temperature reacting flow are described. The accuracy and precision of the instrument have been determined using data collected in a Hencken burner flame. For temperature above 800 K, errors in absolute mole fraction are within 1.5, 0.5, and 1% of the total composition for N2, O2 and H2, respectively. Estimated standard deviations based on 500 single shots are between 10 and 65 K for the temperature, between 0.5 and 1.7% of the total composition for O2, and between 1.5 and 3.4% for N2. The standard deviation of H2 is 10% of the average measured mole fraction. Results obtained in the jet with and without combustion are illustrated, and the capabilities and limitations of the dual-pump CARS instrument discussed.

Simultaneous CO concentration and temperature measurements using tunable diode laser absorption spectroscopy near 2.3 μm

NASA Astrophysics Data System (ADS)

Sane, Anup; Satija, Aman; Lucht, Robert P.; Gore, Jay P.

2014-10-01

Simultaneous measurements of carbon monoxide (CO) mole fraction and temperature using tunable diode laser absorption spectroscopy (TDLAS) near 2.3 μm are reported. The measurement method uses ro-vibrational transitions [R(27): v″ = 1 → v' = 3] and [R(6): v″ = 0 → v' = 2] in the first overtone band of CO near 2.3 μm (~4,278 cm-1). The measurements were performed in the post flame environment of fuel rich premixed ethylene-air flames with a N2 co-flow, stabilized over a water cooled McKenna burner. Non-uniformity in the temperature and CO mole fraction, along the absorption line of sight, in the mixing layer of the co-flow, was considered during data analysis. The TDLAS based temperature measurements (±80 K) were in good agreement with those obtained using N2 vibrational coherent anti-Stokes Raman scattering (±20 K), and the CO mole fraction measurements were in good agreement with the equilibrium values, for equivalence ratios lower than 1.8. A signal to noise ratio of 45 was achieved at an equivalence ratio of 1 for a CO concentration of 0.8 % at 1,854 K.

Direct numerical simulation of turbulent H2-O2 combustion using reduced chemistry

NASA Technical Reports Server (NTRS)

Montgomery, Christopher J.; Kosaly, George; Riley, James J.

1993-01-01

Results of direct numerical simulations of hydrogen-oxygen combustion using a partial-equilibrium chemistry scheme in constant density, decaying, isotropic turbulence are reported. The simulations qualitatively reproduce many features of experimental results, such as superequilibrium radical species mole fractions, with temperature and major species mole fractions closer to chemical equilibrium. It was also observed that the peak reaction rates occur in narrow zones where the stoichiometric surface intersects regions of high scalar dissipation, as might be expected for combustion conditions close to chemical equilibrium. Another finding was that high OH mole fraction correspond more closely to the stoichiometric surface than to areas of high reaction rate for conditions of the simulations. Simulation results were compared to predictions of the Conditional Moment Closure model. This model was found to give good results for all quantities of interest when the conditionally averaged scalar dissipation was used in the prediction. When the nonconditioned average dissipation was used, the predictions compared well to the simulations for most of the species and temperature, but not for the reaction rate. The comparison would be expected to improve for higher Reynolds number flows, however.

Microbial screening test for lignite degradation. Quarterly progress report No. 4, October-December 1985

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yen, T.F.

1985-01-01

Chemical oxidation of lignite by means of hydrogen peroxide - acetic acid was executed. Methanol fractionation of the oxidized product yielded 76.4% methanol solubles, 9.3% methanol insolubles and 11.2% CO/sub 2/. Biodegradation of the methanol fraction by soil bacteria was found to be positive as demonstrated by gel permeation chromatography (GPC). The shift of the average molecular weight throughout biodegradation was estimated to be from 310 g/mole, to 243 g/mole, zero day and four weeks respectively. Biodegradation of lignitic substrates, benzene - methanol fraction (A - 1), aqueous alkaline fraction (A - 2), clean lignite residue (A - 3), rawmore » lignite, and methanol soluble fraction after oxidation, by means of oil - field soil bacteria and Polyporus versicolor ATCC 12679 was attempted. All previous mentioned lignitic substrates yielded positive results for oil-field soil bacteria, while A - 2 fraction and raw lignite yielded positive results for P. versicolor. Unidentified fungi strains, N 1, L 1, and L 2 were also tested on lignitic substrates. Mild growth was observed in these cases.« less

Role of lattice distortion on diffuse phase transition temperatures in Bi0.5Na0.5TiO3-BaTiO3 [BNBTO] solid solutions

NASA Astrophysics Data System (ADS)

Pradhan, Lagen Kumar; Pandey, Rabichandra; Kumar, Sunil; Supriya, Sweety; Kar, Manoranjan

2018-04-01

Effect of lattice distortion on diffuse phase transition in BNBTO solid solutions near Morphotropic phase boundary (MPB) has been investigated. Solid solutions of (Bi0.5Na0.5)1-xBaxTiO3 (with mole % of x= 0.04, 0.05, 0.06, 0.07 and 0.08) were prepared by the planetary ball mill method in ethanol medium. Rietveld refinement technique with rhombohedral (R3c) and tetragonal (P4bm) crystal symmetry has been employed for structural as well as phase analysis of the solid solutions. Both rhombohedral and tetragonal lattice distortion (c/a) tends toward the pseudo-cubic crystal symmetry with the increase of mole fraction of Ba2+ near MPB (x= 6 mole %). Also, the average crystallite size and grain size decrease with increase of mole fraction of Ba2+ in BNT ceramic are due to larger ionic radius of Ba2+ and grain boundary pinning process in the solid solutions respectively. Additionally, depolarization temperature (Td) and maximum temperature (Tm) reduces due to the lattice distortion of both the phases in BNBTO solid solutions, which is explained extensively. Significant increase of dielectric constant has been observed near MPB composition (x=6%) in BNBTO solid solutions.

Change in the Gibbs energy of 18-crown-6 ether transfer from methanol to methanol-acetonitrile mixtures at 298 K

NASA Astrophysics Data System (ADS)

Kuz'mina, I. A.; Usacheva, T. R.; Kuz'mina, K. I.; Volkova, M. A.; Sharnin, V. A.

2015-01-01

The Gibbs energies of the transfer of 18-crown-6 ether from methanol to its mixtures with acetonitrile (χAN = 0.0-1.0 mole fraction) are determined by means of interphase distribution at 298 K. The effect the solvent composition has on the thermodynamic characteristics of the solvation of 18-crown-6 ether is analyzed. An increase in the content of acetonitrile in the mixed solvent enhances the solvation of crown ether due to changes in the energy of the solution. Resolvation of the macrocycle is assumed to be complete at acetonitrile concentrations higher than 0.6 mole fraction.

Viscosity Measurements and Correlation of the Squalane + CO2 Mixture

NASA Astrophysics Data System (ADS)

Tomida, D.; Kumagai, A.; Yokoyama, C.

2007-02-01

Experimental results for the viscosity of squalane + CO2 mixtures are reported. The viscosities were measured using a rolling ball viscometer. The experimental temperatures were 293.15, 313.15, 333.15, and 353.15 K, and pressures were 10.0, 15.0, and 20.0 MPa. The CO2 mole fraction of the mixtures varied from 0 to 0.417. The experimental uncertainties in viscosity were estimated to be within ±3.0%. The viscosity of the mixtures decreased with an increase in the CO2 mole fraction. The experimental data were compared with predictions from the Grunberg-Nissan and McAllister equations, which correlated the experimental data with maximum deviations of 10 and 8.7%, respectively.

Phase equilibrium of methane and nitrogen at low temperatures - Application to Titan

NASA Technical Reports Server (NTRS)

Kouvaris, Louis C.; Flasar, F. M.

1991-01-01

Since the vapor phase composition of Titan's methane-nitrogen lower atmosphere is uniquely determined as a function of the Gibbs phase rule, these data are presently computed via integration of the Gibbs-Duhem equation. The thermodynamic consistency of published measurements and calculations of the vapor phase composition is then examined, and the saturated mole fraction of gaseous methane is computed as a function of altitude up to the 700-mbar level. The mole fraction is found to lie approximately halfway between that computed from Raoult's law, for a gas in equilibrium with an ideal solution of liquid nitrogen and methane, and that for a gas in equilibrium with pure liquid methane.

Selective Adsorption and Selective Transport Diffusion of CO2-CH4 Binary Mixture in Coal Ultramicropores.

PubMed

Zhao, Yongliang; Feng, Yanhui; Zhang, Xinxin

2016-09-06

The adsorption and diffusion of the CO2-CH4 mixture in coal and the underlying mechanisms significantly affect the design and operation of any CO2-enhanced coal-bed methane recovery (CO2-ECBM) project. In this study, bituminous coal was fabricated based on the Wiser molecular model and its ultramicroporous parameters were evaluated; molecular simulations were established through Grand Canonical Monte Carlo (GCMC) and Molecular Dynamic (MD) methods to study the effects of temperature, pressure, and species bulk mole fraction on the adsorption isotherms, adsorption selectivity, three distinct diffusion coefficients, and diffusivity selectivity of the binary mixture in the coal ultramicropores. It turns out that the absolute adsorption amount of each species in the mixture decreases as temperature increases, but increases as its own bulk mole fraction increases. The self-, corrected, and transport diffusion coefficients of pure CO2 and pure CH4 all increase as temperature or/and their own bulk mole fractions increase. Compared to CH4, the adsorption and diffusion of CO2 are preferential in the coal ultramicropores. Adsorption selectivity and diffusivity selectivity were simultaneously employed to reveal that the optimal injection depth for CO2-ECBM is 800-1000 m at 308-323 K temperature and 8.0-10.0 MPa.

Deliquescence and crystallization of ammonium sulfate-glutaric acid and sodium chloride-glutaric acid particles

NASA Astrophysics Data System (ADS)

Pant, Atul; Fok, Abel; Parsons, Matthew T.; Mak, Jackson; Bertram, Allan K.

2004-06-01

In the following, we report the deliquescence relative humidities (DRH) and crystallization relative humidities (CRH) of mixed inorganic-organic particles, specifically ammonium sulfate-glutaric acid and sodium chloride-glutaric acid particles. Knowledge of the DRH and CRH of mixed inorganic-organic particles is crucial for predicting the role of aerosol particles in the atmosphere. Our DRH results are in good agreement with previous measurements, but our CRH results are significantly lower than some of the previous measurements reported in the literature. Our studies show that the DRH and CRH of ammonium sulfate and sodium chloride only decreased slightly when the mole fraction of the acid was less than 0.4. If other organics in the atmosphere behave in a similar manner, then the DRH and CRH of mixed inorganic-organic atmospheric particles will only be slightly less than the DRH and CRH of pure inorganic particles when the organic mole fraction is less than 0.4. Our results also show that if the particles contain a significant amount of organics (mole fraction > 0.5) the crystallization relative humidity decreases significantly and the particles are more likely to remain in the liquid state. Further work is needed to determine if other organics species of atmospheric importance have a similar effect.

Solvatochromism and preferential solvation of 1,4-dihydroxy-2,3-dimethyl-9,10-anthraquinone by UV-vis absorption and laser-induced fluorescence measurements

NASA Astrophysics Data System (ADS)

Sasirekha, V.; Vanelle, P.; Terme, T.; Ramakrishnan, V.

2008-12-01

Solvation characteristics of 1,4-dihydroxy-2,3-dimethyl-9,10-anthraquinone ( 1) in pure and binary solvent mixtures have been studied by UV-vis absorption spectroscopy and laser-induced fluorescence techniques. The binary solvent mixtures used as CCl 4 (tetrachloromethane)-DMF ( N, N-dimethylformamide), AN (acetonitrile)-DMSO (dimethylsulfoxide), CHCl 3 (chloroform)-DMSO, CHCl 3-MeOH (methanol), and MeOH-DMSO. The longest wavelength band of 1 has been studied in pure solvents as well as in binary solvent mixtures as a function of the bulk mole fraction. The Vis absorption band maxima show an unusual blue shift with increasing solvent polarity. The emission maxima of 1 show changes with varying the pure solvents and the composition in the case of binary solvent mixtures. Non-ideal solvation characteristics are observed in all binary solvent mixtures. It has been observed that the quantity [ ν-(Xν+Xν)] serves as a measure of the extent of preferential solvation, where ν˜ and X are the position of band maximum in wavenumbers (cm -1) and the bulk mole fraction values, respectively. The preferential solvation parameters local mole fraction ( X2L), solvation index ( δs2), and exchange constant ( k12) are evaluated.

CLASSICAL AREAS OF PHENOMENOLOGY: Optimization of a solar-blind and middle infrared two-colour photodetector using GaN-based bulk material and quantum wells

NASA Astrophysics Data System (ADS)

Cen, Long-Bin; Shen, Bo; Qin, Zhi-Xin; Zhang, Guo-Yi

2009-12-01

This paper calculates the wavelengths of the interband transitions as a function of the Al mole fraction of A1xGa1-xN bulk material. It is finds that when the Al mole fraction is between 0.456 and 0.639, the wavelengths correspond to the solar-blind (250 nm to 280 nm). The influence of the structure parameters of A1yGa1-yN/GaN quantum wells on the wavelength and absorption coefficient of intersubband transitions has been investigated by solving the Schrödinger and Poisson equations self-consistently. The A1 mole fraction of the A1yGa1-yN barrier changes from 0.30 to 0.46, meanwhile the width of the well changes from 2.9 nm to 2.2 nm, for maximal intersubband absorption in the window of the air (3 μm < λ < 5 μm). The absorption coefficient of the intersubband transition between the ground state and the first excited state decreases with the increase of the wavelength. The results are finally used to discuss the prospects of GaN-based bulk material and quantum wells for a solar-blind and middle infrared two-colour photodetector.

Microwave Determination of Water Mole Fraction in Humid Gas Mixtures

NASA Astrophysics Data System (ADS)

Cuccaro, R.; Gavioso, R. M.; Benedetto, G.; Madonna Ripa, D.; Fernicola, V.; Guianvarc'h, C.

2012-09-01

A small volume (65 cm3) gold-plated quasi-spherical microwave resonator has been used to measure the water vapor mole fraction x w of H2O/N2 and H2O/air mixtures. This experimental technique exploits the high precision achievable in the determination of the cavity microwave resonance frequencies and is particularly sensitive to the presence of small concentrations of water vapor as a result of the high polarizability of this substance. The mixtures were prepared using the INRIM standard humidity generator for frost-point temperatures T fp in the range between 241 K and 270 K and a commercial two-pressure humidity generator operated at a dew-point temperature between 272 K and 291 K. The experimental measurements compare favorably with the calculated molar fractions of the mixture supplied by the humidity generators, showing a normalized error lower than 0.8.

Production and functional characterisation of antioxidative hydrolysates from corn protein via enzymatic hydrolysis and ultrafiltration.

PubMed

Zhou, Kequan; Sun, Shi; Canning, Corene

2012-12-01

Corn protein was hydrolysed by three microbial proteases and further separated by sequential ultra-filtration to 12 hydrolysate fractions which were investigated for free radical scavenging capacity and chelating activity. The oxygen radical absorbance capacity (ORAC) of the hydrolysates varied significantly between 65.6 and 191.4μmoles Trolox equivalents (TE)/g dried weight with a small peptide fraction (NP-F3) produced by neutral protease (NP) possessing the highest antioxidant activity. The 1,1-diphenyl-2-picrylhydrazyl radical (DPPH()) scavenging activities of the hydrolysate fractions also varied significantly between 18.4 and 38.7μmoles TE/g. Two fractions (AP-F2 and AP-F3) produced by alkaline protease (AP) showed the strongest activity. However, no significant difference was detected on the chelating activity of the fractions. NP-F3, AP-F2, and AP-F3 were incorporated into ground beef to determine their effects on lipid oxidation during 15-day storage period. NP-F3 was the only fraction that inhibited lipid oxidation at both 250 and 500μg/g levels by as much as 52.9%. Copyright © 2012 Elsevier Ltd. All rights reserved.

Size-selective separation of polydisperse gold nanoparticles in supercritical ethane.

PubMed

Williams, Dylan P; Satherley, John

2009-04-09

The aim of this study was to use supercritical ethane to selectively disperse alkanethiol-stabilized gold nanoparticles of one size from a polydisperse sample in order to recover a monodisperse fraction of the nanoparticles. A disperse sample of metal nanoparticles with diameters in the range of 1-5 nm was prepared using established techniques then further purified by Soxhlet extraction. The purified sample was subjected to supercritical ethane at a temperature of 318 K in the pressure range 50-276 bar. Particles were characterized by UV-vis absorption spectroscopy, TEM, and MALDI-TOF mass spectroscopy. The results show that with increasing pressure the dispersibility of the nanoparticles increases, this effect is most pronounced for smaller nanoparticles. At the highest pressure investigated a sample of the particles was effectively stripped of all the smaller particles leaving a monodisperse sample. The relationship between dispersibility and supercritical fluid density for two different size samples of alkanethiol-stabilized gold nanoparticles was considered using the Chrastil chemical equilibrium model.

Effects of reflux ratio and feed conditions for the purification of bioethanol in a continuous distillation column

NASA Astrophysics Data System (ADS)

Dasan, Y. K.; Abdullah, M. A.; Bhat, A. H.

2014-10-01

Continuous distillation column was used for the purification of bioethanol from fermentation of molasses using Saccharomyces cerevisia. Bioethanol produced was at 8.32% (v/v) level. The efficiency of continuous distillation process was evaluated based on reflux ratio, and feed condition. The lab results were validated using COFE simulation Software. The analyses showed that both reflux ratio and feed condition had significant effects on the distillation process. Stages increased from 1.79 to 2.26 as the reflux ratio was decreased from 90% to 45% and the saturated feed produced lower mole fraction of desired product. We concluded that the lower reflux ratio with cold feed condition was suitable for higher mole fraction of top product.

Near azeotropic mixture substitute

NASA Technical Reports Server (NTRS)

Jones, Jack A. (Inventor)

1996-01-01

The present invention comprises a refrigerant mixture consisting of a first mole fraction of 1,1,1,2-tetrafluoroethane (R134a) and a second mole fraction of a component selected from the group consisting of a mixture of CHClFCF.sub.3 (R124) and CH.sub.3 CClF.sub.2 (R142b); a mixture of CHF.sub.2 CH.sub.3 (R152a) and CHClFCF.sub.3 (R124); a mixture of CHF.sub.2 CH.sub.3 (R152a) and CH.sub.3 CClF.sub.2 (R142b); and a mixture of CHClFCF.sub.3 (R124), CH.sub.3 CClF.sub.2 (R142b) and CHF.sub.2 CH.sub.3 (R152a).

H2-rich interstellar grain mantles: An equilibrium description

NASA Technical Reports Server (NTRS)

Dissly, Richard W.; Allen, Mark; Anicich, Vincent G.

1994-01-01

Experiments simulating the codeposition of molecular hydrogen and water ice on interstellar grains demonstrate that amorphous water ice at 12 K can incorporate a substantial amount of H2, up to a mole ratio of H2/H2O = 0.53. We find that the physical behavior of approximately 80% of the hydrogen can be explained satisfactorily in terms of an equilibrium population, thermodynamically governed by a wide distribution of binding site energies. Such a description predicts that gas phase accretion could lead to mole fractions of H2 in interstellar grain mantles of nearly 0.3; for the probable conditions of WL5 in the rho Ophiuchi cloud, an H2 mole fraction of between 0.05 and 0.3 is predicted, in possible agreement with the observed abundance reported by Sandford, Allamandola, & Geballe. Accretion of gas phase H2 onto grain mantles, rather than photochemical production of H2 within the ice, could be a general explanation for frozen H2 in interstellar ices. We speculate on the implications of such a composition for grain mantle chemistry and physics.

Study of complex formation of 5,5'-(2 E, 2' E)-2,2'-(ethane-1,2-diylidene)bis(hydrazine-1-yl-2-ylidene)bis(4-amino-4H-1,2,4-triazole-3-thiol) (HYT) macrocyclic ligand with Cd2+ cation in non-aqueous solution by spectroscopic and conductometric methods

NASA Astrophysics Data System (ADS)

Mallaekeh, Hassan; Shams, Alireza; Shaker, Mohammad; Bahramzadeh, Ehsan; Arefi, Donya

2014-12-01

In this paper the complexation reaction of the 5,5'-(2 E,2' E)-2,2'-(ethane-1,2-diylidene)bis(hydrazine-1-yl-2-ylidene)bis(4-amino-4H-1,2,4-triazole-3-thiol) ligand (HYT) with Cd2+ education was studied in some binary mixtures of methanol (MeOH), n-propanol (PrOH) and dimethyl-formamide (DMF) at different temperatures using the conductometry and spectrophotometry. The stability constants of the complex was determined using a GENPLOT computer program. The conductance data and absorbance-mole ratio plots show that in all solvent systems, the stoichiometry of the complex formed between (HYT) and Cd2+ cation is 1: 1. The obtained results show that the stability of (HYT)-Cd complex is sensitive to the mixed solvents composition. The values of thermodynamic parameters (Δ G ∘, Δ H ∘, and Δ S ∘) for formation of (HYT)-Cd complex were obtained from temperature dependence of the stability constant using the van't Hoff plots. The results show that in most cases, the complex are enthalpy destabilized but entropy stabilized and the complex formation is affected by pH, time, temperature and the nature of the solvent.

Diode laser absorption measurement and analysis of HCN in atmospheric-pressure, fuel-rich premixed methane/air flames

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gersen, S.; Mokhov, A.V.; Levinsky, H.B.

Measurements of HCN in flat, fuel-rich premixed methane/air flames at atmospheric pressure are reported. Quartz-microprobe sampling followed by wavelength modulation absorption spectroscopy with second harmonic detection was used to obtain an overall measurement uncertainty of better than 20% for mole fractions HCN on the order of 10 ppm. The equivalence ratio, {phi}, was varied between 1.3 and 1.5, while the flame temperature was varied independently by changing the mass flux through the burner surface at constant equivalence ratio. Under the conditions of the experiments, the peak mole fractions vary little, in the range of 10-15 ppm. Increasing the flame temperaturemore » by increasing the mass flux had little influence on the peak mole fraction, but accelerated HCN burnout substantially. At high equivalence ratio and low flame temperature, HCN burnout is very slow: at {phi}=1.5, {proportional_to}10ppm HCN is still present 7 mm above the burner surface. Substantial quantitative disagreement is observed between the experimental profiles and those obtained from calculations using GRI-Mech 3.0, with the calculations generally overpredicting the results significantly. Changing the rates of key formation and consumption reactions for HCN can improve the agreement, but only by making unreasonable changes in these rates. Inclusion of reactions describing NCN formation and consumption in the calculations improves the agreement with the measurements considerably. (author)« less

H2O absorption spectroscopy for determination of temperature and H2O mole fraction in high-temperature particle synthesis systems.

PubMed

Torek, Paul V; Hall, David L; Miller, Tiffany A; Wooldridge, Margaret S

2002-04-20

Water absorption spectroscopy has been successfully demonstrated as a sensitive and accurate means for in situ determination of temperature and H2O mole fraction in silica (SiO2) particle-forming flames. Frequency modulation of near-infrared emission from a semiconductor diode laser was used to obtain multiple line-shape profiles of H2O rovibrational (v1 + v3) transitions in the 7170-7185-cm(-1) region. Temperature was determined by the relative peak height ratios, and XH2O was determined by use of the line-shape profiles. Measurements were made in the multiphase regions of silane/hydrogen/oxygen/ argon flames to verify the applicability of the diagnostic approach to combustion synthesis systems with high particle loadings. A range of equivalence ratios was studied (phi = 0.47 - 2.15). The results were compared with flames where no silane was present and with adiabatic equilibrium calculations. The spectroscopic results for temperature were in good agreement with thermocouple measurements, and the qualitative trends as a function of the equivalence ratio were in good agreement with the equilibrium predictions. The determinations for water mole fraction were in good agreement with theoretical predictions but were sensitive to the spectroscopic model parameters used to describe collisional broadening. Water absorption spectroscopy has substantial potential as a valuable and practical technology for both research and production combustion synthesis facilities.

Thermodynamic properties of model CdTe/CdSe mixtures

DOE PAGES

van Swol, Frank; Zhou, Xiaowang W.; Challa, Sivakumar R.; ...

2015-02-20

We report on the thermodynamic properties of binary compound mixtures of model groups II–VI semiconductors. We use the recently introduced Stillinger–Weber Hamiltonian to model binary mixtures of CdTe and CdSe. We use molecular dynamics simulations to calculate the volume and enthalpy of mixing as a function of mole fraction. The lattice parameter of the mixture closely follows Vegard's law: a linear relation. This implies that the excess volume is a cubic function of mole fraction. A connection is made with hard sphere models of mixed fcc and zincblende structures. We found that the potential energy exhibits a positive deviation frommore » ideal soluton behaviour; the excess enthalpy is nearly independent of temperatures studied (300 and 533 K) and is well described by a simple cubic function of the mole fraction. Using a regular solution approach (combining non-ideal behaviour for the enthalpy with ideal solution behaviour for the entropy of mixing), we arrive at the Gibbs free energy of the mixture. The Gibbs free energy results indicate that the CdTe and CdSe mixtures exhibit phase separation. The upper consolute temperature is found to be 335 K. Finally, we provide the surface energy as a function of composition. Moreover, it roughly follows ideal solution theory, but with a negative deviation (negative excess surface energy). This indicates that alloying increases the stability, even for nano-particles.« less

Estimating regional CO2 and CH4 fluxes using GOSAT XCO2 and XCH4 observations

NASA Astrophysics Data System (ADS)

Fraser, A. C.; Palmer, P. I.; Feng, L.; Parker, R.; Boesch, H.; Cogan, A. J.

2012-12-01

We infer regional monthly surface flux estimates for CO2 and CH4, June 2009-December 2010, from proxy dry-air column-averaged mole fractions of CO2 and CH4 from the Greenhouse gases Observing SATellite (GOSAT) using an ensemble Kalman Filter combined with the GEOS-Chem chemistry transport model. We compare these flux estimates with estimates inferred from in situ surface mole fraction measurements and from combining in situ and GOSAT measurements in order to quantify the added value of GOSAT data above the conventional surface measurement network. We find that the error reduction, a measure of how much the posterior fluxes are being informed by the assimilated data, at least doubles when GOSAT measurements are used versus the surface only inversions, with the exception of regions that are well covered by the surface network at the spatial and temporal resolution of our flux estimation calculation. We have incorporated a new online bias correction scheme to account for GOSAT biases. We report global and regional flux estimates inferred from GOSAT and/or in situ measurements. While the global posterior fluxes from GOSAT and in situ measurements agree, we find significant differences in the regional fluxes, particularly over the tropics. We evaluate the posterior fluxes by comparing them against independent surface mole fraction, column, and aircraft measurements using the GEOS-Chem model as an intermediary.

Coherent Anti-Stokes Raman Scattering (CARS) as a Probe for Supersonic Hydrogen-Fuel/Air Mixing

NASA Technical Reports Server (NTRS)

Danehy, P. M.; O'Byrne, S.; Cutler, A. D.; Rodriguez, C. G.

2003-01-01

The dual-pump coherent anti-Stokes Raman spectroscopy (CARS) method was used to measure temperature and the absolute mole fractions of N2, O2 and H2 in a supersonic non-reacting fuel-air mixing experiment. Experiments were conducted in NASA Langley Research Center s Direct Connect Supersonic Combustion Test Facility. Under normal operation of this facility, hydrogen and air burn to increase the enthalpy of the test gas and O2 is added to simulate air. This gas is expanded through a Mach 2 nozzle and into a combustor model where fuel is then injected, mixes and burns. In the present experiment the O2 of the test gas is replaced by N2. The lack of oxidizer inhibited combustion of the injected H2 fuel jet allowing the fuel/air mixing process to be studied. CARS measurements were performed 427 mm downstream of the nozzle exit and 260 mm downstream of the fuel injector. Maps were obtained of the mean temperature, as well as the N2, O2 and H2 mean mole fraction fields. A map of mean H2O vapor mole fraction was also inferred from these measurements. Correlations between different measured parameters and their fluctuations are presented. The CARS measurements are compared with a preliminary computational prediction of the flow.

[Gas chromatography with a Pulsed discharge helium ionization detector for measurement of molecular hydrogen(H2) in the atmosphere].

PubMed

Luan, Tian; Fang, Shuang-xi; Zhou, Ling-xi; Wang, Hong-yang; Zhang, Gen

2015-01-01

A high precision GC system with a pulsed discharge helium ionization detector was set up based on the commercial Agilent 7890A gas chromatography. The gas is identified by retention time and the concentration is calculated through the peak height. Detection limit of the system is about 1 x 10(-9) (mole fraction, the same as below). The standard deviation of 140 continuous injections with a standard cylinder( concentration is roughly 600 x 10(-9)) is better than 0.3 x 10(-9). Between 409.30 x 10(-9) and 867.74 x 10(-9) molecular hydrogen mole fractions and peak height have good linear response. By using two standards to quantify the air sample, the precision meets the background molecular hydrogen compatibility goal within the World Meteorological Organization/Global Atmosphere Watch (WMO/GAW) program. Atmospheric molecular hydrogen concentration at Guangzhou urban area was preliminarily measured by this method from January to November 2013. The results show that the atmospheric molecular hydrogen mole fraction varies from 450 x 10(-9) to 700 x 10(-9) during the observation period, with the lowest value at 14:00 (Beijing time, the same as below) and the peak value at 20:00. The seasonal variation of atmospheric hydrogen at Guangzhou area was similar with that of the same latitude stations in northern hemisphere.

Carbon isotope effect during abiogenic oxidation of methane

NASA Astrophysics Data System (ADS)

Kiyosu, Yasuhiro; Roy Krouse, H.

1989-11-01

The oxidation of methane during flow over CuO and Fe 2O 3 has been examined in the temperature range of 400-650°C. The reaction rate and carbon isotope fractionation are dependent upon the choice of oxide and temperature. The activation energy is lower for hematite (8.0 kcal mole -1) than for cupric oxide (16.6 kcal mole -1). The measured ratios of the isotopic rate constants α =k 12/k 13 were found to have temperature dependences given by: 10 3(α - 1) =2.93 × 10 6/T 2 + 8.11 (cupric oxide) 10 3(α - 1) =7.44 × 10 6/T 2 + 6.56 (hematite) Abiogenic oxidation of methane is probably a significant mechanism for fractionating carbon isotopes in nature.

Quantification of OH and HO2 radicals during the low-temperature oxidation of hydrocarbons by Fluorescence Assay by Gas Expansion technique

PubMed Central

Blocquet, Marion; Schoemaecker, Coralie; Amedro, Damien; Herbinet, Olivier; Battin-Leclerc, Frédérique; Fittschen, Christa

2013-01-01

•OH and •HO2 radicals are known to be the key species in the development of ignition. A direct measurement of these radicals under low-temperature oxidation conditions (T = 550–1,000 K) has been achieved by coupling a technique named fluorescence assay by gas expansion, an experimental technique designed for the quantification of these radicals in the free atmosphere, to a jet-stirred reactor, an experimental device designed for the study of low-temperature combustion chemistry. Calibration allows conversion of relative fluorescence signals to absolute mole fractions. Such radical mole fraction profiles will serve as a benchmark for testing chemical models developed to improve the understanding of combustion processes. PMID:24277836

Fire Suppression and Response

NASA Technical Reports Server (NTRS)

Ruff, Gary A.

2004-01-01

This report is concerned with the following topics regarding fire suppression:What is the relative effectiveness of candidate suppressants to extinguish a representative fire in reduced gravity, including high-O2 mole fraction, low -pressure environments? What are the relative advantages and disadvantages of physically acting and chemically-acting agents in spacecraft fire suppression? What are the O2 mole fraction and absolute pressure below which a fire cannot exist? What effect does gas-phase radiation play in the overall fire and post-fire environments? Are the candidate suppressants effective to extinguish fires on practical solid fuels? What is required to suppress non-flaming fires (smoldering and deep seated fires) in reduced gravity? How can idealized space experiment results be applied to a practical fire scenario? What is the optimal agent deployment strategy for space fire suppression?

CCQM-K90, formaldehyde in nitrogen, 2 μmol mol-1 Final report

NASA Astrophysics Data System (ADS)

Viallon, Joële; Flores, Edgar; Idrees, Faraz; Moussay, Philippe; Wielgosz, Robert Ian; Kim, D.; Kim, Y. D.; Lee, S.; Persijn, S.; Konopelko, L. A.; Kustikov, Y. A.; Malginov, A. V.; Chubchenko, I. K.; Klimov, A. Y.; Efremova, O. V.; Zhou, Z.; Possolo, A.; Shimosaka, T.; Brewer, P.; Macé, T.; Ferracci, Valerio; Brown, Richard J. C.; Aoki, Nobuyuki

2017-01-01

The CCQM-K90 comparison is designed to evaluate the level of comparability of national metrology institutes (NMI) or designated institutes (DI) measurement capabilities for formaldehyde in nitrogen at a nominal mole fraction of 2 μmol mol-1. The comparison was organised by the BIPM using a suite of gas mixtures prepared by a producer of specialty calibration gases. The BIPM assigned the formaldehyde mole fraction in the mixtures by comparison with primary mixtures generated dynamically by permeation coupled with continuous weighing in a magnetic suspension balance. The BIPM developed two dynamic sources of formaldehyde in nitrogen that provide two independent values of the formaldehyde mole fraction: the first one based on diffusion of trioxane followed by thermal conversion to formaldehyde, the second one based on permeation of formaldehyde from paraformaldehyde contained in a permeation tube. Two independent analytical methods, based on cavity ring down spectroscopy (CRDS) and Fourier transform infrared spectroscopy (FTIR) were used for the assignment procedure. Each participating institute was provided with one transfer standard and value assigned the formaldehyde mole fraction in the standard based on its own measurement capabilities. The stability of the formaldehyde mole fraction in transfer standards was deduced from repeated measurements performed at the BIPM before and after measurements performed at participating institutes. In addition, 5 control standards were kept at the BIPM for regular measurements during the course of the comparison. Temporal trends that approximately describe the linear decrease of the amount-of-substance fraction of formaldehyde in nitrogen in the transfer standards over time were estimated by two different mathematical treatments, the outcomes of which were proposed to participants. The two treatments also differed in the way measurement uncertainties arising from measurements performed at the BIPM were propagated to the uncertainty of the trend parameters, as well as how the dispersion of the dates when measurements were made by the participants was taken into account. Upon decision of the participants, the Key Comparison Reference Values were assigned by the BIPM using the largest uncertainty for measurements performed at the BIPM, linear regression without weight to calculate the trend parameters, and not taking into account the dispersion of dates for measurements made by the participant. Each transfer standard was assigned its own reference value and associated expanded uncertainty. An expression for the degree of equivalence between each participating institute and the KCRV was calculated from the comparison results and measurement uncertainties submitted by participating laboratories. Results of the alternative mathematical treatment are presented in annex of this report. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Dissolution thermodynamics and solubility of silymarin in PEG 400-water mixtures at different temperatures.

PubMed

Shakeel, Faiyaz; Anwer, Md Khalid

2015-01-01

An isothermal method was used to measure the solubility of silymarin in binary polyethylene glycol 400 (PEG 400) + water co-solvent mixtures at temperatures T = 298.15-333.15 K and pressure p = 0.1 MPa. Apelblat and Yalkowsky models were used to correlate experimental solubility data. The mole fraction solubility of silymarin was found to increase with increasing the temperature and mass fraction of PEG 400 in co-solvent mixtures. The root mean square deviations were observed in the range of 0.48-5.32% and 1.50-9.65% for the Apelblat equation and Yalkowsky model, respectively. The highest and lowest mole fraction solubility of silymarin was observed in pure PEG 400 (0.243 at 298.15 K) and water (1.46 × 10(-5) at 298.15 K). Finally, thermodynamic parameters were determined by Van't Hoff and Krug analysis, which indicated an endothermic and spontaneous dissolution of silymarin in all co-solvent mixtures.

Monolithic poly(1,2-bis(p-vinylphenyl)ethane) capillary columns for simultaneous separation of low- and high-molecular-weight compounds.

PubMed

Greiderer, Andreas; Ligon, S Clark; Huck, Christian W; Bonn, Günther K

2009-08-01

Monolithic poly(1,2-bis(p-vinylphenyl)ethane (BVPE)) capillary columns were prepared by thermally initiated free radical polymerisation of 1,2-bis(p-vinylphenyl)ethane in the presence of inert diluents (porogens) and alpha,alpha'-azoisobutyronitrile (AIBN) as initiator. Polymerisations were accomplished in 200 microm ID fused silica capillaries at 65 degrees C and for 60 min. Mercury intrusion porosimetry measurements of the polymeric RP support showed a broad bimodal pore-size-distribution of mesopores and small macropores in the range of 5-400 nm and flow-channels in the mum range. N(2)-adsorption (BET) analysis resulted in a tremendous enhancement of surface area (101 m(2)/g) of BVPE stationary phases compared to typical organic monoliths (approximately 20 m(2)/g), indicating the presence of a considerable amount of mesopores. Consequently, the adequate proportion of both meso- and (small) macropores allowed the rapid and high-resolution separation of low-molecular-weight compounds as well as biomolecules on the same monolithic support. At the same time, the high fraction of flow-channels provided enhanced column permeability. The chromatographic performance of poly(1,2-bis(p-vinylphenyl)ethane) capillary columns for the separation of biomolecules (proteins, oligonucleotides) and small molecules (alkyl benzenes, phenols, phenons) are demonstrated in this article. Additionally, pressure drop versus flow rate measurements of novel poly(1,2-bis(p-vinylphenyl)ethane) capillary columns confirmed high mechanical robustness, low swelling in organic solvents and high permeability. Due to the simplicity of monolith fabrication, comprehensive studies of the retention and separation behaviour of monolithic BVPE columns resulted in high run-to-run and batch-to-batch reproducibilities. All these attributes prove the excellent applicability of monolithic poly(1,2-bis(p-vinylphenyl)ethane) capillary columns for micro-HPLC towards a huge range of analytes of different chemistries and molecular sizes.

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.

Chemicals and energy co-generation from direct hydrocarbons/oxygen proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Li, W. S.; Lu, D. S.; Luo, J. L.; Chuang, K. T.

A proton exchange membrane fuel cell for chemicals and energy co-generation was set up with hydrocarbons ethane, propane and butane as fuels, and the electrochemical performance of the cell was studied by using linear potential sweep, alternating current impedance and gas chromatography. The cell performance can be improved to a great extent by increasing the platinum load in the catalyst, by treating the membrane with phosphoric acid and by elevating temperature. The improvement of cell performance by the increase of platinum load is ascribed to the increase of reaction sites for hydrocarbon oxidation, that by phosphoric acid treatment to the increase of proton conductivity in Nafion membrane, and that by elevating temperature to the improvement in thermodynamic as well as kinetic aspects. Only a small fraction of the hydrocarbon is converted to carbon dioxide in this cell during its power generation. The current efficiency is 5% for the conversion of ethane to carbon dioxide in the ethane/oxygen fuel cell with 20% carbon-supported platinum as catalyst and phosphoric acid-treated membrane as proton exchange membrane at 0.2 V, 80 °C and ambient pressure. The reaction activity of hydrocarbons at the anode is in the order of propane, butane and ethane. The possible chemicals produced from the cell were hydrocarbons with more than six carbons, which are inactive at the anode under cell conditions.

40 CFR 60.5430 - What definitions apply to this subpart?

Code of Federal Regulations, 2013 CFR

2013-07-01

... natural gas liquids from field gas, the fractionation of the liquids into natural gas products, or other... gas unit means a unit used to cool natural gas to the point at which it is condensed into a liquid... pressurized natural gas. Natural gas liquids means the hydrocarbons, such as ethane, propane, butane, and...

Direct observation of surface ethyl to ethane interconversion upon C2H4 hydrogenation over Pt/Al2O3 catalyst by time-resolved FT-IR spectroscopy.

PubMed

Wasylenko, Walter; Frei, Heinz

2005-09-08

Time-resolved FT-IR spectra of ethylene hydrogenation over alumina-supported Pt catalyst were recorded at 25 ms resolution in the temperature range of 323-473 K using various H2 concentrations (1 atm total gas pressure). Surface ethyl species (2870 and 1200 cm(-1)) were detected at all temperatures along with the gas-phase ethane product (2954 and 2893 cm(-1)). The CH3CH2Pt growth was instantaneous on the time scale of 25 ms under all experimental conditions. At 323 K, the decay time of surface ethyl (122 +/- 10 ms) coincides with the rise time of ethane (144 +/- 14 ms). This establishes direct kinetic evidence for surface ethyl as the relevant reaction intermediate. Such a direct link between the temporal behavior of an unstable surface intermediate and the final product in a heterogeneous catalytic system has not been demonstrated before. A fraction (25%) of the asymptotic ethane growth at 323 K is prompt, indicating that there are surface ethyl species that react much faster than the majority of the CH3CH2Pt intermediates. The dispersive kinetics is attributed to the varying strength of interaction of the ethyl species with the Pt surface caused by heterogeneity of the surface environment. At 473 K, the majority of ethyl intermediates are hydrogenated prior to the recording of the first time slice (24 ms), and a correspondingly large prompt growth of ethane is observed. The yield and kinetics of the surface ethylidyne are in agreement with the known spectator nature of this species.

Preparation, Characterization and Photocatalytic Activity of Ag/TiO2 Nanoparticle Semiconductor Catalysts

NASA Astrophysics Data System (ADS)

Zhang, Yaoyao; Li, Mengyao; Guo, Yinli

2018-01-01

A series of Ag-doped TiO2 powder photocatalysts were prepared by the sol-gel method. The phase structure and morphology of the samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The persistent organic pollutant sodium pentachlorophenol ate (PCP-Na) was selected as the target pollutant, and the photocatalytic property of the material Ag/TiO2 was evaluated by PCP-Na degradation rate. It was found that the calcination at 450 °C was conducive to form the anatase structure with high catalytic activity, and the catalytic activity was higher when the silver mole fraction of Ag/TiO2 was 0.50%. The influence of Ag/TiO2 dosage, hydrogen peroxide volume, silver mole fraction and PCP-Na initial concentration was investigated by the single factor experiment.

Effect of ionic strength on the thermodynamic characteristics of complexation between Fe(III) ion and nicotinamide in water-ethanol and water-dimethyl sulfoxide mixtures

NASA Astrophysics Data System (ADS)

Gamov, G. A.; Grazhdan, K. V.; Gavrilova, M. A.; Dushina, S. V.; Sharnin, V. A.; Baranski, A.

2013-06-01

Solutions of iron(III) perchlorate in water, water-ethanol, and water-dimethyl sulfoxide solvents (x_{H_2 O} = 0.7 and 0.25 mole fractions) at ionic strength values I = 0.1, 0.25, and 0.5 are studied by IR spectroscopy. Analysis of the absorption bands of perchlorate ion shows that it does not participate in association processes. It is demonstrated that in the range of ionic strength values between 0 and 0.5 (NaClO4), it affects neither the results from potentiometric titration to determine the stability constants of the iron(III)-nicotinamide complex nor the thermal effects of complexation determined via direct calorimetry in a binary solvent containing 0.3 mole fractions (m.f.) of a non-aqueous component.

A design strategy for achieving more than 90% of the overlap integral of electron and hole wavefunctions in high-AlN-mole-fraction Al x Ga1- x N multiple quantum wells

NASA Astrophysics Data System (ADS)

Kojima, Kazunobu; Furusawa, Kentaro; Yamazaki, Yoshiki; Miyake, Hideto; Hiramatsu, Kazumasa; Chichibu, Shigefusa F.

2017-01-01

A strategy for increasing the square of an overlap integral of electron and hole wavefunctions (I 2) in polar c-plane Al x Ga1- x N multiple quantum wells (MQWs) is proposed. By applying quadratic modulation to AlN mole fractions along the c-axis, local bandgap energies and concentrations of immobile charges induced by polarization discontinuity are simultaneously controlled throughout the MQW structure, and optimized band profiles are eventually achieved. The I 2 value can be substantially increased to 94% when the well width (L w) is smaller than 4.0 nm. In addition, I 2 greater than 80% is predicted even for thick MQWs with L w of 10 nm.

Carbon Isotopic Compositions in Carbon Dioxide Measured By Micro-Laser Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Li, J.-J.; Li, R.-X.; Dong, H.; Wang, Zh.-H.; Zhao, B.-S.; Wang, N.; Cheng, J.-H.

2017-05-01

We have prepared a series of 12CO2/13CO2 binary mixtures as standard samples at room temperature. Using microlaser Raman spectroscopy, it was found that the relationship between the 12CO2 mole fractions and the peak area ratios of 12CO2/13CO2 in the Raman spectra of CO2 binary mixtures showed a polynomial correlation. The establishment of the experimental working curve paves the way for estimating the mole fractions of each individual fluid inclusion and determining 13C/12C and δ13C u sing micro-Raman spectroscopy. The Raman spectra of 12CO2 and 13CO2 showed a characteristic peak at 1348 cm-1 with an argon laser at 785 nm, which is perhaps due to the formation of dimers.

CARS Temperature and Species Concentration Measurements in a Supersonic Combustor with Normal Injection

NASA Technical Reports Server (NTRS)

Tedder, S. A.; OByrne, S.; Danehy, P. M.; Cutler, A. D.

2005-01-01

The dual-pump coherent anti-Stokes Raman spectroscopy (CARS) method was used to measure temperature and the absolute mole fractions of N2, O2 and H2 in a supersonic combustor. Experiments were conducted in the NASA Langley Direct-Connect Supersonic Combustion Test Facility. CARS measurements were performed at the facility nozzle exit and at three planes downstream of fuel injection. Processing the CARS measurements produced maps of the mean temperature, as well as quantitative N2 and O2 and qualitative H2 mean mole fraction fields at each plane. The CARS measurements were also used to compute correlations between fluctuations of the different simultaneously measured parameters. Comparisons were made between this 90 degree angle fuel injection case and a 30 degree fuel injection case previously presented at the 2004 Reno AIAA Meeting.

Fluctuating micro-heterogeneity in water-tert-butyl alcohol mixtures and lambda-type divergence of the mean cluster size with phase transition-like multiple anomalies

NASA Astrophysics Data System (ADS)

Banerjee, Saikat; Furtado, Jonathan; Bagchi, Biman

2014-05-01

Water-tert-butyl alcohol (TBA) binary mixture exhibits a large number of thermodynamic and dynamic anomalies. These anomalies are observed at surprisingly low TBA mole fraction, with xTBA ≈ 0.03-0.07. We demonstrate here that the origin of the anomalies lies in the local structural changes that occur due to self-aggregation of TBA molecules. We observe a percolation transition of the TBA molecules at xTBA ≈ 0.05. We note that "islands" of TBA clusters form even below this mole fraction, while a large spanning cluster emerges above that mole fraction. At this percolation threshold, we observe a lambda-type divergence in the fluctuation of the size of the largest TBA cluster, reminiscent of a critical point. Alongside, the structure of water is also perturbed, albeit weakly, by the aggregation of TBA molecules. There is a monotonic decrease in the tetrahedral order parameter of water, while the dipole moment correlation shows a weak nonlinearity. Interestingly, water molecules themselves exhibit a reverse percolation transition at higher TBA concentration, xTBA ≈ 0.45, where large spanning water clusters now break-up into small clusters. This is accompanied by significant divergence of the fluctuations in the size of largest water cluster. This second transition gives rise to another set of anomalies around. Both the percolation transitions can be regarded as manifestations of Janus effect at small molecular level.

Fluctuating micro-heterogeneity in water-tert-butyl alcohol mixtures and lambda-type divergence of the mean cluster size with phase transition-like multiple anomalies.

PubMed

Banerjee, Saikat; Furtado, Jonathan; Bagchi, Biman

2014-05-21

Water-tert-butyl alcohol (TBA) binary mixture exhibits a large number of thermodynamic and dynamic anomalies. These anomalies are observed at surprisingly low TBA mole fraction, with x(TBA) ≈ 0.03-0.07. We demonstrate here that the origin of the anomalies lies in the local structural changes that occur due to self-aggregation of TBA molecules. We observe a percolation transition of the TBA molecules at x(TBA) ≈ 0.05. We note that "islands" of TBA clusters form even below this mole fraction, while a large spanning cluster emerges above that mole fraction. At this percolation threshold, we observe a lambda-type divergence in the fluctuation of the size of the largest TBA cluster, reminiscent of a critical point. Alongside, the structure of water is also perturbed, albeit weakly, by the aggregation of TBA molecules. There is a monotonic decrease in the tetrahedral order parameter of water, while the dipole moment correlation shows a weak nonlinearity. Interestingly, water molecules themselves exhibit a reverse percolation transition at higher TBA concentration, x(TBA) ≈ 0.45, where large spanning water clusters now break-up into small clusters. This is accompanied by significant divergence of the fluctuations in the size of largest water cluster. This second transition gives rise to another set of anomalies around. Both the percolation transitions can be regarded as manifestations of Janus effect at small molecular level.

The variability of methane, nitrous oxide and sulfur hexafluoride in Northeast India

NASA Astrophysics Data System (ADS)

Ganesan, A. L.; Chatterjee, A.; Prinn, R. G.; Harth, C. M.; Salameh, P. K.; Manning, A. J.; Hall, B. D.; Mühle, J.; Meredith, L. K.; Weiss, R. F.; O'Doherty, S.; Young, D.

2013-06-01

High-frequency atmospheric measurements of methane (CH4), nitrous oxide (N2O) and sulfur hexafluoride (SF6) from Darjeeling, India are presented from December 2011 (CH4)/March 2012 (N2O and SF6) through February 2013. These measurements were made on a gas chromatograph equipped with a flame ionization detector and electron capture detector and were calibrated on the Tohoku University, the Scripps Institution of Oceanography (SIO)-98 and SIO-2005 scales for CH4, N2O and SF6, respectively. The observations show large variability and frequent pollution events in CH4 and N2O mole fractions, suggesting significant sources in the regions sampled by Darjeeling throughout the year. In contrast, SF6 mole fractions show little variability and only occasional pollution episodes, likely due to weak sources in the region. Simulations using the Numerical Atmospheric dispersion Modelling Environment (NAME) particle dispersion model suggest that many of the enhancements in the three gases result from the transport of pollutants from the densely populated Indo-Gangetic plains of India to Darjeeling. The meteorology of the region varies considerably throughout the year from Himalayan flows in the winter to the strong South Asian summer monsoon. The model is consistent in simulating a diurnal cycle in CH4 and N2O mole fractions that is present during the winter but absent in the summer and suggests that the signals measured at Darjeeling are dominated by large scale (~100 km) flows rather than local (<10 km) flows.

The variability of methane, nitrous oxide and sulfur hexafluoride in Northeast India

NASA Astrophysics Data System (ADS)

Ganesan, A. L.; Chatterjee, A.; Prinn, R. G.; Harth, C. M.; Salameh, P. K.; Manning, A. J.; Hall, B. D.; Mühle, J.; Meredith, L. K.; Weiss, R. F.; O'Doherty, S.; Young, D.

2013-11-01

High-frequency atmospheric measurements of methane (CH4), nitrous oxide (N2O) and sulfur hexafluoride (SF6) from Darjeeling, India are presented from December 2011 (CH4)/March 2012 (N2O and SF6) through February 2013. These measurements were made on a gas chromatograph equipped with a flame ionization detector and electron capture detector, and were calibrated on the Tohoku University, the Scripps Institution of Oceanography (SIO)-98 and SIO-2005 scales for CH4, N2O and SF6, respectively. The observations show large variability and frequent pollution events in CH4 and N2O mole fractions, suggesting significant sources in the regions sampled by Darjeeling throughout the year. By contrast, SF6 mole fractions show little variability and only occasional pollution episodes, likely due to weak sources in the region. Simulations using the Numerical Atmospheric dispersion Modelling Environment (NAME) particle dispersion model suggest that many of the enhancements in the three gases result from the transport of pollutants from the densely populated Indo-Gangetic Plains of India to Darjeeling. The meteorology of the region varies considerably throughout the year from Himalayan flows in the winter to the strong south Asian summer monsoon. The model is consistent in simulating a diurnal cycle in CH4 and N2O mole fractions that is present during the winter but absent in the summer and suggests that the signals measured at Darjeeling are dominated by large-scale (~100 km) flows rather than local (<10 km) flows.

The properties of residual water molecules in ionic liquids: a comparison between direct and inverse Kirkwood-Buff approaches.

PubMed

Kobayashi, Takeshi; Reid, Joshua E S J; Shimizu, Seishi; Fyta, Maria; Smiatek, Jens

2017-07-26

We study the properties of residual water molecules at different mole fractions in dialkylimidazolium based ionic liquids (ILs), namely 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM/BF 4 ) and 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM/BF 4 ) by means of atomistic molecular dynamics (MD) simulations. The corresponding Kirkwood-Buff (KB) integrals for the water-ion and ion-ion correlation behavior are calculated by a direct evaluation of the radial distribution functions. The outcomes are compared to the corresponding KB integrals derived by an inverse approach based on experimental data. Our results reveal a quantitative agreement between both approaches, which paves a way towards a more reliable comparison between simulation and experimental results. The simulation outcomes further highlight that water even at intermediate mole fractions has a negligible influence on the ion distribution in the solution. More detailed analysis on the local/bulk partition coefficients and the partial structure factors reveal that water molecules at low mole fractions mainly remain in the monomeric state. A non-linear increase of higher order water clusters can be found at larger water concentrations. For both ILs, a more pronounced water coordination around the cations when compared to the anions can be observed, which points out that the IL cations are mainly responsible for water pairing mechanisms. Our simulations thus provide detailed insights in the properties of dialkylimidazolium based ILs and their effects on water binding.

Process for enhancing the value of hydrocabonaceous natural recources

DOEpatents

Bunger, James W.; Cogswell, Donald E.

2005-04-05

A process for upgrading hydrocarbonaceous oil containing heteroatom-containing compounds where the hydrocarbonaceous oil is contacted with a solvent system that is a mixture of a major portion of a polar solvent having a dipole moment greater than about 1 debye and a minor portion of water to selectively separate the constituents of the carbonaceous oil into a heteroatom-depleted raffinate fraction and heteroatom-enriched extract fraction. The polar solvent and the water-in-solvent system are formulated at a ratio where the water is an antisolvent in an amount to inhibit solubility of heteroatom-containing compounds and the polar solvent in the raffinate, and to inhibit solubility of non-heteroatom-containing compounds in the extract. The ratio of the hydrocarbonaceous oil to the solvent system is such that a coefficient of separation is at least 50%. The coefficient of separation is the mole percent of heteroatom-containing compounds from the carbonaceous oil that are recovered in the extract fraction minus the mole percent of non-heteroatom-containing compounds from the carbonaceous oil that are recovered in the extract fraction. The solvent-free extract and the raffinate concentrates may be used directly or processed to make valuable petroleum, chemical or industrial products.

User's guide for vectorized code EQUIL for calculating equilibrium chemistry on Control Data STAR-100 computer

NASA Technical Reports Server (NTRS)

Kumar, A.; Graves, R. A., Jr.; Weilmuenster, K. J.

1980-01-01

A vectorized code, EQUIL, was developed for calculating the equilibrium chemistry of a reacting gas mixture on the Control Data STAR-100 computer. The code provides species mole fractions, mass fractions, and thermodynamic and transport properties of the mixture for given temperature, pressure, and elemental mass fractions. The code is set up for the electrons H, He, C, O, N system of elements. In all, 24 chemical species are included.

Measuring zinc in biological nanovesicles by multiple analytical approaches.

PubMed

Piacenza, Francesco; Biesemeier, Antje; Farina, Marco; Piva, Francesco; Jin, Xin; Pavoni, Eleonora; Nisi, Lorenzo; Cardelli, Maurizio; Costarelli, Laura; Giacconi, Robertina; Basso, Andrea; Pierpaoli, Elisa; Provinciali, Mauro; Hwang, James C M; Morini, Antonio; di Donato, Andrea; Malavolta, Marco

2018-07-01

Exosomes are nanovesicles known to mediate intercellular communication. Although it is established that zinc ions can act as intracellular signaling factors, the measurement of zinc in circulating nanovesicles has not yet been attempted. Providing evidence of the existence of this zinc fraction and methods for its measurement might be important to advance our knowledge of zinc status and its relevance in diseases. Exosomes from 0.5 ml of either fresh or frozen human plasma were isolated by differential centrifugation. A morphological and dimensional evaluation at the nanoscale level was performed by atomic force microscopy (AFM) and Transmission Electron Microscopy (TEM). Energy Dispersive X-Ray Microanalysis (EDX) revealed the elemental composition of exosomes and their respective total Zinc content on a quantitative basis. The zinc mole fraction (in at%) was correlated to the phosphorous mole fraction, which is indicative for exosomal membrane material. Both fresh (Zn/P 0.09 ± 0.01) and frozen exosomes (Zn/P 0.08 ± 0.02) had a significant zinc content, which increased up to 1.09 ± 0.12 for frozen exosomes when treated with increasing amounts of zinc (100-500 μM; each p < 0.05). Interestingly, after zinc addition, the Calcium mole fractions decreased accordingly suggesting a possible exchange by zinc. In order to estimate the intra-exosomal labile zinc content, an Imaging Flow Cytometry approach was developed by using the specific membrane permeable zinc-probe Fluozin-3AM. A labile zinc content of 0.59 ± 0.27 nM was calculated but it is likely that the measurement may be affected by purification and isolation conditions. This study suggests that circulating nano-vesicular-zinc can represent a newly discovered zinc fraction in the blood plasma whose functional and biological properties will have to be further investigated in future studies. Copyright © 2018 Elsevier GmbH. All rights reserved.

In Situ Carbon Dioxide and Methane Measurements from a Tower Network in Los Angeles

NASA Astrophysics Data System (ADS)

Verhulst, K. R.; Karion, A.; Kim, J.; Sloop, C.; Salameh, P.; Yadav, V.; Mueller, K.; Pongetti, T.; Newman, S.; Wong, C.; Hopkins, F. M.; Rao, P.; Miller, J. B.; Keeling, R. F.; Weiss, R. F.; Miller, C. E.; Duren, R. M.; Andrews, A. E.

2016-12-01

Urbanization has concentrated a significant fraction of the world's anthropogenic greenhouse gas (GHG) emissions into a relatively small fraction of the earth's land surface. Concern about rising GHG levels has motivated many nations to begin regulating and/or mitigating emissions, motivating the need for robust, consistent, traceable GHG observation methods in complex urban domains. The Los Angeles Megacity Carbon Project involves continuous and flask sampling of GHGs, trace gases, and isotopes at surface sites situated throughout the greater Los Angeles (LA) area. There are three signals of interest for utilizing urban GHG measurements in local or regional inverse modeling studies: (1) changes in the measured mole fraction at one location within a 24-hour period, (2) gradients in the measured mole fraction between locations within the surface measurement network, (3) local enhancements, or the difference between a measurement at one location and an inferred local "background" mole fraction. We report CO2 and CH4 measurements collected from eleven wavelength-scanned cavity ring-down analyzers (Picarro, Inc.). All sites use an internally consistent sampling protocol and calibration strategy. We show that the LA observation sites exhibit significant GHG enhancements relative to background, with evidence of systematic diurnal, weekly, and monthly variability. In Los Angeles, the "ideal" background sampling location could vary substantially depending on the time of year and local meteorology. Use of a single site for background determination may not be sufficient for reliable determination of GHG enhancements. We estimate the total uncertainty in the enhancement and examine how the choice of background influences the GHG enhancement signal. Uncertainty in GHG enhancements will ultimately translate into uncertainty in the fluxes derived from inverse modeling studies. In future work, the LA surface observations will be incorporated into an inverse-modeling framework to provide "top down," spatially-resolved GHG flux estimates, constrained by observations, for comparison with inventory-based ("bottom-up") estimates.

Predictions of Chemical Species via Diode Laser Spectroscopy

NASA Technical Reports Server (NTRS)

Chen, Shin-Juh; Silver, Joel A.; Dahm, Werner J. A.; Piltch, Nancy D.; Salzman, Jack (Technical Monitor)

2001-01-01

A technique to predict temperature and chemical species in flames from absorbance measurement of one chemical species is presented. Predicted temperature and mole fractions of methane and water agreed well with measured and published results.

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

High-efficiency thin-film GaAs solar cells

NASA Technical Reports Server (NTRS)

Stirn, R. J.

1979-01-01

GaAs chemical vapor deposition (CVD) growth on single-crystal GaAs substrates was investigated over a temperature range of 600 to 750 C, As/GA mole-ratio range of 3 to 11, and gas molefraction range 5 x 10 to the minus 9th power to 7x 10 to the minus 7th power for H2S doping. GasAs CVD growth on recrystallized Ge films was investigated for a temperature range of 550 to 700 C, an As/GA mole ratio of 5, and for various H2S mole fraction. The highest efficiency cell observed on these films with 2 mm dots was 4.8% (8% when AR-coated). Improvements in fill factor and opencircuit voltage by about 40% each are required in order to obtain efficiencies of 15% or greater.

CARS Temperature and Species Measurements For Air Vehicle Propulsion Systems

NASA Technical Reports Server (NTRS)

Danehy, Paul M.; Gord, James R.; Grisch, Frederic; Klimenko, Dmitry; Clauss, Walter

2005-01-01

The coherent anti-Stokes Raman spectroscopy (CARS) method has recently been used in the United States and Europe to probe several different types of propulsion systems for air vehicles. At NASA Langley Research Center in the United States, CARS has been used to simultaneously measure temperature and the mole fractions of N2, O2 and H2 in a supersonic combustor, representative of a scramjet engine. At Wright- Patterson Air Force Base in the United States, CARS has been used to simultaneously measure temperature and mole fractions of N2, O2 and CO2, in the exhaust stream of a liquid-fueled, gas-turbine combustor. At ONERA in France and the DLR in Germany researchers have used CARS to measure temperature and species concentrations in cryogenic LOX-H2 rocket combustion chambers. The primary aim of these measurements has been to provide detailed flowfield information for computational fluid dynamics (CFD) code validation.

Stability of nickel(II) glycylglycinate complexes in aqueous solutions of dimethylsulfoxide at 298.15 K

NASA Astrophysics Data System (ADS)

Naumov, V. V.; Isaeva, V. A.; Kovaleva, Yu. A.; Sharnin, V. A.

2013-07-01

Stability constants of nickel(II) glycylglycinate complexes in aqueous solutions of dimethylsulfoxide of variable composition (from 0.00 to 0.60 mole fractions DMSO) are determined according to potentiometry at 298.15 K and an ionic strength of 0.1 M (NaClO4). It is determined that with a rise in the concentration of an organic cosolvent in solution, the stability of nickel(II) complexes with glycylglycinate ion on the whole increases, but the log K stability = f( X DMSO) dependences are of a critical character with a maximum of 0.3 mole fractions DMSO. It is demonstrated that the rise in the stability of complexes is related to the destabilization of ligands in the low concentration range of the organic component, while the presence of a maximum is due to the different dynamics of the solvation contributions from reagents during changes in the Gibbs energy of reaction.

Germanium- and tellurium-doped GaAs for non-alloyed p-type and n-type ohmic contacts

NASA Astrophysics Data System (ADS)

Park, Joongseo; Barnes, Peter A.; Lovejoy, Michael L.

1995-08-01

Epitaxial ohmic contacts to GaAs were grown by liquid phase epitaxy. Heavily Ge-doped GaAs was grown to prepare ohmic contacts to p-GaAs while Te was used for the n-type contacts. Hall measurements were carried out for the samples grown from melts in which the mole fraction of Ge was varied between 1.55 atomic % and 52.2 atomic %, while the Te mole fractions varied between 0.03% and 0.5%. Specific contact resistance, rc, as low as rcp=2.9×10-6 ohm-cm 2 for Ge doping of p=(Na-Nd)=6.0×1019 holes/cm3 was measured for p-contacts and rcn=9.6×10-5 ohm-cm2 was measured for Te doping of n=(Nd-Na)=8.9×1018 electrons/cm3 for GaAs metallized with non-alloyed contacts of Ti/Al.

Origin of the sphere-to-rod transition in cationic micelles with aromatic counterions: specific ion hydration in the interfacial region matters.

PubMed

Geng, Yan; Romsted, Laurence S; Froehner, Sandro; Zanette, Dino; Magid, Linda J; Cuccovia, Iolanda M; Chaimovich, Hernan

2005-01-18

Sphere-to-rod transitions of cetyltrimethylammonium (CTA+) micelles with dichlorobenzoate counterions are remarkably substituent dependent. Simultaneous estimates of the interfacial molarities of H2O, MeOH, and Cl- and 2,6- and 3,5-dichlorobenzoate (2,6OBz and 3,5OBz) counterions were obtained by the chemical trapping method in mixed micelles of CTACl/CTA3,5OBz and CTACl/CTA2,6OBz without added salt. Increasing the CTA3,5OBz mole fraction produces a marked concurrent increase in interfacial 3,5OBz- and a decrease in interfacial H2O concentrations through the sphere-to-rod transition. No abrupt concentration changes are observed with increasing CTA2,6OBz mole fraction. Counterion-specific changes in the interfacial water concentration may be a major contributor to the delicate balance of forces governing micellar morphology.

The multispecies modeling of the premixed, laminar steady-state ozone flame

NASA Technical Reports Server (NTRS)

Heimerl, J. M.; Coffee, T. P.

1980-01-01

Species dependent kinetic, transport and thermodynamic coefficients were employed in a one dimensional model of the premixed, laminar, steady state ozone flame. Convenient expressions for these coefficients are reported. They are based on independent measurements, no arbitrary parameters are used. The governing equations are solved using a relaxation technique and the partial differential equation package, PDECOL. Species and temperature profiles and the burning velocities are found over the range of initial ozone mole fraction of 0.25 to 1.00. The computed burning velocities are no more than 30% greater than the measurements of Streng and Grosses. Comparison with the computed results of Warnatz shows agreement within + or - 12%, even though quite different expressions for some of the kinetic coefficients were used. These differences are most obvious in the atomic oxygen and temperature profiles at an initial ozone mole fraction of unity.

Theoretical evaluation of two dimensional electron gas characteristics of quaternary AlxInyGa1-x-yN/GaN hetero-junctions

NASA Astrophysics Data System (ADS)

Rahbardar Mojaver, Hassan; Manouchehri, Farzin; Valizadeh, Pouya

2016-04-01

The two dimensional electron gas (2DEG) characteristics of gated metal-face wurtzite AlInGaN/GaN hetero-junctions including positions of subband energy levels, fermi energy level, and the 2DEG concentration as functions of physical and compositional properties of the hetero-junction (i.e., barrier thickness and metal mole-fractions) are theoretically evaluated using the variational method. The calculated values of the 2DEG concentration are in good agreement with the sparsely available experimental data reported in the literature. According to our simulation results, a considerable shift in the positive direction of threshold voltage of AlInGaN/GaN hetero-junction field-effect transistors can be achieved by engineering both the spontaneous and the piezoelectric polarizations using a quaternary AlInGaN barrier-layer of appropriate mole-fractions.

Inorganic Halogen Oxidizer Research.

DTIC Science & Technology

1980-03-17

Synthesis, Novel Oxidizers, Solid-Propellant NF3 /F2 Gas Generators, Perfluoro- a- ammonium Salts, Perchlorates, Pentafluorooxouranate, Fluorosulfate...kcal mol I previously reported.’ by immersion into i constant-temperature 140.05 () circulating oil The fact that the small mole fraction ranges of...reactor higher tenperatures over almost t he entire nnole fraction () into the hot oil bath. the reactor was evacnaied. and the pressure range A mxpical

The cancer Warburg effect may be a testable example of the minimum entropy production rate principle

NASA Astrophysics Data System (ADS)

Marín, Dolores; Sabater, Bartolomé

2017-04-01

Cancer cells consume more glucose by glycolytic fermentation to lactate than by respiration, a characteristic known as the Warburg effect. In contrast with the 36 moles of ATP produced by respiration, fermentation produces two moles of ATP per mole of glucose consumed, which poses a puzzle with regard to the function of the Warburg effect. The production of free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) per mole linearly varies with the fraction (x) of glucose consumed by fermentation that is frequently estimated around 0.9. Hence, calculation shows that, in respect to pure respiration, the predominant fermentative metabolism decreases around 10% the production of entropy per mole of glucose consumed in cancer cells. We hypothesize that increased fermentation could allow cancer cells to accomplish the Prigogine theorem of the trend to minimize the rate of production of entropy. According to the theorem, open cellular systems near the steady state could evolve to minimize the rates of entropy production that may be reached by modified replicating cells producing entropy at a low rate. Remarkably, at CO2 concentrations above 930 ppm, glucose respiration produces less entropy than fermentation, which suggests experimental tests to validate the hypothesis of minimization of the rate of entropy production through the Warburg effect.

The cancer Warburg effect may be a testable example of the minimum entropy production rate principle.

PubMed

Marín, Dolores; Sabater, Bartolomé

2017-04-28

Cancer cells consume more glucose by glycolytic fermentation to lactate than by respiration, a characteristic known as the Warburg effect. In contrast with the 36 moles of ATP produced by respiration, fermentation produces two moles of ATP per mole of glucose consumed, which poses a puzzle with regard to the function of the Warburg effect. The production of free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) per mole linearly varies with the fraction (x) of glucose consumed by fermentation that is frequently estimated around 0.9. Hence, calculation shows that, in respect to pure respiration, the predominant fermentative metabolism decreases around 10% the production of entropy per mole of glucose consumed in cancer cells. We hypothesize that increased fermentation could allow cancer cells to accomplish the Prigogine theorem of the trend to minimize the rate of production of entropy. According to the theorem, open cellular systems near the steady state could evolve to minimize the rates of entropy production that may be reached by modified replicating cells producing entropy at a low rate. Remarkably, at CO 2 concentrations above 930 ppm, glucose respiration produces less entropy than fermentation, which suggests experimental tests to validate the hypothesis of minimization of the rate of entropy production through the Warburg effect.

Combining two complementary micrometeorological methods to measure CH4 and N2O fluxes over pasture

NASA Astrophysics Data System (ADS)

Laubach, J.; Barthel, M.; Fraser, A.; Hunt, J. E.; Griffith, D. W. T.

2015-09-01

New Zealand's largest industrial sector is pastoral agriculture, giving rise to a large fraction of the country's emissions of methane (CH4) and nitrous oxide (N2O). We designed a system to continuously measure CH4 and N2O fluxes at the field scale on two adjacent pastures that differed with respect to management. At the core of this system was a closed-cell Fourier-transform infrared spectrometer (FTIR), measuring the mole fractions of CH4, N2O and carbon dioxide (CO2) at two heights at each site. In parallel, CO2 fluxes were measured using eddy-covariance instrumentation. We applied two different micrometeorological ratio methods to infer the CH4 and N2O fluxes from their respective mole fractions and the CO2 fluxes. The first is a variant of the flux-gradient method, where it is assumed that the turbulent diffusivities of CH4 and N2O equal that of CO2. This method was reliable when the CO2 mole-fraction difference between heights was at least 4 times greater than the FTIR's resolution of differences. For the second method, the temporal increases of mole fractions in the stable nocturnal boundary layer, which are correlated for concurrently-emitted gases, are used to infer the unknown fluxes of CH4 and N2O from the known flux of CO2. This method was sensitive to "contamination" from trace gas sources other than the pasture of interest and therefore required careful filtering. With both methods combined, estimates of mean daily CH4 and N2O fluxes were obtained for 60 % of days at one site and 77 % at the other. Both methods indicated both sites as net sources of CH4 and N2O. Mean emission rates for one year at the unfertilised, winter-grazed site were 8.2 (± 0.91) nmol CH4 m-2 s-1 and 0.40 (± 0.018) nmol N2O m-2 s-1. During the same year, mean emission rates at the irrigated, fertilised and rotationally-grazed site were 7.0 (± 0.89) nmol CH4 m-2 s-1 and 0.57 (± 0.019) nmol N2O m-2 s-1. At this site, the N2O emissions amounted to 1.19 (± 0.15) % of the nitrogen inputs from animal excreta and fertiliser application.

Combining two complementary micrometeorological methods to measure CH4 and N2O fluxes over pasture

NASA Astrophysics Data System (ADS)

Laubach, Johannes; Barthel, Matti; Fraser, Anitra; Hunt, John E.; Griffith, David W. T.

2016-03-01

New Zealand's largest industrial sector is pastoral agriculture, giving rise to a large fraction of the country's emissions of methane (CH4) and nitrous oxide (N2O). We designed a system to continuously measure CH4 and N2O fluxes at the field scale on two adjacent pastures that differed with respect to management. At the core of this system was a closed-cell Fourier transform infrared (FTIR) spectrometer, which measured the mole fractions of CH4, N2O and carbon dioxide (CO2) at two heights at each site. In parallel, CO2 fluxes were measured using eddy-covariance instrumentation. We applied two different micrometeorological ratio methods to infer the CH4 and N2O fluxes from their respective mole fractions and the CO2 fluxes. The first is a variant of the flux-gradient method, where it is assumed that the turbulent diffusivities of CH4 and N2O equal that of CO2. This method was reliable when the CO2 mole-fraction difference between heights was at least 4 times greater than the FTIR's resolution of differences. For the second method, the temporal increases of mole fractions in the stable nocturnal boundary layer, which are correlated for concurrently emitted gases, are used to infer the unknown fluxes of CH4 and N2O from the known flux of CO2. This method was sensitive to "contamination" from trace gas sources other than the pasture of interest and therefore required careful filtering. With both methods combined, estimates of mean daily CH4 and N2O fluxes were obtained for 56 % of days at one site and 73 % at the other. Both methods indicated both sites as net sources of CH4 and N2O. Mean emission rates for 1 year at the unfertilised, winter-grazed site were 8.9 (±0.79) nmol CH4 m-2 s-1 and 0.38 (±0.018) nmol N2O m-2 s-1. During the same year, mean emission rates at the irrigated, fertilised and rotationally grazed site were 8.9 (±0.79) nmol CH4 m-2 s-1 and 0.58 (±0.020) nmol N2O m-2 s-1. At this site, the N2O emissions amounted to 1.21 (±0.15) % of the nitrogen inputs from animal excreta and fertiliser application.

Theoretical and Computational Studies of Stability, Transition and Flow Control in High-Speed Flows

DTIC Science & Technology

2011-02-22

A. H. Nayfeh. Nonparallel stability of boundary layers with pressure gradients and suction. Technical Report AGARD - CP -224, 1977. [Squ33] H. B. Squire...only. µ = µr ( T Tr )3/2 Tr + Ts T + Ts , (2.13) 8 K = µcp Pr , (2.14) where µr = 1.7894 × 10−5 Ns/m2, Tr = 288.0 K, Ts = 110.33 K, and cp is the...fraction of species s Cpf = frozen specific heat, cal/g-mole-K Cp ,s = specific heat at constant pressure of species s, cal/g-mole Dij = binary diffusion

Carbon and hydrogen isotopic reversals in deep basin gas: Evidence for limits to the stability of hydrocarbons

USGS Publications Warehouse

Burruss, R.C.; Laughrey, C.D.

2010-01-01

During studies of unconventional natural gas reservoirs of Silurian and Ordovician age in the northern Appalachian basin we observed complete reversal of the normal trend of carbon isotopic composition, such that ??13C methane (C1) >??13C ethane (C2) >??13C propane (C3). In addition, we have observed isotopic reversals in the ??2H in the deepest samples. Isotopic reversals cannot be explained by current models of hydrocarbon gas generation. Previous observations of partial isotopic reversals have been explained by mixing between gases from different sources and thermal maturities. We have constructed a model which, in addition to mixing, requires Rayleigh fractionation of C2 and C3 to cause enrichment in 13C and create reversals. In the deepest samples, the normal trend of increasing enrichment of 13C and 2H in methane with increasing depth reverses and 2H becomes depleted as 13C becomes enriched. We propose that the reactions that drive Rayleigh fractionation of C2 and C3 involve redox reactions with transition metals and water at late stages of catagenesis at temperatures on the order of 250-300??C. Published ab initio calculated fractionation factors for C-C bond breaking in ethane at these temperatures are consistent with our observations. The reversed trend in ??2H in methane appears to be caused by isotopic exchange with formation water at the same temperatures. Our interpretation that Rayleigh fractionation during redox reactions is causing isotopic reversals has important implications for natural gas resources in deeply buried sedimentary basins. ?? 2010.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vercher, E.; Pena, M.P.; Martinez-Andreu, A.

Isobaric experimental data of vapor-liquid equilibrium for the ethanol-water-strontium bromide system at different mole fractions of strontium bromide have been measured at 100.6 kPa. Data were correlated by Jaques and Furter's method. Thermodynamic consistency was checked by Herington's method with satisfactory results.

Isotope and methane dynamics above and below the Trade Wind Inversion at Ascension Island using UAVs

NASA Astrophysics Data System (ADS)

Brownlow, R.; Lowry, D.; Nisbet, E. G.; Fisher, R. E.; France, J.; Lanoisellé, M.; Thomas, R.; Richardson, T.; Greatwood, C.; Freer, J. E.; MacKenzie, A. R.

2015-12-01

Ascension Island (8oS, 14 oW) is a South Atlantic background site for atmospheric measurement. Royal Holloway, in collaboration with the UK Met Office, installed a Picarro 1301 CRDS in 2010 for continuous methane monitoring. This has high precision and accuracy, with a 6-gas calibration and target suite, to measure long term methane mole fraction. Regular flask sampling is also carried out for NOAA and RHUL (co-located), to measure δ13CCH4 isotopic trends.Ascension Island experiences near-constant SE Trade winds below the Trade Wind Inversion (TWI), with air from the remote S. Atlantic. In flask samples and in continuous monitoring at the Airhead location, atmospheric methane mole fraction has been increasing since 2007 whilst the δ13CCH4 isotope record has shifted to more depleted values. Above the normally well-defined TWI (1200 - 1800m altitude), variable tropical air masses pass over Ascension. This air last mixed with the boundary layer over Africa or South America. Field work undertaken in September 2014 and July 2015, in collaboration with U. Bristol and U. Birmingham, using UAVs (octocopters) collected samples with Tedlar bags or aluminium flasks from different heights above and below the TWI. The maximum altitude reached was 2700masl. Sample bags were immediately analysed on Ascension for CH4 mole fraction using the Picarro CRDS and subsequently analysed at RHUL for δ13CCH4 using continuous-flow gas chromatography/isotope-ratio mass spectrometry (CF-GC/IRMS). The TWI was clearly identified by an increase in CH4 mole fraction above the TWI. Back trajectory analysis was used to distinguish the origins of the air masses, with air above showing inputs from the land surfaces of equatorial and southern Africa, and from southern S. America.The campaigns have extended the envelope of altitudes accessed by micro-UAVs for atmospheric science, demonstrating their utility for probing the remote free troposphere and for penetrating the TWI. Sampling at Ascension is able to measure both the deep S. Atlantic air and also the air that has been mixed by convective systems in the equatorial and southern savannah tropics. Biomass burning plumes in southern hemisphere winter may also be accessible. Ascension is thus potentially a measurement site of global significance.

Real-time analysis of δ13C- and δD-CH4 in ambient air with laser spectroscopy: Method development and intercomparison

NASA Astrophysics Data System (ADS)

Harris, E. J.; Eyer, S.; Mohn, J.; Röckmann, T.; Popa, E.; Lowry, D.; Nisbet, E. G.; Fisher, R. E.; Brennwald, M. S.; Fischer, H.; Emmenegger, L.; Tuzson, B.; Zellweger, C.

2015-12-01

Methane (CH4) is the second most important anthropogenically emitted greenhouse gas after carbon dioxide (CO2). Its mole fraction has increased from around 722 ppb in pre-industrial times to 1824 ppb in 2013 and the anthropogenic fraction is estimated to be 60 % of the total emissions. A promising approach to improve the understanding of the CH4 budget is the use of isotopologues to distinguish between various CH4 source processes. In the presented study in situ and simultaneous measurement of the three most abundant isotopologues of methane using mid-infrared laser absorption spectroscopy is demonstrated. A field-deployable, autonomous platform is realized by coupling a compact quantum cascade laser absorption spectrometer (QCLAS) to a preconcentration unit, called TRace gas EXtractor (TREX). This unit enhances CH4 mole fractions by a factor of up to 500 above ambient levels and quantitatively separates interfering trace gases such as N2O and CO2. The analytical precision of the QCLAS isotope measurement on the preconcentrated (750 ppm, parts-per-million, mmole/mole) methane is 0.1‰ and 0.5 ‰ for δ13C- and δD-CH4 at 10 min averaging time. [1] Based on replicate measurements of compressed air during a two-week intercomparison campaign, the repeatability of the TREX-QCLAS was determined to be 0.19 ‰ and 1.9 ‰ for δ13C and δD-CH4, respectively. In this intercomparison campaign the new in situ technique is compared to IRMS based on glass flask and bag sampling and real time CH4 isotope analysis by two commercially available laser spectrometers (Figure). Both laser-based analyzers were limited to methane mole fraction and δ13C-CH4 analysis, and only one of them, a cavity ring down spectrometer, was capable to deliver meaningful data for the isotopic composition. After correcting for scale offsets, the average difference between TREX-QCLAS data and bag/flask sampling-IRMS values are within the extended WMO compatibility goals of 0.2 and 5 ‰ for δ13C- and δD-CH4, respectively. Thus, the intercomparison also reveals the need for reference air samples with accurately determined isotopic composition of CH4 to further improve the interlaboratory compatibility. [1] References: [1] S. Eyer et al. (2015) submitted to AMTD

Constraining N2O emissions since 1940 by firn air isotope measurements in both hemispheres

NASA Astrophysics Data System (ADS)

Prokopiou, Markella; Martinerie, Patricia; Sapart, Celia; Witrant, Emmanuel; Monteil, Guillaume; Ishijima, Kentaro; Kaiser, Jan; Levin, Ingeborg; Sowers, Todd; Blunier, Thomas; Etheridge, David; Dlugokencky, Ed; van de Wal, Roderik; Röckmann, Thomas

2017-04-01

N2O is currently the 3rd most important anthropogenic greenhouse gas in terms of radiative forcing and its atmospheric mole fraction is rising steadily. To quantify the growth rate and its causes, we performed a multi-site reconstruction of the atmospheric N2O mole fraction and isotopic composition using firn air data collected from Greenland and Antarctica in combination with a firn diffusion and densification model. The multi-site reconstruction showed that while the global mean N2O mole fraction increased from (290±1) nmol mol-1 in 1940 to (322±1) nmol mol-1 in 2008 the isotopic δ values of atmospheric N2O decreased by (- 2.2±0.2) ‰ for δ15Nav, (- 1.0±0.3) ‰ for δ18O, (- 1.3±0.6) ‰ for δ15Nα, and (- 2.8±0.6) ‰ for δ15Nβover the same period. The detailed temporal evolution of the mole fraction and isotopic composition derived from the firn air model was then used in a two-box atmospheric model (comprising a stratospheric and a tropospheric box) to infer changes in the isotopic source signature over time. The precise value of the source strength depends on the choice of the N2O lifetime, which we choose to be 123 a. Adopting this lifetime results in total average source isotopic signatures of (- 7.6±0.8) ‰ (vs. Air-N2) for δ15Nav, (32.2±0.2) ‰ (vs. VSMOW) for δ18O, (- 3.0±1.9) ‰ (vs. Air-N2) for δ15Nα, and (- 11.7±2.3) ‰ (vs. Air-N2) for δ15Nβ over the investigated period. δ15Navand δ15Nβ show some temporal variability while the other source isotopic signatures remain unchanged. The 15N site-preference (= δ15Nα - δ15Nβ) can be used to reveal further information on the source emission origins. Based on the changes in the isotopes we conclude that the main contribution to N2O changes in the atmosphere since 1940 is from soils, with agricultural soils being the principal anthropogenic component, which is in line with previous studies.

Constraining N2O emissions since 1940 using firn air isotope measurements in both hemispheres

NASA Astrophysics Data System (ADS)

Prokopiou, Markella; Martinerie, Patricia; Sapart, Célia J.; Witrant, Emmanuel; Monteil, Guillaume; Ishijima, Kentaro; Bernard, Sophie; Kaiser, Jan; Levin, Ingeborg; Blunier, Thomas; Etheridge, David; Dlugokencky, Ed; van de Wal, Roderik S. W.; Röckmann, Thomas

2017-04-01

N2O is currently the third most important anthropogenic greenhouse gas in terms of radiative forcing and its atmospheric mole fraction is rising steadily. To quantify the growth rate and its causes over the past decades, we performed a multi-site reconstruction of the atmospheric N2O mole fraction and isotopic composition using new and previously published firn air data collected from Greenland and Antarctica in combination with a firn diffusion and densification model. The multi-site reconstruction showed that while the global mean N2O mole fraction increased from (290 ± 1) nmol mol-1 in 1940 to (322 ± 1) nmol mol-1 in 2008, the isotopic composition of atmospheric N2O decreased by (-2.2 ± 0.2) ‰ for δ15Nav, (-1.0 ± 0.3) ‰ for δ18O, (-1.3 ± 0.6) ‰ for δ15Nα, and (-2.8 ± 0.6) ‰ for δ15Nβ over the same period. The detailed temporal evolution of the mole fraction and isotopic composition derived from the firn air model was then used in a two-box atmospheric model (comprising a stratospheric box and a tropospheric box) to infer changes in the isotopic source signature over time. The precise value of the source strength depends on the choice of the N2O lifetime, which we choose to fix at 123 years. The average isotopic composition over the investigated period is δ15Nav = (-7.6 ± 0.8) ‰ (vs. air-N2), δ18O = (32.2 ± 0.2) ‰ (vs. Vienna Standard Mean Ocean Water - VSMOW) for δ18O, δ15Nα = (-3.0 ± 1.9) ‰ and δ15Nβ = (-11.7 ± 2.3) ‰. δ15Nav, and δ15Nβ show some temporal variability, while for the other signatures the error bars of the reconstruction are too large to retrieve reliable temporal changes. Possible processes that may explain trends in 15N are discussed. The 15N site preference ( = δ15Nα - δ15Nβ) provides evidence of a shift in emissions from denitrification to nitrification, although the uncertainty envelopes are large.

Methane emissions from natural gas infrastructure and use in the urban region of Boston, Massachusetts.

PubMed

McKain, Kathryn; Down, Adrian; Raciti, Steve M; Budney, John; Hutyra, Lucy R; Floerchinger, Cody; Herndon, Scott C; Nehrkorn, Thomas; Zahniser, Mark S; Jackson, Robert B; Phillips, Nathan; Wofsy, Steven C

2015-02-17

Methane emissions from natural gas delivery and end use must be quantified to evaluate the environmental impacts of natural gas and to develop and assess the efficacy of emission reduction strategies. We report natural gas emission rates for 1 y in the urban region of Boston, using a comprehensive atmospheric measurement and modeling framework. Continuous methane observations from four stations are combined with a high-resolution transport model to quantify the regional average emission flux, 18.5 ± 3.7 (95% confidence interval) g CH4 ⋅ m(-2) ⋅ y(-1). Simultaneous observations of atmospheric ethane, compared with the ethane-to-methane ratio in the pipeline gas delivered to the region, demonstrate that natural gas accounted for ∼ 60-100% of methane emissions, depending on season. Using government statistics and geospatial data on natural gas use, we find the average fractional loss rate to the atmosphere from all downstream components of the natural gas system, including transmission, distribution, and end use, was 2.7 ± 0.6% in the Boston urban region, with little seasonal variability. This fraction is notably higher than the 1.1% implied by the most closely comparable emission inventory.

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

Hydrogen Bond Donor/Acceptor Cosolvent-Modified Choline Chloride-Based Deep Eutectic Solvents.

PubMed

Pandey, Ashish; Bhawna; Dhingra, Divya; Pandey, Siddharth

2017-04-27

Deep eutectic solvents (DESs) have emerged as nontoxic and inexpensive alternatives not only to the common organic solvents but to the ionic liquids as well. Some of the common and popular, and perhaps the most investigated, DESs are the ones comprising an ammonium salt and an appropriate hydrogen bond (HB) donor in a predetermined mole ratio. The formation of the DES is attributed to the H-bonding interaction(s) present between the salt and the HB donor. Consequently, addition of a predominantly HB donor or a predominantly HB acceptor cosolvent to such DESs may result in intriguing features and properties. We present investigation of two DESs constituted of salt choline chloride along with HB donors urea and glycerol, respectively, in 1:2 mol ratio, named reline and glyceline as the cosolvent of very high HB donating acidity and no HB accepting basicity 2,2,2-trifluoroethanol (TFE) and of very high HB accepting basicity and no HB donating acidity hexamethylphosphoramide (HMPA), respectively, is added. TFE shows up to 0.25 mole fraction miscibility with both reline and glyceline. While up to 0.25 mole fraction HMPA in glyceline results in transparent mixtures, this cosolvent is found to be completely immiscible with reline. From the perspective of the solvatochromic absorbance and fluorescence probes, it is established that the cybotactic region dipolarity within up to 0.25 mole fraction TFE/HMPA-added DES strongly depends on the functionalities present on the solute. Fourier transform infrared absorbance and Raman spectroscopic investigations reveal no major shifts in vibrational transitions as TFE/HMPA is added to the DES; spectral band broadening, albeit small, is observed nonetheless. Excess molar volumes and excess logarithmic viscosities of the mixtures indicate that while TFE may interstitially accommodate itself within H-bonded network of reline, it does appear to form H-bonds with the constituents of the glyceline. Increase in overall net repulsive interactions as HMPA is added to glyceline is suggested by both positive excess molar volumes and excess logarithmic viscosities. The addition of HB donor/acceptor cosolvent appears to disturb the salt-HB donor equilibria within DES via complex interplay of interactions within the system.

Changing trends and emissions of hydrochlorofluorocarbons (HCFCs) and their hydrofluorocarbon (HFCs) replacements

NASA Astrophysics Data System (ADS)

Simmonds, Peter G.; Rigby, Matthew; McCulloch, Archie; O'Doherty, Simon; Young, Dickon; Mühle, Jens; Krummel, Paul B.; Steele, Paul; Fraser, Paul J.; Manning, Alistair J.; Weiss, Ray F.; Salameh, Peter K.; Harth, Chris M.; Wang, Ray H. J.; Prinn, Ronald G.

2017-04-01

High-frequency, in situ global observations of HCFC-22 (CHClF2), HCFC-141b (CH3CCl2F), HCFC-142b (CH3CClF2) and HCFC-124 (CHClFCF3) and their main HFC replacements, HFC-134a (CH2FCF3), HFC-125 (CHF2CF3), HFC-143a (CH3CF3) and HFC-32 (CH2F2), have been used to determine their changing global growth rates and emissions in response to the Montreal Protocol and its recent amendments. Global mean mole fractions of HCFC-22, -141b, and -142b have increased throughout the observation period, reaching 234, 24.3 and 22.4 pmol mol-1, respectively, in 2015. HCFC-124 reached a maximum global mean mole fraction of 1.48 pmol mol-1 in 2007 and has since declined by 23 % to 1.14 pmol mol-1 in 2015. The HFCs all show increasing global mean mole fractions. In 2015 the global mean mole fractions (pmol mol-1) were 83.3 (HFC-134a), 18.4 (HFC-125), 17.7 (HFC-143a) and 10.5 (HFC-32). The 2007 adjustment to the Montreal Protocol required the accelerated phase-out of emissive uses of HCFCs with global production and consumption capped in 2013 to mitigate their environmental impact as both ozone-depleting substances and important greenhouse gases. We find that this change has coincided with a stabilisation, or moderate reduction, in global emissions of the four HCFCs with aggregated global emissions in 2015 of 449 ± 75 Gg yr-1, in CO2 equivalent units (CO2 eq.) 0.76 ± 0.1 Gt yr-1, compared with 483 ± 70 Gg yr-1 (0.82 ± 0.1 Gt yr-1 CO2 eq.) in 2010 (uncertainties are 1σ throughout this paper). About 79 % of the total HCFC atmospheric burden in 2015 is HCFC-22, where global emissions appear to have been relatively similar since 2011, in spite of the 2013 cap on emissive uses. We attribute this to a probable increase in production and consumption of HCFC-22 in Montreal Protocol Article 5 (developing) countries and the continuing release of HCFC-22 from the large banks which dominate HCFC global emissions. Conversely, the four HFCs all show increasing mole fraction growth rates with aggregated global HFC emissions of 327 ± 70 Gg yr-1 (0.65 ± 0.12 Gt yr-1 CO2 eq.) in 2015 compared to 240 ± 50 Gg yr-1 (0.47 ± 0.08 Gt yr-1 CO2 eq.) in 2010. We also note that emissions of HFC-125 and HFC-32 appear to have increased more rapidly averaged over the 5-year period 2011-2015, compared to 2006-2010. As noted by Lunt et al. (2015) this may reflect a change to refrigerant blends, such as R-410A, which contain HFC-32 and -125 as a 50 : 50 blend.

Working underground: Respiratory adaptations in the blind mole rat

PubMed Central

Widmer, Hans R.; Hoppeler, Hans; Nevo, Eviatar; Taylor, C. Richard; Weibel, Ewald R.

1997-01-01

Mole rats (Spalax ehrenbergi superspecies) perform the heavy work of digging their subterranean burrows in Israel under highly hypoxic/hypercapnic conditions. Unlike most other mammals, they can achieve high levels of metabolic rate under these conditions, while their metabolic rate at low work rates is depressed. We explored, by comparing mole rats with white rats, whether and how this is related to adaptations in the design of the respiratory system, which determines the transfer of O2 from the lung to muscle mitochondria. At the same body mass, mole rats were found to have a significantly smaller total skeletal muscle mass than ordinary white rats (−22%). In contrast, the fractional volume of muscle mitochondria was larger by 46%. As a consequence, both species had the same total amount of mitochondria and achieved, under normoxia, the same V̇O2max. Whereas the O2 transport capacity of the blood was not different, we found a larger capillary density (+31%) in the mole rat muscle, resulting in a reduced diffusion distance to mitochondria. The structural pulmonary diffusing capacity for O2 was greater in the mole rat (+44%), thus facilitating O2 uptake in hypoxia. We conclude that structural adaptations in lung and muscle tissue improve O2 diffusion conditions and serve to maintain high metabolic rates in hypoxia but have no consequences for achieving V̇O2max under normoxic conditions. PMID:9050905

Keep It in Proportion.

ERIC Educational Resources Information Center

Snider, Richard G.

1985-01-01

The ratio factors approach involves recognizing a given fraction, then multiplying so that units cancel. This approach, which is grounded in concrete operational thinking patterns, provides a standard for science ratio and proportion problems. Examples are included for unit conversions, mole problems, molarity, speed/density problems, and…

Chemical equilibrium of ablation materials including condensed species

NASA Technical Reports Server (NTRS)

Stroud, C. W.; Brinkley, K. L.

1975-01-01

Equilibrium is determined by finding chemical composition with minimum free energy. Method of steepest descent is applied to quadratic representation of free-energy surface. Solution is initiated by selecting arbitrary set of mole fractions, from which point on free-energy surface is computed.

Single-coal-particle combustion in O{sub 2}/N{sub 2} and O{sub 2}/CO{sub 2} environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bejarano, Paula A.; Levendis, Yiannis A.

A fundamental investigation has been conducted on the combustion of single particles of a bituminous coal (45-53, 75-90, and 150-180 {mu}m), of a lignite coal (45-53 and 75-90 {mu}m), and of spherical and monodisperse synthetic chars (43 {mu}m) at increasing O{sub 2} mole fractions in either N{sub 2} or CO{sub 2} balance gases. The synthetic particles were used to facilitate the observation of combustion phenomena with minimum distractions from particle-to-particle variabilities. The laboratory setup consisted of a drop-tube furnace operated at temperatures of 1400 and 1600 K. A calibrated three-color pyrometer, interfaced with the furnace, recorded luminous particle temperature-time profiles.more » Experimental results revealed that coal particles burned at higher mean temperatures and shorter combustion times in O{sub 2}/N{sub 2} than in O{sub 2}/CO{sub 2} environments at analogous oxygen mole fractions. In the case of the bituminous coal used herein and for the experimental combustion conditions tested, measured volatile and char temperatures as in air (21% O{sub 2}) were attained with an oxygen content in the CO{sub 2} mixtures in the neighborhood of 30%. Bituminous coal volatile and char burnout times comparable to those in air (21% O{sub 2}) were attained with oxygen content in the CO{sub 2} mixtures in the range of 30-35%. In the case of the lignite coal burned, the corresponding differences in oxygen mole fractions, which result in similar particle temperatures and burnout times in the two different gas mixtures, were less pronounced. (author)« less

Assessing the British Isles CH4 flux using aircraft and ground-based sampling: a case study on 12 May 2015

NASA Astrophysics Data System (ADS)

Pitt, Joseph

2017-04-01

Aircraft and ground-based sampling of atmospheric greenhouse gas composition over the British Isles was conducted between 2014 and 2016 as part of the Greenhouse gAs UK and Global Emissions (GAUGE) project. We report a case study focussing on two research aircraft flights conducted on 12 May 2015 to sample inflow and outflow across the British Isles. We have employed the NAME Lagrangian dispersion model to simulate CH4 mole fraction enhancements corresponding to aircraft and ground-based sample times and locations, using CH4 surface fluxes derived from a composite flux inventory, which included both anthropogenic and natural sources. For each sampling location, variations in the baseline CH4 mole fraction were derived using the MOZART global chemical transport model, and added to the NAME enhancements to produce a dataset of modelled CH4 mole fractions which can be compared to the measurements. Using a multiple variable regression technique, we derive CH4 fluxes for the British Isles region from both aircraft and ground-based datasets. We discuss the applicability of our approach for both datasets, and conclude that in this case the assumptions inherent in our method are much better satisfied for the aircraft data than for the ground-based data. Using the aircraft data we derive a possible range of scale factors for the prior inventory flux of 0.53 - 0.97, with a central estimate of 0.82 based on our assessment of the most likely apportionment of model uncertainty. This leads to a posterior estimate of the British Isles CH4 flux of 67 kg s-1 - 121 kg s-1, with a central value of 103 kg s-1.

High accuracy measurements of dry mole fractions of carbon dioxide and methane in humid air

NASA Astrophysics Data System (ADS)

Rella, C. W.; Chen, H.; Andrews, A. E.; Filges, A.; Gerbig, C.; Hatakka, J.; Karion, A.; Miles, N. L.; Richardson, S. J.; Steinbacher, M.; Sweeney, C.; Wastine, B.; Zellweger, C.

2012-08-01

Traditional techniques for measuring the mole fractions of greenhouse gas in the well-mixed atmosphere have required extremely dry sample gas streams (dew point < -25 °C) to achieve the inter-laboratory compatibility goals set forth by the Global Atmospheric Watch program of the World Meteorological Organization (WMO/GAW) for carbon dioxide (±0.1 ppm) and methane (±2 ppb). Drying the sample gas to low levels of water vapor can be expensive, time-consuming, and/or problematic, especially at remote sites where access is difficult. Recent advances in optical measurement techniques, in particular Cavity Ring Down Spectroscopy (CRDS), have led to the development of highly stable and precise greenhouse gas analyzers capable of highly accurate measurements of carbon dioxide, methane, and water vapor. Unlike many older technologies, which can suffer from significant uncorrected interference from water vapor, these instruments permit for the first time accurate and precise greenhouse gas measurements that can meet the WMO/GAW inter-laboratory compatibility goals without drying the sample gas. In this paper, we present laboratory methodology for empirically deriving the water vapor correction factors, and we summarize a series of in-situ validation experiments comparing the measurements in humid gas streams to well-characterized dry-gas measurements. By using the manufacturer-supplied correction factors, the dry-mole fraction measurements have been demonstrated to be well within the GAW compatibility goals up to at least 1% water vapor. By determining the correction factors for individual instruments once at the start of life, this range can be extended to at least 2% over the life of the instrument, and if the correction factors are determined periodically over time, the evidence suggests that this range can be extended above 4%.

Numerical simulation of hydrogen-air reacting flows in rectangular channels with catalytic surface reactions

NASA Astrophysics Data System (ADS)

Amano, Ryoichi S.; Abou-Ellail, Mohsen M.; Elhaw, Samer; Saeed Ibrahim, Mohamed

2013-09-01

In this work a prediction was numerically modeled for a catalytically stabilized thermal combustion of a lean homogeneous mixture of air and hydrogen. The mixture flows in a narrow rectangular channel lined with a thin coating of platinum catalyst. The solution using an in-house code is based on the steady state partial differential continuity, momentum and energy conservation equations for the mixture and species involved in the reactions. A marching technique is used along the streamwise direction to solve the 2-D plane-symmetric laminar flow of the gas. Two chemical kinetic reaction mechanisms were included; one for the gas phase reactions consisting of 17 elementary reactions; of which 7 are forward-backward reactions while the other mechanism is for the surface reactions—which are the prime mover of the combustion under a lean mixture condition—consisting of 16 elementary reactions. The results were compared with a former congruent experimental work where temperature was measured using thermocouples, while using PLIF laser for measuring water and hydrogen mole fractions. The comparison showed good agreement. More results for the velocities, mole fractions of other species were carried out across the transverse and along the streamwise directions providing a complete picture of overall mechanism—gas and surface—and on the production, consumptions and travel of the different species. The variations of the average OH mole fraction with the streamwise direction showed a sudden increase in the region where the ignition occurred. Also the rate of reactions of the entire surface species were calculated along the streamwise direction and a surface water production flux equation was derived by calculating the law of mass action's constants from the concentrations of hydrogen, oxygen and the rate of formation of water near the surface.

Continuous-flow extraction system for elemental association study: a case of synthetic metal-doped iron hydroxide.

PubMed

Hinsin, Duangduean; Pdungsap, Laddawan; Shiowatana, Juwadee

2002-12-06

A continuous-flow extraction system originally developed for sequential extraction was applied to study elemental association of a synthetic metal-doped amorphous iron hydroxide phase. The homogeneity and metal association of the precipitates were evaluated by gradual leaching using the system. Leachate was collected in fractions for determination of elemental concentrations. The result obtained as extractograms indicated that the doped metals were adsorbed more on the outermost surface rather than homogeneously distributed in the precipitates. The continuous-flow extraction method was also used for effective removal of surface adsorbed metals to obtain a homogeneous metal-doped synthetic iron hydroxide by a sequential extraction using acetic acid and small volume of hydroxylamine hydrochloride solution. The system not only ensures complete washing, but the extent of metal immobilization in the synthetic iron hydroxide could be determined with high accuracy from the extractograms. The initial metal/iron mole ratio (M/Fe) in solution affected the M/Fe mole ratio in homogeneous doped iron hydroxide phase. The M/Fe mole ratio of metal incorporation was approximately 0.01-0.02 and 0.03-0.06, for initial solution M/Fe mole ratio of 0.025 and 0.100, respectively.

Influence of peroxyacetyl nitrate (PAN) on odd nitrogen in the troposphere and lower stratosphere

NASA Technical Reports Server (NTRS)

Aikin, A. C.; Herman, J. R.; Maier, E. J. R.; Mcquillan, C. J.

1983-01-01

Nonmethane hydrocarbon breakdown in the atmosphere produces aldehydes of which a fraction are transferred into peroxyacetyl nitrates (PAN) in the presence of NO and NO2. Since ethane is destroyed photochemically primarily above 1 km, PAN can be introduced into the upper troposphere and lower stratosphere without the need to be transported from the boundary layer where most hydrocarbons are destroyed and where PAN may be lost due to thermal decomposition and heterogeneous loss. Mixing ratios of ethane in the lower troposphere increase by a factor of 4-8 from equatorial to northern mid-latitudes. This difference is directly translatable into a PAN latitude gradient. At mid-latitudes the concentration of PAN below 20 km is 0.1 ppb comparable to and in some instances larger than predicted HO2NO2 mixing ratios. Like HO2NO2 and HNO3, PAN serves as a reservoir for odd nitrogen.

Detection of capacity imbalance in vanadium electrolyte and its electrochemical regeneration for all-vanadium redox-flow batteries

NASA Astrophysics Data System (ADS)

Roznyatovskaya, Nataliya; Herr, Tatjana; Küttinger, Michael; Fühl, Matthias; Noack, Jens; Pinkwart, Karsten; Tübke, Jens

2016-01-01

A vanadium electrolyte for redox-flow batteries (VRFB) with different VIII and VIV mole fractions has been studied by UV-vis spectroscopy. Spectrophotometric detection enables a rough estimate of the VIV and VIII content, which can be used to detect an electrolyte capacity imbalance, i.e. a deviation in the mole fraction of VIV or VIII away from 50%. The isosbestic point at 600 nm can be used as a reference point in the analysis of common VRFB electrolyte batches. The VRFB electrolyte is observed to have an imbalance after prolonged storage (a couple of years) in a tank under ambient conditions. A regeneration procedure, which involves pre-charging the unbalanced electrolyte and mixing part of it with a portion of initial unbalanced electrolyte, has been tested. The resulting rebalanced electrolyte has been compared with a common electrolyte in a charge-discharge cell test and is shown to be suitable for cell operation.

Equilibrium distribution of rare earth elements between molten KCl-LiCl eutectic salt and liquid cadmium

NASA Astrophysics Data System (ADS)

Sakata, Masahiro; Kurata, Masaki; Hijikata, Takatoshi; Inoue, Tadashi

1991-11-01

Distribution experiments for several rare earth elements (La, Ce, Pr, Nd and Y) between molten KCl-LiCl eutectic salt and liquid Cd were carried out at 450, 500 and 600°C. The material balance of rare earth elements after reaching the equilibrium and their distribution and chemical states in a Cd sample frozen after the experiment were examined. The results suggested the formation of solid intermetallic compounds at the lower concentrations of rare earth metals dissolved in liquid Cd than those solubilities measured in the binary alloy system. The distribution coefficients of rare earth elements between two phases (mole fraction in the Cd phase divided by mole fraction in the salt phase) were determined at each temperature. These distribution coefficients were explained satisfactorily by using the activity coefficients of chlorides and metals in salt and Cd. Both the activity coefficients of metal and chloride caused a much smaller distribution coefficient of Y relative to those of other elements.

N2/O2/H2 Dual-Pump Cars: Validation Experiments

NASA Technical Reports Server (NTRS)

OByrne, S.; Danehy, P. M.; Cutler, A. D.

2003-01-01

The dual-pump coherent anti-Stokes Raman spectroscopy (CARS) method is used to measure temperature and the relative species densities of N2, O2 and H2 in two experiments. Average values and root-mean-square (RMS) deviations are determined. Mean temperature measurements in a furnace containing air between 300 and 1800 K agreed with thermocouple measurements within 26 K on average, while mean mole fractions agree to within 1.6 % of the expected value. The temperature measurement standard deviation averaged 64 K while the standard deviation of the species mole fractions averaged 7.8% for O2 and 3.8% for N2, based on 200 single-shot measurements. Preliminary measurements have also been performed in a flat-flame burner for fuel-lean and fuel-rich flames. Temperature standard deviations of 77 K were measured, and the ratios of H2 to N2 and O2 to N2 respectively had standard deviations from the mean value of 12.3% and 10% of the measured ratio.

Laser-based measurements of OH in high pressure CH4/air flames

NASA Technical Reports Server (NTRS)

Battles, B. E.; Hanson, R. K.

1991-01-01

Narrow-linewidth laser absorption measurements are reported from which mole fraction and temperature of OH are determined in high-pressure (1-10 atm), lean CH4/air flames. These measurements were made in a new high pressure combustion facility which incorporates a traversable flat flame burner, providing spatially and temporally uniform combustion gases at pressures up to 10 am. A commercially avialable CW ring dye laser was used with an intracavity doubling crystal to provide near-UV single mode output at approximately 306 nm. The UV beam was rapidly scanned over 120 GHz (0.1 sec scan duration) to resolve the absorption lineshape of the A-X (0,0) R1(7)/R1(11) doublet of the OH radical. From the doublet's absorption lineshape, the temperature was determined; and from peak absorption, Beer's Law was employed to find the mole fraction of OH. These data were obtained as a function of height above the flame at various pressures.

Method and system for gas flow mitigation of molecular contamination of optics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Delgado, Gildardo; Johnson, Terry; Arienti, Marco

A computer-implemented method for determining an optimized purge gas flow in a semi-conductor inspection metrology or lithography apparatus, comprising receiving a permissible contaminant mole fraction, a contaminant outgassing flow rate associated with a contaminant, a contaminant mass diffusivity, an outgassing surface length, a pressure, a temperature, a channel height, and a molecular weight of a purge gas, calculating a flow factor based on the permissible contaminant mole fraction, the contaminant outgassing flow rate, the channel height, and the outgassing surface length, comparing the flow factor to a predefined maximum flow factor value, calculating a minimum purge gas velocity and amore » purge gas mass flow rate from the flow factor, the contaminant mass diffusivity, the pressure, the temperature, and the molecular weight of the purge gas, and introducing the purge gas into the semi-conductor inspection metrology or lithography apparatus with the minimum purge gas velocity and the purge gas flow rate.« less

Modern inhalation anesthetics: Potent greenhouse gases in the global atmosphere

NASA Astrophysics Data System (ADS)

Vollmer, Martin K.; Rhee, Tae Siek; Rigby, Matt; Hofstetter, Doris; Hill, Matthias; Schoenenberger, Fabian; Reimann, Stefan

2015-03-01

Modern halogenated inhalation anesthetics undergo little metabolization during clinical application and evaporate almost completely to the atmosphere. Based on their first measurements in a range of environments, from urban areas to the pristine Antarctic environment, we detect a rapid accumulation and ubiquitous presence of isoflurane, desflurane, and sevoflurane in the global atmosphere. Over the past decade, their abundances in the atmosphere have increased to global mean mole fractions in 2014 of 0.097ppt, 0.30ppt, and 0.13ppt (parts per trillion, 10-12, in dry air), respectively. Emissions of these long-lived greenhouse gases inferred from the observations suggest a global combined release to the atmosphere of 3.1 ± 0.6 million t CO2 equivalent in 2014 of which ≈80% stems from desflurane. We also report on halothane, a previously widely used anesthetic. Its global mean mole fraction has declined to 9.2ppq (parts per quadrillion, 10-15) by 2014. However, the inferred present usage is still 280 ±120t yr-1.

Evidence for the existence of supercooled ethane droplets under conditions prevalent in Titan's atmosphere.

PubMed

Sigurbjörnsson, Omar F; Signorell, Ruth

2008-11-07

Recent evidence for ethane clouds and condensation in Titan's atmosphere raise the question whether liquid ethane condensation nuclei and supercooled liquid ethane droplets exist under the prevalent conditions. We present laboratory studies on the phase behaviour of pure ethane aerosols and ethane aerosols formed in the presence of other ice nuclei under conditions relevant to Titan's atmosphere. Combining bath gas cooling with infrared spectroscopy, we find evidence for the existence of supercooled liquid ethane aerosol droplets. The observed homogeneous freezing rates imply that supercooled ethane could be a long-lived species in ethane-rich regions of Titan's atmosphere similar to supercooled water in the Earth's atmosphere.

Reductive dechlorination of trichloroethene mediated by humic-metal complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

O`Loughlin, E.J.; Burris, D.R.; Delcomyn, C.A.

1999-04-01

Experiments were conducted to determine if transition metal-humic acid complexes can act as e{sup {minus}} transfer mediators in the reductive dechlorination of trichloroethene (TCE) using Ti(III) citrate as the bulk reductant. In the presence of Ni-Aldrich humic acid (AHA) complexes, TCE reduction was rapid, with complete removal of TCE in less than 23 h. Cu-AHA complexes were less effective as e{sup {minus}} mediators than Ni-AHA complexes; only 60% of TCE was reduced after 150 h. Partially dechlorinated intermediates were observed during TCE reduction; however, they were transitory, and at no time accounted for more than 2% of the initial TCEmore » mass on a mole C basis. Ethane and ethene were the primary end products of TCE reduction; however, a suite of other non-chlorinated hydrocarbons consisting of methane and C{sub 3} to C{sub 6} alkanes and alkenes were also observed. The results suggest that humic-metal complexes may represent a previously unrecognized class of electron mediators in natural environments.« less

Low temperature rate coefficients for the reactions of 1CH2 with reactive and non-reactive species, and the implications for Titan's atmosphere

NASA Astrophysics Data System (ADS)

Douglas, Kevin; Slater, Eloise; Blitz, Mark; Plane, John; Heard, Dwayne; Seakins, Paul

2016-04-01

The Cassini-Huygens mission to Titan revealed unexpectedly large amounts of benzene in the troposphere, and confirmed the absence of a global ethane ocean as predicted by photochemical models of methane conversion over the lifetime of the solar system. An important chemical intermediate in both the production and loss of benzene and ethane is the first electronically excited state of methylene, 1CH2. For example, at room temperature an important reaction of 1CH2 is with acetylene (R1a), leading to the formation of propargyl (C3H3)[1]. The subsequent recombination of propargyl radicals is the major suggested route to benzene in Titan's atmosphere (R2)[2]. In addition to reaction of 1CH2 leading to products, there is also competition between inelastic electronic relaxation to form the ground triplet state 3CH2 (R1b). This ground state 3CH2 has a markedly different reactivity to the singlet, reacting primarily with methyl radicals (CH3) to form ethene (R3). As methyl radical recombination is the primary route to ethane (R4)[3], reactions of 1CH2 will also heavily influence the ethane budget on Titan. 1CH2 + C2H2 → C3H3 + H (R1a) 1CH2 + C2H2 → 3CH2 + C2H2 (R1b) C3H3 + C3H3 → C6H6 (R2) 3CH2 + CH3 → C2H4 + H (R3) CH3 + CH3 (+ M) → C2H6 (R4) Thus this competition between chemical reaction and electronic relaxation in the reactions of 1CH2 with H2, CH4, C2H4, and C2H6 will play an important role in determining the benzene and ethane budgets on Titan. Despite this there are no measurements of any rate constants for 1CH2 at temperatures relevant to Titan's atmosphere (60 - 170 K). Using a pulsed Laval nozzle apparatus coupled with pulsed laser photolysis laser-induced fluorescence, the low temperature reaction kinetics for the removal of 1CH2 with nitrogen, hydrogen, methane, ethane, ethene, acetylene, and oxygen, have been studied. The results revealed an increase in the removal rate of 1CH2 at temperatures below 200 K, with a sharp increase of around a factor of 5 observed at 45±5 K. In addition to measuring total removal rates of 1CH2, the fraction of 1CH2 removed via electronic relaxation verses chemical reaction to products has also been investigated. Results for the reactive species ethane, ethene, and acetylene at 45±5 K, and for hydrogen and methane at 73±9 K indicate that following reactions with 1CH2, removal of 1CH2 is predominantly due to electronic relaxation (> 95 %) and not chemical reaction to products. This is in agreement with previous studies that show that with decreasing temperature, the fraction of reactive removal of 1CH2 to chemical products decreases while the fraction of removal by electronic relaxation increases[4][5]. These results indicate that 1CH2 formed in Titan's atmosphere will be rapidly relaxed to it's ground state via collisions with both reactive and non-reactive species, and thus will play a less significant role in the formation of larger hydrocarbons than previously thought. However for a full understanding of the implications of these results, the new measurements are to be included in a 1D model of Titan's atmosphere to determine the impact of the laboratory measurements on observation/model agreement. [1] K. Gannon et. al., J. Phys. Chem. A, (2010), 114, 9413 [2] E.H. Wilson, S.K. Atreya, J. Geophys. Res., (2004), 109, 6002 [3] M. Fulchignoni, Nature, (2005), 438, 785 [4] K. Gannon, Faraday Discuss., (2010), 147, 173 [5] K. Gannon, J. Phys. Chem. A, (2008), 112, 9575

Thermodynamics on the Molality Scale

ERIC Educational Resources Information Center

Canagaratna, Sebastian G.; Maheswaran, M.

2013-01-01

For physical measurements, the compositions of solutions, especially electrolyte solutions, are expressed in terms of molality rather than mole fractions. The development of the necessary thermodynamic equations directly in terms of molality is not common in textbooks, and the treatment in the literature is not very systematic. We develop a…

Simulations of column-averaged CO2 and CH4 using the NIES TM with a hybrid sigma-isentropic (σ-θ) vertical coordinate

NASA Astrophysics Data System (ADS)

Belikov, D. A.; Maksyutov, S.; Sherlock, V.; Aoki, S.; Deutscher, N. M.; Dohe, S.; Griffith, D.; Kyro, E.; Morino, I.; Nakazawa, T.; Notholt, J.; Rettinger, M.; Schneider, M.; Sussmann, R.; Toon, G. C.; Wennberg, P. O.; Wunch, D.

2013-02-01

We have developed an improved version of the National Institute for Environmental Studies (NIES) three-dimensional chemical transport model (TM) designed for accurate tracer transport simulations in the stratosphere, using a hybrid sigma-isentropic (σ-θ) vertical coordinate that employs both terrain-following and isentropic parts switched smoothly around the tropopause. The air-ascending rate was derived from the effective heating rate and was used to simulate vertical motion in the isentropic part of the grid (above level 350 K), which was adjusted to fit to the observed age of the air in the stratosphere. Multi-annual simulations were conducted using the NIES TM to evaluate vertical profiles and dry-air column-averaged mole fractions of CO2 and CH4. Comparisons with balloon-borne observations over Sanriku (Japan) in 2000-2007 revealed that the tracer transport simulations in the upper troposphere and lower stratosphere are performed with accuracies of ~5% for CH4 and SF6, and ~1% for CO2 compared with the observed volume-mixing ratios. The simulated column-averaged dry air mole fractions of atmospheric carbon dioxide (XCO2) and methane (XCH4) were evaluated against daily ground-based high-resolution Fourier Transform Spectrometer (FTS) observations measured at twelve sites of the Total Carbon Column Observing Network (TCCON) (Bialystok, Bremen, Darwin, Garmisch, Izaña, Lamont, Lauder, Orleans, Park Falls, Sodankylä, Tsukuba, and Wollongong) between January 2009 and January 2011. The comparison shows the model's ability to reproduce the site-dependent seasonal cycles as observed by TCCON, with correlation coefficients typically on the order 0.8-0.9 and 0.4-0.8 for XCO2 and XCH4, respectively, and mean model biases of ±0.2% and ±0.5%, excluding Sodankylä, where strong biases are found. The ability of the model to capture the tracer total column mole fractions is strongly dependent on the model's ability to reproduce seasonal variations in tracer concentrations in the planetary boundary layer (PBL). We found a marked difference in the model's ability to reproduce near-surface concentrations at sites located some distance from multiple emission sources and where high emissions play a notable role in the tracer's budget. Comparisons with aircraft observations over Surgut (West Siberia), in an area with high emissions of methane from wetlands, show contrasting model performance in the PBL and in the free troposphere. Thus, the PBL is another critical region for simulating the tracer total column mole fractions.

Global and regional emissions estimates of 1,1-difluoroethane (HFC-152a, CH3CHF2) from in situ and air archive observations

NASA Astrophysics Data System (ADS)

Simmonds, P. G.; Rigby, M.; Manning, A. J.; Lunt, M. F.; O'Doherty, S.; McCulloch, A.; Fraser, P. J.; Henne, S.; Vollmer, M. K.; Mühle, J.; Weiss, R. F.; Salameh, P. K.; Young, D.; Reimann, S.; Wenger, A.; Arnold, T.; Harth, C. M.; Krummel, P. B.; Steele, L. P.; Dunse, B. L.; Miller, B. R.; Lunder, C. R.; Hermansen, O.; Schmidbauer, N.; Saito, T.; Yokouchi, Y.; Park, S.; Li, S.; Yao, B.; Zhou, L. X.; Arduini, J.; Maione, M.; Wang, R. H. J.; Ivy, D.; Prinn, R. G.

2016-01-01

High frequency, in situ observations from 11 globally distributed sites for the period 1994-2014 and archived air measurements dating from 1978 onward have been used to determine the global growth rate of 1,1-difluoroethane (HFC-152a, CH3CHF2). These observations have been combined with a range of atmospheric transport models to derive global emission estimates in a top-down approach. HFC-152a is a greenhouse gas with a short atmospheric lifetime of about 1.5 years. Since it does not contain chlorine or bromine, HFC-152a makes no direct contribution to the destruction of stratospheric ozone and is therefore used as a substitute for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). The concentration of HFC-152a has grown substantially since the first direct measurements in 1994, reaching a maximum annual global growth rate of 0.84 ± 0.05 ppt yr-1 in 2006, implying a substantial increase in emissions up to 2006. However, since 2007, the annual rate of growth has slowed to 0.38 ± 0.04 ppt yr-1 in 2010 with a further decline to an annual average rate of growth in 2013-2014 of -0.06 ± 0.05 ppt yr-1. The annual average Northern Hemisphere (NH) mole fraction in 1994 was 1.2 ppt rising to an annual average mole fraction of 10.1 ppt in 2014. Average annual mole fractions in the Southern Hemisphere (SH) in 1998 and 2014 were 0.84 and 4.5 ppt, respectively. We estimate global emissions of HFC-152a have risen from 7.3 ± 5.6 Gg yr-1 in 1994 to a maximum of 54.4 ± 17.1 Gg yr-1 in 2011, declining to 52.5 ± 20.1 Gg yr-1 in 2014 or 7.2 ± 2.8 Tg-CO2 eq yr-1. Analysis of mole fraction enhancements above regional background atmospheric levels suggests substantial emissions from North America, Asia, and Europe. Global HFC emissions (so called "bottom up" emissions) reported by the United Nations Framework Convention on Climate Change (UNFCCC) are based on cumulative national emission data reported to the UNFCCC, which in turn are based on national consumption data. There appears to be a significant underestimate ( > 20 Gg) of "bottom-up" reported emissions of HFC-152a, possibly arising from largely underestimated USA emissions and undeclared Asian emissions.

Estimating regional methane surface fluxes: the relative importance of surface and GOSAT mole fraction measurements

NASA Astrophysics Data System (ADS)

Fraser, A.; Palmer, P. I.; Feng, L.; Boesch, H.; Cogan, A.; Parker, R.; Dlugokencky, E. J.; Fraser, P. J.; Krummel, P. B.; Langenfelds, R. L.; O'Doherty, S.; Prinn, R. G.; Steele, L. P.; van der Schoot, M.; Weiss, R. F.

2013-06-01

We use an ensemble Kalman filter (EnKF), together with the GEOS-Chem chemistry transport model, to estimate regional monthly methane (CH4) fluxes for the period June 2009-December 2010 using proxy dry-air column-averaged mole fractions of methane (XCH4) from GOSAT (Greenhouse gases Observing SATellite) and/or NOAA ESRL (Earth System Research Laboratory) and CSIRO GASLAB (Global Atmospheric Sampling Laboratory) CH4 surface mole fraction measurements. Global posterior estimates using GOSAT and/or surface measurements are between 510-516 Tg yr-1, which is less than, though within the uncertainty of, the prior global flux of 529 ± 25 Tg yr-1. We find larger differences between regional prior and posterior fluxes, with the largest changes in monthly emissions (75 Tg yr-1) occurring in Temperate Eurasia. In non-boreal regions the error reductions for inversions using the GOSAT data are at least three times larger (up to 45%) than if only surface data are assimilated, a reflection of the greater spatial coverage of GOSAT, with the two exceptions of latitudes >60° associated with a data filter and over Europe where the surface network adequately describes fluxes on our model spatial and temporal grid. We use CarbonTracker and GEOS-Chem XCO2 model output to investigate model error on quantifying proxy GOSAT XCH4 (involving model XCO2) and inferring methane flux estimates from surface mole fraction data and show similar resulting fluxes, with differences reflecting initial differences in the proxy value. Using a series of observing system simulation experiments (OSSEs) we characterize the posterior flux error introduced by non-uniform atmospheric sampling by GOSAT. We show that clear-sky measurements can theoretically reproduce fluxes within 10% of true values, with the exception of tropical regions where, due to a large seasonal cycle in the number of measurements because of clouds and aerosols, fluxes are within 15% of true fluxes. We evaluate our posterior methane fluxes by incorporating them into GEOS-Chem and sampling the model at the location and time of surface CH4 measurements from the AGAGE (Advanced Global Atmospheric Gases Experiment) network and column XCH4 measurements from TCCON (Total Carbon Column Observing Network). The posterior fluxes modestly improve the model agreement with AGAGE and TCCON data relative to prior fluxes, with the correlation coefficients (r2) increasing by a mean of 0.04 (range: -0.17 to 0.23) and the biases decreasing by a mean of 0.4 ppb (range: -8.9 to 8.4 ppb).

Estimating regional methane surface fluxes: the relative importance of surface and GOSAT mole fraction measurements

NASA Astrophysics Data System (ADS)

Fraser, A.; Palmer, P. I.; Feng, L.; Boesch, H.; Cogan, A.; Parker, R.; Dlugokencky, E. J.; Fraser, P. J.; Krummel, P. B.; Langenfelds, R. L.; O'Doherty, S.; Prinn, R. G.; Steele, L. P.; van der Schoot, M.; Weiss, R. F.

2012-12-01

We use an ensemble Kalman filter (EnKF), together with the GEOS-Chem chemistry transport model, to estimate regional monthly methane (CH4) fluxes for the period June 2009-December 2010 using proxy dry-air column-averaged mole fractions of methane (XCH4) from GOSAT (Greenhouse gases Observing SATellite) and/or NOAA ESRL (Earth System Research Laboratory) and CSIRO GASLAB (Global Atmospheric Sampling Laboratory) CH4 surface mole fraction measurements. Global posterior estimates using GOSAT and/or surface measurements are between 510-516 Tg yr-1, which is less than, though within the uncertainty of, the prior global flux of 529 ± 25 Tg yr-1. We find larger differences between regional prior and posterior fluxes, with the largest changes (75 Tg yr-1) occurring in Temperate Eurasia. In non-boreal regions the error reductions for inversions using the GOSAT data are at least three times larger (up to 45%) than if only surface data are assimilated, a reflection of the greater spatial coverage of GOSAT, with the two exceptions of latitudes > 60° associated with a data filter and over Europe where the surface network adequately describes fluxes on our model spatial and temporal grid. We use CarbonTracker and GEOS-Chem XCO2 model output to investigate model error on quantifying proxy GOSAT XCH4 (involving model XCO2) and inferring methane flux estimates from surface mole fraction data and show similar resulting fluxes, with differences reflecting initial differences in the proxy value. Using a series of observing system simulation experiments (OSSEs) we characterize the posterior flux error introduced by non-uniform atmospheric sampling by GOSAT. We show that clear-sky measurements can theoretically reproduce fluxes within 5% of true values, with the exception of South Africa and Tropical South America where, due to a large seasonal cycle in the number of measurements because of clouds and aerosols, fluxes are within 17% and 19% of true fluxes, respectively. We evaluate our posterior methane fluxes by incorporating them into GEOS-Chem and sampling the model at the location and time of independent surface CH4 measurements from the AGAGE (Advanced Global Atmospheric Gases Experiment) network and column XCH4 measurements from TCCON (Total Carbon Column Observing Network). The posterior fluxes modestly improve the model agreement with AGAGE and TCCON data relative to prior fluxes, with the correlation coefficients (r2) increasing by a mean of 0.04 (range: -0.17, 0.23) and the biases decreasing by a mean of 0.4 ppb (range: -8.9, 8.4 ppb).

Transformations between Extensive and Intensive Versions of Thermodynamic Relationships

ERIC Educational Resources Information Center

Eberhart, James G.

2010-01-01

Most thermodynamic properties are either extensive (e.g., volume, energy, entropy, amount, etc.) or intensive (e.g., temperature, pressure, chemical potential, mole fraction, etc.). By the same token most of the mathematical relationships in thermodynamics can be written in extensive or intensive form. The basic laws of thermodynamics are usually…

A Note on Diffusive Mass Transport.

ERIC Educational Resources Information Center

Haynes, Henry W., Jr.

1986-01-01

Current chemical engineering textbooks teach that the driving force for diffusive mass transport in ideal solutions is the gradient in mole fraction. This is only true for ideal solution liquids. Therefore, it is shown that the appropriate driving force for use with ideal gases is the gradient in partial pressure. (JN)

The time series of carbon monoxide at Zugspitze (2962 m) from 1990 to 2008

NASA Astrophysics Data System (ADS)

Scheel, H.-E.

2009-04-01

Measurements of carbon monoxide have been performed at the alpine site Zugspitze (47 ˚ N, 11 ˚ E) since 1990. Over the years, different types of instrumentation have been employed, comprising gas chromatography with HgO reduction detector (Trace Analytical RGD2) and non-dispersive infrared absorption instruments with and without gas filter correlation technique (TEI 48S and Horiba APMA-360, respectively). For most of the time, two instruments were operated in parallel. Since 2004, a vacuum UV fluorescence CO analyzer (Aerolaser AL5001) has been in operation as the primary instrument. The CO calibration scale, to which the measurements have been linked, was intercompared within a number of international round-robin experiments. The CO time series of 1990-2008 was analyzed statistically, in particular with respect to long-term trend and change in seasonal variation. Over the period of 19 years, the annual average mole fractions range between 120 and 148 ppb and display an overall decrease. Linear regression yields a rate of - 0.8 ppb yr-1. A more detailed trend analysis shows remarkable variations. A period of decreasing trend from about 1999 to 2001 was followed by a CO increase until 2004. Thereafter the trend was reversed again resulting in a decrease since then. Part of the year-to-year variability could be related to periods of enhanced CO emissions due to large-scale forest fires in the northern hemisphere. Particularly noteworthy periods are the second half of 1998 and the time from September 2002 to September 2003, when CO values elevated by about 40 % were observed at several northern hemispheric sites. High CO mole fractions exceeding 300 ppb, as encountered mainly during winter and spring of the first years of the record, have become less frequent over the years. This is probably related to reductions of CO emissions in Europe. The temporal developments within the upper range of the CO mole fractions are reflected by different statistical parameters. In particular, the comparison of half-hourly values from the mid-1990s with more recent data has indicated significant changes of the data structure. The strong decrease of the high-end mole fractions was substantiated by a trend analysis of the differences between specific percentiles (95th, 75th, and 25th, 5th, respectively). Within the context of long-range transport, particularly air masses influenced by the upper troposphere and lower stratosphere are of interest. Therefore, the Zugspitze CO data were filtered according to appropriate criteria, using data filters based on thresholds for humidity and the tracer 7Be. The shape of the average seasonal variation resembles that obtained from the unselected data. Both cycles display an April maximum and a broad minimum extending from July to October. However, the filtered CO data have yielded lower mole fractions of the cycle, with differences of 34 ppb for April and 9 ppb for July (1990-2004 average). A trend estimate based on the same data sets has resulted in a small positive trend of 0.5 ppb yr-1, in contrast to the negative rate of - 0.5 ppb yr-1 calculated from the unfiltered data for the same period. This is indicative of different developments of the CO emissions on regional, continental, and hemispheric scales.

Abundances of isotopologues and calibration of CO2 greenhouse gas measurements

NASA Astrophysics Data System (ADS)

Tans, Pieter P.; Crotwell, Andrew M.; Thoning, Kirk W.

2017-07-01

We have developed a method to calculate the fractional distribution of CO2 across all of its component isotopologues based on measured δ13C and δ18O values. The fractional distribution can be used with known total CO2 to calculate the amount of substance fraction (mole fraction) of each component isotopologue in air individually. The technique is applicable to any molecule where isotopologue-specific values are desired. We used it with a new CO2 calibration system to account for isotopic differences among the primary CO2 standards that define the WMO X2007 CO2-in-air calibration scale and between the primary standards and standards in subsequent levels of the calibration hierarchy. The new calibration system uses multiple laser spectroscopic techniques to measure mole fractions of the three major CO2 isotopologues (16O12C16O, 16O13C16O, and 16O12C18O) individually. The three measured values are then combined into total CO2 (accounting for the rare unmeasured isotopologues), δ13C, and δ18O values. The new calibration system significantly improves our ability to transfer the WMO CO2 calibration scale with low uncertainty through our role as the World Meteorological Organization Global Atmosphere Watch Central Calibration Laboratory for CO2. Our current estimates for reproducibility of the new calibration system are ±0.01 µmol mol-1 CO2, ±0.2 ‰ δ13C, and ±0.2 ‰ δ18O, all at 68 % confidence interval (CI).

Real-time analysis of δ13C- and δD-CH4 in ambient air with laser spectroscopy: method development and first intercomparison results

NASA Astrophysics Data System (ADS)

Eyer, S.; Tuzson, B.; Popa, M. E.; van der Veen, C.; Röckmann, T.; Rothe, M.; Brand, W. A.; Fisher, R.; Lowry, D.; Nisbet, E. G.; Brennwald, M. S.; Harris, E.; Zellweger, C.; Emmenegger, L.; Fischer, H.; Mohn, J.

2015-08-01

In situ and simultaneous measurement of the three most abundant isotopologues of methane using mid-infrared laser absorption spectroscopy is demonstrated. A field-deployable, autonomous platform is realized by coupling a compact quantum cascade laser absorption spectrometer (QCLAS) to a preconcentration unit, called TRace gas EXtractor (TREX). This unit enhances CH4 mole fractions by a factor of up to 500 above ambient levels and quantitatively separates interfering trace gases such as N2O and CO2. The analytical precision of the QCLAS isotope measurement on the preconcentrated (750 ppm, parts-per-million, μmole/mole) methane is 0.1 and 0.5 ‰ for δ13C- and δD-CH4 at 10 min averaging time. Based on replicate measurements of compressed air during a two-week intercomparison campaign, the repeatability of the TREX-QCLAS was determined to be 0.19 and 1.9 ‰ for δ13C and δD-CH4, respectively. In this intercomparison campaign the new in situ technique is compared to isotope-ratio mass-spectrometry (IRMS) based on glass flask and bag sampling and real time CH4 isotope analysis by two commercially available laser spectrometers. Both laser-based analyzers were limited to methane mole fraction and δ13C-CH4 analysis, and only one of them, a cavity ring down spectrometer, was capable to deliver meaningful data for the isotopic composition. After correcting for scale offsets, the average difference between TREX-QCLAS data and bag/flask sampling-IRMS values are within the extended WMO compatibility goals of 0.2 and 5 ‰ for δ13C- and δD-CH4, respectively. Thus, the intercomparison also reveals the need for reference air samples with accurately determined isotopic composition of CH4 to further improve the interlaboratory compatibility.

40 CFR 1065.140 - Dilution for gaseous and PM constituents.

Code of Federal Regulations, 2013 CFR

2013-07-01

... nitrogen. For gaseous emission measurement the diluent must be at least 15 °C. Note that the composition of... chemical balance equations in § 1065.655 to calculate the mole fraction of water in the dilute exhaust... condensation (either measured or from the chemical balance), and set any negative values to zero. This...

40 CFR 1065.140 - Dilution for gaseous and PM constituents.

Code of Federal Regulations, 2011 CFR

2011-07-01

... nitrogen. For gaseous emission measurement the diluent must be at least 15 °C. Note that the composition of... chemical balance equations in § 1065.655 to calculate the mole fraction of water in the dilute exhaust... condensation (either measured or from the chemical balance), and set any negative values to zero. This...

40 CFR 1065.140 - Dilution for gaseous and PM constituents.

Code of Federal Regulations, 2014 CFR

2014-07-01

... nitrogen. References in this part to “dilution air” may include any of these. For gaseous emission... test interval does not exceed the specified limits. (A) Use chemical balance equations in § 1065.655 to... balance), and set any negative values to zero. This difference is the potential mole fraction of the...

40 CFR 1065.140 - Dilution for gaseous and PM constituents.

Code of Federal Regulations, 2010 CFR

2010-07-01

... nitrogen. For gaseous emission measurement the diluent must be at least 15 °C. Note that the composition of... chemical balance equations in § 1065.655 to calculate the mole fraction of water in the dilute exhaust... condensation (either measured or from the chemical balance), and set any negative values to zero. This...

40 CFR 1065.140 - Dilution for gaseous and PM constituents.

Code of Federal Regulations, 2012 CFR

2012-07-01

... nitrogen. For gaseous emission measurement the diluent must be at least 15 °C. Note that the composition of... chemical balance equations in § 1065.655 to calculate the mole fraction of water in the dilute exhaust... condensation (either measured or from the chemical balance), and set any negative values to zero. This...

40 CFR 799.6786 - TSCA water solubility: Generator column method.

Code of Federal Regulations, 2014 CFR

2014-07-01

... quantitative) analysis of solvent extract in paragraph (c)(3)(iv) of this section. The design of the generator.... Finally, the design of most chemical tests and many ecological and health tests requires precise knowledge..., molality, and mole fraction. For example, to convert from weight/volume to molarity molecular mass is...

40 CFR 799.6786 - TSCA water solubility: Generator column method.

Code of Federal Regulations, 2013 CFR

2013-07-01

... quantitative) analysis of solvent extract in paragraph (c)(3)(iv) of this section. The design of the generator.... Finally, the design of most chemical tests and many ecological and health tests requires precise knowledge..., molality, and mole fraction. For example, to convert from weight/volume to molarity molecular mass is...

40 CFR 799.6786 - TSCA water solubility: Generator column method.

Code of Federal Regulations, 2012 CFR

2012-07-01

... quantitative) analysis of solvent extract in paragraph (c)(3)(iv) of this section. The design of the generator.... Finally, the design of most chemical tests and many ecological and health tests requires precise knowledge..., molality, and mole fraction. For example, to convert from weight/volume to molarity molecular mass is...

Broad Specification Fuels Combustion Technology Program. Phase 2

DTIC Science & Technology

1990-10-01

4 4C Where: M is the molecular weight of th hxth specie Nt is the mole fraction of the x specie a is the hydrogen to carbon ratio of the fuel...RATIO F’gure 7-15 Idle Emisions Characteristics of Variable Geometry Cornbusuom geometry combustor configurations as well. The remaining performance

Detection of hydrogen sulfide above the clouds in Uranus's atmosphere

NASA Astrophysics Data System (ADS)

Irwin, Patrick G. J.; Toledo, Daniel; Garland, Ryan; Teanby, Nicholas A.; Fletcher, Leigh N.; Orton, Glenn A.; Bézard, Bruno

2018-04-01

Visible-to-near-infrared observations indicate that the cloud top of the main cloud deck on Uranus lies at a pressure level of between 1.2 bar and 3 bar. However, its composition has never been unambiguously identified, although it is widely assumed to be composed primarily of either ammonia or hydrogen sulfide (H2S) ice. Here, we present evidence of a clear detection of gaseous H2S above this cloud deck in the wavelength region 1.57-1.59 μm with a mole fraction of 0.4-0.8 ppm at the cloud top. Its detection constrains the deep bulk sulfur/nitrogen abundance to exceed unity (>4.4-5.0 times the solar value) in Uranus's bulk atmosphere, and places a lower limit on the mole fraction of H2S below the observed cloud of (1.0 -2.5 ) ×1 0-5. The detection of gaseous H2S at these pressure levels adds to the weight of evidence that the principal constituent of 1.2-3-bar cloud is likely to be H2S ice.

Detection of hydrogen sulfide above the clouds in Uranus's atmosphere

NASA Astrophysics Data System (ADS)

Irwin, Patrick G. J.; Toledo, Daniel; Garland, Ryan; Teanby, Nicholas A.; Fletcher, Leigh N.; Orton, Glenn A.; Bézard, Bruno

2018-05-01

Visible-to-near-infrared observations indicate that the cloud top of the main cloud deck on Uranus lies at a pressure level of between 1.2 bar and 3 bar. However, its composition has never been unambiguously identified, although it is widely assumed to be composed primarily of either ammonia or hydrogen sulfide (H2S) ice. Here, we present evidence of a clear detection of gaseous H2S above this cloud deck in the wavelength region 1.57-1.59 μm with a mole fraction of 0.4-0.8 ppm at the cloud top. Its detection constrains the deep bulk sulfur/nitrogen abundance to exceed unity (>4.4-5.0 times the solar value) in Uranus's bulk atmosphere, and places a lower limit on the mole fraction of H2S below the observed cloud of (1.0 -2.5 ) ×1 0-5. The detection of gaseous H2S at these pressure levels adds to the weight of evidence that the principal constituent of 1.2-3-bar cloud is likely to be H2S ice.

Voyager 2 radio science observations of the Uranian system Atmosphere, rings, and satellites

NASA Technical Reports Server (NTRS)

Tyler, G. L.; Eshleman, V. R.; Hinson, D. P.; Marouf, E. A.; Simpson, R. A.; Sweetnam, D. N.; Anderson, J. D.; Campbell, J. K.; Levy, G. S.; Lindal, G. F.

1986-01-01

The results of preliminary analyses of radio occultation data obtained by Voyager 2 as it passed Uranus are described. The occultations took place between 2-7 deg S latitude and yielded atmospheric temperature profiles between pressure levels of 10-900 mbar, an altitude range of 100 km. The mole fractions of hydrogen and helium in the tropopause were estimated, in conjunction with IR data, to about 0.85 and 0.10-0.20, respectively. Radio signal intensity data indicated the presence of a cloud deck of CH4 ice at a pressure level of 1300 mbar and a temperature of 81 K, implying a CH4 mole fraction of 0.02 at very low altitudes. The ionosphere extended upward, in two levels, to more than 10,000 km altitude. The ring system was different than the one around Saturn and possessed cylindrical substructures. The radio data also permitted mass density estimates for the five major moons, i.e., about 1.40 gr/cu cm, a value which rules out cometary origins.

Effect of size and indium-composition on linear and nonlinear optical absorption of InGaN/GaN lens-shaped quantum dot

NASA Astrophysics Data System (ADS)

Ahmed, S. Jbara; Zulkafli, Othaman; M, A. Saeed

2016-05-01

Based on the Schrödinger equation for envelope function in the effective mass approximation, linear and nonlinear optical absorption coefficients in a multi-subband lens quantum dot are investigated. The effects of quantum dot size on the interband and intraband transitions energy are also analyzed. The finite element method is used to calculate the eigenvalues and eigenfunctions. Strain and In-mole-fraction effects are also studied, and the results reveal that with the decrease of the In-mole fraction, the amplitudes of linear and nonlinear absorption coefficients increase. The present computed results show that the absorption coefficients of transitions between the first excited states are stronger than those of the ground states. In addition, it has been found that the quantum dot size affects the amplitudes and peak positions of linear and nonlinear absorption coefficients while the incident optical intensity strongly affects the nonlinear absorption coefficients. Project supported by the Ministry of Higher Education and Scientific Research in Iraq, Ibnu Sina Institute and Physics Department of Universiti Teknologi Malaysia (UTM RUG Vote No. 06-H14).

A study of 173 nm light emission from discharge cells in plasma display panel

NASA Astrophysics Data System (ADS)

Uhm, Han S.; Choi, Eun H.; Jung, Kyu B.

2005-03-01

Emission properties of the 173nm lights from the electrical discharge cells of the plasma display panel are investigated. The dimer formation and a theoretical model of 173nm emission are presented. It is shown that the diffusion loss of the excited xenon atoms in the metastable level is one of the most important population depreciation factor of excited xenon atoms. The decay time τd of excited atom number increases from zero, reaches its peak, and then decreases to zero, as the gas pressure p increases from zero, agreeing well with experimental data. A simple analytical expression Y of the total emission intensity is described in terms of the diffusion loss df, the three-body collision η, the gas pressure p, and the xenon mole fraction χ. The emission intensity Y of 173nm photon decreases with an increasing value of parameter df. Moreover, the emission intensity Y increases drastically with an increasing value of the gas pressure p and the xenon mole fraction χ. Results from the theoretical model agree remarkably well with experimental data.

Underresolved absorption spectroscopy of OH radicals in flames using broadband UV LEDs

NASA Astrophysics Data System (ADS)

White, Logan; Gamba, Mirko

2018-04-01

A broadband absorption spectroscopy diagnostic based on underresolution of the spectral absorption lines is evaluated for the inference of species mole fraction and temperature in combustion systems from spectral fitting. The approach uses spectrally broadband UV light emitting diodes and leverages low resolution, small form factor spectrometers. Through this combination, the method can be used to develop high precision measurement sensors. The challenges of underresolved spectroscopy are explored and addressed using spectral derivative fitting, which is found to generate measurements with high precision and accuracy. The diagnostic is demonstrated with experimental measurements of gas temperature and OH mole fraction in atmospheric air/methane premixed laminar flat flames. Measurements exhibit high precision, good agreement with 1-D flame simulations, and high repeatability. A newly developed model of uncertainty in underresolved spectroscopy is applied to estimate two-dimensional confidence regions for the measurements. The results of the uncertainty analysis indicate that the errors in the outputs of the spectral fitting procedure are correlated. The implications of the correlation between uncertainties for measurement interpretation are discussed.

Mapping methane plumes and the delta C-13 composition of anthropogenic sources in southwest Germany

NASA Astrophysics Data System (ADS)

Schmidt, Martina; Yeman, Christiane; Dinger, Florian; Ars, Sebastien; Yver Kwok, Camille

2016-04-01

A mobile analyser based on Cavity-Ring-Down Spectroscopy was installed on a vehicle, together with a GPS receiver. This allows us to measure atmospheric methane and carbon dioxide mole fractions and the C-13 isotopes of both gases while driving. Methane mole fraction measurements show a good repeatability even for high frequency measurements whereas the 13CH4 measurements need a longer averaging time of 1 minute for 1 ‰ repeatability and 15 minutes for 0.23 ‰ repeatability. Driving through an emission plume, the signal is typically only 60 seconds long. To overcome the precision problem for the isotope measurements we filled a 25 m tubing when driving through the plume, which was then flushed back through our analyser during 30 minutes. During several campaigns we visited a land fill site, a biogas plant, a dairy cow farm and a natural gas storage and measured an averaged isotopic methane signature(C-13) of -58.3 ±3 ‰, -62.5 ± 1‰, -62.2 ± 2‰, -51 ± 7‰, respectively.

Surface properties of liquid In-Zn alloys

NASA Astrophysics Data System (ADS)

Pstruś, J.; Moser, Z.; Gąsior, W.

2011-02-01

The measurements of surface tension and density of zinc, indium and liquid In-Zn alloys containing 0.9, 0.85, 0.75, 0.70, 0.60, 0.40, 0.25 and 0.10 mole fraction of In were carried out using the method of maximum pressure in gaseous bubbles (MBP) as well as dilatometric technique. The technique of sessile drop was additionally applied in the measurements of surface tension for pure indium and zinc. The measurements were performed at temperature range 474-1151 K. The isotherms of surface tension calculated based on Butler's equation at 700 and 1100 K corresponded well with the experimental values for zinc content lower than 0.6 mole fraction. The surface tension calculated for alloys of higher zinc concentrations (0.6 < XZn < 0.95) had a positive value of the surface tension temperature coefficient (dσ/dT), which did not coincide with the experimental results. The density as well as molar volume of liquid In-Zn alloys showed almost identical behaviour like the ideal solutions. The observed little deviations were contained within assessed experimental errors.

Synthetic Nanopores as a Test Case for Ion Channel Theories: The Anomalous Mole Fraction Effect without Single Filing

PubMed Central

Gillespie, Dirk; Boda, Dezső; He, Yan; Apel, Pavel; Siwy, Zuzanna S.

2008-01-01

The predictions of a theory for the anomalous mole fraction effect (AMFE) are tested experimentally with synthetic nanopores in plastic. The negatively charged synthetic nanopores under consideration are highly cation selective and 50 Å in diameter at their smallest point. These pores exhibit an AMFE in mixtures of Ca2+ and monovalent cations. An AMFE occurs when the conductance through a pore is lower in a mixture of salts than in the pure salts at the same concentration. For ion channels, the textbook interpretation of the AMFE is that multiple ions move through the pore in coordinated, single-file motion. However, because the synthetic nanopores are so wide, their AMFE shows that single filing is not necessary for the AMFE. It is shown that the AMFE in the synthetic nanopores is explained by a theory of preferential ion selectivity. The unique properties of the synthetic nanopores allow us to experimentally confirm several predictions of this theory. These same properties make synthetic nanopores an interesting new platform to test theories of ion channel permeation and selectivity in general. PMID:18390596

The development and evaluation of airborne in situ N2O and CH4 sampling using a Quantum Cascade Laser Absorption Spectrometer (QCLAS)

NASA Astrophysics Data System (ADS)

Pitt, Joseph; Le Breton, Michael; Allen, Grant; Percival, Carl; Gallagher, Martin; Bauguitte, Stephane; O'Shea, Sebastian; Muller, Jennifer; Zahniser, Mark; Pyle, John; Palmer, Paul

2016-04-01

Spectroscopic measurements of atmospheric N2O and CH4 mole fractions were made on board the FAAM (Facility for Airborne Atmospheric Measurements) large Atmospheric Research Aircraft. We evaluate the performance of the mid-IR continuous wave Aerodyne Research Inc. Quantum Cascade Laser Absorption Spectrometer (QCLAS) employed over 17 flights conducted during summer 2014. Two different methods of correcting for the influence of water vapour on the spectroscopic retrievals are compared and evaluated. Test flight data demonstrating the sensitivity of the instrument to changes in cabin pressure is presented, and a new in-flight calibration procedure to account for this issue is described and assessed. Total 1σ uncertainties of 1.81 ppb for CH4 and 0.35 ppb for N2O are derived. We report a mean difference in 1 Hz CH4 mole fraction of 2.05 ppb (1σ = 5.85 ppb) between in-flight measurements made using the QCLAS and simultaneous measurements using a previously characterised Los Gatos Research Fast Greenhouse Gas Analyser (FGGA).

The development and evaluation of airborne in situ N2O and CH4 sampling using a Quantum Cascade Laser Absorption Spectrometer (QCLAS)

NASA Astrophysics Data System (ADS)

Pitt, J. R.; Le Breton, M. R.; Allen, G.; Percival, C.; Gallagher, M. W.; Bauguitte, S.; O'Shea, S.; Muller, J.; Zahniser, M. S.; Pyle, J. A.; Palmer, P. I.

2015-12-01

Spectroscopic measurements of atmospheric N2O and CH4 mole fractions were made on board the FAAM (Facility for Airborne Atmospheric Measurements) large Atmospheric Research Aircraft. We evaluate the performance of the mid-IR continuous wave Aerodyne Research Inc. Quantum Cascade Laser Absorption Spectrometer (QCLAS) employed over 17 flights conducted during summer 2014. Two different methods of correcting for the influence of water vapour on the spectroscopic retrievals are compared and evaluated. Test flight data demonstrating the sensitivity of the instrument to changes in cabin pressure is presented, and a new in-flight calibration procedure to account for this issue is described and assessed. Total 1σ uncertainties of 1.81 ppb for CH4 and 0.35 ppb for N2O are derived. We report a mean difference in 1 Hz CH4 mole fraction of 2.05 ppb (1σ = 5.85 ppb) between in-flight measurements made using the QCLAS and simultaneous measurements using a previously characterised Los Gatos Research Fast Greenhouse Gas Analyser (FGGA).

Measurements of NH 3 and CO 2 with Distributed-Feedback Diode Lasers Near 2.0 m in Bioreactor Vent Gases

NASA Astrophysics Data System (ADS)

Webber, Michael E.; Claps, Ricardo; Englich, Florian V.; Tittel, Frank K.; Jeffries, Jay B.; Hanson, Ronald K.

2001-08-01

Measurements of NH3 and CO2 were made in bioreactor vent gases with distributed-feedback diode-laser sensors operating near 2 m. Calculated spectra of NH3 and CO2 were used to determine the optimum transitions for interrogating with an absorption sensor. For ammonia, a strong and isolated absorption transition at 5016.977 cm-1 was selected for trace gas monitoring. For CO2 , an isolated transition at 5007.787 cm-1 was selected to measure widely varying concentrations [500 parts per million (ppm) to 10% ,] with sufficient signal for low mole fractions and without being optically thick for high mole fractions. Using direct absorption and a 36-m total path-length multipass flow-through cell, we achieved a minimum detectivity of 0.25 ppm for NH3 and 40 ppm for CO2 . We report on the quasi-continuous field measurements of NH3 and CO2 concentration in bioreactor vent gases that were recorded at NASA Johnson Space Center with a portable and automated sensor system over a 45-h data collection window.

Theoretical study of strain-dependent optical absorption in a doped self-assembled InAs/InGaAs/GaAs/AlGaAs quantum dot

PubMed Central

Tankasala, Archana; Hsueh, Yuling; Charles, James; Fonseca, Jim; Povolotskyi, Michael; Kim, Jun Oh; Krishna, Sanjay; Allen, Monica S; Allen, Jeffery W; Rahman, Rajib; Klimeck, Gerhard

2018-01-01

A detailed theoretical study of the optical absorption in doped self-assembled quantum dots is presented. A rigorous atomistic strain model as well as a sophisticated 20-band tight-binding model are used to ensure accurate prediction of the single particle states in these devices. We also show that for doped quantum dots, many-particle configuration interaction is also critical to accurately capture the optical transitions of the system. The sophisticated models presented in this work reproduce the experimental results for both undoped and doped quantum dot systems. The effects of alloy mole fraction of the strain controlling layer and quantum dot dimensions are discussed. Increasing the mole fraction of the strain controlling layer leads to a lower energy gap and a larger absorption wavelength. Surprisingly, the absorption wavelength is highly sensitive to the changes in the diameter, but almost insensitive to the changes in dot height. This behavior is explained by a detailed sensitivity analysis of different factors affecting the optical transition energy. PMID:29719758

Ethane selective IRMOF-8 and its significance in ethane-ethylene separation by adsorption.

PubMed

Pires, João; Pinto, Moisés L; Saini, Vipin K

2014-08-13

The separation of ethylene from ethane is one of the most energy-intensive single distillations practiced. This separation could be alternatively made by an adsorption process if the adsorbent would preferentially adsorb ethane over ethylene. Materials that exhibit this feature are scarce. Here, we report the case of a metal-organic framework, the IRMOF-8, for which the adsorption isotherms of ethane and ethylene were measured at 298 and 318 K up to pressures of 1000 kPa. Separation of ethane/ethylene mixtures was achieved in flow experiments using a IRMOF-8 filled column. The interaction of gas molecules with the surface of IRMOF-8 was explored using density functional theory (DFT) methods. We show both experimentally and computationally that, as a result of the difference in the interaction energies of ethane and ethylene in IRMOF-8, this material presents the preferential adsorption of ethane over ethylene. The results obtained in this study suggest that MOFs with ligands exhibiting high aromaticity character are prone to adsorb ethane preferably over ethylene.

Synthesis of Ternary Borocarbonitrides by High Temperature Pyrolysis of Ethane 1,2-Diamineborane

PubMed Central

Leardini, Fabrice; Massimi, Lorenzo; Flores-Cuevas, Eduardo; Fernández, Jose Francisco; Ares, Jose Ramon; Betti, Maria Grazia; Mariani, Carlo

2015-01-01

Ethane 1,2-diamineborane (EDAB) is an alkyl-containing amine-borane adduct with improved hydrogen desorption properties as compared to ammonia borane. In this work, it is reported the high temperature thermolytic decomposition of EDAB. Thermolysis of EDAB has been investigated by concomitant thermogravimetry-differential thermal analysis-mass spectrometry experiments. EDAB shows up to four H2 desorption events below 1000 °C. Small fractions of CH4, C2H4 and CO/CO2 are also observed at moderate-high temperatures. The solid-state thermolysis product has been characterized by means of different structural and chemical methods, such as X-ray diffraction, Raman spectroscopy, Scanning electron microscopy, Elemental analysis, and X-ray photoelectron spectroscopy (XPS). The obtained results indicate the formation of a ternary borocarbonitride compound with a poorly-crystalline graphitic-like structure. By contrast, XPS measurements show that the surface is rich in carbon and nitrogen oxides, which is quite different to the bulk of the material. PMID:28793545

Nonlinear relationship between the Product Consistency Test (PCT) response and the Al/B ratio in a soda-lime aluminoborosilicate glass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Farooqi, Rahmat Ullah; Hrma, Pavel

2016-06-01

We have investigated the effect of A1/B ratio on the Product Consistency Test (PCT) response. In an aluminoborosilicate soda-lime glass based on a modified International Simple Glass, ISG-3, the A1/B ratio varied from 0 to 0.55 (in mole fractions). In agreement with various models of the PCT response as a function of glass composition, we observed a monotonic increase of B and Na releases with decreasing A1/B mole ratio, but only when the ratio was higher than 0.05. Below this value (A1/B < 0.05), we observed a sharp decrease that we attribute to B in tetrahedral coordination.

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.

A benchmarking method to measure dietary absorption efficiency of chemicals by fish.

PubMed

Xiao, Ruiyang; Adolfsson-Erici, Margaretha; Åkerman, Gun; McLachlan, Michael S; MacLeod, Matthew

2013-12-01

Understanding the dietary absorption efficiency of chemicals in the gastrointestinal tract of fish is important from both a scientific and a regulatory point of view. However, reported fish absorption efficiencies for well-studied chemicals are highly variable. In the present study, the authors developed and exploited an internal chemical benchmarking method that has the potential to reduce uncertainty and variability and, thus, to improve the precision of measurements of fish absorption efficiency. The authors applied the benchmarking method to measure the gross absorption efficiency for 15 chemicals with a wide range of physicochemical properties and structures. They selected 2,2',5,6'-tetrachlorobiphenyl (PCB53) and decabromodiphenyl ethane as absorbable and nonabsorbable benchmarks, respectively. Quantities of chemicals determined in fish were benchmarked to the fraction of PCB53 recovered in fish, and quantities of chemicals determined in feces were benchmarked to the fraction of decabromodiphenyl ethane recovered in feces. The performance of the benchmarking procedure was evaluated based on the recovery of the test chemicals and precision of absorption efficiency from repeated tests. Benchmarking did not improve the precision of the measurements; after benchmarking, however, the median recovery for 15 chemicals was 106%, and variability of recoveries was reduced compared with before benchmarking, suggesting that benchmarking could account for incomplete extraction of chemical in fish and incomplete collection of feces from different tests. © 2013 SETAC.

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

PubMed

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

2008-12-14

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

Structural anomaly and dynamic heterogeneity in cycloether/water binary mixtures: Signatures from composition dependent dynamic fluorescence measurements and computer simulations

NASA Astrophysics Data System (ADS)

Indra, Sandipa; Guchhait, Biswajit; Biswas, Ranjit

2016-03-01

We have performed steady state UV-visible absorption and time-resolved fluorescence measurements and computer simulations to explore the cosolvent mole fraction induced changes in structural and dynamical properties of water/dioxane (Diox) and water/tetrahydrofuran (THF) binary mixtures. Diox is a quadrupolar solvent whereas THF is a dipolar one although both are cyclic molecules and represent cycloethers. The focus here is on whether these cycloethers can induce stiffening and transition of water H-bond network structure and, if they do, whether such structural modification differentiates the chemical nature (dipolar or quadrupolar) of the cosolvent molecules. Composition dependent measured fluorescence lifetimes and rotation times of a dissolved dipolar solute (Coumarin 153, C153) suggest cycloether mole-fraction (XTHF/Diox) induced structural transition for both of these aqueous binary mixtures in the 0.1 ≤ XTHF/Diox ≤ 0.2 regime with no specific dependence on the chemical nature. Interestingly, absorption measurements reveal stiffening of water H-bond structure in the presence of both the cycloethers at a nearly equal mole-fraction, XTHF/Diox ˜ 0.05. Measurements near the critical solution temperature or concentration indicate no role for the solution criticality on the anomalous structural changes. Evidences for cycloether aggregation at very dilute concentrations have been found. Simulated radial distribution functions reflect abrupt changes in respective peak heights at those mixture compositions around which fluorescence measurements revealed structural transition. Simulated water coordination numbers (for a dissolved C153) and number of H-bonds also exhibit minima around these cosolvent concentrations. In addition, several dynamic heterogeneity parameters have been simulated for both the mixtures to explore the effects of structural transition and chemical nature of cosolvent on heterogeneous dynamics of these systems. Simulated four-point dynamic susceptibility suggests formation of clusters inducing local heterogeneity in the solution structure.

High accuracy measurements of dry mole fractions of carbon dioxide and methane in humid air

NASA Astrophysics Data System (ADS)

Rella, C. W.; Chen, H.; Andrews, A. E.; Filges, A.; Gerbig, C.; Hatakka, J.; Karion, A.; Miles, N. L.; Richardson, S. J.; Steinbacher, M.; Sweeney, C.; Wastine, B.; Zellweger, C.

2013-03-01

Traditional techniques for measuring the mole fractions of greenhouse gases in the well-mixed atmosphere have required dry sample gas streams (dew point < -25 °C) to achieve the inter-laboratory compatibility goals set forth by the Global Atmosphere Watch programme of the World Meteorological Organisation (WMO/GAW) for carbon dioxide (±0.1 ppm in the Northern Hemisphere and ±0.05 ppm in the Southern Hemisphere) and methane (±2 ppb). Drying the sample gas to low levels of water vapour can be expensive, time-consuming, and/or problematic, especially at remote sites where access is difficult. Recent advances in optical measurement techniques, in particular cavity ring down spectroscopy, have led to the development of greenhouse gas analysers capable of simultaneous measurements of carbon dioxide, methane and water vapour. Unlike many older technologies, which can suffer from significant uncorrected interference from water vapour, these instruments permit accurate and precise greenhouse gas measurements that can meet the WMO/GAW inter-laboratory compatibility goals (WMO, 2011a) without drying the sample gas. In this paper, we present laboratory methodology for empirically deriving the water vapour correction factors, and we summarise a series of in-situ validation experiments comparing the measurements in humid gas streams to well-characterised dry-gas measurements. By using the manufacturer-supplied correction factors, the dry-mole fraction measurements have been demonstrated to be well within the GAW compatibility goals up to a water vapour concentration of at least 1%. By determining the correction factors for individual instruments once at the start of life, this water vapour concentration range can be extended to at least 2% over the life of the instrument, and if the correction factors are determined periodically over time, the evidence suggests that this range can be extended up to and even above 4% water vapour concentrations.

Removing Traffic Emissions from CO2 Time Series Measured at a Tall Tower Using on-Road Measurements and WRF-Stilt Transport Modeling

NASA Astrophysics Data System (ADS)

Schmidt, A.; Rella, C.; Goeckede, M.; Hanson, C. V.; Yang, Z.; Law, B. E.

2014-12-01

In recent years, measurements of atmospheric carbon dioxide with high precision and accuracy have become increasingly important for climate change research, in particular to inform terrestrial biosphere models. Anthropogenic carbon dioxide emissions from fossil fuel burning have long been recognized to contribute a significant portion of the carbon dioxide in the atmosphere. Here, we present an approach to remove the traffic related carbon dioxide emissions from mole fractions measured at a tall tower by using the corresponding carbon monoxide measurements in combination with footprint analyses and transport modeling. This technique improves the suitability of the CO2 data to be used in inverse modeling approaches of atmosphere-biosphere exchange that do not account for non-biotic portions of CO2. In our study region in Oregon, road traffic emissions are the biggest source of anthropogenic carbon dioxide and carbon monoxide. A three-day mobile campaign covering 1700 km of roads in northwestern Oregon was performed during summer of 2012 using a laser-based Cavity Ring Down Spectrometer. The mobile measurements incorporated different roads including main highways, urban streets, and back-roads, largely within the typical footprint of a tall CO2 observation tower in Oregon's Willamette Valley. For the first time, traffic related CO:CO2 emission ratios were measured directly at the sources during an on-road campaign under a variety of different driving conditions. An average emission ratio of 7.43 (±1.80) ppb CO per ppm CO2 was obtained for the study region and applied to separate the traffic related portion of CO2 from the mole fraction time series. The road traffic related portion of the CO2 mole fractions measured at the tower site reached maximum values from 9.8 to 12 ppm, depending on the height above the surface, during summer 2012.

Removing traffic emissions from CO2 time series measured at a tall tower using mobile measurements and transport modeling

NASA Astrophysics Data System (ADS)

Schmidt, Andres; Rella, Chris W.; Göckede, Mathias; Hanson, Chad; Yang, Zhenlin; Law, Beverly E.

2014-11-01

In recent years, measurements of atmospheric carbon dioxide with high precision and accuracy have become increasingly important for climate change research, in particular to inform terrestrial biosphere models. Anthropogenic carbon dioxide emissions from fossil fuel burning have long been recognized to contribute a significant portion of the carbon dioxide in the atmosphere. Here, we present an approach to remove the traffic related carbon dioxide emissions from mole fractions measured at a tall tower by using the corresponding carbon monoxide measurements in combination with footprint analyses and transport modeling. This technique improves the suitability of the CO2 data to be used in inverse modeling approaches of atmosphere-biosphere exchange that do not account for non-biotic portions of CO2. In our study region in Oregon, road traffic emissions are the biggest source of anthropogenic carbon dioxide and carbon monoxide. A three-day mobile campaign covering 1700 km of roads in northwestern Oregon was performed during summer of 2012 using a laser-based Cavity Ring-Down Spectrometer. The mobile measurements incorporated different roads including main highways, urban streets, and back-roads, largely within the typical footprint of a tall CO/CO2 observation tower in Oregon's Willamette Valley. For the first time, traffic related CO:CO2 emission ratios were measured directly at the sources during an on-road campaign under a variety of different driving conditions. An average emission ratio of 7.43 (±1.80) ppb CO per ppm CO2 was obtained for the study region and applied to separate the traffic related portion of CO2 from the mole fraction time series. The road traffic related portion of the CO2 mole fractions measured at the tower site reached maximum values ranging from 9.8 to 12 ppm, depending on the height above the surface, during summer 2012.

Supercritical water gasification of landfill leachate for hydrogen production in the presence and absence of alkali catalyst.

PubMed

Weijin, Gong; Binbin, Li; Qingyu, Wang; Zuohua, Huang; Liang, Zhao

2018-03-01

Gasification of landfill leachate in supercritical water using batch-type reactor is investigated. Alkali such as NaOH, KOH, K 2 CO 3 , Na 2 CO 3 is used as catalyst. The effect of temperature (380-500 °C), retention time (5-25 min), landfill leachate concentration (1595 mg L -1 -15,225 mg L -1 ), catalyst adding amount (1-10 wt%) on hydrogen mole fraction, hydrogen yield, carbon gasification rate, COD, TOC, TN removal efficiency are investigated. The results showed that gaseous products mainly contained hydrogen, methane, carbon dioxide and carbon monoxide without addition of catalyst. However, the main gaseous products are hydrogen and methane with addition of NaOH, KOH, K 2 CO 3 , Na 2 CO 3 . In the absence of alkali catalyst, the effect of temperature on landfill leachate gasification is positive. Hydrogen mole fraction, hydrogen yield, carbon gasification ratio increase with temperature, which maximum value being 55.6%, 107.15 mol kg -1 , 71.96% is obtained at 500 °C, respectively. Higher raw landfill leachate concentration leads to lower hydrogen production and carbon gasification rate. The suitable retention time is suggested to be 15 min for higher hydrogen production and carbon gasification rate. COD, TOC and TN removal efficiency also increase with increase of temperature, decrease of landfill leachate concentration. In the presence of catalyst, the hydrogen production is obviously promoted by addition of alkali catalyst. the effect of catalysts on hydrogen production is in the following order: NaOH ＞ KOH ＞ Na 2 CO 3  ＞ K 2 CO 3 . The maximum hydrogen mole fraction and hydrogen yield being 74.40%, 70.05 mol kg -1 is obtained with adding amount of 5 wt% NaOH at 450 °C, 28 MPa, 15 min. Copyright © 2017. Published by Elsevier Ltd.

Molecular dynamics simulation for the test of calibrated OPLS-AA force field for binary liquid mixture of tri-iso-amyl phosphate and n-dodecane.

PubMed

Das, Arya; Ali, Sk Musharaf

2018-02-21

Tri-isoamyl phosphate (TiAP) has been proposed to be an alternative for tri-butyl phosphate (TBP) in the Plutonium Uranium Extraction (PUREX) process. Recently, we have successfully calibrated and tested all-atom optimized potentials for liquid simulations using Mulliken partial charges for pure TiAP, TBP, and dodecane by performing molecular dynamics (MD) simulation. It is of immense importance to extend this potential for the various molecular properties of TiAP and TiAP/n-dodecane binary mixtures using MD simulation. Earlier, efforts were devoted to find out a suitable force field which can explain both structural and dynamical properties by empirical parameterization. Therefore, the present MD study reports the structural, dynamical, and thermodynamical properties with different mole fractions of TiAP-dodecane mixtures at the entire range of mole fraction of 0-1 employing our calibrated Mulliken embedded optimized potentials for liquid simulation (OPLS) force field. The calculated electric dipole moment of TiAP was seen to be almost unaffected by the TiAP concentration in the dodecane diluent. The calculated liquid densities of the TiAP-dodecane mixture are in good agreement with the experimental data. The mixture densities at different temperatures are also studied which was found to be reduced with temperature as expected. The plot of diffusivities for TiAP and dodecane against mole fraction in the binary mixture intersects at a composition in the range of 25%-30% of TiAP in dodecane, which is very much closer to the TBP/n-dodecane composition used in the PUREX process. The excess volume of mixing was found to be positive for the entire range of mole fraction and the excess enthalpy of mixing was shown to be endothermic for the TBP/n-dodecane mixture as well as TiAP/n-dodecane mixture as reported experimentally. The spatial pair correlation functions are evaluated between TiAP-TiAP and TiAP-dodecane molecules. Further, shear viscosity has been computed by performing the non-equilibrium molecular dynamics employing the periodic perturbation method. The calculated shear viscosity of the binary mixture is found to be in excellent agreement with the experimental values. The use of the newly calibrated OPLS force field embedding Mulliken charges is shown to be equally reliable in predicting the structural and dynamical properties for the mixture without incorporating any arbitrary scaling in the force field or Lennard-Jones parameters. Further, the present MD simulation results demonstrate that the Stokes-Einstein relation breaks down at the molecular level. The present methodology might be adopted to evaluate the liquid state properties of an aqueous-organic biphasic system, which is of great significance in the interfacial science and technology.

Diurnal, seasonal, and annual trends in atmospheric CO2 at southwest London during 2000-2012: Wind sector analysis and comparison with Mace Head, Ireland

NASA Astrophysics Data System (ADS)

Hernández-Paniagua, Iván Y.; Lowry, David; Clemitshaw, Kevin C.; Fisher, Rebecca E.; France, James L.; Lanoisellé, Mathias; Ramonet, Michel; Nisbet, Euan G.

2015-03-01

In-situ measurements of atmospheric CO2 have been made at Royal Holloway University of London (RHUL) in Egham (EGH), Surrey, UK from 2000 to 2012. The data were linked to the global scale using NOAA-calibrated gases. Measured CO2 varies on time scales that range from minutes to inter-annual and annual cycles. Seasonality and pollution episodes occur each year. Diurnal cycles vary with daylight and temperature, which influence the biological cycle of CO2 and the degree of vertical mixing. Anthropogenic emissions of CO2 dominate the variability during weekdays when transport cycles are greater than at weekends. Seasonal cycles are driven by temporal variations in biological activity and changes in combustion emissions. Maximum mole fractions (μmol/mol) (henceforth referred to by parts per million, ppm) occur in winter, with minima in late summer. The smallest seasonal amplitude observed, peak to trough, was 17.0 ppm CO2 in 2003, whereas the largest amplitude observed was 27.1 ppm CO2 in 2008. Meteorology can strongly modify the CO2 mole fractions at different time scales. Analysis of eight 45° wind sectors shows that the highest CO2 mole fractions were recorded from the E and SE sectors. Lowest mole fractions were observed for air masses from the S and SW. Back-trajectory and meteorological analyses of the data confirm that the dominant sources of CO2 are anthropogenic emissions from London and SE England. The largest annual rate of increase in the annual average of CO2, 3.26 ppm yr-1 (p < 0.05), was for the W sector with a smaller increase, 2.56 ppm yr-1 (p < 0.05), for the E sector. Calm winds showed an annual growth rate of 1.16 ppm yr-1 CO2 (p < 0.05) implying declining local sources. The EGH site shows an average growth rate of 2.5 ppm yr-1 CO2 (p < 0.05) over the measured period, which exceeds the observed global trend and contrasts with the decrease in CO2 emissions reported in UK greenhouse gas inventories. This is presumably because the region has had higher growth in combustion emissions than the global average, though the low growth rate in calm weather implies the local emissions have grown more slowly. The seasonal cycle at EGH had larger amplitudes than those recorded at the Mace Head Atmospheric Research Station (MHD) on the W coast of Ireland. Overall, the growth rate observed in annual average CO2 at EGH was larger than that at MHD by about 0.5 ppm yr-1.

Molecular dynamics simulation for the test of calibrated OPLS-AA force field for binary liquid mixture of tri-iso-amyl phosphate and n-dodecane

NASA Astrophysics Data System (ADS)

Das, Arya; Ali, Sk. Musharaf

2018-02-01

Tri-isoamyl phosphate (TiAP) has been proposed to be an alternative for tri-butyl phosphate (TBP) in the Plutonium Uranium Extraction (PUREX) process. Recently, we have successfully calibrated and tested all-atom optimized potentials for liquid simulations using Mulliken partial charges for pure TiAP, TBP, and dodecane by performing molecular dynamics (MD) simulation. It is of immense importance to extend this potential for the various molecular properties of TiAP and TiAP/n-dodecane binary mixtures using MD simulation. Earlier, efforts were devoted to find out a suitable force field which can explain both structural and dynamical properties by empirical parameterization. Therefore, the present MD study reports the structural, dynamical, and thermodynamical properties with different mole fractions of TiAP-dodecane mixtures at the entire range of mole fraction of 0-1 employing our calibrated Mulliken embedded optimized potentials for liquid simulation (OPLS) force field. The calculated electric dipole moment of TiAP was seen to be almost unaffected by the TiAP concentration in the dodecane diluent. The calculated liquid densities of the TiAP-dodecane mixture are in good agreement with the experimental data. The mixture densities at different temperatures are also studied which was found to be reduced with temperature as expected. The plot of diffusivities for TiAP and dodecane against mole fraction in the binary mixture intersects at a composition in the range of 25%-30% of TiAP in dodecane, which is very much closer to the TBP/n-dodecane composition used in the PUREX process. The excess volume of mixing was found to be positive for the entire range of mole fraction and the excess enthalpy of mixing was shown to be endothermic for the TBP/n-dodecane mixture as well as TiAP/n-dodecane mixture as reported experimentally. The spatial pair correlation functions are evaluated between TiAP-TiAP and TiAP-dodecane molecules. Further, shear viscosity has been computed by performing the non-equilibrium molecular dynamics employing the periodic perturbation method. The calculated shear viscosity of the binary mixture is found to be in excellent agreement with the experimental values. The use of the newly calibrated OPLS force field embedding Mulliken charges is shown to be equally reliable in predicting the structural and dynamical properties for the mixture without incorporating any arbitrary scaling in the force field or Lennard-Jones parameters. Further, the present MD simulation results demonstrate that the Stokes-Einstein relation breaks down at the molecular level. The present methodology might be adopted to evaluate the liquid state properties of an aqueous-organic biphasic system, which is of great significance in the interfacial science and technology.

Critical Temperature Differences of a Standing Wave Thermoacoustic Prime Mover with Various Helium-Based Binary Mixture Working Gases

NASA Astrophysics Data System (ADS)

Setiawan, Ikhsan; Nohtomi, Makoto; Katsuta, Masafumi

2015-06-01

Thermoacoustic prime movers are energy conversion devices which convert thermal energy into acoustic work. The devices are environmentally friendly because they do not produce any exhaust gases. In addition, they can utilize clean energy such as solar-thermal energy or waste heat from internal combustion engines as the heat sources. The output mechanical work of thermoacoustic prime movers are usually used to drive a thermoacoustic refrigerator or to generate electricity. A thermoacoustic prime mover with low critical temperature difference is desired when we intend to utilize low quality of heat sources such as waste heat and sun light. The critical temperature difference can be significantly influenced by the kinds of working gases inside the resonator and stack's channels of the device. Generally, helium gas is preferred as the working gas due to its high sound speed which together with high mean pressure will yield high acoustic power per unit volume of the device. Moreover, adding a small amount of a heavy gas to helium gas may improve the efficiency of thermoacoustic devices. This paper presents numerical study and estimation of the critical temperature differences of a standing wave thermoacoustic prime mover with various helium-based binary-mixture working gases. It is found that mixing helium (He) gas with other common gases, namely argon (Ar), nitrogen (N2), oxygen (O2), and carbon dioxide (CO2), at appropriate pressures and molar compositions, reduce the critical temperature differences to lower than those of the individual components of the gas mixtures. In addition, the optimum mole fractions of Hegas which give the minimum critical temperature differences are shifted to larger values as the pressure increases, and tends to be constant at around 0.7 when the pressure increases more than 2 MPa. However, the minimum critical temperature differences slightly increase as the pressure increases to higher than 1.5 MPa. Furthermore, we found that the lowest critical temperature difference for He-Armixture gas is around 66 °C which is achieved in pressure range of 1.5 MPa - 2.0 MPa and mole fractions of helium of 0.55 - 0.65. The He-N2 and He-O2 mixture gases demonstrate almost the same performances, both have the lowest critical temperature difference around 59 °C atpressures of 1.0 MPa - 1.5 MPa and helium's mole fractions of 0.35 - 0.55. For all tested gases, the lowest critical temperature difference of around 51 °C is provided by He-CO2 mixture gas at pressures of 0.5 MPa - 1.0 MPa with helium's mole fractions of 0.15 - 0.40.

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

PubMed

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

2012-09-12

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

The Potential of Carbonyl Sulfide as a Proxy for Gross Primary Production at Flux Tower Sites

USDA-ARS?s Scientific Manuscript database

Regional and continental scale studies of the seasonal dynamics of atmospheric carbonyl sulfide (OCS) mole fractions and leaf-level studies of plant OCS exchange have shown a close relationship with those for CO2. CO2 has sinks and sources within terrestrial ecosystems, but the primary terrestrial e...

Response of sugarcane to carbon dioxide enrichment and elevated air temperature

USDA-ARS?s Scientific Manuscript database

Four sugarcane cultivars (CP 72-2086, CP 73-1547, CP 88-1508, and CP 80-1827) were grown in elongated temperature-gradient greenhouses (TGG) at ambient or elevated carbon dioxide (CO2) of 360 or 720 µmol CO2 mol-1 air (ppm, mole fraction basis), respectively. Elevated CO2 was maintained by injection...

Direct computation of thermodynamic properties of chemically reacting air with consideration to CFD

NASA Astrophysics Data System (ADS)

Iannelli, Joe

2003-10-01

This paper details a two-equation procedure to calculate exactly mass and mole fractions, pressure, temperature, specific heats, speed of sound and the thermodynamic and jacobian partial derivatives of pressure and temperature for a five-species chemically reacting equilibrium air. The procedure generates these thermodynamic properties using as independent variables either pressure and temperature or density and internal energy, for CFD applications. An original element in this procedure consists in the exact physically meaningful solution of the mass-fraction and mass-action equations. Air-equivalent molecular masses for oxygen and nitrogen are then developed to account, within a mixture of only oxygen and nitrogen, for the presence of carbon dioxide, argon and the other noble gases within atmospheric air. The mathematical formulation also introduces a versatile system non-dimensionalization that makes the procedure uniformly applicable to flows ranging from shock-tube flows with zero initial velocity to aerothermodynamic flows with supersonic/hypersonic free-stream Mach numbers. Over a temperature range of more than 10000 K and pressure and density ranges corresponding to an increase in altitude in standard atmosphere of 30000 m above sea level, the predicted distributions of mole fractions, constant-volume specific heat, and speed of sound for the model five species agree with independently published results, and all the calculated thermodynamic properties, including their partial derivatives, remain continuous, smooth, and physically meaningful.

Selective Adsorption of Ethane over Ethylene in PCN-245: Impacts of Interpenetrated Adsorbent.

PubMed

Lv, Daofei; Shi, Renfeng; Chen, Yongwei; Wu, Ying; Wu, Houxiao; Xi, Hongxia; Xia, Qibin; Li, Zhong

2018-03-07

The separation of ethane from ethylene using cryogenic distillation is an energy-intensive process in the industry. With lower energetic consumption, the adsorption technology provides the opportunities for developing the industry with economic sustainability. We report an iron-based metal-organic framework PCN-245 with interpenetrated structures as an ethane-selective adsorbent for ethylene/ethane separation. The material maintains stability up to 625 K, even after exposure to 80% humid atmosphere for 20 days. Adsorptive separation experiments on PCN-245 at 100 kPa and 298 K indicated that ethane and ethylene uptakes of PCN-245 were 3.27 and 2.39 mmol, respectively, and the selectivity of ethane over ethylene was up to 1.9. Metropolis Monte Carlo calculations suggested that the interpenetrated structure of PCN-245 created greater interaction affinity for ethane than ethylene through the crossing organic linkers, which is consistent with the experimental results. This work highlights the potential application of adsorbents with the interpenetrated structure for ethane separation from ethylene.

40 CFR 721.3248 - Ethane, 1,2,2- trichlorodifluoro-.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ethane, 1,2,2- trichlorodifluoro-. 721... Substances § 721.3248 Ethane, 1,2,2- trichlorodifluoro-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethane, 1,2,2-trichlorodifluoro- (CAS No...

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

NASA Technical Reports Server (NTRS)

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

1992-01-01

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

Laser-Induced Incandescence Measurements in Low Gravity

NASA Technical Reports Server (NTRS)

VanderWal, R. L.

1997-01-01

A low-gravity environment offers advantages to investigations concerned with soot growth or flame radiation by eliminating of buoyancy-induced convection. Basic to each type of study is knowledge of spatially resolved soot volume fraction, (f(sub v). Laser-induced incandescence (LII) has emerged as a diagnostic for soot volume fraction determination because it possesses high temporal and spatial resolution, geometric versatility and high sensitivity. Implementation and system characterization of LII in a drop tower that provides 2.2 sec of low-gravity (micro)g) at the NASA Lewis Research Center are described here. Validation of LII for soot volume fraction determination in (micro)g is performed by comparison between soot volume fraction measurements obtained by light extinction [20] and LII in low-gravity for a 50/50 mixture (by volume) of 0 acetylene/nitrogen issuing into quiescent air. Quantitative soot volume fraction measurements within other laminar flames of ethane and propane and a turbulent diffusion flame in (micro)g via LII are also demonstrated. An analysis of LII images of a turbulent acetylene diffusion flame in 1-g and (micro)g is presented.

Frequent sampling allows detection of short and rapid surges of exhaled ethane during cardiac surgery.

PubMed

Stenseth, R; Nilsen, T; Haaverstad, R; Vitale, N; Dale, O

2007-11-01

During cardiopulmonary bypass (CPB), hypoperfusion and reperfusion may cause oxidative stress and lipid peroxidation that generates ethane. The aim of this pilot study was to assess the feasibility of frequent sampling of exhaled ethane during cardiac surgery. After approval of the Research Ethics Committee, 10 patients undergoing combined aortic valve and coronary artery bypass surgery were enrolled. Breath samples were drawn in the perioperative period and analyzed by a rapid, sensitive and validated gas-chromatographic method. Increased exhaled ethane was regularly seen following sternotomy, after the start of CPB and after aortic clamp removal, whereas no change was seen after termination of bypass. In one patient, the maximum increase in exhaled ethane was 30-fold. Peak durations lasted only 2-4 min. This study demonstrates that frequent sampling of breath ethane is feasible in a clinical setting, allowing detection of rapid ethane surges of short duration.

40 CFR 721.10086 - Ethane, 2-(difluoromethoxy)-1,1,1-trifluoro-.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ethane, 2-(difluoromethoxy)-1,1,1... Specific Chemical Substances § 721.10086 Ethane, 2-(difluoromethoxy)-1,1,1-trifluoro-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethane, 2...

Phase diagram and high-pressure boundary of hydrate formation in the ethane-water system.

PubMed

Kurnosov, Alexander V; Ogienko, Andrey G; Goryainov, Sergei V; Larionov, Eduard G; Manakov, Andrey Y; Lihacheva, Anna Y; Aladko, Eugeny Y; Zhurko, Fridrikh V; Voronin, Vladimir I; Berger, Ivan F; Ancharov, Aleksei I

2006-11-02

Dissociation temperatures of gas hydrate formed in the ethane-water system were studied at pressures up to 1500 MPa. In situ neutron diffraction analysis and X-ray diffraction analysis in a diamond anvil cell showed that the gas hydrate formed in the ethane-water system at 340, 700, and 1840 MPa and room temperature belongs to the cubic structure I (CS-I). Raman spectra of C-C vibrations of ethane molecules in the hydrate phase, as well as the spectra of solid and liquid ethane under high-pressure conditions were studied at pressures up to 6900 MPa. Within 170-3600 MPa Raman shift of the C-C vibration mode of ethane in the hydrate phase did not show any discontinuities, which could be evidence of possible phase transformations. The upper pressure boundary of high-pressure hydrate existence was discovered at the pressure of 3600 MPa. This boundary corresponds to decomposition of the hydrate to solid ethane and ice VII. The type of phase diagram of ethane-water system was proposed in the pressure range of hydrate formation (0-3600 MPa).

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.

Separating methane emissions from agricultural sources and natural gas: direct measurements of excess columns of CH4, C2H6 and NH3 in the Colorado Front Range

NASA Astrophysics Data System (ADS)

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

2017-12-01

Methane (CH4) is a major greenhouse gas emitted from biogenic, thermogenic, and pyrogenic sources. Here we demonstrate a novel approach to separate sources of CH4 emissions based on a network of small portable sensors performing column measurements in the Northern Colorado Front Range (NCFR). In the study area CH4 is emitted from biogenic sources such as concentrated animal feeding operations (CAFOs) and natural gas production and storage. In March 2015 we deployed a network of five Fourier Transform Spectrometers (FTS) to characterize the regional scale methane dome in Colorado's Denver-Julesburg Basin based on excess vertical column measurements (the column enhancement inside the dome over background). Three EM27sun FTS measured CH4, oxygen (O2) and water vapor (H2O) columns at Eaton, CO (inside the dome) and at two boundary sites; the CU mobile SOF (Solar Occultation Flux) measured ethane (C2H6), ammonia (NH3), and H2O at Eaton, CO. The column averaged dry air mole fractions XCH4, XC2H6, and XNH3 were determined using O2 columns for air mass factor normalization, and background column was subtracted to derive excess vertical columns of DXCH4, DXC2H6, DXNH3 at Eaton, CO. Eaton is located both near CAFOs and at the northern edge of oil and natural gas production wells. Our approach for source apportioning methane employs a linear regression analysis that explains DXCH4 in terms of DXC2H6 as tracer for natural gas sources, and DXNH3 as tracer for CAFO emissions. The results of the source apportionment are compared with literature values of the NH3/CH4 and C2H6/CH4 ratio to evaluate the method of excess columns, which is independent of boundary layer height.

Ultrasonic velocity dispersion in ethane-argon mixtures.

NASA Technical Reports Server (NTRS)

Amme, R. C.; Warren, B. E.

1968-01-01

Ultrasonic interferometry to measure velocity dispersion in ethane-Ar mixtures, discussing ethane relaxation characteristics and relaxation characteristics and relaxation times for particle collisions

Anti-fatigue activity of polysaccharide fractions from Lepidium meyenii Walp. (maca).

PubMed

Li, Jing; Sun, Qingrui; Meng, Qingran; Wang, Lei; Xiong, Wentao; Zhang, Lianfu

2017-02-01

The two fractions of polysaccharide MPS-1 and MPS-2 were extracted from Lepidium meyenii Walp. (maca) by water, and purified using a DEAE-52 and a Sephadex G-100 column. The molecular weight (M W ) of MPS-1 was 7.6kDa, and the M W of MPS-2 was 6.7kDa. The MPS-1 was composed of xylose, arabinose, galactose and glucose, with the mole ratio 1:1.7:3.3:30.5; the MPS-2 was composed of arabinose, galactose and glucose, with the mole ratio 1:1.3:36.8. The IR spectrum implied that only α-pyranose existed in MPS-1, and both α-pyranose and β-pyranose existed in MPS-2. The anti-fatigue activities of MPS-1 and MPS-2 were measured by the forced swimming test, along with the determination of blood lactate (BLA), urea nitrogen (BUN), lactic dehydrogenase (LDH) activity and liver glycogen (LG). The results indicated that both MPS-1 and MPS-2 presented dose-dependently positive effects on the fatigue related parameters. Additionally, MPS-2 has a better anti-fatigue effect than MPS-1. Copyright © 2016 Elsevier B.V. All rights reserved.

Mesoporous zirconium titanium oxides. Part 2: Synthesis, porosity, and adsorption properties of beads.

PubMed

Sizgek, G Devlet; Sizgek, Erden; Griffith, Christopher S; Luca, Vittorio

2008-11-04

Mesoporous zirconium titanium mixed-oxide beads having disordered wormhole textures and mole fractions of Zr (x) ranging from x=0.25 to 0.67 have been prepared. The bead preparation method combined the forced hydrolysis of mixtures of zirconium-titanium alkoxides in the presence of long-chain carboxylates with external gelation. Uniformly sized beads could be produced in the size range 0.5-1.1 mm by varying the droplet size and viscosity of the mixed-oxide sol, thus making them suitable for large-scale column chromatographic applications. The beads exhibited narrow pore size distributions with similar mean pore diameters of around 3.7 nm. The specific surface areas of the beads were linked to the Zr mole fraction in the precursor solution and were generally greater than 350 m2/g for x=0.5. A combination of scanning transmission electron microscopy and X-ray absorption fine structure analysis indicated that the pore walls of the beads were composed of atomically dispersed Zr and Ti to form a continuous network of Zr-O-Ti bonds. Mass transport in the beads was evaluated by monitoring the kinetics of vanadate and vanadyl adsorption at pH 10.5 and 0.87, respectively.

Titan's Surface Brightness Temperatures and H2 Mole Fraction from Cassini CIRS

NASA Technical Reports Server (NTRS)

Jennings, Donald E.; Flasar, F. M.; Kunde, V. G.; Samuelson, R. E.; Pearl, J. C.; Nixon, C. A.; Carlson, R. C.; Mamoutkine, A. A.; Brasunas, J. C.; Guandique, E.;

H2O absorption tomography in a diesel aftertreatment system using a polymer film for optical access

NASA Astrophysics Data System (ADS)

Wang, Ze; Sanders, Scott T.; Backhaus, Jacob A.; Munnannur, Achuth; Schmidt, Niklas M.

2017-12-01

Film-optical-access H2O absorption tomography is, for the first time, applied to a practical diesel aftertreatment system. A single rotation stage and a single translation stage are used to move a single laser beam to obtain each of the 3480 line-of-sight measurements used in the tomographic reconstruction. It takes 1 h to acquire one image in a 60-view-angle measurement. H2O images are acquired in a 292.4-mm-diameter selective catalytic reduction (SCR) can with a 5-mm spatial resolution at temperatures in the 158-185 °C range. When no liquid H2O is injected into the gas, the L1 norm-based uniformity index is 0.994, and the average mole fraction error is - 6% based on a separate FTIR measurement. When liquid water is injected through the reductant dosing system designed to inject diesel exhaust fluid, nonuniformity is observed, as evidenced by measured uniformity indices for H2O in the 0.977-0.986 range. A mixing plate installed into the system is able to improve the uniformity of the H2O mole fraction.

Modeling Study of the Low-Temperature Oxidation of Large Methyl Esters from C11 to C19

PubMed Central

Herbinet, Olivier; Biet, Joffrey; Hakka, Mohammed Hichem; Warth, Valérie; Glaude, Pierre Alexandre; Nicolle, André; Battin-Leclerc, Frédérique

2013-01-01

The modeling of the low temperature oxidation of large saturated methyl esters really representative of those found in biodiesel fuels has been investigated. Models have been developed for these species and then detailed kinetic mechanisms have been automatically generated using a new extended version of software EXGAS, which includes reactions specific to the chemistry of esters. A model generated for a binary mixture of n-decane and methyl palmitate was used to simulate experimental results obtained in a jet-stirred reactor for this fuel. This model predicts very well the reactivity of the fuel and the mole fraction profiles of most reaction products. This work also shows that a model for a middle size methyl ester such as methyl decanoate predicts fairly well the reactivity and the mole fractions of most species with a substantial decrease in computational time. Large n-alkanes such as n-hexadecane are also good surrogates for reproducing the reactivity of methyl esters, with an important gain in computational time, but they cannot account for the formation of specific products such as unsaturated esters or cyclic ethers with an ester function. PMID:23814504

Investigation of GDL compression effects on the performance of a PEM fuel cell cathode by lattice Boltzmann method

NASA Astrophysics Data System (ADS)

Molaeimanesh, G. R.; Nazemian, M.

2017-08-01

Proton exchange membrane (PEM) fuel cells with a great potential for application in vehicle propulsion systems will have a promising future. However, to overcome the exiting challenges against their wider commercialization further fundamental research is inevitable. The effects of gas diffusion layer (GDL) compression on the performance of a PEM fuel cell is not well-recognized; especially, via pore-scale simulation technique capturing the fibrous microstructure of the GDL. In the current investigation, a stochastic microstructure reconstruction method is proposed which can capture GDL microstructure changes by compression. Afterwards, lattice Boltzmann pore-scale simulation technique is adopted to simulate the reactive gas flow through 10 different cathode electrodes with dissimilar carbon paper GDLs produced from five different compression levels and two different carbon fiber diameters. The distributions of oxygen mole fraction, water vapor mole fraction and current density for the simulated cases are presented and analyzed. The results of simulations demonstrate that when the fiber diameter is 9 μm adding compression leads to lower average current density while when the fiber diameter is 7 μm the compression effect is not monotonic.

Dual-Pump CARS Temperature and Species Concentration Measurements in a Supersonic Combustor

NASA Technical Reports Server (NTRS)

O'Byrne, S.; Danehy, P. M.; Tedder, S. A.; Cutler, A. D.

2007-01-01

The dual-pump coherent anti-Stokes Raman scattering (CARS) method was used to measure temperature and the mole fractions of N2 and O2 in a supersonic combustor. Experiments were conducted in NASA Langley Research Center s Direct Connect Supersonic Combustion Test Facility. In this facility, H2 and oxygen-enriched air burn to increase the enthalpy of the simulated air test gas. This gas is expanded through a Mach 2 nozzle and into a combustor model consisting of a short constant-area section followed by a small rearward-facing step and another constant-area section. At the end of this straight section, H2 fuel is injected at Mach 2 and at a 30 angle with respect to the freestream. One wall of the duct then expands at a 3 angle for over 1 meter. The ensuing combustion is probed optically through ports in the side of the combustor. Dual-pump CARS measurements were performed at the facility nozzle exit and at four planes downstream of fuel injection. Maps are presented of the mean temperature, as well as N2 and O2 mean mole fraction fields. Correlations between fluctuations of the different measured parameters are also presented.

Effect of Group-III precursors on unintentional gallium incorporation during epitaxial growth of InAlN layers by metalorganic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Kim, Jeomoh; Ji, Mi-Hee; Detchprohm, Theeradetch; Dupuis, Russell D.; Fischer, Alec M.; Ponce, Fernando A.; Ryou, Jae-Hyun

2015-09-01

Unintentional incorporation of gallium (Ga) in InAlN layers grown with different molar flow rates of Group-III precursors by metalorganic chemical vapor deposition has been experimentally investigated. The Ga mole fraction in the InAl(Ga)N layer was increased significantly with the trimethylindium (TMIn) flow rate, while the trimethylaluminum flow rate controls the Al mole fraction. The evaporation of metallic Ga from the liquid phase eutectic system between the pyrolized In from injected TMIn and pre-deposited metallic Ga was responsible for the Ga auto-incorporation into the InAl(Ga)N layer. The theoretical calculation on the equilibrium vapor pressure of liquid phase Ga and the effective partial pressure of Group-III precursors based on growth parameters used in this study confirms the influence of Group-III precursors on Ga auto-incorporation. More Ga atoms can be evaporated from the liquid phase Ga on the surrounding surfaces in the growth chamber and then significant Ga auto-incorporation can occur due to the high equilibrium vapor pressure of Ga comparable to effective partial pressure of input Group-III precursors during the growth of InAl(Ga)N layer.

Low absorption loss p-AlGaN superlattice cladding layer for current-injection deep ultraviolet laser diodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martens, M.; Kuhn, C.; Ziffer, E.

2016-04-11

Current injection into AlGaN-based laser diode structures with high aluminum mole fractions for deep ultraviolet emission is investigated. The electrical characteristics of laser diode structures with different p-AlGaN short period superlattice (SPSL) cladding layers with various aluminum mole fractions are compared. The heterostructures contain all elements that are needed for a current-injection laser diode including cladding and waveguide layers as well as an AlGaN quantum well active region emitting near 270 nm. We found that with increasing aluminum content in the p-AlGaN cladding, the diode turn-on voltage increases, while the series resistance slightly decreases. By introducing an SPSL instead of bulkmore » layers, the operating voltage is significantly reduced. A gain guided broad area laser diode structure with transparent p-Al{sub 0.70}Ga{sub 0.30}N waveguide layers and a transparent p-cladding with an average aluminum content of 81% was designed for strong confinement of the transverse optical mode and low optical losses. Using an optimized SPSL, this diode could sustain current densities of more than 4.5 kA/cm{sup 2}.« less

Formation of Core-Shell Ethane-Silver Clusters in He Droplets.

PubMed

Loginov, Evgeny; Gomez, Luis F; Sartakov, Boris G; Vilesov, Andrey F

2017-08-17

Ethane core-silver shell clusters consisting of several thousand particles have been assembled in helium droplets upon capture of ethane molecules followed by Ag atoms. The composite clusters were studied via infrared laser spectroscopy in the range of the C-H stretching vibrations of ethane. The spectra reveal a splitting of the vibrational bands, which is ascribed to interaction with Ag. A rigorous analysis of band intensities for a varying number of trapped ethane molecules and Ag atoms indicates that the composite clusters consist of a core of ethane that is covered by relatively small Ag clusters. This metastable structure is stabilized due to fast dissipation in superfluid helium droplets of the cohesion energy of the clusters.

Ethane: A Key to Evaluating Natural Gas Industrial Emissions

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Degradation of sulfamethoxazole using ozone and chlorine dioxide - Compound-specific stable isotope analysis, transformation product analysis and mechanistic aspects.

PubMed

Willach, Sarah; Lutze, Holger V; Eckey, Kevin; Löppenberg, Katja; Lüling, Michelle; Terhalle, Jens; Wolbert, Jens-Benjamin; Jochmann, Maik A; Karst, Uwe; Schmidt, Torsten C

2017-10-01

The sulfonamide antibiotic sulfamethoxazole (SMX) is a widely detected micropollutant in surface and groundwaters. Oxidative treatment with e.g. ozone or chlorine dioxide is regularly applied for disinfection purposes at the same time exhibiting a high potential for removal of micropollutants. Especially for nitrogen containing compounds such as SMX, the related reaction mechanisms are largely unknown. In this study, we systematically investigated reaction stoichiometry, product formation and reaction mechanisms in reactions of SMX with ozone and chlorine dioxide. To this end, the neutral and anionic SMX species, which may occur at typical pH-values of water treatment were studied. Two moles of chlorine dioxide and approximately three moles of ozone were consumed per mole SMX degraded. Oxidation of SMX with ozone and chlorine dioxide leads in both cases to six major transformation products (TPs) as revealed by high-resolution mass spectrometry (HRMS). Tentatively formulated TP structures from other studies could partly be confirmed by compound-specific stable isotope analysis (CSIA). However, for one TP, a hydroxylated SMX, it was not possible by HRMS alone to identify whether hydroxylation occurred at the aromatic ring, as suggested in literature before, or at the anilinic nitrogen. By means of CSIA and an analytical standard it was possible to identify sulfamethoxazole hydroxylamine unequivocally as one of the TPs of the reaction of SMX with ozone as well as with chlorine dioxide. H-abstraction and electron transfer at the anilinic nitrogen are suggested as likely initial reactions of ozone and chlorine dioxide, respectively, leading to its formation. Oxidation of anionic SMX with ozone did not show any significant isotopic fractionation whereas the other reactions studied resulted in a significant carbon isotope fractionation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Radiation-induced synthesis and swelling properties of p(2-hydroxyethyl methacrylate/itaconic acid/oligo (ethylene glycol) acrylate) terpolymeric hydrogels

NASA Astrophysics Data System (ADS)

Micic, M.; Stamenic, D.; Suljovrujic, E.

2012-09-01

Since it is presumed that by incorporation of pH-responsive (IA) and temperature-responsive (OEGA) co-monomers, it is possible to prepare P(HEMA/IA/OEGA) hydrogels with dual (pH and thermo) responsiveness, the main purpose of our study is to investigate the influence of different mole fractions of IA and especially OEGA on the diversity of the swelling properties of the obtained hydrogels. For that reason, a series of terpolymeric hydrogels with different mole ratios of 2-hydroxyethyl methacrylate (HEMA), itaconic acid (IA) and oligo(ethylene glycol) acrylates (OEGA) was synthesised by gamma radiation. The obtained hydrogels were characterised by swelling studies in the wide pH (2.2-9.0) and temperature range (20-70 °C), confirming dual (pH and thermo) responsiveness and a large variation in the swelling capability. It was observed that the equilibrium swelling of P(HEMA/IA/OEGA) hydrogels, for a constant amount of IA, increased progressively with an increase in OEGA share. On the other hand, the dissociation of carboxyl groups from IA occurs at pH>4; therefore, small mole fractions of IA render good pH sensitivity and a large increase in the swelling capacity of these hydrogels at higher pH values. Additional characterisation of structure and properties was conducted by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and mechanical measurements, confirming that the inherent properties of P(HEMA/IA/OEGA) hydrogels can be significantly tuned by variation in their composition. According to all presented, it seems that the obtained hydrogels can be a beneficial synergetic combination for controlled delivery of bioactive molecules such as drugs, peptides, proteins, etc.

Detection of CO and HCN in Pluto's atmosphere with ALMA

NASA Astrophysics Data System (ADS)

Lellouch, E.; Gurwell, M.; Butler, B.; Fouchet, T.; Lavvas, P.; Strobel, D. F.; Sicardy, B.; Moullet, A.; Moreno, R.; Bockelée-Morvan, D.; Biver, N.; Young, L.; Lis, D.; Stansberry, J.; Stern, A.; Weaver, H.; Young, E.; Zhu, X.; Boissier, J.

2017-04-01

Observations of the Pluto-Charon system, acquired with the ALMA interferometer on June 12-13, 2015, have led to the detection of the CO(3-2) and HCN(4-3) rotational transitions from Pluto (including the hyperfine structure of HCN), providing a strong confirmation of the presence of CO, and the first observation of HCN in Pluto's atmosphere. The CO and HCN lines probe Pluto's atmosphere up to ∼450 km and ∼900 km altitude, respectively, with a large contribution due to limb emission. The CO detection yields (i) a much improved determination of the CO mole fraction, as 515 ± 40 ppm for a 12 μbar surface pressure (ii) strong constraints on Pluto's mean atmospheric dayside temperature profile over ∼50-400 km, with clear evidence for a well-marked temperature decrease (i.e., mesosphere) above the 30-50 km stratopause and a best-determined temperature of 70 ± 2 K at 300 km, somewhat lower than previously estimated from stellar occultations (81 ± 6 K), and in agreement with recent inferences from New Horizons / Alice solar occultation data. The HCN line shape implies a high abundance of this species in the upper atmosphere, with a mole fraction >1.5 × 10-5 above 450 km and a value of 4 × 10-5 near 800 km. Assuming HCN at saturation, this would require a warm (>92 K) upper atmosphere layer; while this is not ruled out by the CO emission, it is inconsistent with the Alice-measured CH4 and N2 line-of-sight column densities. Taken together, the large HCN abundance and the cold upper atmosphere imply supersaturation of HCN to a degree (7-8 orders of magnitude) hitherto unseen in planetary atmospheres, probably due to a lack of condensation nuclei above the haze region and the slow kinetics of condensation at the low pressure and temperature conditions of Pluto's upper atmosphere. HCN is also present in the bottom ∼100 km of the atmosphere, with a 10-8-10-7 mole fraction; this implies either HCN saturation or undersaturation there, depending on the precise stratopause temperature. The HCN column is (1.6 ± 0.4)× 1014 cm-2 , suggesting a surface-referred vertically-integrated net production rate of ∼2 × 107 cm-2 s-1. Although HCN rotational line cooling affects Pluto's atmosphere heat budget, the amounts determined in this study are insufficient to explain the well-marked mesosphere and upper atmosphere's ∼70 K temperature, which if controlled by HCN cooling would require HCN mole fractions of (3-7) ×10-4 over 400-800 km. We finally report an upper limit on the HC3N column density (<2 × 1013 cm-2) and on the HC15N / HC14N ratio (<1/125).

Atmospheric measurements of ratios between CO2 and co-emitted species from traffic: a tunnel study in the Paris megacity

NASA Astrophysics Data System (ADS)

Ammoura, L.; Xueref-Remy, I.; Gros, V.; Baudic, A.; Bonsang, B.; Petit, J.-E.; Perrussel, O.; Bonnaire, N.; Sciare, J.; Chevallier, F.

2014-12-01

Measurements of CO2, CO, NOx and selected Volatile Organic Compounds (VOCs) mole fractions were performed continuously during a 10-day period in the Guy Môquet tunnel in Thiais, a peri-urban area about 15 km south of the centre of Paris, between 28 September and 8 October 2012. This data set is used here to identify the characteristics of traffic-emitted CO2 by evaluating its ratios to co-emitted species for the first time in the Paris region. High coefficients of determination (r2 > 0.7) are observed between CO2 and certain compounds that are characteristic of the traffic source (CO, NOx, benzene, xylenes and acetylene). Weak correlations (r2 < 0.2) are found with species such as propane, n-butane and i-butane that are associated with fuel evaporation, an insignificant source for CO2. To better characterise the traffic signal we focus only on species that are well-correlated with CO2 and on rush-hour periods characterised by the highest traffic-related mole fractions. From those mole fractions we remove the nighttime-average weekday mole fraction obtained for each species that we infer to be the most appropriate background signal for our study. Then we calculate observed Δspecies / ΔCO2 ratios, which we compare with the ones provided by the 2010 bottom-up high-resolved regional emission inventory from Airparif (the association in charge of monitoring the air quality in Île-de-France), focusing on local emission data for the specific road of the tunnel. We find an excellent agreement (2%) between the local inventory emission CO / CO2 ratio and our observed ΔCO / ΔCO2 ratio. Former tunnel experiments carried out elsewhere in the world provided observed ΔCO / ΔCO2 ratios that differ from 49 to 592% to ours. This variability can be related to technological improvement of vehicles, differences in driving conditions, and fleet composition. We also find a satisfactory agreement with the Airparif inventory for n-propylbenzene, n-pentane and xylenes to CO2 ratios. For most of the other species, the ratios obtained from the local emission inventory overestimate the observed ratios to CO2 by 34 to more than 300%. However, the emission ratios of NOx, o-xylene and i-pentane are underestimated by 30 to 79%. One main cause of such high differences between the inventory and our observations is likely the obsolete feature of the VOCs speciation matrix of the inventory that has not been updated since 1998, although law regulations on some VOCs have occurred since that time. Our study bears important consequences, discussed in the conclusion, for the characterisation of the urban CO2 plume and for atmospheric inverse modelling of urban CO2 emissions.

Osmosis and thermodynamics explained by solute blocking.

PubMed

Nelson, Peter Hugo

2017-01-01

A solute-blocking model is presented that provides a kinetic explanation of osmosis and ideal solution thermodynamics. It validates a diffusive model of osmosis that is distinct from the traditional convective flow model of osmosis. Osmotic equilibrium occurs when the fraction of water molecules in solution matches the fraction of pure water molecules that have enough energy to overcome the pressure difference. Solute-blocking also provides a kinetic explanation for why Raoult's law and the other colligative properties depend on the mole fraction (but not the size) of the solute particles, resulting in a novel kinetic explanation for the entropy of mixing and chemical potential of ideal solutions. Some of its novel predictions have been confirmed; others can be tested experimentally or by simulation.

Osmosis and thermodynamics explained by solute blocking

PubMed Central

Nelson, Peter Hugo

2016-01-01

A solute-blocking model is presented that provides a kinetic explanation of osmosis and ideal solution thermodynamics. It validates a diffusive model of osmosis that is distinct from the traditional convective flow model of osmosis. Osmotic equilibrium occurs when the fraction of water molecules in solution matches the fraction of pure water molecules that have enough energy to overcome the pressure difference. Solute-blocking also provides a kinetic explanation for why Raoult’s law and the other colligative properties depend on the mole fraction (but not the size) of the solute particles, resulting in a novel kinetic explanation for the entropy of mixing and chemical potential of ideal solutions. Some of its novel predictions have been confirmed, others can be tested experimentally or by simulation. PMID:27225298

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 likely that a paleoatmospheric ethane record can be obtained from polar ice cores.

Thermodynamic properties and energy characteristics of water+1-propanol

NASA Astrophysics Data System (ADS)

Alhasov, A. B.; Bazaev, A. R.; Bazaev, E. A.; Osmanova, B. K.

2017-11-01

By using own precise experimental data on p,ρ,T,x- relations differential and integral thermodynamic properties of water+1-propanol homogeneous binary mixtures (0.2, 0.5, and 0.8 mole fractions of 1-propanol) were obtained in one phase (liquid, vapor) region, along coexistence curve phase, at critical and supercritical regions of parameters of state. These values were obtained in the regions of temperatures 373.15 - 673.15 K, densities 3 - 820 kg/m3 and pressures up to 50 MPa. It is found that shape of p,ρ,T,- dependences of water+1-propanol mixtures in investigated range of temperatures is the same with those of pure liquid, but the pressure of the mixture is higher than those of pure water or 1-propanol. The critical line of water+1-propanol binary mixtures as opposed to those of water+methanol and water+ethanol mixtures has convex shape. It is ascertained that using water+1-propanol mixture (0.2 mol.fraction of 1-propanol) instead of pure water allows to decrease lower limit of operating temperatures to 50 K, to increase effective coefficient of efficiency and partially unify thermal mechanical equipment of power plant. Our comparative energy analysis of cycles of steam-turbine plant on water and water+1- propanol mixtures, carried out at the same thermobaric conditionsand showed that thermal coefficient of efficiencyofcycle of steam-turbine plant onwater+1-propanol mixture (0.2 mol.fraction of 1-propanol) is higher than those of pure water.Thus and so we made a conclusion about usability of water+1-propanol mixture (0.2 mole fraction of 1-propanol) as a working substance of steam-turbine plant cycle.

Exhaled ethane: an in vivo biomarker of lipid peroxidation in interstitial lung diseases.

PubMed

Kanoh, Soichiro; Kobayashi, Hideo; Motoyoshi, Kazuo

2005-10-01

Oxidative stress plays a role in the pathogenesis and progression of interstitial lung disease (ILD). Exhaled ethane is a product of lipid peroxidation that has been proposed as a biomarker of oxidative stress in vivo. To determine whether the exhaled ethane level is elevated in patients with ILD and to compare it with other clinical parameters. Breath samples were collected from 34 patients with ILD, including 13 with idiopathic pulmonary fibrosis (IPF), 9 patients with cryptogenic organizing pneumonia, 6 patients with collagen vascular disease-associated interstitial pneumonia, and 6 patients with pulmonary sarcoidosis. Gas samples were obtained at hospital admission and after 3 weeks. After each expired sample was concentrated using a trap-and-purge procedure, the ethane level was analyzed by gas chromatography. Exhaled ethane levels were elevated in ILD patients (n = 34, mean +/- SD, 8.5 +/- 8.0 pmol/dL) compared with healthy volunteers (n = 16, 2.9 +/- 1.0 pmol/dL; p < 0.001). Serial measurements revealed that increase and decrease of ethane levels were largely consistent with the clinical course. Four patients with IPF who had persistently high ethane levels died or deteriorated, whereas those with ethane levels < 5.0 pmol/dL remained stable or improved. Exhaled ethane concentrations were positively correlated with levels of lactate dehydrogenase (Spearman rank correlation coefficient [rs], 0.28, p = 0.026) and C-reactive protein (rs, 0.38, p = 0.025) and were inversely correlated with Pa(O2) (rs, - 0.40, p = 0.0026). Patients showing increased uptake on (67)Ga scintigraphy demonstrated higher ethane levels (n = 19, 7.5 +/- 5.7 pmol/dL) compared with those who did not show increased uptake on scintigraphy (n = 10, 3.0 +/- 2.4 pmol/dL; p < 0.01). Exhaled ethane is elevated in patients with ILD and is correlated with the clinical outcome, suggesting that it provides useful information about ongoing oxidative stress, and thereby disease activity and severity in ILD.

The role of moisture on combustion of pyrolysis gases in wildland fires

Treesearch

Selina C. Ferguson; Ambarish Dahale; Babak Shotorban; S. Mahalingam; David R. Weise

2013-01-01

The role of water vapor, originated from the moisture content in vegetation, on the combustion process was investigated via simulating an opposed diffusion flame and a laminar premixed flame with pyrolysis gases as the fuel and air as the oxidizer. The fuel was mixed with water vapor, and the simulation was repeated for various water mole fractions. In both of the...

Results from the Gas Chromatograph Mass Spectrometer (GCMS) Experiment on the Cassini-Huygens Probe

NASA Technical Reports Server (NTRS)

Niemann, H.; Atreya, S.; Demick-Montelara, J.; Haberman, J.; Harpold, D.; Kasprzak, W.; Owen, T.; Raaen, E.; Way, S.

2006-01-01

The Gas Chromatograph Mass Spectrometer was one of six instruments on the Cassini-Huygens Probe mission to Titan. The GCMS measured in situ the chemical composition of the atmosphere during the probe descent and served as the detector for the pyrolization products for the Aerosol Collector Pyrolyser (ACP) experiment to determine the composition of the aerosol particles. The GCMS collected data from an altitude of 146 km to ground impact. The Probe and the GCMS survived impact and collected data for 1 hour and 9 minutes on the surface. Mass spectra were collected during descent and on the ground over a range of m/z from 2 to 141. The major constituents of the lower atmosphere were confirmed to be N2 and CH4. The methane mole fraction was uniform in the stratosphere. It increased below the tropopause, at about 32 km altitude, monotonically toward the surface, reaching a plateau at about 8 km at a level near saturation. After surface impact a steep increase of the methane signal was observed, suggesting evaporation of surface condensed methane due to heating by the GCMS sample inlet heater. The measured mole fraction of Ar-40 is 4.3x10(exp -5) and of Ar-36 is 2.8x10(exp -7). The other primordial noble gases were below 10(exp -8) mole fraction. The isotope ratios of C-12/C-13 determined from methane measurements are 82.3 and of N-14/N-15 determined from molecular nitrogen are 183. The D/H isotope ratio determined from the H2 and HD measurements is 2.3x10(exp -4). Carbon dioxide, methane, acetylene and cyanogen were detected evaporating from the surface in addition to methane. The GCMS employed a quadrupole mass filter with a secondary electron multiplier detection system and a gas sampling system providing continuous direct atmospheric composition measurements and batch sampling through three gas chromatographic (GC) columns, a chemical scrubber and a hydrocarbon enrichment cell. The GCMS gas inlet was heated to prevent condensation, and to evaporate volatiles from the surface after impact.

The historic surface ozone record, 1896-1975, and its relation to modern measurements

NASA Astrophysics Data System (ADS)

Galbally, I. E.; Tarasick, D. W.; Stähelin, J.; Wallington, T. J.; Steinbacher, M.; Schultz, M.; Cooper, O. R.

2017-12-01

Tropospheric ozone is a greenhouse gas, a key component of atmospheric chemistry, and is detrimental to human health and plant productivity. The historic surface ozone record 1896-1975 has been constructed from measurements selected for (a) instrumentation whose ozone response can be traced to modern tropospheric ozone measurement standards, (b) samples taken when there is low probability of chemical interference and (c) sampling locations, heights and times when atmospheric mixing will minimise vertical gradients of ozone in the planetary boundary layer above and around the measurement location. Early measurements with the Schönbein filter paper technique cannot be related to modern methods with any degree of confidence. The potassium iodide-arsenite technique used at Montsouris for 1876-1910 is valid for measuring ozone; however, due to the presence of the interfering gases sulfur dioxide, ammonia and nitrogen oxides, the measured ozone concentrations are not representative of the regional atmosphere. The use of these data sets for trend analyses is not recommended. In total, 58 acceptable sets of measurements are currently identified, commencing in Europe in 1896, Greenland in 1932 and globally by the late 1950's. Between 1896 and 1944 there were 21 studies (median duration 5 days) with a median mole fraction of 23 nmol mol-1 (range of study averages 15-62 nmol mol-1). Between 1950 and 1975 there were 37 studies (median duration approx. 21 months) with a median mole fraction of 22 nmol mol-1 (range of study averages 13-49 nmol mol-1), all measured under conditions likely to give ozone mole fractions similar to those in the planetary boundary layer. These time series are matched with modern measurements from the Tropospheric Ozone Assessment Report (TOAR) Ozone Database and used to examine changes between the historic and modern observations. These historic ozone levels are higher than previously accepted for surface ozone in the late 19th early 20th Century. This historic surface ozone analysis provides a new test for historical reconstructions by Climate-Chemistry models.

Surface ozone in the Southern Hemisphere: 20 years of data from a site with a unique setting in El Tololo, Chile

NASA Astrophysics Data System (ADS)

Anet, Julien G.; Steinbacher, Martin; Gallardo, Laura; Velásquez Álvarez, Patricio A.; Emmenegger, Lukas; Buchmann, Brigitte

2017-05-01

The knowledge of surface ozone mole fractions and their global distribution is of utmost importance due to the impact of ozone on human health and ecosystems and the central role of ozone in controlling the oxidation capacity of the troposphere. The availability of long-term ozone records is far better in the Northern than in the Southern Hemisphere, and recent analyses of the seven accessible records in the Southern Hemisphere have shown inconclusive trends. Since late 1995, surface ozone is measured in situ at "El Tololo", a high-altitude (2200 m a.s.l.) and pristine station in Chile (30° S, 71° W). The dataset has been recently fully quality controlled and reprocessed. This study presents the observed ozone trends and annual cycles and identifies key processes driving these patterns. From 1995 to 2010, an overall positive trend of ˜ 0.7 ppb decade-1 is found. Strongest trends per season are observed in March and April. Highest mole fractions are observed in late spring (October) and show a strong correlation with ozone transported from the stratosphere down into the troposphere, as simulated with a model. Over the 20 years of observations, the springtime ozone maximum has shifted to earlier times in the year, which, again, is strongly correlated with a temporal shift in the occurrence of the maximum of simulated stratospheric ozone transport at the site. We conclude that background ozone at El Tololo is mainly driven by stratospheric intrusions rather than photochemical production from anthropogenic and biogenic precursors. The major footprint of the sampled air masses is located over the Pacific Ocean. Therefore, due to the negligible influence of local processes, the ozone record also allows studying the influence of El Niño and La Niña episodes on background ozone levels in South America. In agreement with previous studies, we find that, during La Niña conditions, ozone mole fractions reach higher levels than during El Niño conditions.

Raman studies of methane-ethane hydrate metastability.

PubMed

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

2009-03-05

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

Measuring ethane and acetylene in Antarctic ice cores to quantify long-term hydrocarbon emissions from tropical fires

NASA Astrophysics Data System (ADS)

Nicewonger, M. R.; Aydin, M.; Prather, M. J.; Saltzman, E. S.

2017-12-01

This study examines ethane (C2H6) and acetylene (C2H2) in polar ice cores in order to reconstruct variations in the atmospheric levels of these trace gases over the past 2,000 years. Both of these non-methane hydrocarbons are released from fossil fuel, biofuel, and biomass burning. Ethane, but not acetylene, is also emitted from natural geologic outgassing of hydrocarbons. In an earlier study, we reported ethane levels in Greenland and Antarctic ice cores showing roughly equal contributions from biomass burning and geologic emissions to preindustrial atmospheric ethane levels (Nicewonger et al., 2016). Here we introduce acetylene as an additional constraint to better quantify preindustrial variations in the emissions from these natural hydrocarbon sources. Here we present 30 new measurements of ethane and acetylene from the WDC-06A ice core from WAIS Divide and the newly drilled South Pole ice core (SPICECORE). Ethane results display a gradual decline from peak levels of 110 ppt at 1400 CE to a minimum of 60-80 ppt during 1700-1875 CE. Acetylene correlates with ethane (r2 > 0.4), dropping from peak levels of 35 ppt at 1400 CE to 15-20 ppt at 1875 CE. The covariance between the two trace gases implies that the observed changes are likely caused by decreasing emissions from low latitude biomass burning. We will discuss results from chemical transport modeling and sensitivity tests and the implications for the preindustrial ethane and acetylene budgets.

Adult neurogenesis in the hedgehog (Erinaceus concolor) and mole (Talpa europaea).

PubMed

Bartkowska, K; Turlejski, K; Grabiec, M; Ghazaryan, A; Yavruoyan, E; Djavadian, R L

2010-01-01

We investigated adult neurogenesis in two species of mammals belonging to the superorder Laurasiatheria, the southern white-breasted hedgehog (order Erinaceomorpha, species Erinaceus concolor) from Armenia and the European mole (order Soricomorpha, species Talpa europaea) from Poland. Neurogenesis in the brain of these species was examined immunohistochemically, using the endogenous markers doublecortin (DCX) and Ki-67, which are highly conserved among species. We found that in both the hedgehog and mole, like in the majority of earlier investigated mammals, neurogenesis continues in the subventricular zone (SVZ) of the lateral ventricles and in the dentate gyrus (DG). In the DG of both species, DCX-expressing cells and Ki-67-labeled cells were present in the subgranular and granular layers. In the mole, a strong bundle of DCX-labeled processes, presumably axons of granule cells, was observed in the center of the hilus. Proliferating cells (expressing Ki-67) were identified in the SVZ of lateral ventricles of both species, but neuronal precursor cells (expressing DCX) were also observed in the olfactory bulb (OB). In both species, the vast majority of cells expressing DCX in the OB were granule cells with radially orientated dendrites, although some periglomerular cells surrounding the glomeruli were also labeled. In addition, this paper is the first to show DCX-labeled fibers in the anterior commissure of the hedgehog and mole. These fibers must be axons of new neurons making interhemispheric connections between the two OB or piriform (olfactory) cortices. DCX-expressing neurons were observed in the striatum and piriform cortex of both hedgehog and mole. We postulate that in both species a fraction of cells newly generated in the SVZ migrates along the rostral migratory stream to the piriform cortex. This pattern of migration resembles that of the 'second-wave neurons' generated during embryonal development of the neocortex rather than the pattern observed during development of the allocortex. In spite of the presence of glial cells alongside DCX-expressing cells, we never found colocalization of DCX protein with a glial marker (vimentin or glial fibrillary acidic protein). Copyright © 2010 S. Karger AG, Basel.

Exhaled ethane concentration in patients with cancer of the upper gastrointestinal tract - a proof of concept study.

PubMed

Abela, Jo Etienne; Skeldon, Kenneth D; Stuart, Robert C; Padgett, Miles J

2009-06-01

There has been growing interest in the measurement of breath ethane as an optimal non-invasive marker of oxidative stress. High concentrations of various breath alkanes including ethane have been reported in a number of malignancies. Our aim was to investigate the use of novel laser spectroscopy for rapid reporting of exhaled ethane and to determine whether breath ethane concentration is related to a diagnosis of upper gastrointestinal malignancy. Two groups of patients were recruited. Group A (n = 20) had a histo-pathological diagnosis of either esophageal or gastric malignancy. Group B (n = 10) was made up of healthy controls. Breath samples were collected from these subjects and the ethane concentration in these samples was subsequently measured to an accuracy of 0.2 parts per billion, ppb. Group A patients had a corrected exhaled breath ethane concentration of 2.3 +/- 0.8 (mean +/- SEM) ppb. Group B patients registered a mean of 3.1 +/- 0.5 ppb. There was no statistically significant difference between the two groups (p = 0.39). In conclusion, concentrations of ethane in collected breath samples were not significantly elevated in upper gastrointestinal malignancy. The laser spectroscopy system provided a reliable and rapid turnaround for breath sample analysis.

Atmospheric chemistry of ethane and ethylene

NASA Technical Reports Server (NTRS)

Aikin, A. C.; Herman, J. R.; Maier, E. J.; Mcquillan, C. J.

1982-01-01

It is shown by a study of ethane and ethylene photochemistry that the loss of ethane is controlled by OH in the troposphere and Cl in the stratosphere. Ethane observations indicating free Cl concentrations below 30 km that are only 10% of the value predicted by the present model calculations cannot be explained by heterogeneous aerosol concentration processes, and contradict current stratospheric photochemistry. The chemical destruction of ethane and ethylene leads to the generation of such compounds as carbon monoxide and formaldehyde, and it is found that the tropospheric concentrations of the latter are enhanced by nearly a factor of three for an ethylene mixing ratio of 2 ppb.

78 FR 53751 - Dominion NGL Pipelines, LLC; Notice of Petition for Declaratory Order

Federal Register 2010, 2011, 2012, 2013, 2014

2013-08-30

... new ethane pipeline (Natrium Ethane Pipeline) extending from a new natural gas processing and... utilize, or pay for, significant capacity on the Natrium Ethane Pipeline (Committed Shipper); and (3) the...

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.

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.

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.

Phosphate glasses for radioactive, hazardous and mixed waste immobilization

DOEpatents

Cao, H.; Adams, J.W.; Kalb, P.D.

1999-03-09

Lead-free phosphate glass compositions are provided which can be used to immobilize low level and/or high level radioactive wastes in monolithic waste forms. The glass composition may also be used without waste contained therein. Lead-free phosphate glass compositions prepared at about 900 C include mixtures from about 1 mole % to about 6 mole % iron (III) oxide, from about 1 mole % to about 6 mole % aluminum oxide, from about 15 mole % to about 20 mole % sodium oxide or potassium oxide, and from about 30 mole % to about 60 mole % phosphate. The invention also provides phosphate, lead-free glass ceramic glass compositions which are prepared from about 400 C to about 450 C and which includes from about 3 mole % to about 6 mole % sodium oxide, from about 20 mole % to about 50 mole % tin oxide, from about 30 mole % to about 70 mole % phosphate, from about 3 mole % to about 6 mole % aluminum oxide, from about 3 mole % to about 8 mole % silicon oxide, from about 0.5 mole % to about 2 mole % iron (III) oxide and from about 3 mole % to about 6 mole % potassium oxide. Method of making lead-free phosphate glasses are also provided. 8 figs.

Phosphate glasses for radioactive, hazardous and mixed waste immobilization

DOEpatents

Cao, Hui; Adams, Jay W.; Kalb, Paul D.

1998-11-24

Lead-free phosphate glass compositions are provided which can be used to immobilize low level and/or high level radioactive wastes in monolithic waste forms. The glass composition may also be used without waste contained therein. Lead-free phosphate glass compositions prepared at about 900.degree. C. include mixtures from about 1 mole % to about 6 mole % iron (III) oxide, from about 1 mole % to about 6 mole % aluminum oxide, from about 15 mole % to about 20 mole % sodium oxide or potassium oxide, and from about 30 mole % to about 60 mole % phosphate. The invention also provides phosphate, lead-free glass ceramic glass compositions which are prepared from about 400.degree. C. to about 450.degree. C. and which includes from about 3 mole % to about 6 mole % sodium oxide, from about 20 mole % to about 50 mole % tin oxide, from about 30 mole % to about 70 mole % phosphate, from about 3 mole % to about 6 mole % aluminum oxide, from about 3 mole % to about 8 mole % silicon oxide, from about 0.5 mole % to about 2 mole % iron (III) oxide and from about 3 mole % to about 6 mole % potassium oxide. Method of making lead-free phosphate glasses are also provided.

Phosphate glasses for radioactive, hazardous and mixed waste immobilization

DOEpatents

Cao, Hui; Adams, Jay W.; Kalb, Paul D.

1999-03-09

Lead-free phosphate glass compositions are provided which can be used to immobilize low level and/or high level radioactive wastes in monolithic waste forms. The glass composition may also be used without waste contained therein. Lead-free phosphate glass compositions prepared at about 900.degree. C. include mixtures from about 1 mole % to about 6 mole %.iron (III) oxide, from about 1 mole % to about 6 mole % aluminum oxide, from about 15 mole % to about 20 mole % sodium oxide or potassium oxide, and from about 30 mole % to about 60 mole % phosphate. The invention also provides phosphate, lead-free glass ceramic glass compositions which are prepared from about 400.degree. C. to about 450.degree. C. and which includes from about 3 mole % to about 6 mole % sodium oxide, from about 20 mole % to about 50 mole % tin oxide, from about 30 mole % to about 70 mole % phosphate, from about 3 mole % to about 6 mole % aluminum oxide, from about 3 mole % to about 8 mole % silicon oxide, from about 0.5 mole % to about 2 mole % iron (III) oxide and from about 3 mole % to about 6 mole % potassium oxide. Method of making lead-free phosphate glasses are also provided.

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.

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.

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.

Experimental determination of the kinetics of formation of the benzene-ethane co-crystal and implications for Titan

NASA Astrophysics Data System (ADS)

Cable, Morgan L.; Vu, Tuan H.; Hodyss, Robert; Choukroun, Mathieu; Malaska, Michael J.; Beauchamp, Patricia

2014-08-01

Benzene is found on Titan and is a likely constituent of the putative evaporite deposits formed around the hydrocarbon lakes. We have recently demonstrated the formation of a benzene-ethane co-crystal under Titan-like surface conditions. Here we investigate the kinetics of formation of this new structure as a function of temperature. We show that the formation process would reach completion under Titan surface conditions in ~18 h and that benzene precipitates from liquid ethane as the co-crystal. This suggests that benzene-rich evaporite basins around ethane/methane lakes and seas may not contain pure crystalline benzene, but instead benzene-ethane co-crystals. This co-crystalline form of benzene with ethane represents a new class of materials for Titan's surface, analogous to hydrated minerals on Earth. This new structure may also influence evaporite characteristics such as particle size, dissolution rate, and infrared spectral properties.

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

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. Copyright © 2011 Elsevier Inc. All rights reserved.

A potentiostatic study of oxygen transport through poly(2-ethoxyethyl methacrylate-co-2,3-dihydroxypropylmethacrylate) hydrogel membranes.

PubMed

Compañ, Vicente; Tiemblo, Pilar; García, F; García, J M; Guzmán, Julio; Riande, Evaristo

2005-06-01

The oxygen permeability and diffusion coefficients of hydrogel membranes prepared with copolymers of 2-ethoxyethyl methacrylate (EEMA)/2,3-dihydroxypropylmethacrylate (MAG) with mole fraction of the second monomer in the range between 0 and 0.75 are described. Values of the permeability and diffusion coefficients of oxygen are determined by using electrochemical procedures involving the measurement of the steady-state current in membranes prepared by radical polymerization of the monomers. The results obtained for the transport properties were analyzed taking into account the fractional free volumes, the cohesive energy densities and the glass transition temperatures of the hydrogels.

Investigation and Characterization of Defects in Epitaxial Films for Ultraviolet Light Emitting Devices Using FUV Time-Resolved Photoluminescence, Time-Resolved Cathodoluminescence, and Spatio-Time-Resolved Cathodoluminescence Excited Using Femtosecond Laser Pulses

DTIC Science & Technology

2013-05-22

mole fraction AlxGa1-xN alloys, and GaN were studied in this project. For this purpose, we quantified the radiative lifetimes (R) and nonradiative ...61556;R) and nonradiative lifetimes (NR) for the near-band-edge (NBE) emission by measuring the luminescence lifetimes () and...that is a fraction of radiative rate over the sum of radiative and nonradiative rates; i. e. int=(1+R/NR)-1. To improve int of practical devices

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

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

NASA Astrophysics Data System (ADS)

Moazzen-Ahmadi, Nasser; Norooz Oliaee, Jalal

2016-06-01

The interest in laboratory spectroscopy of ethane stems from the desire to understand the methane cycle in the atmospheres of planets and their moons and from the importance of ethane as a trace species in the terrestrial atmosphere. Solar decomposition of methane in the upper part of these atmospheres followed by a series of reactions leads to a variety of hydrocarbon compounds among which ethane is often the second most abundant species. Because of its high abundance, ethane spectra have been measured by Voyager and Cassini in the regions around 30, 12, 7, and 3 μm. Therefore, a complete knowledge of line parameters of ethane is crucial for spectroscopic remote sensing of planetary atmospheres. Experimental characterization of torsion-vibration states of ethane lying below 1400 cm-1 have been made previously, but extension of the Hamiltonian model for treatment of the strongly perturbed νb{8} fundamental and the complex band system of ethane in the 3 micron region requires careful examination of the operators for many new torsionally mediated vibration-rotation interactions. Following the procedures outlined by Hougen, we have re-examined the transformation properties of the total angular momentum, the translational and vibrational coordinates and momenta of ethane, and for vibration-torsion-rotation interaction terms constructed by taking products of these basic operators. It is found that for certain choices of phase, the doubly degenerate vibrational coordinates with and symmetry can be made to transform under the group elements in such a way as to yield real matrix elements for the torsion-vibration-rotation couplings whereas other choices of phase may require complex algebra. In this talk, I will discuss the construction of a very general torsion-vibration-rotation Hamiltonian for ethane, as well as the prospect for using such a Hamiltonian to obtain a global frequency analysis (based in large part on an extension of earlier programs and ethane fits^a from our laboratory) of all the vibrational bands of ethane at or below the 3-micron region. N. Moazzen-Ahmadi and J. Norooz Oliaee, J. Quant. Spectrosc. Radiat. Transfer, submitted. J.T. Hougen, Can. J. Phys., 42, 1920 (1964) J. T. Hougen, Can. J. Phys., 43, 935 (1965)

Increased ethane exhalation, an in vivo index of lipid peroxidation, in alcohol-abusers.

PubMed Central

Lettéron, P; Duchatelle, V; Berson, A; Fromenty, B; Fisch, C; Degott, C; Benhamou, J P; Pessayre, D

1993-01-01

Ethane exhalation was measured in 42 control subjects, 52 patients with various non-alcoholic liver diseases, and 89 alcohol abusers who had been admitted to hospital for alcohol withdrawal and assessment of liver disease (six with normal liver tests, 10 with steatosis with or without fibrosis, six with alcoholic hepatitis, 29 with cirrhosis, 34 with both cirrhosis and alcoholic hepatitis, and four with both cirrhosis and a hepatocellular carcinoma). Ethane exhalation was similar in control subjects and in patients with non-alcoholic liver diseases, but was five times higher in alcohol abusers. Ethane exhalation in alcohol abusers was significantly, but very weakly, correlated with the daily ethanol intake before hospital admission, and the histological score for steatosis, but not with the inflammation or alcoholic hepatitis scores. Ethane exhalation was inversely correlated with the duration of abstinence before the test. In nine alcoholic patients, the exhalation of ethane was measured repeatedly, and showed slow improvement during abstinence. Ethane exhalation was significantly but weakly correlated with the Pugh's score in patients with alcoholic cirrhosis. It is concluded that the mean ethane exhalation is increased in alcohol abusers. One of the possible mechanisms may be the presence of oxidizable fat in the liver. The weak correlation with the Pugh's score is consistent with the contribution of many other factors in the progression to severe liver disease. PMID:8472992

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

DOE PAGES

Patankar, Sumant; Gautam, Siddharth; Rother, Gernot; ...

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/cmmore » 3. Key confinement effects were highlighted through differences between isotherms for the two pore sizes. A comparison was made with previously published isotherms for CO 2 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 CO 2–ethane mixture. Activation energies extracted from the Arrhenius plots show the effects of CO 2 addition on ethane mobility.« less

Thermodynamic analyses of a biomass-coal co-gasification power generation system.

PubMed

Yan, Linbo; Yue, Guangxi; He, Boshu

2016-04-01

A novel chemical looping power generation system is presented based on the biomass-coal co-gasification with steam. The effects of different key operation parameters including biomass mass fraction (Rb), steam to carbon mole ratio (Rsc), gasification temperature (Tg) and iron to fuel mole ratio (Rif) on the system performances like energy efficiency (ηe), total energy efficiency (ηte), exergy efficiency (ηex), total exergy efficiency (ηtex) and carbon capture rate (ηcc) are analyzed. A benchmark condition is set, under which ηte, ηtex and ηcc are found to be 39.9%, 37.6% and 96.0%, respectively. Furthermore, detailed energy Sankey diagram and exergy Grassmann diagram are drawn for the entire system operating under the benchmark condition. The energy and exergy efficiencies of the units composing the system are also predicted. Copyright © 2016 Elsevier Ltd. All rights reserved.

Multifunctional Fuel Additives for Reduced Jet Particulate Emissions

DTIC Science & Technology

2006-06-01

additives, turbine engine emissions, particulates, chemical kinetics, combustion, JP-8 chemistry 16. SECURITY CLASSIFICATION OF: 19a. NAME OF...from the UNICORN CFD code using the full and skeletal versions of the Violi et al JP-8 mechanism ...................114 Figure 64. Comparison of...calculated jet flame benzene mole fraction contours from the UNICORN CFD code using the full and skeletal versions of the Violi et al JP-8 mechanism

Climate Change Mitigation: Can the U.S. Intelligence Community Help?

DTIC Science & Technology

2013-06-01

satellite sensors to establish the concentration of atmospheric CO2 parts per million (ppm mole fraction) in samples collected at multiple...measurements. Spatial sampling density, the number of sensors or—in the case of satellite imagery the number and resolution of the images—likewise influences...Somewhat paradoxically, sensor accuracy from either remote ( satellites ) or in situ sensors is an important consideration, but it must also be evaluated

An optical method for carbon dioxide isotopes and mole fractions in small gas samples: tracing microbial respiration from soil, litter, and lignin.

Treesearch

Steven J. Hall; Wenjuan Huang; Kenneth Hammel

2017-01-01

RATIONALE: Carbon dioxide isotope (Δ13C value) measurements enable quantification of the sources of soil microbial respiration, thus informing ecosystem C dynamics. Tunable diode lasers (TDLs) can precisely measure CO2 isotopes at low cost and high throughput, but are seldom used for small samples (≤5 mL). We developed a...

Enhanced methane emissions from tropical wetlands during the 2011 La Niña

PubMed Central

Pandey, Sudhanshu; Houweling, Sander; Krol, Maarten; Aben, Ilse; Monteil, Guillaume; Nechita-Banda, Narcisa; Dlugokencky, Edward J.; Detmers, Rob; Hasekamp, Otto; Xu, Xiyan; Riley, William J.; Poulter, Benjamin; Zhang, Zhen; McDonald, Kyle C.; White, James W. C.; Bousquet, Philippe; Röckmann, Thomas

2017-01-01

Year-to-year variations in the atmospheric methane (CH4) growth rate show significant correlation with climatic drivers. The second half of 2010 and the first half of 2011 experienced the strongest La Niña since the early 1980s, when global surface networks started monitoring atmospheric CH4 mole fractions. We use these surface measurements, retrievals of column-averaged CH4 mole fractions from GOSAT, new wetland inundation estimates, and atmospheric δ13C-CH4 measurements to estimate the impact of this strong La Niña on the global atmospheric CH4 budget. By performing atmospheric inversions, we find evidence of an increase in tropical CH4 emissions of ∼6–9 TgCH4 yr−1 during this event. Stable isotope data suggest that biogenic sources are the cause of this emission increase. We find a simultaneous expansion of wetland area, driven by the excess precipitation over the Tropical continents during the La Niña. Two process-based wetland models predict increases in wetland area consistent with observationally-constrained values, but substantially smaller per-area CH4 emissions, highlighting the need for improvements in such models. Overall, tropical wetland emissions during the strong La Niña were at least by 5% larger than the long-term mean. PMID:28393869

Evaluating Anthropogenic Carbon Emissions in the Urban Salt Lake Valley through Inverse Modeling: Combining Long-term CO2 Observations and an Emission Inventory using a Multiple-box Atmospheric Model

NASA Astrophysics Data System (ADS)

Catharine, D.; Strong, C.; Lin, J. C.; Cherkaev, E.; Mitchell, L.; Stephens, B. B.; Ehleringer, J. R.

2016-12-01

The rising level of atmospheric carbon dioxide (CO2), driven by anthropogenic emissions, is the leading cause of enhanced radiative forcing. Increasing societal interest in reducing anthropogenic greenhouse gas emissions call for a computationally efficient method of evaluating anthropogenic CO2 source emissions, particularly if future mitigation actions are to be developed. A multiple-box atmospheric transport model was constructed in conjunction with a pre-existing fossil fuel CO2 emission inventory to estimate near-surface CO2 mole fractions and the associated anthropogenic CO2 emissions in the Salt Lake Valley (SLV) of northern Utah, a metropolitan area with a population of 1 million. A 15-year multi-site dataset of observed CO2 mole fractions is used in conjunction with the multiple-box model to develop an efficient method to constrain anthropogenic emissions through inverse modeling. Preliminary results of the multiple-box model CO2 inversion indicate that the pre-existing anthropogenic emission inventory may over-estimate CO2 emissions in the SLV. In addition, inversion results displaying a complex spatial and temporal distribution of urban emissions, including the effects of residential development and vehicular traffic will be discussed.

Fluid Flow and Mass Transfer in Micro/Nano-Channels

NASA Astrophysics Data System (ADS)

Conlisk, A. T.; McFerran, Jennifer; Hansford, Derek; Zheng, Zhi

2001-11-01

In this work the fluid flow and mass transfer due to the presence of an electric field in a rectangular channel is examined. We consider a mixture of water or other neutral solvent and a salt compound such as sodium chloride for which the ionic species are entirely dissociated. Results are produced for the case where the channel height is much greater than the electric double layer(EDL)(microchannel) and for the case where the channel height is of the order or somewhat greater than the width of the EDL(nanochannel). For the electroosmotic flow so induced, the velocity field and the potential are similar. The fluid is assumed to behave as a continuum and the Boltzmann distribution for the mole fractions of the ions emerges from the classical dilute mass transfer equation in the limiting case where the EDL thickness is much less than the channel height. Depending on the relative magnitude of the mole fractions at the walls of the channel, both forward and reversed flow may occur. The volume flow rate is observed to vary linearly with channel height for electrically driven flow in contrast to pressure driven flow which varies as height cubed. This means that power requirements for small channels are much greater for pressure driven flow. Supported by DARPA

Dual-Pump CARS Thermometry and Species Concentration Measurements in a Supersonic Combustor

NASA Technical Reports Server (NTRS)

OByrne, Sean; Danehy, Paul M.; Cutler, Andrew D.

2004-01-01

The dual-pump coherent anti-Stokes Raman spectroscopy (CARS) method was used to measure temperature and the absolute mole fractions of N2, O2 and H2 in a supersonic combustor. Experiments were conducted in NASA Langley Research Center's Direct Connect Supersonic Combustion Test Facility. In this facility, hydrogen and air bum to increase the enthalpy of the test gas; O2 is then added to simulate air. This gas is expanded through a Mach 2 nozzle and into a combustor model consisting of a short constant-area section followed by a small rearward facing step and another constant area section. At the end of this straight section H2 fuel is then injected at Mach 2 and at 30 deg. angle with respect to the freestream. One wall of the duct then expands at a 3 deg. angle for over 1 meter. The ensuing combustion is monitored optically through ports in the side of the combustor. CARS measurements were performed at the nozzle exit and at four different planes downstream fuel injection. Maps were obtained of the mean temperature, as well as quantitative N2 and O2 and qualitative H2 mean mole fraction fields. Correlations between fluctuations of the different measured parameters are presented for one of the planes of data.

Preferential solvation and solvation shell composition of free base and protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin in aqueous organic mixed solvents

NASA Astrophysics Data System (ADS)

Farajtabar, Ali; Jaberi, Fatemeh; Gharib, Farrokh

2011-12-01

The solvatochromic properties of the free base and the protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) were studied in pure water, methanol, ethanol (protic solvents), dimethylsulfoxide, DMSO, (non-protic solvent), and their corresponding aqueous-organic binary mixed solvents. The correlation of the empirical solvent polarity scale ( ET) values of TPPS with composition of the solvents was analyzed by the solvent exchange model of Bosch and Roses to clarify the preferential solvation of the probe dyes in the binary mixed solvents. The solvation shell composition and the synergistic effects in preferential solvation of the solute dyes were investigated in terms of both solvent-solvent and solute-solvent interactions and also, the local mole fraction of each solvent composition was calculated in cybotactic region of the probe. The effective mole fraction variation may provide significant physico-chemical insights in the microscopic and molecular level of interactions between TPPS species and the solvent components and therefore, can be used to interpret the solvent effect on kinetics and thermodynamics of TPPS. The obtained results from the preferential solvation and solvent-solvent interactions have been successfully applied to explain the variation of equilibrium behavior of protonation of TPPS occurring in aqueous organic mixed solvents of methanol, ethanol and DMSO.

One-pot ultrasonic-assisted method for preparation of Ag/AgCl sensitized ZnO nanostructures as visible-light-driven photocatalysts

NASA Astrophysics Data System (ADS)

Naghizadeh-Alamdari, Sara; Habibi-Yangjeh, Aziz; Pirhashemi, Mahsa

2015-02-01

Ultrasonic-assisted method was applied for preparation of Ag/AgCl sensitized ZnO nanostructures by one-pot procedure in water without using any post preparation treatments. The resultant nanocomposites were characterized by XRD, EDX, SEM, DRS, XPS, BET, and PL techniques. In the nanocomposites, ZnO and AgCl have wurtzite hexagonal and cubic crystalline phases, respectively and their surface morphologies remarkably change with increasing mole fraction of silver chloride. The EDX and XPS techniques show that the prepared samples are extremely pure. Ability of the nanocomposites for absorption of visible-light irradiation enhanced with increasing AgCl content. Photocatalytic examination of the nanocomposites was carried out using aqueous solution of methylene blue under visible-light irradiation. The degradation rate constant on the nancomposite rapidly increases with mole fraction of silver chloride up to 0.237. Enhancing activity of the nanocomposite was attributed to its ability for absorbing visible light and separation of electron-hole pairs. Furthermore, influence of ultrasonic irradiation time, calcination temperature, catalyst weight, pH of solution, and scavengers of reactive species on the degradation activity was investigated and the results were discussed. Finally, the photocatalyst has good activity after five successive cycles.

A low-volume cavity ring-down spectrometer for sample-limited applications

NASA Astrophysics Data System (ADS)

Stowasser, C.; Farinas, A. D.; Ware, J.; Wistisen, D. W.; Rella, C.; Wahl, E.; Crosson, E.; Blunier, T.

2014-08-01

In atmospheric and environmental sciences, optical spectrometers are used for the measurements of greenhouse gas mole fractions and the isotopic composition of water vapor or greenhouse gases. The large sample cell volumes (tens of milliliters to several liters) in commercially available spectrometers constrain the usefulness of such instruments for applications that are limited in sample size and/or need to track fast variations in the sample stream. In an effort to make spectrometers more suitable for sample-limited applications, we developed a low-volume analyzer capable of measuring mole fractions of methane and carbon monoxide based on a commercial cavity ring-down spectrometer. The instrument has a small sample cell (9.6 ml) and can selectively be operated at a sample cell pressure of 140, 45, or 20 Torr (effective internal volume of 1.8, 0.57, and 0.25 ml). We present the new sample cell design and the flow path configuration, which are optimized for small sample sizes. To quantify the spectrometer's usefulness for sample-limited applications, we determine the renewal rate of sample molecules within the low-volume spectrometer. Furthermore, we show that the performance of the low-volume spectrometer matches the performance of the standard commercial analyzers by investigating linearity, precision, and instrumental drift.

Effect of Group-III precursors on unintentional gallium incorporation during epitaxial growth of InAlN layers by metalorganic chemical vapor deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Jeomoh, E-mail: jkim610@gatech.edu; Ji, Mi-Hee; Detchprohm, Theeradetch

2015-09-28

Unintentional incorporation of gallium (Ga) in InAlN layers grown with different molar flow rates of Group-III precursors by metalorganic chemical vapor deposition has been experimentally investigated. The Ga mole fraction in the InAl(Ga)N layer was increased significantly with the trimethylindium (TMIn) flow rate, while the trimethylaluminum flow rate controls the Al mole fraction. The evaporation of metallic Ga from the liquid phase eutectic system between the pyrolized In from injected TMIn and pre-deposited metallic Ga was responsible for the Ga auto-incorporation into the InAl(Ga)N layer. The theoretical calculation on the equilibrium vapor pressure of liquid phase Ga and the effectivemore » partial pressure of Group-III precursors based on growth parameters used in this study confirms the influence of Group-III precursors on Ga auto-incorporation. More Ga atoms can be evaporated from the liquid phase Ga on the surrounding surfaces in the growth chamber and then significant Ga auto-incorporation can occur due to the high equilibrium vapor pressure of Ga comparable to effective partial pressure of input Group-III precursors during the growth of InAl(Ga)N layer.« less

Computer Programs for Calculating the Isentropic Flow Properties for Mixtures of R-134a and Air

NASA Technical Reports Server (NTRS)

Kvaternik, Raymond G.

2000-01-01

Three computer programs for calculating the isentropic flow properties of R-134a/air mixtures which were developed in support of the heavy gas conversion of the Langley Transonic Dynamics Tunnel (TDT) from dichlorodifluoromethane (R-12) to 1,1,1,2 tetrafluoroethane (R-134a) are described. The first program calculates the Mach number and the corresponding flow properties when the total temperature, total pressure, static pressure, and mole fraction of R-134a in the mixture are given. The second program calculates tables of isentropic flow properties for a specified set of free-stream Mach numbers given the total pressure, total temperature, and mole fraction of R-134a. Real-gas effects are accounted for in these programs by treating the gases comprising the mixture as both thermally and calorically imperfect. The third program is a specialized version of the first program in which the gases are thermally perfect. It was written to provide a simpler computational alternative to the first program in those cases where real-gas effects are not important. The theory and computational procedures underlying the programs are summarized, the equations used to compute the flow quantities of interest are given, and sample calculated results that encompass the operating conditions of the TDT are shown.

Application of time-division-multiplexed lasers for measurements of gas temperature and CH4 and H2O concentrations at 30 kHz in a high-pressure combustor.

PubMed

Caswell, Andrew W; Kraetschmer, Thilo; Rein, Keith; Sanders, Scott T; Roy, Sukesh; Shouse, Dale T; Gord, James R

2010-09-10

Two time-division-multiplexed (TDM) sources based on fiber Bragg gratings were applied to monitor gas temperature, H(2)O mole fraction, and CH(4) mole fraction using line-of-sight absorption spectroscopy in a practical high-pressure gas turbine combustor test article. Collectively, the two sources cycle through 14 wavelengths in the 1329-1667 nm range every 33 μs. Although it is based on absorption spectroscopy, this sensing technology is fundamentally different from typical diode-laser-based absorption sensors and has many advantages. Specifically, the TDM lasers allow efficient, flexible acquisition of discrete-wavelength information over a wide spectral range at very high speeds (typically 30 kHz) and thereby provide a multiplicity of precise data at high speeds. For the present gas turbine application, the TDM source wavelengths were chosen using simulated temperature-difference spectra. This approach is used to select TDM wavelengths that are near the optimum values for precise temperature and species-concentration measurements. The application of TDM lasers for other measurements in high-pressure, turbulent reacting flows and for two-dimensional tomographic reconstruction of the temperature and species-concentration fields is also forecast.

Absolute, pressure-dependent validation of a calibration-free, airborne laser hygrometer transfer standard (SEALDH-II) from 5 to 1200 ppmv using a metrological humidity generator

NASA Astrophysics Data System (ADS)

Buchholz, Bernhard; Ebert, Volker

2018-01-01

Highly accurate water vapor measurements are indispensable for understanding a variety of scientific questions as well as industrial processes. While in metrology water vapor concentrations can be defined, generated, and measured with relative uncertainties in the single percentage range, field-deployable airborne instruments deviate even under quasistatic laboratory conditions up to 10-20 %. The novel SEALDH-II hygrometer, a calibration-free, tuneable diode laser spectrometer, bridges this gap by implementing a new holistic concept to achieve higher accuracy levels in the field. We present in this paper the absolute validation of SEALDH-II at a traceable humidity generator during 23 days of permanent operation at 15 different H2O mole fraction levels between 5 and 1200 ppmv. At each mole fraction level, we studied the pressure dependence at six different gas pressures between 65 and 950 hPa. Further, we describe the setup for this metrological validation, the challenges to overcome when assessing water vapor measurements on a high accuracy level, and the comparison results. With this validation, SEALDH-II is the first airborne, metrologically validated humidity transfer standard which links several scientific airborne and laboratory measurement campaigns to the international metrological water vapor scale.

Impact of a new wavelength-dependent representation of methane photolysis branching ratios on the modeling of Titan’s atmospheric photochemistry

NASA Astrophysics Data System (ADS)

Gans, B.; Peng, Z.; Carrasco, N.; Gauyacq, D.; Lebonnois, S.; Pernot, P.

2013-03-01

A new wavelength-dependent model for CH4 photolysis branching ratios is proposed, based on the values measured recently by Gans et al. (Gans, B. et al. [2011]. Phys. Chem. Chem. Phys. 13, 8140-8152). We quantify the impact of this representation on the predictions of a photochemical model of Titan’s atmosphere, on their precision, and compare to earlier representations. Although the observed effects on the mole fraction of the species are small (never larger than 50%), it is possible to draw some recommendations for further studies: (i) the Ly-α branching ratios of Wang et al. (Wang, J.H. et al. [2000]. J. Chem. Phys. 113, 4146-4152) used in recent models overestimate the CH2:CH3 ratio, a factor to which a lot of species are sensitive; (ii) the description of out-of-Ly-α branching ratios by the “100% CH3” scenario has to be avoided, as it can bias significantly the mole fractions of some important species (C3H8); and (iii) complementary experimental data in the 130-140 nm range would be useful to constrain the models in the Ly-α deprived 500-700 km altitude range.

Exerting control over the helical chirality in the main chain of sergeants-and-soldiers-type poly(quinoxaline-2,3-diyl)s by changing from random to block copolymerization protocols.

PubMed

Nagata, Yuuya; Nishikawa, Tsuyoshi; Suginome, Michinori

2015-04-01

Chiral random poly(quinoxaline-2,3-diyl) polymers of the sergeants-and-soldiers-type (sergeant units bearing (S)-3-octyloxymethyl groups) adopt an M- or P-helical conformation in the presence of achiral units bearing propoxymethyl or butoxy groups (soldier units), respectively. Unusual bidirectional induction of the helical sense can be observed for a copolymer with butoxy soldier units upon changing the mole fraction of the sergeant units. In the presence of 16-20% of sergeant units, the selective induction of a P-helix was observed, while the selective induction of an M-helix was observed for a mole fraction of sergeant units of more than 60%. This phenomenon could be successfully employed to control the helical chirality of copolymers by applying either random or block copolymerization protocols. Random or block copolymerization of sergeant and soldier monomers in a 18:82 ratio resulted in the formation of 250mers with almost absolute P- or M-helical conformation, respectively (>99% ee). Incorporation of a small amount of coordination sites into the random and block copolymers resulted in chiral macromolecular ligands, which allowed the enantioselective synthesis of both enantiomers in the Pd-catalyzed asymmetric hydrosilylation of β-methylstyrene.

Quantification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Elusive Intermediates during Low-Temperature Oxidation of Dimethyl Ether.

PubMed

Moshammer, Kai; Jasper, Ahren W; Popolan-Vaida, Denisia M; Wang, Zhandong; Bhavani Shankar, Vijai Shankar; Ruwe, Lena; Taatjes, Craig A; Dagaut, Philippe; Hansen, Nils

2016-10-04

This work provides new temperature-dependent mole fractions of elusive intermediates relevant to the low-temperature oxidation of dimethyl ether (DME). It extends the previous study of Moshammer et al. [ J. Phys. Chem. A 2015 , 119 , 7361 - 7374 ] in which a combination of a jet-stirred reactor and molecular beam mass spectrometry with single-photon ionization via tunable synchrotron-generated vacuum-ultraviolet radiation was used to identify (but not quantify) several highly oxygenated species. Here, temperature-dependent concentration profiles of 17 components were determined in the range of 450-1000 K and compared to up-to-date kinetic modeling results. Special emphasis is paid toward the validation and application of a theoretical method for predicting photoionization cross sections that are hard to obtain experimentally but essential to turn mass spectral data into mole fraction profiles. The presented approach enabled the quantification of the hydroperoxymethyl formate (HOOCH 2 OCH 2 O), which is a key intermediate in the low-temperature oxidation of DME. The quantification of this keto-hydroperoxide together with the temperature-dependent concentration profiles of other intermediates including H 2 O 2 , HCOOH, CH 3 OCHO, and CH 3 OOH reveals new opportunities for the development of a next-generation DME combustion chemistry mechanism.

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

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

Thermodynamics of Silicon-Hydroxide Formation in H2O Containing Atmospheres

NASA Technical Reports Server (NTRS)

Copland, Evan; Myers, Dwight; Opila, Elizabeth J.; Jacobson, Nathan S.

2001-01-01

The formation of volatile silicon-hydroxide species from SiO2 in water containing atmospheres has been identified as a potentially important mode of degradation of Si-based ceramics. Availability of thermodynamic data for these species is a major problem. This study is part of an ongoing effort to obtain reliable, experimentally determined thermodynamic data for these species. The transpiration method was used to measure the pressure of Si-containing vapor in equilibrium with SiO2 (cristobalite) and Ar + H2O(g) with various mole fractions of water vapor, X(sub H2O), at temperatures ranging from 1000 to 1780 K. Enthalpies and entropies for the reaction, SiO2(s) + 2H2O(g) = Si(OH)4(g), were obtained, at X(sub H2O) = 0.15 and 0.37, from the variation of lnK with 1/T according to the 'second law method'. The following data were obtained: delta(H)deg = 52.9 +/- 3.7 kJ/mole and delta(S)deg = -68.6 +/- 2.5 J/mole K at an average temperature of 1550 K, and delta(H)deg = 52.5+/-2.0 kJ/mole and delta(S)deg= -69.7 +/- 1.5 J/moleK at an average temperature of 1384 K, for X(sub H2O)= 0.15 and 0.37, respectively. These data agree with results from the literature obtained at an average temperature of 1600 K, and strongly suggest Si(OH)4(g) is the dominant vapor species. Contradictory results were obtained with the determination of the dependence of Si-containing vapor pressure on the partial pressure of water vapor at 1187 and 1722 K. These results suggested the Si-containing vapor could be a mixture of Si(OH)4 + SiO(OH)2. Further pressure dependent studies are in progress to resolve these issues.

Prediction of supercritical ethane bulk solvent densities for pyrazine solvation shell average occupancy by 1, 2, 3, and 4 ethanes: combined experimental and ab initio approach.

PubMed

Hrnjez, Bruce J; Sultan, Samuel T; Natanov, Georgiy R; Kastner, David B; Rosman, Michael R

2005-11-17

We introduce a method that addresses the elusive local density at the solute in the highly compressible regime of a supercritical fluid. Experimentally, the red shift of the pyrazine n-pi electronic transition was measured at infinite dilution in supercritical ethane as a function of pressure from 0 to about 3000 psia at two temperatures, one close (35.0 degrees C) to the critical temperature and the other remote (55.0 degrees C). Computationally, stationary points were located on the potential surfaces for pyrazine and one, two, three, and four ethanes at the MP2/6-311++G(d,p) level. The vertical n-pi ((1)B(3u)) transition energies were computed for each of these geometries with a TDDFT/B3LYP/6-311++G(d,p) method. The combination of experiment and computation allows prediction of supercritical ethane bulk densities at which the pyrazine primary solvation shell contains an average of one, two, three, and four ethane molecules. These density predictions were achieved by graphical superposition of calculated shifts on the experimental shift versus density curves for 35.0 and 55.0 degrees C. Predicted densities are 0.0635, 0.0875, and 0.0915 g cm(-3) for average pyrazine primary solvation shell occupancy by one, two, and three ethanes at both 35.0 and 55.0 degrees C. Predicted densities are 0.129 and 0.150 g cm(-3) for occupancy by four ethanes at 35.0 and 55.0 degrees C, respectively. An alternative approach, designed to "average out" geometry specific shifts, is based on the relationship Deltanu = -23.9n cm(-1), where n = ethane number. Graphical treatment gives alternative predicted densities of 0.0490, 0.0844, and 0.120 g cm(-3) for average pyrazine primary solvation shell occupancy by one, two, and three ethanes at both 35.0 and 55.0 degrees C, and densities of 0.148 and 0.174 g cm(-3) for occupancy by four ethanes at 35.0 and 55.0 degrees C, respectively.

Photoprotecting action and phytochemical analysis of a multiple radical scavenger lipophilic fraction obtained from the leaf of the seagrass Thalassia testudinum.

PubMed

Regalado, Erik L; Rodríguez, María; Menéndez, Roberto; Fernandez, Xavier; Hernández, Ivones; Morales, Ruth A; Fernández, Miguel D; Thomas, Olivier P; Pino, Jorge A; Concepción, Angel R; Laguna, Abilio

2011-01-01

The apolar fraction F1 of Thalassia testudinum was chemically characterized by gas chromatography-mass spectrometry, which led to the identification of 43 metabolites, all of them reported for the first time in the genus Thalassia. More than 80% of the F1 composition was constituted by aromatic metabolites including the major components 1,1-bis(p-tolyl)ethane (6.0%), 4,4'-diisopropylbiphenyl (4.8%) and a 1,1-bis(p-tolyl)ethane isomer (4.7%). This lipophilic fraction was assayed for its antioxidant effects and skin protective action. In vitro assays showed that F1 strongly scavenged DPPH* (IC(50) 312.0 ± 8.0 μg mL(-1)), hydroxyl (IC(50) 23.8 ± 0.5 μg mL(-1)) and peroxyl radical (IC(50) 6.6 ± 0.3 μg mL(-1) ), as well as superoxide anion (IC(50) 50.0 ± 0.7 μg mL(-1)). Also, F1 markedly inhibited the spontaneous lipid peroxidation (LPO) in brain homogenates (IC(50) 93.0 ± 6.0 μg mL(-1)) and the LPS-stimulated nitrite generation on RAW624.7 macrophages (58.6 ± 3.2%, 400 μg mL(-1)). In agreement with these findings, its topical application at 250 and 500 μg cm(-2) strikingly reduced skin damage on mice exposed to acute UVB radiation by 45% and 70%, respectively and significantly attenuated the LPO developed following the first 48 h after acute exposure to UVB irradiation, as manifested by the decreased malondialdehide level and by the increased of reduced gluthatione content. Our results suggest that F1 may contribute to skin repair by attenuating oxidative stress due to its antioxidant activity. © 2011 The Authors. Photochemistry and Photobiology © 2011 The American Society of Photobiology.

Patterns of peroxidative ethane emission from submerged rice seedlings indicate that damage from reactive oxygen species takes place during submergence and is not necessarily a post-anoxic phenomenon.

PubMed

Santosa, I E; Ram, P C; Boamfa, E I; Laarhoven, L J J; Reuss, J; Jackson, M B; Harren, F J M

2007-06-01

Using ethane as a marker for peroxidative damage to membranes by reactive oxygen species (ROS) we examined the injury of rice seedlings during submergence in the dark. It is often expressed that membrane injury from ROS is a post-submergence phenomenon occurring when oxygen is re-introduced after submergence-induced anoxia. We found that ethane production, from rice seedlings submerged for 24-72 h, was stimulated to 4-37 nl gFW(-1), indicating underwater membrane peroxidation. When examined a week later the seedlings were damaged or had died. On de-submergence in air, ethane production rates rose sharply, but fell back to less than 0.1 nl gFW(-1) h(-1) after 2 h. We compared submergence-susceptible and submergence-tolerant cultivars, submergence starting in the morning (more damage) and in the afternoon (less damage) and investigated different submergence durations. The seedlings showed extensive fatality whenever total ethane emission exceeded about 15 nl gFW(-1). Smaller amounts of ethane emission were linked to less extensive injury to leaves. Partial oxygen shortage (O(2) levels <1%) imposed for 2 h in gas phase mixtures also stimulated ethane production. In contrast, seedlings under anaerobic gas phase conditions produced no ethane until re-aerated: then a small peak was observed followed by a low, steady ethane production. We conclude that damage during submergence is not associated with extensive anoxia. Instead, injury is linked to membrane peroxidation in seedlings that are partially oxygen deficient while submerged. On return to air, further peroxidation is suppressed within about 2 h indicating effective control of ROS production not evident during submergence itself.

Potential for cometabolic biodegradation of 1,4-dioxane in aquifers with methane or ethane as primary substrates.

PubMed

Hatzinger, Paul B; Banerjee, Rahul; Rezes, Rachael; Streger, Sheryl H; McClay, Kevin; Schaefer, Charles E

2017-12-01

The objective of this research was to evaluate the potential for two gases, methane and ethane, to stimulate the biological degradation of 1,4-dioxane (1,4-D) in groundwater aquifers via aerobic cometabolism. Experiments with aquifer microcosms, enrichment cultures from aquifers, mesophilic pure cultures, and purified enzyme (soluble methane monooxygenase; sMMO) were conducted. During an aquifer microcosm study, ethane was observed to stimulate the aerobic biodegradation of 1,4-D. An ethane-oxidizing enrichment culture from these samples, and a pure culture capable of growing on ethane (Mycobacterium sphagni ENV482) that was isolated from a different aquifer also biodegraded 1,4-D. Unlike ethane, methane was not observed to appreciably stimulate the biodegradation of 1,4-D in aquifer microcosms or in methane-oxidizing mixed cultures enriched from two different aquifers. Three different pure cultures of mesophilic methanotrophs also did not degrade 1,4-D, although each rapidly oxidized 1,1,2-trichloroethene (TCE). Subsequent studies showed that 1,4-D is not a substrate for purified sMMO enzyme from Methylosinus trichosporium OB3b, at least not at the concentrations evaluated, which significantly exceeded those typically observed at contaminated sites. Thus, our data indicate that ethane, which is a common daughter product of the biotic or abiotic reductive dechlorination of chlorinated ethanes and ethenes, may serve as a substrate to enhance 1,4-D degradation in aquifers, particularly in zones where these products mix with aerobic groundwater. It may also be possible to stimulate 1,4-D biodegradation in an aerobic aquifer through addition of ethane gas. Conversely, our results suggest that methane may have limited importance in natural attenuation or for enhancing biodegradation of 1,4-D in groundwater environments.

Laser-based trace gas detection of ethane as a result of photo-oxidative damage in chilled cucumber leaves (invited)

NASA Astrophysics Data System (ADS)

Santosa, I. E.; Laarhoven, L. J. J.; Harbinson, J.; Driscoll, S.; Harren, F. J. M.

2003-01-01

At low temperatures, high light intensity induces strong photooxidative lipid peroxidation in chilling sensitive cucumber leaves. A sensitive laser-based photoacoustic detector was employed to monitor on-line the evolution of ethane, one of the end products of lipid peroxidation. The Δv=2 CO laser operated in the 2.62-4.06 μm infrared wavelength region with a maximum intracavity power of 11 W. In combination with an intracavity placed photoacoustic cell the laser was able to detect ethane down to 0.5 part per billion. Cucumber leaf disks chilled in the light produce ethane; the rate of ethane production depends on the applied temperature, light intensity, and period of chilling.

Self-assembled highly ordered ethane-bridged periodic mesoporous organosilica and its application in HPLC.

PubMed

Huang, Lili; Lu, Juan; Di, Bin; Feng, Fang; Su, Mengxiang; Yan, Fang

2011-09-01

Monodisperse spherical periodic mesoporous organosilicas (PMOs) with ethane integrated in the framework were synthesized and their application as stationary phase for chromatographic separation is demonstrated. The ethane-PMOs were prepared by condensation of 1,2-bis(triethoxysilyl)ethane (BTSE) in basic condition using octadecyltrimethylammonium chloride (C(18)TMACl) as template and ethanol as co-solvent. The morphology and mesoporous structure of ethane-PMOs were controlled under different concentrations of sodium hydroxide (NaOH) and EtOH. The results of scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), nitrogen sorption measurement, Fourier transform infrared spectroscopy (FT-IR) and elemental analysis showed that ethane-PMOs have spherical morphology, uniform particle distribution, highly ordered pore structure, high surface area and narrow pore-size distribution. The column packed with these materials exhibits good permeability, high chemical stability and good selectivity of mixtures of aromatic hydrocarbons in normal phase high-performance liquid chromatography (HPLC). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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.

The abundances of ethane and acetylene in the atmospheres of Jupiter and Saturn

NASA Technical Reports Server (NTRS)

Noll, K. S.; Knacke, R. F.; Tokunaga, A. T.; Lacy, J. H.; Beck, S.

1986-01-01

The present determination of the stratospheric abundances of ethane and acetylene on Jupiter and Saturn on the basis of IR spectra near 780/cm uses atmospheric models whose thermal and density profiles have constant mixing ratios. The ratio of ethane to acetylene is noted to be insensitive to model atmosphere assumptions; it is 55 + or - 31 for Jupiter and 23 + or - 12 where model mixing ratios are uniform. Atmospheric model density profiles adapted from theoretical photochemical models are noted to also yield a higher ethane/acetylene ratios for Jupiter.

The abundances of ethane to acetylene in the atmospheres of Jupiter and Saturn

NASA Technical Reports Server (NTRS)

Noll, K. S.; Knacke, R. F.; Tokunaga, A. T.; Lacy, J. H.; Beck, S.; Serabyn, E.

1986-01-01

The present determination of the stratospheric abundances of ethane and acetylene on Jupiter and Saturn on the basis of IR spectra near 780/cm uses atmospheric models whose thermal and density profiles have constant mixing ratios. The ratio of ethane to acetylene is noted to be insensitive to model atmosphere assumptions; it is 55 + or - 31 for Jupiter and 23 + or - 12 where model mixing ratios are uniform. Atmospheric model density profiles adapted from theoretical photochemical models are noted to also yield a higher ethane/acetylene ratios for Jupiter.

Variability of Neptune's 12.2-micron ethane emission feature

NASA Technical Reports Server (NTRS)

Hammel, H. B.; Young, Leslie A.; Hackwell, J.; Lynch, D. K.; Russell, R.; Orton, Glenn S.

1992-01-01

It is presently shown that the ratio of ethane emission to methane emission in Neptune's 7-14 micron spectrum increased by a factor of 1.47 +/- 0.11 in the period between 1985 and 1991, and that the 12.2-micron ethan feature (rather than that of methane at 7.7 microns) is implicated in the greater part of that change. It is speculated that this variation is due either to a nonuniform increase in stratospheric temperature, or (more likely) to an increase in the ethane concentration by over 15 percent.

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.

Evidence for a polar ethane cloud on Titan.

PubMed

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

2006-09-15

Spectra from Cassini's Visual and Infrared Mapping Spectrometer reveal the presence of a vast tropospheric cloud on Titan at latitudes 51 degrees to 68 degrees north and all longitudes observed (10 degrees to 190 degrees 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.

A reconnaissance study of 13C-13C clumping in ethane from natural gas

NASA Astrophysics Data System (ADS)

Clog, Matthieu; Lawson, Michael; Peterson, Brian; Ferreira, Alexandre A.; Santos Neto, Eugenio V.; Eiler, John M.

2018-02-01

Ethane is the second most abundant alkane in most natural gas reservoirs. Its bulk isotopic compositions (δ13C and δD) are used to understand conditions and progress of cracking reactions that lead to the accumulation of hydrocarbons. Bulk isotopic compositions are dominated by the concentrations of singly-substituted isotopologues (13CH3-12CH3 for δ13C and 12CDH2-12CH3 for δD). However, multiply-substituted isotopologues can bring additional independent constraints on the origins of natural ethane. The 13C2H6 isotopologue is particularly interesting as it can potentially inform the distribution of 13C atoms in the parent biomolecules whose thermal cracking lead to the production of natural gas. This work presents methods to purify ethane from natural gas samples and quantify the abundance of the rare isotopologue 13C2H6 in ethane at natural abundances to a precision of ±0.12 ‰ using a high-resolution gas source mass spectrometer. To investigate the natural variability in carbon-carbon clumping, we measured twenty-five samples of thermogenic ethane from a range of geological settings, supported by two hydrous pyrolysis of shales experiments and a dry pyrolysis of ethane experiment. The natural gas samples exhibit a range of 'clumped isotope' signatures (Δ13C2H6) at least 30 times larger than our analytical precision, and significantly larger than expected for thermodynamic equilibration of the carbon-carbon bonds during or after formation of ethane, inheritance from the distribution of isotopes in organic molecules or different extents of cracking of the source. However we show a relationship between the Δ13C2H6 and the proportion of alkanes in natural gas samples, which we believe can be associated to the extent of secondary ethane cracking. This scenario is consistent with the results of laboratory experiments, where breaking down ethane leaves the residue with a low Δ13C2H6 compared to the initial gas. Carbon-carbon clumping is therefore a new potential tracer suitable for the study of kinetic processes associated with natural gas.

Kinetics of Ethane Clathrate Hydrate Formation under Titan-Like Conditions

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

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.

40 CFR 60.614 - Test methods and procedures.

Code of Federal Regulations, 2012 CFR

2012-07-01

... or TOC (less methane and ethane) reduction efficiency shall be prior to the inlet of the control... TOC (minus methane and ethane), dry basis, ppm by volume. %O2d=Concentration of O2, dry basis, percent.... (ii) The emission reduction (R) of TOC (minus methane and ethane) shall be determined using the...

40 CFR 60.664 - Test methods and procedures.

Code of Federal Regulations, 2012 CFR

2012-07-01

... (less methane and ethane) reduction efficiency shall be prior to the inlet of the control device and... methane and ethane), dry basis, ppm by volume. %O2d=Concentration of O2, dry basis, percent by volume. (4... emission reduction (R) of TOC (minus methane and ethane) shall be determined using the following equation...

10 CFR 221.11 - Natural gas and ethane.

Code of Federal Regulations, 2010 CFR

2010-01-01

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

40 CFR 721.10265 - Ethane, 2-bromo-1, 1-difluoro-.

Code of Federal Regulations, 2013 CFR

2013-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10265 Ethane, 2-bromo-1, 1-difluoro-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethane, 2-bromo-1,1-difluoro-. (PMN P-04...

40 CFR 721.10265 - Ethane, 2-bromo-1, 1-difluoro-.

Code of Federal Regulations, 2014 CFR

2014-07-01

... SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10265 Ethane, 2-bromo-1, 1-difluoro-. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethane, 2-bromo-1,1-difluoro-. (PMN P-04...

10 CFR 221.11 - Natural gas and ethane.

Code of Federal Regulations, 2011 CFR

2011-01-01

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

The Formation of Ethane from Carbon Dioxide under Cold Plasma

NASA Astrophysics Data System (ADS)

Zhang, Xiu-ling; Zhang, Lin; Dai, Bin; Gong, Wei-min; Liu, Chang-hou

2001-04-01

Pulsed-corona plasma has been used as a new method for ethane dehydrogenation at low temperature and normal pressure using carbon dioxide as an oxidant in this paper. The effect of carbon dioxide content in the feed, power input, and flow rate of the reactants on the ethane dehydrogenation has been investigated. The experimental results show that the conversion of ethane increases with the increase in the amount of carbon dioxide in the feed. The yield of ethylene and acetylene decreases with the increase in the yield of carbon monoxide, indicating that the increased carbon dioxide leads to the part of ethylene and acetylene being oxidized to carbon monoxide. Power input is primarily an electrical parameter in pulsed-corona plasma, which plays an important role in reactant conversion and product formation. When the power input reaches 16 W, ethane conversion is 41.0% and carbon dioxide conversion is 26.3%. The total yield of ethylene and acetylene is 15.6%. The reduced flow rate of feed improves the conversion of ethane, carbon dioxide and the yield of acetylene, and induces carbon deposit as well.

On two alternative mechanisms of ethane activation over ZSM-5 zeolite modified by Zn2+ and Ga1+ cations.

PubMed

Kazansky, V B; Subbotina, I R; Rane, N; van Santen, R A; Hensen, E J M

2005-08-21

The activation of ethane over zinc- and gallium-modified HZSM-5 dehydrogenation catalysts was studied by diffuse reflectance infrared spectroscopy. Hydrocarbon activation on HZSM-5 modified by bivalent Zn and univalent Ga cations proceeds via two distinctly different mechanisms. The stronger molecular adsorption of ethane by the acid-base pairs formed by distantly separated cationic Zn2+ and basic oxygen sites results already at room temperature in strong polarizability of adsorbed ethane and subsequent heterolytic dissociative adsorption at moderate temperatures. In contrast, molecular adsorption of ethane on Ga+ cations is weak. At high temperatures dissociative hydrocarbon adsorption takes place, resulting in the formation of ethyl and hydride fragments coordinating to the cationic gallium species. Whereas in the zinc case a Brønsted acid proton is formed upon ethane dissociation, decomposition of the ethyl fragment on gallium results in gallium dihydride species and does not lead to Brønsted acid protons. This difference in alkane activation has direct consequences for hydrocarbon conversions involving dehydrogenation.

Abnormal exhaled ethane concentrations in scleroderma.

PubMed

Cope, K A; Solga, S F; Hummers, L K; Wigley, F M; Diehl, A M; Risby, T H

2006-01-01

Scleroderma (systemic sclerosis) is a chronic multisystem autoimmune disease in which oxidative stress is suspected to play a role in the pathophysiology. Therefore, it was postulated that patients with scleroderma would have abnormally high breath ethane concentrations, which is a volatile product of free-radical-mediated lipid peroxidation, compared with a group of controls. There was a significant difference (p<0.05) between the mean exhaled ethane concentration of 5.27 pmol ml(-1) CO(2) (SEM=0.76) in the scleroderma patients (n=36) versus the mean exhaled concentration of 2.72 pmol ml(-1) CO(2) (SEM=0.71) in a group of healthy controls (n=21). Within the scleroderma group, those subjects taking a calcium channel blocker had lower ethane concentrations compared with patients who were not taking these drugs (p=0.05). There was a significant inverse association between lung diffusion capacity for carbon monoxide (per cent of predicted) and ethane concentration (b=-2.8, p=0.026, CI=-5.2 to -0.35). These data support the presence of increased oxidative stress among patients with scleroderma that is detected by measuring breath ethane concentrations.

Ocean Ridges and Oxygen

NASA Astrophysics Data System (ADS)

Langmuir, C. H.

2014-12-01

The history of oxygen and the fluxes and feedbacks that lead to its evolution through time remain poorly constrained. It is not clear whether oxygen has had discrete steady state levels at different times in Earth's history, or whether oxygen evolution is more progressive, with trigger points that lead to discrete changes in markers such as mass independent sulfur isotopes. Whatever this history may have been, ocean ridges play an important and poorly recognized part in the overall mass balance of oxidants and reductants that contribute to electron mass balance and the oxygen budget. One example is the current steady state O2 in the atmosphere. The carbon isotope data suggest that the fraction of carbon has increased in the Phanerozoic, and CO2 outgassing followed by organic matter burial should continually supply more O2 to the surface reservoirs. Why is O2 not then increasing? A traditional answer to this question would relate to variations in the fraction of burial of organic matter, but this fraction appears to have been relatively high throughout the Phanerozoic. Furthermore, subduction of carbon in the 1/5 organic/carbonate proportions would contribute further to an increasingly oxidized surface. What is needed is a flux of oxidized material out of the system. One solution would be a modern oxidized flux to the mantle. The current outgassing flux of CO2 is ~3.4*1012 moles per year. If 20% of that becomes stored organic carbon, that is a flux of .68*1012 moles per year of reduced carbon. The current flux of oxidized iron in subducting ocean crust is ~2*1012 moles per year of O2 equivalents, based on the Fe3+/Fe2+ ratios in old ocean crust compared to fresh basalts at the ridge axis. This flux more than accounts for the incremental oxidizing power produced by modern life. It also suggests a possible feedback through oxygenation of the ocean. A reduced deep ocean would inhibit oxidation of ocean crust, in which case there would be no subduction flux of oxidized material, and oxygen could rise. Once the ocean becomes fully oxidized, a substantial subduction flux operates as a negative feedback. Plate tectonic geochemical cycles may have played a very significant role in the oxygen balance in both the ancient and modern Earth.

Solubility and thermodynamics of apremilast in different mono solvents: Determination, correlation and molecular interactions.

PubMed

Shakeel, Faiyaz; Haq, Nazrul; Alanazi, Fars K; Alsarra, Ibrahim A

2017-05-15

The solubility data of recently launched poorly soluble antipsoriatic drug apremilast (APM) in any mono solvent or cosolvent mixtures with respect to temperature are not available in literature. Hence, in this research work, the solubility of APM in twelve different mono solvents namely "water, methanol, ethanol, isopropanol (IPA), ethylene glycol (EG), propylene glycol (PG), 1-butanol, 2-butanol, ethyl acetate (EA), dimethyl sulfoxide (DMSO), polyethylene glycol-400 (PEG-400) and Transcutol ® " was determined at temperatures "T=298.2K to 318.2K" and pressure "p=0.1 MPa". Eexperimental solubilities of APM in mole fraction were determined by a static equilibrium method using high performance liquid chromatography at 254nm. Experimental solubilities of APM in mole fraction were correlated well with "Van't Hoff and Apelblat models". The solubilities of APM in mole fraction were recorded highest in DMSO (9.91×10 -2 ), followed by EA (2.54×10 -2 ), Transcutol (2.51×10 -2 ), PEG-400 (2.16×10 -2 ),PG (4.01×10 -3 ), EG (1.61×10 -3 ), IPA (4.96×10 -4 ), 1-butanol (4.18×10 -4 ), 2-butanol (3.91×10 -4 ), methanol (2.25×10 -4 ), ethanol (2.20×10 -4 ) and water (1.29×10 -6 ) at "T=318.2K" and similar results were also obtained at each temperature evaluated. The molecular interactions between solute and solvent molecules were evaluated by the determination of activity coefficients. Based on activity coefficients, the higher solute-solvents molecular interactions were recorded in APM-DMSO, APM-EA, APM-Transcutol and APM-PEG-400 in comparison with other combination of solute and solvents. "Apparent standard thermodynamic parameters" of APM indicated an "endothermic and entropy-driven dissolution" of APM in all mono solvents evaluated. Based on these results, APM was proposed as freely soluble in DMSO, EA and Transcutol, sparingly soluble in PEG0-400, slightly soluble in methanol, ethanol, IPA, EG, PG, 1-butanol and 2-butanol and practically insoluble in water. Hence, DMSO, EA and Transcutol were selected as the best solvents and water and ethanol were selected as the anti-solvents for APM. Copyright © 2017 Elsevier B.V. All rights reserved.

Measurements of 4 Atmospheric Trace Gases Outside Homes Adjacent to a Multiwell Pad During Drilling, Hydraulic Fracturing, and Production Phases, Using Low-Cost Sensors and Artificial Neural Network Quantification Techniques

NASA Astrophysics Data System (ADS)

Casey, J. G.; Ilie, A. M. C.; Coffey, E.; Collier-Oxandale, A. M.; Hannigan, M.; Vaccaro, C.

2017-12-01

In Colorado and elsewhere in North America, the oil and gas production industry has been growing alongside and in the midst of increasing urban and rural populations. These coinciding trends have resulted in a growing number of people living in close proximity to petroleum production and processing activities, leading to potential public health impacts. Combustion-related emissions from heavy-duty diesel vehicle traffic, generators, compressors, and production stream flaring can potentially lead to locally enhanced levels of nitrogen oxides (NOx), carbon monoxide (CO), and carbon dioxide (CO2). Venting and fugitive emissions of production stream constituents can potentially lead to locally enhanced levels of methane (CH4) and volatile organic compounds (VOCs), some of which (like benzene) are known carcinogens. NOx and VOC emissions can also potentially increase local ozone (O3) production. After learning of a large new multiwell pad on the outskirts of Greeley, Colorado, we were able to quickly mobilize portable air quality monitors outfitted with low-cost gas sensors that respond to CH4, CO2, CO, and O3. The air quality monitors were installed outside homes adjacent to the new multiwell pad several weeks prior to the first spud date. An anemometer was also installed outside one of the homes in order to monitor wind speed and direction. Measurements continued during drilling, hydraulic fracturing, and production phases. The sensors were periodically collocated with reference instruments at a nearby regulatory air quality monitoring site towards calibration via field normalization and validation. Artificial Neural Networks were employed to map sensor signals to trace gas mole fractions during collocation periods. We present measurements of CH4, CO2, CO, and O3 in context with wellpad activities and local meteorology. CO and O3 observations are presented in context with regional measurements and National Ambient Air Quality Standards for each. Wind speed and direction measurements were used to indicate when air masses originated from the direction of the multiwell pad. CO2 mole fractions were used to estimate planetary boundary layer height and CH4 mole fractions were used to identify periods conducive to the pooling and accumulation of production stream venting and fugitive emissions.

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

Balance among Cognitive Control Processes: A Case Study of A Gifted Youth

ERIC Educational Resources Information Center

Urben, Sébastien; Camos, Valérie; Habersaat, Stéphanie; Constanty, Lauriane; Stéphan, Philippe

2018-01-01

This case study analyzed the cognitive strategies of Ethan, a gifted youth, when performing a Stop Signal Task assessing cognitive control processes including response inhibition as well as proactive and reactive adjustments of response. In the case of Ethan, the response inhibition score was biased, revealing that Ethan did not follow the…

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,

Computationally Efficient Modeling of Hydrocarbon Oxidation Chemistry and Flames Using Constituents and Species

DTIC Science & Technology

2012-02-10

1 Nc X l Dil bNl = 1 Nc X l Dil ÃX k bClkNk! . (19) Finally, it is necessary to compute, from the Dil coefficients, a global diffusion coefficient...exists a mole fraction XCk such that Nk ’ NcXCk. Therefore, X l,k Dil bClk XCk = 1 Nc X l Dil bNl = 1 Nc X l Dil ÃX k bClkNk! . (20) Finally, it is

Correlation of Helium Solubility in Liquid Nitrogen

NASA Technical Reports Server (NTRS)

VanDresar, Neil T.; Zimmerli, Gregory A.

2012-01-01

A correlation has been developed for the equilibrium mole fraction of soluble gaseous helium in liquid nitrogen as a function of temperature and pressure. Experimental solubility data was compiled and provided by National Institute of Standards and Technology (NIST). Data from six sources was used to develop a correlation within the range of 0.5 to 9.9 MPa and 72.0 to 119.6 K. The relative standard deviation of the correlation is 6.9 percent.

Aggregation of Cobalt (II) Tetrasulfonated Phthalocyanine in Methanol- Water Solutions

DTIC Science & Technology

1983-06-01

the presence of ethanol was measured over the same temperature range with methanol rcent mole fraction from 0.4 to 9.8. The temperature dependence...similar temperature dependence for the free energy of denaturation of proteins in ethanol -water solution. 6 5, 6 6 Since -C is proportional to AC 0 , a...8217-" -- : oi - -• solutions at various temperatures ; The-d&mýiarzation constant was determined by a nonlinear least-squares fit o absorbance versus

Partitioning of lysolipids, fatty acids and their mixtures in aqueous lipid bilayers: solute concentration/composition effects.

PubMed

Singh, Jasmeet; Lai, Amy Jo; Alaee, Yasmin; Ranganathan, Radha

2014-01-01

Distributions of lysopalmitoylphosphatidylcholine (LPPC), palmitic acid (PA) and their 1:1 mixtures between water and dipalmitoylphosphatidylcholine (DPPC) bilayer were determined using a fluorescence probe that selectively detects only the solutes in water. Water solute concentrations were obtained at each of several lipid concentrations. Dynamic Light Scattering experiments confirmed that the lipid/solute aggregates were vesicles in the concentration range investigated. Lipid concentration dependence of the solute component in water was fit to a thermodynamic model of solute distribution between two coexisting solvents. Water/bilayer partition coefficient and the free energy of transfer, for each of these solutes were determined from the fit. Main findings are: (1) Water/bilayer partition coefficient of solute is greater for 2 to 10% solute mole fraction than for 0 to 2%, signaling solute induced bilayer perturbation that increases bilayer solubility, beginning at 2% solute mole fraction. (2) Partition coefficients are in the order LPPC

Partitioning of Lysolipids, Fatty Acids and Their Mixtures in Aqueous Lipid Bilayers: Solute Concentration / Composition Effects

PubMed Central

Singh, Jasmeet; Lai, Amy Jo; Alaee, Yasmin; Ranganathan, Radha

2013-01-01

Distribution of lysopalmitoylphosphatidylcholine (LPPC), Palmitic acid (PA) and their 1:1 mixtures between water and dipalmitoylphosphatidylcholine (DPPC) bilayer were determined using a fluorescence probe that selectively detects only the solutes in water. Water solute concentrations were obtained at each of several lipid concentrations. Dynamic Light Scattering experiments confirmed that the lipid/solute aggregates were vesicles in the concentration range investigated. Lipid concentration dependence of the solute component in water was fit to a thermodynamic model of solute distribution between two coexisting solvents. Water/bilayer partition coefficient and the free energy of transfer, for each of these solutes were determined from the fit. Main findings are: (1) Water/bilayer partition coefficient of solute is greater for 2 to 10 % solute mole fraction than for 0 to 2 %, signaling solute induced bilayer perturbation that increases bilayer solubility, beginning at 2 % solute mole fraction. (2) Partition coefficients are in the order LPPC

Diffusion coefficients of nitric oxide in water: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Pokharel, Sunil; Pantha, Nurapati; Adhikari, N. P.

2016-09-01

Self-diffusion coefficients along with the mutual diffusion coefficients of nitric oxide (NO) and SPC/E water (H2O) as solute and solvent of the mixture, have been studied within the framework of classical molecular dynamics level of calculations using GROMACS package. The radial distribution function (RDF) of the constituent compounds are calculated to study solute-solute, solute-solvent and solvent-solvent molecular interactions as a function of temperature. A dilute solution of five NO molecules (mole fraction 0.018) and 280 H2O molecules (mole fraction 0.982) has been taken as the sample. The self-diffusion coefficient of the solvent is calculated by using mean square displacement (MSD) where as that for solute (NO) is calculated by using MSD and velocity auto-correlation function (VACF). The results are then compared with the available experimental values. The results from the present work for water come in good agreement, very precise at low temperatures, with the experimental values. The diffusion coefficients of NO, on the other hands, agree well with the available theoretical studies, and also with experiment at low temperatures (up to 310 K). The results at the higher temperatures (up to 333 K), however, deviate significantly with the experimental observations. Also, the mutual diffusion coefficients of NO in water have been calculated by using Darken’s relation. The temperature dependence of the calculated diffusion coefficients follow the Arrhenius behavior.

Dielectric and piezoelectric properties of lead-free Ba0.85Ca0.15Ti0.9-xZr0.1CuxO3 ceramics synthesized by a hydrothermal method

NASA Astrophysics Data System (ADS)

Hunpratub, Sitchai; Phokha, Sumalin; Maensiri, Santi; Chindaprasirt, Prinya

2016-04-01

Ba0.85Ca0.15Ti0.9Zr0.1-xCuxO3 (BCTZC) nanopowders were synthesized using a hydrothermal method after which they were pressed into discs and sintered in air at 1300 °C for 3 h to form ceramic samples. The phase and microstructure of the powder and ceramic samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The XRD results indicated that the ceramic samples exhibited a tetragonal structure and that CuO, BaZrO3 or CaTiO3 impurity phases, which had been present in the powder samples, were not observed. The average grain sizes in the ceramic samples were found to be 17.0, 16.1, 20.0, 18.1 and 19.6 μm for Cu mole fractions x of 0.002, 0.004, 0.006, 0.008 and 0.01, respectively. The dielectric constants, ferroelectric hysteresis loops and piezoelectric charge coefficients of the BCZTC ceramic samples were also investigated. Optimum values for the relative dielectric constant (ɛ‧), tan δ and piezoelectric charge coefficient (d33) of the samples were 3830, 0.03 and 306 pC/N, respectively, in the Cu mole fraction samples with x = 0.002.

Cooperative Order-Disorder Transition of Carboxylated Schizophyllan in Water-Dimethylsulfoxide Mixtures.

PubMed

Yoshiba, Kazuto; Dobashi, Toshiaki; Ulset, Ann-Sissel T; Christensen, Bjørn E

2018-06-18

Carboxylated schizophyllan ("sclerox") is a chemically modified polysaccharide obtained by partial periodate oxidation and subsequent chlorite oxidation of schizophyllan, a water-soluble neutral polysaccharide having a β-1,3-linked glucan backbone and a β-1,6-linked d-glucose residue side chain at every third residue of the main chain. The triple helix of schizophyllan in water has a cooperative order-disorder transition associated with the side chains. The transition is strongly affected by the presence (mole fraction) of dimethylsulfoxide (DMSO). In the present study, the solvent effects on the order-disorder transition of sclerox with different degrees of carboxylation (DS) in water-DMSO mixtures were investigated with differential scanning calorimetry and optical rotation. The transition temperature ( T r ) and transition enthalpy (Δ H r ) strongly depended on the mole fraction of DMSO ( x D ). Data were further analyzed with the statistical theory for the linear cooperative transition, taking into account the solvent effect, where DMSO molecules are selectively associated with the unmodified side chains. The modified side chain does not contribute to the transition; hence, Δ H r decreases with increasing DS. The dependence of T r on the DMSO content becomes weaker than that for unmodified schizophyllan. The theoretical analyses indicated that the number of sites binding with the DMSO molecule and the successive ordered sequence of the ordered unit of the triple helix are changed by carboxylation.

Glass transition temperature and conductivity in Li2O and Na2O doped borophosphate glasses

NASA Astrophysics Data System (ADS)

Ashwajeet, J. S.; Sankarappa, T.; Ramanna, R.; Sujatha, T.; Awasthi, A. M.

2015-08-01

Two alkali doped Borophosphate glasses in the composition, (B2O3)0.2. (P2O5)0.3. (Na2O)(0.5-x). (Li2O)x, where x = 0.05 to 0.50 were prepared by standard melt quenching method at 1200K. Non-crystalline nature was confirmed by XRD studies. Room temperature density was measured by Archimedes principle. DC conductivity in the temperature range from 300K to 575K has been measured. Samples were DSC studied in the temperature range from 423K to 673K and glass transition temperature was determined. Glass transition temperature passed through minima for Li2O con.2centration between 0.25 and 0.30 mole fractions. Activation energy of conduction has been determined by analyzing temperature variation of conductivity determining Arrhenius law. Conductivity passed through minimum and activation passed through maximum for Li2O content from 0.25 to 0.30 mole fractions. Glass transition temperature passed through minimum for the same range of Li2O content. These results revealed mixed alkali effect taking place in these glasses. It is for the first time borophosphate glasses doped with Li2O and Na2O have been studied for density and dc conductivity and, the mixed alkali effect (MAE) has been observed.

Experimental study on the minimum ignition temperature of coal dust clouds in oxy-fuel combustion atmospheres.

PubMed

Wu, Dejian; Norman, Frederik; Verplaetsen, Filip; Van den Bulck, Eric

2016-04-15

BAM furnace apparatus tests were conducted to investigate the minimum ignition temperature of coal dusts (MITC) in O2/CO2 atmospheres with an O2 mole fraction from 20 to 50%. Three coal dusts: Indonesian Sebuku coal, Pittsburgh No.8 coal and South African coal were tested. Experimental results showed that the dust explosion risk increases significantly with increasing O2 mole fraction by reducing the minimum ignition temperature for the three tested coal dust clouds dramatically (even by 100°C). Compared with conventional combustion, the inhibiting effect of CO2 was found to be comparatively large in dust clouds, particularly for the coal dusts with high volatile content. The retardation effect of the moisture content on the ignition of dust clouds was also found to be pronounced. In addition, a modified steady-state mathematical model based on heterogeneous reaction was proposed to interpret the observed experimental phenomena and to estimate the ignition mechanism of coal dust clouds under minimum ignition temperature conditions. The analysis revealed that heterogeneous ignition dominates the ignition mechanism for sub-/bituminous coal dusts under minimum ignition temperature conditions, but the decrease of coal maturity facilitates homogeneous ignition. These results improve our understanding of the ignition behaviour and the explosion risk of coal dust clouds in oxy-fuel combustion atmospheres. Copyright © 2015 Elsevier B.V. All rights reserved.

The development and evaluation of airborne in situ N2O and CH4 sampling using a quantum cascade laser absorption spectrometer (QCLAS)

NASA Astrophysics Data System (ADS)

Pitt, J. R.; Le Breton, M.; Allen, G.; Percival, C. J.; Gallagher, M. W.; Bauguitte, S. J.-B.; O'Shea, S. J.; Muller, J. B. A.; Zahniser, M. S.; Pyle, J.; Palmer, P. I.

2016-01-01

Spectroscopic measurements of atmospheric N2O and CH4 mole fractions were made on board the FAAM (Facility for Airborne Atmospheric Measurements) large atmospheric research aircraft. We present details of the mid-infrared quantum cascade laser absorption spectrometer (QCLAS, Aerodyne Research Inc., USA) employed, including its configuration for airborne sampling, and evaluate its performance over 17 flights conducted during summer 2014. Two different methods of correcting for the influence of water vapour on the spectroscopic retrievals are compared and evaluated. A new in-flight calibration procedure to account for the observed sensitivity of the instrument to ambient pressure changes is described, and its impact on instrument performance is assessed. Test flight data linking this sensitivity to changes in cabin pressure are presented. Total 1σ uncertainties of 2.47 ppb for CH4 and 0.54 ppb for N2O are derived. We report a mean difference in 1 Hz CH4 mole fraction of 2.05 ppb (1σ = 5.85 ppb) between in-flight measurements made using the QCLAS and simultaneous measurements using a previously characterised Fast Greenhouse Gas Analyser (FGGA, Los Gatos Research, USA). Finally, a potential case study for the estimation of a regional N2O flux using a mass balance technique is identified, and the method for calculating such an estimate is outlined.

The development and evaluation of airborne in situ N2O and CH4 sampling using a Quantum Cascade Laser Absorption Spectrometer (QCLAS)

NASA Astrophysics Data System (ADS)

Pitt, J. R.; Le Breton, M.; Allen, G.; Percival, C. J.; Gallagher, M. W.; Bauguitte, S. J.-B.; O'Shea, S. J.; Muller, J. B. A.; Zahniser, M. S.; Pyle, J.; Palmer, P. I.

2015-08-01

Spectroscopic measurements of atmospheric N2O and CH4 mole fractions were made on board the FAAM (Facility for Airborne Atmospheric Measurements) large Atmospheric Research Aircraft. We present details of the mid-IR Aerodyne Research Inc. Quantum Cascade Laser Absorption Spectrometer (QCLAS) employed, including its configuration for airborne sampling, and evaluate its performance over 17 flights conducted during summer 2014. Two different methods of correcting for the influence of water vapour on the spectroscopic retrievals are compared and evaluated. A new in-flight calibration procedure to account for the observed sensitivity of the instrument to ambient pressure changes is described, and its impact on instrument performance is assessed. Test flight data linking this sensitivity to changes in cabin pressure is presented. Total 1σ uncertainties of 1.81 ppb for CH4 and 0.35 ppb for N2O are derived. We report a mean difference in 1 Hz CH4 mole fraction of 2.05 ppb (1σ = 5.85 ppb) between in-flight measurements made using the QCLAS and simultaneous measurements using a previously characterised Los Gatos Research Fast Greenhouse Gas Analyser (FGGA). Finally, a potential case study for the estimation of a regional N2O flux using a mass balance technique is identified, and the method for calculating such an estimate is outlined.

Maxwell-Stefan diffusion: a framework for predicting condensed phase diffusion and phase separation in atmospheric aerosol

NASA Astrophysics Data System (ADS)

Fowler, Kathryn; Connolly, Paul J.; Topping, David O.; O'Meara, Simon

2018-02-01

The composition of atmospheric aerosol particles has been found to influence their micro-physical properties and their interaction with water vapour in the atmosphere. Core-shell models have been used to investigate the relationship between composition, viscosity and equilibration timescales. These models have traditionally relied on the Fickian laws of diffusion with no explicit account of non-ideal interactions. We introduce the Maxwell-Stefan diffusion framework as an alternative method, which explicitly accounts for non-ideal interactions through activity coefficients. e-folding time is the time it takes for the difference in surface and bulk concentration to change by an exponential factor and was used to investigate the interplay between viscosity and solubility and the effect this has on equilibration timescales within individual aerosol particles. The e-folding time was estimated after instantaneous increases in relative humidity to binary systems of water and an organic component. At low water mole fractions, viscous effects were found to dominate mixing. However, at high water mole fractions, equilibration times were more sensitive to a range in solubility, shown through the greater variation in e-folding times. This is the first time the Maxwell-Stefan framework has been applied to an atmospheric aerosol core-shell model and shows that there is a complex interplay between the viscous and solubility effects on aerosol composition that requires further investigation.

A diode laser sensor for rapid, sensitive measurements of gas temperature and water vapour concentration at high temperatures and pressures

NASA Astrophysics Data System (ADS)

Rieker, G. B.; Li, H.; Liu, X.; Jeffries, J. B.; Hanson, R. K.; Allen, M. G.; Wehe, S. D.; Mulhall, P. A.; Kindle, H. S.

2007-05-01

A near-infrared diode laser sensor is presented that is capable of measuring time-varying gas temperature and water vapour concentration at temperatures up to 1050 K and pressures up to 25 atm with a bandwidth of 7.5 kHz. Measurements with noise-equivalent-absorbances of the order of 10-3 (10-5 Hz-1/2) are made possible in dynamic environments through the use of wavelength modulation spectroscopy (WMS) with second harmonic detection (2f) on two water vapour spectral features near 7203.9 and 7435.6 cm-1. Laser performance characteristics that become important at the large modulation depths needed at high pressures are accounted for in the WMS-2f signal analysis, and the utility of normalization by the 1f signal to correct for variations in laser intensity, transmission and detector gain is presented. Laboratory measurements with the sensor system in a static cell with known temperature and pressure agree to 3% RMS in temperature and 4% RMS in H2O mole fraction for 500 < T < 900 K and 1 < P < 25 atm. The sensor time response is demonstrated in a high-pressure shock tube where shock wave transients are successfully captured, the average measured post-shock temperature agrees within 1% of the expected value, and H2O mole fraction agrees within 8%.

Wavelength modulation diode laser absorption spectroscopy for high-pressure gas sensing

NASA Astrophysics Data System (ADS)

Sun, K.; Chao, X.; Sur, R.; Jeffries, J. B.; Hanson, R. K.

2013-03-01

A general model for 1 f-normalized wavelength modulation absorption spectroscopy with nf detection (i.e., WMS- nf) is presented that considers the performance of injection-current-tuned diode lasers and the reflective interference produced by other optical components on the line-of-sight (LOS) transmission intensity. This model explores the optimization of sensitive detection of optical absorption by species with structured spectra at elevated pressures. Predictions have been validated by comparison with measurements of the 1 f-normalized WMS- nf (for n = 2-6) lineshape of the R(11) transition in the 1st overtone band of CO near 2.3 μm at four different pressures ranging from 5 to 20 atm, all at room temperature. The CO mole fractions measured by 1 f-normalized WMS-2 f, 3 f, and 4 f techniques agree with calibrated mixtures within 2.0 %. At conditions where absorption features are significantly broadened and large modulation depths are required, uncertainties in the WMS background signals due to reflective interference in the optical path can produce significant error in gas mole fraction measurements by 1 f-normalized WMS-2 f. However, such potential errors can be greatly reduced by using the higher harmonics, i.e., 1 f-normalized WMS- nf with n > 2. In addition, less interference from pressure-broadened neighboring transitions has been observed for WMS with higher harmonics than for WMS-2 f.

Prediction of solubilities for ginger bioactive compounds in hot water by the COSMO-RS method

NASA Astrophysics Data System (ADS)

Zaimah Syed Jaapar, Syaripah; Azian Morad, Noor; Iwai, Yoshio

2013-04-01

The solubilities in water of four main ginger bioactives, 6-gingerol, 6-shogaol, 8-gingerol and 10-gingerol, were predicted using a conductor-like screening model for real solvent (COSMO-RS) calculations. This study was conducted since no experimental data are available for ginger bioactive solubilities in hot water. The σ-profiles of these selected molecules were calculated using Gaussian software and the solubilities were calculated using the COSMO-RS method. The solubilities of these ginger bioactives were calculated at 50 to 200 °C. In order to validate the accuracy of the COSMO-RS method, the solubilities of five hydrocarbon molecules were calculated using the COSMO-RS method and compared with the experimental data in the literature. The selected hydrocarbon molecules were 3-pentanone, 1-hexanol, benzene, 3-methylphenol and 2-hydroxy-5-methylbenzaldehyde. The calculated results of the hydrocarbon molecules are in good agreement with the data in the literature. These results confirm that the solubilities of ginger bioactives can be predicted using the COSMO-RS method. The solubilities of the ginger bioactives are lower than 0.0001 at temperatures lower than 130 °C. At 130 to 200 °C, the solubilities increase dramatically with the highest being 6-shogaol, which is 0.00037 mole fraction, and the lowest is 10-gingerol, which is 0.000039 mole fraction at 200 °C.

Application of laser spectroscopy for measurement of exhaled ethane in patients with lung cancer.

PubMed

Skeldon, K D; McMillan, L C; Wyse, C A; Monk, S D; Gibson, G; Patterson, C; France, T; Longbottom, C; Padgett, M J

2006-02-01

There is increasing interest in ethane (C(2)H(6)) in exhaled breath as a non-invasive marker of oxidative stress (OS) and thereby a potential indicator of disease. However, the lack of real-time measurement techniques has limited progress in the field. Here we report on a novel Tunable Diode Laser Spectrometer (TDLS) applied to the analysis of exhaled ethane in patients with lung cancer. The patient group (n=52) comprised randomly selected patients presenting at a respiratory clinic. Of these, a sub-group (n=12) was subsequently diagnosed with lung cancer. An age-matched group (n=12) corresponding to the lung cancer group was taken from a larger control group of healthy adults (n=58). The concentration of ethane in a single exhaled breath sample collected from all subjects was later measured using the TDLS. This technique is capable of real-time analysis of samples with accuracy 0.1 parts per billion (ppb), over 10 times less than typical ambient levels in the northern hemisphere. After correcting for ambient background, ethane in the control group (26% smokers) ranged from 0 to 10.54 ppb (median of 1.9 ppb) while ethane in the lung cancer patients (42% smokers) ranged from 0 to 7.6 ppb (median of 0.7 ppb). Ethane among the non-lung cancer patients presenting for investigation of respiratory disease ranged from 0 to 25 ppb (median 1.45 ppb). We conclude that, while the TDLS proved effective for accurate and rapid sample analysis, there was no significant difference in exhaled ethane among any of the subject groups. Comments are made on the suitability of the technique for monitoring applications.

Evidence from in vivo 31-phosphorus magnetic resonance spectroscopy phosphodiesters that exhaled ethane is a biomarker of cerebral n-3 polyunsaturated fatty acid peroxidation in humans.

PubMed

Puri, Basant K; Counsell, Serena J; Ross, Brian M; Hamilton, Gavin; Bustos, Marcelo G; Treasaden, Ian H

2008-04-17

This study tested the hypothesis that exhaled ethane is a biomarker of cerebral n-3 polyunsaturated fatty acid peroxidation in humans. Ethane is released specifically following peroxidation of n-3 polyunsaturated fatty acids. We reasoned that the cerebral source of ethane would be the docosahexaenoic acid component of membrane phospholipids. Breakdown of the latter also releases phosphorylated polar head groups, giving rise to glycerophosphorylcholine and glycerophosphorylethanolamine, which can be measured from the 31-phosphorus neurospectroscopy phosphodiester peak. Schizophrenia patients were chosen because of evidence of increased free radical-mediated damage and cerebral lipid peroxidation in this disorder. Samples of alveolar air were obtained from eight patients and ethane was analyzed and quantified by gas chromatography and mass spectrometry (m/z = 30). Cerebral 31-phosphorus spectra were obtained from the same patients at a magnetic field strength of 1.5 T using an image-selected in vivo spectroscopy sequence (TR = 10 s; 64 signal averages localized on a 70 x 70 x 70 mm3 voxel). The quantification of the 31-phosphorus signals using prior knowledge was carried out in the temporal domain after truncating the first 1.92 ms of the signal to remove the broad component present in the 31-phosphorus spectra. The ethane and phosphodiester levels, expressed as a percentage of the total 31-phosphorus signal, were positively and significantly correlated (rs = 0.714, p < 0.05). Our results support the hypothesis that the measurement of exhaled ethane levels indexes cerebral n-3 lipid peroxidation. From a practical viewpoint, if human cerebral n-3 polyunsaturated fatty acid catabolism can be measured by ethane in expired breath, this would be more convenient than determining the area of the 31-phosphorus neurospectroscopy phosphodiester peak.

Increased levels of ethane, a non-invasive, quantitative, direct marker of n-3 lipid peroxidation, in the breath of patients with schizophrenia.

PubMed

Puri, Basant K; Ross, Brian M; Treasaden, Ian H

2008-04-01

This study directly assessed whether there was a change in the level of exhaled ethane, which provides a non-invasive, quantitative, direct measure of n-3 lipid peroxidation, in the breath of patients with schizophrenia. Samples of alveolar air were obtained from 20 subjects with schizophrenia and 23 age- and sex-matched healthy control subjects. The air samples were analyzed for ethane using mass spectrometry. The mean level of ethane in the schizophrenia sample [5.15 (S.E. 0.56) ppb] was significantly higher than that of the healthy controls [2.63 (S.E. 0.31) ppb; p<0.0005]. A further sub-analysis showed that nicotine dependence was unlikely to be the cause of this difference. These results suggest that the measurement of exhaled ethane levels may offer a non-invasive direct biomarker of increased n-3 lipid peroxidation in schizophrenia.

Ethane and acetylene abundances in the Jovian atmosphere

NASA Technical Reports Server (NTRS)

Tokunaga, A.; Knacke, R. F.; Owen, T.

1976-01-01

The paper reports spectra of Jupiter in the spectral region from 755 to 850 kaysers, which covers the nu-9 fundamental of ethane and contains lines from the R branch of the nu-5 fundamental of acetylene. The monochromatic absorption coefficient of the central Q branch of the nu-9 fundamental of ethane, which was determined in the laboratory, is applied in a radiative-transfer calculation to evaluate the ethane mixing ratio in the Jovian atmosphere; the present data are also used to place an upper limit on the acetylene mixing ratio. For the radiative-transfer calculation, emission intensity is computed for the region above the 0.02-atm level assuming both an isothermal inversion layer and a previously reported temperature profile. The resulting maximum mixing ratios consistent with the observations are 0.00003 for ethane and 7.5 by 10 to the -8th power for acetylene.

Ethane and n-pentane in exhaled breath are biomarkers of exposure not effect.

PubMed

Gorham, Katrine A; Sulbaek Andersen, Mads P; Meinardi, Simone; Delfino, Ralph J; Staimer, Norbert; Tjoa, Thomas; Rowland, F Sherwood; Blake, Donald R

2009-02-01

The relationship of exhaled ethane and n-pentane to exhaled NO, carbonylated proteins, and indoor/outdoor atmospheric pollutants were examined in order to evaluate ethane and n-pentane as potential markers of airway inflammation and/or oxidative stress. Exhaled NO and carbonylated proteins were found to have no significant associations with either ethane (p = 0.96 and p = 0.81, respectively) or n-pentane (p = 0.44 and 0.28, respectively) when outliers were included. In the case where outliers were removed n-pentane was found to be inversely associated with carbonylated proteins. Exhaled hydrocarbons adjusted for indoor hydrocarbon concentrations were instead found to be positively associated with air pollutants (NO, NO(2) and CO), suggesting pollutant exposure is driving exhaled hydrocarbon concentrations. Given these findings, ethane and n-pentane do not appear to be markers of airway inflammation or oxidative stress.

Ethane and n-pentane in exhaled breath are biomarkers of exposure not effect

PubMed Central

Gorham, Katrine A.; Sulbaek Andersen, Mads P.; Meinardi, Simone; Delfino, Ralph J.; Staimer, Norbert; Tjoa, Thomas; Rowland, F. Sherwood; Blake, Donald R.

2013-01-01

The relationship of exhaled ethane and n-pentane to exhaled NO, carbonylated proteins, and indoor/outdoor atmospheric pollutants were examined in order to evaluate ethane and n-pentane as potential markers of airway inflammation and/or oxidative stress. Exhaled NO and carbonylated proteins were found to have no significant associations with either ethane (p = 0.96 and p = 0.81, respectively) or n-pentane (p = 0.44 and 0.28, respectively) when outliers were included. In the case where outliers were removed n-pentane was found to be inversely associated with carbonylated proteins. Exhaled hydrocarbons adjusted for indoor hydrocarbon concentrations were instead found to be positively associated with air pollutants (NO, NO2 and CO), suggesting pollutant exposure is driving exhaled hydrocarbon concentrations. Given these find-ings, ethane and n-pentane do not appear to be markers of airway inflammation or oxidative stress. PMID:19283520

Tropospheric and lower stratospheric vertical profiles of ethane and acetylene

NASA Technical Reports Server (NTRS)

Cronn, D.; Robinson, E.

1979-01-01

The first known vertical distributions of ethane and acetylene which extend into the lower stratosphere are reported. The average upper tropospheric concentrations, between 20,000 ft and 35,000 ft, near 37 deg N-123 deg W were 1.2 micrograms/cu m (1.0 ppb) for ethane and 0.24 micrograms /cu m (0.23 ppb) for acetylene while the values near 9 N-80 W were 0.95 micrograms/cu m (0.77 ppb) and 0.09 micrograms/cu m (0.09 ppb), respectively. Detectable quantities of both ethane and acetylene are present in the lower stratosphere. There is a sharp decrease in the levels of these two compounds as one crosses the tropopause and ascends into the lower stratosphere. The observed levels of ethane and acetylene may allow some impact on the background chemistry of the troposphere and stratosphere.

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.

Ethane and Xenon mixing: density functional theory (DFT) simulations and experiments on Sandia's Z machine

NASA Astrophysics Data System (ADS)

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

2012-02-01

The combination of ethane and xenon is one of the simplest binary mixtures in which bond breaking is expected to play a role under shock conditions. At cryogenic conditions, xenon is often understood to mix with alkanes such as Ethane as if it were also an alkane, but this model is expected to break down at higher temperatures and pressures. To investigate the breakdown, we have performed density functional theory (DFT) calculations on several xenon/ethane mixtures. Additionally, we have performed shock compression experiments on Xenon-Ethane using the Sandia Z - accelerator. The DFT and experimental results are compared to hydrodynamic simulations using different mixing models in the equation of state. Sandia National Laboratories is a multi-program laboratory operated by Sandia Corporation, a wholly owned subsidiary of the Lockheed Martin company, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Fractionation and characterization of semi polar and polar compounds from leaf extract Nicotiana tabaccum L. reflux ethanol extraction results

NASA Astrophysics Data System (ADS)

Rahardjo, Andhika Priotomo; Fauzantoro, Ahmad; Gozan, Misri

2018-02-01

The decline in cigarette production as the solution of health problems can interfere with the welfare of tobacco farmers in Indonesia. So, it is required to utilize the alternative uses of tobacco with chemical compounds inside it as the raw material for producing alternative products. One of the methods that is efficient in separating chemical compounds from plant extracts is fractionation and characterization method. This method has never been used for Nicotiana tabaccum L. extract using semi polar and polar solvents. This study begins with preparing Nicotiana tabaccum L. extract ingredients obtained through reflux ethanol extraction process. Extracts are analyzed by HPLC which serves to determine the chemical compounds in tobacco extract qualitatively. Extract that has been analyzed, is then fractionated using column chromatography with semi polar (ethyl acetate) and polar (ethane) solvents sequentially. Chemical compounds from tobacco extracts will be dissolved in accordance with the polarity of each solvents. The chemical compound is then characterized using HPLC quantitatively and qualitatively. Then, the data that has been obtained is used to find the partition coefficient of the main components in Nicotiana tabaccum L., which is Nicotine (kN) in Virginia 1 (Ethyl Acetate) fraction at 0.075; Virginia 2 (Ethyl Acetate) fraction at 0.037; And Virginia 3 (Ethyl Acetate) fraction at 0.043.

Lateral organization of mixed, two-phosphatidylcholine liposomes as investigated by GPS, the slope of Laurdan generalized polarization spectra.

PubMed

Vallejo, Alba A; Velázquez, Jesús B; Fernández, Marta S

2007-10-01

The effect of the excitation or emission wavelengths on Laurdan generalized polarization (GP) can be evaluated by GPS, a quantitative, simplified determination of the GP spectrum slope, the thermotropic dependence of which allows the assessment of phospholipid lamellar membrane phase, as shown in a recent publication of our laboratory [J.B. Velázquez, M.S. Fernández, Arch. Biochem. Biophys. 455 (2006) 163-174]. In the present work, we applied Laurdan GPS to phase transition studies of mixed, two-phosphatidylcholine liposomes prepared from variable proportions of dimyristoyl- and dipalmitoylphosphatidylcholine (DMPC and DPPC, respectively). We have found that the GPS function reports a clear limit between the gel/liquid-crystalline phase coexistence region and the liquid-crystalline state, not only at a certain temperature T(c) for liposomes of constant composition submitted to temperature scans, but also at a defined mole fraction X(c), for two-component liposomes of variable composition at constant temperature. The T(c) or the X(c) values obtained from GPS vs. temperature or GPS vs. composition plots, respectively, allow the construction of a partial phase diagram for the DMPC-DPPC mixtures, showing the boundary between the two-phase coexisting region and the liquid-crystalline state. Likewise, at the onset of the transition region, i.e., the two-phase coexisting region as detected by GPS, it is possible to determine, although with less precision, a temperature T(o) or a mole fraction X(o) defining a boundary located below but near the limit between the gel and ripple phase, reported in the literature. These GPS results are consistent with the proposal by several authors that a fraction of L(alpha) phospholipids coexists with gel phospholipids in the rippled phase.

Carbon Tetrachloride Emissions from the US during 2008 - 2012 Derived from Atmospheric Data Using Bayesian and Geostatistical Inversions

NASA Astrophysics Data System (ADS)

Hu, L.; Montzka, S. A.; Miller, B.; Andrews, A. E.; Miller, J. B.; Lehman, S.; Sweeney, C.; Miller, S. M.; Thoning, K. W.; Siso, C.; Atlas, E. L.; Blake, D. R.; De Gouw, J. A.; Gilman, J.; Dutton, G. S.; Elkins, J. W.; Hall, B. D.; Chen, H.; Fischer, M. L.; Mountain, M. E.; Nehrkorn, T.; Biraud, S.; Tans, P. P.

2015-12-01

Global atmospheric observations suggest substantial ongoing emissions of carbon tetrachloride (CCl4) despite a 100% phase-out of production for dispersive uses since 1996 in developed countries and 2010 in other countries. Little progress has been made in understanding the causes of these ongoing emissions or identifying their contributing sources. In this study, we employed multiple inverse modeling techniques (i.e. Bayesian and geostatistical inversions) to assimilate CCl4 mole fractions observed from the National Oceanic and Atmospheric Administration (NOAA) flask-air sampling network over the US, and quantify its national and regional emissions during 2008 - 2012. Average national total emissions of CCl4 between 2008 and 2012 determined from these observations and an ensemble of inversions range between 2.1 and 6.1 Gg yr-1. This emission is substantially larger than the mean of 0.06 Gg/yr reported to the US EPA Toxics Release Inventory over these years, suggesting that under-reported emissions or non-reporting sources make up the bulk of CCl4 emissions from the US. But while the inventory does not account for the magnitude of observationally-derived CCl4 emissions, the regional distribution of derived and inventory emissions is similar. Furthermore, when considered relative to the distribution of uncapped landfills or population, the variability in measured mole fractions was most consistent with the distribution of industrial sources (i.e., those from the Toxics Release Inventory). Our results suggest that emissions from the US only account for a small fraction of the global on-going emissions of CCl4 (30 - 80 Gg yr-1 over this period). Finally, to ascertain the importance of the US emissions relative to the unaccounted global emission rate we considered multiple approaches to extrapolate our results to other countries and the globe.

40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

Code of Federal Regulations, 2013 CFR

2013-07-01

...-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis(2,1-ethanediyl oxy)]bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis (2,1-ethane diyloxy)] bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[[1-[(2-propenyloxy) methyl]-1,2-ethanediyl] bis(oxy)]bis-, bis(4-methylbenzene...

40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

Code of Federal Regulations, 2012 CFR

2012-07-01

...-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis(2,1-ethanediyl oxy)]bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis (2,1-ethane diyloxy)] bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[[1-[(2-propenyloxy) methyl]-1,2-ethanediyl] bis(oxy)]bis-, bis(4-methylbenzene...

40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

Code of Federal Regulations, 2014 CFR

2014-07-01

...-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis(2,1-ethanediyl oxy)]bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis (2,1-ethane diyloxy)] bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[[1-[(2-propenyloxy) methyl]-1,2-ethanediyl] bis(oxy)]bis-, bis(4-methylbenzene...

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

... DEPARTMENT OF ENERGY Federal Energy Regulatory Commission [Docket No. OR14-1-000] MarkWest Liberty Ethane Pipeline L.L.C.; Notice of Petition for Declaratory Order Take notice that on October 3, 2013...), MarkWest Liberty Ethane Pipeline L.L.C. (MarkWest) filed a petition requesting a declaratory order...

Density control of dodecamanganese clusters anchored on silicon(100).

PubMed

Condorelli, Guglielmo G; Motta, Alessandro; Favazza, Maria; Nativo, Paola; Fragalà, Ignazio L; Gatteschi, Dante

2006-04-24

A synthetic strategy to control the density of Mn12 clusters anchored on silicon(100) was investigated. Diluted monolayers suitable for Mn12 anchoring were prepared by Si-grafting mixtures of the methyl 10-undecylenoate precursor ligand with 1-decene spectator spacers. Different ratios of these mixtures were tested. The grafted surfaces were hydrolyzed to reveal the carboxylic groups available for the subsequent exchange with the [Mn12O12(OAc)16(H2O)4]4 H2O2 AcOH cluster. Modified surfaces were analyzed by attenuated total reflection (ATR)-FTIR spectroscopy, X-ray photoemission spectroscopy (XPS), and AFM imaging. Results of XPS and ATR-FTIR spectroscopy show that the surface mole ratio between grafted ester and decene is higher than in the source solution. The surface density of the Mn12 cluster is, in turn, strictly proportional to the ester mole fraction. Well-resolved and isolated clusters were observed by AFM, using a diluted ester/decene 1:1 solution.

Kinetic theory of oxygen isotopic exchange between minerals and water

USGS Publications Warehouse

Criss, R.E.; Gregory, R.T.; Taylor, H.P.

1987-01-01

Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in "closed" and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation of mass equation. The simultaneous solutions to these equations generate curved exchange trajectories on ??-?? plots. Families of such trajectories generated under conditions allowing for different fluid mole fractions, different fluid isotopic compositions, or different fluid flow rates are connected by positive-sloped isochronous lines. These isochrons reproduce the effects observed in hydrothermally exchanged mineral pairs including 1) steep positive slopes, 2) common reversals in the measured fractionation factors (??), and 3) measured fractionations that are highly variable over short distances where no thermal gradient can be geologically demonstrated. ?? 1987.

An investigation of the matrix sensitivity of refinery gas analysis using gas chromatography with flame ionisation detection.

PubMed

Ferracci, Valerio; Brown, Andrew S; Harris, Peter M; Brown, Richard J C

2015-02-27

The response of a flame ionisation detector (FID) on a gas chromatograph to methane, ethane, propane, i-butane and n-butane in a series of multi-component refinery gas standards was investigated to assess the matrix sensitivity of the instrument. High-accuracy synthetic gas standards, traceable to the International System of Units, were used to minimise uncertainties. The instrument response exhibited a small dependence on the component amount fraction: this behaviour, consistent with that of another FID, was thoroughly characterised over a wide range of component amount fractions and was shown to introduce a negligible bias in the analysis of refinery gas samples, provided a suitable reference standard is employed. No significant effects of the molar volume, density and viscosity of the gas mixtures on the instrument response were observed, indicating that the FID is suitable for the analysis of refinery gas mixtures over a wide range of component amount fractions provided that appropriate drift-correction procedures are employed. Copyright © 2015 Elsevier B.V. All rights reserved.

Thermal and Oxidation Response of UHTC Leading Edge Samples Exposed to Simulated Hypersonic Flight Conditions (Postprint)

DTIC Science & Technology

2013-03-01

such that the oxygen mole fraction of the test gas matches that of clean air. A supersonic nozzle then acceler- ates the test gas to the proper Mach...25 km. Its key limitation is that the gas chemistry is different from air, with lower oxygen and higher moisture and carbon-dioxide levels.5 Among the...Refs. 33,34 Briefly, it is a scramjet engine built to study supersonic combustion over a range of simulated flight J. Smialek—contributing editor

Formulation of an RP-1 Pyrolysis Surrogate from Shock Tube Measurements of Fuel and Ethylene Time Histories

DTIC Science & Technology

2012-04-01

They also provide modelers (in both kinetics and computational fluid dynamics) with a method of representing, during simulation, a fuel that may have...1 and RP-2 from [Huber 2009a] Composition, mole fraction Fluid RP-1 surrogate RP-2 surrogate -methyldecalin 0.354 0.354 5-methylnonane 0.150...modeling and experimental results. Experimental Thermal and Fluid Science, 28(7):701–708, 2004. L. F. Albright, B. L. Crynes, and W. H. Corcoran

Thermodynamic and transport combustion properties of hydrocarbons with air. Part 2: Compositions corresponding to Kelvin temperature schedules in part 1

NASA Technical Reports Server (NTRS)

Gordon, S.

1982-01-01

The equilibrium compositions that correspond to the thermodynamic and transport combustion properties for a wide range of conditions for the reaction of hydrocarbons with air are presented. Initially 55 gaseous species and 3 coin condensed species were considered in the calculations. Only 17 of these 55 gaseous species had equilibrium mole fractions greater than 0.000005 for any of the conditions studied and therefore these were the only ones retained in the final tables.

Electrical Activation Studies of Silicon Implanted Aluminum Gallium Nitride with High Aluminum Mole Fraction

DTIC Science & Technology

2007-12-01

realized with silicon due to its indirect band gap that results in poor quantum efficiency . The first LEDs and laser diodes were developed with...deep UV (λ < 340 nm) still face many challenges and have low internal quantum efficiency . Jong Kyu Kim et al. have developed a light emitting triode...LET) to try to overcome some of the challenges and 16 have produced a lighting device with increased quantum efficiency (16). AlxGa1-xN has been

Investigation of Electrical and Optical Properties of Bulk III-V Ternary Semiconductors

DTIC Science & Technology

2009-03-01

metalorganic vapour phase epitaxial grown (MOVPE) InxGa1-xSb with indium mole fractions less than 0.06. [28] They observed that GaSb and InxGa1-xSb had...Treideris, A. Krotkus, and K. Grigoras, “Picosecond GaAs and InGaAs photoconductive switches obtained by low-temperature metal-organic chemical vapour ...Time Dependent Annealing Study of Silicon Implanted Aluminum Gallium Nitride,” Master’s Thesis, Air Force Institute of Technology (AU), Wright

Phase change material for temperature control and material storage

NASA Technical Reports Server (NTRS)

Wessling, Jr., Francis C. (Inventor); Blackwood, James M. (Inventor)

2011-01-01

A phase change material comprising a mixture of water and deuterium oxide is described, wherein the mole fraction of deuterium oxide is selected so that the mixture has a selected phase change temperature within a range between 0.degree. C. and 4.degree. C. The mixture is placed in a container and used for passive storage and transport of biomaterials and other temperature sensitive materials. Gels, nucleating agents, freezing point depression materials and colorants may be added to enhance the characteristics of the mixture.

The Orbiting Carbon Observatory Mission: Watching the Earth Breathe Mapping CO2 from Space

NASA Technical Reports Server (NTRS)

Boain, Ron

2007-01-01

Approach: Collect spatially resolved, high resolution spectroscopic observations of CO2 and O2 absorption in reflected sunlight. Use these data to resolve spatial and temporal variations in the column averaged CO2 dry air mole fraction, X(sub CO2) over the sunlit hemisphere. Employ independent calibration and validation approaches to produce X(sub CO2) estimates with random errors and biases no larger than 1-2 ppm (0.3-0.5%) on regional scales at monthly intervals.

Utilizing Near-IR Tunable Laser Absorption Spectroscopy to Study Detonation and Combustion Systems

DTIC Science & Technology

2014-03-27

debris, such as soot . Velocity curves for the other equivalence ratios studied in this experiment are shown in Appendix A. Some of these curves show a...James R. Gord. “Measurements of OH mole fraction and temperature up to 20 kHz by using a diode-laser based UV absorption sensor ”. Applied Optics, 44...Davidson, and R.K. Hanson. “CO concentration and temperature sensor for combustion gases using quantum-cascade laser absorption near 4.7µm”. Applied

Phosphate glasses for radioactive, hazardous and mixed waste immobilization

DOEpatents

Cao, H.; Adams, J.W.; Kalb, P.D.

1998-11-24

Lead-free phosphate glass compositions are provided which can be used to immobilize low level and/or high level radioactive wastes in monolithic waste forms. The glass composition may also be used without waste contained therein. Lead-free phosphate glass compositions prepared at about 900 C include mixtures from about 1--6 mole % iron (III) oxide, from about 1--6 mole % aluminum oxide, from about 15--20 mole % sodium oxide or potassium oxide, and from about 30--60 mole % phosphate. The invention also provides phosphate, lead-free glass ceramic glass compositions which are prepared from about 400 C to about 450 C and which includes from about 3--6 mole % sodium oxide, from about 20--50 mole % tin oxide, from about 30--70 mole % phosphate, from about 3--6 mole % aluminum oxide, from about 3--8 mole % silicon oxide, from about 0.5--2 mole % iron (III) oxide and from about 3--6 mole % potassium oxide. Method of making lead-free phosphate glasses are also provided. 8 figs.

Moles

MedlinePlus

... noticeable, or they may contain dark hairs. Having hairs in a mole doesn't make it more dangerous. Moles can ... steroid drugs. There is little risk of melanoma cancer developing in these moles. Atypical moles (dysplastic nevi or Clarks nevi) An ...

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

PubMed

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

2010-09-09

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

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

PubMed Central

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

2016-01-01

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 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

Discrepancy between simulated and observed ethane and propane levels explained by underestimated fossil emissions

NASA Astrophysics Data System (ADS)

Dalsøren, Stig B.; Myhre, Gunnar; Hodnebrog, Øivind; Myhre, Cathrine Lund; Stohl, Andreas; Pisso, Ignacio; Schwietzke, Stefan; Höglund-Isaksson, Lena; Helmig, Detlev; Reimann, Stefan; Sauvage, Stéphane; Schmidbauer, Norbert; Read, Katie A.; Carpenter, Lucy J.; Lewis, Alastair C.; Punjabi, Shalini; Wallasch, Markus

2018-03-01

Ethane and propane are the most abundant non-methane hydrocarbons in the atmosphere. However, their emissions, atmospheric distribution, and trends in their atmospheric concentrations are insufficiently understood. Atmospheric model simulations using standard community emission inventories do not reproduce available measurements in the Northern Hemisphere. Here, we show that observations of pre-industrial and present-day ethane and propane can be reproduced in simulations with a detailed atmospheric chemistry transport model, provided that natural geologic emissions are taken into account and anthropogenic fossil fuel emissions are assumed to be two to three times higher than is indicated in current inventories. Accounting for these enhanced ethane and propane emissions results in simulated surface ozone concentrations that are 5-13% higher than previously assumed in some polluted regions in Asia. The improved correspondence with observed ethane and propane in model simulations with greater emissions suggests that the level of fossil (geologic + fossil fuel) methane emissions in current inventories may need re-evaluation.

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.

Characterization of a microbial consortium capable of rapid and simultaneous dechlorination of 1,1,2,2-tetrachloroethane and chlorinated ethane and ethene intermediates

USGS Publications Warehouse

Jones, E.J.P.; Voytek, M.A.; Lorah, M.M.; Kirshtein, J.D.

2006-01-01

A study was carried out to develop a culture of microorganisms for bioaugmentation treatment of chlorinated-ethane contaminated groundwater at sites where dechlorination is incomplete or rates are too slow for effective remedation. Mixed cultures capable of dechlorinating chlorinated ethanes and ethenes were enriched from contaminated wetland sediment at Aberdeen Proving Ground (APG) Maryland. The West Branch Consortium (WBC-2) was capable of degrading 1,1,2,2-tetrachloroethane (TeCA), trichloroethylene (TCE), cis and trans 1,2-dichloroethylene (DCE), 1,1,2-trichloroethane (TCA), 1,2-dichloroethane, and vinyl chloride to nonchlorinated end products ethylene and ethane. WBC-2 dechlorinated TeCA, TCA, and cisDCE rapidly and simultaneously. Methanogens in the consortium were members of the class Methanomicrobia, which includes acetoclastic methanogens. The WBC-2 consortium provides opportunities for the in situ bioremediation of sites contaminated with mixtures of chlorinated ethylenes and ethanes.

Portable optical spectroscopy for accurate analysis of ethane in exhaled breath

NASA Astrophysics Data System (ADS)

Patterson, Claire S.; McMillan, Lesley C.; Longbottom, Christopher; Gibson, Graham M.; Padgett, Miles J.; Skeldon, Kenneth D.

2007-05-01

We report on a maintenance-free, ward-portable, tunable diode laser spectroscopy system for the ultra-sensitive detection of ethane gas. Ethane is produced when cellular lipids are oxidized by free radicals. As a breath biomarker, ethane offers a unique measure of such oxidative stress. The ability to measure real-time breath ethane fluctuations will open up new areas in non-invasive healthcare. Instrumentation for such a purpose must be highly sensitive and specific to the target gas. Our technology has a sensitivity of 70 parts per trillion and a 1 s sampling rate. Based on a cryogenically cooled lead-salt laser, the instrument has a thermally managed closed-loop refrigeration system, eliminating the need for liquid coolants. Custom LabVIEW software allows automatic control by a laptop PC. We have field tested the instrument to ensure that target performance is sustained in a range of environments. We outline the novel applications underway with the instrument based on an in vivo clinical assessment of oxidative stress.

Analysis of Non-Methane Hydrocarbon Data from 2004-2016 in a Subtropical Area close to the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Rappenglueck, B.

2017-12-01

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 along with NO, NO2, NOx, O3 have been collected continuously from January 2004-December 2016 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.

Crystal structures of three co-crystals of 1,2-bis-(pyridin-4-yl)ethane with 4-alk-oxy-benzoic acids: 4-eth-oxy-benzoic acid-1,2-bis-(pyridin-4-yl)ethane (2/1), 4-n-propoxybenzoic acid-1,2-bis(pyridin-4-yl)ethane (2/1) and 4-n-but-oxy-benzoic acid-1,2-bis-(pyridin-4-yl)ethane (2/1).

PubMed

Tabuchi, Yohei; Gotoh, Kazuma; Ishida, Hiroyuki

2015-11-01

The crystal structures of three hydrogen-bonded co-crystals of 4-alk-oxy-benzoic acid-1,2-bis-(pyridin-4-yl)ethane (2/1), namely, 2C9H10O3·C12H12N2, (I), 2C10H12O3·C12H12N2, (II), and 2C11H14O3·C12H12N2, (III), have been determined at 93, 290 and 93 K, respectively. In (I), the asymmetric unit consists of one 4-eth-oxy-benzoic acid mol-ecule and one half-mol-ecule of 1,2-bis-(pyridin-4-yl)ethane, which lies on an inversion centre. In (II) and (III), the asymmetric units each comprise two crystallographically independent 4-alk-oxy-benzoic acid mol-ecules and one 1,2-bis-(pyridin-4-yl)ethane mol-ecule. In each crystal, the two components are linked by O-H⋯N hydrogen bonds, forming a linear hydrogen-bonded 2:1unit of the acid and the base. Similar to the structure of 2:1 unit of (I), the units of (II) and (III) adopt nearly pseudo-inversion symmetry. The 2:1 units of (I), (II) and (III) are linked via C-H⋯O hydrogen bonds, forming tape structures.

Study of ethane level in exhaled breath in patients with age-related macular degeneration: preliminary study.

PubMed

Cagini, C; Giordanelli, A; Fiore, T; Giardinieri, R; Malici, B; De Medio, G E; Pelli, M A; De Bellis, F; Capodicasa, E

2011-01-01

A variety of factors have been implicated in the pathogenesis of age-related macular degeneration (ARMD), and oxidative stress plays an important role in the onset and progression of the disease. Breath ethane is now considered a specific and non-invasive test for determining and monitoring the trend of lipid peroxidation and free radical-induced damage in vivo. This test provides an index of the patients' overall oxidative stress level. We evaluated the breath ethane concentration in exhaled air in patients with advanced ARMD. In this study, we enrolled 13 patients with advanced ARMD and a control group, and a breath analysis was carried out by gas chromatography. The mean ethane level in the ARMD patients was 0.82 ± 0.93 nmol/l (range: 0.01-2.7 nmol/l) and the mean ethane value in the control group was 0.12 ± 0.02 nmol/l (range: 0.08-0.16 nmol/l). The difference between the values of the 2 groups was statistically significant (p < 0.005). Receiver operating characteristic analysis showed an elevated area under the curve (0.831; 95% CI: 0.634-0.948), with a significance level of p < 0.0014 (area = 0.5). These preliminary results seem to indicate that breath ethane levels are higher in most patients with ARMD. The breath ethane test could thus be a useful method for evaluating the level of oxidative stress in patients with ARMD. To our knowledge, there are no data on this type of analysis applied to ARMD. Copyright © 2011 S. Karger AG, Basel.

High rates of anaerobic oxidation of methane, ethane and propane coupled to thiosulphate reduction.

PubMed

Suarez-Zuluaga, Diego A; Weijma, Jan; Timmers, Peer H A; Buisman, Cees J N

2015-03-01

Anaerobic methane oxidation coupled to sulphate reduction and the use of ethane and propane as electron donors by sulphate-reducing bacteria represent new opportunities for the treatment of streams contaminated with sulphur oxyanions. However, growth of microbial sulphate-reducing populations with methane, propane or butane is extremely slow, which hampers research and development of bioprocesses based on these conversions. Thermodynamic calculations indicate that the growth rate with possible alternative terminal electron acceptors such as thiosulphate and elemental sulphur may be higher, which would facilitate future research. Here, we investigate the use of these electron acceptors for oxidation of methane, ethane and propane, with marine sediment as inoculum. Mixed marine sediments originating from Aarhus Bay (Denmark) and Eckernförde Bay (Germany) were cultivated anaerobically at a pH between 7.2 and 7.8 and a temperature of 15 °C in the presence of methane, ethane and propane and various sulphur electron acceptors. The sulphide production rates in the conditions with methane, ethane and propane with sulphate were respectively 2.3, 2.2 and 1.8 μmol S L(-1) day(-1). For sulphur, no reduction was demonstrated. For thiosulphate, the sulphide production rates were up to 50 times higher compared to those of sulphate, with 86.2, 90.7 and 108.1 μmol S L(-1) day(-1) for methane, ethane and propane respectively. This sulphide production was partly due to disproportionation, 50 % for ethane but only 7 and 14 % for methane and propane respectively. The oxidation of the alkanes in the presence of thiosulphate was confirmed by carbon dioxide production. This is, to our knowledge, the first report of thiosulphate use as electron acceptor with ethane and propane as electron donors. Additionally, these results indicate that thiosulphate is a promising electron acceptor to increase start-up rates for sulphate-reducing bioprocesses coupled to short-chain alkane oxidation.

Evidence from in vivo 31-phosphorus magnetic resonance spectroscopy phosphodiesters that exhaled ethane is a biomarker of cerebral n-3 polyunsaturated fatty acid peroxidation in humans

PubMed Central

Puri, Basant K; Counsell, Serena J; Ross, Brian M; Hamilton, Gavin; Bustos, Marcelo G; Treasaden, Ian H

2008-01-01

Background This study tested the hypothesis that exhaled ethane is a biomarker of cerebral n-3 polyunsaturated fatty acid peroxidation in humans. Ethane is released specifically following peroxidation of n-3 polyunsaturated fatty acids. We reasoned that the cerebral source of ethane would be the docosahexaenoic acid component of membrane phospholipids. Breakdown of the latter also releases phosphorylated polar head groups, giving rise to glycerophosphorylcholine and glycerophosphorylethanolamine, which can be measured from the 31-phosphorus neurospectroscopy phosphodiester peak. Schizophrenia patients were chosen because of evidence of increased free radical-mediated damage and cerebral lipid peroxidation in this disorder. Methods Samples of alveolar air were obtained from eight patients and ethane was analyzed and quantified by gas chromatography and mass spectrometry (m/z = 30). Cerebral 31-phosphorus spectra were obtained from the same patients at a magnetic field strength of 1.5 T using an image-selected in vivo spectroscopy sequence (TR = 10 s; 64 signal averages localized on a 70 × 70 × 70 mm3 voxel). The quantification of the 31-phosphorus signals using prior knowledge was carried out in the temporal domain after truncating the first 1.92 ms of the signal to remove the broad component present in the 31-phosphorus spectra. Results The ethane and phosphodiester levels, expressed as a percentage of the total 31-phosphorus signal, were positively and significantly correlated (rs = 0.714, p < 0.05). Conclusion Our results support the hypothesis that the measurement of exhaled ethane levels indexes cerebral n-3 lipid peroxidation. From a practical viewpoint, if human cerebral n-3 polyunsaturated fatty acid catabolism can be measured by ethane in expired breath, this would be more convenient than determining the area of the 31-phosphorus neurospectroscopy phosphodiester peak. PMID:18433512

In situ high temperature MAS NMR study of the mechanisms of catalysis. Ethane aromatization on Zn-modified zeolite BEA.

PubMed

Arzumanov, Sergei S; Gabrienko, Anton A; Freude, Dieter; Stepanov, Alexander G

2009-04-01

Ethane conversion into aromatic hydrocarbons over Zn-modified zeolite BEA has been analyzed by high-temperature MAS NMR spectroscopy. Information about intermediates (Zn-ethyl species) and reaction products (mainly toluene and methane), which were formed under the conditions of a batch reactor, was obtained by (13)C MAS NMR. Kinetics of the reaction, which was monitored by (1)H MAS NMR in situ at the temperature of 573K, provided information about the reaction mechanism. Simulation of the experimental kinetics within the frames of the possible kinetic schemes of the reaction demonstrates that a large amount of methane evolved under ethane aromatization arises from the stage of direct ethane hydrogenolysis.

Moles and Mole Control on British Farms, Amenities and Gardens after Strychnine Withdrawal

PubMed Central

Baker, Sandra E.; Ellwood, Stephen A.; Johnson, Paul J.; Macdonald, David W.

2016-01-01

Simple Summary Moles are burrowing mammals that are regarded as pests in Britain, and until 2006 they could legally be killed using strychnine poison. When strychnine was withdrawn there were fears that mole populations would increase. We surveyed farmers, amenity managers and householders about moles and mole control on their land in 2007, post strychnine withdrawal. Kill-trapping was by far the preferred control method used and control may be used more than can be justified by damage levels or the effect of control on damage. Mole traps are unregulated, unlike most other spring traps, and some might not meet current welfare standards. We found no evidence that mole activity had increased since a 1992 survey of farms. Abstract Moles are considered pests in Britain, but this issue has been little studied. Lower welfare standards have been tolerated for moles than for most other managed wild mammal species, as use of both the controversial poison, strychnine, and unregulated traps have been permitted. Strychnine was withdrawn in 2006 and there were fears that mole populations would increase as a result. In 2007, we conducted a comprehensive, nationwide survey of land manager perceptions, opinions and behaviour regarding moles and mole control on farms, amenities and domestic gardens in Britain. We surveyed 2150 land managers (achieving a 59% response rate) and ground-truthed 29 responses. Moles were reported to be present on most farms and amenities, and 13% of gardens, and were more common in lighter soils. Where present, moles were usually considered pests, this being more likely in Wales, Scotland and northern England, on livestock and mixed farms, and on large, high-value amenities, e.g., racecourses and golf courses. Mole control followed similar patterns to mole presence. More control may occur than is economically, and therefore potentially ethically, justified. Control should be more carefully considered and, where necessary, more effectively targeted. Kill-trapping was the favoured recent and future method on farms and amenities, even if strychnine was to be reintroduced; however, because mole traps are currently unregulated, some might not meet current welfare standards if tested. We found no evidence for an increase in moles since a farm questionnaire survey conducted in 1992; this could have wider implications for future wildlife management policy changes. PMID:27338484

Porous media for catalytic renewable energy conversion

NASA Astrophysics Data System (ADS)

Hotz, Nico

2012-05-01

A novel flow-based method is presented to place catalytic nanoparticles into a reactor by sol-gelation of a porous ceramic consisting of copper-based nanoparticles, silica sand, ceramic binder, and a gelation agent. This method allows for the placement of a liquid precursor containing the catalyst into the final reactor geometry without the need of impregnating or coating of a substrate with the catalytic material. The so generated foam-like porous ceramic shows properties highly appropriate for use as catalytic reactor material, e.g., reasonable pressure drop due to its porosity, high thermal and catalytic stability, and excellent catalytic behavior. The catalytic activity of micro-reactors containing this foam-like ceramic is tested in terms of their ability to convert alcoholic biofuel (e.g. methanol) to a hydrogen-rich gas mixture with low concentrations of carbon monoxide (up to 75% hydrogen content and less than 0.2% CO, for the case of methanol). This gas mixture is subsequently used in a low-temperature fuel cell, converting the hydrogen directly to electricity. A low concentration of CO is crucial to avoid poisoning of the fuel cell catalyst. Since conventional Polymer Electrolyte Membrane (PEM) fuel cells require CO concentrations far below 100 ppm and since most methods to reduce the mole fraction of CO (such as Preferential Oxidation or PROX) have CO conversions of up to 99%, the alcohol fuel reformer has to achieve initial CO mole fractions significantly below 1%. The catalyst and the porous ceramic reactor of the present study can successfully fulfill this requirement.

Monte Carlo simulation of two-component bilayers: DMPC/DSPC mixtures.

PubMed Central

Sugár, I P; Thompson, T E; Biltonen, R L

1999-01-01

In this paper, we describe a relatively simple lattice model of a two-component, two-state phospholipid bilayer. Application of Monte Carlo methods to this model permits simulation of the observed excess heat capacity versus temperature curves of dimyristoylphosphatidylcholine (DMPC)/distearoylphosphatidylcholine (DSPC) mixtures as well as the lateral distributions of the components and properties related to these distributions. The analysis of the bilayer energy distribution functions reveals that the gel-fluid transition is a continuous transition for DMPC, DSPC, and all DMPC/DSPC mixtures. A comparison of the thermodynamic properties of DMPC/DSPC mixtures with the configurational properties shows that the temperatures characteristics of the configurational properties correlate well with the maxima in the excess heat capacity curves rather than with the onset and completion temperatures of the gel-fluid transition. In the gel-fluid coexistence region, we also found excellent agreement between the threshold temperatures at different system compositions detected in fluorescence recovery after photobleaching experiments and the temperatures at which the percolation probability of the gel clusters is 0.36. At every composition, the calculated mole fraction of gel state molecules at the fluorescence recovery after photobleaching threshold is 0.34 and, at the percolation threshold of gel clusters, it is 0.24. The percolation threshold mole fraction of gel or fluid lipid depends on the packing geometry of the molecules and the interchain interactions. However, it is independent of temperature, system composition, and state of the percolating cluster. PMID:10096905

Molecular Properties of neurotoxin receptors sites associated with sodium channels from mammalian brain.

PubMed

Catterall, W A; Hartshorne, R P; Beneski, D A

1982-01-01

Neurotoxins that act at specific receptor sites on voltage-sensitive sodium channels have been used as molecular probes to identify and purify protein components of sodium channels from mammalian brain. Photoreactive derivatives of scorpion toxin have been prepared and used to covalently label sodium channels in intact synaptosomes. Two polypeptides, alpha with Mr approximately 270,000 and beta with Mr approximately 38,000, are specifically labeled indicating that they are components of the scorpion toxin receptor site on the sodium channel. The sodium channel can be solubilized with retention of specific binding of [3H] saxitoxin using nonionic detergents such as Triton X-100. The solubilized saxitoxin receptor has molecular weight of 316,000 +/- 63,000 and binds 0.9 g of Triton X-100 and phospholipid per g of protein. The solubilized receptor can be purified 750-fold by ion exchange chromatography, wheat germ lectin/Sepharose chromatography and sucrose gradient sedimentation to a final specific activity of 1488 pmol/mg. Analysis of the polypeptide chain composition of the most highly purified fractions indicates that alpha and beta comprise 65% of the protein of these fractions and are only the polypeptides whose presence correlates with saxitoxin binding activity. These studies lead to a working hypothesis of sodium channel structure in which the intact channel is comprised of a complex with Mr of approximately 316,000 containing one mole of alpha (Mr approximately 270,000) and one to three moles of beta (Mr approximately 38,000).

Decarboxylation of 6-nitrobenzisoxazole-3-carboxylate in mixed micelles of zwitterionic and positively charged surfactants.

PubMed

Maximiano, Flavio A; Chaimovich, Hernan; Cuccovia, Iolanda M

2006-09-12

The rate of decarboxylation of 6-nitrobenzisoxazole-3-carboxylate, NBOC, was determined in micelles of N-hexadecyl-N,N,N-trimethylammonium bromide or chloride (CTAB or CTAC), N-hexadecyl-N,N-dimethyl-3-ammonium-1-propanesulfonate (HPS), N-dodecyl-N,N-dimethyl-3-ammonium-1-propanesulfonate (DPS), N-dodecyl-N,N,N-trimethylammonium bromide (DTAB), hexadecylphosphocholine (HPC), and their mixtures. Quantitative analysis of the effect on micelles on the velocity of NBOC decarboxylation allowed the estimation of the rate constants in the micellar pseudophase, k(m), for the pure surfactants and their mixtures. The extent of micellar catalysis for NBOC decarboxylation, expressed as the ratio k(m)/k(w), where k(w) is the rate constant in water, varied from 240 for HPS to 62 for HPC. With HPS or DPS, k(m) decreased linearly with CTAB(C) mole fraction, suggesting ideal mixing. With HPC, k(m) increased to a maximum at a CTAB(C) mole fraction of ca. 0.5 and then decreased at higher CTAB(C). Addition of CTAB(C) to HPC, where the negative charge of the surfactant is close to the hydrophobic core, produces tight ion pairs at the interface and, consequently, decreases interfacial water contents. Interfacial dehydration at the surface in equimolar HPC/CTAB(C) mixtures, and interfacial solubilization site of the substrate, can explain the observed catalytic synergy, since the rate of NBOC decarboxylation increases markedly with the decrease in hydrogen bonding to the carboxylate group.

Measurement of InAsSb bandgap energy and InAs/InAsSb band edge positions using spectroscopic ellipsometry and photoluminescence spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Webster, P. T.; Riordan, N. A.; Liu, S.

2015-12-28

The structural and optical properties of lattice-matched InAs{sub 0.911}Sb{sub 0.089} bulk layers and strain-balanced InAs/InAs{sub 1−x}Sb{sub x} (x ∼ 0.1–0.4) superlattices grown on (100)-oriented GaSb substrates by molecular beam epitaxy are examined using X-ray diffraction, spectroscopic ellipsometry, and temperature dependent photoluminescence spectroscopy. The photoluminescence and ellipsometry measurements determine the ground state bandgap energy and the X-ray diffraction measurements determine the layer thickness and mole fraction of the structures studied. Detailed modeling of the X-ray diffraction data is employed to quantify unintentional incorporation of approximately 1% Sb into the InAs layers of the superlattices. A Kronig-Penney model of the superlattice miniband structure ismore » used to analyze the valence band offset between InAs and InAsSb, and hence the InAsSb band edge positions at each mole fraction. The resulting composition dependence of the bandgap energy and band edge positions of InAsSb are described using the bandgap bowing model; the respective low and room temperature bowing parameters for bulk InAsSb are 938 and 750 meV for the bandgap, 558 and 383 meV for the conduction band, and −380 and −367 meV for the valence band.« less

A 60-yr record of atmospheric carbon monoxide reconstructed from Greenland firn air

NASA Astrophysics Data System (ADS)

Petrenko, V. V.; Martinerie, P.; Novelli, P.; Etheridge, D. M.; Levin, I.; Wang, Z.; Blunier, T.; Chappellaz, J.; Kaiser, J.; Lang, P.; Steele, L. P.; Hammer, S.; Mak, J.; Langenfelds, R. L.; Schwander, J.; Severinghaus, J. P.; Witrant, E.; Petron, G.; Battle, M. O.; Forster, G.; Sturges, W. T.; Lamarque, J.-F.; Steffen, K.; White, J. W. C.

2012-08-01

We present a reconstruction of the Northern Hemisphere (NH) high latitude atmospheric carbon monoxide (CO) mole fraction from Greenland firn air. Firn air samples were collected at three deep ice core sites in Greenland (NGRIP in 2001, Summit in 2006 and NEEM in 2008). CO records from the three sites agree well with each other as well as with recent atmospheric measurements, indicating that CO is well preserved in the firn at these sites. CO atmospheric history was reconstructed back to the year 1950 from the measurements using a combination of two forward models of gas transport in firn and an inverse model. The reconstructed history suggests that Arctic CO was already higher in 1950 than it is today. CO mole fractions rose gradually until the 1970s and peaked in the 1970s or early 1980s, followed by a decline to today's levels. We compare the CO history with the atmospheric histories of methane, light hydrocarbons, molecular hydrogen, CO stable isotopes and hydroxyl radical (OH), as well as with published CO emission inventories and results of a historical run from a chemistry-transport model. We find that the reconstructed Greenland CO history cannot be reconciled with available emission inventories unless large changes in OH are assumed. We argue that the available CO emission inventories chronically underestimate NH emissions, and fail to capture the emission decline starting in the late 1970s, which was most likely due to reduced emissions from road transportation in North America and Europe.

Methane, Ethane, and Nitrogen Stability on Titan

NASA Astrophysics Data System (ADS)

Hanley, J.; Grundy, W. M.; Thompson, G.; Dustrud, S.; Pearce, L.; Lindberg, G.; Roe, H. G.; Tegler, S.

2017-12-01

Many outer solar system bodies are likely to have a combination of methane, ethane and nitrogen. In particular the lakes of Titan are known to consist of these species. Understanding the past and current stability of these lakes requires characterizing the interactions of methane and ethane, along with nitrogen, as both liquids and ices. Our cryogenic laboratory setup allows us to explore ices down to 30 K through imaging, and transmission and Raman spectroscopy. Our recent work has shown that although methane and ethane have similar freezing points, when mixed they can remain liquid down to 72 K. Concurrently with the freezing point measurements we acquire transmission or Raman spectra of these mixtures to understand how the structural features change with concentration and temperature. Any mixing of these two species together will depress the freezing point of the lake below Titan's surface temperature, preventing them from freezing. We will present new results utilizing our recently acquired Raman spectrometer that allow us to explore both the liquid and solid phases of the ternary system of methane, ethane and nitrogen. In particular we will explore the effect of nitrogen on the eutectic of the methane-ethane system. At high pressure we find that the ternary creates two separate liquid phases. Through spectroscopy we determined the bottom layer to be nitrogen rich, and the top layer to be ethane rich. Identifying the eutectic, as well as understanding the liquidus and solidus points of combinations of these species, has implications for not only the lakes on the surface of Titan, but also for the evaporation/condensation/cloud cycle in the atmosphere, as well as the stability of these species on other outer solar system bodies. These results will help interpretation of future observational data, and guide current theoretical models.

A review of acetylene, ethylene and ethane molecular spectroscopy for planetary applications

NASA Technical Reports Server (NTRS)

Maguire, W. C.

1982-01-01

Spectroscopic work in acetylene, ethylene and ethane, are of particular interest since the Voyager IRIS observations of Jupiter. Acetylene and ethane but not ethylene were observed in the Jovian spectrum. Two fundamental bands of the observed gases are used to determine the spatial distribution of these hydrocarbons on Jupiter and to illuminate the photochemistry of these species. The 100 to 1000 cm region is discussed and selected examples of current laboratory work are given.

Low-Temperature and Rapid Growth of Large Single-Crystalline Graphene with Ethane.

PubMed

Sun, Xiao; Lin, Li; Sun, Luzhao; Zhang, Jincan; Rui, Dingran; Li, Jiayu; Wang, Mingzhan; Tan, Congwei; Kang, Ning; Wei, Di; Xu, H Q; Peng, Hailin; Liu, Zhongfan

2018-01-01

Future applications of graphene rely highly on the production of large-area high-quality graphene, especially large single-crystalline graphene, due to the reduction of defects caused by grain boundaries. However, current large single-crystalline graphene growing methodologies are suffering from low growth rate and as a result, industrial graphene production is always confronted by high energy consumption, which is primarily caused by high growth temperature and long growth time. Herein, a new growth condition achieved via ethane being the carbon feedstock to achieve low-temperature yet rapid growth of large single-crystalline graphene is reported. Ethane condition gives a growth rate about four times faster than methane, achieving about 420 µm min -1 for the growth of sub-centimeter graphene single crystals at temperature about 1000 °C. In addition, the temperature threshold to obtain graphene using ethane can be reduced to 750 °C, lower than the general growth temperature threshold (about 1000 °C) with methane on copper foil. Meanwhile ethane always keeps higher graphene growth rate than methane under the same growth temperature. This study demonstrates that ethane is indeed a potential carbon source for efficient growth of large single-crystalline graphene, thus paves the way for graphene in high-end electronical and optoelectronical applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2011-08-10

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

The case for refining bottom-up methane emission inventories using top-down measurements

NASA Astrophysics Data System (ADS)

Kelly, Bryce F. J.; Iverach, Charlotte P.; Ginty, Elisa; Bashir, Safdar; Lowry, Dave; Fisher, Rebecca E.; France, James L.; Nisbet, Euan G.

2017-04-01

Bottom-up global methane emission estimates are important for guiding policy development and mitigation strategies. Such inventories enable rapid and consistent proportioning of emissions by industrial sectors and land use at various scales from city to country to global. There has been limited use of top-down measurements to guide refining emission inventories. Here we compare the EDGAR gridmap data version 4.2 with over 5000 km of daytime ground level mobile atmospheric methane surveys in eastern Australia. The landscapes and industries surveyed include: urban environments, dryland farming, intensive livestock farming (both beef and lamb), irrigation agriculture, open cut and underground coal mining, and coal seam gas production. Daytime mobile methane surveys over a 2-year period show that at the landscape scale there is a high level of repeatability for the mole fraction of methane measured in the ground level atmosphere. Such consistency in the mole fraction of methane indicates that these data can be used as a proxy for flux. A scatter plot of the EDGAR emission gridmap Log[ton substance / 0.1 degree x 0.1 degree / year] versus the median mole fraction of methane / 0.1 degree x 0.1 degree in the ground level atmosphere highlights that the extent of elevated methane emissions associated with coal mining in the Hunter coalfields, which covers an area of 56 km by 24 km, has been under-represented in the EDGAR input data. Our results also show that methane emissions from country towns (population < 100,000) are underestimated in the EDGAR inventory. This is possibly due to poor information on the extent of urban gas leaks. Given the uncertainties associated with the base land use and industry data for each country, we generalise the Australian observations to the global inventory with caution. The extensive comparison of top-down measurements versus the EDGAR version 4.2 methane gridmaps highlights the need for adjustments to the base resource data and/or the emission factors applied for coal mining, especially emissions from underground-mine venting. Also, more detail is required on the areal extent and rate of leakage from the gas distribution systems. This is likely to be the case for many other countries. Our results highlight the value of mobile methane surveys for guiding the refinement of bottom-up emission estimates, and they also suggest the expansion of all forms of top-down emission estimates would result in reduced uncertainty in the global methane budget.

Structure-Property Relationships of Bismaleimides

NASA Technical Reports Server (NTRS)

Tenteris-Noebe, Anita D.

1997-01-01

The purpose of this research was to control and systematically vary the network topology of bismaleimides through cure temperature and chemistry (addition of various coreactants) and subsequently attempt to determine structure-mechanical property relationships. Characterization of the bismaleimide structures by dielectric, rheological, and thermal analyses, and density measurements was subsequently correlated with mechanical properties such as modulus, yield strength, fracture energy, and stress relaxation. The model material used in this investigation was 4,4'-BismaleiMidodIphenyl methane (BMI). BMI was coreacted with either 4,4'-Methylene Dianiline (MDA), o,o'-diallyl bisphenol A (DABA) from Ciba Geigy, or Diamino Diphenyl Sulfone (DDS). Three cure paths were employed: a low- temperature cure of 140 C where chain extension should predominate, a high-temperature cure of 220 C where both chain extension and crosslinking should occur simultaneously, and a low-temperature (140 C) cure followed immediately by a high-temperature (220 C) cure where the chain extension reaction or amine addition precedes BMI homopolymerization or crosslinking. Samples of cured and postcured PMR-15 were also tested to determine the effects of postcuring on the mechanical properties. The low-temperature cure condition of BMI/MDA exhibited the highest modulus values for a given mole fraction of BMI with the modulus decreasing with decreasing concentration of BMI. The higher elastic modulus is the result of steric hindrance by unreacted BMI molecules in the glassy state. The moduli values for the high- and low/high-temperature cure conditions of BMI/MDA decreased as the amount of diamine increased. All the moduli values mimic the yield strength and density trends. For the high-temperature cure condition, the room- temperature modulus remained constant with decreasing mole fraction of BMT for the BMI/DABA and BMI/DDS systems. Postcuring PMR-15 increases the modulus over that of the cured material even though density values of cured and postcured PMR were essentially the same. Preliminary results of a continuous and intermittent stress relaxation experiment for BMI:MDA in a 2:1 molar ratio indicate that crosslinking is occurring when the sample is in the undeformed state. Computer simulation of properties such as density, glass transition temperature, and modulus for the low- temperature cure conditions of BMI/MDA and BMI/DABA were completed. The computer modeling was used to help further understand and confirm the structure characterization results. The simulations correctly predicted the trends of these properties versus mole fraction BMI and were extended to other BMI/diamine systems.

Spectrum of excess partial molar absorptivity. Part II: a near infrared spectroscopic study of aqueous Na-halides.

PubMed

Sebe, Fumie; Nishikawa, Keiko; Koga, Yoshikata

2012-04-07

Our earlier thermodynamic studies suggested that F(-) and Cl(-) form hydration shells with the hydration number 14 ± 2 and 2.3 ± 0.6, respectively, and leave the bulk H(2)O away from hydration shells unperturbed. Br(-) and I(-), on the other hand, form hydrogen bonds directly with the momentarily existing hydrogen bond network of H(2)O, and retard the degree of entropy-volume cross fluctuation inherent in liquid H(2)O. The effect of the latter is stronger for I(-) than Br(-). Here we seek additional information about this qualitative difference between Cl(-) and (Br(-) and I(-)) pair by near infrared (NIR) spectroscopy. We analyze the ν(2) + ν(3) band of H(2)O in the range 4600-5500 cm(-1) of aqueous solutions of NaCl, NaBr and NaI, by a new approach. From observed absorbance, we calculate excess molar absorptivity, ε(E), excess over the additive contributions of solute and solvent. ε(E) thus contains information about the effect of inter-molecular interactions in the ν(2) + ν(3) spectrum. The spectrum of ε(E) shows three bands; two negative ones at 5263 and 4873 cm(-1), and the positive band at 5123 cm(-1). We then define and calculate the excess partial molar absorptivity of each salt, ε(E)(salt). From the behaviour of ε(E)(salt) we suggest that the negative band at 5263 cm(-1) represents free H(2)O without much hydrogen bonding under the influence of local electric field of ions. Furthermore, from a sudden change in the x(salt) (mole fraction of salt) dependence of ε(E)(salt), we suggest that there is an ion-pairing in x(salt) > 0.032, 0.036, and 0.04 for NaCl, NaBr and NaI respectively. The positive band of ε(E) at 5123 cm(-1) is attributed to a modestly organized hydrogen bond network of H(2)O (or liquid-likeness), and the x(salt) dependence of ε indicated a qualitative difference in the effect of Cl(-) from those of Br(-) and I(-). Namely, the values of ε(E)(salt) stay constant for Cl(-) but those for Br(-) and I(-) decrease smoothly on increasing the salt mole fraction. The mole fraction dependence of ε(E)(salt) at the 4873 cm(-1) band, due to ice-likeness in H(2)O, shows a subtle difference between Cl(-) and (Br(-), I(-)) pair.

Bursting Bubbles and Bilayers

PubMed Central

Wrenn, Steven P.; Dicker, Stephen M.; Small, Eleanor F.; Dan, Nily R.; Mleczko, Michał; Schmitz, Georg; Lewin, Peter A.

2012-01-01

This paper discusses various interactions between ultrasound, phospholipid monolayer-coated gas bubbles, phospholipid bilayer vesicles, and cells. The paper begins with a review of microbubble physics models, developed to describe microbubble dynamic behavior in the presence of ultrasound, and follows this with a discussion of how such models can be used to predict inertial cavitation profiles. Predicted sensitivities of inertial cavitation to changes in the values of membrane properties, including surface tension, surface dilatational viscosity, and area expansion modulus, indicate that area expansion modulus exerts the greatest relative influence on inertial cavitation. Accordingly, the theoretical dependence of area expansion modulus on chemical composition - in particular, poly (ethylene glyclol) (PEG) - is reviewed, and predictions of inertial cavitation for different PEG molecular weights and compositions are compared with experiment. Noteworthy is the predicted dependence, or lack thereof, of inertial cavitation on PEG molecular weight and mole fraction. Specifically, inertial cavitation is predicted to be independent of PEG molecular weight and mole fraction in the so-called mushroom regime. In the “brush” regime, however, inertial cavitation is predicted to increase with PEG mole fraction but to decrease (to the inverse 3/5 power) with PEG molecular weight. While excellent agreement between experiment and theory can be achieved, it is shown that the calculated inertial cavitation profiles depend strongly on the criterion used to predict inertial cavitation. This is followed by a discussion of nesting microbubbles inside the aqueous core of microcapsules and how this significantly increases the inertial cavitation threshold. Nesting thus offers a means for avoiding unwanted inertial cavitation and cell death during imaging and other applications such as sonoporation. A review of putative sonoporation mechanisms is then presented, including those involving microbubbles to deliver cargo into a cell, and those - not necessarily involving microubbles - to release cargo from a phospholipid vesicle (or reverse sonoporation). It is shown that the rate of (reverse) sonoporation from liposomes correlates with phospholipid bilayer phase behavior, liquid-disordered phases giving appreciably faster release than liquid-ordered phases. Moreover, liquid-disordered phases exhibit evidence of two release mechanisms, which are described well mathematically by enhanced diffusion (possibly via dilation of membrane phospholipids) and irreversible membrane disruption, whereas liquid-ordered phases are described by a single mechanism, which has yet to be positively identified. The ability to tune release kinetics with bilayer composition makes reverse sonoporation of phospholipid vesicles a promising methodology for controlled drug delivery. Moreover, nesting of microbubbles inside vesicles constitutes a truly “theranostic” vehicle, one that can be used for both long-lasting, safe imaging and for controlled drug delivery. PMID:23382772

Bursting bubbles and bilayers.

PubMed

Wrenn, Steven P; Dicker, Stephen M; Small, Eleanor F; Dan, Nily R; Mleczko, Michał; Schmitz, Georg; Lewin, Peter A

2012-01-01

This paper discusses various interactions between ultrasound, phospholipid monolayer-coated gas bubbles, phospholipid bilayer vesicles, and cells. The paper begins with a review of microbubble physics models, developed to describe microbubble dynamic behavior in the presence of ultrasound, and follows this with a discussion of how such models can be used to predict inertial cavitation profiles. Predicted sensitivities of inertial cavitation to changes in the values of membrane properties, including surface tension, surface dilatational viscosity, and area expansion modulus, indicate that area expansion modulus exerts the greatest relative influence on inertial cavitation. Accordingly, the theoretical dependence of area expansion modulus on chemical composition-- in particular, poly (ethylene glyclol) (PEG)--is reviewed, and predictions of inertial cavitation for different PEG molecular weights and compositions are compared with experiment. Noteworthy is the predicted dependence, or lack thereof, of inertial cavitation on PEG molecular weight and mole fraction. Specifically, inertial cavitation is predicted to be independent of PEG molecular weight and mole fraction in the so-called mushroom regime. In the "brush" regime, however, inertial cavitation is predicted to increase with PEG mole fraction but to decrease (to the inverse 3/5 power) with PEG molecular weight. While excellent agreement between experiment and theory can be achieved, it is shown that the calculated inertial cavitation profiles depend strongly on the criterion used to predict inertial cavitation. This is followed by a discussion of nesting microbubbles inside the aqueous core of microcapsules and how this significantly increases the inertial cavitation threshold. Nesting thus offers a means for avoiding unwanted inertial cavitation and cell death during imaging and other applications such as sonoporation. A review of putative sonoporation mechanisms is then presented, including those involving microbubbles to deliver cargo into a cell, and those--not necessarily involving microubbles--to release cargo from a phospholipid vesicle (or reverse sonoporation). It is shown that the rate of (reverse) sonoporation from liposomes correlates with phospholipid bilayer phase behavior, liquid-disordered phases giving appreciably faster release than liquid-ordered phases. Moreover, liquid-disordered phases exhibit evidence of two release mechanisms, which are described well mathematically by enhanced diffusion (possibly via dilation of membrane phospholipids) and irreversible membrane disruption, whereas liquid-ordered phases are described by a single mechanism, which has yet to be positively identified. The ability to tune release kinetics with bilayer composition makes reverse sonoporation of phospholipid vesicles a promising methodology for controlled drug delivery. Moreover, nesting of microbubbles inside vesicles constitutes a truly "theranostic" vehicle, one that can be used for both long-lasting, safe imaging and for controlled drug delivery.

A Computational Investigation of Sooting Limits of Spherical Diffusion Flames

NASA Technical Reports Server (NTRS)

Lecoustre, V. R.; Chao, B. H.; Sunderland, P. B.; Urban, D. L.; Stocker, D. P.; Axelbaum, R. L.

2007-01-01

Limiting conditions for soot particle inception in spherical diffusion flames were investigated numerically. The flames were modeled using a one-dimensional, time accurate diffusion flame code with detailed chemistry and transport and an optically thick radiation model. Seventeen normal and inverse flames were considered, covering a wide range of stoichiometric mixture fraction, adiabatic flame temperature, and residence time. These flames were previously observed to reach their sooting limits after 2 s of microgravity. Sooting-limit diffusion flames with residence times longer than 200 ms were found to have temperatures near 1190 K where C/O = 0.6, whereas flames with shorter residence times required increased temperatures. Acetylene was found to be a reasonable surrogate for soot precursor species in these flames, having peak mole fractions of about 0.01.

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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Increased breath ethane levels in medicated patients with schizophrenia and bipolar disorder are unrelated to erythrocyte omega-3 fatty acid abundance.

PubMed

Ross, Brian M; Maxwell, Ross; Glen, Iain

2011-03-30

Oxidative stress has been reported to be elevated in mental illness. Preliminary evidence suggests this phenomenon can be assessed non-invasively by determining breath levels of the omega-3 polyunsaturated fatty acid (PUFA) oxidation product ethane. This study compares alkane levels in chronic, medicated, patients with schizophrenia or bipolar disorder with those in healthy controls. Both ethane and butane levels were significantly increased in patients with schizophrenia or bipolar disorder, although elevated butane levels were likely due to increased ambient gas concentrations. Ethane levels were not correlated with symptom severity or with erythrocyte omega-3 PUFA levels. Our results support the hypothesis that oxidative stress is elevated in patients with schizophrenia and bipolar disorder leading to increased breath ethane abundance. This does not appear to be caused by increased abundance of omega-3 PUFA, but rather is likely due to enhanced oxidative damage of these lipids. As such, breath hydrocarbon analysis may represent a simple, non-invasive means to monitor the metabolic processes occurring in these disorders. Copyright © 2010 Elsevier Inc. All rights reserved.

Identifying different types of catalysts for CO 2 reduction by ethane through dry reforming and oxidative dehydrogenation

DOE PAGES

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

2015-11-10

In this study, the recent shale gas boom combined with the requirement to reduce atmospheric CO 2 have created an opportunity for using both raw materials (shale gas and CO 2) 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 CO 2 reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H 2). The second route is oxidative dehydrogenation which produces ethylene using CO 2 as a softmore » oxidant. The results of this study indicate that the Pt/CeO 2 catalyst shows promise for the production of synthesis gas, while Mo 2C-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

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.

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.

Biological formation of ethane and propane in the deep marine subsurface.

PubMed

Hinrichs, Kai-Uwe; Hayes, John M; Bach, Wolfgang; Spivack, Arthur J; Hmelo, Laura R; Holm, Nils G; Johnson, Carl G; Sylva, Sean P

2006-10-03

Concentrations and isotopic compositions of ethane and propane in cold, deeply buried sediments from the southeastern Pacific are best explained by microbial production of these gases in situ. Reduction of acetate to ethane provides one feasible mechanism. Propane is enriched in (13)C relative to ethane. The amount is consistent with derivation of the third C from inorganic carbon dissolved in sedimentary pore waters. At typical sedimentary conditions, the reactions yield free energy sufficient for growth. Relationships with competing processes are governed mainly by the abundance of H(2). Production of C(2) and C(3) hydrocarbons in this way provides a sink for acetate and hydrogen but upsets the general belief that hydrocarbons larger than methane derive only from thermal degradation of fossil organic material.

Biological formation of ethane and propane in the deep marine subsurface

PubMed Central

Hinrichs, Kai-Uwe; Hayes, John M.; Bach, Wolfgang; Spivack, Arthur J.; Hmelo, Laura R.; Holm, Nils G.; Johnson, Carl G.; Sylva, Sean P.

2006-01-01

Concentrations and isotopic compositions of ethane and propane in cold, deeply buried sediments from the southeastern Pacific are best explained by microbial production of these gases in situ. Reduction of acetate to ethane provides one feasible mechanism. Propane is enriched in 13C relative to ethane. The amount is consistent with derivation of the third C from inorganic carbon dissolved in sedimentary pore waters. At typical sedimentary conditions, the reactions yield free energy sufficient for growth. Relationships with competing processes are governed mainly by the abundance of H2. Production of C2 and C3 hydrocarbons in this way provides a sink for acetate and hydrogen but upsets the general belief that hydrocarbons larger than methane derive only from thermal degradation of fossil organic material. PMID:16990430

NMR study of methane + ethane structure I hydrate decomposition.

PubMed

Dec, Steven F; Bowler, Kristen E; Stadterman, Laura L; Koh, Carolyn A; Sloan, E Dendy

2007-05-24

The thermally activated decomposition of methane + ethane structure I hydrate was studied with use of 13C magic-angle spinning (MAS) NMR as a function of composition and temperature. The observed higher decomposition rate of large sI cages initially filled with ethane gas can be described in terms of a model where a distribution of sI unit cells exists such that a particular unit cell contains zero, one, or two methane molecules in the unit cell; this distribution of unit cells is combined to form the observed equilibrium composition. In this model, unit cells with zero methane molecules are the least stable and decompose more rapidly than those populated with one or two methane molecules leading to the observed overall faster decomposition rate of the large cages containing ethane molecules.

Why Occam's razor doesn't work for atmospheric methane

NASA Astrophysics Data System (ADS)

Manning, Martin; Brailsford, Gordon; Dlugokencky, Ed; Moss, Rowena; Nisbet, Euan; Schaefer, Hinrich; White, James

2017-04-01

With the CH4 mole fraction in clean air increasing since 2007, after being relatively stable for seven years, there are a growing number of papers with different explanations. Examples include: a continuing debate about the fraction of CH4 coming from fossil fuels[1] and whether this source is increasing[2]. Then, more generally, whether increasing sources are predominantly anthropogenic[3,4] or from tropical wetlands[5-7]; and that increasing sources may also be competing with increasing removal rates[8,9]. The increasing amount of δ13CCH4 data and the recent reversal of its long-term trend should help to clarify changes in the CH4 budget, but δ13C has both nonlinear and longer term responses to changes in sources or removal than the mole fraction[10]. Furthermore, the seasonal cycle in δ13CCH4 means that it is never in equilibrium and that its short-term response to a budget change depends on the time of year when that occurs. Then to complicate matters further, while it has been shown that changes in the total removal rate cannot explain the recent δ13CCH4 observations[7], changes in the more highly fractionating removal by Cl can produce very similar responses to changes in the sources. So far changes in the CH4 budget are only in the order of 3%, but its mole fraction is diverging from scenarios that achieve the 2°C climate change target, and at the upper end of the range considered in climate models. To understand the reasons for this requires a multidisciplinary approach with clearer links to atmospheric chemistry, more analyses of potential changes in methanogenic and methanotrophic processes, and resolving the major discrepancies between current bottom-up and top-down CH4 budget analyses. One contribution to this comes from the last 26 years of Southern Hemisphere 14CO data that are now showing OH has been quite stable, despite a large perturbation caused by the Mount Pinatubo eruption. This is also suggesting that trends seen in atmospheric transport[11,12] may now be altering the balance between sources and removal. 1. Schwietzke, S. et al. Nature 538, 88-91 (2016). 2. Hausmann, P., et al. Atmospheric Chemistry and Physics 16, 3227-3244 (2016). 3. Bergamaschi, P. et al. Journal of Geophysical Research 118, 7350-7369 (2013). 4. Schaefer, H. et al. Science 352, 80-84 (2016). 5. Bousquet, P. et al. Atmospheric Chemistry and Physics 11, 3689-3700 (2011). 6. Houweling, S. et al. Atmospheric Chemistry and Physics 14, 3991-4012 (2014). 7. Nisbet, E. G. et al. Global Biogeochemical Cycles 13, 1356-1370 (2016). 8. Dalsøren, S. B. et al. Atmospheric Chemistry and Physics 16, 3099-3126 (2016). 9. Ghosh, A. et al. Atmospheric Chemistry and Physics 15, 2595-2612 (2015). 10. Tans, P. P. Global Biogeochemical Cycles 11, 77-81 (1997). 11. Min, S.-K. & Son, S.-W. Journal of Geophysical Research 118, 3007-3015 (2013). 12. Eyring, V. et al. Journal of Geophysical Research 118, 5029-5060 (2013).

Theoretical analysis of the rotational barrier of ethane.

PubMed

Mo, Yirong; Gao, Jiali

2007-02-01

The understanding of the ethane rotation barrier is fundamental for structural theory and the conformational analysis of organic molecules and requires a consistent theoretical model to differentiate the steric and hyperconjugation effects. Due to recently renewed controversies over the barrier's origin, we developed a computational approach to probe the rotation barriers of ethane and its congeners in terms of steric repulsion, hyperconjugative interaction, and electronic and geometric relaxations. Our study reinstated that the conventional steric repulsion overwhelmingly dominates the barriers.

Percussive mole boring device with electronic transmitter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stangl, G.A.; Lee, D.W.; Wilson, D.A.

This patent describes an improvement in an unguided percussive mole boring device. It is for use with a flexible hose connected to the mole boring device for providing a source of percussive power to drive the mole boring device, percussive means connected to the flexible hose and driven by a percussive power source for impacting the mole boring device.

Observation and simulation of ethane at 23 FTIR sites

NASA Astrophysics Data System (ADS)

Bader, W. M. J.; Mahieu, E.; Franco, B.; Pozzer, A.; Taraborrelli, D.; Prignon, M.; Servais, C. P.; De Maziere, M.; Vigouroux, C.; Mengistu Tsidu, G.; Sufa, G.; Mellqvist, J.; Blumenstock, T.; Hase, F.; Schneider, M.; Sussmann, R.; Nagahama, T.; Sudo, K.; Hannigan, J. W.; Ortega, I.; Morino, I.; Nakajima, H.; Smale, D.; Makarova, M.; Poberovsky, A.; Murata, I.; Grutter de la Mora, M.; Guarin, C. A.; Stremme, W.; Té, Y.; Jeseck, P.; Notholt, J.; Palm, M.; Conway, S. A.; Lutsch, E.; Strong, K.; Griffith, D. W. T.; Jones, N. B.; Paton-Walsh, C.; Friedrich, M.; Smeekes, S.

2017-12-01

Ethane is the most abundant non-methane hydrocarbon (NMHC) in the Earth atmosphere. Its main sources are of anthropogenic origin, with globally 62% from leakage during production and transport of natural gas, 20% from biofuel combustion and 18% from biomass burning. In the Southern hemisphere, anthropogenic emissions are lower which makes biomass burning emissions a more significant source. The main removal process is oxidation by the hydroxyl radical (OH), leading to a mean atmospheric lifetime of 2 months. Until recently, a prolonged decrease of its abundance has been documented, at rates of -1 to -2.7%/yr, with global emissions dropping from 14 to 11 Tg/yr over 1984-2010 owing to successful measures reducing fugitive emissions from its fossil fuel sources. However, subsequent investigations have reported on an upturn in the ethane trend, characterized by a sharp rise from about 2009 onwards. The ethane increase is attributed to the oil and natural gas production boom in North America, although significant changes in OH could also be at play. In the present contribution, we report the trend of ethane at 23 ground-based Fourier Transform Infrared (FTIR) sites spanning the 80ºN to 79ºS latitude range. Over 2010-2015, a significant ethane rise of 3-5%/yr is determined for most sites in the Northern Hemisphere, while for the Southern hemisphere the rates of changes are not significant at the 2-sigma uncertainty level . Dedicated model simulations by EMAC (ECHAM5/MESSy Atmospheric Chemistry; 1.8×1.8 degrees) implementing various emission scenarios are included in order to support data interpretation. The usual underestimation of the NMHCs emissions in the main inventories is confirmed here for RCP85 (Representative Concentration Pathway Database v8.5). Scaling them by 1.5 is needed to capture the background levels of atmospheric ethane. Moreover, additional and significant emissions ( 7 Tg over 2009-2015) are needed to capture the ethane rise in the Northern hemisphere. Attributing them to the oil and gas sector and locating them in North America allows EMAC to produce adequate trends in the Northern hemisphere, but not in the Southern hemisphere, where they are overestimated. Possible causes for this difference are discussed.

Thermodynamics of iron-aluminum alloys at 1573 K

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Mehrotra, Gopal M.

1993-01-01

The activities of iron and aluminum were measured in Fe-Al alloys at 1573 K, using the ion-current-ratio technique in a high-temperature Knudsen cell mass spectrometer. The Fe-Al solutions exhibited negative deviations from ideality over the entire composition range. The activity coefficients gamma(Fe), and gamma(Al) are given by six following equations as a function of mole fraction, X(Fe), X(Al). The results show good agreement with those obtained from previous investigations at other temperatures by extrapolation of the activity data to 1573 K.

Thermochemical characteristics of nicotinamide protolytic equilibria in water-dimethylsulfoxide mixtures

NASA Astrophysics Data System (ADS)

Grazhdan, K. V.; Gamov, G. A.; Dushina, S. V.; Sharnin, V. A.

2012-04-01

The heat effects of nicotinamide protonation in water-dimethylsulfoxide (DMSO) solutions over the concentration range 0-0.75 DMSO mole fractions were determined calorimetrically at 25.00 ± 0.01°C and ionic strength 0.25 (NaClO4). Changes in the enthalpy of protonation as the content of DMSO increased were found to be described by an S-shaped curve. This curve shape was caused by the dynamics of reagent solvation contributions as the concentration of DMSO grew with the predominance of the nicotinamide solvation contribution.

AGE Bio Diesel Emissions Evaluation

DTIC Science & Technology

2003-12-01

329 44 788 Vratd) Standard Meter Volume, m° 1.336 1.214 1.255 1,268 am Average Sampling Rate, dscfm 0786 0 714 0 739 0 746 P, Stack Pressure, inches...sat) Moisture (at saturation), % by volume 70864 248 8 36676 V.d Standard Water Vapor Volume, ft’ 2.198 1 624 1 911 1-B• Dry Mole Fraction 0 941 0946...Clock Meter Dry Gas Sample Time, Volume, Rotameter Meter Temp., Vacuum, Probe Time (min) (24-hr) (liter) Setting (OF) (in.Hg) jTpr, OF /o5 f / 52 / 6 14V_

The second virial coefficient of system ((nitrogen-water))

NASA Astrophysics Data System (ADS)

Podmurnaya, O. A.

2004-01-01

The virial coefficient data of various components of atmosphere are interesting because permit to evaluate a deviation from ideal gas model. These data may be useful while investigating the clusters generation and determination their contribution in absorption. The second cross virial coefficient Baw for system ((nitrogen water)) has been calculated form +9°C to +50°C using the last experimental data about water vapor mole fraction. The reliability of this coefficient has been tested by analysing of errors sources and by comparing the results with other available experimental data.

Phase equilibrium in a water + n-hexane system with a high water content

NASA Astrophysics Data System (ADS)

Rasulov, S. M.; Orakova, S. M.; Isaev, Z. A.

2017-02-01

The P, ρ, and T-properties of a water + n-hexane system immiscible under normal conditions are measured piezometrically in the water mole fraction range of 0.918-0.977 at 309-685 K and pressures of up to 66 MPa. Two phase transitions are observed on each isochore corresponding to phase transitions of hydrocarbon liquid into gas or the dissolution of n-hexane in water and the transition of aqueous liquid into gas. The boundaries of phase transitions and their critical parameters are determined.

Wavefunction Engineering of Spintronic devices in ZnO/MgO and GaN/AlN Quantum Structures Doped with Transition Metal Ions

DTIC Science & Technology

2006-08-01

2005). 7. " Dependence of the interband transitions on the In mole-fraction and the applied electric field in InxGaj_xAs/In0. 52Al0.48As multiple... tunneling boundary conditions for open structures. The boundary conditions at interfaces require the maintenance of derivative operator ordering...computational methods for the solution of Schr6dinger’s equations for scattering/ tunneling structures as well as for the eigenvalue problems that arise for

Long period grating refractive-index sensor: optimal design for single wavelength interrogation.

PubMed

Kapoor, Amita; Sharma, Enakshi K

2009-11-01

We report the design criteria for the use of long period gratings (LPGs) as refractive-index sensors with output power at a single interrogating wavelength as the measurement parameter. The design gives maximum sensitivity in a given refractive-index range when the interrogating wavelength is fixed. Use of the design criteria is illustrated by the design of refractive-index sensors for specific application to refractive-index variation of a sugar solution with a concentration and detection of mole fraction of xylene in heptane (paraffin).

Low temperature synthesis of monolithic transparent Ta2O5 gels from hydrolysis of metal alkoxide

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.

1993-01-01

Tantalum oxide gels in the form of transparent monoliths and powder were prepared from hydrolysis of tantalum pentaethoxide under controlled conditions using different mole ratios of Ta(OC2H5)5:C2H50H:H20:HCl. Alcohol acts as the mutual solvent and HCl as the deflocculating agent. For a fixed alkoxide:water:HCl ratio, time of gel formation increased with the alcohol to alkoxide mole ratio. Thermal evolution of the physical and structural changes in the gel was monitored by differential thermal analysis, thermogravimetric analysis, x-ray diffraction, and infrared spectroscopy. On heating to approximately 400 C, the amorphous gel crystallized into the low temperature orthorhombic phase Beta-Ta2O5, which transformed into the high temperature tetragonal phase Alpha-Ta2O5 when further heated to approximately 1450 C. The volume fraction of the crystalline phase increased with the firing temperature. The Alpha-Ta205 converted back into the low temperature phase, Beta-Ta2O5, on slow cooling through the transformation temperature of 1360 C indicating a slow but reversible transformation.

GaAsSb bandgap, surface fermi level, and surface state density studied by photoreflectance modulation spectroscopy

NASA Astrophysics Data System (ADS)

Hwang, J. S.; Tsai, J. T.; Su, I. C.; Lin, H. C.; Lu, Y. T.; Chiu, P. C.; Chyi, J. I.

2012-05-01

The bandgap, surface Fermi level, and surface state density of a series of GaAs1-xSbx surface intrinsic-n+ structures with GaAs as substrate are determined for various Sb mole fractions x by the photoreflectance modulation spectroscopy. The dependence of the bandgap on the mole composition x is in good agreement with previous measurements as well as predictions calculated using the dielectric model of Van Vechten and Bergstresser in Phys. Rev. B 1, 3551 (1970). For a particular composition x, the surface Fermi level is always strongly pinned within the bandgap of GaAs1-xSbx and we find its variation with composition x is well described by a function EF = 0.70 - 0.192 x for 0 ≦ x ≦ 0.35, a result which is notably different from that reported by Chouaib et al. [Appl. Phys. Lett. 93, 041913 (2008)]. Our results suggest that the surface Fermi level is pinned at the midgap of GaAs and near the valence band of the GaSb.

High concentration agglomerate dynamics at high temperatures.

PubMed

Heine, M C; Pratsinis, S E

2006-11-21

The dynamics of agglomerate aerosols are investigated at high solids concentrations that are typical in industrial scale manufacture of fine particles (precursor mole fraction larger than 10 mol %). In particular, formation and growth of fumed silica at such concentrations by chemical reaction, coagulation, and sintering is simulated at nonisothermal conditions and compared to limited experimental data and commercial product specifications. Using recent chemical kinetics for silica formation by SiCl4 hydrolysis and neglecting aerosol polydispersity, the evolution of the diameter of primary particles (specific surface area, SSA), hard- and soft-agglomerates, along with agglomerate effective volume fraction (volume occupied by agglomerate) is investigated. Classic Smoluchowski theory is fundamentally limited for description of soft-agglomerate Brownian coagulation at high solids concentrations. In fact, these high concentrations affect little the primary particle diameter (or SSA) but dominate the soft-agglomerate diameter, structure, and volume fraction, leading to gelation consistent with experimental data. This indicates that restructuring and fragmentation should affect product particle characteristics during high-temperature synthesis of nanostructured particles at high concentrations in aerosol flow reactors.

40 CFR 60.612 - Standards.

Code of Federal Regulations, 2011 CFR

2011-07-01

... maximum production rate at which the affected facility will be operated, or 180 days after the initial... (minus methane and ethane) by 98 weight-percent, or to a TOC (minus methane and ethane) concentration of...

40 CFR 60.612 - Standards.

Code of Federal Regulations, 2012 CFR

2012-07-01

... maximum production rate at which the affected facility will be operated, or 180 days after the initial... (minus methane and ethane) by 98 weight-percent, or to a TOC (minus methane and ethane) concentration of...

40 CFR 60.612 - Standards.

Code of Federal Regulations, 2013 CFR

2013-07-01

... maximum production rate at which the affected facility will be operated, or 180 days after the initial... (minus methane and ethane) by 98 weight-percent, or to a TOC (minus methane and ethane) concentration of...

40 CFR 60.612 - Standards.

Code of Federal Regulations, 2014 CFR

2014-07-01

... maximum production rate at which the affected facility will be operated, or 180 days after the initial... (minus methane and ethane) by 98 weight-percent, or to a TOC (minus methane and ethane) concentration of...

40 CFR 60.612 - Standards.

Code of Federal Regulations, 2010 CFR

2010-07-01

... start-up, whichever date comes first. Each owner or operator shall either: (a) Reduce emissions of TOC (minus methane and ethane) by 98 weight-percent, or to a TOC (minus methane and ethane) concentration of...

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.

Microwave Plasma-Activated Chemical Vapor Deposition of Nitrogen-Doped Diamond. II: CH4/N2/H2 Plasmas

PubMed Central

2016-01-01

We report a combined experimental and modeling study of microwave-activated dilute CH4/N2/H2 plasmas, as used for chemical vapor deposition (CVD) of diamond, under very similar conditions to previous studies of CH4/H2, CH4/H2/Ar, and N2/H2 gas mixtures. Using cavity ring-down spectroscopy, absolute column densities of CH(X, v = 0), CN(X, v = 0), and NH(X, v = 0) radicals in the hot plasma have been determined as functions of height, z, source gas mixing ratio, total gas pressure, p, and input power, P. Optical emission spectroscopy has been used to investigate, with respect to the same variables, the relative number densities of electronically excited species, namely, H atoms, CH, C2, CN, and NH radicals and triplet N2 molecules. The measurements have been reproduced and rationalized from first-principles by 2-D (r, z) coupled kinetic and transport modeling, and comparison between experiment and simulation has afforded a detailed understanding of C/N/H plasma-chemical reactivity and variations with process conditions and with location within the reactor. The experimentally validated simulations have been extended to much lower N2 input fractions and higher microwave powers than were probed experimentally, providing predictions for the gas-phase chemistry adjacent to the diamond surface and its variation across a wide range of conditions employed in practical diamond-growing CVD processes. The strongly bound N2 molecule is very resistant to dissociation at the input MW powers and pressures prevailing in typical diamond CVD reactors, but its chemical reactivity is boosted through energy pooling in its lowest-lying (metastable) triplet state and subsequent reactions with H atoms. For a CH4 input mole fraction of 4%, with N2 present at 1–6000 ppm, at pressure p = 150 Torr, and with applied microwave power P = 1.5 kW, the near-substrate gas-phase N atom concentration, [N]ns, scales linearly with the N2 input mole fraction and exceeds the concentrations [NH]ns, [NH2]ns, and [CN]ns of other reactive nitrogen-containing species by up to an order of magnitude. The ratio [N]ns/[CH3]ns scales proportionally with (but is 102–103 times smaller than) the ratio of the N2 to CH4 input mole fractions for the given values of p and P, but [N]ns/[CN]ns decreases (and thus the potential importance of CN in contributing to N-doped diamond growth increases) as p and P increase. Possible insights regarding the well-documented effects of trace N2 additions on the growth rates and morphologies of diamond films formed by CVD using MW-activated CH4/H2 gas mixtures are briefly considered. PMID:27718565

The change in students' understanding of the mole concept in introductory college chemistry

NASA Astrophysics Data System (ADS)

Smith, Shane Harvie

This study investigated the difference between the students' understanding of the mole concept in chemistry at the beginning and at the end of the first semester of introductory chemistry courses. The study also identified the relationship between the criterion variable understanding of the mole concept in chemistry and the independent variables of cognitive level, type of introductory college chemistry class, and the number of lectures spent teaching the mole concept. In addition, this study examined (a) the students' misconceptions and (b) the aspects of the traditional teaching methods used in the introductory college chemistry courses that helped the students' understanding of the mole concept. This study was conducted using 180 volunteer students in their first semester of an introductory college chemistry course. These students were given a pretest instrument called the Mole Concepts Examination (MCE) to measure their understanding of the mole concept, the Group Assessment of Logical Thinking (GALT) to measure the students' cognitive level of logical thinking, and a posttest of the MCE to measure the students' understanding of the mole concept at the end of the semester. In addition, an interview was given to a selected group of 18 students to find out if the students remember the teaching techniques used to help them understand the mole concept and to determine some of the misconceptions that the students retained at the end of the semester. Results indicated a statistically significant relationship between students' understanding of the mole concept and their cognitive level. There was no significant relationship between students' understanding of the mole concept and the type of class, or the number of lectures spent teaching the mole concept. Qualitative results indicated that students were able to explain their answers to the posttest questions; students were able to identify some instructional techniques that helped them to understand the mole concept, and students of all cognitive levels retained misconceptions about the mole concept at the end of the semester.

Seasonal variations of temperature, acetylene and ethane in Saturn's atmosphere from 2005 to 2010, as observed by Cassini-CIRS

NASA Astrophysics Data System (ADS)

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

2013-07-01

Acetylene (C2H2) and ethane (C2H6) are by-products of complex photochemistry in the stratosphere of Saturn. Both hydrocarbons are important to the thermal balance of Saturn's stratosphere and serve as tracers of vertical motion in the lower stratosphere. Earlier studies of Saturn's hydrocarbons using Cassini-CIRS observations have provided only a snapshot of their behaviour. Following the vernal equinox in August 2009, Saturn's northern and southern hemispheres have entered spring and autumn, respectively, however the response of Saturn's hydrocarbons to this seasonal shift remains to be determined. In this paper, we investigate how the thermal structure and concentrations of acetylene and ethane have evolved with the changing season on Saturn. We retrieve the vertical temperature profiles and acetylene and ethane volume mixing ratios from Δν˜=15.5cm-1 Cassini-CIRS observations. In comparing 2005 (solar longitude, Ls ˜ 308°), 2009 (Ls ˜ 3°) and 2010 (Ls ˜ 15°) results, we observe the disappearance of Saturn's warm southern polar hood with cooling of up to 17.1 K ± 0.8 K at 1.1 mbar at high-southern latitudes. Comparison of the derived temperature trend in this region with a radiative climate model (Section 4 of Fletcher et al., 2010 and Greathouse et al. (2013, in preparation)) indicates that this cooling is radiative although dynamical changes in this region cannot be ruled out. We observe a 21 ± 12% enrichment of acetylene and a 29 ± 11% enrichment of ethane at 25°N from 2005 to 2009, suggesting downwelling at this latitude. At 15°S, both acetylene and ethane exhibit a decrease in concentration of 6 ± 11% and 17 ± 9% from 2005 to 2010, respectively, which suggests upwelling at this latitude (though a statistically significant change is only exhibited by ethane). These implied vertical motions at 15°S and 25°N are consistent with a recently-developed global circulation model of Saturn's tropopause and stratosphere(Friedson and Moses, 2012), which predicts this pattern of upwelling and downwelling as a result of a seasonally-reversing Hadley circulation. Ethane exhibits a general enrichment at mid-northern latitudes from 2005 to 2009. As the northern hemisphere approaches summer solstice in 2017, this feature might indicate an onset of a meridional enrichment of ethane, as has been observed in the southern hemisphere during/after southern summer solstice.

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 of methyl chloride (CH3Cl) in the 3.4 μm region (Bray et al., 2011) will be quantified. The ethane a priori volume mixing ratio (VMR) profile and associated covariance are based on synthetic data from the chemical transport model (CTM) of the University of Oslo. In this contribution, we will present updated ethane total and tropospheric column retrievals, using the SFIT-2 algorithm (v3.91) and high-resolution Fourier Transform Infrared (FTIR) solar absorption observations recorded with a Bruker 120HR instrument, at the high altitude research station of the Jungfraujoch (46.5° N, 8° E, 3580 m asl), within the framework of the Network for the Detection of Atmospheric Composition Change (NDACC, visit http://www.ndacc.org). We will characterize three microwindows encompassing the strongest ethane features after careful selection of a priori VMR profiles, spectroscopic parameters, accounting at best for all interfering species. We will then present the retrieval strategy representative of the best combination of those three characterized micro-windows in order to minimize the fitting residuals while maximizing the information content, the precision and the reliability of the retrieved product. The long-term C2H6 column time series will be produced using the Jungfraujoch observational database. Comparisons with synthetic data produced by two chemical transport model (CHASER and the one of the University of Oslo) will also be presented and analyzed, aiming at the determination and interpretation of long-term trends and interannual variations of ethane at Northern mid-latitudes. Acknowledgments The University of Liège involvement has primarily been supported by the PRODEX program funded by the Belgian Federal Science Policy Office, Brussels and by the Swiss GAW-CH program. E. Mahieu is Research Associate with the F.R.S. - FNRS. The FRS-FNRS and the Fédération Wallonie-Bruxelles are further acknowledged for observational activities support. We thank the International Foundation High Altitude Research Stations Jungfraujoch and Gornergrat (HFSJG, Bern) for supporting the facilities needed to perform the observations. We further acknowledge the vital contribution from all the Belgian colleagues in performing the Jungfraujoch observations used here. We further thank G.C. Toon (NASA-JPL, Pasadena) for the conversion of the ethane cross sections into pseudolines which can be used by our retrieval algorithm.

Comparative morphology of the penis and clitoris in four species of moles (Talpidae)

PubMed Central

Sinclair, Adriane Watkins; Glickman, Stephen; Catania, Kenneth; Shinohara, Akio; Baskin, Lawrence; Cunha, Gerald R.

2017-01-01

The penile and clitorial anatomy of four species of Talpid moles (broad-footed, star-nosed, hairy-tailed, and Japanese shrew moles) were investigated to define penile and clitoral anatomy and to examine the relationship of the clitoral anatomy with the presence or absence of ovotestes. The ovotestis contains ovarian tissue and glandular tissue resembling fetal testicular tissue and can produce androgens. The ovotestis is present in star-nosed and hairy-tailed moles, but not in broad-footed and Japanese shrew moles. Using histology, 3D reconstruction, and morphometric analysis, sexual dimorphism was examined in regard to a nine feature masculine trait score that included perineal appendage length (prepuce), anogenital distance, and presence/absence of bone. The presence/absence of ovotestes was discordant in all four mole species for sex differentiation features. For many sex differentiation features, discordance with ovotestes was observed in at least one mole species. The degree of concordance with ovotestes was highest for hairy-tailed moles and lowest for broad-footed moles. In relationship to phylogenetic clade, sex differentiation features also did not correlate with the similarity/divergence of the features and presence/absence of ovotestes. Hairy-tailed and Japanese shrew moles reside in separated clades, but they exhibit a high degree of congruence. Broad-footed and hairy-tailed moles reside within the same clade but had one of the lowest correlations in features and presence/absence of ovotestes. Thus, phylogenetic affinity and the presence/absence of ovotestes are poor predictors for most sex differentiation features within mole external genitalia. PMID:28251823

40 CFR 60.702 - Standards.

Code of Federal Regulations, 2010 CFR

2010-07-01

... first. Each owner or operator shall either: (a) Reduce emissions of TOC (less methane and ethane) by 98 weight-percent, or to a TOC (less methane and ethane) concentration of 20 ppmv, on a dry basis corrected...

40 CFR 60.662 - Standards.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., whichever date comes first. Each owner or operator shall either: (a) Reduce emissions of TOC (less methane and ethane) by 98 weight-percent, or to a TOC (less methane and ethane) concentration of 20 ppmv, on a...

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

NASA Technical Reports Server (NTRS)

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

1973-01-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yiming; Li, Baiyan; Wu, Zili

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-SO 3Ag. The interactions with ethylene from both OMS and -complexation in MIL-101-Cr-SO 3Ag have been investigated by in situ IR spectroscopic studies and computational calculations, which suggest -complexation contributes dominantly to the high ethylene/ethane adsorption selectivity.

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

DOE PAGES

Zhang, Yiming; Li, Baiyan; Wu, Zili; ...

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-SO 3Ag. The interactions with ethylene from both OMS and -complexation in MIL-101-Cr-SO 3Ag have been investigated by in situ IR spectroscopic studies and computational calculations, which suggest -complexation contributes dominantly to the high ethylene/ethane adsorption selectivity.

Disilane as a growth rate catalyst of plasma deposited microcrystalline silicon thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dimitrakellis, P.; Amanatides, E., E-mail: lef@plasmatech.gr; Mataras, D.

2016-07-15

The effect of small disilane addition on the gas phase properties of silane-hydrogen plasmas and the microcrystalline silicon thin films growth is presented. The investigation was conducted in the high pressure regime and for constant power dissipation in the discharge with the support of plasma diagnostics, thin film studies and calculations of discharge microscopic parameters and gas dissociation rates. The experimental data and the calculations show a strong effect of disilane on the electrical properties of the discharge in the pressure window from 2 to 3 Torr that is followed by significant raise of the electron number density and themore » drop of the sheaths electric field intensity. Deposition rate measurements show an important four to six times increase even for disilane mole fractions as low as 0.3 %. The deposition rate enhancement was followed by a drop of the material crystalline volume fraction but films with crystallinity above 40 % were deposited with different combinations of total gas pressure, disilane and silane molar ratios. The enhancement was partly explained by the increase of the electron impact dissociation rate of silane which rises by 40% even for 0.1% disilane mole fraction. The calculations of the gas usage, the dissociation and the deposition efficiencies show that the beneficial effect on the growth rate is not just the result of the increase of Si-containing molecules density but significant changes on the species participating to the deposition and the mechanism of the film growth are caused by the disilane addition. The enhanced participation of the highly sticking to the surface radical such as disilylene, which is the main product of disilane dissociation, was considered as the most probable reason for the significant raise of the deposition efficiency. The catalytic effect of such type of radical on the surface reactivity of species with lower sticking probability is further discussed, while it is also used to explain the restricted and sensitive process window where the disilane effect appears.« less

Disilane as a growth rate catalyst of plasma deposited microcrystalline silicon thin films

NASA Astrophysics Data System (ADS)

Dimitrakellis, P.; Kalampounias, A. G.; Spiliopoulos, N.; Amanatides, E.; Mataras, D.; Lahootun, V.; Coeuret, F.; Madec, A.

2016-07-01

The effect of small disilane addition on the gas phase properties of silane-hydrogen plasmas and the microcrystalline silicon thin films growth is presented. The investigation was conducted in the high pressure regime and for constant power dissipation in the discharge with the support of plasma diagnostics, thin film studies and calculations of discharge microscopic parameters and gas dissociation rates. The experimental data and the calculations show a strong effect of disilane on the electrical properties of the discharge in the pressure window from 2 to 3 Torr that is followed by significant raise of the electron number density and the drop of the sheaths electric field intensity. Deposition rate measurements show an important four to six times increase even for disilane mole fractions as low as 0.3 %. The deposition rate enhancement was followed by a drop of the material crystalline volume fraction but films with crystallinity above 40 % were deposited with different combinations of total gas pressure, disilane and silane molar ratios. The enhancement was partly explained by the increase of the electron impact dissociation rate of silane which rises by 40% even for 0.1% disilane mole fraction. The calculations of the gas usage, the dissociation and the deposition efficiencies show that the beneficial effect on the growth rate is not just the result of the increase of Si-containing molecules density but significant changes on the species participating to the deposition and the mechanism of the film growth are caused by the disilane addition. The enhanced participation of the highly sticking to the surface radical such as disilylene, which is the main product of disilane dissociation, was considered as the most probable reason for the significant raise of the deposition efficiency. The catalytic effect of such type of radical on the surface reactivity of species with lower sticking probability is further discussed, while it is also used to explain the restricted and sensitive process window where the disilane effect appears.

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 studied.

Experimental estimation of the bisulfite isomer quotient as a function of temperature: Implications for sulfur isotope fractionations in aqueous sulfite solutions

NASA Astrophysics Data System (ADS)

Eldridge, Daniel L.; Mysen, Bjorn O.; Cody, George D.

2018-01-01

Bisulfite (HSO3-) and sulfite (SO32-) compounds play key roles in numerous geochemical and biochemical processes extending from the atmosphere to the subseafloor biosphere. Despite decades of spectroscopic investigations, the molecular composition of HSO3- in solution remains uncertain and, thus, the role of bisulfite in (bio)chemical and isotope fractionation processes is unclear. We report new experimental estimates for the bisulfite isomer quotient (Qi = [(HO)SO2-]/[(HS)O3-]; [] = concentration) as a function of temperature from the interpretation of Raman spectra collected from aqueous NaHSO3 solutions contained in fused silica capsules. In pure NaHSO3 solutions (1Na+:1HSO3-, stoichiometric) over [NaHSO3] = 0.2-0.4 m (moles/kg H2O), the following relationship is obtained:

Compliant sealants for solid oxide fuel cells and other ceramics

DOEpatents

Bloom, I.D.; Ley, K.L.

1995-09-26

A glass or glass-ceramic sealant is described for a SOFC having a coefficient of thermal expansion in the range of from about 8 to about 13{times}10{sup {minus}6}/C and a viscosity of at least 10{sup 3}Pa-s at cell operating temperature. The sealant has a composition of SrO present in the range of from about 5 to about 60 mole percent, La{sub 2}O{sub 3} present in the range of from 0 to about 45 mole percent, Al{sub 2}O{sub 3} present in the range from 0 to about 15 mole percent, B{sub 2}O{sub 3} present in the range of from about 15 mole percent to about 80 mole percent, and SiO{sub 2} present in the range of from 0 to about 40 mole percent, wherein the material is a viscous fluid at cell operating temperatures of from about 600 C to about 1000 C. The sealant may also be compounds of CaO present in the range of from 0 to about 35 mole percent, Al{sub 2}O{sub 3} present in the range from 0 to about 15 mole percent, B{sub 2}O{sub 3} present in the range of from about 35 mole percent to about 85 mole percent, and SiO{sub 2} present in the range of from 0 to about 30 mole percent. 2 figs.

Compliant sealants for solid oxide fuel cells and other ceramics

DOEpatents

Bloom, Ira D.; Ley, Kevin L.

1995-01-01

A glass or glass-ceramic sealant for a SOFC having a coefficient of thermal expansion in the range of from about 8 to about 13.times.10.sup.-6 /.degree.C. and a viscosity of at least 10.sup.3 Pa-s at cell operating temperature. The sealant has a composition of SrO present in the range of from about 5 to about 60 mole percent, La.sub.2 O.sub.3 present in the range of from 0 to about 45 mole percent, Al.sub.2 O.sub.3 present in the range from 0 to about 15 mole percent, B.sub.2 O.sub.3 present in the range of from about 15 mole percent to about 80 mole percent, and SiO.sub.2 present in the range of from 0 to about 40 mole percent, wherein the material is a viscous fluid at cell operating temperatures of from about 600.degree. C. to about 1000.degree. C. The sealant may also be compounds of CaO present in the range of from 0 to about 35 mole percent, Al.sub.2 O.sub.3 present in the range from 0 to about 15 mole percent, B.sub.2 O.sub.3 present in the range of from about 35 mole percent to about 85 mole percent, and SiO.sub.2 present in the range of from 0 to about 30 mole percent.

Structural optimization of interpenetrated pillared-layer coordination polymers for ethylene/ethane separation.

PubMed

Kishida, Keisuke; Horike, Satoshi; Watanabe, Yoshihiro; Tahara, Mina; Inubushi, Yasutaka; Kitagawa, Susumu

2014-06-01

With the goal of achieving effective ethylene/ethane separation, we evaluated the gas sorption properties of four pillared-layer-type porous coordination polymers with double interpenetration, [Zn2(tp)2(bpy)]n (1), [Zn2(fm)2(bpe)]n (2), [Zn2(fm)2(bpa)]n (3), and [Zn2(fm)2(bpy)]n (4) (tp = terephthalate, bpy = 4,4'-bipyridyl, fm = fumarate, bpe = 1,2-di(4-pyridyl)ethylene and bpa = 1,2-di(4-pyridyl)ethane). It was found that 4, which contains the narrowest pores of all of these compounds, exhibited ethylene-selective sorption profiles. The ethylene selectivity of 4 was estimated to be 4.6 at 298 K based on breakthrough experiments using ethylene/ethane gas mixtures. In addition, 4 exhibited a good regeneration ability compared with a conventional porous material. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Production of methanol from heat-stressed pepper and corn leaf disks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, J.A.

Early Calwonder'' pepper (Capsicum annuum L.) and Jubilee'' corn (Zea mays L.) leaf disks exposed to high temperature stress produced ethylene, ethane, methanol, acetaldehyde, and ethanol based on comparison of retention times during gas chromatography to authentic standards. Methanol, ethanol, and acetaldehyde were also identified by mass spectroscopy. Corn leaf disks produced lower levels of ethylene, ethane, and methanol, but more acetaldehyde and ethanol than pepper. Production of ethane, a by-product of lipid peroxidation, coincided with an increase in electrolyte leakage (EL) in pepper but not in corn. Compared with controls, pepper leaf disks infiltrated with linolenic acid evolved significantlymore » greater amounts of ethane, acetaldehyde, and methanol and similar levels of ethanol. EL and volatile hydrocarbon production were not affected by fatty acid infiltration in corn. Infiltration of pepper leaves with buffers increasing in pH from 5.5 to 9.5 increased methanol production.« less

Dechlorination of 1,1,1-Trichloro-2,2-bis(p-chlorophenyl)ethane by Aerobacter aerogenes

USGS Publications Warehouse

Wedemeyer, Gary

1967-01-01

Whole cells or cell-free extracts of Aerobacter aerogenes catalyze the degradation of 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) in vitro to at least seven metabolites: 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (DDE); 1,1-dichloro-2,2-bis(p-chlorophenyl)ethane (DDD); 1-chloro-2,2-bis(p-chlorophenyl)ethylene (DDMU); 1-chloro-2,2-bis(p-chlorophenyl)ethane (DDMS); unsym-bis(p-chlorophenyl)ethylene (DDNU); 2,2-bis(p-chlorophenyl)acetate (DDA); and 4,4′-dichlorobenzophenone (DBP). The use of metabolic inhibitors together with pH and temperature studies indicated that discrete enzymes are involved. By use of the technique of sequential analysis, the metabolic pathway was shown to be: DDT → DDD →DDMU →DDMS → DDNU → DDA → DBP, or DDT → DDE. Dechlorination was marginally enhanced by light-activated flavin mononucleotide.

Microbial mineralization of ethene under sulfate-reducing conditions

USGS Publications Warehouse

Bradley, P.M.; Chapelle, F.H.

2002-01-01

A limited investigation of the potential for anaerobic ethylene biodegradation under SO4-reducing conditions was performed. Microorganisms indigenous to a lake-bed sediment completely mineralized [1,2-14C] ethylene to 14CO2 when incubated under SO4-reducing conditions. Reliance on ethylene and/or ethane accumulation as a quantitative indicator of complete reductive dechlorination of chloroethylene contaminants may not be warranted. SO4 addition stimulated SO4 reduction as indicated by decreasing SO4 concentrations (> 40% decrease) and production of dissolved sulfide (880 ??M). SO4 amendment completely suppressed the production of ethane and methane. The concomitant absence of ethane and methane production under SO4-amended conditions was consistent with previous conclusions that reduction of ethylene to ethane occurred under methanogenic conditions. A lack of ethylene accumulation under SO4-reducing conditions may reflect insignificant reductive dechlorination of vinyl chloride or efficient anaerobic mineralization of ethylene to CO2.

Experimental study and detailed modeling of toluene degradation in a low-pressure stoichiometric premixed CH4/O2/N2 flame.

PubMed

Bakali, A El; Dupont, L; Lefort, B; Lamoureux, N; Pauwels, J F; Montero, M

2007-05-17

Temperature and mole fraction profiles have been measured in laminar stoichiometric premixed CH4/O2/N2 and CH4/1.5%C6H5CH3/O2/N2 flames at low pressure (0.0519 bar) by using thermocouple, molecular beam/mass spectrometry (MB/MS), and gas chromatography/mass spectrometry (GC/MS) techniques. The present study completes our previous work performed on the thermal degradation of benzene in CH4/O2/N2 operating at similar conditions. Mole fraction profiles of reactants, final products, and reactive and stable intermediate species have been analyzed. The main intermediate aromatic species analyzed in the methane-toluene flame were benzene, phenol, ethylbenzene, benzylalcohol, styrene, and benzaldehyde. These new experimental results have been modeled with our previous model including submechanisms for aromatics (benzene up to p-xylene) and aliphatic (C1 up to C7) oxidation. Good agreement has been observed for the main species analyzed. The main reaction paths governing the degradation of toluene in the methane flame were identified, and it occurs mainly via the formation of benzene (C6H5CH3 + H = C6H6 + CH3) and benzyl radical (C6H5CH3 + H = C6H5CH2 + H2). Due to the abundance of methyl radicals, it was observed that recombination of benzyl and methyl is responsible for main monosubstitute aromatic species analyzed in the methane-toluene flame. The oxidation of these substitute species led to cyclopentadienyl radical as observed in a methane-benzene flame.

The Mauna Loa Carbon Dioxide Record.

NASA Astrophysics Data System (ADS)

Tans, P. P.

2005-12-01

Continuous measurements of atmospheric carbon dioxide were started in 1958 by Dave Keeling as part of the International Geophysical Year. Precision and accuracy were both high from the very beginning, facilitating after only a few years the unambiguous discovery of the seasonal cycle of CO2, as well as the year-to-year rise in concentration. Essential to the definitive nature of the Mauna Loa CO2 and similar records are the careful and continuing attention to calibration procedures, the creation of a calibration scale for CO2-in- air based on the determination of its mole fraction through primary methods, and the deployment of some "redundant" independent methods duplicating the CO2 measurements at several sites. The example of Mauna Loa demonstrated the principles that were incorporated into the design of later measurement networks that are now coordinated in the Global Atmosphere Watch Programme of the World Meteorological Organization. The high quality of the CO2 measurements allowed the later discoveries of the trends in the seasonal cycle, the trend in the gradient from north to south, and the relationship of the growth rate of CO2 to climate variations. The high quality is also the basis for all inverse modeling, which uses numerical models of atmospheric transport to translate quite small differences in space and time of the mole fraction of CO2 to deduce patterns of sources and sinks that are consistent with the observations. Some examples will be shown of the information that would be irretrievably lost if the high standards of these measurements are not maintained.

Fluorocarbons as oxygen carriers. II. An NMR study of partially or totally fluorinated alkanes and alkenes

NASA Astrophysics Data System (ADS)

Ali Hamza, M'Hamed; Serratrice, Guy; Stébé, Marie-José; Delpuech, Jean-Jacques

Highly fluorinated compounds of the general type R FR H or R FR H'R F, with R F: n-C nF 2 n+1 n = 6, 7, or 8; R H: C 2H 5, CHCH 2, n-C 8H 17; R H': CHCH, CH 2CH 2, are studied either as pure degassed liquids or as solvents of oxygen, using 13C relaxation times T 1 measurements in each case. Comparison of the relaxation data for the degassed liquids with those relative to the analogous n-alkanes provides evidence for slower internal segmental motions in the perfluoroalkyl chains. This rate decrease is shown to arise mainly from purely inertial effects and not from increased rotational potential barriers, thus suggesting similar flexibilities of both hydrocarbon and perfluorocarbon chains. Solubilities of oxygen (in mole fractions) are higher in fluoroalkanes than in previously studied hexafluorobenzene (J-J. Delpuech, M. A. Hamza, G. Serratrice, and M. J. Stebe, J. Chem. Phys.70, 2680 (1979)). Relaxation data are expressed by the variation rates qx of relaxation rates T1-1 per mole fraction of dissolved oxygen. Values of qx. roughly decrease with the total length of the aliphatic chains, and from the ends of the center of each chain, except for C 6F 13CHCHC 6F 13. These results are not consistent with specific attractive oxygen-fluorine forces, the major factor for solubility being the liquid structure of the solvent, mainly determined by the shape of molecules, according to Chandler's viewpoint.

Seasonality and interannual variability of CH4 fluxes from the eastern Amazon Basin inferred from atmospheric mole fraction profiles.

PubMed

Basso, Luana S; Gatti, Luciana V; Gloor, Manuel; Miller, John B; Domingues, Lucas G; Correia, Caio S C; Borges, Viviane F

2016-01-16

The Amazon Basin is an important region for global CH 4 emissions. It hosts the largest area of humid tropical forests, and around 20% of this area is seasonally flooded. In a warming climate it is possible that CH 4 emissions from the Amazon will increase both as a result of increased temperatures and precipitation. To examine if there are indications of first signs of such changes we present here a 13 year (2000-2013) record of regularly measured vertical CH 4 mole fraction profiles above the eastern Brazilian Amazon, sensitive to fluxes from the region upwind of Santarém (SAN), between SAN and the Atlantic coast. Using a simple mass balance approach, we find substantial CH 4 emissions with an annual average flux of 52.8 ± 6.8 mg CH 4 m -2  d -1 over an area of approximately 1 × 10 6  km 2 . Fluxes are highest in two periods of the year: in the beginning of the wet season and during the dry season. Using a CO:CH 4 emission factor estimated from the profile data, we estimated a contribution of biomass burning of around 15% to the total flux in the dry season, indicating that biogenic emissions dominate the CH 4 flux. This 13 year record shows that CH 4 emissions upwind of SAN varied over the years, with highest emissions in 2008 (around 25% higher than in 2007), mainly during the wet season, representing 19% of the observed global increase in this year.

Highly elevated atmospheric levels of volatile organic compounds in the Uintah Basin, Utah.

PubMed

Helmig, D; Thompson, C R; Evans, J; Boylan, P; Hueber, J; Park, J-H

2014-05-06

Oil and natural gas production in the Western United States has grown rapidly in recent years, and with this industrial expansion, growing environmental concerns have arisen regarding impacts on water supplies and air quality. Recent studies have revealed highly enhanced atmospheric levels of volatile organic compounds (VOCs) from primary emissions in regions of heavy oil and gas development and associated rapid photochemical production of ozone during winter. Here, we present surface and vertical profile observations of VOC from the Uintah Basin Winter Ozone Studies conducted in January-February of 2012 and 2013. These measurements identify highly elevated levels of atmospheric alkane hydrocarbons with enhanced rates of C2-C5 nonmethane hydrocarbon (NMHC) mean mole fractions during temperature inversion events in 2013 at 200-300 times above the regional and seasonal background. Elevated atmospheric NMHC mole fractions coincided with build-up of ambient 1-h ozone to levels exceeding 150 ppbv (parts per billion by volume). The total annual mass flux of C2-C7 VOC was estimated at 194 ± 56 × 10(6) kg yr(-1), equivalent to the annual VOC emissions of a fleet of ∼100 million automobiles. Total annual fugitive emission of the aromatic compounds benzene and toluene, considered air toxics, were estimated at 1.6 ± 0.4 × 10(6) and 2.0 ± 0.5 × 10(6) kg yr(-1), respectively. These observations reveal a strong causal link between oil and gas emissions, accumulation of air toxics, and significant production of ozone in the atmospheric surface layer.

Comparison of nitrous oxide (N2O) analyzers for high-precision measurements of atmospheric mole fractions

NASA Astrophysics Data System (ADS)

Lebegue, B.; Schmidt, M.; Ramonet, M.; Wastine, B.; Yver Kwok, C.; Laurent, O.; Belviso, S.; Guemri, A.; Philippon, C.; Smith, J.; Conil, S.; Jost, H. J.; Crosson, E. R.

2015-10-01

Over the last few decades, in-situ measurements of atmospheric N2O mole fractions have been performed using gas chromatographs (GCs) equipped with electron capture detectors (ECDs). When trying to meet the World Meteorological Organization's (WMO) quality goal, this technique becomes very challenging as the detectors are highly non-linear and the GCs at remote stations require a considerable amount of maintenance by qualified technicians to maintain good short-term and long-term repeatability. With more robust optical spectrometers being now available for N2O measurements, we aim to identify a robust and stable analyzer that can be integrated into atmospheric monitoring networks, such as the Integrated Carbon Observation System (ICOS). In this study, we tested seven analyzers that were developed and commercialized from five different companies and compared the results with established techniques. Each instrument was characterized during a time period of approximately eight weeks. The test protocols included the characterization of the short-term and long-term repeatability, drift, temperature dependence, linearity and sensitivity to water vapor. During the test period, ambient air measurements were compared under field conditions at the Gif-sur-Yvette station. All of the analyzers showed a standard deviation better than 0.1 ppb for the 10 min averages. Some analyzers would benefit from improvements in temperature stability to reduce the instrument drift, which could then help in reducing the frequency of calibrations. For most instruments, the water vapor correction algorithms applied by companies are not sufficient for high-precision atmospheric measurements, which results in the need to dry the ambient air prior to analysis.

Optimization of a Coupling Process for Insulin Degludec According to a Quality by Design (QbD) Paradigm.

PubMed

Nie, Lei; Hu, Mingming; Yan, Xu; Guo, Tingting; Wang, Haibin; Zhang, Sheng; Qu, Haibin

2018-05-03

This case study described a successful application of the quality by design (QbD) principles to a coupling process development of insulin degludec. Failure mode effects analysis (FMEA) risk analysis was first used to recognize critical process parameters (CPPs). Five CPPs, including coupling temperature (Temp), pH of desB30 solution (pH), reaction time (Time), desB30 concentration (Conc), and molar equivalent of ester per mole of desB30 insulin (MolE), were then investigated using a fractional factorial design. The curvature effect was found significant, indicating the requirement of second-order models. Afterwards, a central composite design was built with an augmented star and center points study. Regression models were developed for the CPPs to predict the purity and yield of predegludec using above experimental data. The R 2 and adjusted R 2 were higher than 96 and 93% for the two models respectively. The Q 2 values were more than 80% indicating a good predictive ability of models. MolE was found to be the most significant factor affecting both yield and purity of predegludec. Temp, pH, and Conc were also significant for predegludec purity, while Time appeared to remarkably influence the yield model. The multi-dimensional design space and normal operating region (NOR) with a robust setpoint were determined using a probability-based Monte-Carlo simulation method. The verified experimental results showed that the design space was reliable and effective. This study enriches the understanding of acetylation process and is instructional to other complicated operations in biopharmaceutical engineering.

Development of a field-deployable method for simultaneous, real-time measurements of the four most abundant N2O isotopocules.

PubMed

Ibraim, Erkan; Harris, Eliza; Eyer, Simon; Tuzson, Béla; Emmenegger, Lukas; Six, Johan; Mohn, Joachim

2018-03-01

Understanding and quantifying the biogeochemical cycle of N 2 O is essential to develop effective N 2 O emission mitigation strategies. This study presents a novel, fully automated measurement technique that allows simultaneous, high-precision quantification of the four main N 2 O isotopocules ( 14 N 14 N 16 O, 14 N 15 N 16 O, 15 N 14 N 16 O and 14 N 14 N 18 O) in ambient air. The instrumentation consists of a trace gas extractor (TREX) coupled to a quantum cascade laser absorption spectrometer, designed for autonomous operation at remote measurement sites. The main advantages this system has over its predecessors are a compact spectrometer design with improved temperature control and a more compact and powerful TREX device. The adopted TREX device enhances the flexibility of the preconcentration technique for higher adsorption volumes to target rare isotope species and lower adsorption temperatures for highly volatile substances. All system components have been integrated into a standardized instrument rack to improve portability and accessibility for maintenance. With an average sampling frequency of approximately 1 h -1 , this instrumentation achieves a repeatability of 0.09, 0.13, 0.17 and 0.12 ‰ for δ 15 N α , δ 15 N β , δ 18 O and site preference of N 2 O, respectively, for pressurized ambient air. The repeatability for N 2 O mole fraction measurements is better than 1 ppb (parts per billion, 10 -9 moles per mole of dry air).

Storage and recovery of methane-ethane mixtures in single shale pores

NASA Astrophysics Data System (ADS)

Wu, Haiyi; Qiao, Rui

2017-11-01

Natural gas production from shale formations has received extensive attention recently. While great progress has been made in understanding the adsorption and transport of single-component gas inside shales' nanopores, the adsorption and transport of multicomponent shale gas under reservoir conditions (CH4 and C2H6 mixture) has only begun to be studied. In this work, we use molecular simulations to compute the storage of CH4 and C2H6 mixtures in single nanopores and their subsequent recovery. We show that surface adsorption contributes greatly to the storage of CH4 and C2H6 inside the pores and C2H6 is enriched over CH4. The enrichment of C2H6 is enhanced as the pore is narrowed, but is weakened as the pressure increases. We show that the recovery of gas mixtures from the nanopores approximately follows the diffusive scaling law. The ratio of the production rates of C2H6 and CH4 is close to their initial mole ratio inside the pore despite that the mobility of pure C2H6 is much smaller than that of pure CH4 inside the pores. By using scale analysis, we show that the strong coupling between the transport of CH4 and C2H6 is responsible for the effective recovery of C2H6 from the nanopores.

Adult neurogenesis and its anatomical context in the hippocampus of three mole-rat species

PubMed Central

Amrein, Irmgard; Becker, Anton S.; Engler, Stefanie; Huang, Shih-hui; Müller, Julian; Slomianka, Lutz; Oosthuizen, Maria K.

2014-01-01

African mole-rats (family Bathyergidae) are small to medium sized, long-lived, and strictly subterranean rodents that became valuable animal models as a result of their longevity and diversity in social organization. The formation and integration of new hippocampal neurons in adult mammals (adult hippocampal neurogenesis, AHN) correlates negatively with age and positively with habitat complexity. Here we present quantitative data on AHN in wild-derived mole-rats of 1 year and older, and briefly describe its anatomical context including markers of neuronal function (calbindin and parvalbumin). Solitary Cape mole-rats (Georychus capensis), social highveld mole-rats (Cryptomys hottentotus pretoriae), and eusocial naked mole-rats (Heterocephalus glaber) were assessed. Compared to other rodents, the hippocampal formation in mole-rats is small, but shows a distinct cytoarchitecture in the dentate gyrus and CA1. Distributions of the calcium-binding proteins differ from those seen in rodents; e.g., calbindin in CA3 of naked mole-rats distributes similar to the pattern seen in early primate development, and calbindin staining extends into the stratum lacunosum-moleculare of Cape mole-rats. Proliferating cells and young neurons are found in low numbers in the hippocampus of all three mole-rat species. Resident granule cell numbers are low as well. Proliferating cells expressed as a percentage of resident granule cells are in the range of other rodents, while the percentage of young neurons is lower than that observed in surface dwelling rodents. Between mole-rat species, we observed no difference in the percentage of proliferating cells. The percentages of young neurons are high in social highveld and naked mole-rats, and low in solitary Cape mole-rats. The findings support that proliferation is regulated independently of average life expectancy and habitat. Instead, neuronal differentiation reflects species-specific demands, which appear lower in subterranean rodents. PMID:24904308

Effects of potential models on the adsorption of ethane and ethylene on graphitized thermal carbon black. Study of two-dimensional critical temperature and isosteric heat versus loading.

PubMed

Do, D D; Do, H D

2004-12-07

Adsorption of ethylene and ethane on graphitized thermal carbon black and in slit pores whose walls are composed of graphene layers is studied in detail to investigate the packing efficiency, the two-dimensional critical temperature, and the variation of the isosteric heat of adsorption with loading and temperature. Here we used a Monte Carlo simulation method with a grand canonical Monte Carlo ensemble. A number of two-center Lennard-Jones (LJ) potential models are investigated to study the impact of the choice of potential models in the description of adsorption behavior. We chose two 2C-LJ potential models in our investigation of the (i) UA-TraPPE-LJ model of Martin and Siepmann for ethane and Wick et al. for ethylene and (ii) AUA4-LJ model of Ungerer et al. for ethane and Bourasseau et al. for ethylene. These models are used to study the adsorption of ethane and ethylene on graphitized thermal carbon black. It is found that the solid-fluid binary interaction parameter is a function of adsorbate and temperature, and the adsorption isotherms and heat of adsorption are well described by both the UA-TraPPE and AUA models, although the UA-TraPPE model performs slightly better. However, the local distributions predicted by these two models are slightly different. These two models are used to explore the two-dimensional condensation for the graphitized thermal carbon black, and these values are 110 K for ethylene and 120 K for ethane.

Effect of maximal dynamic exercise on exhaled ethane and carbon monoxide levels in human, equine, and canine athletes.

PubMed

Wyse, Cathy; Cathcart, Andy; Sutherland, Rona; Ward, Susan; McMillan, Lesley; Gibson, Graham; Padgett, Miles; Skeldon, Kenneth

2005-06-01

Exercise-induced oxidative stress (EIOS) refers to a condition where the balance of free radical production and antioxidant systems is disturbed during exercise in favour of pro-oxidant free radicals. Breath ethane is a product of free radical-mediated oxidation of cell membrane lipids and is considered to be a reliable marker of oxidative stress. The heatshock protein, haem oxygenase, is induced by oxidative stress and degrades haemoglobin to bilirubin, with concurrent production of carbon monoxide (CO). The aim of this study was to investigate the effect of maximal exercise on exhaled ethane and CO in human, canine, and equine athletes. Human athletes (n = 8) performed a maximal exercise test on a treadmill, and canine (n = 12) and equine (n = 11) athletes exercised at gallop on a sand racetrack. Breath samples were taken at regular intervals during exercise in the human athletes, and immediately before and after exercise in the canine and equine athletes. Breath samples were stored in gas-impermeable bags for analysis of ethane by laser spectroscopy, and CO was measured directly using an electrochemical CO monitor. Maximal exercise was associated with significant increases in exhaled ethane in the human, equine, and canine athletes. Decreased concentrations of exhaled CO were detected after maximal exercise in the human athletes, but CO was rarely detectable in the canine and equine athletes. The ethane breath test allows non-invasive and real-time detection of oxidative stress, and this method will facilitate further investigation of the processes mediating EIOS in human and animal athletes.

Pigmentary characteristics and moles in relation to melanoma risk.

PubMed

Titus-Ernstoff, Linda; Perry, Ann E; Spencer, Steven K; Gibson, Jennifer J; Cole, Bernard F; Ernstoff, Marc S

2005-08-10

Although benign and atypical moles are considered key melanoma risk factors, previous studies of their influence were small and/or institution-based. We conducted a population-based case-control study in the state of New Hampshire. Individuals of ages 20-69 with an incident diagnosis of first primary cutaneous melanoma were ascertained through the New Hampshire State Cancer Registry. Controls were identified through New Hampshire driver's license lists and frequency-matched by age and gender to cases. We interviewed 423 eligible cases and 678 eligible controls. Host characteristics, including mole counts, were evaluated using logistic regression analyses. Our results showed that pigmentary factors, including eye color (OR = 1.57 for blue eyes compared to brown), hair color (OR = 1.85 for blonde/red hair color compared to brown/black), freckles before age 15 (OR = 2.39 for freckles present compared to absent) and sun sensitivity (OR = 2.25 for peeling sunburn followed by no tan or a light tan and 2.42 for sunburn followed by tan compared to tanning immediately), were related to melanoma risk; these associations held after adjustment for sun-related factors and for moles. In analyses confined to skin examination participants, the covariate-adjusted effects of benign and atypical moles were moderately strong. Compared to 0-4 benign moles, risk increased steadily for 5-14 moles (OR = 1.71), 15-24 moles (OR = 3.55) and >or= 25 moles (OR = 4.33). Risk also increased with the number of atypical moles; compared to none, the ORs for having 1, 2-3, or >or= 4 atypical moles were 2.08, 1.84 and 3.80, respectively. Although risk was highest for those with multiple benign and atypical moles, the interaction was not of statistical significance. Our findings, arising from the first population- and incidence-based study to evaluate atypical moles in relation to melanoma risk, confirm the importance of host susceptibility, represented by pigmentary factors and the tendency to develop benign or atypical moles, in the etiology of this disease. (c) 2005 Wiley-Liss, Inc.

Analysis of Ethane and Diethylbenzene Bridged Sorbents

DTIC Science & Technology

2017-12-13

Leska; P.T. Charles; B.J. Melde; J.R. Taft, "Electrochemical Detection with Preconcentration: Nitroenergetic Contaminants ," Chemosensors 2, 131...monitoring of contaminants in groundwater: Sorbent development; Naval Research Laboratory: 2013. Analysis of Ethane and Diethylbenzene Bridged Sorbents 7...

Size and Site Dependence of the Catalytic Activity of Iridium Clusters toward Ethane Dehydrogenation.

PubMed

Ge, Yingbin; Jiang, Hao; Kato, Russell; Gummagatta, Prasuna

2016-12-01

This research focuses on optimizing transition metal nanocatalyst immobilization and activity to enhance ethane dehydrogenation. Ethane dehydrogenation, catalyzed by thermally stable Ir n (n = 8, 12, 18) atomic clusters that exhibit a cuboid structure, was studied using the B3LYP method with triple-ζ basis sets. Relativistic effects and dispersion corrections were included in the calculations. In the dehydrogenation reaction Ir n + C 2 H 6 → H-Ir n -C 2 H 5 → (H) 2 -Ir n -C 2 H 4 , the first H-elimination is the rate-limiting step, primarily because the reaction releases sufficient heat to facilitate the second H-elimination. The catalytic activity of the Ir clusters strongly depends on the Ir cluster size and the specific catalytic site. Cubic Ir 8 is the least reactive toward H-elimination in ethane: Ir 8 + C 2 H 6 → H-Ir 8 -C 2 H 5 has a large (65 kJ/mol) energy barrier, whereas Ir 12 (3 × 2 × 2 cuboid) and Ir 18 (3 × 3 × 2 cuboid) lower this energy barrier to 22 and 3 kJ/mol, respectively. The site dependence is as prominent as the size effect. For example, the energy barrier for the Ir 18 + C 2 H 6 → H-Ir 18 -C 2 H 5 reaction is 3, 48, and 71 kJ/mol at the corner, edge, or face-center sites of the Ir 18 cuboid, respectively. Energy release due to Ir cluster insertion into an ethane C-H bond facilitates hydrogen migration on the Ir cluster surface, and the second H-elimination of ethane. In an oxygen-rich environment, oxygen molecules may be absorbed on the Ir cluster surface. The oxygen atoms bonded to the Ir cluster surface may slightly increase the energy barrier for H-elimination in ethane. However, the adsorption of oxygen and its reaction with H atoms on the Ir cluster releases sufficient heat to yield an overall thermodynamically favored reaction: Ir n + C 2 H 6 + 1 / 2 O 2 → Ir n + C 2 H 4 + H 2 O. These results will be useful toward reducing the energy cost of ethane dehydrogenation in industry.

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 mass anomalies are compensated at shallow depth by denser ethane-rich clathrates. This work has been performed at the Jet Propulsion Laboratory, California Institute of Technology, under contract to NASA. [1] Choukroun M. and Sotin C. (2012) GRL, 39, L04201. [2] Gao and Stevenson (2013) Icarus, 226, 1185-1191.

The Mole Mapper Study, mobile phone skin imaging and melanoma risk data collected using ResearchKit.

PubMed

Webster, Dan E; Suver, Christine; Doerr, Megan; Mounts, Erin; Domenico, Lisa; Petrie, Tracy; Leachman, Sancy A; Trister, Andrew D; Bot, Brian M

2017-02-14

Sensor-embedded phones are an emerging facilitator for participant-driven research studies. Skin cancer research is particularly amenable to this approach, as phone cameras enable self-examination and documentation of mole abnormalities that may signal a progression towards melanoma. Aggregation and open sharing of this participant-collected data can be foundational for research and the development of early cancer detection tools. Here we describe data from Mole Mapper, an iPhone-based observational study built using the Apple ResearchKit framework. The Mole Mapper app was designed to collect participant-provided images and measurements of moles, together with demographic and behavioral information relating to melanoma risk. The study cohort includes 2,069 participants who contributed 1,920 demographic surveys, 3,274 mole measurements, and 2,422 curated mole images. Survey data recapitulates associations between melanoma and known demographic risks, with red hair as the most significant factor in this cohort. Participant-provided mole measurements indicate an average mole size of 3.95 mm. These data have been made available to engage researchers in a collaborative, multidisciplinary effort to better understand and prevent melanoma.