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NASA NTRS2010

Extraterrestrial Amino Acids in the Almahata Sitta Meteorite

Amino acid analysis of a meteorite fragment of asteroid 2008 TC3 called Almahata Sitta was carried out using reverse-phase liquid chromatography coupled with UV fluorescence detection and time-of-flight mass spectrometry (LC-FD/ToF-MS) as part of a sample analysis consortium. LC-FD/ToF-MS analyses of hot-water extracts from the meteorite revealed a complex distribution of two- to seven-carbon aliphatic amino acids and one- to three-carbon amines with abundances ranging from 0.5 to 149 parts-per-billion (ppb). The enantiomeric ratios of the amino acids alanine, R-amino-n-butyric acid (beta-ABA), 2-amino-2-methylbutanoic acid (isovaline), and 2-aminopentanoic acid (norvaline) in the meteorite were racemic (D/L approximately 1), indicating that these amino acids are indigenous to the meteorite and not terrestrial contaminants. Several other non-protein amino acids were also identified in the meteorite above background levels including alpha-aminoisobutyric acid (alpha-AIB), 4-amino-2- methylbutanoic acid, 4-amino-3-methylbutanoic acid, and 3-, 4-, and 5-aminopentanoic acid. The total abundances of isovaline and alpha-AIB in Almahata Sitta are 1000 times lower than the abundances of these amino acids found in the CM carbonaceous chondrite Murchison. The extremely low abundances and unusual distribution of five carbon amino acids in Almahata Sitta compared to Cl, CM, and CR carbonaceous chondrites may reflect extensive thermal alteration of amino acids on the parent asteroid by partial melting during formation or subsequent impact shock heating. It is also possible that amino acids were synthesized by catalytic reactions on the parent body after asteroid 2008 TC3 cooled to lower temperatures.

Glavin, Daniel P.↗
NASA NTRS1972

Detection of soil microorganism in situ by combined gas chromatography mass spectrometry

Experimental tests were made to determine whether analysis of volatile metabolic products, formed in situ, is a viable procedure for an extraterrestrial life detection system. Laboratory experiments, carried out under anaerobic conditions with addition of carbon source, extended to include a variety of soils and additional substrates. In situ experiments were conducted without amendment using a vacuum sampling system.

Alexander, M.↗
NASA NTRS1982

Comet composition and density analyzer

Distinctions between cometary material and other extraterrestrial materials (meteorite suites and stratospherically-captured cosmic dust) are addressed. The technique of X-ray fluorescence (XRF) for analysis of elemental composition is involved. Concomitant with these investigations, the problem of collecting representative samples of comet dust (for rendezvous missions) was solved, and several related techniques such as mineralogic analysis (X-ray diffraction), direct analysis of the nucleus without docking (electron macroprobe), dust flux rate measurement, and test sample preparation were evaluated. An explicit experiment concept based upon X-ray fluorescence analysis of biased and unbiased sample collections was scoped and proposed for a future rendezvous mission with a short-period comet.

Clark, B. C.↗
NASA NTRS1998

Shock Modifications of Organic Compounds in Carbonaceous Chondrite Parent Bodies

Impacts among asteroidal objects would have altered or destroyed pre-existing organic matter in both targets and projectiles to a greater or lesser degree depending upon impact velocities. To begin filling a knowledge gap on the shock metamorphism of organic compounds, we are studying the effects of shock impacts on selected classes of organic compounds utilizing laboratory shock facilities. Our approach is to subject mixtures of organic compounds, embedded in the matrix of the Murchison meteorite, to simulated hypervelocity impacts by firing them into targets at various pressures. The mixtures are then analyzed to determine the amount of each compound that survives as well as to determine if new compounds are being synthesized. The initial compounds added to the matrix (with the exception of thiosulfate). The sulfonic acids were chosen in part because they are relatively abundant in Murchison, relatively stable, and because they and the phosphonic acids are the first well-characterized homologous series of organic sulfur and phosphorus compounds identified in an extraterrestrial material. Experimental procedures were more fully described in the original proposal. A 20 mm gun, with its barrel extending into a vacuum chamber (10(exp -2) torr), was used to launch the projectile containing the sample at approx. 1.6 km/sec (3,600 mi/hr) into the target material. Maximum pressure of impact depend on target/projectile materials. The target was sufficiently thin to assure minimum pressure decay over the total sample thickness.

Cooper, George W.↗
NASA NTRS2012

Enantiomer Ratios of Meteoritic Sugar Derivatives

Carbonaceous meteorites contain a diverse suite of soluble organic compounds. Studies of these compounds reveal the Solar System's earliest organic chemistry. Among the classes of organic compounds found in meteorites are keto acids (pyruvic acid, etc.), hydroxy tricarboxylic acids (1), amino acids, amides, purines and pyrimidines. The Murchison and Murray meteorites are the most studied for soluble and insoluble organic compounds and organic carbon phases. The majority of (indigenous) meteoritic compounds are racemic, (i.e., their D/L enantiomer ratios are 50:50). However, some of the more unusual (non-protein) amino acids contain slightly more of one enantiomer (usually the L) than the other. This presentation focuses on the enantiomer analyses of three to six-carbon (3C to 6C) meteoritic sugar acids. The molecular and enantiomer analysis of corresponding sugar alcohols will also be discussed. Detailed analytical procedures for sugar-acid enantiomers have been described. Results of several meteorite analyses show that glyceric acid is consistently racemic (or nearly so) as expected of non-biological mechanisms of synthesis. Also racemic are 4-C deoxy sugar acids: 2-methyl glyceric acid; 2,4-dihydroxybutyric acid; 2,3-dihydroxybutyric acid (two diastereomers); and 3,4-dihydroxybutyric acid. However, a 4C acid, threonic acid, has never been observed as racemic, i.e., it possesses a large D excess. In several samples of Murchison and one of GRA 95229 (possibly the most pristine carbonaceous meteorite yet analyzed) threonic acid has nearly the same D enrichment. In Murchison, preliminary isotopic measurements of individual threonic acid enantiomers point towards extraterrestrial sources of the D enrichment. Enantiomer analyses of the 5C mono-sugar acids, ribonic, arabinonic, xylonic, and lyxonic also show large D excesses. It is worth noting that all four of these acids (all of the possible straight-chained 5C sugar acids) are present in meteorites, including the rare lyxonic acid, and their relative abundances are in equilibrium proportions. In addition (in contrast to the above D-only excesses), some of the above acids are found in biology as the L enantiomer. Whether rare are common, all of the 6C sugar acids that are present in sufficient amounts to allow enantiomer analysis (Mannonic, gluconic, altronic, talonic, idonic, gulonic, and galactonic) also, apparently, possess significant D excesses.

Cooper, George↗
NASA NTRS2010

The Origins and Evolution of Molecules in Icy Solids

Astronomical observations of the past few decades have revealed the existence of a variety of molecules in extraterrestrial ices. These molecules include H2O, CO, and CO2, and organics such as CH4, CH30H, and C2H6. Some ices are dominated by polar molecules, while non-polar species appear to dominate others. Observations, mainly in the radio and IR regions, have allowed the inference of other solid-phase molecules whose formation remains difficult to explain by gas-phase chemistry alone. Several laboratory research groups have reported on extensive experiments on the solid-phase reaction chemistry of icy materials, generally as initiated by either ionizing radiation or vacuum-UV photons. These experiments not only permit molecular identifications to be made from astronomical observations, but also allow predictions of yet unidentified molecules. This laboratory approach has evolved over more than 30 years with much of the earliest work focusing on complex mixtures thought to represent either cometary or interstellar ices. Although those early experiments documented a rich solid-state photo- and radiation chemistry, they revealed few details of reactions for particular molecules, partly due to the multi-component nature of the samples. Since then, model systems have been examined that allow the chemistry of individual species and specific reactions to be probed. Reactions involving most of the smaller astronomical molecules have now been studied and specific processes identified. Current laboratory work suggests that a variety of reactions occur in extraterrestrial ices, including acid-base processes, radical dimerizations, proton transfers, oxidations, reductions, and isomerizations. This workshop presentation will focus on chemical reactions relevant to solar system and interstellar ices. While most of the work will be drawn from that to which the speaker has contributed, results from other laboratories also will be included. Suggestions for future studies will be made, with an emphasis on some present deficiencies. The speaker's work has been generously supported by these NASA research programs: Cassini Data Analysis, Exobiology, Mars Fundamental Research, Outer Planets Research, Planetary Atmospheres, Planetary Geology and Geophysics, and the NASA Astrobiology Institute.

Hudson, Reggie L.↗
NASA NTRS2003

Modern Microbial Fossilization Processes as Signatures for Interpreting Ancient Terrestrial and Extraterrestrial Microbial Forms

Terrestrial biotas from microbially dominated hypersaline environments will help us understand microbial fossilization processes. Hypersaline tolerant biota from Storr's Lake, San Salvador Island (Bahamas), Mono Lake (California), and the Dead Sea (Israel) represent marine and nonmarine sites for comparative studies of potential analogs for interpreting some Mars meteorites and Mars sample return rocks [1,2,3,4,5,6]. The purpose of this study is to compare microbial fossilization processes, the dominant associated minerals, and potential diagenic implications.

Morris, Penny A.↗
NASA NTRS1974

Investigations in space-related molecular biology

Improved instrumentation and preparation techniques for high resolution, high voltage cryo-electron microscopic and diffraction studies on terrestrial and extraterrestrial specimens are reported. Computer correlated ultrastructural and biochemical work on hydrated and dried cell membranes and related biological systems provided information on membrane organization, ice crystal formation and ordered water, RNA virus linked to cancer, lunar rock samples, and organometallic superconducting compounds. Apollo 11, 12, 14, and 15 specimens were analyzed

Fernandez-Moran, H.↗
NASA NTRS1988

Evidence for a single impact at the Cretaceous-Tertiary boundary from trace elements

Not only meteoritic elements (Ir, Ni, Au, Pt metals), but also some patently non-meteoritic elements (As, Sb) are enriched at the K-T boundary. Eight enriched elements at 7 K-T sites were compared and it was found that: All have fairly constant proportions to Ir and Kilauea (invoked as an example of a volcanic source of Ir by opponents of the impact theory) has too little of 7 of these 8 elements to account for the boundary enrichments. The distribution of trace elements at the K-T boundary was reexamined using data from 11 sites for which comprehensive are available. The meteoritic component can be assessed by first normalizing the data to Ir, the most obviously extraterrestrial element, and then to Cl chondrites. The double normalization reduces the concentration range from 11 decades to 5 and also facilitates the identification of meteoritic elements. At sites where trace elements were analyzed in sub-divided samples of boundary clay, namely, Caravaca (SP), Stevns Klint (DK), Flaxbourne River (NZ) and Woodside Creek (NZ), Sb, As and Zn are well correlated with Ir across the boundary implying a common deposition mechanism. Elemental carbon is also enriched by up to 10,000 x in boundary clay from 5 K-T sides and is correlated with Ir across the boundary at Woodside Creek. While biomass would appear to be the primary fuel source for this carbon a contribution from a fossil fuel source may be necessary in order to account for the observed C abundance.

Gilmour, Iain↗
NASA NTRSDate not supplied

Micromechanics-based Modeling of Cement Solidified in the Microgravity

Given the prohibitive expense of transporting raw materials into space, in-situ resources alongside cement-like binders is envisioned to realize large-scale habitats on celestial bodies like the Moon and Mars. However, understanding the mechanical properties of cementitious materials in reduced gravity environments is crucial for effective design and engineering in extraterrestrial construction projects. Using micromechanics-based approach, this research focuses on analyzing the impact of microgravity on the mechanical properties of cementitious materials by employing distinctive Scanning Electron Microscopy (SEM) images of tricalcium silicate (C 3 S) samples hydrated aboard the International Space Station (ISS).

Namiko Yamamoto↗
NASA NTRS2013

Medicine Delivery Device with Integrated Sterilization and Detection

Sterile delivery devices can be created by integrating a medicine delivery instrument with surfaces that are coated with germicidal and anti-fouling material. This requires that a large-surface-area template be developed within a constrained volume to ensure good contact between the delivered medicine and the germicidal material. Both of these can be integrated using JPL-developed silicon nanotip or cryo-etch black silicon technologies with atomic layer deposition (ALD) coating of specific germicidal layers. The application of semiconductor processing techniques and technologies to the problems of fluid manipulation and delivery has enabled the integration of chemical, electrical, and mechanical manipulation of samples all within a single microfluidic device. This approach has been successfully applied at JPL to the automated processing, detection, and analysis of minute quantities (parts per trillion level) of biomaterials to develop instruments for in situ exploration or extraterrestrial bodies. The same nanofabrication techniques that are used to produce a microfluidics device are also capable of synthesizing extremely high-surface-area templates in precise locations, and coating those surfaces with conformal films to manipulate their surface properties. This methodology has been successfully applied at JPL to produce patterned and coated silicon nanotips (also known as black silicon) to manipulate the hydrophilicity of surfaces to direct the spreading of fluids in microdevices. JPL's ALD technique is an ideal method to produce the highly conformal coatings required for this type of application. Certain materials, such as TiO2, have germicidal and anti-fouling properties when they are illuminated with UV light. The proposed delivery device contacts medicine with this high-surface-area black silicon surface coated with a thin-film germicidal deposited conformally with ALD. The coating can also be illuminated with ultraviolet light for the purpose of sterilization or identification of the medicine itself. This constrained volume that is located immediately prior to delivery into a patient, ensures that the medicine delivery device is inherently sterile. An additional benefit to integrating a high-surface-area template within the fluid channel of a medicine delivery device is that one can envision a number of different functional coatings that could facilitate the capture and analysis of either microbial contaminants or the medicine itself. For example, one could attach antibodies or some other binding agent with a specific affinity to the silicon nanotip template. Once a target molecule or microbe is bound to the high-surface- area template, one could use an optical analytical technique such as fluorescence or adsorption to determine the identity and potentially the concentration of the species of interest. By illuminating the bound species from the back, it may also be possible to probe only the molecules with an evanescent wave, making detection of the species from the front side of the device much simpler.

Shearn, Michael J.↗
NASA NTRS1981

Interplanetary dust - Its physical nature and entry into the atmosphere of terrestrial planets

Studies of extraterrestrial particles collected in the stratosphere and from the sea floor indicate that the majority of interplanetary dust is a black, fine grained material similar to carbonaceous chondrites but different from known meteorites in mineralogy and structure. If the analyzed samples are typical interplanetary particles then they are probably cometary materials similar to the vast numbers of cometary particles which have continuously entered the earth's atmosphere for the lifetime of the solar system. If comets do not contain large strong rocks capable of producing conventional meteorites then dust is the only form in which organic materials from comets can be accreted by the earth.

Brownlee, D. E.↗
NASA NTRS1976

Labeled Release - An experiment in radiorespirometry

The Labeled Release extraterrestrial life detection experiment onboard the Viking spacecraft is described as it will be implemented on the surface of Mars in 1976. This experiment is designed to detect heterotrophic life by supplying a dilute solution of radioactive organic substrates to a sample of Martian soil and monitoring for evolution of radioactive gas. A significantly attenuated response by a heat-sterilized control sample of the same soil would confirm a positive metabolic response. Experimental assumptions as well as criteria for the selection of organic substrates are presented. The Labeled Release nutrient has been widely tested, is versatile in eliciting terrestrial metabolic responses, and is stable to heat sterilization and to the long-term storage required before its use on Mars. A testing program has been conducted with flight-like instruments to acquire science data relevant to the interpretation of the Mars experiment. Factors involved in the delineation of a positive result are presented and the significance of the possible results discussed.

Levin, G. V.↗
NASA NTRS2002

Initial Results on the Extraterrestrial Component of New Sediment Cores Containing Deposits of the Eltanin Impact Event

Background: The impact of the Eltanin asteroid into the Bellingshausen Sea (2.15 Ma) is the only known impact in a deep-ocean (approx. 5 km) basin. In 1995, Polarstern expedition ANT XII/4 made the first geological survey of the suspected impact region. Three sediment cores sampled around the San Martin seamounts (approx. 57.5 S, 91 W) contained well-preserved impact deposits. Sediments of Eocene age and younger were ripped up and redeposited by the impact. The depositional sequence produced by the impact has three units: a chaotic assemblage of sediment fragments up to 50 cm, followed by laminated sands deposited as a turbulent flow, and finally silts and clays that accumulated from dispersed sediments in the water column. The meteoritic impact ejecta, which is composed of shock-melted asteroidal materials and unmelted meteorites, settled through the water column and concentrated near the top of the laminated sands.

Kyte, Frank T.↗
NASA NTRS2026

Polarized Resonant Soft X-ray Scattering (P-RSoXS) as a New Technique for Characterizing Amorphous Astromaterials

In the coming years, samples will be returned from several asteroids, the lunar surface, and the first material returned directly from the Martian surface. Previous in-situ and remote studies indicate these samples will contain abundant amorphous or weakly crystalline materials. However, detailed characterization and quantification of these amorphous materials remains challenging. Conventional techniques, including electron microscopy and X-ray diffraction, provide important information on material structure, but are generally limited to crystalline materials. Polarized resonant soft X-ray scattering (P-RSoXS) is a synchrotron-based X-ray scattering technique that has been used to characterize and quantify weakly crystalline systems, including soft materials. This research aims to translate this technique to geologic and extraterrestrial materials, building off the knowledge of using P-RSoXS to interrogate soft materials. P-RSoXS is well-suited to interrogate geologic materials, which are often multiphase, heterogeneous systems with crystalline and amorphous components, and domain sizes on the order of tens of nanometers. It is anticipated that future work will help reveal new chemical and structural information in geologic materials. Maturation of this preliminary work to develop P-RSoXS to characterize astromaterial-relevant samples will provide new understanding of the secondary processes responsible for the development of amorphous astromaterials and further elucidate our knowledge of the geologic history and past alteration processes.

Joshua H Litofsky↗
NASA NTRS1972

Evidence for amino-acids of extraterrestrial origin in the Orgueil meteorite.

The problems of separation of contaminant from indigenous amino-acids in meteorites can be largely overcome by applying gas chromatographic techniques for the separation of D,L enantiomers of amino-acids as their diastereomeric derivatives and the identification of these compounds by gas chromatographic retention times and mass spectral fragmentation patterns. Two samples of Orgueil meteorite were examined. The results show that there are amino-acids indigenous to the Orgueil meteorite in addition to those present as contaminants.

Lawless, J. G.↗
NASA NTRS1996

Planetary protection, legal ambiguity and the decision making process for Mars sample return

As scientists and mission planners develop planetary protection requirements for future Mars sample return missions, they must recognize the socio-political context in which decisions about the mission will be made and pay careful attention to public concerns about potential back contamination of Earth. To the extent that planetary protection questions are unresolved or unaddressed at the time of an actual mission, they offer convenient footholds for public challenges in both legal and decision making realms, over which NASA will have little direct control. In this paper, two particular non-scientific areas of special concern are discussed in detail: 1) legal issues and 2) the decision making process. Understanding these areas is critical for addressing legitimate public concerns as well as for fulfilling procedural requirements regardless whether sample return evokes public controversy. Legal issues with the potential to complicate future missions include: procedural review under National Environmental Policy Act (NEPA); uncertainty about institutional control and authority; conflicting regulations and overlapping jurisdictions; questions about international treaty obligations and large scale impacts; uncertanities about the nature of the organism; and constitutional and regulatory concerns about quarantine, public health and safety. In light of these important legal issues, it is critical that NASA consider the role and timing of public involvement in the decision making process as a way of anticipating problem areas and preparing for legitimate public questions and challenges to sample return missions.

NASA Discipline Number 59-10↗
NASA NTRS2005

Cutting Silica Aerogel for Particle Extraction

The detailed laboratory analyses of extraterrestrial particles have revolutionized our knowledge of planetary bodies in the last three decades. This knowledge of chemical composition, morphology, mineralogy, and isotopics of particles cannot be provided by remote sensing. In order to acquire these detail information in the laboratories, the samples need be intact, unmelted. Such intact capture of hypervelocity particles has been developed in 1996. Subsequently silica aerogel was introduced as the preferred medium for intact capturing of hypervelocity particles and later showed it to be particularly suitable for the space environment. STARDUST, the 4th NASA Discovery mission to capture samples from 81P/Wild 2 and contemporary interstellar dust, is the culmination of these new technologies. In early laboratory experiments of launching hypervelocity projectiles into aerogel, there was the need to cut aerogel to isolate or extract captured particles/tracks. This is especially challenging for space captures, since there will be many particles/tracks of wide ranging scales closely located, even collocated. It is critical to isolate and extract one particle without compromising its neighbors since the full significance of a particle is not known until it is extracted and analyzed. To date, three basic techniques have been explored: mechanical cutting, lasers cutting and ion beam milling. We report the current findings.

Tsou, P.↗