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NASA NTRS2003

Organizing Diverse, Distributed Project Information

SemanticOrganizer is a software application designed to organize and integrate information generated within a distributed organization or as part of a project that involves multiple, geographically dispersed collaborators. SemanticOrganizer incorporates the capabilities of database storage, document sharing, hypermedia navigation, and semantic-interlinking into a system that can be customized to satisfy the specific information-management needs of different user communities. The program provides a centralized repository of information that is both secure and accessible to project collaborators via the World Wide Web. SemanticOrganizer's repository can be used to collect diverse information (including forms, documents, notes, data, spreadsheets, images, and sounds) from computers at collaborators work sites. The program organizes the information using a unique network-structured conceptual framework, wherein each node represents a data record that contains not only the original information but also metadata (in effect, standardized data that characterize the information). Links among nodes express semantic relationships among the data records. The program features a Web interface through which users enter, interlink, and/or search for information in the repository. By use of this repository, the collaborators have immediate access to the most recent project information, as well as to archived information. A key advantage to SemanticOrganizer is its ability to interlink information together in a natural fashion using customized terminology and concepts that are familiar to a user community.

Keller, Richard M.↗

NASA NTRS2012

Organic Combustion in the Presence of Ca-Carbonate and Mg-Perchlorate: A Possible Source for the Low Temperature CO2 Release Seen in Mars Phoenix Thermal and Evolved Gas Analyzer Data

Two of the most important discoveries of the Phoenix Lander were the detection of approx.0.6% perchlorate [1] and 3-5% carbonate [2] in landing site soils. The Thermal and Evolved Gas Analyzer (TEGA) instrument on the Phoenix lander could heat samples up to approx.1000 C and monitor evolved gases with a mass spectrometer. TEGA detected a low (approx.350 C) and high (approx.750 C) temperature CO2 release. The high temp release was attributed to the thermal decomposition of Ca-carbonate (calcite). The low temperature CO2 release could be due to desorption of CO2, decomposition of a different carbonate mineral, or the combustion of organic material. A new hypothesis has also been proposed that the low temperature CO2 release could be due to the early breakdown of calcite in the presence of the decomposition products of certain perchlorate salts [3]. We have investigated whether or not this new hypothesis is also compatible with organic combustion. Magnesium perchlorate is stable as Mg(ClO4)2-6H2O on the martian surface [4]. During thermal decomposition, this perchlorate salt releases H2O, Cl2, and O2 gases. The Cl2 can react with water to form HCl which then reacts with calcite, releasing CO2 below the standard thermal decomposition temperature of calcite. However, when using concentrations of perchlorate and calcite similar to what was detected by Phoenix, the ratio of high:low temperature CO2 evolved is much larger in the lab, indicating that although this process might contribute to the low temp CO2 release, it cannot account for all of it. While H2O and Cl2 cause calcite decomposition, the O2 evolved during perchlorate decomposition can lead to the combustion of any reduced carbon present in the sample [5]. We investigate the possible contribution of organic molecules to the low temperature CO2 release seen on Mars.

Archer, Douglas↗

NASA NTRS2012

Organic Synthesis via Irradiation and Warming of Ice Grains in the Solar Nebula

Complex organic compounds, including many important to life on Earth, are commonly found in meteoritic and cometary samples, though their origins remain a mystery. We examined whether such molecules could be produced within the solar nebula by tracking the dynamical evolution of ice grains in the nebula and recording the environments they were exposed to. We found that icy grains originating in the outer disk, where temperatures were less than 30 K, experienced UV irradiation exposures and thermal warming similar to that which has been shown to produce complex organics in laboratory experiments. These results imply that organic compounds are natural byproducts of protoplanetary disk evolution and should be important ingredients in the formation of all planetary systems, including our own.

Ciesla, Fred J.↗

NASA NTRS2012

Nucleobases and Prebiotic Molecules in Organic Residues Produced from the Ultraviolet Photo-Irradiation of Pyrimidine in NH3 and H2O+NH3 Ices

Although not yet identified in the interstellar medium (ISM), N-heterocycles including nucleobases the information subunits of DNA and RNA are present in carbonaceous chondrites, which indicates that molecules of biological interest can be formed in non-terrestrial environments via abiotic pathways. Recent laboratory experiments and ab-initio calculations have already shown that the irradiation of pyrimidine in pure H2O ices leads to the formation of a suite of oxidized pyrimidine derivatives, including the nucleobase uracil. In the present work, NH3:pyrimidine and H2O:NH3:pyrimidine ice mixtures with different relative proportions were irradiated with UV photons under astrophysically relevant conditions. Liquid- and gas-chromatography analysis of the resulting organic residues has led to the detection of the nucleobases uracil and cytosine, as well as other species of prebiotic interest such as urea and small amino acids. The presence of these molecules in organic residues formed under abiotic conditions supports scenarios in which extraterrestrial organics that formed in space and were subsequently delivered to telluric planets via comets and meteorites could have contributed to the inventory of molecules that triggered the first biological reactions on their surfaces.

Nuevo, Michel↗

NASA NTRS2012

Detecting Organic Compounds Released from Iron Oxidizing Bacteria using Sample Analysis at Mars (SAM) Like Instrument Protocols

Mars is a planet of great interest for Astrobiology since its past environmental conditions are thought to have been favourable for the emergence life. At present, the Red Planet is extremely cold and dry and the surface is exposed to intense UV and ionizing radiation, conditions generally considered to be incompatible with life as we know it on Earth. It was proposed that the shallow subsurface of Mars, where temperatures can be above freezing and liquid water can exist on rock surfaces, could harbor chemolithoautotrophic bacteria such as the iron oxidizing microorganism Pseudomonas sp. HerB. The Mars Science Laboratory (MSL) mission will provide the next opportunity to carry out in situ measurements for organic compounds of possible biological origin on Mars. One instrument onboard MSL, called the Sample Analysis at Mars (SAM) instrument suite, will carry out a broad and sensitive search for organic compounds in surface samples using either high temperature pyrolysis or chemical extraction followed by gas chromatography mass spectrometry. We present gas chromatograph mass spectrometer (GC/MS) data on crushed olivine rock powders that have been inoculated with Pseudomonas sp. HerB at different concentrations ranging from approx 10(exp 2) to 10(exp 7) cells per gram. The inoculated olivine samples were heated under helium carrier gas flow at 500 C and the pyrolysis products concentrated using a SAM-like hydrocarbon trap set at -20 C followed by trap heating and analysis by GC/Ms. In addition, the samples were also extracted using a low temperature "one-pot" chemical extraction technique using N-methyl, N-(tert-butyldimethylsilyl) trifluoroacetamide (MTBSTFA) as the silylating agent prior to GC/MS analysis. We identified several aldehydes, thiols, and alkene nitriles after pyrolysis GC/MS analysis of the bacteria that were not found in the olivine control samples that had not been inoculated with bacteria. The distribution of pyrolysis products extracted from the bacteria was clearly distinct from similar GC/MS analyses of the carbonaceous meteorite Murchison that was dominated by sulfur containing aromatic compounds. A similar comparison, if organic compounds are detected by SAM on Mars, could be useful to help discriminate between meteoritic or biological origins.

Glavin, D. P.↗

NASA NTRS2013

Organic Contamination Baseline Study on NASA JSC Astromaterial Curation Gloveboxes

Future planned sample return missions to carbon-rich asteroids and Mars in the next two decades will require strict handling and curation protocols as well as new procedures for reducing organic contamination. After the Apollo program, astromaterial collections have mainly been concerned with inorganic contamination [1-4]. However, future isolation containment systems for astromaterials, possibly nitrogen enriched gloveboxes, must be able to reduce organic and inorganic cross-contamination. In 2012, a baseline study was orchestrated to establish the current state of organic cleanliness in gloveboxes used by NASA JSC astromaterials curation labs that could be used as a benchmark for future mission designs.

Calaway, Michael J.↗

NASA NTRS2013

High-Resolution Infrared Spectroscopic Measurements of Comet 2PlEncke: Unusual Organic Composition and Low Rotational Temperatures

We present high-resolution infrared spectroscopic measurements of the ecliptic comet 2P/Encke, observed on 4-6 Nov. 2003 during its close approach to the Earth, using the Near Infrared Echelle Spectrograph on the Keck II telescope. We present flux-calibrated spectra, production rates, and mixing ratios for H2O, CH3OH, HCN, H2CO, C2H2, C2H6, CH4 and CO. Comet 2P/Encke is a dynamical end-member among comets because of its short period of 3.3 years. Relative to "organics-normal" comets, we determined that 2PlEncke is depleted in HCN, H2CO, C2H2, C2H6, CH4 and CO, but it is enriched in CH3OH. We compared mixing ratios of these organic species measured on separate dates, and we see no evidence of macroscopic chemical heterogeneity in the nucleus of 2P/Encke, however, this conclusion is limited by sparse temporal sampling. The depleted abundances of most measured species suggest that 2P/Encke may have formed closer to the young Sun, before its insertion to the Kuiper belt, compared with "organics-normal" comets - as was previously suggested for other depleted comets (e.g. C/1999 S4 (LINEAR)). We measured very low rotational temperatures of 20 - 30 K for H2O, CH3OH and HCN in the near nucleus region of 2P/Encke, which correlate with one of the lowest cometary gas production rates (approx. 2.6 x 10(exp 27) molecules/s) measured thus far in the infrared. This suggests that we are seeing the effects of more efficient radiative cooling, insufficient collisional excitation, and/or inefficient heating by fast H-atoms (and icy grains) in the observed region of the coma. Its extremely short orbital period, very low gas production rate, and classification as an ecliptic comet, make 2PlEncke an important addition to our growing database, and contribute significantly to the establishment of a chemical taxonomy of comets.

Radeva, Yana L.↗

NASA NTRS2012

Compact Two-step Laser Time-of-Flight Mass Spectrometer for in Situ Analyses of Aromatic Organics on Planetary Missions

RATIONALE A miniature time-of-flight mass spectrometer has been adapted to demonstrate two-step laser desorption-ionization (LOI) in a compact instrument package for enhanced organics detection. Two-step LDI decouples the desorption and ionization processes, relative to traditional laser ionization-desorption, in order to produce low-fragmentation conditions for complex organic analytes. Tuning UV ionization laser energy allowed control ofthe degree of fragmentation, which may enable better identification of constituent species. METHODS A reflectron time-of-flight mass spectrometer prototype measuring 20 cm in length was adapted to a two-laser configuration, with IR (1064 nm) desorption followed by UV (266 nm) postionization. A relatively low ion extraction voltage of 5 kV was applied at the sample inlet. Instrument capabilities and performance were demonstrated with analysis of a model polycyclic aromatic hydrocarbon, representing a class of compounds important to the fields of Earth and planetary science. RESULTS L2MS analysis of a model PAH standard, pyrene, has been demonstrated, including parent mass identification and the onset o(tunable fragmentation as a function of ionizing laser energy. Mass resolution m/llm = 380 at full width at half-maximum was achieved which is notable for gas-phase ionization of desorbed neutrals in a highly-compact mass analyzer. CONCLUSIONS Achieving two-step laser mass spectrometry (L2MS) in a highly-miniature instrument enables a powerful approach to the detection and characterization of aromatic organics in remote terrestrial and planetary applications. Tunable detection of parent and fragment ions with high mass resolution, diagnostic of molecular structure, is possible on such a compact L2MS instrument. Selectivity of L2MS against low-mass inorganic salt interferences is a key advantage when working with unprocessed, natural samples, and a mechanism for the observed selectivity is presented.

Getty, Stephanie↗

NASA NTRS2013

Complex Indigenous Organic Matter Embedded in Apollo 17 Volcanic Black Glass Surface Deposits

Papers presented at the first Lunar Science Conference [1] and those published in the subsequent Science Moon Issue [2] reported the C content of Apollo II soils, breccias, and igneous rocks as rang-ing from approx.50 to 250 parts per million (ppm). Later Fegley & Swindle [3] summarized the C content of bulk soils from all the Apollo missions as ranging from 2.5 (Apollo 15) to 280 ppm (Apollo 16) with an overall average of 124+/- 45 ppm. These values are unexpectedly low given that multiple processes should have contributed (and in some cases continue to contribute) to the lunar C inventory. These include exogenous accretion of cometary and asteroidal dust, solar wind implantation, and synthesis of C-bearing species during early lunar volcanism. We estimate the contribution of C from exogenous sources alone is approx.500 ppm, which is approx.4x greater than the reported average. While the assessm ent of indigenous organic matter (OM) in returned lunar samples was one of the primary scientific goals of the Apollo program, extensive analysis of Apollo samples yielded no evidence of any significant indigenous organic species. Furthermore, with such low concentrations of OM reported, the importance of discriminating indigenous OM from terrestrial contamination (e.g., lunar module exhaust, sample processing and handling) became a formidable task. After more than 40 years, with the exception of CH4 [5-7], the presence of indigenous lunar organics still remains a subject of considerable debate. We report for the first time the identification of arguably indigenous OM present within surface deposits of black glass grains collected on the rim of Shorty crater during the Apollo 17 mission by astronauts Eugene Cernan and Harrison Schmitt.

Thomas-Keprta, Kathie L.↗

NASA NTRS2008

Applying Knowledge Management to an Organization's Transformation

Although workers in the information age have more information at their fingertips than ever before, the ability to effectively capture and reuse actual knowledge is still a surmounting challenge for many organizations. As high tech organizations transform from providing complex products and services in an established domain to providing them in new domains, knowledge remains an increasingly valuable commodity. This paper explores the supply and demand elements of the "knowledge market" within the International Space Station and Spacecraft Processing Directorate (ISSSPD) of NASA's Kennedy Space Center (KSC). It examines how knowledge supply and knowledge demand determine the success of an organization's knowledge management (KM) activities, and how the elements of a KM infrastructure (tools, culture, and training), can be used to create and sustain knowledge supply and demand

Potter, Shannon↗

NASA NTRS2013

Characteristics of Mesoscale Organization in WRF Simulations of Convection during TWP-ICE

Compared to satellite-derived heating profiles, the Goddard Institute for Space Studies general circulation model (GCM) convective heating is too deep and its stratiform upper-level heating is too weak. This deficiency highlights the need for GCMs to parameterize the mesoscale organization of convection. Cloud-resolving model simulations of convection near Darwin, Australia, in weak wind shear environments of different humidities are used to characterize mesoscale organization processes and to provide parameterization guidance. Downdraft cold pools appear to stimulate further deep convection both through their effect on eddy size and vertical velocity. Anomalously humid air surrounds updrafts, reducing the efficacy of entrainment. Recovery of cold pool properties to ambient conditions over 5-6 h proceeds differently over land and ocean. Over ocean increased surface fluxes restore the cold pool to prestorm conditions. Over land surface fluxes are suppressed in the cold pool region; temperature decreases and humidity increases, and both then remain nearly constant, while the undisturbed environment cools diurnally. The upper-troposphere stratiform rain region area lags convection by 5-6 h under humid active monsoon conditions but by only 1-2 h during drier break periods, suggesting that mesoscale organization is more readily sustained in a humid environment. Stratiform region hydrometeor mixing ratio lags convection by 0-2 h, suggesting that it is strongly influenced by detrainment from convective updrafts. Small stratiform region temperature anomalies suggest that a mesoscale updraft parameterization initialized with properties of buoyant detrained air and evolving to a balance between diabatic heating and adiabatic cooling might be a plausible approach for GCMs.

Del Genio, Anthony D.↗

NASA NTRS2013

Irradiated Benzene Ice Provides Clues to Meteoritic Organic Chemistry

Aromatic hydrocarbons account for a significant portion of the organic matter in carbonaceous chondrite meteorites, as a component of both the low molecular weight, solvent-extractable compounds and the insoluble organic macromolecular material. Previous work has suggested that the aromatic compounds in carbonaceous chondrites may have originated in the radiation-processed icy mantles of interstellar dust grains. Here we report new studies of the organic residue made from benzene irradiated at 19 K by 0.8 MeV protons. Polyphenyls with up to four rings were unambiguously identified in the residue by gas chromatography-mass spectrometry. Atmospheric pressure photoionization Fourier transform mass spectrometry was used to determine molecular composition, and accurate mass measurements suggested the presence of polyphenyls, partially hydrogenated polyphenyls, and other complex aromatic compounds. The profile of low molecular weight compounds in the residue compared well with extracts from the Murchison and Orgueil meteorites. These results are consistent with the possibility that solid phase radiation chemistry of benzene produced some of the complex aromatics found in meteorites.

benzene↗

NASA NTRS2014

Interstellar Organics, the Solar Nebula, and Saturn's Satellite Phoebe

The diffuse interstellar medium inventory of organic material (Pendleton et al. 1994, Pe 2002) was likely incorporated into the molecular cloud in which the solar nebula condensed. This provided the feedstock for the fo planets, and the smaller icy bodies in the region outside Neptune's orbit (transneptunian objects, or TNOs). Saturn's satellites Phoeb open a window to the composition of one class of TNO as revealed by the near-infrared mapping spectrometer (VIMS) on the Cass Phoebe (mean diameter 213 km) is a former TNO now orbiting Saturn. VIMS spectral maps of Phoebe's surface reveal a complex consisting of prominent aromatic (CH) and aliphatic hydrocarbon (CH2, CH3) absorption bands (3.2-3.6 μm). Phoebe is the source encircling Saturn, and from which particles (~5-20 μm size) spiral inward toward Saturn. They encounter Iapetus and Hyperion wh blanket the native H2O ice of those two bodies. Quantitative analysis of the hydrocarbon bands on Iapetus demonstrates that aroma abundant as aliphatic CH2+CH3, significantly exceeding the strength of the aromatic signature in interplanetary dust particles, com carbonaceous meteorites (Cruikshank et al. 2013). A similar excess of aromatics over aliphatics is seen in the qualitative analysis o itself (Dalle Ore et al. 2012). The Iapetus aliphatic hydrocarbons show CH2/CH3 ~4, which is larger than the value found in the di as Phoebe is a primitive body that formed in the outer regions of the solar nebula and has preserved some of the original nebula inv understanding the content and degree of processing of that nebular material. There are other Phoebe-like TNOs that are presently b in the organic spectral region, but JWST will open that possibility for a number of objects. We now need to explore and understand organic-bearing Solar System material to the solar nebula and the inventory of ISM materials incorporated therein.

Interstellar↗

NASA NTRS2014

An Evaluation of Technology to Remove Problematic Organic Compounds from the International Space Station Potable Water

Since activation of the Water Processor Assembly (WPA) on the International Space Station (ISS) in November of 2008, there have been three events in which the TOC (Total Organic Carbon) in the product water has increased to approximately 3 mg/L and has subsequently recovered. Analysis of the product water in 2010 identified the primary component of the TOC as dimethylsilanediol (DMSD). An investigation into the fate of DMSD in the WPA ultimately determined that replacement of both Multifiltration (MF) Beds is the solution to recovering product water quality. The MF Beds were designed to ensure that ionic breakthrough occurs before organic breakthrough. However, DMSD saturated both MF Beds in the series, requiring removal and replacement of both MF Beds with significant life remaining. Analysis of the MF Beds determined that the adsorbent was not effectively removing DMSD, trimethylsilanol, various polydimethylsiloxanes, or dimethylsulfone. Coupled with the fact that the current adsorbent is now obsolete, the authors evaluated various media to identify a replacement adsorbent as well as media with greater capacity for these problematic organic contaminants. This paper provides the results and recommendations of this collaborative study.

Rector, Tony↗

NASA NTRS2014

Performance of the Linear Ion Trap Mass Spectrometer for the Mars Organic Molecule Analyzer (MOMA) Investigation on the 2018 Exomars Rover

The 2018 ExoMars rover mission includes the Mars Organic Molecule Analyzer (MOMA) investigation. MOMA will examine the chemical composition of samples acquired from depths of up to two meters below the martian surface, where organics may be protected from degradation derived from cosmic radiation and/or oxidative chemical reactions. When combined with the complement of instruments in the rover's Pasteur Payload, MOMA has the potential to reveal the presence of a wide range of organics preserved in a variety of mineralogical environments, and to begin to understand the structural character and potential origin of those compounds. The MOMA investigation is led by the Max Planck Institute for Solar System Research (MPS) with the mass spectrometer subsystem provided by NASA GSFC. MOMA's linear ion trap mass spectrometer (ITMS) is designed to analyze molecular composition of: (i) gas evolved from pyrolyzed powder samples and separated in a gas chromatograph; and, (ii) ions directly desorbed from crushed solid samples at Mars ambient pressure, as enabled by a pulsed UV laser system, fast-actuating aperture valve and capillary ion inlet. Breadboard ITMS and associated electronics have been advanced to high end-to-end fidelity in preparation for flight hardware delivery to Germany in 2015.

linear ion trap mass spectrometer↗

NASA NTRS2015

Nanophase Carbonates on Mars: Does Evolved Gas Analysis of Nanophase Carbonates Reveal a Large Organic Carbon Budget in Near-Surface Martian Materials?

Evolved Gas Analysis (EGA), which involves heating a sample and monitoring the gases released, has been performed on Mars by the Viking gas chromatography/mass spectrometry instruments, the Thermal and Evolved Gas Analyzer (TEGA) on the Phoenix lander, and the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory. All of these instruments detected CO2 released during sample analysis at abundances of approx. 0.1 to 5 wt% assuming a carbonate source. The source of the CO2 can be constrained by evaluating the temperature of the gas release, a capability of both the TEGA and SAM instruments. The samples analyzed by SAM show that the majority of the CO2 is released below 400C, much lower than traditional carbonate decomposition temperatures which can be as low as 400C for some siderites, with magnesites and calcites decomposing at even higher temperatures. In addition to mineralogy, decomposition temperature can depend on particle size (among other factors). If carbonates formed on Mars under low temperature and relative humidity conditions, the resulting small particle size (nanophase) carbonates could have low decomposition temperatures. We have found that calcite can be synthesized by exposing CaO to water vapor and CO2 and that the resulting mineral has an EGA peak of approx. 550C for CO2, which is about 200C lower than for other calcites. Work is ongoing to produce Fe and Mg-bearing carbonates using the same process. Current results suggest that nanophase calcium carbonates cannot explain the CO2 released from martian samples. If the decomposition temperatures of Mg and Fe-bearing nanophase carbonates are not significantly lower than 400C, other candidate sources include oxalates and carboxylated organic molecules. If present, the abundance of organic carbon in these samples could be greater than 0.1 wt % (1000s of ppm), a signficant departure from the paradigm of the organic-poor Mars based on Viking results.

Archer, P. Douglas, Jr.↗

NASA NTRS2015

Organic Aerosol Volatility Parameterizations and Their Impact on Atmospheric Composition and Climate

Despite their importance and ubiquity in the atmosphere, organic aerosols are still very poorly parameterized in global models. This can be explained by two reasons: first, a very large number of unconstrained parameters are involved in accurate parameterizations, and second, a detailed description of semi-volatile organics is computationally very expensive. Even organic aerosol properties that are known to play a major role in the atmosphere, namely volatility and aging, are poorly resolved in global models, if at all. Studies with different models and different parameterizations have not been conclusive on whether the additional complexity improves model simulations, but the added diversity of the different host models used adds an unnecessary degree of variability in the evaluation of results that obscures solid conclusions.

Volatility↗

NASA NTRS2015

Organic Aerosol Volatility Parameterizations and Their Impact on Atmospheric Composition and Climate

Aerosols↗