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At least 91 records · Page 5

Carbon Isotope Systematics in Mineral-Catalyzed Hydrothermal Organic Synthesis Processes at High Temperature and Pressures

Observation of methane in the Martian atmosphere has been reported by different detection techniques. Reduction of CO2 and/or CO during serpentization by mineral surface catalyzed Fischer-Tropsch Type (FTT) synthesis may be one possible process responsible for methane generation on Mars. With the evidence a recent study has discovered for serpentinization in deeply buried carbon rich sediments, and more showing extensive water-rock interaction in Martian history, it seems likely that abiotic methane generation via serpentinization reactions may have been common on Mars. Experiments involving mineral-catalyzed hydrothermal organic synthesis processes were conducted at 750 C and 5.5 Kbars. Alkanes, alcohols and carboxylic acids were identified as organic compounds. No "isotopic reversal" of delta C-13 values was observed for alkanes or carboxylic acids, suggesting a different reaction pathway than polymerization. Alcohols were proposed as intermediaries formed on mineral surfaces at experimental conditions. Carbon isotope data were used in this study to unravel the reaction pathways of abiotic formation of organic compounds in hydrothermal systems at high temperatures and pressures. They are instrumental in constraining the origin and evolution history of organic compounds on Mars and other planets.

Fu, Qi↗

Organic Analysis of Catalytic Fischer-Tropsch Synthesis Products and Ordinary Chondrite Meteorites by Stepwise Pyrolysis-GCMS: Organics in the Early Solar Nebula

Abiotic generation of complex organic compounds, in the early solar nebula that formed our solar system, is hypothesized by some to occur via Fischer-Tropsch (FT) synthesis. In its simplest form, FT synthesis involves the low temperature (<300degC) catalytic reaction of hydrogen and carbon monoxide gases to form more complex hydrocarbon compounds, primarily n-alkanes, via reactive nano-particulate iron, nickel, or cobalt, for example. Industrially, this type of synthesis has been utilized in the gas-to-liquid process to convert syngas, produced from coal, natural gas, or biomass, into paraffin waxes that can be cracked to produce liquid diesel fuels. In general, the effect of increasing reaction temperature (>300degC) produces FT products that include lesser amounts of n-alkanes and greater alkene, alcohol, and polycyclic aromatic hydrocarbon (PAH) compounds. We have begun to experimentally investigate FT synthesis in the context of abiotic generation of organic compounds in the early solar nebula. It is generally thought that the early solar nebula included abundant hydrogen and carbon monoxide gases and nano-particulate matter such as iron and metal silicates that could have catalyzed the FT reaction. The effect of FT reaction temperature, catalyst type, and experiment duration on the resulting products is being investigated. These solid organic products are analyzed by thermal-stepwise pyrolysis-GCMS and yield the types and distribution of hydrocarbon compounds released as a function of temperature. We show how the FT products vary by reaction temperature, catalyst type, and experimental duration and compare these products to organic compounds found to be indigenous to ordinary chondrite meteorites. We hypothesize that the origin of organics in some chondritic meteorites, that represent an aggregation of materials from the early solar system, may at least in part be from FT synthesis that occurred in the early solar nebula.

Locke, Darren R.↗

Pyrolysis-GCMS Analysis of Solid Organic Products from Catalytic Fischer-Tropsch Synthesis Experiments

Abiotic synthesis of complex organic compounds in the early solar nebula that formed our solar system is hypothesized to occur via a Fischer-Tropsch type (FTT) synthesis involving the reaction of hydrogen and carbon monoxide gases over metal and metal oxide catalysts. In general, at low temperatures (less than 200 C), FTT synthesis is expected to form abundant alkane compounds while at higher temperatures (greater than 200 C) it is expected to product lesser amounts of n-alkanes and greater amounts of alkene, alcohol, and polycyclic aromatic hydrocarbons (PAHs). Experiments utilizing a closed-gas circulation system to study the effects of FTT reaction temperature, catalysts, and number of experimental cycles on the resulting solid insoluble organic products are being performed in the laboratory at NASA Goddard Space Flight Center. These experiments aim to determine whether or not FTT reactions on grain surfaces in the protosolar nebula could be the source of the insoluble organic matter observed in meteorites. The resulting solid organic products are being analyzed at NASA Johnson Space Center by pyrolysis gas chromatography mass spectrometry (PY-GCMS). PY-GCMS yields the types and distribution of organic compounds released from the insoluble organic matter generated from the FTT reactions. Previously, exploratory work utilizing PY-GCMS to characterize the deposited organic materials from these reactions has been reported. Presented here are new organic analyses using magnetite catalyst to produce solid insoluble organic FTT products with varying reaction temperatures and number of experimental cycles.

Locke, Darren R.↗

Aspects of Cool-Flame Supported Droplet Combustion in Microgravity

Droplet combustion experiments performed on board the International Space Station have shown that normal-alkane fuels with negative temperature coefficient (NTC) chemistry can support quasi-steady, low-temperature combustion without any visible flame. Here we review the results for n-decane, n-heptane, and n-octane droplets burning in carbon dioxidehelium diluted environments at different pressures and initial droplet sizes. Experimental results for cool-flame burning rates, flame standoff ratios, and extinction diameters are compared against simplified theoretical models of the phenomenon. A simplified quasi-steady model based on the partial-burning regime of Lin predicts the burning rate, and flame standoff ratio reasonably well for all three normal alkanes. The second-stage cool-flame burning and extinction following the first-stage hot-flame combustion, however, shows a small dependence on the initial droplet size, thus deviating from the quasi-steady results. An asymptotic model that estimates the oxygen depletion by the hot flame and its influence on cool-flame burning rates is shown to correct the quasi-steady results and provide a better comparison with the measured burning-rate results.This work was supported by the NASA Space Life and Physical Sciences Research and Applications Program and the International Space Station Program.

cool flames↗

Observations of VOC Emissions and Photochemical Products over US Oil- and Gas-Producing Regions Using High-Resolution H3O+ CIMS (PTR-ToF-MS)

VOCs (Volatile Organic Compounds) related to oil and gas extraction operations in the United States were measured by H3O (sup plus) chemical ionization time-of-flight mass spectrometry (H3O (sup plus) ToFCIMS/PTR-ToF-MS (Time of Flight Chemical Ionization Mass Spectrometry/Proton Transfer Reaction-Time of Flight-Mass Spectroscopy) from aircraft during the Shale Oil and Natural Gas Nexus (SONGNEX) campaign in March-April 2015. This work presents an overview of major VOC species measured in nine oil- and gas-producing regions, and a more detailed analysis of H3O (sup plus) ToF-CIMS measurements in the Permian Basin within Texas and New Mexico. Mass spectra are dominated by small photochemically produced oxygenates and compounds typically found in crude oil: aromatics, cyclic alkanes, and alkanes. Mixing ratios of aromatics were frequently as high as those measured downwind of large urban areas. In the Permian, the H3O (sup plus) ToF-CIMS measured a number of underexplored or previously unreported species, including aromatic and cycloalkane oxidation products, nitrogen heterocycles including pyrrole (C4H5N) and pyrroline (C4H7N), H2S, and a diamondoid (adamantane) or unusual monoterpene. We additionally assess the specificity of a number of ion masses resulting from H3O (sup plus) ion chemistry previously reported in the literature, including several new or alternate interpretations.

mass spectrometr↗

A Search for Butane in Titan’s Atmosphere using Cassini CIRS Infrared Spectra

The atmosphere of Saturn’s moon, Titan, is unlike any other. Photochemistry and ion chemistry in the upper atmosphere process the major atmospheric constituents, molecular nitrogen (N2) and methane (CH4), into larger and more complex molecules including hydrocarbons and nitriles. To date there are ten hydrocarbons heavier than methane that have been detected, including large quantities of the saturated hydrocarbons (alkanes) ethane (C2H6) and propane (C3H8). In addition to being significant trace gases of the atmosphere, these species condense, rain out and add to the volume of Titan’s hydrocarbon lakes and seas. The fourth lightest alkane, butane (C4H10),comes in two structural forms: an unbranched carbon chain (n-butane) and a branched chain (i-butane). The relative production rates of both these isomers are presently unknown, although the circumstantial case for butane to be present in detectable amounts is strong, based on photochemical models and from Cassini low-resolution mass spectrometry of the ionosphere. Butane, like its lighter siblings ethane and propane, is thought to be present in Titan’s lakes and seas where it may be active in forming molecular ‘co-crystals’ with acetylene (C2H2). We report on our recent attempts to detect both forms of butane in Titan’s atmosphere by analysis of Cassini infrared spectra collected during 2004-2017 by the Composite Infrared Spectrometer(CIRS) instrument. This multi-year effort has encompassed the collection of new laboratory spectra of both isomers at several institutions, followed by a concerted attempt to find their signatures in CIRS spectra. We search for butane by high precision modeling and removal of overlying emissions due to other, already-known gases to reveal signatures that match those of the butane isomers. The current status of the search will be discussed, including improved upper limits for both isomers, and directions of future research to detect both species.

Conor Nixon↗

Physics

Singlet-D atomic oxygen reaction with alkanes, Coulomb integral of continuum functions, and rigid motions in conformal space-time

ALKANE↗

The hydrocarbons of coorongite

Hydrocarbon content of coorongite derived from algae analyzed by IR spectrometry, gas chromatography and mass spectrometry, discussing alkanes and alkenes occurrence

Douglas, A. G.↗