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At least 433 records · Page 24

Integration of In-Flight and Post-Flight Water Monitoring Resources in Addressing the U.S. Water Processor Assembly Total Organic Carbon (TOC) Anomaly

Beginning in June of 2010, the total organic carbon (TOC) concentration in the U.S. Water Processor Assembly (WPA) product water started to increase. A surprisingly consistent upward TOC trend was observed through weekly ISS total organic carbon analyzer (TOCA) monitoring. As TOC is a general organic compound indicator, return of water archive samples was needed to make better-informed crew health decisions on the specific compounds of concern and to aid in WPA troubleshooting. TOCA-measured TOC was more than halfway to the health-based screening limit of 3,000 g/L before archive samples were returned. Archive samples were returned on 22 Soyuz in September 2010 and on ULF5 in November of 2010. The samples were subjected to extensive analysis. Although TOC was confirmed to be elevated, somewhat surprisingly, none of the typical target compounds were detected at high levels. After some solid detective work, it was confirmed that the TOC was associated with a compound known as dimethylsilanediol (DMSD). DMSD is believed to be a breakdown product of siloxanes which are thought to be ubiquitous in the ISS atmosphere. A toxicological limit was set for DMSD and a forward plan was developed for conducting operations in the context of understanding the composition of the TOC measured in flight. This required careful consideration of existing ISS flight rules, coordination with ISS stakeholders, and development of a novel approach for the blending of inflight TOCA data with archive results to protect crew health. Among other challenges, team members had to determine how to utilize TOCA readings when making decisions about crew consumption of WPA water. This involved balancing very real concerns associated with the assumption that TOC would continue to be comprised of only DMSD. Demonstrated teamwork, multidisciplinary awareness, and innovative problem-solving were required to respond effectively to this anomaly.

Straub, John E., II↗

Carbonaceous Meteorites Contain a Wide Range of Extraterrestrial Nucleobases

All terrestrial organisms depend on nucleic acids (RNA and DNA), which use pyrimidine and purine nucleobases to encode genetic information. Carbon-rich meteorites may have been important sources of organic compounds required for the emergence of life on the early Earth; however, the origin and formation of nuc1eobases in meteorites has been debated for over 50 y. So far, the few nuc1eobases reported in meteorites are biologically common and lacked the structural diversity typical of other indigenous meteoritic organics. Here, we investigated the abundance and distribution of nucleobases and nucleobase analogs in formic acid extracts of 12 different meteorites by liquid chromatography-mass spectrometry. The Murchison and Lonewolf Nunataks 94102 meteorites contained a diverse suite of nucleobases, which included three unusual and terrestrially rare nucleobase analogs; purine, 2,6-diminopurine, and 6,8-diaminopurine. In a parallel experiment, we found an identical suite of nucleobases and nucleobase analogs generated in reactions of ammonium cyanide. Additionally, these nucleobase analoge were not detected above our parts-per-billion detection limits in any of the procedural blanks, control samples, a terrestrial soil sample, and an Antarctic ice sample. Our results demonstrate that the purines detected in meteorites are consistent with products of ammonium cyanide chemistry, which provides a plausible mechanism for their synthesis in the asteroid parent bodies, and strongly supports an extraterrestrial origin. The discovery of new nucleobase analogs in meteorites also expands the prebiotic molecular inventory available for constructing the first genetic molecules.

Callahan, Michael P.↗

Amino Acids in Asteroids and Comets: Implications for the Origin of Life on Earth and Possibly Elsewhere

Meteorites provide a record of the chemical processes that occurred in the early solar system before life began on Earth. The delivery of organic matter by asteroids, comets, and their fragments to the Earth and other planetary bodies in our solar system could have been an important source of the prebiotic organic inventory needed for the emergence of life. Amino acids are essential components of proteins and enzymes in life on Earth and these prebiotic organic compounds have been detected in a wide variety of carbon-rich meteorites, the majority of which have been determined to be extraterrestrial in origin. In addition, many amino acids are structurally chiral (they possess handedness) and with a few very rare exceptions, only left handed (L) amino acids are found in biology, while all known abiotic syntheses of amino acids result in equal mixtures of left and right handed (L~D) amino acids. The discovery of a significant left handed amino acid imbalance of up to 20% in several different carbonaceous meteorites, could point toward a possible prebiotic contribution to the origin of biological homochirality by the exogenous delivery of extraterrestrial organic material to the early Earth. In this talk, I will focus on recent state-of-the-art measurements of the distribution, chirality, and isotopic composition of amino acids in meteorites and cometary samples carried out at the Goddard Astrobiology Analytical Laboratory. Results from the analyses of a variety of Antarctic meteorites, samples from comet Wild 2 returned by the STARDUST mission, and meteorite fragments of asteroid 2008 TC3 called Almahata Sitta recovered from northern Sudan will be discussed

Glavin, Daniel↗

Plasma Methane Pyrolysis for Spacecraft Oxygen Loop Closure

Life support is a critical function of any crewed space vehicle or habitat. Human life support systems on the International Space Station (ISS) include a number of atmosphere revitalization (AR) technologies to provide breathable air and a comfortable living environment to the crew. The Trace Contaminant Control System removes harmful volatile organic compounds and other trace contaminants from the circulating air. The Carbon Dioxide Removal Assembly (CDRA) removes metabolic carbon dioxide (CO2) and returns air to the cabin. Humidity is kept at comfortable levels by a number of condensing heat exchangers. The Oxygen Generation Assembly (OGA) electrolyzes water to produce oxygen for the crew and hydrogen (H2) as a byproduct. A Sabatier reaction-based CO2 Reduction Assembly (CRA) was launched to the ISS in 2009 and became fully operational in June 2011.The CRA interfaces with both the OGA and CDRA. Carbon dioxide from the CDRA is compressed and stored in tanks until hydrogen is available from OGA water electrolysis. When the OGA is operational and there is CO2 available, the CRA is activated and produces methane and water via the Sabatier reaction shown in Equation 1... One approach to achieve these higher recovery rates builds upon the ISS AR architecture and includes adding a methane post-processor to recover H2 from CRA methane. NASA has been developing the Plasma Pyrolysis Assembly (PPA) to fill the role of a methane post-processor.

Greenwood, Z. W.↗

Metallization with generic metallo-organic inks

The use and fabrication of metallo-organic films are discussed. Metallo-organic compounds are ones in which a metal is linked to a long chain carbon ligand through a hetero atom such as O, S, N, P or As. Films formed by the thermal decomposition of these metallo-organics are called MOD films. In order that the products of decomposition contain only CO2, H2O, and in rare cases nitrogen compounds, and to avoid S containing products, the use of a set of metallo-organic compounds for ink fabrication where the linking hetero atom was oxygen was pioneered. These links were made from commercially available carboxylates, or synthesized from commonly available reagents. The processing is described and the molecular design criteria are given. The particular carboxylates or amine carboxylates selected were the octoates or neodecanoates, and they are described.

Vest, G. M.↗

Influence of iodine on the treatment of spacecraft humidity condensate to produce potable water

Several compounds in the ersatz humidity condensate do react with iodine to form iodine-substituted organic compounds (TOI), most notably phenol, acetaldehyde, ethanol, and sodium formate. Iodination of the ersatz humidity condensate produced 3.0 to 3.5 mg/L of TOI within 24 hours. The TOI that was produced by the passage of the ersatz humidity condensate through the first iodinated resin (IR) in the adsorption system was removed by the granular activated carbon that followed. TOI detected in the final effluent was formed by the reaction of the non-adsorbable condensate compounds with the final IR in the treatment series. The activated carbon bed series in the adsorption system performed poorly in its removal of TOC. The rapid breakthrough of TOC was not surprising, as the ersatz humidity condensate contained several highly soluble organic compounds, alcohols and organic acids.

Symons, James M.↗

Powder containing 2H-type silicon carbide produced by reacting silicon dioxide and carbon powder in nitrogen atmosphere in the presence of aluminum

The production of powder which contains silicon carbide consisting of 40% of 2H-type silicon carbide, beta type silicon carbide and less than 3% of nitrogen is discussed. The reaction temperature to produce the powder containing 40% of 2H-type silicon carbide is set at above 1550 degrees C in an atmosphere of aluminum or aluminum compounds and nitrogen gas or an antioxidation atmosphere containing nitrogen gas. The mixture ratio of silicon dioxide and carbon powder is 0.55 - 1:2.0 and the contents of aluminum or aluminum compounds within silicon dioxide is less than 3% in weight.

Kuramoto, N.↗

Geochemical characteristics of organic compounds in a permafrost sediment core sample from northeast Siberia, Russia

We studied total organic carbon (TOC), hydrocarbons and fatty acids in a permafrost sediment core sample (well 6-90, length 32.0 m, 1.5-2.5 Ma BP) from northeast Siberia (approximately 70 degrees N, 158 degrees E), Russia, to elucidate their geochemical features in relation to source organisms and paleoenvironmental conditions. Long-chain n-alkanes and n-alkanoic acids (>C19) were most predominant hydrocarbons and fatty acids, respectively, so organic matter in the sediment core was derived mainly from vascular plants and, to a much smaller extent, from bacteria. Low concentrations of unsaturated fatty acids revealed that organic matter in the sediment core was considerably degraded during and/or after sedimentation. The predominance of vascular plant components, the major ionic components of nonmarine sources, and geological data strongly implied that the sediment layers were formed in shallow lacustrine environments, such as swamp with large influences of tundra or forest-tundra vegetation. Also, no drastic changes in paleoenvironmental conditions for biological activity or geological events, such as sea transgressions or ice-sheet influences, occurred at the sampling site approximately 100 km from the coast of the East Siberian Sea during the late Pliocene an early Pleistocene periods.

NASA Discipline Exobiology↗

Concentration-time data in toxicity tests and resulting relationships

Periodic analyses for carbon monoxide and methane in the animal exposure chamber during pyrolysis of polyethylene at 800 C without forced air flow showed that the concentrations of these compounds increased with exposure time. These observations, and similar observations for polyurethane flexible foam, permitted the calculation of carbon monoxide toxicity in terms of a DP (Death Product Concentration) value, in addition to flammability in terms of HC (Hydro Carbon) value. Observed DP values exceeding the critical DP(CO) value of 47,200 ppm-min for carbon monoxide may indicate that lethal exposures were reached earlier but not immediately manifested because of the time delay involved in physiological processes. On the basis of this DP(CO) value, carbon monoxide could have been the sole toxicant in the case of polyethylene, polypropylene, polyoxymethylene, polystyrene, polycarbonate, ethylene propylene diene rubber, and wood.

Hilado, C. J.↗

Could life originate now?

Abiogenesis, discussing hydrogen, oxygen, carbon, nitrogen and sulfur conversion into amino acids for simple organic compounds formation

Fox, S. W.↗

Model systems for life processes on Mars

In the evolution of life forms nonphotosynthetic mechanisms are developed. The question remains whether a total life system could evolve which is not dependent upon photosynthesis. In trying to visualize life on other planets, the photosynthetic process has problems. On Mars, the high intensity of light at the surface is a concern and alternative mechanisms need to be defined and analyzed. In the UV search for alternate mechanisms, several different areas may be identified. These involve activated inorganic compounds in the atmosphere, such as the products of photodissociation of carbon dioxide and the organic material which may be created by natural phenomena. In addition, a life system based on the pressure of the atmospheric constituents, such as carbon dioxide, is a possibility. These considerations may be important for the understanding of evolutionary processes of life on another planet. Model systems which depend on these alternative mechanisms are defined and related to presently planned and future planetary missions.

Mitz, M. A.↗

Scientific Assessment of Stratospheric Ozone: 1989, volume 2. Appendix: AFEAS Report

The results are presented of the Alternative Fluorocarbon Environmental Acceptability Study (AFEAS), which was organized to evaluate the potential effects on the environment of alternate compounds targeted to replace fully halogenated chlorofluorocarbons (CFCs). All relevant current scientific information to determine the environmental acceptability of the alternative fluorocarbons. Special emphasis was placed on: the potential of the compounds to affect stratospheric ozone; their potential to affect tropospheric ozone; their potential to contribute to model calculated global warming; the atmospheric degradation mechanisms of the compounds, in order to identify their products; and the potential environmental effects of the decomposition products. The alternative compounds to be studied were hydrofluorocarbons (HFCs) with one or two carbon atoms and one or more each of fluorine and hydrogen.

Source record↗

The meteoritic record of presolar and early solar system organic chemistry

Carbon, hydrogen, and nitrogen isotopic analyses of various classes of organic compounds done in collaboration with Epstein and Krishnamurthy (Caltech) have shown these compounds to be enriched to varying degrees in the heavier isotopes. These results, in particular the large deuterium enrichments, have been interpreted as indicating an interstellar origin for the meteorite compounds or their precursors. Such isotopic fractionations, of hydrogen especially, are characteristic of low temperature ion-molecule reactions in cold interstellar clouds. There is also evidence from the large corresponding suites of alpha-amino and alpha-hydroxy acids found in meteorites suggesting that aqueous phase chemistry on the meteorite parent body played an important role in the formation of these compounds. These data support the hypothesis that interstellar compounds survived in the solar nebula at a radial distance corresponding to the asteroid belt, were incorporated into the parent body in icy, volatile-rich, planetesinals, and underwent further reactions during a period of aqueous activity within the early parent body to give the present suite of meteorite compounds. This formation hypothesis will be discussed and the results of recent isotopic and molecular analyses bearing on it will be presented.

Cronin, John R.↗

Sol-gel Technology and Advanced Electrochemical Energy Storage Materials

Advanced materials play an important role in the development of electrochemical energy devices such as batteries, fuel cells, and electrochemical capacitors. The sol-gel process is a versatile solution for use in the fabrication of ceramic materials with tailored stoichiometry, microstructure, and properties. This processing technique is particularly useful in producing porous materials with high surface area and low density, two of the most desirable characteristics for electrode materials. In addition,the porous surface of gels can be modified chemically to create tailored surface properties, and inorganic/organic micro-composites can be prepared for improved material performance device fabrication. Applications of several sol-gel derived electrode materials in different energy storage devices are illustrated in this paper. V2O5 gels are shown to be a promising cathode material for solid state lithium batteries. Carbon aerogels, amorphous RuO2 gels and sol-gel derived hafnium compounds have been studied as electrode materials for high energy density and high power density electrochemical capacitors.

Chung-tse Chu↗

Joining Carbon-Carbon Composites and High-Temperature Materials with High Energy Electron Beams

1. Program goals addressed during this period. Experimental work was directed at formation of a low-stress bond between carbon- carbon and aluminum, with the objective of minimizing the heating of the aluminum substrate, thereby minimizing stresses resulting from the coefficient of thermal expansion (CTE) difference between the aluminum and carbon-carbon. A second objective was to form a bond between carbon-carbon and aluminum with good thermal conductivity for electronic thermal management (SEM-E) application. 2. Substrates and joining materials selected during this period. Carbon-Carbon Composite (CCC) to Aluminum. CCC (Cu coated) to Aluminum. Soldering compounds based on Sn/Pb and Sn/Ag/Cu/Bi compositions. 3. Soldering experiments performed. Conventional techniques. High Energy Electron Beam (HEEB) process.

Goodman, Daniel↗

Development and Performance of the Oxygen Sensor in the CSA-CP Aboard the International Space Station

A combustion products analyzer (CPA) was built for use on Shuttle in response to several thermodegradation incidents that had occurred during early flights. The CPA contained sensors that measured carbon monoxide, hydrogen chloride, hydrogen cyanide, and hydrogen fluoride. These marker compounds, monitored by the CPA, were selected based upon the likely products to be released in a spacecraft fire. When the Toxicology Laboratory group at Johnson Space Center (JSC) began to assess the air quality monitoring needs for the International Space Station (ISS), the CPA was the starting point for design of an instrument to monitor the atmosphere following a thermodegradation event. The final product was significantly different from the CPA and was named the compound specific analyzer-combustion products (CSA-CP). The major change from the CPA that will be the focus of this paper was the replacement of an unreliable hydrogen fluoride (HF) sensor with an oxygen sensor. A reliable HF sensor was not commercially available, but as the toxicology group reviewed the overall monitoring strategy for ISS, it appeared that a portable oxygen sensor to backup the major constituent analyzer was needed. Therefore, an oxygen sensor replaced the HF sensor in the new instrument. This paper will describe the development, deployment, and performance of the CSA-CP oxygen sensor on both Shuttle and ISS. Also, data for CSA-CP oxygen sensor accuracy at nominal and reduced pressures will be presented.

Limero, Thomas↗

Radial Breathing Modes in Cosmochemistry and Meteoritics

One area of continuing interest in cosmochemistry and meteoritics (C&M) is the identification of the nature of Q-phase, although some researchers in C&M are not reporting relevant portions of Raman spectral data. Q is the unidentified carrier of noble gases in carbonaceous chondrites (CCs). Being carbonaceous, the focus has been on any number of Q-candidates arising from the sp2 hybridization of carbon (C). These all derive from various forms of graphene, a monolayer of C atoms packed into a two-dimensional (2D) hexagonal honeycomb lattice that is the basic building block for graphitic materials of all other dimensions for sp2 allotropes of C. As a basic lattice, 2D graphene can be curled into fullerenes (0D), wrapped into carbon nanotubes or CNTs (1D), and stacked into graphite (3D). These take such additional forms as scroll-like carbon whiskers, carbon fibers, carbon onions, GPCs (graphite polyhedral crystals) [6], and GICs (graphite intercalation compounds). Although all of these have been observed in meteoritics, the issue is which can explain the Q-abundances. In brief, one or more of the 0D-3D sp2 hybridization forms of C is Q. For some Q-candidates, the radial breathing modes (RBMs) are the most important Raman active vibrational modes that exist, and bear a direct relevance to solving this puzzle. Typically in C&M they are ignored when present. Their importance is addressed here as smoking-gun signatures for certain Q-candidates and are very relevant to the ultimate identification of Q.

Wilson, T.L.↗

Discovery and Identification of Dimethylsilanediol as a Contaminant in ISS Potable Water

In September of 2010, analysis of ISS potable water samples was undertaken to determine the contaminant responsible for a rise in total organic carbon (TOC). As analysis of the routine target list of organic compounds did not reveal the contaminant, efforts to look for unknown compounds was initiated, resulting in an unknown peak being discovered in the gas chromatography/mass spectrometry (GC/MS) analysis for glycols. A mass spectrum of the contaminant was then generated by concentrating one of the samples by evaporation and analyzing by GC/MS in full-scan mode. Although a computer match of the compound s identity could not be obtained with the instrument s database, a search with a more up to date mass spectral library yielded a good match with dimethylsilanediol (DMSD). Inductively Coupled Plasma/Mass Spectrometry (ICP/MS) analyses showed abnormally high silicon levels in the samples, confirming that the unknown contained silicon. DMSD was then synthesized to confirm the identification and provide a standard to develop a calibration curve. Further confirmation was provided by external Direct Analysis in Real Time (DART) GC/MS analysis. A preliminary GC/MS method was then developed and archived samples from various locations on ISS were analyzed to determine the extent of the contamination and provide data for troubleshooting. This paper describes these events in more detail as well as problems encountered in routine GC/MS analyses and the subsequent development of high performance liquid chromatography and LC/MS/MS methods for quantitation of DMSD.

Rutz, Jeffrey A.↗