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At least 289 records · Page 16

Predictive isotopic biogeochemistry: hydrocarbons from anoxic marine basins

Carbon isotopic compositions were determined for individual hydrocarbons in water column and sediment samples from the Cariaco Trench and Black Sea. In order to identify hydrocarbons derived from phytoplankton, the isotopic compositions expected for biomass of autotrophic organisms living in surface waters of both localities were calculated based on the concentrations of CO2(aq) and the isotopic compositions of dissolved inorganic carbon. These calculated values are compared to measured delta values for particulate organic carbon and for individual hydrocarbon compounds. Specifically, we find that lycopane is probably derived from phytoplankton and that diploptene is derived from the lipids of chemoautotrophs living above the oxic/anoxic boundary. Three acyclic isoprenoids that have been considered markers for methanogens, pentamethyleicosane and two hydrogenated squalenes, have different delta values and apparently do not derive from a common source. Based on the concentration profiles and isotopic compositions, the C31 and C33 n-alkanes and n-alkenes have a similar source, and both may have a planktonic origin. If so, previously assigned terrestrial origins of organic matter in some Black Sea sediments may be erroneous.

Non-NASA Center↗

Process for derivatizing carbon nanotubes with diazonium species and compositions thereof

Methods for the chemical modification of carbon nanotubes involve the derivatization of multi- and single-wall carbon nanotubes, including small diameter (ca. 0.7 nm) single-wall carbon nanotubes, with diazonium species. The method allows the chemical attachment of a variety of organic compounds to the side and ends of carbon nanotubes. These chemically modified nanotubes have applications in polymer composite materials, molecular electronic applications, and sensor devices. The methods of derivatization include electrochemical induced reactions, thermally induced reactions, and photochemically induced reactions. Moreover, when modified with suitable chemical groups, the derivatized nanotubes are chemically compatible with a polymer matrix, allowing transfer of the properties of the nanotubes (such as, mechanical strength or electrical conductivity) to the properties of the composite material as a whole. Furthermore, when modified with suitable chemical groups, the groups can be polymerized to form a polymer that includes carbon nanotubes.

Tour, James M.↗

Carbon-13 and proton nuclear magnetic resonance analysis of shale-derived refinery products and jet fuels and of experimental referee broadened-specification jet fuels

A proton and carbon-13 nuclear magnetic resonance (NMR) study was conducted of Ashland shale oil refinery products, experimental referee broadened-specification jet fuels, and of related isoprenoid model compounds. Supercritical fluid chromatography techniques using carbon dioxide were developed on a preparative scale, so that samples could be quantitatively separated into saturates and aromatic fractions for study by NMR. An optimized average parameter treatment was developed, and the NMR results were analyzed in terms of the resulting average parameters; formulation of model mixtures was demonstrated. Application of novel spectroscopic techniques to fuel samples was investigated.

Dalling, D. K.↗

Advanced onboard storage concepts for natural gas-fueled automotive vehicles

The evaluation of several advanced concepts for storing natural gas at reduced pressure is presented. The advanced concepts include adsorption on high surface area carbon, adsorption in high porosity zeolite, storage in clathration compounds, and storage by dissolution in liquid solvents. High surface area carbons with high packing density are the best low pressure storage mediums. A simple mathematical model is used to compare adsorption storage on a state of the art carbon with compression storage. The model indicates that a vehicle using adsorption storage of natural gas at 3.6 MPa will have 36 percent of the range, on the EPA city cycle, of a vehicle operating on a compression storage system having the same physical size and a peak storage pressure of 21 MPa. Preliminary experiments and current literature suggest that the storage capacity of state of the art carbons could be improved by as much as 50 percent, and that adsorption systems having a capacity equal to compression storage at 14 MPa are possible without exceeding a maximum pressure of 3.6 MPa.

Remick, R. J.↗

Alteration of the Carbon and Nitrogen Isotopic Composition in the Martian Surface Rocks Due to Cosmic Ray Exposure

C-13/C-12 and N-15/N-14 isotopic ratios are pivotal for our understanding of the Martian carbon cycle, history of the Martian atmospheric escape, and origin of the organic compounds on Mars. Here we demonstrate that the carbon and nitrogen isotopic composition of the surface rocks on Mars can be significantly altered by the continuous exposure of Martian surface to cosmic rays. Cosmic rays can effectively produce C-13 and N-15 isotopes via spallation nuclear reactions on oxygen atoms in various Martian rocks. We calculate that in the top meter of the Martian rocks, the rates of production of both C-13 and N-15 due to galactic cosmic rays (GCRs) exposure can vary within 1.5-6 atoms/cm3/s depending on rocks' depth and chemical composition. We also find that the average solar cosmic rays can produce carbon and nitrogen isotopes at a rate comparable to GCRs in the top 5-10 cm of the Martian rocks. We demonstrate that if the total carbon content in a surface Martian rock is <10 ppm, then the "light," potentially "biological" C-13/C-12 ratio would be effectively erased by cosmic rays over 3.5 billion years of exposure. We found that for the rocks with relatively short exposure ages (e.g., 100 million years), cosmogenic changes in N-15/N-14 ratio are still very significant. We also show that a short exposure to cosmic rays of Allan Hills 84001 while on Mars can explain its high-temperature heavy nitrogen isotopic composition (N-15/N-14). Applications to Martian meteorites and the current Mars Science Laboratory mission are discussed.

cosmic ray exposure↗

Carbon Isotopes of Alkanes in Hydrothermal Abiotic Organic Synthesis Processes at High Temperatures and Pressures: An Experimental Study

Observation of methane in the Martian atmosphere has been reported by different detection techniques [1-4]. With more evidence showing extensive water-rock interaction in Martian history [5-7], abiotic formation by Fischer-Tropsch Type (FTT) synthesis during serpentization reactions may be one possible process responsible for methane generation on Mars [8, 9]. While the experimental studies performed to date leave little doubt that chemical reactions exist for the abiotic synthesis of organic compounds by mineral surface-catalyzed reactions [10-12], little is known about the reaction pathways by which CO2 and/or CO are reduced under hydrothermal conditions. Carbon and hydrogen isotope measurements of alkanes have been used as an effective tool to constrain the origin and reaction pathways of hydrocarbon formation. Alkanes generated by thermal breakdown of high molecular weight organic compounds have carbon and hydrogen isotopic signatures completely distinct from those formed abiotically [13-15]. Recent experimental studies, however, showed that different abiogenic hydrocarbon formation processes (e.g., polymerization vs. depolymerization) may have different carbon and hydrogen isotopic patterns [16]. Results from previous experiments studying decomposition of higher molecular weight organic compounds (lignite) also suggested that pressure could be a crucial factor affecting fractionation of carbon isotopes [17]. Under high pressure conditions, no experimental data are available describing fractionation of carbon isotope during mineral catalyzed FTT synthesis. Thus, hydrothermal experiments present an excellent opportunity to provide the requisite carbon isotope data. Such data can also be used to identify reaction pathways of abiotic organic synthesis under experimental conditions.

Fu, Qi↗

Simple spectroscope used with solid state image amplifier over wide spectral range

Prism plus image amplifier panel provides visual image of many infrared spectral lines from carbon arc impregnated with metal compound. Different metal compounds generate various desired spectra. Panel also aligns and focuses simple spectroscopes for detecting spectral lines inside and outside visible region.

Brown, R. L., Sr.↗

Process for purification of waste water produced by a Kraft process pulp and paper mill

The water from paper and pulp wastes obtained from a mill using the Kraft process is purified by precipitating lignins and lignin derivatives from the waste stream with quaternary ammonium compounds, removing other impurities by activated carbon produced from the cellulosic components of the water, and then separating the water from the precipitate and solids. The activated carbon also acts as an aid to the separation of the water and solids. If recovery of lignins is also desired, then the precipitate containing the lignins and quaternary ammonium compounds is dissolved in methanol. Upon acidification, the lignin is precipitated from the solution. The methanol and quaternary ammonium compound are recovered for reuse from the remainder.

Humphrey, M. F.↗

Abiotic synthesis of fatty acids

The formation of fatty acids by Fischer-Tropsch-type synthesis was investigated with ferric oxide, ammonium carbonate, potassium carbonate, powdered Pueblito de Allende carbonaceous chondrite, and filings from the Canyon Diablo meteorite used as catalysts. Products were separated and identified by gas chromatography and mass spectrometry. Iron oxide, Pueblito de Allende chondrite, and Canyon Diablo filings in an oxidized catalyst form yielded no fatty acids. Canyon Diablo filings heated overnight at 500 C while undergoing slow purging by deuterium produced fatty acids only when potassium carbonate was admixed; potassium carbonate alone also produced these compounds. The active catalytic combinations gave relatively high yields of aliphatic and aromatic hydrocarbons; substantial amounts of n-alkenes were almost invariably observed when fatty acids were produced; the latter were in the range C6 to C18, with maximum yield in C9 or 10.

Leach, W. W.↗

Polyimides Containing Carbonyl and Ether Connecting Groups

Semicrystallinity gives rise to tough, solvent-resistant polymers. New polyimides prepared from reaction of aromatic dianhydrides with new diamines containing carbonyl and ether connecting groups between aromatic rings. Damines prepared from reaction of 4-aminophenol with activated aromatic difluoro compounds in presence of potassium carbonate. These types of polymers have potential applications in molded products, films, adhesives, and composites.

Hergenrother, Paul M.↗

Catalytic Destruction Of Toxic Organic Compounds

Proposed process disposes of toxic organic compounds in contaminated soil or carbon beds safely and efficiently. Oxidizes toxic materials without producing such other contaminants as nitrogen oxides. Using air, fuel, catalysts, and steam, system consumes less fuel and energy than decontamination processes currently in use. Similar process regenerates carbon beds used in water-treatment plants.

Voecks, Gerald E.↗

Microgravity smoldering combustion on the USML-1 Space Shuttle mission

Preliminary results from an experimental study of the smolder characteristics of a porous combustible material (flexible polyurethane foam) in normal and microgravity are presented. The experiments, limited in fuel sample size and power available for ignition, show that the smolder process was primarily controlled by heat losses from the reaction to the surrounding environment In microgravity, the reduced heat losses due to the absence of natural convection result in only slightly higher temperatures in the quiescent microgravity test than in normal gravity, but a dramatically larger production of combustion products in all microgravity tests. Particularly significant is the proportionately larger amount of carbon monoxide and light organic compounds produced in microgravity, despite comparable temperatures and similar char patterns. This excessive production of fuel-rich combustion products may be a generic characteristic of smoldering polyurethane in microgravity, with an associated increase in the toxic hazard of smolder in spacecraft.

Stocker, Dennis P.↗

Evolution of Interstellar Grains

During the past two decades observations combined with laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the raw materials from which planets, comets and stars form. Most interstellar material is concentrated in large molecular clouds where simple molecules are formed by dust-grain and gas-phase reactions. Gaseous species striking the cold (10K) dust stick, forming an icy grain mantle. This accretion, coupled with UV photolysis, produces a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. Ices in molecular clouds contain the very simple molecules H2O, CH3OH, CO, CO2, H2, and perhaps some NH3 and H2CO, as well as more complex species. The evidence for these compounds, as well as carbon-rich materials, will be reviewed and the possible connections with comets and meteorites will be presented in the first part of the talk . The second part of the presentation will focus on interstellar/precometary ice photochemical evolution and the species likely to be found in comets. The chemical composition and photochemical evolution of realistic interstellar/pre-cometary ice analogs will be discussed. Ultraviolet photolysis of these ices produces H2, H2CO, CO2, CO, CH4, HCO, and more complex molecules. When ices representative of interstellar grains and comets are exposed to UV radiation at low temperature a series of moderately complex organic molecules are formed in the ice including: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), and R-C=N (nitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. After warming to room temperature an organic residue remains. This is composed primarily of hexamethylenetetramine (HMT, C6H12N4), with lesser amounts of polyoxymethylene-related species (POMs), amides, and ketones. This is in sharp contrast to the organic residues produced by irradiating unrealistic interstellar ice analogs or thermally promoted polymerization-type reactions in unirradiated realistic ice mixtures.

Allamandola, Lou J.↗

Microgravity Smoldering Combustion on the USML-1 Space Shuttle Mission

Preliminary results from an experimental study of the smolder characteristics of a porous combustible material (flexible polyurethane foam) in normal and microgravity are presented. The experiments, limited in fuel sample size and power available for ignition, show that the smolder process was primarily controlled by heat losses from the reaction to the surrounding environment. In microgravity, the reduced heat losses due to the absence of natural convection result in only slightly higher temperatures in the quiescent microgravity test than in normal gravity but a dramatically larger production of combustion products in all microgravity tests. Particularly significant is the proportionately larger amount of carbon monoxide and light organic compounds produced in microgravity, despite comparable temperatures and similar char patterns. This excessive production of fuel-rich combustion products may be a generic characteristic of smoldering polyurethane in microgravity, with an associated increase in the toxic hazard of smolder in spacecraft.

Stocker, Dennis P.↗

Oxidation-reduction catalyst and its process of use

This invention relates generally to a ruthenium stabilized oxidation-reduction catalyst useful for oxidizing carbon monoxide, and volatile organic compounds, and reducing nitrogen oxide species in oxidizing environments, substantially without the formation of toxic and volatile ruthenium oxide species upon said oxidizing environment being at high temperatures.

Jordan, Jeffrey D.↗

Astrobiology Sample Analysis Program (ASAP) for Advanced Life Detection Instrumentation Development and Calibration

Scientific ground-truth measurements for near-term Mars missions, such as the 2009 Mars Science Laboratory (MSL) mission, are essential for validating current in situ flight instrumentation and for the development of advanced instrumentation technologies for life-detection missions over the next decade. The NASA Astrobiology Institute (NAI) has recently funded a consortium of researchers called the Astrobiology Sample Analysis Program (ASAP) to analyze an identical set of homogenized martian analog materials in a "round-robin" style using both state-of-the-art laboratory techniques as well as in-situ flight instrumentation including the SAM gas chromatograph mass spectrometer and CHEMIN X-ray diffraction/fluorescence instruments on MSL and the Urey and MOMA organic analyzer instruments under development for the 2013 ExoMars missions. The analog samples studied included an Atacama Desert soil from Chile, the Murchison meteorite, a gypsum sample from the 2007 AMASE Mars analog site, jarosite from Panoche Valley, CA, a hydrothermal sample from Rio Tinto, Spain, and a "blind" sample collected during the 2007 MSL slow-motion field test in New Mexico. Each sample was distributed to the team for analysis to: (1) determine the nature and inventory of organic compounds, (2) measure the bulk carbon and nitrogen isotopic composition, (3) investigate elemental abundances, mineralogy and matrix, and (4) search for biological activity. The experimental results obtained from the ASAP Mars analog research consortium will be used to build a framework for understanding the biogeochemistry of martian analogs, help calibrate current spaceflight instrumentation, and enhance the scientific return from upcoming missions.

Glavin, Daniel↗

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.↗