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At least 631 records · Page 35
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NASA NTRS1990

Catalytic carbide formation at aluminium-carbon interfaces

X-ray photoelectron spectroscopy investigations of the reaction of several monolayer-thick films of aluminum with glassy carbon substrates are presented. The influence of molecular oxygen and water vapor on the rate of reaction is examined. It is concluded that water vapor catalyzed the formation of aluminum carbide from aluminum and carbon by forming active sites which weakened carbon-carbon bonds at the glassy carbon surface, thus assisting their cleavage. The rate of carbide formation for undosed and molecular oxygen-dosed examples was less as neither metallic aluminum nor oxygen-formed alumina could bond to the carbon atom with sufficient strength to dissociate it quickly.

Maruyama, B.↗
NASA NTRS1992

On the isotopic composition of magmatic carbon in SNC meteorites

SNC meteorites are thought, from many lines of evidence, to come from Mars. A line of investigation which has been pursued in our laboratory over the years involves measurement of the stable isotopic composition of carbon, in its various forms, in SNC meteorites. In order to establish a firm basis for studying the isotopic systematics of carbon in the martian surface environment, it is first necessary to try and constrain the delta C-13 of bulk Mars. Taking all of the available information, it would seem that the delta C-13 of the Earth's mantle lies somewhere in the range of -5 to -7 percent. Preliminary assessment of magnetic carbon in SNC meteorites, would tend to suggest a delta C-13 of 20 to 30 percent, which is conspicuously different from that of the terrestrial mantle. It is not obvious why there should be such a difference between the two planets, although many explanations are possible. One of these possibilities, that previous delta C-13 measurements for magnetic carbon in SNC meteorites are in error to some degree, is being actively investigated. The most recent results seem to constrain the theta C-13 of the magnetic carbon in SNC meteorites to about -20 percent, which is not at odds with previous estimates. As such, it is considered that a detailed investigation of the carbon isotopic systematics of martian surface materials does have the necessary information with which to proceed.

Wright, I. P.↗
NASA NTRS1992

Studies on the reactive melt infiltration of silicon and silicon-molybdenum alloys in porous carbon

Investigations on the reactive melt infiltration of silicon and silicon-1.7 and 3.2 at percent molybdenum alloys into porous carbon preforms have been carried out by process modeling, differential thermal analysis (DTA) and melt infiltration experiments. These results indicate that the initial pore volume fraction of the porous carbon preform is a critical parameter in determining the final composition of the raction-formed silicon carbide and other residual phases. The pore size of the carbon preform is very detrimental to the exotherm temperatures due to liquid silicon-carbon reactions encountered during the reactive melt infiltration process. A possible mechanism for the liquid silicon-porous (glassy) carbon reaction has been proposed. The composition and microstructure of the reaction-formed silicon carbide has been discussed in terms of carbon preform microstructures, infiltration materials, and temperatures.

Singh, M.↗
NASA NTRS1992

Carbon petrology in cometary dust

Chondritic porous (CP) interplanetary dust particles (IDP's) are collected in the Earth's stratosphere. There exists an extensive database on major and minor element chemistry, stable isotopes, noble gas abundances and mineralogy of many CP IDP's, as well as infrared and Raman spectroscopic properties. For details on the mineralogy, chemistry and physical properties of IDP's, I refer to the reviews by Mackinnon and Rietmeijer (1987), Bradley et al. (1988) and Sandford (1987). Texture, mineralogy (Mackinnon and Rietmeijer, 1987) and chemistry (Schramm et al., 1989; Flynn and Sutton, 1991) support the notion that CP IDP's are a unique group of ultrafine-grained extraterrestiral materials that are distinct from any known meteorite class. Their fluffy, or porous, morphology suggests that CP IDP's probably endured minimal alteration by protoplanetary processes since their formation. It is generally accepted that CP IDP's are solid debris from short-period comets. The evidence is mostly circumstantial but this notion gained significant support based on the comet Halley dust data (Brownlee, 1990). In this paper, I will accept that CP IDP's are indeed cometary dust. The C/Si ratio in CP IDP's is 3.3 times higher than in CI carbonaceous chondrites (Schramm et al. 1989). The intraparticle carbon distribution is heteorogeneous (Rietmeijer and McKay, 1986). Carbon occurs both in oxidized and reduced forms. Analytical electron microscope (AEM) and Raman spectroscopic analyses have shown the presence of several carbon forms in CP IDP's but the data are scattered in the literature. Carbons in cometary CP IDP's are among the most pristine Solar System carbons available for laboratory study. Similar to a recently developed petrological model for the diversity of layer silicates in CP IDP's (Zolensky, 1991) that is useful to constrain in situ aqueous alteration in comets (Rietmeijer and Mackinnon, 1987a), I here present the first effort to develop a petrological concept of carbons in CP IDP's. This concept is useful to constrain comet evolution. I also present the philosophical constraint facing Earth Scientists in studies of protoplanets that require a new approach to cometary dust studies.

Rietmeijer, Frans J. M.↗
NASA NTRS1992

Carbon isotope evidence for the stepwise oxidation of the Proterozoic environment

The oxidation of the earth's crust and the increase in atmospheric oxygen early in earth history have been linked to the accumulation of reduced carbon in sedimentary rocks. Trends in the carbon isotope composition of sedimentary organic carbon and carbonate show that during the Proterozoic aeon (2.5-0.54 Gyr ago) the organic carbon reservoir grew in size, relative to the carbonate reservoir. This increase, and the concomitant release of oxidizing power in the environment, occurred mostly during episodes of global rifting and orogeny.

Des Marais, David J.↗
NASA NTRS1993

Volcanic recycling of carbonates on Mars

Thermal erosion of carbonate deposits by turbulently-flowing lava is investigated as a means of recycling carbon dioxide back into the atmosphere of Mars. Erosion rates of several meters/day are found, implying that up to hundreds of meters of carbonate could be removed over the lifetime of a flow. A large fraction of the northern plains and other parts of Mars were covered by lava during the Hesperian, and may have released the carbon dioxide trapped in carbonate deposits. This period of time, several times 10 exp 8 yrs, is comparable to that for the redeposition of such carbonate deposits. Therefore, there could have existed a relatively dense atmosphere, and enhanced weathering and erosion, after the Noachian era. This may help explain the apparent observational evidence for late fluvial and lacustrine activity on Mars.

Schaefer, M. W.↗
NASA NTRS1993

Earth's partial pressure of CO2 over the past 100-500 Ma; evidence from Ce anomalies in mostly shallow seas (less than 200 m) as recorded in carbonate sediments, 2

We reported the direct relationship of Ce anomalies recorded in 0.2-119 Ma CaCO3 sediments (Ce(sup A*)) to the Ce anomalies in the parental Pacific deep seawater (Ce(sup A)) and their relationship to atmospheric P(CO2) relative to present P(CO2). We have analyzed continental CaCO3 samples that were deposited in ancient oceans and shallow sea platforms less than 200 m over central USA, central Europe, China, and Saudi-Arabia/Oman. We have plotted Ce(sup A*) over the 75-470 Ma interval. For P(CO2) calculations, we assumed as a reference standard the less than 200 m mixed Pacific Ocean with a Ce(sup A) geometric mean of 0.22 and a range of 0.10-0.43. Because P(CO2) values obtained from reliable deep Pacific Ocean carbonates in the 67-119 Ma interval were similar to the present P(CO2) values, we have drawn a 1.0 ratio for that interval. Although there is considerable scatter among the approximately 150 Ma carbonates, the average Ce(sup A*) value suggests that P(CO2) increased during the early Cretaceous, from 1.0X at approximately 120 Ma to about 1.4X at approximately 150 Ma. At approximately 250 Ma, the average Ce(sup A*) in 13 shallow sea China carbonates agrees well with the single and more reliable approximately 250 Ma China carbonate deposited in deeper open platform. We suggest that P(CO2) ranged from 1.4-1.7X over the Jurassic and Triassic periods. At approximately 280 Ma, three China carbonates deposited in deeper open platforms and therefore considered more reliable are consistent with a European carbonate, which indicate Ce(sup A) and P(CO2) values similar to the present. The minimum at this time corresponds to the great Permo-Carboniferous glaciation. From 280 Ma to 470 Ma, the trend favors increasing Ce(sup A*) and corresponding P(CO2) values between 1.9-2.7X, with a more reliable value closer to 2.7X at 430 Ma because of the unknown higher temperature in the less than 100 m seawater over continental USA which was located just south of the equator at approximately 430 Ma.

Liu, Y.-G.↗
NASA NTRS1993

A carbon isotope mass balance for an anoxic marine sediment: Isotopic signatures of diagenesis

A carbon isotope mass balance was determined for the sediments of Cape Lookout Bight, NC to constrain the carbon budgets published previously. The diffusive, ebullitive and burial fluxes of sigma CO2 and CH4, as well as the carbon isotope signatures of these fluxes, were measured. The flux-weighted isotopic signature of the remineralized carbon (-18.9 plus or minus 2.7 per mil) agreed with the isotopic composition of the remineralized organic carbon determined from the particulate organic carbon (POC) delta(C-13) profiles (-19.2 plus or minus 0.2), verifying the flux and isotopic signature estimates. The measured delta(C-13) values of the sigma CO2 and CH4 diffusive fluxes were significantly different from those calculated from porewater gradients. The differences appear to be influenced by methane oxidation at the sediment-water interface, although other potential processes cannot be excluded. The isotope mass balance provides important information concerning the locations of potential diagenetic isotope effects. Specifically, the absence of downcore change in the delta(C-13) value of the POC fraction and the identical isotopic composition of the POC and the products of remineralization indicate that no isotopic fractionation is expressed during the initial breakdown of the POC, despite its isotopically heterogeneous composition.

Boehme, Susan E.↗
NASA NTRS1993

The carbon components in SNC meteorites of feldspathic harzburgite composition

Two meteorites collected in Antarctica, ALH A77005 and LEW 88516, have characteristics which link them to the shergottite group of SNC meteorites. Essentially, ALH A77005 and LEW 88516 are feldspathic harzburgites, being comprised of roughly equal quantities of olivine and pyroxene, with an additional few percent of feldspar which has subsequently been converted to maskelynite by shock. The meteorites represent samples of a cumulate rock which is itself composed of two different lithologies: in one, large pyroxenes poikilitically enclose olivine crystals, while the other consists of interstitial areas made up of pyroxene, olivine, maskelynite, whitlockite, troilite, ilmenite and chlorapatite. It has been proposed that meteorites such as ALH A77005 (and LEW 88516) are relict samples of the source peridotite from which the other shergottites formed. As such it should be informative to study in detail the carbon components present within these samples, in order to make comparisons with data from other shergottites. Although not plutonic in origin, and therefore not sampling a truly deep source, analyses of ALH A77005 and LEW 88516 should assist with attempts to define the bulk carbon isotopic composition of Mars. This has been assessed previously through analyses of carbon of presumed magmatic origin in other SNC meteorites, but the carbon isotopic compositions obtained seem to be at variance with what might be expected. It is important to constrain the carbon isotopic composition of Mars as well as possible so that models of atmospheric evolution, based on carbon isotopic data, can yield the most reliable results.

Wright, I. P.↗
NASA NTRS1993

Further carbon isotope measurements of LEW 88516

Douglas et al. have previously analyzed the carbon content and isotopic composition of a crushed sample (sub-sample 13) of the shergottite, LEW 88516. The powder, which was from a relatively large portion of the meteorite in order to obtain a representative sample, was distributed amongst the scientific community. However, it is probable that the preparation procedure was not optimized for the purposes of carbon measurements. Indeed, it was found that LEW 88516,13 contained over 1200 ppm carbon, a concentration which is greater than that present in any other SNC meteorite. That a close relative, ALH A77005, contains only 141 ppm carbon seems to implicate the preparation procedure as being responsible for the apparently high carbon content of LEW 88516. However, it may also be the nature of the fine powder which has resulted in contamination. The observation of high carbon content in LEW 88516,13 highlights the extreme difficulty of trying to obtain representative samples of whole meteorites for this kind of investigation. Presented herein are some further measurements of LEW 88516 which should serve to clarify some of the issues raised by the previous investigation.

Wright, I. P.↗
NASA NTRS1995

Carbon in photon dominated regions: C II/C I/CO observations of NGC 2024

We present observations of the large-scale distribution of the major forms of carbon, neutral and singly ionized atomic carbon and carbon monoxide, in the NGC 2024/Orion B cloud. The overall extent and morphology of the different types of emission are similar, consistent with a picture in which the atomic carbon lies on the UV-illuminated surfaces of molecular clumps throughout the cloud. However, emission from ionized carbon extends considerably farther to the west than the CO emission. Integrated over the region mapped in the 158 mu m (C II) line, about half of the gas-phase carbon is in a form other than CO.

Jaffe, Dan T.↗
NASA NTRS1995

Latitudinal distribution of black carbon soot in the upper troposphere and lower stratosphere

Black carbon soot from the upper troposphere and lower stratosphere has been systematically collected at latitudes from 90 deg N to 45 deg S. The measured latitudinal distribution of this soot at 10 to 11 km altitude is found to covary with commercial air traffic fuel use, suggesting that aircraft fuel combustion at altitude is the principal source. In addition, at latitudes where the commercial air traffic is high, measured black carbon soot values are high even at 20 km altitude, suggesting that aircraft-generated soot injected just above the tropopause may be transported to higher altitudes. During the volcanically influenced period in which these samples were collected, the number abundances, total mass, and calculated total surface area of black carbon soot are 2-3 orders of magnitude lower than similar measures of sulfuric acid aerosol. During volcanically quiescent periods, the calculated total surface area of black carbon soot aerosol is of the same order of magnitude as that of the background sulfuric acid aerosol. It appears from this comparison that black carbon soot is only capable of influencing lower stratosphere or upper troposphere chemistry during periods when the aerosol budget is not dominated by volcanic activity. It remains to determine the extent to which black carbon soot particles act as nuclei for sulfuric acid aerosol formation. However, mass balance calculations suggest that aircraft soot injected at altitude does not represent a significant source of condensation nuclei for sulfuric acid aerosols.

Blake, David F.↗
NASA NTRS1996

Experimental evaluation of the ignition process of carbon monoxide and oxygen in a rocket engine

Carbon monoxide and oxygen ignition boundaries were determined in a spark torch igniter as a function of propellant inlet temperatures. The oxygen temperature was varied from ambient to -258 F, and the carbon monoxide temperature was varied from ambient to -241 F. With the oxygen and carbon monoxide at -253 F and -219 F, respectively, they successfully ignited between mixture ratios of 2.42 and 3.10. Analysis of the results indicated that the lower ignition boundary was more sensitive to oxygen temperature than to carbon monoxide temperature. Another series of tests was performed in a small simulated rocket engine with oxygen at -197 F and carbon monoxide at -193 F. An oxygen/hydrogen flame was used to initiate combustion of the oxygen and carbon monoxide. Tests performed at the optimum operating mixture ratio of 0.55 obtained steady-state combustion in every test.

Linne, Diane L.↗
NASA NTRS1995

The 11 Micron Emissions of Carbon Stars

A new classification scheme of the IRAS LRS carbon stars is presented. It comprises the separation of 718 probable carbon stars into 12 distinct self-similar spectral groupings. Continuum temperatures are assigned and range from 470 to 5000 K. Three distinct dust species are identifiable: SiC, alpha:C-H, and MgS. In addition to the narrow 11 + micron emission feature that is commonly attributed to SiC, a broad 11 + micron emission feature, that is correlated with the 8.5 and 7.7 micron features, is found and attributed to alpha:C-H. SiC and alpha:C-H band strengths are found to correlate with the temperature progression among the Classes. We find a spectral sequence of Classes that reflects the carbon star evolutionary sequence of spectral types, or alternatively developmental sequences of grain condensation in carbon-rich circumstellar shells. If decreasing temperature corresponds to increasing evolution, then decreasing temperature corresponds to increasing C/O resulting in increasing amounts of carbon rich dust, namely alpha:C-H. If decreasing the temperature corresponds to a grain condensation sequence, then heterogeneous, or induced nucleation scenarios are supported. SiC grains precede alpha:C-H and form the nuclei for the condensation of the latter material. At still lower temperatures, MgS appears to be quite prevalent. No 11.3 micron PAH features are identified in any of the 718 carbon stars. However, one of the coldest objects, IRAS 15048-5702, and a few others, displays an 11.9 micron emission feature characteristic of laboratory samples of coronene. That feature corresponds to the C-H out of plane deformation mode of aromatic hydrocarbon. This band indicates the presence of unsaturated, sp(sup 3), hydrocarbon bonds that may subsequently evolve into saturated bonds, sp(sup 2), if, and when, the star enters the planetary nebulae phase of stellar evolution. The effusion of hydrogen from the hydrocarbon grain results in the evolution in wavelength of this 11.9 micron emission feature to the 11.3 micron feature.

Goebel, J. H.↗
NASA NTRS1997

Energy from Redox Disproportionation of Sugar Carbon Drives Biotic and Abiotic Synthesis

To identify the energy source that drives the biosynthesis of amino acids, lipids, and nucleotides from glucose, we calculated the free energy change due to redox disproportionation of the substrate carbon of: (1) 26-carbon fermentation reactions and (2) the biosynthesis of amino acids and lipids of E. coli from glucose. The free energy (cal/mmol of carbon) of these reactions was plotted as a function of the degree of redox disproportionation of carbon (disproportionative electron transfers (mmol)/mmol of carbon). The zero intercept and proportionality between energy yield and degree of redox disproportionation exhibited by this plot demonstrate that redox disproportionation is the principal energy source of these redox reactions (slope of linear fit = -10.4 cal/mmol of disproportionative electron transfers). The energy and disproportionation values of E. coli amino acid and lipid biosynthesis from glucose lie near this linear curve fit with redox disproportionation accounting for 84% and 96% (and ATP only 6% and 1 %) of the total energy of amino acid and lipid biosynthesis, respectively. These observations establish that redox disproportionation of carbon, and not ATP, is the primary energy source driving amino acid and lipid biosynthesis from glucose. In contrast, we found that nucteotide biosynthesis involves very little redox disproportionation, and consequently depends almost entirely on ATP for energy. The function of sugar redox disproportionation as the major source of free energy for the biosynthesis of amino acids and lipids suggests that sugar disproportionation played a central role in the origin of metabolism, and probably the origin of life.

Weber, Arthur L.↗
NASA NTRS1997

Energy from Redox Disproportionation of Sugar Carbon Drives Biotic and Abiotic Synthesis

To identify the energy source that drives the biosynthesis of amino acids, lipids, and nucleotides from glucose, we calculated the free energy change due to redox disproportionation of the substrate carbon of: (1) 26-carbon fermentation reactions and (2) the biosynthesis of amino acids and lipids of E. coli from glucose. The free energy (cal/mmol of carbon) of these reactions was plotted as a function of the degree of redox disproportionation of carbon (disproportionative electron transfers (mmol)/mmol of carbon). The zero intercept and proportionality between energy yield and degree of redox disproportionation exhibited by this plot demonstrate that redox disproportionation is the principal energy source of these redox reactions (slope of linear fit = -10.4 cal/mmol of disproportionative electron transfers). The energy and disproportionation values of E. coli amino acid and lipid biosynthesis from glucose lie near this linear curve fit with redox disproportionation accounting for 84% and 96% (and ATP only 6% and 1%) of the total energy of amino acid and lipid biosynthesis, respectively. These observations establish that redox disproportionation of carbon, and not ATP, is the primary energy source driving amino acid and lipid biosynthesis from glucose. In contrast, we found that nucleotide biosynthesis involves very little redox disproportionation, and consequently depends almost entirely on ATP for energy. The function of sugar redox disproportionation as the major source of free energy for the biosynthesis of amino acids and lipids suggests that sugar disproportionation played a central role in the origin of metabolism, and probably the origin of life.

Weber, Arthur L.↗
NASA NTRS1999

Solid State Carbon Monoxide Sensor

A means for detecting carbon monoxide which utilizes an un-heated catalytic material to oxidize carbon monoxide at ambient temperatures. Because this reaction is exothermic, a thermistor in contact with the catalytic material is used as a sensing element to detect the heat evolved as carbon monoxide is oxidized to carbon dioxide at the catalyst surface, without any heaters or external heating elements for the ambient air or catalytic element material. Upon comparison to a reference thermistor, relative increases in the temperature of the sensing thermistor correspond positively with an increased concentration of carbon monoxide in the ambient medium and are thus used as an indicator of the presence of carbon monoxide.

Upchurch, Billy T.↗
NASA NTRS1992

Carbon Isotope Evidence for the Stepwise Oxidation of the Proterozoic Environment

The oxidation of the Earth's crust and the increase in atmospheric oxygen early in Earth history have been linked to the accumulation of reduced carbon in sedimentary rocks. Trends in the carbon isotope composition of sedimentary organic carbon and carbonate show that during the Proterozoic aeon (2.5-0.54 Gyr ago) the organic carbon reservoir grew in size, relative to the carbonate reservoir. This increase, and the concomitant release of oxidizing power in the environment, occurred mostly during episodes of global rifting and orogeny.

DesMarais, David J.↗