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At least 379 records · Page 21

Comparison of the properties of some synthetic crudes with petroleum crudes

Physical properties and chemical compositions of six synthetic crudes were determined. The results were compared to those of typical petroleum crudes, with the interest being the feasibility of making jet fuels from oil shale and coal syncrudes. The specific gravity, viscosity, and pour point were measured, showing that these crudes would be described as heavier rather than lighter crudes. The boiling range distribution of the crudes was determined by distillation and by gas chromatography. In addition, gel permeation chromatograms were obtained, giving a unique molecular weight distribution profile for each crude. Analyses for carbon, hydrogen, nitrogen and sulfur concentrations were performed, as well as for hydrocarbon group type and trace element concentrations. It was found that the range in concentration of vanadium, an element whose presence in turbine fuels is of major concern, was lower than that of petroleum crudes. Sodium and potassium, other elements of concern, were present in comparatively high concentrations.

Antoine, A. C.↗

Measurement techniques for trace metals in coal-plant effluents: A brief review

The strong features and limitations of techniques for determining trace elements in aerosols emitted from coal plants are discussed. Techniques reviewed include atomic absorption spectroscopy, charged particle scattering and activation, instrumental neutron activation analysis, gas/liquid chromatography, gas chromatographic/mass spectrometric methods, X-ray fluorescence, and charged-particle-induced X-ray emission. The latter two methods are emphasized. They provide simultaneous, sensitive multielement analyses and lend themselves readily to depth profiling. It is recommended that whenever feasible, two or more complementary techniques should be used for analyzing environmental samples.

Singh, J. J.↗

Abiotic synthesis of fatty acids

The formation of fatty acids by Fischer-Tropsch-type synthesis was investigated with ferric oxide, ammonium carbonate, potassium carbonate, powdered Pueblito de Allende carbonaceous chondrite, and filings from the Canyon Diablo meteorite used as catalysts. Products were separated and identified by gas chromatography and mass spectrometry. Iron oxide, Pueblito de Allende chondrite, and Canyon Diablo filings in an oxidized catalyst form yielded no fatty acids. Canyon Diablo filings heated overnight at 500 C while undergoing slow purging by deuterium produced fatty acids only when potassium carbonate was admixed; potassium carbonate alone also produced these compounds. The active catalytic combinations gave relatively high yields of aliphatic and aromatic hydrocarbons; substantial amounts of n-alkenes were almost invariably observed when fatty acids were produced; the latter were in the range C6 to C18, with maximum yield in C9 or 10.

Leach, W. W.↗

The solubility of carbon monoxide in silicate melts at high pressures and its effect on silicate phase relations

Autoradiographic analysis and gas chromatography were used to measure the solubility in silicate melts of CO-CO2 vapors (30 to 40% CO by thermodynamic calculation) in equilibrium with graphite at temperatures up to 1700 deg C and pressures to 30 kbar. At near-liquidus temperatures CO-CO2 vapors were found to be slightly more soluble than CO2 alone. As a result of the apparently negative temperature dependence of CO solubility, the solubility of CO-CO2 at superliquidus temperatures is less than that of CO2. Melting points of two silicates were depressed more by CO than by CO2. Phase boundary orientations suggest that CO/CO + CO2 is greater in the liquid than in the vapor. The effect of the presence of CO on periodotite phase relations was investigated, and it was found that melts containing both CO and CO2 are nearly as polymerized as those containing only CO2. These results suggest that crystallization processes in planetary interiors can be expected to be about the same, whether the melts contain CO2 alone or CO2 and CO.

Eggler, D. H.↗

Analyses of moisture in polymers and composites

A suitable method for the direct measurement of moisture concentrations after humidity/thermal exposure on state of the art epoxy and polyimide resins and their graphite and glass fiber reinforcements was investigated. Methods for the determination of moisture concentration profiles, moisture diffusion modeling and moisture induced chemical changes were examined. Carefully fabricated, precharacterized epoxy and polyimide neat resins and their AS graphite and S glass reinforced composites were exposed to humid conditions using heavy water (D20), at ambient and elevated temperatures. These specimens were fixtured to theoretically limit the D20 permeation to a unidirectional penetration axis. The analytical techniques evaluated were: (1) laser pyrolysis gas chromatography mass spectrometry; (2) solids probe mass spectrometry; (3) laser pyrolysis conventional infrared spectroscopy; and (4) infrared imaging thermovision. The most reproducible and sensitive technique was solids probe mass spectrometry. The fabricated exposed specimens were analyzed for D20 profiling after humidity/thermal conditioning at three exposure time durations.

Ryan, L. E.↗

Amino acids in the Yamato carbonaceous chrondrite from Antarctica

Evidence for the presence of amino acids of extraterrestrial origin in the Antarctic Yamato carbonaceous chrondrite is presented. Hydrolyzed and nonhydrolyzed water-extracted amino acid samples from exterior, middle and interior portions of the meteorite were analyzed by an amino acid analyzer and by gas chromatography of N-TFA-isopropyl amino acid derivatives. Nine protein and six nonprotein amino acids were detected in the meteorite at abundances between 34 and less than one nmole/g, with equal amounts in interior and exterior portions. Nearly equal abundances of the D and L enantiomers of alanine, aspartic acid and glutamic acid were found, indicating the abiotic, therefore extraterrestrial, origin of the amino acids. The Antarctic environment and the uniformity of protein amino acid abundances are discussed as evidence against the racemization of terrestrially acquired amino acids, and similarities between Yamato amino acid compositions and the amino acid compositions of the Murchison and Murray type II carbonaceous chrondrites are indicated.

Shimoyama, A.↗

Quantification of monocarboxylic acids in the Murchison carbonaceous meteorite

The abundances of some of the straight- and branched-chain isomers of the monocarboxylic acids found in the Murchison carbonaceous chondrite are determined. Monocarboxylic acids extracted from a crushed sample of Murchison interior were quantified by means of gas chromatography and mass spectroscopy after a spiking solution of deuterated analogues of 11 carboxylic acids had been added. Monocarboxylic acid abundances are found to range between 1.83 and 0.01 micromole/g, which is significantly higher than Murchison amino acid concentrations, and to decrease with increasing carbon number for both branched and unbranched molecules. The results are interpreted to support the abiotic extraterrestrial synthesis of monocarboxylic acids. Possible mechanisms leading to the equal synthesis of branched and each unbranched carboxylic acid with the same carbon number are considered, noting that the Fischer-Tropsch Type mechanism by itself is incapable of accounting for the observed distributions.

Lawless, J. G.↗

Vertical profiles of CO and CH4 in the lower and middle troposphere over the Eastern United States January 1978

Samples of tropospheric air were obtained over the Eastern United States during January of 1978. These samples were analyzed by gas chromatography using flame ionization detection to produce vertical profiles of carbon monoxide and methane from the surface to 8 km. The carbon monoxide mixing ratios at 35 deg N and 45 deg N agree with previously published values; however, the mixing ratio at 25 deg N was significantly lower than most published values. The methane mixing ratio was weakly dependent on latitude and has an average value of 1.64 ppm.

Reichle, H. G., Jr.↗

Simulation of the Viking biology experiments - An overview

In the present paper, ground-based investigations of the Viking Martian biology data, which have resulted in reasonable simulations of these data, are reviewed. These simulations, which in strong oxidants, UV-treated materials, iron-containing clays, or iron salts were used as Martian analogs, are capable of explaining the ambiguity between the GCMS (gas-chromatography mass-spectrometry) experiments, in which no organic compounds were found on Mars, and the Labeled Release experiments, in which added organics were decomposed.

Klein, H. P.↗

Experiments on the amplification of optical activity

Chemical mechanisms for the amplification of small, abiotically produced enantiomeric excesses leading to the complete stereo specificity of all biochemical reactions observed in the present-day biosphere are investigated quantitatively. Partial copolymerization of a mixture of R- and S-leucine or R- and S-valine N-carboxy anhydrides containing a known excess of one enantiomer was induced and the enantiomeric composition of the resulting oligomer was analyzed by gas chromatography. It is found that the 50% polymerization of leucine mixtures having excesses of 8 to 70% of either enantiomer leads to a significant enhancement of the enantiomeric excess of the polymer, accompanied by a corresponding decrease in the enantiomeric excess of the unpolymerized residue. On the other hand, 25-50% polymerization of valine mixtures is observed to result in polymers showing a decreased enantiomeric excess relative to the starting mixture and corresponding increases in those of the residue. Results of the leucine polymerization are interpreted as supporting the theory of steric interactions between the monomer and the helical structure of the polymer leading to the enrichment of one enantiomer, and possible mechanisms for the reverse stereospecificity observed in valine are discussed.

Blair, N. E.↗

Concentration distribution of methyl chloride in the atmosphere

Electron capture gas chromatography techniques were used to obtain measurements of methyl chloride concentrations in the atmosphere, at latitudes ranging from about 65 N to 90 S. Most of the measurements were made over the Pacific Ocean. Average global concentrations within the boundary layer were found to be 815 plus or minus 25 pptv in 1977 and 755 plus or minus 37 pptv in 1978. Lower concentrations were observed above the boundary layer with average values of 629 plus or minus 23 pptv and 618 plus or minus 23 pptv in 1977 and 1978, respectively. Within 20 deg of the equator, the boundary layer concentrations were significantly higher than those above the boundary layer. The sources, the sinks, the budgets, and the latitudinal distributions of methyl chloride are discussed in the paper.

Rasmussen, R. A.↗

Quantification of monocarboxylic acids from a spark discharge synthesis

A suite of sixteen monocarboxylic acids having carbon numbers 2 to 7, formed by the Miller-Urey spark discharge process, was identified and quantified by gas chromatography and mass fragmentography using a deuterium spiking technique. The molar concentration and isomeric distribution of these laboratory synthesized monocarboxylic acids are compared to those previously reported for the Murchison meteorite. They show similar trends, namely, decreasing molar concentration with increasing molecular weight, and a ratio of normal/branched isomers tending toward smaller values with increasing carbon numbers.

Yuen, G. U.↗

Analysis of volatile metabolites in biological fluids as indicators of prodromal disease condition

The volatile profile cannot be defined as a single class of substances, rather it is a broad spectrum of materials of different polarities characterized by having a boiling-point in the low to medium range (up to approximately 300 C) and the fact that the compounds are suitable for gas chromatography without derivatization. The organic volatile profiles are very complex mixtures of metabolic byproducts, intermediates, and terminal products of enzymatic degradations composed mainly of alcohols, ketones, aldehydes, pyrazines, sulfides, isothiocyanates, pyrroles, and furans. The concentration of organic volatiles in biological fluids covers a wide range with many important components present at trace levels. The complexity of the organic volatile fraction requires the use of capillary columns for their separation.

Zlatkis, A.↗

Measurements of the global distribution of carbon monoxide in the troposphere

Carbon monoxide and methane grab samples were obtained simultaneously with ozone, aerosol, nitric oxide and DACOM CO measurements. Eighty grab samples were collected at various altitudes up to 19,000 ft. along a north-south flight path from Wallops Flight Center, VA to 11 N. CO and CH were analyzed by flame ionization gas chromatography with cryogenic preconcentration. The relationship between CO and O3 concentrated is examined. A comparative analysis between trends in aerosol and CO concentration is performed.

Hinton, R. R.↗

Irradiation of NH3-CH4 mixtures as a model of photochemical processes in the Jovian planets and Titan

The reactions occurring upon the ultraviolet irradiation of ammonia-methane mixtures are investigated in a simulation of the atmospheric chemistry of the Jovian planets and Titan. Gas mixtures were irradiated at 185 nm at temperatures from 156-298 K, and product and reactant concentrations were determined by means of gas chromatography. The ratio of the moles of CH4 lost per mole of NH3 decomposed is found to be 0.25, with the extent of CH4 decomposition independent of temperature. The absence of a temperature effect suggests that nonthermal atoms, probably hydrogen, initiate CH4 decomposition by the extraction of a hydrogen atom. A decrease in CH4 loss with increasing pressure or the addition of other gases to the photolysis mixture, and the lack of an increase in NH3 photolysis with CH4 pressure support this mechanism. Major reaction products obtained include C2H2, C3H8 or CH3NH2, and C4H10. Considerations of atmospheric concentrations of H2 and He indicate that NH3 photolysis does not contribute to CH4 decomposition on Jupiter, Saturn, Uranus, and Neptune, although it may have had a role in the formation of the Titan atmosphere.

Ferris, J. P.↗

The radiolysis and radioracemization of amino acids on silica surfaces

Results are presented of experiments on the radioracemization of amino acids in the presence of silica surfaces such as may have been found on the prebiotic earth. L-leucine and a DL-leucine mixture deposited on samples of 1-quartz and an amorphous silica preparation (Syloid 63) was subjected to Co-60 gamma-ray irradiation, then analyzed by gas chromatography to determine the radiolysis and racemization rates. The quartz surface is found to have a marginal efficacy in enhancing radiolysis when compared with a crystalline L-leucine control, although enhancing radioracemization symmetrically by a factor of two. Both the radiolysis and radioracemization of L-leucine and DL-leucine on a Syloid-63 silica surface are observed to increase with increasing radiation dose, and to be substantially greater than in the crystalline controls. Additional experiments with the nonprotein amino acid isovaline deposited on Syloid 63 confirm the greater radiolysis susceptibility of amino acids deposited on silica with respect to the crystalline state, although racemization is not observed. The observations suggest that the presence of a silica surface would have a deleterious effect on any mechanism for the origin of molecular chirality relying on stereoselective beta-radiolysis.

Bonner, W. A.↗

Search for effect of longitudinally polarized protons on optically active amino acids

The influence of irradiation by longitudinally polarized protons on the differential decomposition of amino acid is investigated in a test of the Vester Ulbricht hypothesis that L-amino acids were produced in preference to the D isomers on the primitive earth due to the effects of parity violation in beta decay. Samples of DL-leucine were irradiated with protons of both positive and negative longitudinal polarization, then analyzed by gas chromatography. Despite advantages of higher polarization, lower velocity and higher ionization density of protons with respect to electrons, proton irradation is found to lead to no detectable asymmetries in DL-leucine degradation, even at 50% gross degradation.

Lemmon, R. M.↗

Organic solids produced by electrical discharge in reducing atmospheres - Tholin molecular analysis

The complex dark brown solid of a class called tholins, produced on passage of an electrical discharge through a roughly equimolar mixture of methane and ammonia with 2.6% water vapor, is analyzed by vacuum pyrolysis followed by gas chromatography and mass spectrometry. Pyrolyzates include a wide range of aliphatic and aromatic nitriles, alkanes, alkenes, aromatic hydrocarbons, pyrrole, and pyridine. This tholin is remarkably stable to 950 C. It and its degradation products are candidate constituents of planetary aerosols in the outer solar system and of the grains in the interstellar medium.

Khare, B. N.↗