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At least 19 records

The role of minerals in the thermal alteration of organic matter. IV - Generation of n-alkanes, acyclic isoprenoids, and alkenes in laboratory experiments

The effect of common sedimentary minerals (illite, Na-montmorillonite, or calcite) under different water concentrations on the generation and release of n-alkanes, acyclic isoprenoids, and select alkenes from oil-prone kerogens was investigated. Matrices containing Green River Formation kerogen or Monterey Formation kerogen, alone or in the presence of minerals, were heated at 200 or 300 C for periods of up to 1000 hours, and the pyrolysis products were analyzed. The influence of the first two clay minerals was found to be critically dependent on the water content. Under the dry pyrolysis conditions, both minerals significantly reduced alkene formation; the C12+ n-alkanes and acyclic isoprenoids were mostly destroyed by montmorillonite, but underwent only minor alteration with illite. Under hydrous conditions (mineral/water of 2/1), the effects of both minerals were substantially reduced. Calcite had no significant effect on the thermal evolution of the hydrocarbons.

Huizinga, Bradley J.↗

Origin of organic matter in early solar system. V - Further studies of meteoritic hydrocarbons and a discussion of their origin.

The Murchison meteorite contains aliphatic and aromatic hydrocarbons similar to those made in static Fischer-Tropsch-type syntheses. Principal compound classes above C8 are n-alkanes, mono- and dimethylalkanes, alkenes, alkylbenzenes and -naphthalenes. Below C8, n-alkanes are virtually absent; instead, benzene, toluene, branched alkanes dominate. The CH4/C2H6 ratio is greater than 30, possibly greater than 700. Isoprenoids from C17 to C20 occur in a surface rinse but not in subsequent extracts and appear to be terrestrial contaminants. Thiophenes, porphyrin-like pigments, and chlorobenzenes were also found; the latter appear to be contaminants. In the Allende meteorite, only methane, benzene, toluene and an aromatic polymer seem to be indigeneous. A comprehensive review of current evidence shows that Fischer-Tropsch-type reactions can account for most principal features of meteorite organic matter.

Studier, M. H.↗

Lipids of recently-deposited algal mats at Laguna Mormona, Baja California

A preliminary survey of the lipid composition of the core of a recently deposited algal mat of a subtropical, hypersaline coastal pond is described. Two layers of the core were examined: the upper, 2-cm-thick layer, comprising the fresh algal mat of predominantly the blue-green species Microcoleus chthonoplastes, and the black anaerobic algal ooze at a depth of 10 cm. About 75% of the n-alkanes in the mat were accounted for by n-C17, with smaller amounts of higher homologues maximizing at n-C27. The ooze was characterized by a bimodal distribution with maxima at n-C17 and n-C27. The n-alkanoic acids distributions were similar to the corresponding n-alkane distributions. A marked decrease in the ratio of monounsaturated to saturated acids in the ooze relative to the mat was observed, which indicates a preferential removal of unsaturated components. Certain triterpenes of the hopane skeletal type were present in the mat and ooze. The presence of stanols and sterenes in the ooze with similar carbon number distributions suggests a relationship between them.

Cardoso, J.↗

Pyrolysis-high resolution gas chromatography and pyrolysis gas chromatography-mass spectrometry of kerogens and kerogen precursors

A series of kerogens and kerogen precursors isolated from DSDP samples, oil shales and recent algal mats have been examined by Curie point pyrolysis-high resolution gas chromatography and gas chromatography-mass spectrometry. This study has shown that the three main types of kerogens (marine, terrestrial and mixtures of both) can be characterized using these techniques. The marine (algal) kerogens yield principally aliphatic products and the terrestrial kerogens yield more aromatic and phenolic products with some n-alkanes and n-alkenes. The yields of n-alkanes and n-alkenes increase and phenols decrease with increasing geologic age, however, pyrolysis-GC cannot be used to characterize the influence of short term diagenesis on the kerogen structure.

Van De Meent, D.↗

Compound-specific isotopic analyses: a novel tool for reconstruction of ancient biogeochemical processes

Patterns of isotopic fractionation in biogeochemical processes are reviewed and it is suggested that isotopic fractionations will be small when substrates are large. If so, isotopic compositions of biomarkers will reflect those of their biosynthetic precursors. This prediction is tested by consideration of results of analyses of geoporphyrins and geolipids from the Greenhorn Formation (Cretaceous, Western Interior Seaway of North America) and the Messel Shale (Eocene, lacustrine, southern Germany). It is shown (i) that isotopic compositions of porphyrins that are related to a common source, but which have been altered structurally, cluster tightly and (ii) that isotopic differences between geolipids and porphyrins related to a common source are equal to those observed in modern biosynthetic products. Both of these observations are consistent with preservation of biologically controlled isotopic compositions during diagenesis. Isotopic compositions of individual compounds can thus be interpreted in terms of biogeochemical processes in ancient depositional environments. In the Cretaceous samples, isotopic compositions of n-alkanes are covariant with those of total organic carbon, while delta values for pristane and phytane are covariant with those of porphyrins. In this unit representing an open marine environment, the preserved acyclic polyisoprenoids apparently derive mainly from primary material, while the extractable, n-alkanes derive mainly from lower levels of the food chain. In the Messel Shale, isotopic compositions of individual biomarkers range from -20.9 to -73.4% vs PDB. Isotopic compositions of specific compounds can be interpreted in terms of origin from methylotrophic, chemautotrophic, and chemolithotrophic microorganisms as well as from primary producers that lived in the water column and sediments of this ancient lake.

Non-NASA Center↗

Hydrocarbons identified in extracts from estuarine water accommodated no. 2 fuel oil by gas chromatography-mass spectrometry

Results are presented on a computerized gas chromatograph-mass spectrometer analysis of methylene chloride and n-heptane extracts of a No. 2 fuel oil accommodated estuarine water sample. The analytical method is briefly described, and the limitations on the identifications are categorized. Some attempt was made to determine major and trace constituents in the water accommodate. Altogether 66 hydrocarbon compounds were identified specifically, and 75 compounds were partially identified. Seven compounds could be recognized as major constituents of the water accommodated oil and ten were present only as traces. The aromatic compounds found were alkyl benzenes, naphthalene, tetralin, indane, biphenyl, fluorene, anthracene, and some of their alkyl substituted isomers in the range of carbon numbers C7 to C15. Four n-alkanes, C10 to C13, were found along with four other assorted hydrocarbons.

Lewis, B. W.↗

Thermal alteration experiments on organic matter from recent marine sediments in relation to petroleum genesis

Three fractions of organic matter: lipid (benzene:methanol-extractable), humic acid (alkali-extractable) and kerogen (residue) were extracted from a young marine sediment (Tanner Basin, offshore southern California) and heated for different times (5-116 hr) and temperatures (150-410 C). The volatile (gases) and liquid products, as well as residual material, were then analyzed. On a weight basis, the lipid fraction produced 58% of the total identified n-alkanes, the kerogen fraction 41%, and the humic acid less than 1%. The volatiles produced by heating the lipid and humic acid fractions were largely CO2 and water, whereas those produced from heated kerogen also included methane, hydrogen gas and small amounts of C2-C4 hydrocarbons. A mechanism for hydrocarbon production due to the thermal alteration of organic constituents of marine sediment is discussed.

Ishiwatari, R.↗

Organic matter in eolian dusts over the Atlantic Ocean

The elemental and mineralogical composition and the microfossil and detritus content of particulate fallout from the lower troposphere over the Atlantic Ocean have been extensively documented in earlier work, and it was possible to ascribe terrigenous source areas to such fallout. A brief review of the organic geochemistry of eolian dusts is also presented here. The lipids of eolian dusts sampled from the air mass over the eastern Atlantic from about 35 deg N to 30 deg S were analyzed here. These lipids consisted mainly of normal alkanes, carboxylic acids and alcohols. The n-alkanes were found to range from n-C23 to n-C35 with high CPI values and maximizing at n-C27 in the North Atlantic, at n-C29 in the equatorial Atlantic and at n-C31 in the South Atlantic. The n-fatty acids had mostly bimodal distributions, ranging from n-C12 to n-C30 (high CPI), with maxima at n-C16 and in the northern samples at n-C24 and in the southern samples at n-C26. The n-alcohols ranged from n-C12 to n-C32, with high CPI values and maxima mainly at n-C28. The compositions of these lipids indicated that their terrigenous sources were comprised mainly of higher plant vegetation and desiccated lacustrine mud flats on the African continent.

Simoneit, B. R. T.↗

Color of kerogen as index of organic maturity

Kerogen from the Tanner basin off southern California was heated under nitrogen at different temperatures and times and subsequently was studied under the transmitted light microscope. Samples darken in color from yellow through shades of brown to black with increasing thermal maturation. The transition from dark brown to very dark brown marks the range of maximum n-alkane generation where the residue attains an atomic H/C of about 0.80 plus or minus 0.05. The apparent activation energy for this transition was about 45 plus or minus 5 kcal per mole.

Peters, K. E.↗

Evaluation of the application of some gas chromatographic methods for the determination of properties of synthetic fuels

The purpose of the investigation was to evaluate the applicability, to some synthetic fuels, of some gas chromatographic methods now under development for use with petroleum based fuels. Thirty-two jet and diesel fuel samples which were prepared from oil shale and coal syncrudes were examined. The boiling range distribution of each was determined by gas chromatography, and from that data distillation properties were calculated. The calculated results gave sufficient agreement with the measured values that the equations could be useable in their present form. Bulk fuel properties were calculated for the sixteen JP-5 and Diesel No. 2 type fuels. The results show that the equations would not give useable results. Capillary column gas chromatography was used to determine the n-alkane content of the eight JP-5 type samples and the results related to the observed freezing points. The results show that the concentrations of the long straight chain molecules in the fuels exert influence on the freezing point but are not the complete controlling factor.

Antoine, A. C.↗

Evaluation of the application of some gas chromatographic methods for the determination of properties of synthetic fuels

The purpose of the investigation was to evaluate the applicability, to some synthetic fuels, of some gas chromatographic methods now under development for use with petroleum based fuels. Thirty-two jet and diesel fuel samples which were prepared from oil shale and coal syncrudes were examined. The boiling range distribution of each was determined by gas chromatography, and from that data distillation properties were calculated. The calculated results gave sufficient agreement with the measured values that the equations could be useable in their present form. Bulk fuel properties were calculated for the 16 JP-5 and Diesel No. 2 type fuels. The results show that the equations would not give useable results. Capillary column gas chromatography was used to determine the n-alkane content of the eight JP-5 type samples and the results related to the observed freezing points. The results show that the concentrations of the long straight chain molecules in the fuels exert influence on the freezing point but are not the complete controlling factor.

Antoine, A. C.↗

Comparison of Michigan Basin crude oils

Michigan Basin oils from the Ordovician Trenton, Silurian Niagaran, and Devonian Dundee formations have been geochemically compared by GC, GC-MS, and carbon isotope mass spectrometry. One oil from each formation was selected for detailed analysis which included measurement of individual n-alkane delta 13 C values. The Ordovician and Devonian oils are strikingly similar to one another, yet clearly different from the Silurian oil. This pattern is unexpected because Ordovician and Devonian reservoirs are physically separated by the Silurian strata. From time-temperature considerations, the Devonian oil probably was formed in older strata and has migrated to its present location. Our analyses suggest a common source for the Devonian and Ordovician oils.

Vogler, E. A.↗

Low temperature hydrothermal maturation of organic matter in sediments from the Atlantis II Deep, Red Sea

Hydrocarbons and bulk organic matter of two sediment cores within the Atlantis II Deep are analyzed, and microbial inputs and minor terrestrial sources are found to represent the major sedimentary organic material. Results show that extensive acid-catalyzed reactions are occurring in the sediments, and the Atlantis II Deep is found to exhibit a lower degree of thermal maturation than other hydrothermal or intrusive systems. The lack of carbon number preference noted among the n-alkanes suggests that the organic matter of these sediments has undergone some degree of catagenesis, though yields of hydrocarbons are much lower than those found in other hydrothermal areas, probably due to the effect of lower temperature and poor source-rock characteristics.

Simoneit, Bernd R. T.↗

Degradation mechanisms of sulfur and nitrogen containing compounds during thermal stability testing of model fuels

The degradation behavior of n-dodecane (singly or in combination with S- and N-containing dopants) was studied using a modified Jet Fuel Thermal Oxidation Tester facility between 200 and 400 C. The products were analyzed by gas chromatography and mass spectrometry. The soluble products consisted mainly of n-alkanes and 1-alkenes, aldehydes, tetrahydrofuran derivatives, dodecanol and dodecanone isomers, C21-C24 alkane isomers, and dodecylhydroperoxide (ROOH) decomposition products. The major products were always the same, with and without dopants, but their distributions varied considerably. The 3,4-dimercaptotoluene and dibutylsulfide dopants added individually to n-dodecane interferred with the hydrocarbon oxidation at the alkylperoxy radical and the alkylhydroperoxide link, respectively, while the 2,5-dimethylpyrrole dopant inhibited ROOH formation. Pyridine, pyrrole, and dibenzothiophene added individually showed few significant effects.

Reddy, K. T.↗

Modified reaction mechanism of aerated n-dodecane liquid flowing over heated metal tubes

The degradation mechanism of the n-dodecane was studied using a modified jet fuel thermal oxidation tester containing a sample withdrawal system as a reaction vessel. The reaction products were identified using gas chromatography and mass spectorometry. The soluble products were found to consist mainly of C5-C10 n-alkanes and 1-alkenes, C7-C10 aldehydes, tetrahydrofuran derivatives, dodecanol and dodecanone isomers, dodecyl hydroperoxide (ROOH) decomposition products, and C24 alkane isomers. The data from the experiments agreed with those of Hazlett et al. (1977). It was found that alkyl peroxide radical reactions dominate in the autooxidation temperature regime (at T not above 300 C); the dominant path is for the alkyl peroxyl radical to react bimolecularly with fuel to yield primarily alkyl hydroperoxides. The alkyl peroxide radical also undergoes self-termination and unimolecular isomerization and decomposition reactions, to yield smaller amounts of C12 alcohol plus ketone products and tetrahydrofuran derivatives, respectively.

Reddy, K. T.↗