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NASA NTRS1983

Biologically mediated isotope fractionations - Biochemistry, geochemical significance and preservation in the earth's oldest sediments

Preferential metabolization of isotopically light carbon and sulfur has resulted in a fractionation of the stable isotopes of these elements on a global scale, with the light species (C-12, S-32) markedly concentrated in biogenic materials. Since the biological effects are basically retained when carbon and sulfur are incorporated in sediments, the respective fractionations are propagated into the rock section of the geochemical cycle, this having consequently caused a characteristic bipartition of both elements between 'light' and 'heavy' crustal reservoirs. Preservation of the biological isotope effects in sedimentary rocks makes it possible to trace the underlying biochemical processes back over most of the geological record. According to the available evidence, biological (autotrophic) carbon fixation arose prior to 3.5(if not 3.8) billion years ago, while the emergence of dissimilatory sulfate reduction antedates the appearance of the oldest presumably bacteriogenic sulfur isotope patterns in rocks between 2.7 and 2.8 billion years old. Hence, biological control of the terrestrial carbon and sulfur cycles has been established very early in the earth's history.

Schidlowski, M.↗

NASA NTRS2002

Limits on the UV Photodecomposition of Carbonates on Mars

The effect of UV (ultraviolet) light on the stability of calcium carbonate in a simulated martian atmosphere was experimentally investigated. Sample cells containing C-13 labeled calcite were irradiated with a Xe arc lamp in 10 mbar of simulated martian atmosphere and a quadrupole mass spectrometer was used to monitor the headspace gases for the production of (13)CO2. We found no experimental evidence of the UV photodecomposition of calcium carbonate in a simulated martian atmosphere. Extrapolating the lower limit of detection of our experimental system to an upper limit of carbonate decomposition on Mars yields a quantum efficiency of 3.5 x 10(exp -8) molecules/photon over the wavelength interval of 190-390 nm and a maximum UV photodecomposition rate of 1.2 x 10(exp -13) kg m(exp -2) s(exp -1) from a calcite surface. The maximum loss of bulk calcite due to this process would be 2.5 nm yr(exp -1). However, calcite is expected to be thermodynamically stable on the surface of Mars and potential UV photodecomposition reaction mechanisms indicate that while calcium carbonate may decompose under vacuum, it would be stable in a CO2 atmosphere. Given the expected stability of carbonate on Mars and our inability to detect carbonate decomposition, we conclude that it is unlikely that the apparent absence of carbonate on the martian surface is due to UV photo decomposition of calcite in the current environment.

Quinn, Richard↗

NASA NTRS2021

Evaluation of Aqua MODIS Thermal Emissive Bands Stability through Radiative Transfer Modeling

Moderate Resolution Imaging Spectroradiometer (MODIS) on Aqua has been inoperation providing continuous global observations for science research and applications since2002. The long-term stability of thermal emissive bands (TEBs) of Aqua MODIS was monitoredthrough inter-comparisons with measurements by hyperspectral or multi-spectral infraredsensors or through vicarious monitoring over cold targets such as Dome-C and deep convectiveclouds. The radiative transfer modeling (RTM)-based simulation models are developed to per-form the long-term monitoring of the stability of Aqua MODIS TEBs. Long-term EuropeanCentre for Medium-Range Weather Forecasts global atmospheric reanalysis data are used asinputs to the RTM simulation. By confining ocean in low to middle latitudes as the area ofinterest, the long-term stabilities of Aqua MODIS TEBs are monitored through observationminus background (O-B) brightness temperature (BT) bias between MODIS measurements andsimulations from the RTM. In general, the RTM-based O-B analysis shows that the long-termstability of Aqua MODIS TEBs are maintained well. It is shown that Aqua MODIS surfacebands are all radiometrically stable with yearly BT bias drifts <0.005 K∕yearfor B20, B22,and B23 and∼0.01 K∕yearfor B31 and B32. The carbon dioxide (CO2) absorption channelsof Aqua MODIS, e.g., B33 to B36, are stable with a BT bias drift <0.005 K∕year. It is also foundthat after accounting for the long-term growth of greenhouse gasN2O, the O-B bias trends forB24 and B25 are quite stable with yearly BT bias drifts around 0.0002 and0.0055 K∕year,respectively. The stabilities of the moisture-sensitive channels B27 to B29 and the ozone channelB30 of Aqua MODIS are also evaluated and the remnant small variations in the O-B bias trend-ing of these channels are further discussed. The RTM-based inter-comparison of MODIS TEBmeasurements with global atmospheric and climate re-analysis data provides validation of thelong-term radiometric stability of Aqua MODIS TEBs. The analysis in this paper also demon-strates that the comparison of well-calibrated MODIS TEB measurements with RTM simulationhelps quantify the long-term impacts of global greenhouse gas concentration growth on the BTdecreases in the MODIS greenhouse gas-sensitive channels.

MODIS↗

NASA NTRS2003

Silicon Carbide Nanotube Synthesized

Carbon nanotubes (CNTs) have generated a great deal of scientific and commercial interest because of the countless envisioned applications that stem from their extraordinary materials properties. Included among these properties are high mechanical strength (tensile and modulus), high thermal conductivity, and electrical properties that make different forms of single-walled CNTs either conducting or semiconducting, and therefore, suitable for making ultraminiature, high-performance CNT-based electronics, sensors, and actuators. Among the limitations for CNTs is their inability to survive in high-temperature, harsh-environment applications. Silicon carbon nanotubes (SiCNTs) are being developed for their superior material properties under such conditions. For example, SiC is stable in regards to oxidation in air to temperatures exceeding 1000 C, whereas carbon-based materials are limited to 600 C. The high-temperature stability of SiCNTs is envisioned to enable high-temperature, harsh-environment nanofiber- and nanotube-reinforced ceramics. In addition, single-crystal SiC-based semiconductors are being developed for hightemperature, high-power electronics, and by analogy to CNTs with silicon semiconductors, SiCNTs with single-crystal SiC-based semiconductors may allow high-temperature harsh-environment nanoelectronics, nanosensors, and nanoactuators to be realized. Another challenge in CNT development is the difficulty of chemically modifying the tube walls, which are composed of chemically stable graphene sheets. The chemical substitution of the CNTs walls will be necessary for nanotube self-assembly and biological- and chemical-sensing applications. SiCNTs are expected to have a different multiple-bilayer wall structure, allowing the surface Si atoms to be functionalized readily with molecules that will allow SiCNTs to undergo self-assembly and be compatible with a variety of materials (for biotechnology applications and high-performance fiber-reinforced ceramics).

Lienhard, Michael A.↗

NASA NTRS1990

Down-to-earth studies of carbon clusters

Recent advances in supersonic beam experiments with laser-vaporization sources of clusters have provided some interesting new insights into the nature of the small clusters of carbon, and the processes through which carbon condenses. One cluster in particular, C(sub 60), appears to play a central role. It is argued that this cluster takes the shape of a soccerball: a hollow sphere composed of a shell of 60 carbon atoms connected by a lattice of hexagonal and pentagonal rings, in a pattern of overall icosahedral symmetry. Although C(sub 60) appears to be uniquely stable due to its perfect symmetry, all other even-numbered carbon clusters in the 32 to 100+ atom size range seem to favor similar closed spheroidal forms. These species are interpreted as relatively unreactive side products in condensation reactions of carbon vapor involving spiraling graphitic sheets. The prevalence of C(sub 60) in laser-vaporized carbon vapors and sooting flames suggests that it may be formed readily whenever carbon condenses. Such ready formation and extraordinary stability may have substantial astrophysical implications.

Smalley, R. E.↗

NASA NTRS1993

Derivation of the midinfrared (5.0-25.0 micron) optical constants of hydrous carbonate and sulfate

There is ample theoretical and observational evidence suggesting liquid water was once stable at the surface of Mars. Because water is essential to the evolution of life, it is important to understand the types of environments in which the liquid water was present. For example, if water were present early in Mars' history, then this raises the possibility that biological activity may have evolved only to eventually become extinct as liquid water became scarce. Alternatively, if liquid water were stable only later in Mars' history, then it becomes problematic to envision mechanisms by which biological activity evolved and remained viable without water until more favorable conditions existed. Even without biological activity, atmospheric carbon dioxide dissolved in water can assist the chemical weathering of primary igneous minerals producing common secondary phases such as hydartes, carbonates, and sulfates. While the identification of hydrates, carbonates, and sulfates on Mars cannot provide direct evidence of biological activity, it can provide significant information regarding the presence and duration of an environment that would support the presence of liquid water at the surface. The specific mineralogy of these secondary phases can provide insight into the environments of their formation. For example, the slow precipitation that occurs in large standing bodies of water, e.g. oceans or lakes, commonly results in the formation of calcite, magnesite, dolomite, siderite, and rhodochrosite. Rapid precipitation that occurs in ephemeral bodies of water, e.g. hypersaline lakes or playas, can result in the formation of all of the above phases as well as aragonite, vaterite, hydrated carbonates, alkali carbonates, bicarbonates, and other poorly ordered phases. Absorption features identified in recent near-infrared spectra of Mars have been interpreted as being due to bicarbonate and bisulfate located in the mineral scaplite. Spectral data returned by the Mariner 6 and 7 spacecraft have been inerpreted as remaining consistent with the presence of hydrated carbonates. Additional, airborne thermal infrared spectra of Mars have been interpreted as implying the presence of carbonates, sulfates, and hydrates. Modeling of the thermal infrared data relied upon the optical constants of calcite anhydrite and a mixture of water in basalt because of their availability. The derived abundances of carbonate and sulfate were 1-3 percent and 10-15 percent by volume. However, the observed complexity and positions of the bands suggested other carbonate-, and sulfate-bearing species. We have already derived optical constants for hydrous and anhydrous silicates, and we are now applying these techniques to the derivation of the optical constants of hydrous carbonate and sulfate.

Roush, Ted L.↗

NASA NTRS1977

Geochemical and mineralogical interpretation of the Viking inorganic chemical results

The current status of geochemical, mineralogical, petrological interpretation of refined Viking Lander data is reviewed, and inferences that can be drawn from data on the composition of Martian surface materials are presented. The materials are dominantly fine silicate particles admixed with, or including, iron oxide particles. Both major element and trace element abundances in all samples are indicative of mafic source rocks (rather than more highly differentiated salic materials). The surface fines are nearly identical in composition at the two widely separated Lander sites, except for some lithologic diversity at the 100-m scale. This implies that some agency (presumably aeolian processes) has thoroughly homogenized them on a planetary scale. The most plausible model for the mineralogical constitution of the fine-grained surface materials at the two Lander sites is a fine-grained mixture dominated by iron-rich smectites, or their degradation products, with ferric oxides, probably including maghemite and carbonates (such as calcite), but not such less stable phases as magnesite or siderite.

Toulmin, P., III↗

NASA NTRS1993

A search for C60 in carbonaceous chondrites

Analysis of interior samples of the Murchison meteorite by two routes yielded an upper limit of 2 ppb for its C60 content, as compared to parts per million levels for individual polycyclic aromatic hydrocarbons (PAHs ). Provided the samples contain an interstellar component, which is probable since Murchison hydrocarbons contain excess deuterium, this result argues against the ubiquitous presence of C60 in the interstellar medium. A possible explanation for the absence of C60 was found in experiments showing how PAHs replace fullerenes as stable end products when hydrogen is present during carbon condensation. As a secondary result we found high molecular weight PAHs in the Murchison and Allende meteorites. Coronene and its methyl derivatives are especially interesting since features in the coronene spectrum have been shown to match some of the unidentified interstellar infrared emission bands.

De Vries, M. S.↗

NASA NTRS1994

Exopaleontology and the search for a fossil record on Mars

Although present Martian surface conditions appear unfavorable for life as we know it, there is compelling geological evidence that the climate of early Mars was much more Earth-like, with a denser atmosphere and abundant surface water. The fact that life developed on the Earth within the first billion years of its history makes it quite plausible that life may have also developed on Mars. If life did develop on Mars, it is likely to have left behind a fossil record. This has led to the development of a new subdiscipline of paleontology, herein termed 'exopaleontology', which deals with the exploration for fossils on other planets. The most important factor enhancing microbial fossilization is the rapid entombment of microorganisms by fine-grained, stable mineral phases, such as silica, phosphate, or carbonate. The oldest body fossils on Earth are preserved in this way, occurring as permineralized cells in fine-grained siliceous sediments (cherts) associated with ancient volcanic terranes in Australia and South Africa. Modern terrestrial environments where minerals may precipitate in the presence of microorganisms include subaerial thermal springs and shallow hydrothermal systems, sub-lacustrine springs and evaporitic alkaline lakes, zones of mineralization within soils where 'hardpans' (e.g. calcretes, silcretes) form, and high latitude frozen soils or ground ice.

Farmer, Jack D.↗

NASA NTRS1997

Biogeochemistry of DMS in Surface Waters

Dimethylsulfide (DMS) is important in influencing the formation of aerosols in the troposphere over large areas of the world's oceans. Understanding the dynamics of aerosols is important to understanding the earth's radiation balance. In evaluating the factors controlling DMS in the troposphere it is vital to understand the dynamics of DMS in the surface ocean. The biogeochemical processes controlling DMS concentration in seawater are myriad; modeling and theoretical estimation are problematic. At the beginning of this project we believed that we were on the verge of simplifying the ship-track measurement of DMS, and we proposed to deploy such a system to develop a database relating high frequency DMS measurements to biological and physicochemical and optical properties of surface water that can be quantified by remote sensing techniques. We designed a system to measure DMS concomitantly with other basic chemical and biological data in a flow-through system. The project was collaborative between Woods Hole Oceanographic Institution (WHOI) and Bermuda Biological Station for Research (BBSR). The project on which we are reporting was budgeted for only one year with a one year no-cost extension. At WHOI our effort was directed towards designing traps which would be used to concentrate DMS from seawater and allow storage for subsequent analysis. At that time, GC systems were too large for easy long-term deployment on a research vessel like R/V Weatherbird, so we focused on simplifying the shipboard sampling procedure. Initial studies of sample recovery with high levels of DMS suggested that Carboxen 1000, a relatively new carbon molecular sieve, could be used as a stable storage medium. The affinity of Carboxen for DMS is several orders of magnitude higher than gold wool (another adsorbent used for DMS collection) on a weight or volume basis. Furthermore, Carboxen's affinity for DMS is also far less susceptible to humidity than gold wool. Unfortunately, further experiments with low level DMS indicated that recovery of DMS after storage was not quantitative. The material has proven to be completely acceptable for short term storage and has been incorporated into a micro-GC system. Since working on this project, we have collaborated with RVM Scientific in Santa Barbara in the design and construction of small portable micro-GC's that will make feasible at-sea measurement in moving ships, making rapid gas analysis and quantification feasible in a ship-track mode. Throughout this period at both WHOI and BBSR, we continued to analyze field data to understand that patterns of time and space variability in DMS and the processes that govern it. These insights will be crucial to determining the specifications for our automated sampling program. The data from this, the longest continuous sampling program for ocean DMS, provided insights into year to year and short-term variability.

Dacey, J. W. H.↗

NASA NTRS2009

Silica-Aerogel Composites Opacified with La(0.7)Sr(0.3)MnO3

As part of an effort to develop improved lightweight thermal-insulation tiles to withstand temperatures up to 1,000 C, silica aerogel/fused-quartz-fiber composite materials containing La0.7Sr0.3MnO3 particles as opacifiers have been investigated as potentially offering thermal conductivities lower than those of the otherwise equivalent silica-aerogel composite materials not containing La(0.7)Sr(0.3)MnO3 particles. The basic idea of incorporating opacifying particles into silica-aerogels composite to reduce infrared radiative contributions to thermal conductivities at high temperatures is not new: it has been reported in a number of previous NASA Tech Briefs articles. What is new here is the selection of La(0.7)Sr(0.3)MnO3 particles as candidate opacifiers that, in comparison with some prior opacifiers (carbon black and metal nanoparticles), are more thermally stable. The preparation of a composite material of the present type includes synthesis of the silica-aerogel component in a sol-gel process. The La(0.7)Sr(0.3)MnO3 particles, made previously in a separate process, are mixed into the sol, which is then cast onto fused-quartz-fiber batting. Then the aerogel-casting solution is poured into the mold, where it permeates the silica fiber felt. After the sol has gelled, the casting is aged and then subjected to supercritical drying to convert the gel to the final aerogel form. The separate process for making the La(0.7)Sr(0.3)MnO3 particles begins with the slow addition of corresponding proportions of La(CH3COOH)3, Mn(CH3COOH)3, and Sr(NO3)2 to a solution of H2O2 in H2O. The solution is then peptized by drop-wise addition of NH4OH to obtain a sol. Next, the sol is dried in an oven at a temperature of 120 C to obtain a glassy solid. The solid is calcined at 700 C to convert it to La(0.7)Sr(0.3)MnO3. Then La(0.7)Sr(0.3)MnO3 particles are made by ball-milling the calcined solid. The effectiveness of La(0.7)Sr(0.3)MnO3 particles as opacifiers and thermal-conductivity reducers depends on the statistical distribution of particle sizes as well as the relative proportions of La(0.7)Sr(0.3)MnO3 and aerogel. For experiments performed thus far, samples of aerogel/fiber composites were formulated to have, variously, silica target density of 0.07 or 0.14 g/cu cm and to contain 30 percent of La(0.7)Sr(0.3)MnO3 in average particle size of 0.3 or 3 microns. The thermal conductivities of the samples containing the 3 micron La(0.7)Sr(0.3)MnO3 particles were found to be lower than those of the samples containing the 0.3 micron La(0.7)Sr(0.3)MnO3 particles. The optimum particle size is believed to be between 1 and 5 microns.

Rhine, Wendell↗

NASA NTRS2002

Wetting Angles and Surface Tension of Ge(1-x)Si(x) Melts on Different Substrate Materials

The wetting angles and the surface tension of Ge(1-x)Si(x) melts (0.02 less than x less than 0.13) have been measured on various substrate materials using the sessile drop technique. Fused quartz, sapphire, SiC, glassy carbon, pBN, AIN, and Si3N4 have been used as substrates. The highest and most stable wetting angles were found for pBN substrates with 164 +/- 8 deg., either under forming gas with an additional carbon getter in the system or under active vacuum. The surface tension measurements resulted in a value of +2.2 x 10(exp -3) N/m.at%Si for the concentration dependence delta(gamma)/(delta)C. For the composition range measured, the temperature dependence (delt)gamma/(delta)T showed values similar to those of pure Ge, on average -0.07 x 10(exp -3) N/mK.

Croell, A.↗

NASA NTRS1985

The evolution of CELSS for lunar bases

A bioregenerative life support system designed to address the fundamental requirements of a functioning independent lunar base is presented in full. Issues to be discussed are associated with CELSS weight, volume and cost of operation. The fundamental CELSS component is a small, highly automated module containing plants which photosynthesize and provide the crew with food, water and oxygen. Hydrogen, nitrogen and carbon dioxide will be initially brought in from earth, recycled and their waste products conserved. As the insufficiency of buffers necessitates stringent cybernetic control, a stable state will be maintained by computer control. Through genetic engineering and carbon dioxide, temperature, and nutrient manipulation, plant productivity can be increased, while the area necessary for growth and illumination energy decreased. In addition, photosynthetic efficiency can be enhanced through lamp design, fiber optics and the use of appropriate wavelengths. Crop maintenance will be performed by robotics, as a means of preventing plant ailments.

Macelroy, R. D.↗

NASA NTRS2006

Preparation and Properties of Nanocomposites Prepared From Shortened, Functionalized Single-Walled Carbon Nanotubes

As part of a continuing materials development activity, low color space environmentally stable polymeric materials that possess sufficient electrical conductivity for electrostatic charge dissipation (ESD) have been investigated. One method of incorporating sufficient electrical conductivity for ESD without detrimental effects on other polymer properties of interest (i.e., optical and thermo-optical) is through the incorporation of single-walled carbon nanotubes (SWNTs). However, SWNTs are difficult to fully disperse in the polymer matrix. One means of improving dispersion is by shortening and functionalizing SWNTs. While this improves dispersion, other properties (i.e., electrical) of the SWNTs can be affected which can in turn alter the final nanocomposite properties. Additionally, functionalization of the polymer matrix can also influence nanocomposite properties obtained from shortened, functionalized SWNTs. The preparation and characterization of nanocomposites fabricated from a polyimide, both functionalized and unfunctionalized, and shortened, functionalized SWNTs will be presented.

Smith, J. G., Jr.↗

NASA NTRS2002

Carbon Nanotube/Space Durable Polymer Nanocomposite Films for Electrostatic Charge Dissipation

Low solar absorptivity, space environmentally stable polymeric materials possessing sufficient electrical conductivity for electrostatic charge dissipation (ESD) are of interest for potential applications on spacecraft as thin film membranes on antennas, solar sails, large lightweight space optics, and second surface mirrors. One method of imparting electrical conductivity while maintaining low solar absorptivity is through the use of single wall carbon nanotubes (SWNTs). However, SWNTs are difficult to disperse. Several preparative methods were employed to disperse SWNTs into the polymer matrix. Several examples possessed electrical conductivity sufficient for ESD. The chemistry, physical, and mechanical properties of the nanocomposite films will be presented.

Smith, J. G., Jr.↗

NASA NTRS1972

Preferential orientation of CO adsorption on Ni as determined by extended Hueckel calculations.

The adsorption of CO on the nickel surface has been calculated using a modified extended Hueckel technique for a number of different orientations of the CO with respect to the nickel surface. The calculations show that double site adsorption with the CO molecule normal to the surface and the carbon atom closest to the metal gives the most stable configuration (2.57 eV). The single site absorbs with an energy of 2.39 eV. However, other configurations also give fairly large bonding energies. The CO normal to the surface with oxygen closest to the metal gives a heat of adsorption of 0.37 eV. Two-center adsorption with the CO axis parallel to the surface and the molecule symmetrically placed between the nearest neighbors gives a chemisorption energy of 1.34 eV. These values compare with an experimental value of 1.98 eV.

Robertson, J. C.↗

NASA NTRS1993

Gelled Electrolytes For Lithium Batteries

Gelled polymer electrolyte consists of polyacrylonitrile (PAN), LiBF4, and propylene carbonate (PC). Thin films of electrolyte found to exhibit stable bulk conductivities of order of 10 to the negative 3rd power S/cm at room temperature. Used in thinfilm rechargeable lithium batteries having energy densities near 150 W h/kg.

Nagasubramanian, Ganesan↗

NASA NTRS2015

No-Oven, No-Autoclave Composite Processing

Very large composite structures, such as those used in NASA's Space Launch System, push the boundaries imposed by current autoclaves. New technology is needed to maintain composite performance and free manufacturing engineers from the restraints of curing equipment size limitations. Recent efforts on a Phase II project by Cornerstone Research Group, Inc. (CRG), have advanced the technology and manufacturing readiness levels of a unique two-part epoxy resin system. Designed for room-temperature infusion of a dry carbon preform, the system includes a no-heat-added cure that delivers 350 F composite performance in a matter of hours. This no-oven, no-autoclave (NONA) composite processing eliminates part-size constraints imposed by infrastructure and lowers costs by increasing throughput and reducing capital-specific, process-flow bottlenecks. As a result of the Phase II activity, NONA materials and processes were used to make high-temperature composite tooling suitable for further production of carbon-epoxy laminates and honeycomb/ sandwich-structure composites with an aluminum core. The technology platform involves tooling design, resin infusion processing, composite part design, and resin chemistry. The various technology elements are combined to achieve a fully cured part. The individual elements are not unusual, but they are combined in such a way that enables proper management of the heat generated by the epoxy resin during cure. The result is a self-cured carbon/ epoxy composite part that is mechanically and chemically stable at temperatures up to 350 F. As a result of the successful SBIR effort, CRG has launched NONA Composites as a spinoff subsidiary. The company sells resin to end users, fabricates finished goods for customers, and sells composite tooling made with NONA materials and processes to composite manufacturers.

Rauscher, Michael D.↗