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At least 847 records · Page 47

Exploring Carbon Mineral Systems: Recent Advances in C Mineral Evolution, Mineral Ecology, and Network Analysis

Large and growing data resources on the spatial and temporal diversity and distribution of the more than 400 carbon-bearing mineral species reveal patterns of mineral evolution and ecology. Recent advances in analytical and visualization techniques leverage these data and are propelling mineralogy from a largely descriptive field into one of prediction within complex, integrated, multidimensional systems. These discoveries include: (1) systematic changes in the character of carbon minerals and their networks of coexisting species through deep time; (2) improved statistical predictions of the number and types of carbon minerals that occur on Earth but are yet to be discovered and described; and (3) a range of proposed and ongoing studies related to the quantification of network structures and trends, relation of mineral “natural kinds” to their genetic environments, prediction of the location of mineral species across the globe, examination of the tectonic drivers of mineralization through deep time, quantification of preservational and sampling bias in the mineralogical record, and characterization of feedback relationships between minerals and geochemical environments with microbial populations. These aspects of Earth’s carbon mineralogy underscore the complex coevolution of the geosphere and biosphere and highlight the possibility for scientific discovery in Earth and planetary systems.

Carbon↗

Recent Advances in Structural Carbon Nanotube Composites

Carbon nanotubes (CNT) have been a subject of investigation for more than two decades. Part of the interest in CNTs was driven by CNT tensile mechanical properties at the nanoscale that suggest their potential to outperform state-of-the-art (SOA) lightweight structural materials. Early work on the development of CNT nanocomposites involved the dispersion of CNT powder into polymer matrices. Although low levels of CNT doping resulted in meaningful increases in electrical conductivity to enable applications such as electrostatic charge dissipation, the highest concentrations of CNTs in these lightly doped nanocomposites did not yield mechanical properties that could compete with SOA carbon fiber composites. The maximum concentration of CNTs in lightly doped nanocomposites was limited to about 5% due to increases in viscosity that prevent the fabrication of good quality nanocomposites. At the lower concentrations, properties of the resulting nanocomposites were analogous to those of composites made with very short, chopped carbon fibers. About ten years ago, CNTs became available in continuous fiber form, allowing the investigation of processing methods to incorporate much higher CNT content into composites. Recent developments in CNT composite fabrication have yielded improved mechanical properties and indicate that while some standard carbon fiber composite processing methods can be used, CNTs have unique microstructural features that require techniques tailored to access the hierarchical features of CNTs. This presentation will discuss the evolution of structural CNT mechanical property advancements and collaboration mechanisms for research across federal labs, academia, and industry that accelerated the maturation of structural CNTs.

Carbon Nanotubes↗

Carbon Dioxide Reduction Systems

The Methoxy system for regenerating oxygen from carbon dioxide was studied. Experiments indicate that the reaction between carbon dioxide and hydrogen can be carried out with ease in an efficient manner and with excellent heat conservation. A small reactor capable of handling the C02 expired by three men has been built and operated. The decomposition of methane by therma1,arc and catalytic processes was studied. Both the arc and catalytic processes gave encouraging results with over 90 percent of the methane being decomposed to carbon and hydrogen in some of the catalytic processes. Control of the carbon deposition in both the catalytic and arc processes is of great importance to prevent catalyst deactivation and short circuiting of electrical equipment. Sensitive analytical techniques have been developed for all of the components present in the reactor effluent streams.

METHOXY SYSTEM↗

Stable carbon isotope fractionation by sulfate-reducing bacteria

Biogeochemical transformations occurring in the anoxic zones of stratified sedimentary microbial communities can profoundly influence the isotopic and organic signatures preserved in the fossil record. Accordingly, we have determined carbon isotope discrimination that is associated with both heterotrophic and lithotrophic growth of pure cultures of sulfate-reducing bacteria (SRB). For heterotrophic-growth experiments, substrate consumption was monitored to completion. Sealed vessels containing SRB cultures were harvested at different time intervals, and delta(13)C values were determined for gaseous CO(2), organic substrates, and products such as biomass. For three of the four SRB, carbon isotope effects between the substrates, acetate or lactate and CO(2), and the cell biomass were small, ranging from 0 to 2 per thousand. However, for Desulfotomaculum acetoxidans, the carbon incorporated into biomass was isotopically heavier than the available substrates by 8 to 9 per thousand. SRB grown lithoautotrophically consumed less than 3% of the available CO(2) and exhibited substantial discrimination (calculated as isotope fractionation factors [alpha]), as follows: for Desulfobacterium autotrophicum, alpha values ranged from 1.0100 to 1.0123; for Desulfobacter hydrogenophilus, the alpha value was 0.0138, and for Desulfotomaculum acetoxidans, the alpha value was 1.0310. Mixotrophic growth of Desulfovibrio desulfuricans on acetate and CO(2) resulted in biomass with a delta(13)C composition intermediate to that of the substrates. The extent of fractionation depended on which enzymatic pathways were used, the direction in which the pathways operated, and the growth rate, but fractionation was not dependent on the growth phase. To the extent that environmental conditions affect the availability of organic substrates (e.g., acetate) and reducing power (e.g., H(2)), ecological forces can also influence carbon isotope discrimination by SRB.

Deltaproteobacteria/growth & development/metabolis↗

Carbon isotopic composition of individual Precambrian microfossils

Ion microprobe measurements of carbon isotope ratios were made in 30 specimens representing six fossil genera of microorganisms petrified in stromatolitic chert from the approximately 850 Ma Bitter Springs Formation, Australia, and the approximately 2100 Ma Gunflint Formation, Canada. The delta 13C(PDB) values from individual microfossils of the Bitter Springs Formation ranged from -21.3 +/- 1.7% to -31.9 +/- 1.2% and the delta 13C(PDB) values from microfossils of the Gunflint Formation ranged from -32.4 +/- 0.7% to -45.4 +/- 1.2%. With the exception of two highly 13C-depleted Gunflint microfossils, the results generally yield values consistent with carbon fixation via either the Calvin cycle or the acetyl-CoA pathway. However, the isotopic results are not consistent with the degree of fractionation expected from either the 3-hydroxypropionate cycle or the reductive tricarboxylic acid cycle, suggesting that the microfossils studied did not use either of these pathways for carbon fixation. The morphologies of the microfossils suggest an affinity to the cyanobacteria, and our carbon isotopic data are consistent with this assignment.

Non-NASA Center↗

Molecular indicators for palaeoenvironmental change in a Messinian evaporitic sequence (Vena del Gesso, Italy). II: High-resolution variations in abundances and 13C contents of free and sulphur-bound carbon skeletons in a single marl bed

The extractable organic matter of 10 immature samples from a marl bed of one evaporitic cycle of the Vena del Gesso sediments (Gessoso-solfifera Fm., Messinian, Italy) was analyzed quantitatively for free hydrocarbons and organic sulphur compounds. Nickel boride was used as a desulphurizing agent to recover sulphur-bound lipids from the polar and asphaltene fractions. Carbon isotopic compositions (delta vs PDB) of free hydrocarbons and of S-bound hydrocarbons were also measured. Relationships between these carbon skeletons, precursor biolipids, and the organisms producing them could then be examined. Concentrations of S-bound lipids and free hydrocarbons and their delta values were plotted vs depth in the marl bed and the profiles were interpreted in terms of variations in source organisms, 13 C contents of the carbon source, and environmentally induced changes in isotopic fractionation. The overall range of delta values measured was 24.7%, from -11.6% for a component derived from green sulphur bacteria (Chlorobiaceae) to -36.3% for a lipid derived from purple sulphur bacteria (Chromatiaceae). Deconvolution of mixtures of components deriving from multiple sources (green and purple sulphur bacteria, coccolithophorids, microalgae and higher plants) was sometimes possible because both quantitative and isotopic data were available and because either the free or S-bound pool sometimes appeared to contain material from a single source. Several free n-alkanes and S-bound lipids appeared to be specific products of upper-water-column primary producers (i.e. algae and cyanobacteria). Others derived from anaerobic photoautotrophs and from heterotrophic protozoa (ciliates), which apparently fed partly on Chlorobiaceae. Four groups of n-alkanes produced by algae or cyanobacteria were also recognized based on systematic variations of abundance and isotopic composition with depth. For hydrocarbons probably derived from microalgae, isotopic variations are well correlated with those of total organic carbon. A resistant aliphatic biomacromolecule produced by microalgae is, therefore, probably an important component of the kerogen. These variations reflect changes in the depositional environment and early diagenetic transformations. Changes in the concentrations of S-bound lipids induced by variations in conditions favourable for sulphurization were discriminated from those related to variations in primary producer assemblages. The water column of the lagoonal basin was stratified and photic zone anoxia occurred during the early and middle stages of marl deposition. During the last stage of the marl deposition the stratification collapsed due to a significant shallowing of the water column. Contributions from anaerobic photoautotrophs were apparently associated with variations in depth of the chemocline.

Non-NASA Center↗

Origin of petroporphyrins. 2. Evidence from stable carbon isotopes

Compared with the carbon-13 isotopic composition of the ubiquitous C32DPEP (DPEP, deoxophylloerythroetioporphyrin) the heavy but equivalent carbon-13 isotopic composition for the porphyrin structures 15(2)-methyl-15,17-ethano-17-nor-H-C30DPEP and 15,17-butano-, 13,15-ethano-13(2),17-propano-, and 13(1)-methyl-13,15-ethano-13(2),17-propanoporphyrin suggests a common precursor, presumably chlorophyll c, for these petroporphyrins isolated from the marine Julia Creek oil shale and the lacustrine Condor oil shale. Similarly, the heavy but variable carbon-13 isotopic composition of 7-nor-H-C31DPEP compared with C32DPEP is consistent with an origin from both chlorophyll b and chlorophyll c3. The equivalent carbon-13 isotopic composition for 13(2)-methyl-C33DPEP compared with C32DPEP suggests a common origin resulting from a weighted average of chlorophyll inputs.

NASA Program Exobiology↗

Iron catalyst chemistry in modeling a high-pressure carbon monoxide nanotube reactor

The high-pressure carbon monoxide (HiPco) technique for producing single-wall carbon nanotubes (SWNTs) is analyzed with the use of a chemical reaction model coupled with flow properties calculated along streamlines, calculated by the FLUENT code for pure carbon monoxide. Cold iron pentacarbonyl, diluted in CO at about 30 atmospheres, is injected into a conical mixing zone, where hot CO is also introduced via three jets at 30 degrees with respect to the axis. Hot CO decomposes the Fe(CO)5 to release atomic Fe. Then iron nucleates and forms clusters that catalyze the formation of SWNTs by a disproportionation reaction (Boudouard) of CO on Fe-containing clusters. Alternative nucleation rates are estimated from the theory of hard sphere collision dynamics with an activation energy barrier. The rate coefficient for carbon nanotube growth is estimated from activation energies in the literature. The calculated growth was found be about an order of magnitude greater than measured, regardless of the nucleation rate. A study of cluster formation in an incubation zone prior to injection into the reactor shows that direct dimer formation from Fe atoms is not as important as formation via an exchange reaction of Fe with CO in FeCO.

Evaluation Studies↗

A tenuous carbon dioxide atmosphere on Jupiter's moon Callisto

An off-limb scan of Callisto was conducted by the Galileo near-infrared mapping spectrometer to search for a carbon dioxide atmosphere. Airglow in the carbon dioxide nu3 band was observed up to 100 kilometers above the surface and indicates the presence of a tenuous carbon dioxide atmosphere with surface pressure of 7.5 x 10(-12) bar and a temperature of about 150 kelvin, close to the surface temperature. A lifetime on the order of 4 years is suggested, based on photoionization and magnetospheric sweeping. Either the atmosphere is transient and was formed recently or some process is currently supplying carbon dioxide to the atmosphere.

unmanned↗

Low-temperature carbonate concretions in the Martian meteorite ALH84001: evidence from stable isotopes and mineralogy

The martian meteorite ALH84001 contains small, disk-shaped concretions of carbonate with concentric chemical and mineralogical zonation. Oxygen isotope compositions of these concretions, measured by ion microprobe, range from delta18O = +9.5 to +20.5 per thousand. Most of the core of one concretion is homogeneous (16.7 +/- 1.2 per thousand) and over 5 per thousand higher in delta18O than a second concretion. Orthopyroxene that hosts the secondary carbonates is isotopically homogeneous (delta18O = 4.6 +/- 1.2 per thousand). Secondary SiO2 has delta18O = 20.4 per thousand. Carbon isotope ratios measured from the core of one concretion average delta13C = 46 +/- 8 per thousand, consistent with formation on Mars. The isotopic variations and mineral compositions offer no evidence for high temperature (>650 degrees C) carbonate precipitation and suggest non-equilibrium processes at low temperatures (< approximately 300 degrees C).

NASA Center JSC↗

Woven TPS Enabling Missions Beyond Heritage Carbon Phenolic

NASAs Office of the Chief Technologist (OCT) Game Changing Division recently funded an effort to advance a Woven TPS (WTPS) concept. WTPS is a new approach to producing TPS architectures that uses precisely engineered 3D weaving techniques to customize material characteristics needed to meet specific missions requirements for protecting space vehicles from the intense heating generated during atmospheric entry. Using WTPS, sustainable, scalable, mission-optimized TPS solutions can be achieved with relatively low life cycle costs compared with the high costs and long development schedules currently associated with material development and certification. WTPS leverages the mature state-of-the-art weaving technology that has evolved from the textile industry to design TPS materials with tailorable performance. Currently, missions anticipated encountering heat fluxes in the range of 1500 4000 Wcm2 and pressures greater than 1.5 atm are limited to using fully dense Carbon Phenolic. However, fully dense carbon phenolic is only mass efficient at higher heat fluxes g(reater than 4000 Wcm2), and current mission designs suffer this mass inefficiency for lack of an alternative mid-density TPS. WTPS not only bridges this mid-density TPS gap but also offers a replacement for carbon phenolic, which itself requires a significant and costly redevelopment effort to re-establish its capability for use in the high heat flux missions recently prioritized in the NRC Decadal survey, including probe missions to Venus, Saturn and Neptune. This presentation will overview the WTPS concept and present some results from initial testing completed comparing WTPS architectures to heritage carbon phenolic.

Woven Thermal protection materials↗

Improved Composites Using Crosslinked, Surface-Modified Carbon Nanotube Materials

Individual carbon nanotubes (CNTs) exhibit exceptional tensile strength and stiffness; however, these properties have not translated well to the macroscopic scale. Premature failure of bulk CNT materials under tensile loading occurs due to the relatively weak frictional forces between adjacent CNTs, leading to poor load transfer through the material. When used in polymer matrix composites (PMCs), the weak nanotube-matrix interaction leads to the CNTs providing less than optimal reinforcement.Our group is examining the use of covalent crosslinking and surface modification as a means to improve the tensile properties of PMCs containing carbon nanotubes. Sheet material comprised of unaligned multi-walled carbon nanotubes (MWCNT) was used as a drop-in replacement for carbon fiber in the composites. A variety of post-processing methods have been examined for covalently crosslinking the CNTs to overcome the weak inter-nanotube shear interactions, resulting in improved tensile strength and modulus for the bulk sheet material. Residual functional groups from the crosslinking chemistry may have the added benefit of improving the nanotube-matrix interaction. Composites prepared using these crosslinked, surface-modified nanotube sheet materials exhibit superior tensile properties to composites using the as received CNT sheet material.

polymer matrix composite↗

Covalent Crosslinking of Carbon Nanotube Materials for Improved Tensile Strength

Carbon nanotubes have attracted much interest in recent years due to their exceptional mechanical properties. Currently, the tensile properties of bulk carbon nanotube-based materials (yarns, sheets, etc.) fall far short of those of the individual nanotube elements. The premature failure in these materials under tensile load has been attributed to inter-tube sliding, which requires far less force than that needed to fracture individual nanotubes.1,2 In order for nanotube materials to achieve their full potential, methods are needed to restrict this tube-tube shear and increase inter-tube forces.Our group is examining covalent crosslinking between the nanotubes as a means to increase the tensile properties of carbon nanotube materials. We are working with multi-walled carbon nanotube (MWCNT) sheet and yarn materials obtained from commercial sources. Several routes to functionalize the nanotubes have been examined including nitrene, aryl diazonium, and epoxide chemistries. The functional nanotubes were crosslinked through small molecule or polymeric bridges. Additionally, electron beam irradiation induced crosslinking of the non-functional and functional nanotube materials was conducted. For example, a nanotube sheet material containing approximately 3.5 mol amine functional groups exhibited a tensile strength of 75 MPa and a tensile modulus of 1.16 GPa, compared to 49 MPa and 0.57 GPa, respectively, for the as-received material. Electron beam irradiation (2.2x 1017 ecm2) of the same amine-functional sheet material further increased the tensile strength to 120 MPa and the modulus to 2.61 GPa. This represents approximately a 150 increase in tensile strength and a 360 increase in tensile modulus over the as-received material with only a 25 increase in material mass. Once we have optimized the nanotube crosslinking methods, the performance of these materials in polymer matrix composites will be evaluated.

polymer matrix composites↗

Development of Advanced Conformal Ablative TPS Fabricated from Rayon- and PAN-Based Carbon Felts

The conformal ablative TPS first developed under NASA's Hypersonics Project in the early 2000's demonstrated very low through the thickness conductivity compared to state-ofthe- art PICA. However, in initial arcjet testing of Conformal-1, surface recession rates were 2x higher than PICA. Because commercial carbon felts are currently available as very thin substrates, this was a concern if conformal TPS were to be considered for a mission that required thicker material. Discussed in this paper are the results of the development of an Advanced Conformal TPS derived from thicker, higher density carbon felt. Two substrate systems were evaluated, the first material was a needled rayon-based carbon felt and the other a needled PAN-based carbon felt. Both substrates were impregnated with phenolic resin following the PICA/CPICA process to add a low density phenolic matrix to the system prior to aerothermal screening at the LaRC HyMETS facility and larger scale testing in the NASA ARC Interaction Heating Facility (IHF) at heating fluxes ranging from 250-1700 W/cm2.

Arcjet Testing↗

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↗

Filtration of Carbon Particulate Emissions from a Plasma Pyrolysis Assembly

NASA is investigating plasma pyrolysis as a candidate technology that will enable the recovery of hydrogen from the methane produced by the ISS Sabatier Reactor. The Plasma Pyrolysis Assembly (PPA) is the current prototype of this technology which converts the methane product from the Carbon Dioxide Reduction Assembly (CRA) to acetylene and hydrogen with 90% or greater conversion efficiency. A small amount of solid carbon particulates are generated as a side product and must be filtered before the acetylene is removed and the hydrogen-rich gas stream is recycled back to the CRA. We discuss developmental work on several options for filtering out the carbon particulate emissions from the PPA exit gas stream. The filtration technologies and concepts investigated range from fibrous media to monolithic ceramic and sintered metal media. This paper describes the different developed filter prototypes and characterizes their performance from integrated testing at the Environmental Chamber (E-Chamber) at MSFC. In addition, characterization data on the generated carbon particulates, that help to define filter requirements, are also presented.

methane↗

Woven TPS Enabling Missions Beyond Heritage Carbon Phenolic

WTPS is a new approach to producing TPS architectures that uses precisely engineered 3D weaving techniques to customize material characteristics needed to meet specific missions requirements for protecting space vehicles from the intense heating generated during atmospheric entry. Using WTPS, sustainable, scalable, mission-optimized TPS solutions can be achieved with relatively low life cycle costs compared with the high costs and long development schedules currently associated with material development and certification. WTPS leverages the mature state-of-the-art weaving technology that has evolved from the textile industry to design TPS materials with tailorable performance. Currently, missions anticipated encountering heat fluxes in the range of 1500 4000 Wcm2 and pressures greater than 1.5 atm are limited to using fully dense Carbon Phenolic. However, fully dense carbon phenolic is only mass efficient at higher heat fluxes greater than 4000 Wcm2), and current mission designs suffer this mass inefficiency for lack of an alternative mid-density TPS. WTPS not only bridges this mid-density TPS gap but also offers a replacement for carbon phenolic, which itself requires a significant and costly redevelopment effort to re-establish its capability for use in the high heat flux missions recently prioritized in the NRC Decadal survey, including probe missions to Venus, Saturn and Neptune. This presentation will overview the WTPS concept and present some results from initial testing completed comparing WTPS architectures to heritage carbon phenolic.

ablators↗

Overview of Solar-Induced Chlorophyll Fluorescence (SIF) from the Orbiting Carbon Observatory-2: Retrieval, Cross-Mission Comparison, and Global Monitoring for GPP

The Orbiting Carbon Observatory-2 (OCO-2), launched in July 2014, is capable of measuring Solar-Induced chlorophyll Fluorescence (SIF), a functional proxy for terrestrial gross primary productivity (GPP). Although its primary mission is to measure the column-averaged mixing ratio of CO2 (Xco(sub 2)) to constrain global carbon source/sink distribution, one of the OCO-2 spectrometers allows for a robust SIF retrieval solely based on solar Fraunhofer lines. Here we present a technical overview of the OCO-2 SIF product, aiming to provide the scientific community guidance on best practices for data analysis, interpretation, and application. This overview consists of the retrieval algorithms, OCO-2 specific bias correction, retrieval uncertainty evaluation, cross-mission comparison with other existing SIF products, and a global-scale examination of the SIF-GPP relationship. With the initial three years of data (September 2014 onward), we compared OCO-2 SIF with retrievals from Greenhouse Gases Observing Satellite (GOSAT) and Global Ozone Monitoring Experiment-2 (GOME-2), and examined its relationship with FLUXCOM and MODIS GPP datasets. Our results show that OCO-2 SIF, along with GOSAT products, closely resemble the mean spatial and temporal patterns of FLUXCOM GPP from regions to the globe. Compared with GOME-2, however, OCO-2 depicts a more realistic spatial contrast between the tropics and extra-tropics. The linear relationship between OCO-2 SIF and existing modeled GPP products diverges somewhat across biomes at the global scale, consistent with previous GOSAT or GOME-2 based findings when modeled GPP products were used, but in contrast to a consistent cross-biome SIF-GPP relationship obtained at flux tower sites with OCO-2 products. This contrast suggests a critical need to reconcile differences in diverse SIF and GPP products and the relationships among them. Overall, the OCO-2 SIF products are robust and valuable for monitoring the global terrestrial carbon cycle and for constraining the carbon source/sink strengths of the Earth system. Finally, insights are offered for future satellite missions optimized for SIF retrievals.

GPP↗