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NASA NTRS2012

Possible Calcite and Magnesium Perchlorate Interaction in the Mars Phoenix Thermal and Evolved Gas Analyzer (TEGA)

The Mars Phoenix Lander's TEGA instrument detected a calcium carbonate phase decomposing at high temperatures (approx.700 C) from the Wicked Witch soil sample [1]. TEGA also detected a lower temperature CO2 release between 400 C and 680 C [1]. Possible explanations given for this lower temperature CO2 release include thermal decomposition of Mg or Fe carbonates, a zeolitictype desorption reaction, or combustion of organic compounds in the soil [2]. The detection of 0.6 wt % soluble perchlorate by the Wet Chemistry Laboratory (WCL) on Phoenix [3] has implications for the possibility of organic molecules in the soil. Ming et al. [4] demonstrated that perchlorates could have oxidized organic compounds to CO2 in TEGA, preventing detection of their characteristic mass fragments. Here, we propose that a perchlorate salt and calcium carbonate present in martian soil reacted to produce the 400 C - 680 C TEGA CO2 release. The parent salts of the perchlorate on Mars are unknown, but geochemical models using WCL data support the possible dominance of Mg-perchlorate salts [5]. Mg(ClO4)2 6H2O is the stable phase at ambient martian conditions [6], and breaks down at lower temperatures than carbonates giving off Cl2 and HCl gas [7,8]. Devlin and Herley [7] report two exotherms at 410-478 C and 473-533 C which correspond to the decomposition of Mg(ClO4)2.

Cannon, K. M.↗

NASA NTRS2015

Survival of Organic Materials in Ancient Cryovolcanically-Produced Halite Crystals

Spectroscopic evidence supports the presence of Mg-Na-K salts derived from cryovolcanism on the surface of Europa. Halite (NaCl) is effective at very long-term preservation of organic phases and structures. Collection of salt crystals from Europan plumes would provide solid inclusions of organics, potentially also biomaterials, all suitable for analysis. Two thermally-metamorphosed ordinary chondrite regolith breccias (Monahans 1998 (H5) and Zag (H3-6)) contain fluid and solid inclusion-bearing halite crystals, dated to approximately 4.5 billion years, and thus the trapped aqueous fluids and solids are at least as old. Heating/freezing studies of the aqueous fluid inclusions in these halites demonstrated that they were trapped near 25 degrees Centigrade, and their continued presence in the halite grains requires that their incorporation into the H chondrite asteroid occurred after that body's metamorphism ended, since heating would have dessicated the halite. O and H isotopes of the trapped fluids are consistent with mixing of asteroidal and cometary water. Cryovolcanic Origin of the Halite: We hypothesize that these meteoritic halites derive from ancient cryovolcanism based on the following points. (1) Salts crystals are observed as products of current cryovolcanism on Enceladus. (2) In-situ spacecraft analysis of some of the icy grains associated with the Enceladus salt found minor organic or siliceous components, including methane, also found in the Monahans halite. (3) Cryovolcanic fluids are observed to be in chemical disequilibrium, reflecting incomplete reactions between interior volatiles and rocky materials. The coexistence of N2 and HCN in Enceladus' cryovolcanic fluids requires that the plume consists of a mixture of materials whose sources experienced different degrees of aqueous processing, including primordial material trapped in ice that has not been in contact with liquid water. The observed mineral assemblage within the Monahans and Zag halites is also far from equilibrium. Cryovolcanoes on Ceres are a potential source of our halite, however the processes that form halite should also be operating within Europa. Dissolution of Monahans halite grains has revealed a remarkable variety of organics, which dominate the population of solid inclusions. Thermal alteration of this macromolecular carbon (measured by Raman spectroscopy) shows remarkable diversity. We have identified highly-condensed aromatics, diamond, carbonates and chloromethane. Light organic compounds like methane tend to be water soluble and require cold formation temperatures at high hydrogen fugacity - i.e. require water ice. Another indication that these halites have not been heated is that light organics readily volatilize or aromaticize into PAHs. We are currently analyzing the organics by Raman and C-XANES, and measuring the content and exploring the potential chirality of amino acids in the halite. Implications for Europa Plumes: Organic materials and structures erupted by a Europa cryovolcano should be similarly preserved within halite, and other salts, which will be a convenient form for capture and analysis, since halite will serve to encapsulate and protect the organics from spacecraft contamination. Also, being transparent at many wavelengths halite will permit analysis by spacecraft-mounted spectroscopic techniques. In addition, halite is readily dissolved, permitting further analysis of entrained organics.

Zolensky, M.↗

NASA NTRS2013

Assessing Habitability: Lessons from the Phoenix Mission

The Phoenix mission's key objective was to search for a habitable zone. The Phoenix lander carried a robotic arm with digging scoop to collect soil and icy material for analysis with an instrument payload that included volatile mineral and organic analysis(3) and soil ionic chemistry analysis (4). Results from Phoenix along with theoretical modeling and other previous mission results were used to evaluate the habitability of the landing site by considering four factors that characterize the environments ability to support life as we know it: the presence of liquid water, the presence of an energy source to support metabolism, the presence of nutrients containing the fundamental building blocks of life, and the absence of environmental conditions that are toxic to or preclude life. Phoenix observational evidence for the presence of liquid water (past or present) includes clean segregated ice, chemical etching of soil grains, calcite minerals in the soil and variable concentrations of soluble salts5. The maximum surface temperature measured was 260K so unfrozen water can form only in adsorbed films or saline brines but warmer climates occur cyclically on geologically short time scales due to variations in orbital parameters. During high obliquity periods, temperatures allowing metabolism extend nearly a meter into the subsurface. Phoenix discovered ~1%w/w perchlorate salt in the soil, a chemical energy source utilized by a wide range of microbes. Nutrient sources including C, H, N, O, P and S compounds are supplied by known atmospheric sources or global dust. Environmental conditions are within growth tolerance for terrestrial microbes. Summer daytime temperatures are sufficient for metabolic activity, the pH is 7.8 and is well buffered and the projected water activity of a wet soil will allow growth. In summary, martian permafrost in the north polar region is a viable location for modern life. Stoker et al. presented a formalism for comparing the habitability of various regions visited to date on Mars that involved computing a habitability probability, defined as the product of probabilities for the presence of liquid water (P(sub lw)), energy (P(sub e)), nutrients (P(sub ch)), and a benign environment (P(sub b)). Using this formalism, they argued that the Phoenix site was the most habitable of any site visited to date by landed missions and warranted a follow up mission to search for modern evidence of life. This paper will review that conclusion in view of more recent information from the Mars Exploration Rovers and Mars Science Lander missions.

Stoker, Carol R.↗

NASA NTRS1995

Aerosol measurements over the Pacific Ocean in support of the IR aerosol backscatter program

The major efforts under NASA contract NAG8-841 included: (1) final analyses of the samples collected during the first GLOBE survey flight that occurred in November 1989 and collections and analysis of aerosol samples during the second GLOBE survey flight in May and June 1990. During the first GLOBE survey flight, daily samples were collected at four stations (Midway, Rarotonga, American Samoa, and Norfolk Island) throughout the month of November 1989. Weekly samples were collected at Shemya, Alaska, and at Karamea, New Zealand. During the second GLOBE survey flight, daily samples were collected at Midway, Oahu, American Samoa, Rarotonga, and Norfolk Island; weekly samples were collected at Shemya. These samples were all analyzed for sodium (sea-salt), chloride, nitrate, sulfate, and methanesulfonate at the University of Miami and for aluminum at the University of Rhode Island (under a subcontract). (2) Samples continued to be collected on a weekly basis at all stations during the periods between and after the survey flights. These weekly samples were also analyzed at the University of Miami for the suite of water-soluble species. (3) In August 1990, the results obtained from the above studies were submitted to the appropriate personnel at NASA Marshall Space Flight Center to become part of the GLOBE data base for comparison with data from instruments used aboard the aircraft. In addition, the data will be compared with data previously obtained at these stations as part of the Sea-Air Exchange (SEAREX) Program. This comparison will provide valuable information on the representativeness of the periods in terms of the longer term aerosol climatology over the Pacific Ocean. (4) Several publications have been written using data from this grant. The data will continue to be used in the future as part of a continuing investigation of the long-term trends and interannual variations in aerosol species concentrations over the Pacific Ocean.

Prospero, Joseph M.↗

NASA NTRS2011

On the Effect of Dust Particles on Global Cloud Condensation Nuclei and Cloud Droplet Number

Aerosol-cloud interaction studies to date consider aerosol with a substantial fraction of soluble material as the sole source of cloud condensation nuclei (CCN). Emerging evidence suggests that mineral dust can act as good CCN through water adsorption onto the surface of particles. This study provides a first assessment of the contribution of insoluble dust to global CCN and cloud droplet number concentration (CDNC). Simulations are carried out with the NASA Global Modeling Initiative chemical transport model with an online aerosol simulation, considering emissions from fossil fuel, biomass burning, marine, and dust sources. CDNC is calculated online and explicitly considers the competition of soluble and insoluble CCN for water vapor. The predicted annual average contribution of insoluble mineral dust to CCN and CDNC in cloud-forming areas is up to 40 and 23.8%, respectively. Sensitivity tests suggest that uncertainties in dust size distribution and water adsorption parameters modulate the contribution of mineral dust to CDNC by 23 and 56%, respectively. Coating of dust by hygroscopic salts during the atmospheric aging causes a twofold enhancement of the dust contribution to CCN; the aged dust, however, can substantially deplete in-cloud supersaturation during the initial stages of cloud formation and can eventually reduce CDNC. Considering the hydrophilicity from adsorption and hygroscopicity from solute is required to comprehensively capture the dust-warm cloud interactions. The framework presented here addresses this need and can be easily integrated in atmospheric models.

Karydis, V. A.↗

NASA NTRS2004

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↗

NASA NTRSDate not supplied

Extraterrestrial Molecular Indicators of Life Investigation (EMILI)

Future missions to Enceladus, Europa, Mars, and beyond may seek the molecular signs of extraterrestrial life through chemical analysis of acquired samples. Particularly on ocean worlds such as Enceladus and Europa, samples may contain trace ocean-borne molecular biosignatures of extant life that may or may not share similarities to those of terrestrial life. In situ analyses must be prepared to detect and characterize a wide range of possible molecular species, structures, and patterns, typically with exquisite sensitivity and within a complex, poorly-characterized planetary environment. The Extraterrestrial Molecular Indicators of Life Investigation (EMILI) is designed to meet or exceed the requirements of such missions for organic molecular analysis through a powerful combination of dual chemical separation and both optical and mass spectrometry detection techniques, realized in an integrated, compact instrument package fully compatible with anticipated flight resources and conditions. The full EMILI instrument combines two sample analysis subsystems to provide wide-ranging and complementary detection of organic compounds and inorganic salts. The Gas Analysis Processing System (GAPS) uses a chemical derivatization protocol with gas chromatography (GC) separation prior to detection in an ion trap mass spectrometer (ITMS) to enable full characterization of lower-polarity, volatile and semi-volatile molecules such as fatty acids and hydrocarbons. The Organic Capillary Electrophoresis ANalysis System (OCEANS) uses a liquid-based extraction protocol with CE separation to enable precise analysis of more water-soluble/polar compounds. OCEANS features a laser-induced fluorescence detection mode to perform ultra-sensitive quantitative analysis of chiral amino acids. In EMILI, OCEANS is additionally coupled to the same ITMS through a novel electrospray ionization interface. The common ITMS allows EMILI to identify and cross-correlate molecular species and patterns, detected through either or both protocols, of molecular weights to over 1000 u, potentially even revealing complex biosignatures such as alien oligopeptides and informational polymers.

Europa↗

NASA NTRS1977

Solar photolysis of water

Hydrogen is produced by the solar photolysis of water in a first photooxidation vessel with a transparent wall in the presence of a water soluble photooxidizable reagent and an insoluble hydrogen recombination catalyst. Simultaneously oxygen is produced in a second photoreduction reactor with a transparent wall in the presence of an insoluble photoreduction reagent catalyst. When spent, the solution from the first reactor is fed into the second reactor. A reaction occurs in the dark in which the redox reagents are regenerated, and the regenerated photooxidation reagent solution is recycled to the first reactor. The photoreduction-catalyst is a bifunctional reagent catalyst including a transition metal salt together with a hydroxyl or chlorohydroxyl decomposition catalyst of high area.

Ryason, P. R.↗

NASA NTRS2014

Characterization of Encapsulated Corrosion Inhibitors for Environmentally Friendly Smart Coatings

Research efforts are under way to replace current corrosion inhibitors with more environmentally friendly alternatives. However, problems with corrosion inhibition efficiency, coating compatibility and solubility have hindered the use of many of these materials as simple pigment additives.This paper will present technical details on how the Corrosion Technology Lab at NASAs Kennedy Space Center (KSC) has addressed these issues by encapsulating environmentally friendly inhibitors into organic and inorganic microparticles and microcapsules. The synthetic process for polymer particles was characterized and post-synthesis analysis was performed to determine the interactions between the inhibitors and the encapsulation material. The pH-controlled release of inhibitors from various particle formulations in aqueous base was monitored and compared to both electrochemical and salt immersion accelerated corrosion experiment. Furthermore, synergistic corrosion inhibition effects observed during the corrosion testing of several inhibitor combinations will be presented.

Environmentally Friendly↗

NASA NTRS1994

Ammonia on the prebiotic Earth: Iron(II) reduction of nitrite

Theories for the origin of life require the availability of reduced nitrogen. In the non-reducing atmosphere suggested by geochemical evidence, production in the atmosphere and survival of NH3 against photochemical destruction are problematic. Electric discharges and impact shocks would produce NO rather than HCN or NH3. Conversion of NO to nitrous and nitric acid (by way of HNO) and precipitation in acid rain would provide a source of fixed nitrogen to the early ocean. One solution to the NH3 problem may have been the reduction of nitrite/nitrate in the ocean with aqueous ferrous iron, Fe(2+): 6Fe(+2) + 7 H2O + NO2(-) yields 3Fe2O3 + 11 H(+) + NH3. We have measured the kinetics of this reaction as a function of temperature, pH, and concentrations of salts, Fe(+2), and NO2(-). Cations (Na(+), Mg(2+), K(+)) and anions (Cl(-), Br(-), SO4(2-)) increase the rate by factors of 4 to 8. Although a competing pathway yields N2, the efficiency of the conversion of nitrite to ammonia ranges from 25% to 85%. Nitrate reduction was not consistently reproducible; however, when it was observed, its rate was slower by at least 8X than that of nitrite reduction. If the prebiotic atmosphere contained 0.2 to 10 atmospheres CO2 as suggested by Walker (1985), the Fe(+2) concentration and the rate would have been limited by siderite (FeCO3) solubility.

Summers, David P.↗

NASA NTRS1991

Stability of Y-Ba-Cu-oxide phases in salt flux

The results of an investigation into the possibility of growing YBa2Cu3O7 (or Y123) single crystals from a NaCl-KCl flux (salt flux) are presented. They are compared with results for Y123 crystals grown from a Ba-Cu-oxide flux system. The chosen salt flux composition was 1:1 (NaCl:KCl). The preparation method of the solutes is presented, with particular attention given to the compounds surrounding the Y123 phase, such as Y2BaCuO6 (Y211). Optical microscopy was introduced to study the morphology of the sample; X-ray diffraction was used for phase identification; and a chemical analysis was effected. The Y123, Y211, and BaCuO2 phases were shown to be dissociated in the NaCl-KCl flux, and could not be recrystallized. A small amount of the flux could be added to create large-grain Y123 crystals, but single-crystal growth was not possible in a top-seeded NaCl-KCl solution. This is attributed to significant differences in solubility of the crystal elements, and phase separation caused by CuO crystal formation.

Tao, Y. K.↗

NASA NTRS2016

Igneous and Sedimentary Compositions from Four Landing Sites on Mars from the Alpha Particle X-Ray Spectrometer (APXS)

The APXS - supported and promoted strongly by Heinrich Waenke - on all four Mars Rovers has returned compositional data from about 1000 rocks and soil targets along the combined traverses of over 60 kilometers. Providing precise and accurate bulk chemistry with typically 16 quantified elements, the APXS is a powerful and versatile tool that when combined with the ability to traverse to key rocks and soils has provided critical information needed to understand the geologic evolution of Mars. APXS data allow comparisons among landing sites, provide ground truth for orbiters and connections back to SNC meteorites. The soils and dust are basaltic in character and represent the average Mars composition similar to Adirondack basalts from Gusev crater but with unambiguous elevated and correlated S, Cl and Zn contents. At all four landing sites the APXS found several rocks with a felsic composition. The similarity is best assessed in a logarithmic ratio plot of rock normalized to the average soil composition (Fig.1). High alkaline, Al, and low Mg, Fe, low S, Cl and Ni, Zn as well as an Fe/Mn ratio of approximately 50 indicate a likely unaltered and igneous origin. Sediments, e.g. the Burns formation, with approximately 25 wt% SO3 at Meridiani Planum have been documented over 10s of kilometers (Fig. 2). This formation is compositionally homogeneous, but showing the removal of MgSO4 and a threefold increase in Cl downhill in 2 craters. The degraded rim of the Noachian crater Endeavour resembles average Mars crust, with local Ca, Mg and Fe sulfate alteration and elevated Mn, some felsic rocks, and high Al, Si and low Fe rocks, possibly indicating clays. Unusual soils at Gusev crater in the area surrounding Home Plate include some very rich in ferric sulfate salts (up to 35 wt% SO3) and some with 90% wt% SiO2, possibly indicating fumerolic activities. Rocks in the Columbia Hills show significant signs of alteration including elevated S, Cl and Br in the abraded interior. At Gale Crater, mudstones with approximately 20% clay, less than 1% SO3 and overall average Mars composition indicate a former habitable environment with low acidity. A remarkable diversity of compositions was found during Curiosity's traverses, which likely stems from material influx from the northern Gale rim. At Pahrump, the base of Mount Sharp, a homogeneous mudstone with lower Mg and Ca was encountered. The composition of this Murray unit can be traced over several kilometers with smooth trends of higher Fe/Mn and lower soluble trace elements Ni and Zn at higher elevation. The likely aeolian Stimson formation with average Mars crustal composition intersects in several places in sharp contact with the Murray formation. Both units show local alteration halos with highly elevated SiO2 of up to 75%, usually correlated with increase in Ti and often P.

Gellert, R.↗

NASA NTRS1991

Attempted nonenzymatic template-directed oligomerizations on a polyadenylic acid template: implications for the nature of the first genetic material

Previous attempts to produce nonenzymatic template-directed oligomerizations of activated pyrimidines on polypurine templates have been unsuccessful. The only efficient reactions are those where the template is composed primarily of pyrimidines, especially cytosine. Because molecular evolution requires that a synthesized daughter polynucleotide be capable of acting as a template for the synthesis of the original polynucleotide, the one-way replication achieved thus far is inadequate to initiate an evolving system. Several uracil analogs were used in this investigation in order to search for possible replacements for uracil. The monomers used in this investigation were the imidazolides of UMP, xanthosine 5'-monophosphate, the bis-monophosphates of the acyclic nucleosides of uracil, and 2,4-quinazolinedione. The concentrations of various salts, buffers, pH, and temperature were among the different variables investigated in attempts to find conditions that would permit template-directed oligomerizations. Although the different monomers in this study demonstrated varying abilities to form very short oligomers, we were unable to detect any enhancement of this oligomerization that could be attributed to the poly(A) template. Although special conditions might be found that would allow purine-rich templates to work, these reactions cannot be considered robust. The results of our experiments suggest that pyrimidines were not part of the original replicating system on the primitive Earth. It has already been shown that ribose is an unlikely component of the first replicating systems, and we now suggest that phosphate was absent as well. This is due to the low solubility of phosphate in the present ocean (3 x 10(-6) M), as well as the difficulty of prebiotic activation of phosphates.

Non-NASA Center↗

NASA NTRS2010

The Biotoxicity of Mars Soils

Recent evidence from the Opportunity and Spirit rovers suggests that the soils on Mars might be very high in biotoxic materials induding sulfate salts, chlorides, and acidifying agents. Yet, very little is known about how the chemistries of Mars soils might affect the survival and growth of terrestrial microorganisms. The primary objectives of the proposed research will be to: (1) prepare and characterize Mars analog soils amended with potential biotoxic levels of sulfates, chlorides, and acidifying minerals; (2) use the stimulants to conduct a series of toxicology assays to determine if terrestrial microorganisms from spacecraft or extreme environments can survive direct exposure to the biotoxic soils, and (3) mix soils from extreme environments on Earth into Mars analog soils to determine if terrestrial microorganisms can grow and replicate under Martian conditions. The Mars analog soils will be thoroughly characterized by a wide diversity of soil chemistry assays to determine the exact nature of the soluble biotoxic components following hydration. The microbial experiments will be designed to test the effects of Mars stimulants on microbial survival, growth and replication during direct challenge experiments. Toxicology experiments will be designed to mimic terrestrial microbes coming into contact with biotoxic soils with and without liquid water. Results are expected to help" ... characterize the limits of life in ... planetary environments ... " and may help constrain the search for life on Mars.

Kerney, Krystal↗

NASA NTRS1994

Isotopic analyses of nitrogenous compounds from the Murchison meteorite: ammonia, amines, amino acids, and polar hydrocarbons

The combined volatile bases (ammonia, aliphatic amines, and possibly other bases), ammonia, amino acids, and polar hydrocarbons were prepared from the Murchison meteorite for isotopic analyses. The volatile bases were obtained by cryogenic transfer after acid-hydrolysis of a hot-water extract and analyzed by combined gas chromatography-mass spectrometry of pentafluoropropionyl derivatives. The aliphatic amines present in this preparation comprise a mixture that includes both primary and secondary isomers through C5 at a total concentration of > or = 100 nmoles g-1. As commonly observed for meteoritic organic compounds, almost all isomers through C5 are present, and the concentrations within homologous series decrease with increasing chain length. Ammonia was chromatographically separated from the other volatile bases and found at a concentration of 1.1-1.3 micromoles g-1 meteorite. The ammonia analyzed includes contributions from ammonium salts and the hydrolysis of extractable organic compounds, e.g., carboxamides. Stable isotope analyses showed the volatile bases to be substantially enriched in the heavier isotopes, relative to comparable terrestrial compounds delta D < or = +1221%; delta 13C = +22%; delta 15N = +93%). Ammonia, per se, was found to have a somewhat lower delta 15N value (+69%) than the total volatile bases; consequently, a higher delta 15N (>93%) can be inferred for the other bases, which include the amines. Solvent-extractable polar hydrocarbons obtained separately were found to be enriched in 15N (delta 15N = +104%). Total amino acids, prepared from a hydrolyzed hot-water extract by cation exchange chromatography, gave a delta 15N of +94%, a value in good agreement with that obtained previously. Nitrogen isotopic data are also given for amino acid fractions separated chromatographically. The delta 15N values of the Murchison soluble organic compounds analyzed to date fall within a rather narrow range (delta 15N = +94 +/- 8%), an observation consistent with their formation, or formation of their precursors, by interstellar chemistry.

Non-NASA Center↗

NASA NTRS1985

Factors controlling dimethylsulfide emission from salt marshes

The factors that control the emission of methylated gases from salt marshes are being studied. Research focusses on dimethylsulfide (DMS) formation and the mechanism of DMS and CH4 emission to the atmosphere. The approach is to consider the plants as valves regulating the emission of methylated gases to the atmosphere with the goal of developing appropriate methods for emission measurement. In the case of CH4, the sediment is the source and transport to the atmosphere occurs primarily through the internal gas spaces in the plants. The source of DMS appears to be dimethyl sulfoniopropionate (DMSP) which may play a role in osmoregulation in plant tissues. Concentrations of DMSP in leaves are typically several-fold higher than in roots and rhizomes. Even so, the large below ground biomass of this plant means that 2/3 of the DMSP in the ecosystem is below ground on the aerial basis. Upon introduction to sediment water, DMSP rapidly decomposes to DMS and acrylic acid. The solubility of a gas (its equilibrium vapor pressure) is a fundamental aspect of gas exchange kinetics. The first comprehensive study was conducted of DMS solubility in freshwater and seawater. Data suggest that the Setchenow relation holds for H at intermediate salinities collected. These data support the concept that the concentration of DMS in the atmosphere is far from equilibrium with seawater.

Dacey, John W. H.↗

NASA NTRS2005

Valiant 'Zero-Valent' Effort Restores Contaminated Grounds

Dense non-aqueous phase liquids (DNAPLs) are chemical compounds that can contaminate soil and groundwater to the point of irreparability. These substances are only slightly soluble in water, and are much denser than water. Because of their solubility, DNAPLs form separate liquid phases in groundwater, and because of their density, DNAPLs sink in aquifers instead of floating at the water table, making it extremely difficult to detect their presence. If left untreated in the ground, they can taint fresh water sources. Common DNAPLs include chlorinated hydrocarbon compounds such as carbon tetrachloride, chloroform, tetrachloroethylene, and trichloroethylene. Trichloroethylene was used during the early days of the Space Program, as a solvent for flushing rocket engines, and for metal cleaning and degreasing of equipment, electronics, and heavy machinery. As a result, areas of Cape Canaveral s Launch Complex 34, the site of several historic Saturn rocket launches occurring from 1959 to 1968, were polluted with chlorinated DNAPLs. Through the direction and guidance of Dr. Jacqueline Quinn, an environmental engineer in the Spaceport Engineering and Technology Directorate at NASA s Kennedy Space Center, a biodegradable environmental cleanup technology was developed to reductively dechlorinate DNAPL sources in polluted water at Launch Complex 34. It was important for Kennedy to nip this problem in the bud, in light of the fact that the Space Center is also a National Wildlife Refuge, home to thousands of shorebirds, endangered sea turtles and eagles, manatees, alligators, and diverse habitats that include brackish marshes and salt water estuaries. The success in remediating this historic launch site has led to numerous commercial applications that are restoring the health of our environmental surroundings.

Source record↗

NASA NTRS2004

Evidence for Differential Comminution/Aeolian Sorting and Chemical Weathering of Martian Soils Preserved in Mars Meteorite EET79001

Impact-melt glasses containing Martian atmospheric gases in Mars meteorite EET79001 are formed from Martian soil fines that had undergone meteoroid-comminution and aeolian sorting accompanied by chemical weathering near Mars surface. Using SiO2 and SO3 as proxy for silicates and salts respectively in Mars soils, we find that SiO2 and SO3 correlate negatively with FeO and MgO and positively with Al2O3 and CaO in these glasses, indicating that the mafic and felsic components are depleted and enriched relative to the bulk host (Lith A/B) respectively as in the case of Moon soils. Though the overall pattern of mineral fractionation is similar between the soil fines on Mars and Moon, the magnitudes of the enrichments/depletions differ between these sample-suites because of pervasive aeolian activity on Mars. In addition to this mechanical processing, the Martian soil fines, prior to impact-melting, have undergone acid-sulfate dissolution under oxidizing/reducing conditions. The S03 content in EET79001,507 (Lith B) glass is approx.18% compared to < 2% in EET79001, 506 (Lith A). SiO2 and SO3 negatively correlate with each other in ,507 glasses similar to Pathfinder soils. The positive correlation found between FeO and SO3 in ,507 glasses as well as Pathfinder rocks and soils is consistent with the deposition of ferric-hydroxysulfate on regolith grains in an oxidizing environment. As in the case of Pathfinder soils, the Al 2O3 vs SiO2 positive correlation and FeO VS S102 negative correlation observed in ,507 glasses indicate that SiO2 from the regolith is mobilized as soluble silicic acid at low pH. The large off-set in the end-member FeO abundance ( SO3=0) between Pathfinder soil-free rock and sulfur-free rock in ,507 glass precursors suggests that the soils comprising the ,507 glasses contain much larger proportion of fine-grained Martian soil fraction that registers strong mafic depletion relative to Lith B. This inference is strongly supported by the Al2O3 - SO3 negative correlation observed in both ,507 glasses and pathfinder soils. Furthermore, the flat MgO-SO3 correlation observed in the case of ,507 glasses shows that the solubilized MgSO4 is mobilized by the aqueous solutions leaving behind the rock-residue with approx.2-3% MgO. This value is similar to the approx.2% MgO found for the soil-free rock at the Pathfinder site. The EET79001 ,506 glasses, in contrast, show that Al2O3 and CaO positively correlate with SO3 indicating that Al is precipitated as amorphous hydroxysulfate at relatively high pH. The FeO - SO3 negative correlation observed in ,506 glasses yields an end-member FeO abundance of approx.21% for the sulfur-free rock, which is consistent with the 22% FeO deduced for the Viking soil-free rock. Further, the FeO and MgO negative correlation with S03 observed in ,506 glasses indicates that the divalent Fe and Mg released from ferromagnesian minerals by acid sulfate dissolution are mobilized away from the reaction sites as soluble sulfates under reducing environment. A similar negative correlation between FeO and SO3 and a positive correlation between Al2O3 and SO3 found in Viking soils suggest that they also had undergone acid-sulfate dissolution under relatively reducing conditions.

Rao, M. N.↗