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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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NASA NTRS2009

Carbon Isotopic Ratios of Amino Acids in Stardust-Returned Samples

NASA's Stardust spacecraft returned to Earth samples from comet 81P/Wild 2 in January 2006. Preliminary examinations revealed the presence of a suite of organic compounds including several amines and amino acids, but the origin of these compounds could not be identified. Here. we present the carbon isotopic ratios of glycine and E-aminocaproic acid (EACH), the two most abundant amino acids observed, in Stardust-returned foil samples measured by gas chromatography-combustion-isotope ratio crass spectrometry coupled with quadrupole mass spectrometry (GC-QMS/IRMS).

Elsila, Jamie E.↗
NASA NTRS2009

The Formation and Stability of Carbonic Acid on Outer Solar System Bodies

The radiation chemistry, thermal stability, and vapor pressure of solid-phase carbonic acid (H2CO3) have been studied with mid-infrared spectroscopy. A new procedure for measuring this molecule's radiation stability has been used to obtain intrinsic IR band strengths and half-lives for radiolytic destruction. Results are compared to literature values. We report, for the first time, measurements of carbonic acid's vapor pressure and its heat of sublimation. We also report the first observation of a chemical reaction involving solid-phase carbonic acid. Possible applications of these findings are discussed, with an emphasis on the outer Solar System.

Peeters, Z.↗
NASA NTRS2009

On the Search for the Amino Acids on the Lunar Surface as it Relates to Other Extraterrestrial Bodies

The early search for the amino acids on the lunar surface fines indicated such a low amount of the amino acids that it was deemed insignifi cant. While the later studies seemed to depart in some ways from the earlier results, they were not pursued. In this paper we critically ev aluate the results from the Apollo missions from the new perspective with considerations of the sensitivity of the instrumentation availabl e at the time. We discuss the possible relevance of the lunar results to the findings of the amino acids on the surfaces of other extraterrestrial bodies, such as Mars.

Hoover, Richard B.↗
NASA NTRS2009

Cometary Amino Acids from the STARDUST Mission

NASA's Stardust spacecraft returned samples from comet 81 P/WiId 2 to Earth in January 2006. Examinations of the organic compounds in cometary samples can reveal information about the prebiotic organic inventory present on the early Earth and within the early Solar System, which may have contributed to the origin of life. Preliminary studies of Stardust material revealed the presence of a suite of organic compounds including several amines and amino acids, but the origin of these compounds (cometary vs. terrestrial contamination) could not be identified. We have recently measured the carbon isotopic ratios of these amino acids to determine their origin, leading to the first detection of a cometary amino acid.

Cook, Jamie Elsila↗
NASA NTRS2009

Amino Acids from a Comet

NASA's Stardust spacecraft returned samples from comet 81P/Wild 2 to Earth in January 2006. Examinations of the organic compounds in cometary samples can reveal information about the prebiotic organic inventory present on the early Earth and within the early Solar System, which may have contributed to the origin of life. Preliminary studies of Stardust material revealed the presence of a suite of organic compounds including several amines and amino acids, but the origin of these compounds (cometary- vs. terrestrial contamination) could not be identified. We have recently measured the carbon isotopic ratios of these amino acids to determine their origin, leading to the first detection of a coetary amino acid.

Cook, Jamie Elisla↗
NASA NTRS2010

Ion Irradiation of Sulfuric Acid: Implications for its Stability on Europa

The Galileo near-infrared mapping spectrometer (NIMS) detected regions on Europa's surface containing distorted H2O bands. This distortion likely indicates that there are other molecules mixed with the water ice. Based on spectral comparison, some of the leading possibilities are sulfuric acid, salts. or possibly H3O(+). Previous laboratory studies have shown that sulfuric acid can be created by irradiation of H2OSO2 mixtures, and both molecules are present on Europa. In this project, we were interested in investigating the radiation stability of sulfuric acid (H2SO4) and determining its lifetime on the surface of Europa.

Loeffler, M. J.↗
NASA NTRS2011

Experimental Acid Weathering of Fe-Bearing Mars Analog Minerals and Rocks: Implications for Aqueous Origin of Hematite-Bearing Sediments in Meridiani Planum, Mars

A working hypothesis for Meridiani evaporite formation involves the evaporation of fluids derived from acid weathering of Martian basalts and subsequent diagenesis [1, 2]. However, there are no reported experimental studies for the formation of jarosite and gray hematite (spherules), which are characteristic of Meridiani rocks from Mars analog precursor minerals. A terrestrial analog for hematite spherule formation from basaltic rocks under acidic hydrothermal conditions has been reported [3], and we have previously shown that the hematite spherules and jarosite can be synthetically produced in the laboratory using Fe3+ -bearing sulfate brines under hydrothermal conditions [4]. Here we expand and extend these studies by reacting Mars analog minerals with sulfuric acid to form Meridiani-like rock-mineral compositions. The objective of this study is to provide environmental constraints on past aqueous weathering of basaltic materials on Mars.

Golden, D. C.↗
NASA NTRS2009

Investigation of Isovaline Enantiomeric Excesses and Other C5 Amino Acids in Carbonaceous Meteorites

The origin of biological homochirality is one of the most perplexing puzzles to understanding the emergence of life on Earth. While many models have been proposed, the only reported non-biologically generated. compounds that show a significant enantiomeric excess are a few amino acids in the CM2 Murchison and Murray meteorites (e.g. Pizzarello and Cronin 2000; Pizzarello et al, 2008). Of these isovaline (alpha-ethyl-alanine) is of particular interest since it is typically abundant in CM2 meteorites, is exceedingly rare in biology, and due to its chemical structure is likely to maintain its primordial D/L ratio. Instead of the gas chromatography-mass spectrometry (GC-MS) technique employed by Pizzarello et al., we have used liquid chromatography-fluorescence detection/time of flight-mass spectrometry (LC-FD/ToF-MS) to study the enantiomeric ratio of isovaline in the CM2 meteorites Murchison and LEW90500 and the CR2 QUE99177. We have placed particular emphasis on understanding the suite of C5 amino acids in these meteorites. In doing so, we have determined that D and L 3-aminopentanoic acid co-elutes with Lisovaline and L-valine under common chromatographic conditions (Glavin and Dworkin 2006) for omicron-phthaldialdehyde/N-acetyl-L-cysteine (OPA/NAC). We have devised a method to separate these compounds and we will report the actual D/ L ratios of isovaline in these meteorites and how they compare to the GC-MS measurements of Pizzarello and co-workers.

Dworkin, Jason P.↗
NASA NTRS2012

Compound-Specific Isotopic Analysis of Meteoritic Amino Acids as a Tool for Evaluating Potential Formation Pathways

Measurements of stable hydrogen, carbon, and nitrogen isotopic ratios (delta D, delta C-13, delta N-15) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may point towards the most likely of these proposed pathways. The technique of gas chromatography coupled with mass spectrometry and isotope ratio mass spectrometry provides compound-specific structural and isotopic information from a single splitless injection, enhancing the amount of information gained from small amounts of precious samples such as carbonaceous chondrites. We have applied this technique to measure the compound-specific C, N, and H isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites. We are using these measurements to evaluate predictions of expected isotopic enrichments from potential formation pathways and environments, leading to a better understanding of the origin of these compounds.

Elsila, Jamie E.↗
NASA NTRS2015

Sulfate Mineral Formation from Acid-Weathered Phyllosilicates: Implications for the Aqueous History of Mars

Phyllosilicates on Mars are thought to have formed under neutral to alkaline conditions during Mars' earliest Noachian geologic era (approx. 4.1-3.7 Gya). Sulfate formation, on the other hand, requires more acidic conditions which are thought to have occurred later during Mars' Hesperian era (approx. 3.7-3.0 Gya). Therefore, regions on Mars where phyllosilicates and sulfates are found in close proximity to each other provide evidence for the geologic and aqueous conditions during this global transition. Both phyllosilicates and sulfates form in the presence of water and thus give clues to the aqueous history of Mars and its potential for habitability. Phyllosilicates that formed during the Noachian era may have been weathered by the prevailing acidic conditions that characterize the Hesperian. Therefore, the purpose of this study is to characterize the alteration products resulting from acid-sulfate weathered phyllosilicates in laboratory experiments. This study focuses on two phyllosilicates commonly identified with sulfates on Mars: nontronite and saponite. We also compare our results to observations of phyllosilicates and sulfates on Mars to better understand the formation process of sulfates in close proximity to phyllosilicates on Mars and constrain the aqueous conditions of these regions on Mars.

Craig, P. I.↗
NASA NTRS2016

Insights Into the Aqueous History of Mars from Acid-Sulfate Weathered Phyllosilicates

Phyllosilicates on Mars are thought to have formed during Mars' earliest Noachian geologic era (approx. 4.1-3.7 Ga). Sulfate formation, on the other hand, requires more acidic conditions which are thought to have occurred later during Mars' Hesperian era (approx. 3.7-3.0 Ga). Therefore, regions on Mars where phyllosilicates and sulfates are found in close proximity to each other provide evidence for the aqueous conditions during this global transition. Both phyllosilicates and sulfates form in the presence of water and thus give clues to the aqueous history of Mars and its potential for habitability. Phyllosilicates that formed during the Noachian era would have been weathered by the prevailing acidic conditions that define the Hesperian. Therefore, the purpose of this study is to characterize the alteration products of acid-sulfate weathered phyllosilicates in laboratory experiments, focusing on the Fe/Mg-smectites commonly identified on Mars. We also compare our results to observations of phyllosilicates and sulfates on Mars in regions such as Endeavour Crater and Mawrth Vallis to understand the formation process of sulfates and constrain the aqueous history of these regions.

Craig, P. I.↗
NASA NTRS2017

Smectite Formation in Acid Sulfate Environments on Mars

Phyllosilicates of the smectite group detected in Noachian and early Hesperian terrains on Mars were hypothesized to form under aqueous conditions that were globally neutral to alkaline. These pH conditions and the presence of a CO2-rich atmosphere should have been favorable for the formation of large carbonate deposits. However, large-scale carbonate deposits have not been detected on Mars. We hypothesized that smectite deposits are consistent with perhaps widespread acidic aqueous conditions that prevented carbonate precipitation. The objective of our work was to investigate smectite formation under acid sulfate conditions in order to provide insight into the possible geochemical conditions required for smectite formation on Mars. Hydrothermal batch incubation experiments were performed with Mars-analogue, glass-rich, basalt simulant in the presence of sulfuric acid of variable concentration.

Peretyazhko, T. S.↗
NASA NTRS2017

Effect of Tube-Based X-Ray Microtomography Imaging on the Amino Acid and Amine Content of the Murchison CM2 Chondrite

X-ray and synchrotron X-ray micro-computed tomography (micro-CT) are increasingly being used for three dimensional reconnaissance imaging of chondrites and returned extraterrestrial material prior to detailed chemical and mineralogical analyses. Although micro-CT imaging is generally considered to be a non-destructive technique since silicate and metallic minerals in chondrites are not affected by X-ray exposures at the intensities and wavelengths typically used, there are concerns that the use of micro-CT could be detrimental to the organics in carbonaceous chondrites. We recently conducted a synchrotron micro-CT experiment on a powdered sample of the Murchison CM2 carbonaceous chondrite exposed to a monochromatic high energy (approximately 48 kiloelectronvolts) total X-ray radiation dose of approximately 1 kilogray (kGy) using the Advanced Photon Source beamline 13-BMD (13-Bending Magnet-D Beamline) at Argonne National Laboratory and found that there were no detectable changes in the amino acid abundances or enantiomeric compositions in the chondrite after exposure relative to a Murchison control sample that was not exposed. However, lower energy bremsstrahlung X-rays could interact more with amino acids and other lower molecular weight amines in meteorites. To test for this possibility, three separate micro-CT imaging experiments of the Murchison meteorite using the GE Phoenix v/tome/x s 240 kilovolt microfocus high resolution tungsten target X-ray tube instrument at the American Museum of Natural History (AMNH) were conducted and the amino acid abundances and enantiomeric compositions were determined. We also investigated the abundances of the C1-C5 amines in Murchison which were not analyzed in the first study.

Microtomography Imaging↗
NASA NTRS2017

The Effect of Fatty Acids to Protect Forward Osmosis Membranes from Damage

NASA has conducted research and development on forward osmosis (FO) membranes for wastewater reclamation in space since 1993. The lessons learned during operation of the International Space Station and FO based technologies on the ground taught us that reliability is a key limitation. Membranes are susceptible to organic fouling, oxidation and calcium scaling, and these factors tend to damage the membrane reducing their operating life and performance. The development of a Synthetic Biological Membrane (SBM), a membrane that mimics naturally occurring biological processes, will mitigate membrane damage and improve reliability. The SBM is a lipid-based membrane with a protective fatty acid layer configured for use in a FO water purification system. In this configuration, the protective layer on the surface of the lipid membrane is composed of fatty acids (FA). The FA interact with the chemicals found in the wastewater feed, and protect the membrane from damage. In this study, we conducted preliminary experiments to determine the feasibility of using fatty acids to alleviate damage from calcium scaling, oxidation and organic fouling.

Romero Mangado, Jaione↗
NASA NTRS2018

Molecular Distribution, 13C-Isotope, and Enantiomeric Compositions of Carbonaceous Chondrite Monocarboxylic Acids

The water-soluble organic compounds in carbonaceous chondrite meteorites constitute a record of the synthetic reactions occurring at the birth of the solar system and those taking place during parent body alteration and may have been important for the later origins and development of life on Earth. In this present work, we have developed a novel methodology for the simultaneous analysis of the molecular distribution, compound-specific (delta)(exp 13)C, and enantiomeric compositions of aliphatic monocarboxylic acids (MCA) extracted from the hot-water extracts of 16 carbonaceous chondrites from CM, CR, CO, CV, and CK groups. We observed high concentrations of meteoritic MCAs, with total carbon weight percentages which in some cases approached those of carbonates and insoluble organic matter. Moreover, we found that the concentration of MCAs in CR chondrites is higher than in the other meteorite groups, with acetic acid exhibiting the highest concentration in all samples. The abundance of MCAs decreased with increasing molecular weight and with increasing aqueous and/or thermal alteration experienced by the meteorite sample. The (delta)(exp 13)C isotopic values of MCAs ranged from 52 to +27(0/00), and aside from an inverse relationship between (delta)(exp 13)C value and carbon straight-chain length for C3–C6 MCAs in Murchison, the 13C-isotopic values did not correlate with the number of carbon atoms per molecule. We also observed racemic compositions of 2-methylbutanoic acid in CM and CR chondrites. We used this novel analytical protocol and collective data to shed new light on the prebiotic origins of chondritic MCAs.

Aponte, Jose C.↗
NASA NTRSDate not supplied

Investigating Amino Acid Heterogeneity in Milligram-Scale Samples of the Murchison CM2 Carbonaceous Chondrite

Analyses of different aliquots of the Tagish Lake meteorite have resulted in amino acid abundance variations of an order of magnitude or more, even when performed using the same techniques, by the same personnel, in the same laboratories (e.g., Simkus et al. 2019). Up to ~five-fold variations have been observed for specific amino acids in different samples of the same meteorite, such as α aminoisobutryic acid (AIB) in Murchison. These variations are often attributed differing sample composition or differing alteration history, neither of which is mutually exclusive. Distinguishing between these two explanations is challenging and time consuming, requiring detailed mineralogical analyses to be performed in conjunction with high precision organics analysis. The potential for innate sample-level heterogeneity presents a significant complication when parsing the effects of different processes or conditions during preparation of meteorite samples for analysis, as differences in organic yields or abundances could be due to differences in laboratory processing or differences among the samples themselves. In this work, we investigated the degree of innate organic heterogeneity present in a single ~250 mg chip of divided into 21 samples.

A. S. Burton↗