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At least 505 records · Page 28

Analysis of Chiral Carboxylic Acids in Meteorites

Homochirality of amino acids in proteins and sugars in DNA and RNA is a critical feature of life on Earth. In the absence of a chiral driving force, however, reactions leading to the synthesis of amino acids and sugars result in racemic mixtures. It is currently unknown whether homochirality was necessary for the origins of life or if it was a product of early life. The observation of enantiomeric excesses of certain amino acids of extraterrestrial origins in meteorites provides evidence to support the hypothesis that there was a mechanism for the preferential synthesis or destruction of a particular amino acid enantiomer [e.g., 1-3]. The cause of the observed chiral excesses is un-clear, although at least in the case of the amino acid isovaline, the degree of aqueous alteration that occurred on the meteorite parent body is correlated to the isovaline L-enantiomeric excess [3, 4]. This suggests that chiral symmetry is broken and/or amplified within the meteorite parent bodies. Besides amino acids, there have been only a few reports of other meteoritic compounds found in enantiomeric excess: sugars and sugar acids [5, 6] and the hydroxy acid lactic acid [7]. Determining whether or not additional types of molecules in meteorites are also present in enantiomeric excesses of extraterrestrial information will provide insights into mechanisms for breaking chiral symmetry. Though the previous measurements (e.g., enantiomeric composition of lactic acid [7], and chiral carboxylic acids [8]) were made by gas chromatography-mass spectrometry, the potential for increased sensitivity of liquid chromatography-mass spectrometry (LC-MS) analyses is important because for many meteorite samples, only small sample masses are available for study. Furthermore, at least in the case of amino acids, many of the largest amino acid enantiomeric excesses were observed in samples that contained lower abundances (tens of ppb) of a given amino acid enantiomer. In the present work, we describe our efforts to develop highly sensitive LC-MS methods for the analysis of chiral carboxylic acids including hydroxy acids.

Burton, A. S.↗

Interpretation of Ferroan Anorthosite Ages and Implications for the Lunar Magma Ocean

Ferroan Anorthosites (FANs) are considered to have purportedly crystallized directly from the lunar magma ocean (LMO) as a flotation crust. LMO modeling suggests that such anorthosites started to form only after greater than 70 percent of the LMO had crystallized. Recent age dates for FANs have questioned this hypothesis as they span too large of an age range. This means a younger age for the Moon-forming giant impact or the LMO hypothesis is flawed. However, FANs are notoriously difficult to age-date using the isochron method. We have proposed a mechanism for testing the LMO hypothesis through using plagioclase trace element abundances to calculate equilibrium liquids and compare them with LMO crystallization models. We now examine the petrography of the samples that have Sm-Nd (Samarium-Neodymium) age dates (Rb-Sr (Rubidium-Strontium) isotopic systematics may have been disturbed) and propose a relative way to age date FANs.

Neal, C. R.↗

Experimental Studies on the Effect of Impact Processes on the Formation and Evolution of Amino Acids

Introduction: A critical step in the emergence of life on Earth was the synthesis of larger organic molecules from simple building blocks such as NH3, CO2, H2O, and CH3OH. The presence of amino acids and other complex organics in comets and meteorites demonstrates that widespread organic synthesis likely occurred across the early solar system. Building on previous work [e.g., 1-3], we systematically explore impact-driven chemical evolution of exogenous organics and their precursors. Collisional processes may also have provided a source of energy for the formation of more complex organics from endogenous building blocks. The high flux of impactors to Earth immediately prior to and during the origins of life suggests that impacts could have played a critical role. Key Questions: 1. How are the formation and evolution of amino acids affected by the presence of a mineral matrix during cometary and asteroidal impacts onto the early Earth? 2. Do some minerals (e.g., phyllosilicates) provide a more robust protective framework or reactive surface site for amino-acid formation and/or polymerization? 3. Does the abundance of ices and/or amino acids relative to that of the mineral matrix affect the formation and evolution of amino acids? 4. Are there impact velocities/shock pressures at which formation or polymerization of amino acids is favored or precluded? Experimental Approach: This study systematically examines the conditions under which amino acids and other organic molecules can form, be polymerized, and/or be destroyed during impact events into particulate regolith simulants. Variable parameters include the modal composition of this regolith (silicate matrices, ratios of ices, silicates, and amino acids) and impact velocities/shock pressures. Impacts experiments were performed using the two-stage light-gas gun (LGG), vertical gun (VG), and flat-plate accelerator (FPA) in the Experimental Impact Lab at JSC. FPA experiments were performed over a range of shock pressures (11.3-31.5 GPa) using CM chondrite simulant mixed with amino acids at ratios of 0:10, 1:10, 1:103, and 1:106 (amino acid:host). Techniques for mixing cometary ices have been optimized and test runs have been performed using the LGG (see figure below). Analysis: Post-impact, samples are heated in water to extract amino acids and peptides. Extracts are characterized via liquid chromatography-mass spectrometry (LC-MS) and the mineralogies of solid residues are characterized using X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Additional LC-MS and mineralogical analyses are underway.

Eve L Berger↗

Use of olivine and plagioclase saturation surfaces for the petrogenetic modeling of recrystallized basic plutonic systems

During petrogenetic studies of basic plutonic rocks, there are at least three major questions to be considered: (1) what were the relative proportions of cumulate crystals and intercumulus melt in a given sample? (2) what is the composition and variation in composition of the melts within the pluton? and (3) what is the original composition of the liquids, their source and evolution prior to the time of emplacement? Use of both saturation surfaces can place strong limits on the compositions of potential cumulate phases and intercumulus melts. Consideration of appropriate trace elements can indicate whether a sample is an orthocumulate, adcumulate or mesocumulate. Thus, when trace element and petrographic data are considered together with the saturation surfaces, it should be possible to begin to answer the three major questions given above, even for strongly recrystallized basic plutons.

Hanson, G. N.↗

Interaction of gases with lunar materials

The surface properties of lunar fines were investigated. Results indicate that, for the most part, these properties are independent of the chemical composition and location of the samples on the lunar surface. The leaching of channels and pores by adsorbed water vapor is a distinguishing feature of their surface chemistry. The elements of air, if adsorbed in conjunction with water vapor or liquid water, severely impedes the leaching process. In the absence of air, liquid water is more effective than water vapor in attacking the grains. The characteristics of Apollo 17 orange fines were evaluated and compared with those of other samples. The interconnecting channels produced by water vapor adsorption were found to be wider than usual for other types of fines. Damage tracks caused by heavy cosmic ray nuclei and an unusually high halogen content might provide for stronger etching conditions upon exposure to water vapor.

Holmes, H. F.↗

Beamline Electrostatic Levitator (BESL) for in-situ High Energy K-Ray Diffraction Studies of Levitated Solids and Liquids at High Temperature

Determinations of the phase formation sequence, the crystal structures and the thermodynamic properties of materials at high temperatures are difficult because of contamination from the sample container and environment. Containerless processing techniques, such as electrostatic (ESL), electromagnetic (EML), aerodynamic, and acoustic levitation, are most suitable these studies. An adaptation of ESL for in-situ structural studies of a wide range of materials, including metals, semiconductors, insulators using high energy (125 keV) synchrotron x-rays is described here. This beamline ESL (BESL) allows the in-situ determination of the atomic structures of equilibrium solid and liquid phases, including undercooled liquids, as well as real-time studies of solid-solid and liquid-solid phase transformations. The use of image plate (MAR345) or GE-Angio detectors enables fast (30 ms - 1s) acquisition of complete diffraction patterns over a wide q-range (4 - 140/mm). The wide temperature range (300 - 2500 K), containerless processing under high vacuum (10(exp -7) - 10(exp -8) torr), and fast data acquisition, make BESL particularly suitable for phase diagram studies of high temperature materials. An additional, critically important, feature of BESL is the ability to also make simultaneous measurement of a host of thermo-physical properties, including the specific heat, enthalpy of transformation, solidus and liquidus temperatures, density, viscosity, and surface tension; all on the same sample and simultaneous with the structural measurements.

Gangopadhyay, A. K.↗

Know Your Enemy - Implementation of Bioremediation within a Suspected DNAPL Source Zone Following High-Resolution Site Characterization at Contractors Road Heavy Equipment Area, Kennedy Space Center, Florida

The National Aeronautics and Space Administration (NASA), Kennedy Space Center (KSC), has adopted high-resolution site characterization (HRSC) sampling techniques during baseline sampling prior to implementation of remedies to confirm and refine the conceptual site model (CSM). HRSC sampling was performed at Contractors Road Heavy Equipment Area (CRHE) prior to bioremediation implementation to verify the extent of the trichloroethene (TCE) dense non-aqueous phase liquid (DNAPL) source area (defined as the area with TCE concentrations above 1% solubility) and its daughter product dissolved plume that had been identified during previous HRSC events. The results of HRSC pre-bioremediation implementation sampling suggested that the TCE source area was larger than originally identified during initial site characterization activities, leading to a design refinement to improve electron donor distribution and increase the likelihood of achieving remedial objectives. Approach/Activities: HRSC was conducted from 2009 through 2014 to delineate the vertical and horizontal extent of chlorinated volatile organic compounds (CVOCs) in the groundwater. Approximately 2,340 samples were collected from 363 locations using direct push technology (DPT) groundwater sampling techniques. Samples were collected from up to 14 depth intervals at each location using a 4-foot sampling screen. This HRSC approach identified a narrow (approx. 5 to 30 feet wide), approximately 3,000 square foot TCE DNAPL source area (maximum detected TCE concentration of 160,000 micrograms per liter [micro-g/L] at DPT sampling location DPT0225). Prior to implementation of a bioremediation interim measure, HRSC baseline sampling was conducted using DPT groundwater sampling techniques. Concentrations of TCE were an order of magnitude lower than previous reported (12,000 micro-g/L maximum at DPT sampling location DPT0225) at locations sampled adjacent to previous sampling locations. To further evaluate the variability in concentrations observed additional sampling was conducted in 2016. The results identified higher concentrations than originally detected within the previously defined source area and the presence of source zone concentrations upgradient of the previously defined source area (maximum concentration observed 570,000 micro-g/L). The HRSC baseline sampling data allowed for a revision of the bioremediation design prior to implementation. Bioremediation was implemented within the eastern portion of the source area in November and December 2016 and quarterly performance monitoring was completed in March and June 2017. Reductions in CVOC concentrations from baseline were observed at all performance monitoring wells in the treatment area, and by June 2017, an approximate 95% CVOC mass reduction was observed based on monitoring well sampling results. Results/Lessons Learned: The results of this project suggest that, due to the complexity of DNAPL source zones, HRSC during pre-implementation baseline sampling in the TCE source zone was an essential strategy for verifying the treatment area and depth prior to remedy implementation. If the upgradient source zone mass was not identified prior to bioremediation implementation, the mass would have served as a long-term source for the dissolved plume.

Chrest, Anne↗

The Physics of Hard Spheres Experiment on MSL-1: Required Measurements and Instrument Performance

The Physics of HArd Spheres Experiment (PHaSE), one of NASA Lewis Research Center's first major light scattering experiments for microgravity research on complex fluids, flew on board the Space Shuttle's Microgravity Science Laboratory (MSL-1) in 1997. Using colloidal systems of various concentrations of micron-sized plastic spheres in a refractive index-matching fluid as test samples, illuminated by laser light during and after crystallization, investigations were conducted to measure the nucleation and growth rate of colloidal crystals as well as the structure, rheology, and dynamics of the equilibrium crystal. Together, these measurements support an enhanced understanding of the nature of the liquid-to-solid transition. Achievement of the science objectives required an accurate experimental determination of eight fundamental properties for the hard sphere colloidal samples. The instrument design met almost all of the original measurement requirements, but with compromise on the number of samples on which data were taken. The instrument performs 2-D Bragg and low angle scattering from 0.4 deg. to 60 deg., dynamic and single-channel static scattering from 10 deg. to 170 deg., rheology using fiber optics, and white light imaging of the sample. As a result, PHaSE provided a timely microgravity demonstration of critical light scattering measurement techniques and hardware concepts, while generating data already showing promise of interesting new scientific findings in the field of condensed matter physics.

Doherty, Michael P.↗

Metastable phase formation in undercooled liquid lead alloys

During non-equilibrium processes metastable phases are formed instead of stable phases due to the operation of various kinetic or structural constraints. By removing the most effective nucleation sites for the stable phase using emulsified droplet samples, stable phase formation can be prohibited in a broad range of undercooling and the phase space available in the metastable regime can be mapped out. With this method the thermodynamic properties of the undercooled liquid and the metastable phase boundaries corresponding to reversible metastable (solid + liquid) phase equilibria are examined from experimental data. The analysis reveals important implications for the nucleation kinetics and the choice of the kinetically most favored solidification path.

Fecht, Hans J.↗

Characterization of microbial and chemical composition of shuttle wet waste with permanent gas and volatile organic compound analyses

Solid-waste treatment in space for Advanced Life Support, ALS, applications requires that the material can be safely processed and stored in a confined environment. Many solid-wastes are not stable because they are wet (40-90% moisture) and contain levels of soluble organic compounds that can contribute to the growth of undesirable microorganisms with concomitant production of noxious odors. In the absence of integrated Advanced Life Support systems on orbit, permanent gas, trace volatile organic and microbiological analyses were performed on crew refuse returned from the volume F "wet" trash of three consecutive Shuttle missions (STS-105, 109, and 110). These analyses were designed to characterize the short-term biological stability of the material and assess potential crew risks resulting from microbial decay processes during storage. Waste samples were collected post-orbiter landing and sorted into packaging material, food waste, toilet waste, and bulk liquid fractions deposited during flight in the volume F container. Aerobic and anaerobic microbial loads were determined in each fraction by cultivation on R2A and by acridine orange direct count (AODC). Dry and ash weights were performed to determine both water and organic content of the materials. Experiments to determine the aerobic and anaerobic biostability of refuse stored for varying periods of time were performed by on-line monitoring of CO2 and laboratory analysis for production of hydrogen sulfide and methane. Volatile organic compounds and permanent gases were analyzed using EPA Method TO15 by USEPA et al. [EPA Method TO15, The Determination of Volatile Organic Compounds (VOCs) in Ambient Air using SUMMA, Passivated Canister Sampling and Gas Chromatographic Analysis,1999] with gas chromatography/mass spectrometry and by gas chromatography with selective detectors. These baseline measures of waste stream content, labile organics, and microbial load in the volume F Shuttle trash provide data for waste subsystem analysis and atmospheric management within the ALS Project. Published by Elsevier Ltd on behalf of COSPAR.

NASA Center KSC↗

Mars Rover Sample Return: A sample collection and analysis strategy for exobiology

For reasons defined elsewhere it is reasonable to search for biological signatures, both chemical and morphological, of extinct life on Mars. Life on Earth requries the presence of liquid water, therefore, it is important to explore sites on Mars where standing bodies of water may have once existed. Outcrops of layered deposits within the Valles Marineris appear to be ancient lake beds. Because the outcrops are well exposed, relatively shallow core samples would be very informative. The most important biological signature to detect would be organics, microfossils, or larger stromato-like structures, although the presence of cherts, carbonates, clays, and shales would be significant. In spite of the limitations of current robotics and pattern recognition, and the limitations of rover power, computation, Earth communication bandwidth, and time delays, a partial scenario was developed to implement such a scientific investigation. The rover instrumentation and the procedures and decisions and IR spectrometer are described in detail. Preliminary results from a collaborative effort are described, which indicate the rover will be able to autonomously detect stratification, and hence will ease the interpretation burden and lead to greater scientific productivity during the rover's lifetime.

Sims, M. H.↗

Comprehensive modeling of a liquid rocket combustion chamber

An analytical model for the simulation of detailed three-phase combustion flows inside a liquid rocket combustion chamber is presented. The three phases involved are: a multispecies gaseous phase, an incompressible liquid phase, and a particulate droplet phase. The gas and liquid phases are continuum described in an Eulerian fashion. A two-phase solution capability for these continuum media is obtained through a marriage of the Implicit Continuous Eulerian (ICE) technique and the fractional Volume of Fluid (VOF) free surface description method. On the other hand, the particulate phase is given a discrete treatment and described in a Lagrangian fashion. All three phases are hence treated rigorously. Semi-empirical physical models are used to describe all interphase coupling terms as well as the chemistry among gaseous components. Sample calculations using the model are given. The results show promising application to truly comprehensive modeling of complex liquid-fueled engine systems.

Liang, P.-Y.↗

Astrobiology Exploration Strategies for the Mars Polar Regions Using Balloon Platforms

Montgolfiere balloons can provide a unique near-surface platform for an extended traverse over the polar regions of Mars. During the polar summer, such solar powered balloons would remain in the constant sun of the polar summer and could remain airborne for many weeks or even months as the atmospheric circulation would drive the balloons around the polar region many times before the balloon would cross the terminator. Such a platform for scientific measurements could provide in situ sampling of the atmosphere for trace disequilibrium species that might be indicators of present geological or biological activity in this region. It could furthermore provide high resolution imaging, deep electromagnetic (EM) sounding for subsurface stratigraphy and liquid water, and high spatial resolution neutron measurements of subsurface ice. Technologies for robust balloon deployment on entry and controlled encounters with the surface and near subsurface for sample acquisition in otherwise inaccessible regions are presently being studied and developed with support from NASA.

Mahaffy, P. R.↗

Astrobiology Exploration Strategies for the Mars Polar Regions Using Balloon Platforms

Montgolfiere balloons can provide a unique near-surface platform for an extended traverse over the polar regions of Mars. During the polar summer, such solar powered balloons would remain in the constant sun of the polar summer and could remain airborne for many weeks or even months as the atmospheric circulation would drive the balloons around the polar region many times before the balloon would cross the terminator. Such a platform for scientific measurements could provide in situ sampling of the atmosphere for trace disequilibrium species that might be indicators of present geological or biological activity in this regon. It could furthermore provide high resolution imaging, deep electromagnetic (EM) sounding for subsurface stratigraphy and liquid water, and high spatial resolution neutron measurements of subsurface ice. Technologies for robust balloon deployment on entry and controlled encounters with the surface and near subsurface for sample acquisition in otherwise inaccessible regions are presently being studied and developed with support from NASA.

Mahaffy, P. R.↗

Gentamicin: effect on E. coli in space

Previous investigations have shown that liquid bacterial cultures grown in space flight were not killed as effectively by antibiotic treatments as were cultures grown on Earth. However, the cause for the decreased antibiotic effectiveness remains unknown. Possible explanations include modified cell proliferation and modified antibiotic transport in the culture medium. Escherichia coli cultures were grown in space flight (STS-69 and STS-73), with and without gentamicin, on a solid agar substrate thus eliminating fluid effects and reducing the unknowns associated with space-flight bacterial cultures in suspension. This research showed that E. coli cultures grown in flight on agar for 24 to 27 hours experienced a heightened growth compared to simultaneous controls. However, addition of gentamicin to the agar killed the bacteria such that both flight and ground control E. coli samples had similar final cell concentrations. Therefore, while the reported existence of a decrease in antibiotic effectiveness in liquid cultures remains unexplained, these data suggest that gentamicin in space flight was at least as effective as, if not more effective than, on Earth, when E. coli cells were grown on agar.

STS-69 Shuttle Project↗

Combustion Synthesis of Fullerenes and Fullerenic Nanostructures In Microgravity

The objectives of the proposed research were to determine the effects of gravity on fullerenes formation in flames and, based on the observed effects, to develop fundamental understanding of fullerenes formation and to identify engineering principles for fullerenes production. The research method consisted of the operation of laminar diffusion flames under normal- and reduced-gravity conditions, and the collection from the flames and subsequent analysis of condensables including any fullerenes present, using coupled high performance liquid chromatography/mass spectrometry and high resolution transmission electron microscopy. The focus included fullerene molecules C60 and C70 and fullerenic nanostructures including tubes, spherules and other shapes. The normal-gravity experiments were performed at MIT and complementary reduced-gravity experiments were to have been contributed by NASA. The independent variables of interest are gravity, fuel type, fuel/oxygen ratio, pressure, gas velocity at burner, diluent type and concentration. Given the large number of variables and the absence of data on either fullerene formation in diffusion flames or gravitational effects on fullerene formation in diffusion or premixed flames, the first part of the work was exploratory while the later part involved detailed study of the most interesting mechanisms. Samples of condensable material from laminar low pressure benzene/argon/oxygen diffusion flames were collected and analyzed by high-performance liquid chromatography to determine the yields of fullerenes, and by high-resolution transmission electron microscopy (HRTEM) to characterize the fullerenic material, i.e., curved-layer nanostructures, on and within the soot particles. The highest concentration of fullerenes was always detected just above the visible stoichiometric surface of a flame. The percentage of fullerenes in the condensable material increases with decreasing pressure. The overall highest amount of fullerenes was found for a surprisingly high dilution fuel with argon. The maximum flame temperature seems to be of minor importance in fullerene formation. The HRTEM analysis of the soot showed an increase of the curvature of the carbon layers, and hence increased fullerenic character. After this maximum, the curvature decreases. In addition to the soot, the samples included fullerenic nanostructures, such as tubes and spheroids including highly-ordered multilayered or onion-like structures. The soot itself shows highly ordered regions that appear to have been cells of ongoing fullerenic nanostructure formation.

Howard, Jack B.↗

Phylogenetic and physiological diversity of microorganisms isolated from a deep greenland glacier ice core

We studied a sample from the GISP 2 (Greenland Ice Sheet Project) ice core to determine the diversity and survival of microorganisms trapped in the ice at least 120,000 years ago. Previously, we examined the phylogenetic relationships among 16S ribosomal DNA (rDNA) sequences in a clone library obtained by PCR amplification from genomic DNA extracted from anaerobic enrichments. Here we report the isolation of nearly 800 aerobic organisms that were grouped by morphology and amplified rDNA restriction analysis patterns to select isolates for further study. The phylogenetic analyses of 56 representative rDNA sequences showed that the isolates belonged to four major phylogenetic groups: the high-G+C gram-positives, low-G+C gram-positives, Proteobacteria, and the Cytophaga-Flavobacterium-Bacteroides group. The most abundant and diverse isolates were within the high-G+C gram-positive cluster that had not been represented in the clone library. The Jukes-Cantor evolutionary distance matrix results suggested that at least 7 isolates represent new species within characterized genera and that 49 are different strains of known species. The isolates were further categorized based on the isolation conditions, temperature range for growth, enzyme activity, antibiotic resistance, presence of plasmids, and strain-specific genomic variations. A significant observation with implications for the development of novel and more effective cultivation methods was that preliminary incubation in anaerobic and aerobic liquid prior to plating on agar media greatly increased the recovery of CFU from the ice core sample.

Bacteria/classification/genetics/isolation & purif↗

Laboratory studies of actinide partitioning relevant to 244Pu chronometry

Actinide partitioning and light lanthanide fractionation have been studied to gain an understanding of Pu chemistry under meteoritic and lunar conditions. The goal of the study was to identify conditions and samples from which chronological information can be retrieved. The laboratory investigations involved particle track radiography of the crystal/liquid partitioning of Th, U and Pu among diopsidic clinopyroxene, whitlockite and liquid. It is found that trivalent Pu plays an important role in partitioning for lunar and most meteoritic conditions. The use of Pu/Nd for relative age assessments is supported to some extent by the investigations; samples with unfractionated U, Th and Nd abundances (relative to average solar system values) may be suitable for Pu chronometry.

Benjamin, T.↗