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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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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

Carbon isotope effects associated with aceticlastic methanogenesis

The carbon isotope effects associated with synthesis of methane from acetate have been determined for Methanosarcina barkeri 227 and for methanogenic archaea in sediments of Wintergreen Lake, Michigan. At 37 degrees C, the 13C isotope effect for the reaction acetate (methyl carbon) --> methane, as measured in replicate experiments with M. barkeri, was - 21.3% +/- 0.3%. The isotope effect at the carboxyl portion of acetate was essentially equal, indicating participation of both positions in the rate-determining step, as expected for reactions catalyzed by carbon monoxide dehydrogenase. A similar isotope effect, - 19.2% +/- 0.3% was found for this reaction in the natural community (temperature = 20 degrees C). Given these observations, it has been possible to model the flow of carbon to methane within lake sediment communities and to account for carbon isotope compositions of evolving methane. Extension of the model allows interpretation of seasonal fluctuations in 13C contents of methane in other systems.

NASA Discipline Exobiology↗
NASA NTRS1986

A non-mass-dependent oxygen isotope effect in the production of ozone from molecular oxygen - The role of molecular symmetry in isotope chemistry

It was previously reported that the reaction products from the synthesis of ozone in an electric discharge through molecular oxygen display a nonmass-dependent (NoMaDic) oxygen isotope effect. In this paper, a detailed characterization of the isotope effect, including the effect of molecular oxygen pressure, and the presence of a chemically inert third body (helium), is reported. The NoMaDic effect is due to an isotopically selective stabilization of the O3 formation reaction intermediate, possibly resulting from the ability of the different isotopomers to exhibit different molecular symmetries.

Heidenreich, J. E., III↗
NASA NTRS1989

Carbon isotope effects associated with autotrophic acetogenesis

The carbon kinetic isotope effects associated with synthesis of acetate from CO2 and H2 during autotrophic growth of Acetobacterium woodii at 30 degrees C have been measured by isotopic analyses of CO2, methyl-carbon, and total acetate. Closed systems allowing construction of complete mass balances at varying stages of growth were utilized, and the effects of the partitioning of carbon between CO2 and HCO3- were taken account. For the overall reaction, total carbonate --> total acetate, isotope effects measured in replicate experiments ranged from -59.0 +/- 0.9% to -57.2 +/- 2.3%. Taking into account all measurements, the weighted mean and standard deviation are -58.6 +/- 0.7%. There is no evidence for intramolecular ordering in the acetate. The carbon isotopic composition of sedimentary acetate, otherwise expected to be near that of sedimentary organic carbon, is likely to be depleted in environments in which autotrophic acetogenesis is occurring.

Non-NASA Center↗
NASA NTRS1987

Carbon kinetic isotope effect in the reaction of CH4 with HO

The carbon kinetic isotope effect in the CH4 + HO reaction is measured experimentally and the use of carbon isotope ratios to diagnose atmospheric methane is examined. The chemical, photolysis, and analytical experimental conditions and procedures are described. It is determined that the CH4 + HO reaction has a carbon kinetic isotope effect of 1.010 + or 0.007 for k(12)k(13) (rate constants ratio) at 297 + or - 3 K. This value is compared with the data of Rust and Stevens (1980). Causes for the poor correlation between the data at high methane conversions are discussed. It is supposed that the difference between the k(12) and k(13) values is due to a difference in the activation energy of the two reactions.

Davidson, J. A.↗
NASA NTRS1986

Sulfur isotope effects associated with protonation of HS- and volatilization of H2S

The isotope effects associated with: (1) formation of H2S from HS- by protonation in aqueous solution; and (2) volatilization of H2S have been experimentally determined. Both isotopic distributions in closed systems at equilibrium and differential rates of volatilization of isotopic species in open systems were measured at 22 +/- 1 degrees C. It was found that, at equilibrium aqueous H2S is enriched in 34S by 2.0 - 2.7% relative to HS- and that H2S volatilized from solution is depleted in 34S by 0.5% relative to dissolved H2S. A small kinetic isotope effect accompanying volatilization of H2S was observed in the open-system experiments.

NASA Discipline Exobiology↗
NASA NTRS1989

A mass-independent sulfur isotope effect in the nonthermal formation

A nonmass-dependent sulfur isotope effect is present in the rotationally symmetric S2F10 molecule, produced in an electrical discharge through sulfur tetrafluoride. A similar isotopic fractionation was observed in the product S2F10 from the electrodissociation of SF5Cl and in the reaction between fluorine atoms produced by F2 photolysis and SF2, collectively ruling out the SF5 formation process as the source of the mass-independent fractionation. The secondary dissociation of S2F10 as a source of the mass-independent fractionation is ruled out by control S2F10 dissociation experiments which are shown to produce small mass-dependent fractionations. Mass-dependent effects such as sulfur isotopic exchange and secondary dissociation reactions are significant processes for the system under study, and have been quantitatively accounted for. The role of symmetry in nonmass-dependent isotope effects is strengthened by the present experiments, and the search and characterization of mass-independent effects is extended to sulfur-containing molecules.

Bains-Sahota, Swroop K.↗
NASA NTRS1988

Sulfur isotope effects associated with oxidation of sulfide by O2 in aqueous solution

Normal sulfur isotope effects averaging epsilon = -5.2 +/- 1.4% (s.d.) were consistently observed for the oxidation of sulfide in aqueous solution. Reaction products were sulfate, thiosulfate and sulfite at pH 10.8-11 in distilled water; S0 was formed in two experiments with synthetic seawater at pH 8-9.5. Because the -5.2% normal isotope effect differs significantly from the previously measured +2% inverse effect associated with anaerobic oxidation of sulfide by photosynthetic bacteria, stable sulfur isotopic measurements are potentially useful for distinguishing aerobic vs. anaerobic sulfide oxidation in marine and freshwater sulfureta.

NASA Program Exobiology↗
NASA NTRS1985

Isotope effects associated with the anaerobic oxidation of sulfite and thiosulfate by the photosynthetic bacterium, Chromatium vinosum

The purple photosynthetic bacterium Chromatium vinosum, strain D, catalyzes several oxidations of reduced sulfur compounds under anaerobic conditions in the light: e.g., sulfide --> sulfur --> sulfate, sulfite --> sulfate, and thiosulfate --> sulfur + sulfate. Here it is shown that no sulfur isotope effect is associated with the last of these processes; isotopic compositions of the sulfur and sulfate produced can differ, however, if the sulfane and sulfonate positions within the thiosulfate have different isotopic compositions. In the second process, an observed change from an inverse to a normal isotope effect during oxidation of sulfite may indicate the operation of 2 enzymatic pathways. In contrast to heterotrophic anaerobic reduction of oxidized sulfur compounds, anaerobic oxidations of inorganic sulfur compounds by photosynthetic bacteria are characterized by relatively small isotope effects.

Non-NASA Center↗
NASA NTRS2002

Isotopic Effects in Nuclear Fragmentation and GCR Transport Problems

Improving the accuracy of the galactic cosmic ray (GCR) environment and transport models is an important goal in preparing for studies of the projected risks and the efficiency of potential mitigations methods for space exploration. In this paper we consider the effects of the isotopic composition of the primary cosmic rays and the isotopic dependence of nuclear fragmentation cross sections on GCR transport models. Measurements are used to describe the isotopic composition of the GCR including their modulation throughout the solar cycle. The quantum multiple-scattering approach to nuclear fragmentation (QMSFRG) is used as the data base generator in order to accurately describe the odd-even effect in fragment production. Using the Badhwar and O'Neill GCR model, the QMSFRG model and the HZETRN transport code, the effects of the isotopic dependence of the primary GCR composition and on fragment production for transport problems is described for a complete GCR isotopic-grid. The principle finding of this study is that large errors ( 100%) will occur in the mass-flux spectra when comparing the complete isotopic-grid (141 ions) to a reduced isotopic-grid (59 ions), however less significant errors 30%) occur in the elemental-flux spectra. Because the full isotopic-grid is readily handled on small computer work-stations, it is recommended that they be used for future GCR studies.

Cucinotta, Francis A.↗
NASA NTRS1986

Theoretical analysis of isotope effects on ozone formation in oxygen photochemistry

In situ measurements of stratospheric ozone and laboratory studies of ozone production in electric discharge through oxygen have shown previously that ozone containing heavy isotopes of oxygen (O-17, O-18) may be formed preferentially. In order to assess the relevance of thee latter experiment to the stratospheric measurements, detailed understanding of the effect of isotopic substitution on the O3 formation reaction O + O2 + M yields O3 + M and on the O atom exchange reaction O + O2 + O yields O2 + O is necessary. In this work, an estimate of the effect of isotopic substitution on the recombination rate is made by us of approximate dynamical theories and statistical mechanics. The results indicate the possibility of isotope effects on the O + O2 recombination rate of the order of several percent at stratospheric temperatures. In general, recombination reactions involving heavy (mass 49, 50) O3 formation are found to be slower than the reaction leading to normal (mass 48) O3 formation. The calculated isotope effects are sufficiently small that the uncertainties in the model input and the approximations in the dynamical theories will probably make the quantitative nature of these results subject to considerable uncertainty. This isotope effect should not be observable in the atmosphere given the precision of the current measurements but may be crucial in the understanding of the laboratory experiments, where observed enhancements are only of the order of several percent. Possible reasons for this discrepancy between the observed enhancement and predicted depletion are presented.

Kaye, J. A.↗
NASA NTRS1985

The non-mass-dependent oxygen isotope effect in the electrodissociation of carbon dioxide - A step toward understanding NoMaD chemistry

A non-mass dependent (NoMaD) oxygen isotope effect is demonstrated in the dissociation of CO2 similar to that observed in the electrosynthesis of ozone. The molecular oxygen produced carries the signature of two separate isotopic fractionation processes; a mass-dependent fractionation probably due to CO2 + O isotopic exchange, and a secondary NoMaD fractionation (delta O-17 = 0.97 + or - 0.09 delta O-18, with the O2 depleted in O-17 and O-18). It is suggested that the effect is due to either the formation or relaxation of ozone in an excited electronic state. This represents the latest advance in the understanding of chemical NoMaD effects which may be essential to the explanation of non-mass-dependent fractionations observed in meteorites.

Heidenreich, J. E., III↗
NASA NTRS1989

The C-13/C-12 kinetic isotope effect for soil oxidation of methane at ambient atmospheric concentrations

During a survey of the Alaskan North Slope to estimate the isotopic composition and fluxes of methane (CH4) from the tundra, two sites were encountered that showed net methane consumption within flux chambers. Methane concentrations decreased from ambient (1.78 ppmv) by up to 50 percent, and the delta C-13 increased by up to 10 percent in the two chamber deployments showing CH4 consumption. CH4 consumption rates were measured to be 1.2 and 0.6 mg CH4/sq m per day; the corresponding carbon kinetic isotope effects (k13/k12) were 0.974 and 0.984, respectively.

King, Stagg L.↗