Isoprenoids and other hydrocarbons in terrestrial graphite.
Aromatic and nonaromatic hydrocarbon fractions in terrestrial graphite, discussing classification and analysis by chromatography and mass spectrometry
Gelpi, E.↗
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Elemental abundances of lunar soil and rocks from Apollo 12
Apollo 12 lunar soil, breccia and igneous rock samples, determining elemental abundances with spark source mass spectrometry and neutron activation analysis
Burdo, R. A.↗
Trace geochemistry of lunar material
The lunar samples from the Apollo 16 and 17 flights which were analyzed include soil, igneous rock, anorthositic gabbro, orange soil, subfloor basalt, and norite breccia. Up to 57 elements including majors, minors, rare earths and other trace elements were determined in the lunar samples. The analytical techniques used were spark source mass spectrometry and neutron activation analysis. The latter was done either instrumentally or with group radiochemical separations. The differences in abundances of the elements in lunar soils at the various sites are discussed. With regard to the major elements only Si is about the same at all the sites. A detailed analysis which was performed on a sample of the Allende meteorite is summarized.
Morrison, G. H.↗
Applications of high pressure differential scanning calorimetry to aviation fuel thermal stability research
High pressure differential scanning calorimetry (DSC) was studied as an alternate method for performing high temperature fuel thermal stability research. The DSC was used to measure the heat of reaction versus temperature of a fuel sample heated at a programmed rate in an oxygen pressurized cell. Pure hydrocarbons and model fuels were studied using typical DSC operating conditions of 600 psig of oxygen and a temperature range from ambient to 500 C. The DSC oxidation onset temperature was determined and was used to rate the fuels on thermal stability. Kinetic rate constants were determined for the global initial oxidation reaction. Fuel deposit formation is measured, and the high temperature volatility of some tetralin deposits is studied by thermogravimetric analysis. Gas chromatography and mass spectrometry are used to study the chemical composition of some DSC stressed fuels.
Neveu, M. C.↗
The determination of the global average OH concentration using a deuteroethane tracer
It is proposed to measure the decreasing global concentration of an OH reactive isotopic tracer, G sub 2 D sub 6, after its introduction into the troposphere in a manner to facilitate uniform global mixing. Analyses at the level of 2 x 10 to the -19th power fraction, corresponding to one kg uniformly distributed globally, should be possible by a combination of cryogenic absorption techniques to separate ethane from air and high sensitivity isotopic analysis of ethane by mass spectrometry. Aliquots of C sub 2 D sub 6 totaling one kg would be introduced to numerous southern and northern latitudes over a 10 day period in order to achieve a uniform global concentration within 3 to 6 months by the normal atmospheric circulation. Then samples of air of 1000 l (STP) would be collected periodically at a tropical and temperate zone location in each hemisphere and spiked with a known amount of another isotopic species of ethane, C-13 sub 2 H sub 6, at the level of 10 to the -11th power mole fraction. After separation of the ethanes from air, the absolute concentration of C sub 2 D sub 6 would be analyzed using the Argonne 100-inch radius mass spectrometer.
Stevens, Charles M.↗
Stability of Materials in High Temperature Water Vapor: SOFC Applications
Solid oxide fuel cell material systems require long term stability in environments containing high-temperature water vapor. Many materials in fuel cell systems react with high-temperature water vapor to form volatile hydroxides which can degrade cell performance. In this paper, experimental methods to characterize these volatility reactions including the transpiration technique, thermogravimetric analysis, and high pressure mass spectrometry are reviewed. Experimentally determined data for chromia, silica, and alumina volatility are presented. In addition, data from the literature for the stability of other materials important in fuel cell systems are reviewed. Finally, methods for predicting material recession due to volatilization reactions are described.
Opila, E. J.↗
In Situ Carbon and Sulfur Isotope Analysis of Archean Organic Matter and Pyrite
Stable isotopic compositions of biologically important elements (e.g., C and S) in sedimentary rocks are valuable biosignatures to the extent that they indicate the presence and variable expression of microbial metabolisms in space and time. Strong interactions between the carbon and sulfur cycles (e.g., via organic matter remineralization during microbial sulfate reduction) make coordinated, in situ C and S isotope analysis by secondary ion mass spectrometry (SIMS) a particularly powerful tool. In rocks ranging in age from 2.7-2.5 Ga, expansions in the ranges of delta C-13 of organic matter and delta S-34 of pyrite likely reflect the increasing influence of oxygenic photosynthesis in the surface ocean (as well as methane and sulfur metabolisms in deeper waters), whereas the large range of mass independent sulfur isotope fractionation (Delta S-33) suggests that the atmosphere remained anoxic until approx 2.4 Gyr ago. We report in situ delta C-13 measurements of organic matter in the approx 2.7-2.6 Ga Carawine Dolomite, Marra Mamba Iron Formation, and Jeerinah, Wittenoom, and Tumbiana Formations, as well as the approx 2.5 Ga Mount McRae Shale. We also report in situ delta S-24 and Delta S-33 measurements of pyrite associated with organic matter in a subset of these samples. In a single square cm sample of the Tumbiana Formation with bulk delta C-13(sub org) of -49.7% (VPDB), two distinct kerogen types have delta C-13 values, measured in situ, consistent with oxygenic photosynthesis (-33%) and methane metabolism (-52%). In a sample from the ABDP-9 core, radiobitumen associated with a uraniferous mineral grain is C-13-enriched by 8% (-26.8%0) relative to average in situ kerogen (-34.9%0) and similar in delta C-13 to solvent extractable hydrocarbons from the Mount McRae Shale (avg delta C-13 = -27.1 %). Average reproducibility for delta C-13 was 0.4% (2 SD) using a 6 micron spot and 0.8% using a 3 micron spot. In situ sulfur isotope analyses of 33 authigenic pyrite grains in 3 samples of the ABDP-9 core using a 10 micron spot (2 SD reproducibility = 0.4% for delta S-34 and -0.1% for Delta S-33) show a range of 28.1 % in delta S-34 (-10.3 to 17.8%) and 13.3%0 in Delta S-33 (-3.8 to 9.5%), whereas the range from 132 bulk analyses across 84 m of core is 19.4% for delta S-34 and 11.5% for Delta S-33. Coordinated, in situ carbon and sulfur isotope analyses in one ABDP-9 sample are shown. In situ values from this kerogen-pyrite association are within 0.1% of the bulk value in the case of delta C-13 and higher by several permil in the case of delta S-34 and Delta S-33. Coordinated in situ carbon and sulfur isotope analyses in rocks deposited during key intervals of environmental change (e.g., the Great Oxidation Event) can refine our understanding of the mode and tempo of change. In Earth's oldest sedimentary rocks, and in extraterrestrial samples, these coordinated in situ analyses may reveal biosignatures in the form of isotopic correlations at the scale of individual microorganisms and their microhabitats.
Williford, K. H.↗
Organic Molecules in the Sheepbed Mudstone, Gale Crater, Mars
The Sample Analysis at Mars (SAM) instrument on the Curiosity rover is designed to determine the inventory of organic and inorganic volatiles thermally released from solid samples using a combination of evolved gas analysis (EGA), gas chromatography mass spectrometry (GCMS), and tunable laser spectroscopy. Here we report on various chlorinated hydrocarbons (chloromethanes, chlorobenzene and dichloroalkanes) detected at elevated levels above instrument background at the Cumberland (CB) drill site, and discuss their possible sources.
Freissinet, C.↗
Origin of Chlorobenzene Detected by the Curiosity Rover in Yellowknife Bay: Evidence for Martian Organics in the Sheepbed Mudstone
The Sample Analysis at Mars (SAM) instrument on the Curiosity rover is designed to determine the inventory of organic and inorganic volatiles thermally evolved from solid samples using a combination of evolved gas analysis (EGA), gas chromatography mass spectrometry (GCMS), and tunable laser spectroscopy. Here we discuss the SAM EGA and GCMS measurements of volatiles released from the Sheepbed mudstone. We focus primarily on the elevated CBZ detections at CB and laboratory analog experiments conducted to help determine if CBZ is derived from primarily terrestrial, martian, or a combination of sources. Here we discuss the SAM EGA and GCMS measurements of volatiles released from the Sheepbed mudstone. We focus primarily on the elevated CBZ detections at CB and laboratory analog experiments conducted to help determine if CBZ is derived from primarily terrestrial, martian, or a combination of sources.
Glavin, D.↗
Origin of Chlorobenzene Detected by the Curiosity Rover in Yellowknife Bay: Evidence for Martian Organics in the Sheepbed Mudstone?
The Sample Analysis at Mars (SAM) instrument on the Curiosity rover is designed to determine the inventory of organic and inorganic volatiles thermally evolved from solid samples using a combination of evolved gas analysis (EGA), gas chromatography mass spectrometry (GCMS), and tunable laser spectroscopy. The first solid samples analyzed by SAM, a scoop of windblown dust and sand at Rocknest (RN), revealed chlorinated hydrocarbons derived primarily from reactions between a martian oxychlorine phase (e.g. perchlorate) and terrestrial carbon from N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA) vapor present in the SAM instrument background. Chlorobenzene (CBZ) was also identified by SAM GCMS at RN at trace levels (approx.0.007 nmol) and was attributed to the reaction of chlorine with the Tenax polymers used in the hydrocarbon traps. After the RN analyses, Curiosity traveled to Yellowknife Bay and drilled two separate holes designated John Klein (JK) and Cumberland (CB). Analyses of JK and CB by both SAM and the CheMin x-ray diffraction instrument revealed a mudstone consisting of approx.20 wt% smectite clays, which on Earth are known to aid the concentration and preservation of organic matter. In addition, higher abundances and a more diverse suite of chlorinated hydrocarbons in CB compared to RN suggests that martian or meteoritic organic sources may be preserved in the mudstone. Here we discuss the SAM EGA and GCMS measurements of volatiles released from the Sheepbed mudstone. We focus primarily on the elevated CBZ detections at CB and laboratory analog experiments conducted to help determine if CBZ is derived from primarily terrestrial, martian, or a combination of sources.
origin of↗
Martian Chlorobenzene Identified by Curiosity in Yellowknife Bay: Evidence for the Preservation of Organics in a Mudstone on Mars
The Sample Analysis at Mars (SAM) instrument on the Curiosity rover is designed to determine the inventory of organic and inorganic volatiles thermally evolved from solid samples using a combination of evolved gas analysis (EGA), gas chromatography mass spectrometry (GCMS), and tunable laser spectroscopy. The first sample analyzed by SAM at the Rocknest (RN) aeolian deposit revealed chlorohydrocarbons derived primarily from reactions between a martian oxychlorine phase (e.g. perchlorate) and terrestrial carbon from N-methyl-N-(tert-butyldimethylsilyl) trifluoroacetamide (MTBSTFA) vapor present in the SAM instrument background. No conclusive evidence for martian chlorohydrocarbons in the RN sand was found. After RN, Curiosity traveled to Yellowknife Bay and drilled two holes separated by 2.75 m designated John Klein (JK) and Cumberland (CB). Analyses of JK and CB by both SAM and the CheMin x-ray diffraction instrument revealed a mudstone (called Sheepbed) consisting of approx.20 wt% smectite clays, which on Earth are known to aid the concentration and preservation of organic matter. Last year at LPSC we reported elevated abundances of chlorobenzene (CBZ) and a more diverse suite of chlorinated hydrocarbons including dichloroalkanes in CB compared to RN, suggesting that martian or meteoritic organic compounds may be preserved in the mudstone. Here we present SAM data from additional analyses of the CB sample and of Confidence Hills (CH), another drill sample collected at the base of Mt. Sharp. This new SAM data along with supporting laboratory analog experiments indicate that most of the chlorobenzene detected in CB is derived from martian organic matter preserved in the mudstone.
Glavin, D.↗
New Martian Meteorite Is One of the Most Oxidized Found to Date
As of 2013, about 60 meteorites from the planet Mars have been found and are being studied. Each time a new Martian meteorite is found, a wealth of new information comes forward about the red planet. The most abundant type of Martian meteorite is a shergottite; its lithologies are broadly similar to those of Earth basalts and gabbros; i.e., crustal igneous rocks. The entire suite of shergottites is characterized by a range of trace element, isotopic ratio, and oxygen fugacity values that mainly reflect compositional variations of the Martian mantle from which these magmas came. A newly found shergottite, NWA 5298, was the focus of a study performed by scientists within the Astromaterials Research and Exploration Science (ARES) Directorate at the Johnson Space Center (JSC) in 2012. This sample was found in Morocco in 2008. Major element analyses were performed in the electron microprobe (EMP) laboratory of ARES at JSC, while the trace elements were measured at the University of Houston by laser inductively coupled plasma mass spectrometry (ICPMS). A detailed analysis of this stone revealed that this meteorite is a crystallized magma that comes from the enriched end of the shergottite spectrum; i.e., trace element enriched and oxidized. Its oxidation comes in part from its mantle source and from oxidation during the magma ascent. It represents a pristine magma that did not mix with any other magma or see crystal accumulation or crustal contamination on its way up to the Martian surface. NWA 5298 is therefore a direct, albeit evolved, melt from the Martian mantle and, for its lithology (basaltic shergottite), it represents the oxidized end of the shergottite suite. It is thus a unique sample that has provided an end-member composition for Martian magmas.
Hui, Hejiu↗
Analysis of Mixed Aryl/Alkyl Esters by Pyrolysis Gas Chromatography-Mass Spectrometry in the Presence of Perchlorate
Mars is an important target for Astrobiology. A key goal of the MSL mission was to determine whether Mars was habitable in the past, a que-tion that has now been definitely determined to be yes. Another key goal for Mars exploration is to understand the origin and distribution of organic material on Mars; this question is being addressed by the SAM instrument on MSL, and will also be informed by two upcoming Mars exploration missions, ExoMars and Mars 2020. These latter two missions have instrumentation capable of detecting and characterize organic molecules. Over the next decade, these missions will analyze organics in surface, near-surface and sub-surface samples. Each mission has the capability to analyze organics by different methods (pyrolysis gas chromatography-mass spectrometry [py-GC-MS]; laser desorption and thermal volatilization GC-MS; and Raman spectroscopy). Plausibly extraterrestrial organics were recently discovered by the Mars Science Laboratory (MSL), providing an important first step towards understanding the organic inventory on Mars [1]. The compounds detected were chlorobenzenes and chloroalkanes, but it was argued that chlorination of these compounds occurred during pyrolysis of samples containing unchlorinated organics in the presence of perchlorate. A recent report analyzed a suite of aromatic (benzene, toluene, benzoic acid, phthalic acid, and mellitic acid) and aliphatic (acetic acid, propane, propanol, and hexane) by pyrolysis under SAM-like conditions in the presence of perchlorate to attempt to constrain possible precursor molecules for the organic molecules detected on Mars. For aromatic compounds, the aromatic acids all readily produced SAM-relevant chlorobenzes, whereas benzene and toluene did not. This observation suggests that the chlorobenzene detected on Mars could have derived from compounds like mellitic acid, consistent with the previous hypothesis by Benner et al. [3]. Among the aliphatic molecules, it was shown that pyrolysis of alkanes and alcohols in the presence of perchlorates produced polychlorine containing chloro-alkanes similar to what was observed on Mars. Surpris-ingly, however, similar treatment of acetic acid pro-duced chloroketones, instead, and no chloroalkanes were reported. This suggests that the chloroalkanes detected in the Sheepbed mudstone were not derived from aliphatic carboxylic acids, but instead were from more reduced alcohols or even alkanes, or perhaps were degradation products of more complicated organic material. Because organics analyses on mars will rely heavily on py-GC-MS of perchlorate-containing samples over the next decade, it is important to understand the fate of organic molecules of biotic and abiotic origin under such conditions. In this work we begin a series of experiments to improve our understanding of products generated during py-GC-MS of increasingly complex organic molecules (esters, amides, peptides, nucleic acids, fatty acids) in the presence of perchlorate.
Burton, A. S.↗
Amino Acid Abundances and Compositions in Iron and Stony-Iron Meteorites
The organic compositions of carbonaceous chondrite meteorites have been extensively studied; however, there have been fewer reports of other meteorite classes, and almost none from iron meteorites, which contain much less carbon than carbonaceous chondrites but make up ~4% of observed meteorite falls. Here, we report the bulk amino acid content of three iron meteorites (Campo del Cielo, IAB; Canyon Diablo, IAB; and Cape York, IIIAB) and both the metal and silicate portions of a pallasite (Imilac). We developed a novel method to prepare the samples for analysis, followed by hot water extraction and analysis via liquid chromatography‐mass spectrometry. Free amino acid abundances ranging from 301 to 1216 pmol/g were observed in the meteorites, with the highest abundance in the silicate portion of the pallasite. Although some of the amino acid content could be attributed to terrestrial contamination, evidence suggests that some compounds are indigenous. A suite of C(5) amino acids was observed with a distinct distribution favoring a straight chain (n‐pentanoic acid) structure; this straight chain dominance is suggestive of that observed in thermally altered stony meteorites. Amino acids were also observed in terrestrial iron granules that were milled and analyzed in the same way as the meteorites, although the distribution of detected amino acids was different. It is possible that similar formation mechanisms existed in both the meteorites and the terrestrial iron, or that observed amino acids resulted from reactions of precursors during sample preparation. This work suggests that iron meteorites should not be overlooked for contributions of amino acids and likely other soluble organic molecules to the early Earth. Future studies of iron–nickel meteorites and asteroids, such as Psyche, may provide further insights into their potential organic inventory.
Jamie E. Elsila↗
A Compact Two-Step Laser Time-Of-Flight Mass Spectrometer for In Situ Analysis of Planetary Surfaces
Two-step laser mass spectrometry (L2MS) has proved to be a powerful tool for the analysis of aromatic organics in icy planetary simulants, meteorites, asphaltenes on Earth, and returned cometary particles from the Stardust mission. L2MS employs two lasers to separate the desorption and ionization processes of laser desorption ionization into distinct steps. In the first step, an infrared laser desorbs neutrals from a solid sample surface; in the second step, an ultraviolet laser forms molecular ions within the neutral plume through a resonance-enhanced process to minimize fragment at ion of complex species. We have recently demonstrated that the L2MS technique is compatible with a compact TOF-MS that could form the center piece of a future in situ landed planetary mission emphasizing surface chemistry or astrobiology. The increased sensitivity and selectivity offered by this technique has been demonstrated in analyses of various planetary analog mixtures and meteorite powders, and representative results of these analyses will be presented.
Getty, Stephanie A.↗
Mass spectrometry without ions.
Molecular flow mass spectrometer analysis of porous metal membranes for gases of different molecular weights
POROUS MATERIAL↗
A Compact Tandem Two-Step Laser Time-of-Flight Mass Spectrometer for In Situ Analysis of Non-Volatile Organics on Planetary Surfaces
Two-step laser desorption mass spectrometry is a well suited technique to the analysis of high priority classes of organics, such as polycyclic aromatic hydrocarbons, present in complex samples. The use of decoupled desorption and ionization laser pulses allows for sensitive and selective detection of structurally intact organic species. We have recently demonstrated the implementation of this advancement in laser mass spectrometry in a compact, flight-compatible instrument that could feasibly be the centerpiece of an analytical science payload as part of a future spaceflight mission to a small body or icy moon.
time-of-flight↗
Discovery and Identification of Dimethylsilanediol as a Contaminant in ISS Potable Water
In September of 2010, analysis of ISS potable water samples was undertaken to determine the contaminant responsible for a rise in total organic carbon (TOC). As analysis of the routine target list of organic compounds did not reveal the contaminant, efforts to look for unknown compounds was initiated, resulting in an unknown peak being discovered in the gas chromatography/mass spectrometry (GC/MS) analysis for glycols. A mass spectrum of the contaminant was then generated by concentrating one of the samples by evaporation and analyzing by GC/MS in full-scan mode. Although a computer match of the compound s identity could not be obtained with the instrument s database, a search with a more up to date mass spectral library yielded a good match with dimethylsilanediol (DMSD). Inductively Coupled Plasma/Mass Spectrometry (ICP/MS) analyses showed abnormally high silicon levels in the samples, confirming that the unknown contained silicon. DMSD was then synthesized to confirm the identification and provide a standard to develop a calibration curve. Further confirmation was provided by external Direct Analysis in Real Time (DART) GC/MS analysis. A preliminary GC/MS method was then developed and archived samples from various locations on ISS were analyzed to determine the extent of the contamination and provide data for troubleshooting. This paper describes these events in more detail as well as problems encountered in routine GC/MS analyses and the subsequent development of high performance liquid chromatography and LC/MS/MS methods for quantitation of DMSD.
Rutz, Jeffrey A.↗