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At least 397 records · Page 22

Influence of Oxygenated Compounds on Reaction Products in a Microwave Plasma Methane Pyrolysis Assembly for Post-Processing of Sabatier Methane

The state-of-the-art Carbon Dioxide Reduction Assembly (CRA) was delivered to the International Space Station (ISS) in April 2010. The system is designed to accept carbon dioxide from the Carbon Dioxide Removal Assembly and hydrogen from the Oxygen Generation Assembly. The two gases are reacted in the CRA in a Sabatier reactor to produce water and methane. Venting of methane results in an oxygen resupply requirement of about 378 lbs per crew member per year. If the oxygen is supplied as water, the total weight for resupply is about 476 lb per crew member per year. For long-term missions beyond low Earth orbit, during which resupply capabilities will be further limited, recovery of hydrogen from methane is highly desirable. For this purpose, NASA is pursuing development of a Plasma Pyrolysis Assembly (PPA) capable of recovering hydrogen from methane. Under certain conditions, water vapor and carbon dioxide (nominally intended to be separated from the CRA outlet stream) may be present in the PPA feed stream. Thus, testing was conducted in 2010 to determine the effect of these "oxygenated" compounds on PPA performance, particularly the effect of inlet carbon dioxide and water variations on the PPA product stream. This paper discusses the test set-up, analysis, and results of this testing

Mansell, J. Matthew↗

Influence of Oxygenated Compounds on Reaction Products in a Microwave Plasma Methane Pyrolysis Assembly for Post-Processing of Sabatier Methane

The state-of-the-art Carbon Dioxide Reduction Assembly (CRA) was delivered to the International Space Station (ISS) in April 2010. The system is designed to accept carbon dioxide from the Carbon Dioxide Removal Assembly and hydrogen from the Oxygen Generation Assembly. The two gases are reacted in the CRA in a Sabatier reactor to produce water and methane. Venting of methane results in an oxygen resupply requirement of about 378 lbs per crew member per year. If the oxygen is supplied as water, the total weight for resupply is about 476 lb per crew member per year. For long-term missions beyond low Earth orbit, during which resupply capabilities will be further limited, recovery of hydrogen from methane is highly desirable. For this purpose, NASA is pursuing development of a Plasma Pyrolysis Assembly (PPA) capable of recovering hydrogen from methane. Under certain conditions, water vapor and carbon dioxide (nominally intended to be separated from the CRA outlet stream) may be present in the PPA feed stream. Thus, testing was conducted in 2010 to determine the effect of these oxygenated compounds on PPA performance, particularly the effect of inlet carbon dioxide and water variations on the PPA product stream. This paper discusses the test set-up, analysis, and results of this testing.

Mansell, J. Matthew↗

Assessing Organic Preservation and the Implications for Potential Biosignatures in the Bastide Member of the Séítah Formation, Jezero Crater

Introduction: Olivine has the highest CO2 trapping potential of ultramafic minerals, due to its rapid rate of dissolution and high percentage of divalent cations/unpolymerized silicate tetrahedra [1]. It generates divalent carbonates from CO2 and sequesters CO2 into the mineral matrix of the target lithology. The co-occurrence of olivine and carbonate within abraded targets from the Bastide Member of the Séítah Formation (Fm) of the Jezero crater floor [2] suggests the carbonation of olivine occurred within the mineral matrix hosted in a subsurface system. Hydrothermal origins for the subsurface system are hypothesized from orbital data [3]. This is supported by the detection of hydration features within the rock as well as the carbonate features are solely detected within the abrasion patch but not the rock’s surface. Organic preservation potential of abrasion patches: We incorporated the SHERLOC/WATSON results acquired from the Dourbes, Garde, and Quartier abrasion patches in the Séítah Fm to investigate the organomineral associations, and determine the biosignature preservation potential of these rocks. Dourbes is dominated by olivine and has minor amounts of carbonate, hydrated Ca-sulfate, and amorphous or microcrystalline silicate. Fluorescence features (330-340 nm) are detected in discrete locales and could be consistent with double ring aromatic organic molecules; yet, these features do not appear to be associated with an identified mineral phase. Dark subhedral to euhedral olivine grains within the Garde abrasion patch often co-occur with carbonate-consistent spectral signatures in all analyzed scans. The availability of Fe2+ is a known influence on olivine dissolution rates [1] and SuperCam estimates of the olivine composition (Forsterite-60 average for Sols 202-234) may thereby provide a constraint on the carbonation extent. Carbonated olivine phenocrysts within the matrix may be due to aqueous alteration, as the carbonation of nodules is consistent with observations in other hydrothermal systems and within Martian meteorites (ALH84001) [4]. In comparison, the Quartier abrasion patch represents an extensively altered endmember within the Bastide Member of the Séítah Fm. It contains a fluorescence doublet at 305/325 nm that coexists with multiple species of Na-sulfate and Mg-sulfate, Mg-carbonates, olivine [5]. Aqueous alteration and implications for habitability: The identification of primary and secondary mineral phases observed in the Bastide Member suggests the release of cations from primary ultramafic minerals through aqueous alteration. Within Garde, the carbonate detected appears to be Mg-rich and likely formed from the in situ alteration of Mg-rich olivine within the region as carbonate has only been detected within the rock via in situ analysis. Carbonates derived from abiotic and biotic reactions preserve biosignatures (i.e. indices of habitability) on Earth. The detected carbonate phase found in association with fluorescent features within the rock matrix may also indicate potential organic compounds preserved in a putative hydrothermal system. Fluorescent features (~330 nm) are unique to Garde and Dourbes, though they are co-located to carbonate signatures solely within Garde, and between the light toned minerals. Identification of these fluorescent features may be consistent with 1-2 ring aromatic compounds. The limit of detection for Raman is multiple orders of magnitude greater than the limit of detection required for fluorescence [6]. Implications for provenance: Hydrothermal systems represent disequilibrium chemical conditions that are hypothesized to have supported the emergence of life and also preserve ancient carbon within precipitated carbonates [7]. Hydrothermal system associated carbonates are capable of preserving biosignatures up to an estimated ~3.77 – 4.28 Gya [8]. Thus, carbonated olivine found within the Séítah Fm may represent a high-potential biosignature preserving environment on Mars. The formation of carbonates by an aqueous alteration process, such as carbonation of olivine is also consistent with hypotheses for carbonate within the greater regional-olivine bearing unit [2,3], which contains Garde, Dourbes, and Quartier. Acknowledgments: This work was carried out at the Jet Propulsion Laboratory, The California Institute of Technology under a contract from NASA. References: [1] Wood et al., (2019) ES&T, 6, 10. [2] Stack, K. et al., (2020) Space Sci Rev, 216, 127. [3] Tarnas, J. et al., (2021) JGR: Planets, 126, 11. [4] Steele et al., (2007) Meteorit. Planet. Sci., 42, 9. [5] Murphy, A.E. et al., (2022) LPSC [6] Bhartia et al., (2021) Space Sci Rev, 217, 58. [7] Luther (2021) GRL, 48, e2021GL094869. [8] Dodd et al., (2017) Nature, 543, 60-64

E L Cardarelli↗

Lipid synthesis under hydrothermal conditions by Fischer-Tropsch-type reactions

Ever since their discovery in the late 1970's, mid-ocean-ridge hydrothermal systems have received a great deal of attention as a possible site for the origin of life on Earth (and environments analogous to mid-ocean-ridge hydrothermal systems are postulated to have been sites where life could have originated or Mars and elsewhere as well). Because no modern-day terrestrial hydrothermal systems are free from the influence of organic compounds derived from biologic processes, laboratory experiments provide the best opportunity for confirmation of the potential for organic synthesis in hydrothermal systems. Here we report on the formation of lipid compounds during Fischer-Tropsch-type synthesis from aqueous solutions of formic acid or oxalic acid. Optimum synthesis occurs in stainless steel vessels by heating at 175 degrees C for 2-3 days and produces lipid compounds ranging from C2 to > C35 which consist of n-alkanols, n-alkanoic acids, n-alkenes, n-alkanes and alkanones. The precursor carbon sources used are either formic acid or oxalic acid, which disproportionate to H2, CO2 and probably CO. Both carbon sources yield the same lipid classes with essentially the same ranges of compounds. The synthesis reactions were confirmed by using 13C labeled precursor acids.

Non-NASA Center↗

Lightweight Ceramic Insulation

Fiber burnout process yields low densities. Low density attained by process of sacrificial burnout. Graphite or carbon fibers mixed into slurry of silica, alumina, and boron-compound fibers in amounts ranging from 25 to 75 percent of total fiber content by weight. Mixture formed into blocks and dried. Blocks placed in kiln and heated to 1,600 degrees F(870 degrees C) for several hours. Graphite or carbon fibers slowly oxidize away, leaving voids and reducing block density. Finally, blocks heated to 2,350 degrees F (1,290 degrees C) for 90 minutes to bond remaining ceramic fibers together. Developed for use on Space Shuttle and other spacecraft, rigid insulation machined to requisite shape and bonded in place.

Wheeler, W. H.↗

Sabatier Catalyst Poisoning Investigation

The Carbon Dioxide Reduction Assembly (CRA) on the International Space Station (ISS) has been operational since 2010. The CRA uses a Sabatier reactor to produce water and methane by reaction of the metabolic CO2 scrubbed from the cabin air and the hydrogen byproduct from the water electrolysis system used for metabolic oxygen generation. Incorporating the CRA into the overall air revitalization system has facilitated life support system loop closure on the ISS reducing resupply logistics and thereby enhancing longer term missions. The CRA utilizes CO2 which has been adsorbed in a 5A molecular sieve within the Carbon Dioxide Removal Assembly, CDRA. There is a potential of compounds with molecular dimensions similar to, or less than CO2 to also be adsorbed. In this fashion trace contaminants may be concentrated within the CDRA and subsequently desorbed with the CO2 to the CRA. Currently, there is no provision to remove contaminants prior to entering the Sabatier catalyst bed. The risk associated with this is potential catalyst degradation due to trace organic contaminants in the CRA carbon dioxide feed acting as catalyst poisons. To better understand this risk, United Technologies Aerospace System (UTAS) has teamed with MSFC to investigate the impact of various trace contaminants on the CRA catalyst performance at relative ISS cabin air concentrations and at about 200/400 times of ISS concentrations, representative of the potential concentrating effect of the CDRA molecular sieve. This paper summarizes our initial assessment results.

Nallette, Tim↗

Chirality of Meteoritic Free and IOM-Derived Monocarboxylic Acids and Implications for Prebiotic Organic Synthesis

The origin of homochirality and its role in the development of life on Earth are among the most intriguing questions in science. It has been suggested that carbonaceous chondrites seeded primitive Earth with the initial organic compounds necessary for the origin of life. One of the strongest pieces of evidence supporting this theory is that certain amino acids in carbonaceous chondrites display a significant L-enantiomeric excess (ee), similar to those use by terrestrial life. Analyses of ee in meteoritic molecules other than amino acids would shed more light on the origins of homochirality. In this study we investigated the stereochemistry of two groups of compounds: (1) free monocarboxylic acids (MCAs) from CM2 meteorites LON 94101 and Murchison; and (2) the aliphatic side chains present in the insoluble organic matter (IOM) and extracted in the form of monocarboxylic acids (MCAs) from EET 87770 (CR2) and Orgueil (CI1). Contrary to the well-known ee observed for amino acids in meteorites, we found that meteoritic branched free and IOM-derived MCAs with 5-8 carbon atoms are essentially racemic. The racemic nature of these compounds is used to discuss the possible influence of ultraviolet circularly polarized light (UVCPL) and aqueous alterations on the parent body on chirality observed in in carbonaceous chondrites. 2014 Elsevier Ltd. All rights reserved.

monocarboxylic acids↗

The carbon chemistry of meteorites: Relationships to comets

The carbonaceous meteorites exhibiting alteration by liquid water bear a strong relationship to comets. Not only is their elemental composition closer to solar in relative abundances than other meteorites, they are water rich; and they contain isotopic compositions among refractory and volatile elements indicative of presolar components. Some of these isotopic anomalies occur in organic compounds and carbonaceous grains signifying the presence of discrete and identifiable carbon components derived from interstellar and circumstellar matter. Insofar as comets and meteorites are ultimately formed from interstellar gas and dust, and comets have been subjected to considerably less aqueous and thermal evolution than carbonaceous meteorites, the interstellar imprint should be much stronger and better preserved in comets.

Chang, S.↗

Multisorbent tubes for collecting volatile organic compounds in spacecraft air

The sampling capability of Tenax-TA tubes, used in the National Aeronautics and Space Administration's solid sorbent air sampler to trap and concentrate contaminants from air aboard spacecraft, was improved by incorporating two sorbents within the tubes. Existing tubes containing only Tenax-TA allowed highly volatile compounds to "break through" during collection of a 1.5 L air sample. First the carbon molecular sieve-type sorbents Carboxen 569 and Carbosieve S-III were tested for their ability to quantitatively trap the highly volatile compounds. Breakthrough volumes were determined with the direct method, whereby low ppm levels of methanol or Freon 12 in nitrogen were flowed through the sorbent tubes at 30 mL/min, and breakthrough was detected by gas chromatography. Breakthrough volumes for methanol were about 9 L/g on Carboxen 569 and 11 L/g on Carbosieve S-III; breakthrough volumes for Freon 12 were about 7 L/g on Carboxen 569 and > 26 L/g on Carbosieve S-III. Next, dual-bed tubes containing either Tenax-TA/Carbosieve S-III, Tenax-TA/Carboxen 569, or Carbotrap/Carboxen 569 to a 10-component gas mixture were exposed, in dry and in humidified air (50% relative humidity), and percentage recoveries of each compound were determined. The Tenax-TA/Carboxen 569 combination gave the best overall recoveries (75-114% for the 10 compounds). Acetaldehyde had the lowest recovery (75%) of the 10 compounds, but this value was still an improvement over either the other two sorbent combinations or the original single-sorbent tubes.

NASA Center JSC↗

Organic Biomarker-Based Assays to Evaluate Total Bioburden and Organic Compounds on Space Flight Hardware

Meeting planetary protection (PP) requirements for space flight hardware may involve bioburden reduction by dry heat microbial reduction (DHMR). The NASA standard assay to demonstrate the reduction of organisms involves the swabbing of surfaces, heat shock of the extracted samples, plating of the samples on Trypticase Soy Agar (TSA), and counting colony forming units after an incubation period. The standard assay uses enumeration of heat tolerant spore-formers as a proxy for total bioburden and is generally expected to provide a lower limit. We suggest that a better estimate of the total bioburden could be obtained through sampling and analysis of organic biomarkers. As biological organisms are fundamentally organic in chemistry (i.e. carbon containing materials) it is important to characterize the biomarker compounds that are released from organisms that 1) exist on flight hardware before microbial reduction and 2) left behind from the killed organisms following microbial reduction.

Locke, Darren R.↗

C-13 N.M.R. study of charge transfer in alkali metal-ammonia graphite compounds

The usefulness of C-13 NMR spectroscopy and chemical shift for the study of charge transfer in graphite intercalation compounds is demonstrated. A linear relationship is established between the chemical shifts and the square root of the absolute value of the electronic charge per carbon atom. The method is applied to the ternary alkali metal-ammonia-graphite compounds. Weak solvations of electronic charges by ammonia are observed.

Tsang, T.↗

Development of a Contingency Gas Analyzer for the Orion Crew Exploration Vehicle

NASA's experience with electrochemical sensors in a hand-held toxic gas monitor serves as a basis for the development of a fixed on-board instrument, the Contingency Gas Analyzer (CGA), for monitoring selected toxic combustion products as well as oxygen and carbon dioxide on the Orion Crew Exploration Vehicle (CEV). Oxygen and carbon dioxide are major components of the cabin environment and accurate measurement of these compounds is critical to maintaining a safe working environment for the crew. Fire or thermal degradation events may produce harmful levels of toxic products, including carbon monoxide (CO), hydrogen cyanide (HCN), and hydrogen chloride (HCl) in the environment. These three components, besides being toxic in their own right, can serve as surrogates for a panoply of hazardous combustion products. On orbit monitoring of these surrogates provides for crew health and safety by indicating the presence of toxic combustion products in the environment before, during and after combustion or thermal degradation events. Issues identified in previous NASA experiences mandate hardening the instrument and components to endure the mechanical and operational stresses of the CEV environment while maintaining high analytical fidelity. Specific functional challenges involve protecting the sensors from various anticipated events- such as rapid pressure changes, low cabin pressures, and extreme vibration/shock exposures- and extending the sensor lifetime and calibration periods far beyond the current state of the art to avoid the need for on-orbit calibration. This paper focuses on lessons learned from the earlier NASA hardware, current testing results, and engineering solutions to the identified problems. Of particular focus will be the means for protecting the sensors, addressing well known cross-sensitivity issues and the efficacy of a novel self monitoring mechanism for extending sensor calibration periods.

Niu, Bill↗

Development and testing of dry chemicals in advanced extinguishing systems for jet engine nacelle fires

The effectiveness of dry chemical in extinguishing and delaying reignition of fires resulting from hydrocarbon fuel leaking onto heated surfaces such as can occur in jet engine nacelles is studied. The commercial fire extinguishant dry chemical tried are sodium and potassium bicarbonate, carbonate, chloride, carbamate (Monnex), metal halogen, and metal hydroxycarbonate compounds. Synthetic and preparative procedures for new materials developed, a new concept of fire control by dry chemical agents, descriptions of experiment assemblages to test dry chemical fire extinguishant efficiencies in controlling fuel fires initiated by hot surfaces, comparative testing data for more than 25 chemical systems in a 'static' assemblage with no air flow across the heated surface, and similar comparative data for more than ten compounds in a dynamic system with air flows up to 350 ft/sec are presented.

Altman, R. L.↗

Conditions of the Martian atmosphere and surface in the remote past and their relevance to the question of life on Mars

Although the Viking Landers failed to find any evidence of life on the surface of Mars, much remains unknown. Study of returned samples can answer some of these questions. The search for organic compounds, the building blocks of life forms based on carbon chemistry, should continue. The question of life on Mars is still an open one, and deserves to be addressed by the study of returned samples. Whether life developed and evolved on Mars or not depends critically on the history of the Martian atmosphere and hydrosphere. The exobiology of Mars is thus inextrically intertwined with the nature of its paleoatmosphere and the ancient state of the planet's regolith, which may still be preserved in the polar caps and underground. Core samples from such sites could answer some of the questions.

Pang, Kevin D.↗

A Combustion Products Analyzer for contingency use during thermodegradation events on spacecraft

This paper will describe the Combustion Products Analyzer (CPA), which is being developed under the direction of the Toxicology Laboratory at Johnson Space Center to provide necessary data on air quality in the Shuttle following a thermodegradation incident. Using separate electrochemical sensors, the CPA monitors four gases (hydrogen fluoride/carbonyl fluoride, hydrogen chloride, hydrogen cyanide, and carbon monoxide), which were selected as the most hazardous compounds likely to be released during thermodegradation of synthetic materials. Electrochemical sensors have been available for several years; the CPA sensors, which are unique because of their small size and zero-gravity compatibility, will be described in detail.

Limero, Thomas↗

Comets and the origins and evolution of life; Proceedings of the Conference, Univ. of Wisconsin, Eau Claire, Sept. 30-Oct. 2, 1991

Papers are presented on comets and the formation of biochemical compounds on the primitive earth; the cometary origin of carbon, nitrogen, and water on the earth; comets as a possible source of prebiotic molecules; comet impacts and chemical evolution on the bombarded earth; and cometary supply of terrestrial organics (lessons from the K/T and the present epoch). Other papers are on a computational study of radiation chemical processing in comet nuclei, the origin of the polycyclic aromatic hydrocarbons in meteorites, the fate of organic matter during planetary accretion (preliminary studies of the organic chemistry of experimentally shocked Murchison meteorite), recent observations of interstellar molecules (detection of CCO and a limit on H2C3O), terrestrial and extraterrestrial sources of molecular monochirality, and dark matter in the solar system (hydrogen cyanide polymers).

Thomas, Paul J.↗

A Quantitative NMR Analysis of Phosphorus in Carbonaceous and Ordinary Chondrites

Phosphorus is important in a number of biochemical molecules, from DNA to ATP. Early life may have depended on meteorites as a primary source of phosphorus as simple dissolution of crustal apatite may not produce the necessary concentration of phosphate. Phosphorus is found in several mineral phases in meteorites. Apatite and other Ca- and Mg phosphate minerals tend to be the dominant phosphorus reservoir in stony meteorites, whereas in more iron-rich or reduced meteorites, the phosphide minerals schreibersite, (Fe, Ni)3P, and perryite, (Ni, Fe)5(Si, P)2 are dominant. However, in CM chondrites that have experienced significant aqueous alteration, phosphorus has been detected in more exotic molecules. A series of phosphonic acids including methyl-, ethyl-, propyl- and butyl- phosphonic acids were observed by GC-MS in Murchison. Phosphorian sulfides are in Murchison and Murray. NMR spectrometry is capable of detecting multiple substances with one experiment, is non-destructive, and potentially quantitative, as discussed below. Despite these advantages, NMR spectrometry is infrequently applied to meteoritic studies due in large part to a lack of applicability to many compounds and the relatively high limit of detection requirements. Carbon-13 solid-state NMR has been applied to macromolecular carbon in Murchison. P-31 NMR has many advantages over aqueous carbon-13 NMR spectrometry. P-31 is the only isotope of phosphorus, and P-31 gives a signal approximately twice as strong as C-13. These two factors together with the relative abundances of carbon and phosphorus imply that phosphorus should give a signal approximately 20 as strong as carbon in a given sample. A discussion on the preparation of the quantitative standard and NMR studies are presented

Pasek, M. A.↗

The role of biomineralization in microbiologically influenced corrosion

Synthetic iron oxides (goethite, alpha-FeO.OH; hematite, Fe2O3; and ferrihydrite, Fe(OH)3) were used as model compounds to simulate the mineralogy of surface films on carbon steel. Dissolution of these oxides exposed to pure cultures of the metal-reducing bacterium, Shewanella putrefaciens, was followed by direct atomic absorption spectroscopy measurement of ferrous iron coupled with microscopic analyses using confocal laser scanning and environmental scanning electron microscopies. During an 8-day exposure the organism colonized mineral surfaces and reduced solid ferric oxides to soluble ferrous ions. Elemental composition, as monitored by energy dispersive x-ray spectroscopy, indicated mineral replacement reactions with both ferrihydrite and goethite as iron reduction occurred. When carbon steel electrodes were exposed to S. putrefaciens, microbiologically influenced corrosion was demonstrated electrochemically and microscopically.

Non-programmatic↗