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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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Geochemical characteristics of organic compounds in a permafrost sediment core sample from northeast Siberia, Russia

We studied total organic carbon (TOC), hydrocarbons and fatty acids in a permafrost sediment core sample (well 6-90, length 32.0 m, 1.5-2.5 Ma BP) from northeast Siberia (approximately 70 degrees N, 158 degrees E), Russia, to elucidate their geochemical features in relation to source organisms and paleoenvironmental conditions. Long-chain n-alkanes and n-alkanoic acids (>C19) were most predominant hydrocarbons and fatty acids, respectively, so organic matter in the sediment core was derived mainly from vascular plants and, to a much smaller extent, from bacteria. Low concentrations of unsaturated fatty acids revealed that organic matter in the sediment core was considerably degraded during and/or after sedimentation. The predominance of vascular plant components, the major ionic components of nonmarine sources, and geological data strongly implied that the sediment layers were formed in shallow lacustrine environments, such as swamp with large influences of tundra or forest-tundra vegetation. Also, no drastic changes in paleoenvironmental conditions for biological activity or geological events, such as sea transgressions or ice-sheet influences, occurred at the sampling site approximately 100 km from the coast of the East Siberian Sea during the late Pliocene an early Pleistocene periods.

NASA Discipline Exobiology↗

Organic geochemistry of sediments from the continental margin off southern New England, U.S.A.--Part II. Lipids

Organic geochemical measurements of the lipid fraction, comparing saturated and aromatic hydrocarbons, fatty acids, alcohols and sterols, have been carried out on six sediments cores collected from the Atlantic shelf, slope and the rise areas to evaluate the cross-shelf transport of the organic carbon. The concentration of most of the organic compound classes studied is correlated with the total organic carbon, which decreases from the shelf through slope to the rise. Terrigenous carbon is recognizable even in the slope and rise sediments, but terrestrial influx decreases relative to marine generated lipids in the slope and rise organic matter. We estimate that approximately 50% of the shelf organic matter is exported to the slope. Data of sediment trap material collected at 1200 m from 1250 m water depth are discussed and compared with that of surface sediment from 1280 m water depth (slope). Fluxes for specific organic compound classes have been computed. The fluxes are of the same magnitude as for equatorial North Atlantic trap particulates at comparable water depth, studied by other investigations.

NASA Discipline Exobiology↗

An isotopic biogeochemical study of the Green River oil shale

Thirty-five different samples from three different sulfur cycles were examined in this stratigraphically oriented study of the Shell 22x-l well (U.S.G.S. C177 core) in the Piceance Basin, Colorado. Carbon isotopic compositions of constituents of Green River bitumens indicate mixing of three main components: products of primary photoautotrophs and their immediate consumers (delta approximately -30% vs PDB), products of methanotrophic bacteria (delta approximately -85%), and products of unknown bacteria (delta approximately -40%). For individual compounds synthesized by primary producers, delta-values ranged from -28 to -32%. 13C contents of individual primary products (beta-carotane, steranes, acyclic isoprenoids, tricyclic triterpenoids) were not closely correlated, suggesting diverse origins for these materials. 13C contents of numerous hopanoids were inversely related to sulfur abundance, indicating that they derived both from methanotrophs and from other bacteria, with abundances of methanotrophs depressed when sulfur was plentiful in the paleoenvironment. gamma-Cerane coeluted with 3 beta(CH3),17 alpha(H),21 beta(H)-hopane, but delta-values could be determined after deconvolution. gamma-Cerane (delta approximately -25%) probably derives from a eukaryotic heterotroph grazing on primary materials, the latter compound (delta approximately -90%) must derive from methanotrophic organisms. 13C contents of n-alkanes in bitumen differed markedly from those of paraffins generated pyrolytically. Isotopic and quantitative relationships suggest that alkanes released by pyrolysis derived from a resistant biopolymer of eukaryotic origin and that this was a dominant constituent of total organic carbon.

Non-NASA Center↗

Isotope-ratio-monitoring gas chromatography-mass spectrometry: methods for isotopic calibration

In trial analyses of a series of n-alkanes, precise determinations of 13C contents were based on isotopic standards introduced by five different techniques and results were compared. Specifically, organic-compound standards were coinjected with the analytes and carried through chromatography and combustion with them; or CO2 was supplied from a conventional inlet and mixed with the analyte in the ion source, or CO2 was supplied from an auxiliary mixing volume and transmitted to the source without interruption of the analyte stream. Additionally, two techniques were investigated in which the analyte stream was diverted and CO2 standards were placed on a near-zero background. All methods provided accurate results. Where applicable, methods not involving interruption of the analyte stream provided the highest performance (sigma = 0.00006 at.% 13C or 0.06% for 250 pmol C as CO2 reaching the ion source), but great care was required. Techniques involving diversion of the analyte stream were immune to interference from coeluting sample components and still provided high precision (0.0001 < or = sigma < or = 0.0002 at.% or 0.1 < or = sigma < or = 0.2%).

NASA Discipline Exobiology↗

Acquisition and processing of data for isotope-ratio-monitoring mass spectrometry

Methods are described for continuous monitoring of signals required for precise analyses of 13C, 18O, and 15N in gas streams containing varying quantities of CO2 and N2. The quantitative resolution (i.e. maximum performance in the absence of random errors) of these methods is adequate for determination of isotope ratios with an uncertainty of one part in 10(5); the precision actually obtained is often better than one part in 10(4). This report describes data-processing operations including definition of beginning and ending points of chromatographic peaks and quantitation of background levels, allowance for effects of chromatographic separation of isotopically substituted species, integration of signals related to specific masses, correction for effects of mass discrimination, recognition of drifts in mass spectrometer performance, and calculation of isotopic delta values. Characteristics of a system allowing off-line revision of parameters used in data reduction are described and an algorithm for identification of background levels in complex chromatograms is outlined. Effects of imperfect chromatographic resolution are demonstrated and discussed and an approach to deconvolution of signals from coeluting substances described.

NASA Discipline Exobiology↗

Diploptene: an indicator of terrigenous organic carbon in Washington coastal sediments

The pentacyclic triterpene 17 beta(H),21 beta(H)-hop-22(29)-ene (diploptene) occurs in sediments throughout the Columbia River drainage basin and off the southern coast of Washington state in concentrations comparable to long-chain plantwax n-alkanes. The same relationship is evident for diploptene and long-chain n-alkanes in soils from the Willamette Valley. Microorganisms indigenous to soils and soil erosion are indicated as the biological source and physical process, respectively, for diploptene in coastal sediments. Similarity between the stable carbon isotopic composition (delta 13CPDB) of diploptene isolated from soil in the Willamette Valley (-31.2 +/- 0.3%) and from sediments deposited throughout the Washington coastal environment (-31.2 +/- 0.5%) supports this argument. Values of delta for diploptene in river sediments are variable and 8-17% lighter, indicating that an additional biological source such as methane-oxidizing bacteria makes a significant contribution to the diploptene record in river sediments. Selective biodegradation resulting from a difference in the physicochemical association within eroded particles can explain the absence of the more-13C-depleted form of diploptene in Washington coastal sediments, but this mechanism remains unproven.

Non-NASA Center↗

Performance and optimization of a combustion interface for isotope ratio monitoring gas chromatography/mass spectrometry

Conditions and systems for on-line combustion of effluents from capillary gas chromatographic columns and for removal of water vapor from product streams were tested. Organic carbon in gas chromatographic peaks 15 s wide and containing up to 30 nanomoles of carbon was quantitatively converted to CO2 by tubular combustion reactors, 200 x 0.5 mm, packed with CuO or NiO. No auxiliary source of O2 was required because oxygen was supplied by metal oxides. Spontaneous degradation of CuO limited the life of CuO reactors at T > 850 degrees C. Since NiO does not spontaneously degrade, its use might be favored, but Ni-bound carbon phases form and lead to inaccurate isotopic results at T < 1050 degrees C if gas-phase O2 is not added. For all compounds tested except CH4, equivalent isotopic results are provided by CuO at 850 degrees C, NiO + O2 (gas-phase mole fraction, 10(-3)) at 1050 degrees C and NiO at 1150 degrees C. The combustion interface did not contribute additional analytical uncertainty, thus observed standard deviations of 13C/12C ratios were within a factor of 2 of shot-noise limits. For combustion and isotopic analyses of CH4, in which quantitative combustion required T approximately 950 degrees C, NiO-based systems are preferred, and precision is approximately 2 times lower than that observed for other analytes. Water must be removed from the gas stream transmitted to the mass spectrometer or else protonation of CO2 will lead to inaccuracy in isotopic analyses. Although thresholds for this effect vary between mass spectrometers, differential permeation of H2O through Nafion tubing was effective in both cases tested, but the required length of the Nafion membrane was 4 times greater for the more sensitive mass spectrometer.

NASA Discipline Exobiology↗