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At least 73 records · Page 4

Sensitive gas chromatographic detection of acetaldehyde and acetone using a reduction gas detector

The response of a newly available mercuric oxide Reduction Gas Detector (RGD-2) to subpicomole and larger quantities of acetaldehyde and acetone is tested. The RGD-2 is found to be capable of subpicomole detection for these carbonyls and is more sensitive than an FID (Flame Ionization Detector) by an order of magnitude. Operating parameters can be further optimized to make the RGD-2 some 20-40 times more sensitive than an FID. The detector is linear over a wide range and is easily adapted to a conventional gas chromatograph (GC). Such a GC-RGD-2 system should be suitable for atmospheric carbonyl measurements in clean as well as polluted environments.

O'Hara, Dean↗

Microfluidic Icy-World Chemical Analyzer

Measurements made with the Wet Chemistry Laboratory (WCL), including oxidation-reduction potential (E h ), regolith/soil pH, stable oxidants relevant to chemosynthetic metabolism (e.g., perchlorate, sulfate), and strong electrolytes were key to understanding habitability at the Phoenix Mars landing site. The Microfluidic Icyworld Chemical Analyzer (MICA), the next-generation WCL, is a standalone instrument package that incorporates the same classes of electrochemical sensors as WCL, but in a microfluidic format, enabling habitability assessment in a smaller instrument package (~2.3 kg, ~2 L).

R.C. Quinn↗

Gossans on Mars

The appearance of rusty iron-rich oxidized cappings over sulfide-bearing rocks on earth indicates that similar gossans may have formed on the surface of Mars. Electrochemical processes and thermodynamic relationships linking acidity to oxidation-reduction reactions between primary sulfide minerals and their oxidative weathering products present in the regolith of Mars are discussed. Remote-sensed visible spectra of the Martian surface are in keeping with the presence of poorly-crystalline FeOOH, jarosite, silica, and clay silicates found in gossans, while incompletely weathered pyrrhotite may represent the magnetic material observed in Martian regolith.

Burns, Roger G.↗

Searching for Biogeochemical Cycles on Mars

The search for life on Mars clearly benefits from a rigorous, yet broad, definition of life that compels us to consider all possible lines of evidence for a martian biosphere. Recent studies in microbial ecology illustrate that the classic definition of life should be expanded beyond the traditional definition of a living cell. The traditional defining characteristics of life are threefold. First, life is capable of metabolism, that is, it performs chemical reactions that utilize energy and also synthesize its cellular constituents. Second, life is capable of self-replication. Third, life can evolve in order to adapt to environmental changes. An expanded, ecological definition of life also recognizes that life is a community of organisms that must interact with their nonliving environment through processes called biogeochemical cycles. This regenerative processing maintains, in an aqueous conditions, a dependable supply of nutrients and energy for growth. In turn, life can significantly affect those processes that control the exchange of materials between the atmosphere, ocean, and upper crust. Because metabolic processes interact directly with the environment, they can alter their surroundings and thus leave behind evidence of life. For example, organic matter is produced from single-carbon-atom precursors for the biosynthesis of cellular constituents. This leads to a reservoir of reduced carbon in sediments that, in turn, can affect the oxidation state of the atmosphere. The harvesting of chemical energy for metabolism often employs oxidation-reduction reactions that can alter the chemistry and oxidation state of the redox-sensitive elements carbon, sulfur, nitrogen, iron, and manganese. Have there ever been biogeochemical cycles on Mars? Certain key planetary processes can offer clues. Active volcanism provides reduced chemical species that biota can use for organic synthesis. Volcanic carbon dioxide and methane can serve as greenhouse gases. Thus the persistence of volcanism on Mars may well have influenced the persistence of a martian biosphere. The geologic processing of the crust can affect the availability of nutrients and also control the deposition of minerals that could have served as a medium for the preservation of fossil information. Finally, the activity of liquid water is crucial to life. Was there ever an Earth-like hydrologic cycle with rainfall? Has aqueous activity instead been restricted principally to hydrothermal activity below the surface? To what extent did the inorganic chemistry driven by sunlight and hydrothermal activity influence organic chemistry (prebiotic chemical evolution)? This paper addresses these and other key questions.

DesMarais, David J.↗

Workshop on Oxygen in the Terrestrial Planets

This volume contains abstracts that have been accepted for presentation at the Workshop on Oxygen in the Terrestrial Planets, July 20-23,2004, Santa Fe, New Mexico. The contents include: 1) Experimental Constraints on Oxygen and Other Light Element Partitioning During Planetary Core Formation; 2) In Situ Determination of Fe(3+)/SigmaFe of Spinels by Electron Microprobe: An Evaluation of the Flank Method; 3) The Effect of Oxygen Fugacity on Large-Strain Deformation and Recrystallization of Olivine; 4) Plagioclase-Liquid Trace Element Oxygen Barometry and Oxygen Behaviour in Closed and Open System Magmatic Processes; 5) Core Formation in the Earth: Constraints from Ni and Co; 6) Oxygen Isotopic Compositions of the Terrestrial Planets; 7) The Effect of Oxygen Fugacity on Electrical Conduction of Olivine and Implications for Earth s Mantle; 8) Redox Chemical Diffusion in Silicate Melts: The Impact of the Semiconductor Condition; 9) Ultra-High Temperature Effects in Earth s Magma Ocean: Pt and W Partitioning; 10) Terrestrial Oxygen and Hydrogen Isotope Variations: Primordial Values, Systematics, Subsolidus Effects, Planetary Comparisons, and the Role of Water; 11) Redox State of the Moon s Interior; 12) How did the Terrestrial Planets Acquire Their Water?; 13) Molecular Oxygen Mixing Ratio and Its Seasonal Variability in the Martian Atmosphere; 14) Exchange Between the Atmosphere and the Regolith of Mars: Discussion of Oxygen and Sulfur Isotope Evidence; 15) Oxygen and Hydrogen Isotope Systematics of Atmospheric Water Vapor and Meteoric Waters: Evidence from North Texas; 16) Implications of Isotopic and Redox Heterogeneities in Silicate Reservoirs on Mars; 17) Oxygen Isotopic Variation of the Terrestrial Planets; 18) Redox Exchanges in Hydrous Magma; 19) Hydrothermal Systems on Terrestrial Planets: Lessons from Earth; 20) Oxygen in Martian Meteorites: A Review of Results from Mineral Equilibria Oxybarometers; 21) Non-Linear Fractionation of Oxygen Isotopes Implanted in Lunar Metal Grains: Solar, Lunar or Terrestrial Origin? 22) Isotopic Zoning in the Inner Solar System; 23) Redox Conditions on Small Bodies; 24) Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update; 25) Mantle Redox Evolution and the Rise of Atmospheric O2; 26) Variation of Kd for Fe-Mg Exchange Between Olivine and Melt for Compositions Ranging from Alkaline Basalt to Rhyolite; 27) Determining the Partial Pressure of Oxygen (PO,) in Solutions on Mars; 28) The Influence of Oxygen Environment on Kinetic Properties of Silicate Rocks and Minerals; 29) Redox Evolution of Magmatic Systems; 30) The Constancy of Upper Mantlefo, Through Time Inferred from V/Sc Ratios in Basalts: Implications for the Rise in Atmospheric 0 2; 31) Nitrogen Solubility in Basaltic Melt. Effects of Oxygen Fugacity, Melt Composition and Gas Speciation; 32) Oxygen Isotope Anomalies in the Atmospheres of Earth and Mars; 33) The Effect of Oxygen Fugacity on Interdiffusion of Iron and Magnesium in Magnesiowiistite 34) The Calibration of the Pyroxene Eu-Oxybarometer for the Martian Meteorites; 35) The Europium Oxybarometer: Power and Pitfalls; 36) Oxygen Fugacity of the Martian Mantle from PigeoniteMelt Partitioning of Samarium, Europium and Gadolinium; 37) Oxidation-Reduction Processes on the Moon: Experimental Verification of Graphite Oxidation in the Apollo 17 Orange Glasses; 38) Oxygen and Core Formation in the Earth; 39) Geologic Record of the Atmospheric Sulfur Chemistry Before the Oxygenation of the Early Earth s Atmosphere; 40) Comparative Planetary Mineralogy: V/(CrCAl) Systematics in Chromite as an Indicator of Relative Oxygen Fugacity; 41) How Well do Sulfur Isotopes Constrain Oxygen Abundance in the Ancient Atmospheres? 42) Experimental Constraints on the Oxygen Isotope (O-18/ O-16) Fractionation in the Ice vapor and Adsorbant vapor Systems of CO2 at Conditions Relevant to the Surface of Mars; 43) Micro-XANES Measurements on Experimental Spinels andhe Oxidation State of Vanadium in Spinel-Melt Pairs; 44) Testing the Magma Ocean Hypothesis Using Metal-Silicate Partitioning of Te, Se and S; 45) Solubility of Oxygen in Liquid Iron at High Pressure and Consequences for the Early Differentiation of Earth and Mars Metallic Liquid Segregation in Planetesimals; 46) Oxygen Fugacity of Lunar Basalts and the Lunar Mantle. Range of fo2 and the Effectiveness of Oxybarometers; 47) Thermodynamic Study of Dissociation Processes of Molecular Oxygen in Vapor over Oxide Compounds; 48) Oxygen Profile of a Thermo-Haliophilic Community in the Badwater Salt Flat; 49) Oxygen Barometry Using Synchrotron MicroXANES of Vanadium; 50) Mass-Independent Isotopic Fractionation of Sulfur from Sulfides in the Huronian Supergroup, Canada; 51) Mass Independent Isotopes and Applications to Planetary Atmospheres; 52) Electrical Conductivity, Oxygen Fugacity, and Mantle Materials; 53) Crustal Evolution and Maturation on Earth: Oxygen Isotope Evidence; 54) The Oxygen Isotope Composition of the Moon: Implications for Planet Formation; 55) Oxygen Isotope Composition of Eucrites and Implications for the Formation of Crust on the HED Parent Body; and 56) The Role of Water in Determining the Oxygen Isotopic Composition of Planets.

Source record↗

Method of making formulated plastic separators for soluble electrode cells

A method making a membrane comprised of a hydrochloric acid-insoluble sheet of a mixture of a rubber and a powdered ion transport material is disclosed. The sheet can be present as a coating upon a flexible and porous substrate. These membranes can be used in oxidation-reduction electrical accumulator cells wherein the reduction of one member of a couple is accompained by the oxidation of the other member of the couple on the other side of the cell and this must be accompained by a change in chloride ion concentration in both sides. The method comprises preparing a mixture of fine rubber particles, a solvent for the rubber and a powdered ion transport material. The mixture is formed into a sheet and dried to produce a microporous sheet. The ion transport material includes particles ranging from about 0.01 to 10 microns in size and comprises from 20 to 50 volume percent of the microporous sheet.

Sheibley, D. W.↗

Formulated plastic separators for soluble electrode cells

The fabrication and milling of membranes comprising a hydrochloric acid-insoluble sheet of a mixture of a rubber and a powdered ion transport material are described. The sheet can be present as a coating upon a flexible and porous substrate. These membranes can be used in oxidation-reduction electrical accumulator cells wherein the reduction of one member of a couple is accompanied by the by the oxidation of the other member of the couple on the other side of the cell and this must be accompanied by a change in chloride ion concentration in both sides.

Sheibley, D. W.↗

A Simplified Test for Blanching Susceptibility of Copper Alloys

GRCop-84 (Cu-8Cr-4Nb) is a dispersion-strengthened alloy developed for space-launch rocket engine applications, as a liner for the combustion chamber and nozzle ramp. Its main advantage over rival alloys, particularly NARloy-Z (Cu-Ag-Zr), the current liner alloy, is in high temperature mechanical properties. Further validation required that the two alloys be compared with respect to service performance and durability. This has been done, under conditions resembling those expected in reusable launch engine applications. GRCop-84 was found to have a superior resistance to static and cyclic oxidation up to approx. 700 C. In order to improve its performance above 700 C, Cu-Cr coatings have also been developed and evaluated. The major oxidative issue with Cu alloys is blanching, a mode of degradation induced by oxidation-reduction fluctuations in hydrogen-fueled engines. That fluctuation cannot be addressed with conventional static or cyclic oxidation testing. Hence, a further evaluation of the alloy substrates and Cu-Cr coating material necessitated our devising a test protocol that involves oxidaton-reduction cycles. This paper describes the test protocols used and the results obtained.

Thomas-Ogbuji, Linus U.↗

Bismuth Passivation Technique for High-Resolution X-Ray Detectors

The Athena-plus team requires X-ray sensors with energy resolution of better than one part in 3,000 at 6 keV X-rays. While bismuth is an excellent material for high X-ray stopping power and low heat capacity (for large signal when an X-ray is stopped by the absorber), oxidation of the bismuth surface can lead to electron traps and other effects that degrade the energy resolution. Bismuth oxide reduction and nitride passivation techniques analogous to those used in indium passivation are being applied in a new technique. The technique will enable improved energy resolution and resistance to aging in bismuth-absorber-coupled X-ray sensors. Elemental bismuth is lithographically integrated into X-ray detector circuits. It encounters several steps where the Bi oxidizes. The technology discussed here will remove oxide from the surface of the Bi and replace it with nitridized surface. Removal of the native oxide and passivating to prevent the growth of the oxide will improve detector performance and insulate the detector against future degradation from oxide growth. Placing the Bi coated sensor in a vacuum system, a reduction chemistry in a plasma (nitrogen/hydrogen (N2/H2) + argon) is used to remove the oxide and promote nitridization of the cleaned Bi surface. Once passivated, the Bi will perform as a better X-ray thermalizer since energy will not be trapped in the bismuth oxides on the surface. A simple additional step, which can be added at various stages of the current fabrication process, can then be applied to encapsulate the Bi film. After plasma passivation, the Bi can be capped with a non-diffusive layer of metal or dielectric. A non-superconducting layer is required such as tungsten or tungsten nitride (WNx).

Chervenak, James↗

Hydrogen and oxygen sensor development

A reliable and low cost gas sensor was investigated for instantaneously detecting H2 in N2, H2 in air, and O2 in N2. The major portion of the research was spent in developing a sensor which would instantaneously detect H2 to + or - 50 ppm even in the presence of trace amounts of other gases. The experimental procedures used to provide the performance characteristics for the various oscillators are discussed describing the equipment with help of schematics and photographs where applicable. The resulting performance is given in graphical form. In some cases both hydrogen and helium may be present and since both of them effect gas sensors similarly, a method was found to determine the concentration of each. The methods developed are grouped into the following four broad categories: pure metal response, variation in heat conductivity, reduction methods, and exotic processes. From the above it was decided for the present to use a copper oxide reduction process as this process was demonstrated to be capable of determining the concentrations of hydrogen and helium respectively in a gas mixture with air or nitrogen.

Farber, E. A.↗

Powder-Derived High-Conductivity Coatings for Copper Alloys

Makers of high-thermal-flux engines prefer copper alloys as combustion chamber liners, owing to a need to maximize heat dissipation. Since engine environments are strongly oxidizing in nature and copper alloys generally have inadequate resistance to oxidation, the liners need coatings for thermal and environmental protection; however, coatings must be chosen with great care in order to avoid significant impairment of thermal conductivity. Powder-derived chromia- and alumina- forming alloys are being studied under NASA's programs for advanced reusable launch vehicles to succeed the space shuttle fleet. NiCrAlY and Cu-Cr compositions optimized for high thermal conductivity have been tested for static and cyclic oxidation, and for susceptibility to blanching - a mode of degradation arising from oxidation-reduction cycling. The results indicate that the decision to coat the liners or not, and which coating/composition to use, depends strongly on the specific oxidative degradation mode that prevails under service conditions.

Thomas-Ogbuji, Linus U.↗

Records of our Early Biosphere Illuminate our Origins and Guide our Search for Life Beyond Earth

A scientific "mission of exploration to early Earth" will help us chart the distribution of life elsewhere. We must discriminate between attributes of biospheres that are universal versus those attributes that represent principally the outcomes of long-term survival specifically on Earth. In addition to the basic physics and chemistry of matter, the geologic evolution of rocky habitable planets and their climates might be similar elsewhere in the Universe. Certain key agents that drive long-term environmental change (e.g., stellar evolution, impacts, geothermal heat flow, tectonics, etc.) can help us to reconstruct ancient climates and to compare their evolution among populations of Earth- like planets. Early Earth was tectonically more active than today and therefore it exhaled reduced chemical species into the more oxidized surface environment at greater rates. This tectonic activity thus sustained oxidation-reduction reactions that provided the basis for the development of biochemical pathways that harvest chemical energy ("bioenergetics"). Most examples of bioenergetics today that extract energy by reacting oxidized and reduced chemicals in the environment were likely more pervasive among our microbial ancestors than are the presently known examples of photosynthesis. The geologic rock record indicates that, as early as 3.5 billion years ago (3.5 Ga), microbial biofilms were widespread within the coastal environments of small continents and tectonically unstable volcanic islands. Non oxygen-producing (non-oxygenic) photosynthesis preceded oxygenic photosynthesis, but all types of photosynthesis contributed substantially to the long-term increase in global primary biological productivity. Evidence of photosynthesis is tentative by 3.5 Ga and compelling by 2.7 Ga. Evidence of oxygenic photosynthesis is strong by 2.7 Ga and compelling by 2.3 Ga. These successive innovations transformed life from local communities that survived principally by catalyzing chemical equilibration to a globally dominant agent that created and sustained widespread chemical disequilibria in the environment and shallow crust. Major biogeochemical perturbations ca. 2.3 to 2.0 Ga, 1.3 Ga, and also 0.8 to 0.6 Ga, contributed to the irreversible oxidation of the global environment and perhaps also triggered evolutionary innovations (e.g., the development of multi-cellular biota) that became the foundations of our modern biosphere. Understanding the nature and timing of this ascent of life is crucial for discerning our o m beginnings. This understanding also empowers OUT search for the origins, evolution and distribution of life elsewhere in our solar system and beyond.

DesMarais, David J.↗

Quantitative Relationships between Photosynthetic, Nitrogen Fixing, and Fermentative H2 Metabolism in a Photosynthetic Microbial Mat

The ultimate potential of any microbial ecosystem to contribute chemically to its environment - and therefore, to impact planetary biogeochemistry or to generate recognizable biosignatures - depends not only on the individual metabolic capabilities of constituent organisms, but also on how those capabilities are expressed through interactions with neighboring organisms. This is particularly important for microbial mats, which compress an extremely broad range of metabolic potential into a small and dynamic system. H2 participates in many of these metabolic processes, including the major elemental cycling processes of photosynthesis, nitrogen fixation, sulfate reduction, and fermentation, and may therefore serve as a mediator of microbial interactions within the mat system. Collectively, the requirements of energy, electron transfer, and biomass element stoichiometry suggest quantitative relationships among the major element cycling processes, as regards H2 metabolism We determined experimentally the major contributions to 32 cycling in hypersaline microbial mats from Baja California, Mexico, and compared them to predicted relationships. Fermentation under dark, anoxic conditions is quantitatively the most important mechanism of H2 production, consistent with expectations for non-heterocystous mats such as those under study. Up to 16% of reducing equivalents fixed by photosynthesis during the day may be released by this mechanism. The direct contribution of nitrogen fixation to H2 production is small in comparison, but this process may indirectly stimulate substantial H2 generation, by requiring higher rates of fermentation. Sulfate reduction, aerobic consumption, diffusive and ebulitive loss, and possibly H2-based photoreduction of CO2 serve as the principal H2 sinks. Collectively, these processes interact to create an orders-of-magnitude daily variation in H2 concentrations and fluxes, and thereby in the oxidation-reduction potential that is imposed on microbial processes occuring within the mat matrix.

Hoehler, Tori M.↗

Some thoughts on GAIA and the sulfur cycle

The data hypothesis states that the composition, oxidation reduction state, and temperature of the troposphere are actively regulated by the biota for the biota. One of the early predictions of the Gaia hypothesis was that there should be a sulfur compound made by the biota in the oceans. It would need to be stable enough against oxidation in water to allow its transfer to the air. Either the sulfur compound itself or its atmospheric oxidation product would have to return sulfur from the sea to the land surfaces. The most likely candidate for this role was dimethyl sulfide. Another sulfur compound of interest from a Gaian viewpoint CS2 (carbon disulfide) is discussed. Theories on the production of dimethyl sulfide and carbon disulfide related to the Gaian hypothesis are examined.

Lovelock, J. E.↗

Oxidation Behavior of Copper Alloy Candidates for Rocket Engine Applications (Technical Poster)

A rocket engine's combustion chamber is lined with material that is highly conductive to heat in order to dissipate the huge thermal load (evident in a white-hot exhaust plume). Because of its thermal conductivity copper is the best choice of liner material. However, the mechanical properties of pure copper are inadequate to withstand the high stresses, hence, copper alloys are needed in this application. But copper and its alloys are prone to oxidation and related damage, especially "blanching" (an oxidation-reduction mode of degradation). The space shuttle main engine combustion chamber is lined with a Cu-Ag-Zr alloy, "NARloy-Z", which exhibits blanching. A superior liner is being sought for the next generation of RLVs (Reusable Launch Vehicles) It should have improved mechanical properties and higher resistance to oxidation and blanching, but without substantial penalty in thermal conductivity. GRCop84, a Cu-8Cr-4Nb alloy (Cr2Nb in Cu matrix), developed by NASA Glenn Research Center (GRC) and Case Western Reserve University, is a prime contender for RLV liner material. In this study, the oxidation resistance of GRCop-84 and other related/candidate copper alloys are investigated and compared

Ogbuji, Linus U. J.↗

Investigating Biological Responses to Deep Space Radiation for Missions Beyond Low Earth Orbit (LEO) using Yeast

To enable long-term spaceflight missions and establish habitation on the Moon and Mars, we require a comprehensive understanding of the effects of chronic deep space radiation exposure on humans. BioSentinel is NASA’s first biological CubeSat to venture beyond Low Earth Orbit (LEO). It utilizes Saccharomyces cerevisiae (budding yeast) as a model organism to study biological responses to deep space radiation. Yeast share significant genetic homology with humans, including basic cellular metabolism and DNA repair mechanisms. In addition, unlike human cell cultures, yeast can survive the duration and constraints of a deep space mission. BioSentinel measures biological responses using an optical system and alamarBlue oxidation-reduction (redox) dye. Two strains of yeast are studied - a wild-type and a rad51 mutant strain that is deficient in DNA repair. Changes in metabolism and growth are monitored throughout the nominal 6-month mission. Preliminary tests indicate a significant change in the alamarBlue response to low-dose ionizing radiation (IR). Additionally, rad51 cells have shown an IR dose-dependent decrease in glucose uptake and accumulation of oxidized NADH (NAD+). These biomolecules are involved in reactions responsible for basic cell processes, including growth and development, signaling, and respiration. The current study expanded upon previous data by exposing yeast to deep space-relevant radiation. Glucose and NADH/NAD+ assays were conducted on yeast subjected to varying dosages of high-energy Fe-56 and simulated galactic cosmic rays (GCRs). The resulting data was analyzed using Excel and GraphPad Prism. A particular focus was to identify biomolecules resulting from aerobic respiration, which requires the presence of oxygen, or anaerobic processes. As long-term spaceflight missions draw near, it is increasingly important to characterize biological processes affected by the conditions of deep space. Studying biomolecular damage caused by deep space radiation may enable the development of engineering controls or biomedical therapeutics that mitigate health complications for future astronauts.

Kyra Keenan↗