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At least 235 records · Page 13

Astrochemistry: Recent Advances in the Study of Carbon Molecules in Space

Carbon molecules and ions play an important role in space. Polycyclic Aromatic Hydrocarbons (PAHs) are the best-known candidates to account for the infrared emission bands (UIR bands) and PAH spectral features are now being used as probes of the interstellar medium in Galactic and extra-galactic environments. PAHs are also thought to be among the carriers of the diffuse interstellar absorption bands (DIBs). In the model dealing with the interstellar spectral features, PAHs are present as a mixture of radicals, ions and neutral species. PAH ionization states reflect the ionization balance of the medium while PAH size, composition, and structure reflect the energetic and chemical history of the medium. A major challenge for laboratory Astrochemistry is to reproduce (in a realistic way) the physical conditions that exist in the emission and absorption interstellar zones. An extensive laboratory program has been developed in various laboratories to characterize the physical and chemical properties of PAHs in astrophysical environments and to describe how they influence the radiation and energy balance in space and the interstellar chemistry. In particular, laboratory experiments provide measurements of the spectral characteristics of interstellar PAH analogs from the ultraviolet and visible range to the infrared range for comparison with astronomical data. The harsh physical conditions of the interstellar medium - characterized by a low temperature, an absence of collisions and strong ultraviolet radiation fields - are simulated in the laboratory by associating a molecular beam with an ionizing discharge to generate a cold plasma expansion. PAH ions are formed from the neutral precursors in an isolated environment at low temperature (of the order of 100 K). The spectra of neutral and ionized PAHs are measured using the high sensitivity methods of cavity ring down spectroscopy (CRDS). These experiments provide unique information on the spectra of free, cold large carbon molecules and ions in the gas phase.

Salama, Farid↗

Diamagnetic studies on as-processed carbon fibers

The Faraday method has been used to measure the diamagnetic susceptibilities of small bundles of aligned carbon fibers of different types at room temperature. It was found that the tensor trace susceptibility of the fibers varies systematically over the range 0.8-20 (in units of -10 to the -6th emu/g) as a function of precursor type and processing history. The susceptibility increases, in general, with increasing nominal treatment temperature and hot stretching, and with increasing tensile elastic modulus. The anisotropy ratio of fibers increases approximately linearly with tensile elastic modulus for all fibers from about 1 for a modulus of about 70 GN/sq m to about 22 for a modulus of 700 GN/sq m in air, and is quantitatively consistent with the layer-plane orientation textures determined by X-ray diffraction when appropriate values of the crystallite principal susceptibilities are used.

Scott, C. B.↗

Polymeric routes to silicon carbide and silicon oxycarbide CMC

An overview of two approaches to the formation of ceramic composite matrices from polymeric precursors is presented. Copolymerization of alkyl- and alkenylsilanes (RSiH3) represents a new precursor system for the production of Beta-SiC on pyrolysis, with copolymer composition controlling polymer structure, char yield, and ceramic stoichiometry and morphology. Polysilsesquioxanes which are synthesized readily and can be handled in air serve as precursors to Si-C-O ceramics. Copolymers of phenyl and methyl silsesquioxanes display rheological properties favorable for composite fabrication; these can be tailored by control of pH, water/methoxy ratio and copolymer composition. Composites obtained from these utilize a carbon coated, eight harness satin weave Nicalon cloth reinforcement. The material exhibits nonlinear stress-strain behavior in tension.

Hurwitz, Frances I.↗

Polymeric routes to silicon carbide and silicon oxycarbide CMC

An overview of two approaches to the formation of ceramic composite matrices from polymeric precursors is presented. Copolymerization of alkyl- and alkenylsilanes (RSiH3) represents a new precursor system for the production of Beta-SiC on pyrolysis, with copolymer composition controlling polymer structure, char yield, and ceramic stoichiometry and morphology. Polysilsesquioxanes which are synthesized readily and can be handled in air serve as precursors to Si-C-O ceramics. Copolymers of phenyl and methyl silsesquioxanes display rheological properties favorable for composite fabrication; these can be tailored by control of pH, water/methoxy ratio and copolymer composition. Composites obtained from these utilize a carbon coated, eight harness satin weave Nicalon cloth reinforcement. The material exhibits nonlinear stress-strain behavior in tension.

Hurwitz, Frances I.↗

Carbon, CAIs and chondrules

It has been shown that C is present in CAI's and chondrules. It can be distinguished from matrix C both by its thermal stability and isotopic composition, which implies that it was not introduced after parent body accretion. It is concluded that C must have been present in the chondrule and CAI precursor material. Therefore any models of chondrule and CAI formation and inferences drawn about solar system conditions during these events must take into account the consequences of the presence of C on inclusion chemistry, mineralogy, and oxidation state.

Ash, R. D.↗

Synthesis and Spectroscopy of Large Carbon Molecules with Ames' COSmIC Facility in Support of NASA's Space Missions

We present and discuss the unique characteristics and capabilities of the laboratory facility, COSmIC, that was developed at NASA Ames to generate, process and analyze interstellar and planetary analogs in the laboratory. COSmIC stands for Cosmic Simulation Chamber and is dedicated to the study of molecules and ions under the low temperature and high vacuum conditions that are required to simulate interstellar, circumstellar and planetary physical environments in space. COSmIC integrates a variety of state-of-the-art instruments that allow forming, processing and monitoring simulated space conditions for planetary, circumstellar and interstellar materials in the laboratory. COSmIC is composed of a Pulsed Discharge Nozzle (PDN) expansion that generates a free jet supersonic expansion coupled to two ultrahigh-sensitivity, complementary in situ diagnostics: a Cavity Ring Down Spectroscopy (CRDS) system for photonic detection and a Reflectron Time-Of-Flight Mass Spectrometer (ReTOF-MS) for mass detection. Recent, unique, laboratory astrophysics results that were obtained using the capabilities of COSmIC will be discussed, in particular the progress that have been achieved in monitoring in the laboratory the formation of solid gains from their gas-phase molecular precursors in environments as varied as stellar/circumstellar outflow and planetary atmospheres. Plans for future, next generation, laboratory experiments on cosmic molecules and grains in the growing field of laboratory astrophysics will also be addressed.

Spectroscopy↗

Climatic changes resulting from mass extinctions at the K-T boundary (and other bio-events)

The mass extinctions at the Cretaceous-Tertiary (K-T) boundary include about 90 percent of marine calcareous nannoplankton (coccoliths), and carbon-isotope data show that marine primary productivity was drastically reduced for about 500,000 years after the boundary event, the so-called Strangelove Ocean effect. One result of the elimination of most marine phytoplankton would have been a severe reduction in production of dimethyl sulfide (DMS), a biogenic gas that is believed to be the major precursor of cloud condensation nuclei (CCN) over the oceans. A drastic reduction in marine CCN should lead to a cloud canopy with significantly lower reflectivity, and hence cause a significant warming at the earth's surface. Calculations suggest that, all other things being held constant, a reduction in CCN of more than 80 percent (a reasonable value for the K-T extinctions) could have produced a rapid global warming of 6 C or more. Oxygen-isotope analyses of marine sediments, and other kinds of paleoclimatic data, have provided for a marked warming, and a general instability of climate coincident with the killoff of marine plankton at the K-T boundary. Similar reductions in phytoplankton abundance at other boundaries, as indicated by marked shifts in carbon-isotope curves, suggest that severe temperature changes may have accompanied other mass extinctions, and raises the intriguing possibility that the extinction events themselves could have contributed to the climatic instabilities at critical bio-events in the geologic record.

Rampino, Michael R.↗

The 2001 Mars In-Situ-Propellant-Production Precursor (MIP) Flight Demonstration

The successful performance of the five individual demonstrations of MARS IN-SITU-PROPELLANT-PRODUCTION PRECURSOR (MIP) will provide both knowledge of and confidence in the reliability of this technology. At the completion of this flight demonstration, the MIP Team will be able to: a) recommend preferred hardware configurations for the intake and adsorption of carbon dioxide from the Martian atmosphere; b) understand the performance characteristics of zirconia cells to generate propellant-grade oxygen; c) understand long-term performance characteristics of advanced solar cells/arrays operated in the actual Mars environment; d) evaluate the functionality of methods to mitigate the deposition of airborne dust onto solar arrays; and e) recommend preferred hardware designs for innovative thermal management including the radiation of heat to the outside environment.

Kaplan, David I.↗

Highly Siderophile Elements and Osmium Isotope Systematics in Ureilites: Are the Carbonaceous Veins Primary Components?

Ureilites are an enigmatic group of primitive carbon-bearing achondrites of ultramafic composition. The majority of the ~143 ureilite meteorites consist primarily of olivine and pyroxene (and occasionally chromite) [1]. They are coarse-grained, slowly cooled, and depleted in incompatible lithophile elements. Minor amounts of dark interstitial material consisting of carbon, metal, sulfides, and fine-grained silicates occur primarily along silicate grain boundaries, but also intrude the silicates along fractures and cleavage planes. Variable degrees of impact shock features have also been imparted on ureilites. The prevailing two origins proposed for these rocks are either as melting residues of carbonaceous chondritic material [2], [3], or alternatively, derivation as mineral cumulates from such melts [4], [5], [6]. It has recently been proposed that ureilites are the residues of a smelting event, i.e. residues of a partial melting event under highly reducing conditions, where a solid Fe-bearing phase reacts with a melt and carbon to form Fe metal and carbon monoxide [7]. Rapid, localized extraction and loss of the basaltic component into space resulting from high eruption velocities could preserve unequilibrated oxygen isotopes and produce the observed olivine-pyroxene residues via 25-30% partial melting of chondritic-like precursor material.

Rankenburg, K.↗

Benzimidazole Based Aerogel Materials

The present invention provides aerogel materials based on imidazoles and polyimidazoles. The polyimidazole based aerogel materials can be thermally stable up to 500 C or more, and can be carbonized to produce a carbon aerogel having a char yield of 60% or more, specifically 70% or more. The present invention also provides methods of producing polyimidazole based aerogel materials by reacting at least one monomer in a suitable solvent to form a polybenzimidazole gel precursor solution, casting the polybenzimidazole gel precursor solution into a fiber reinforcement phase, allowing the at least one gel precursor in the precursor solution to transition into a gel material, and drying the gel materials to remove at least a portion of the solvent, to obtain an polybenzimidazole-based aerogel material.

Rhine, Wendell E.↗

The Chemical Evolution of Cosmic Carbon: Laboratory Studies with the COSmIC Facility

Cosmic dust plays an essential role in our understanding of the chemical and physical evolution of the universe. Our understanding of cosmic dust relies on a combination of astronomical observations (either remote or on extraterrestrial dust samples), astrophysical modeling and laboratory studies of realistic analogs of cosmic dust grains. The COSmIC facility was developed at NASA Ames to study the evolution of cosmic carbon from circumstellar outflows to interstellar clouds to planetary atmospheres in the laboratory [1]. COSmIC stands for “Cosmic Simulation Chamber” and is dedicated to the study of neutral and ionized molecules and grain particles under the low temperature and density conditions that are required to simulate space environments. COSmIC integrates a variety of instruments that allow generating, processing, and monitoring simulated space conditions in the laboratory. It is composed of a Pulsed Discharge Nozzle (PDN) expansion that generates a plasma in a free supersonic jet expansion, coupled to high-sensitivity, complementary in situ diagnostic tools used for the detection and characterization of the species present in the expansion: Cavity Ring Down Spectroscopy (CRDS) and fluorescence spectroscopy systems for photonic detection and an orthogonal Reflectron Time-Of-Flight Mass Spectrometer (oReTOF-MS) for mass detection. Recent advances achieved in laboratory astrophysics using COSmIC’s laboratory data in synergy with observational data will be presented. These results include the formation of dust grains and aerosols from gas-phase molecular precursors in environments as varied as circumstellar outflows of late AGB stars [2] and planetary atmospheres [3] and the evolution of our understanding of the diffuse interstellar bands (DIBs) with applications to the ESO Diffuse Interstellar Bands Large Exploration Survey (EDIBLES [4, 5]). Plans for future laboratory developments and techniques to study the evolution of cosmic carbon molecules and grains (including NIR-MIR CRDS, laser induced fluorescence (LIF) and incandescence (LII)) will also be addressed as well as their astronomical applications.

Salama, F.↗

Thermoplastic polymides and composites therefrom

A new class polyimide and polyimide precursors based on diaryl oxyalkylene diamines, such as 1,3-bis[4-aminophenoxy]-2,2-dimethyl propane, a process for their preparation and their use as the continuous phase for the manufacture of composites and composite laminates reinforced by reinforcing agents such as carbon fibers, Kevlar.TM., and other similar high strength reinforcing agents. The polyimides and molecular composites obtained from the diamines according to the invention show thermoplastic properties, excellent flex fatigue and fracture resistance, and excellent thermal and oxidative stability.

Harris, Frank W.↗

Low-Temperature Formation of Carbonaceous Grains from PAHs

Astronomical observations have detected interstellar carbon in the form of polycyclic aromatic hydrocarbons(PAHs) as well as carbonaceous dust, confirming its presence in both gaseous and solid phases. The goal of this study is to experimentally investigate low-temperature chemical pathways between these two phases in order to better understand the evolution of cosmic carbon. Cosmic dust analogs are produced in the supersonic expansion of an argon jet seeded with aromatic molecules: benzene, naphthalene, anthracene, phenanthrene, and pyrene. These are prototype aromatic molecules of compact and non compact structure, and are used to evaluate the effect of precursor structure on the molecular complexity of the resulting grains. The seeded jet is exposed to an electrical discharge and the carbonaceous grains are collected and probed ex situ via laser desorption mass spectrometry. Mass spectra reveal a rich molecular diversity within the grains, including fragments of the parent molecule but also growth into larger complex organic molecules (COMs). In all experiments, the largest number of products is found in the m/z range 200-250, and C16H10 (attributed to pyrene and/or its isomers) is found to be a dominant product, pointing at the formation of this stable PAH as a preferential route in the growth to larger PAHs. Comparison to mass spectra from the Murchison meteorite reveals a similar dominance of compounds related toC16H10 at m/z = 202. Evidence of the methyl addition-cyclization mechanism in the anthracene experiment is reported. PAH structure is found to impact the dust production yield, as seen by the greater yield for the anthracene compared to the phenanthrene experiment. PAH growth at low temperatures via barrierless routes involving the addition of alkyl- and phenyl-type radicals is suggested as a viable pathway to COMs. These results suggest that PAH growth and dust formation from PAHs are feasible at low temperatures in photon-dominated regions and circumstellar envelopes.

L Gavilan↗

Description and Evaluation of Brown Carbon Representation in GISS ModelE

Brown carbon (BrC) is an absorbing organic aerosol primarily emitted by the combustion of biomass and biofuel. While field and laboratory studies have shown that BrC exhibits light absorption unique from black carbon (BC) and organic carbon (OC) aerosols, the radiative forcing of BrC is still highly uncertain. We present the implementation of BrC in the One-Moment Aerosol (OMA) module of the GISS ModelE ESM. Primary BrC is emitted from biomass burning with a range of optical properties and is processed through a unique chemical aging scheme. Brown secondary organic aerosols (SOA), formed from several biogenic and anthropogenic precursors, are also represented. Several simulations–with varied emissions, optical properties, and chemistry–have been run to assess the sensitivity of this BrC implementation within ModelE. Initial results show a peak in BrC concentrations near the tropopause, around 200 mb. As BC aerosols do not reach this height in ModelE, this suggests a new source of absorption in the upper troposphere. Organic aerosol representation can be further evaluated through comparison to AERONET retrieval data of BrC mass and optical depth, and total aerosol optical depth.

Brown carbon↗

MIP: the First ISRU Flight Experiment

The Mars ISPP Precursor, “MIP”, was a flight experiment on the 2001 Mars Surveyor Lander that was designed to demonstrate In-situ Propellant Production-- ISPP-- for the first time on Mars. The experiment was designed to show that it was possible to produce oxygen from the carbon dioxide atmosphere, and to demonstrate the individual technology components that would go into a full-scale production plant. The aimpoint of the oxygen production was to showcase the possibility of producing oxygen for use as rocket fuel, ultimately as an enabling technology for a future human expedition to Mars. The MIP team built and qualified flight hardware for the experiment to fly on the Surveyor-2001 lander, but following the failure of the 1999 Mars Polar Lander spacecraft, the Surveyor-2001 lander mission was cancelled, and the MIP experiment was never flown. The experience in building and testing the hardware did show that the carbon dioxide electrolysis process was feasible, and led to incorporation of in-situ propellant production into the NASA reference plans for human Mars missions. Twenty years later, the technology is flying to Mars in the form of the MOXIE experiment on the Perseverance rover.

Geoffrey A Landis↗

Cyanobacteria in CELSS: Growth strategies for nutritional variation and nitrogen cycling

Cyanobacteria (blue-green algae) are versatile organisms which are capable of adjusting their cellular levels of carbohydrate, protein, and lipid in response to changes in the environment. Under stress conditions there is an imbalance between nitrogen metabolism and carbohydrate/lipid synthesis. The lesion in nitrogen assimilation is at the level of transport: the stress condition diverts energy from the active accumulation of nitrate to the extrusion of salt, and probably inhibits a cold-labile ATP'ace in the case of cold shock. Both situations affect the bioenergetic status of the cell such that the nitrogenous precursors for protein synthesis are depleted. Dispite the inhibition of protein synthesis and growth, photosynthetic reductant generation is relatively unaffected. The high O2 reductant would normally lead to photo-oxidative damage of cellular components; however, the organism copes by channeling the 'excess' reductant into carbon storage products. The increase in glycogen (28 to 35 percent dry weight increase) and the elongation of lipid fatty acid side chains (2 to 5 percent dry weight increase) at the expense of protein synthesis (25 to 34 percent dry weight decrease) results in carbohydrate, lipid and protein ratios that are closer to those required in the human diet. In addition, the selection of nitrogen fixing mutants which excrete ammonium ions present an opportunity to tailor these micro-organisms to meet the specific need for a sub-system to reverse potential loss of fixed nitrogen material.

Fry, I. V.↗

Global Air Quality and Climate

Emissions of air pollutants and their precursors determine regional air quality and can alter climate. Climate change can perturb the long-range transport, chemical processing, and local meteorology that influence air pollution. We review the implications of projected changes in methane (CH4), ozone precursors (O3), and aerosols for climate (expressed in terms of the radiative forcing metric or changes in global surface temperature) and hemispheric-to-continental scale air quality. Reducing the O3 precursor CH4 would slow near-term warming by decreasing both CH4 and tropospheric O3. Uncertainty remains as to the net climate forcing from anthropogenic nitrogen oxide (NOx) emissions, which increase tropospheric O3 (warming) but also increase aerosols and decrease CH4 (both cooling). Anthropogenic emissions of carbon monoxide (CO) and non-CH4 volatile organic compounds (NMVOC) warm by increasing both O3 and CH4. Radiative impacts from secondary organic aerosols (SOA) are poorly understood. Black carbon emission controls, by reducing the absorption of sunlight in the atmosphere and on snow and ice, have the potential to slow near-term warming, but uncertainties in coincident emissions of reflective (cooling) aerosols and poorly constrained cloud indirect effects confound robust estimates of net climate impacts. Reducing sulfate and nitrate aerosols would improve air quality and lessen interference with the hydrologic cycle, but lead to warming. A holistic and balanced view is thus needed to assess how air pollution controls influence climate; a first step towards this goal involves estimating net climate impacts from individual emission sectors. Modeling and observational analyses suggest a warming climate degrades air quality (increasing surface O3 and particulate matter) in many populated regions, including during pollution episodes. Prior Intergovernmental Panel on Climate Change (IPCC) scenarios (SRES) allowed unconstrained growth, whereas the Representative Concentration Pathway (RCP) scenarios assume uniformly an aggressive reduction, of air pollutant emissions. New estimates from the current generation of chemistry-climate models with RCP emissions thus project improved air quality over the next century relative to those using the IPCC SRES scenarios. These two sets of projections likely bracket possible futures. We find that uncertainty in emission-driven changes in air quality is generally greater than uncertainty in climate-driven changes. Confidence in air quality projections is limited by the reliability of anthropogenic emission trajectories and the uncertainties in regional climate responses, feedbacks with the terrestrial biosphere, and oxidation pathways affecting O3 and SOA.

ozone↗

Carbon isotope evidence for the substrates and mechanisms of prebiotic synthesis in the early solar system

Meteorites contain prebiotic, bio-relevant organic compounds including amino acids. Their syntheses could result from diverse sources and mechanisms and provide a window on the conditions and materials present in the early solar system. Here we constrain alanine’s synthetic history in the Murchison meteorite using site-specific 13C/12C measurements, reported relative to the VPDB standard. The δ13CVPDB values of −29 ± 10‰, 142 ± 20‰, and −36 ± 20‰ for the carboxyl, amine-bound, and methyl carbons, respectively, are consistent with Strecker synthesis of interstellar-medium-derived aldehydes, ammonia, and low-δ13C nebular or interstellar-medium-derived CN. We report experimentally measured isotope effects associated with Strecker synthesis, and use them to constrain the δ13C values of the alanine precursors, which we then use to construct a model that predicts the molecular-average δ13C values of 19 other organic compounds of prebiotic significance found in Murchison if they were made by our proposed synthetic network. Most of these predictions agree with previous measurements, suggesting that interstellar-medium-derived aldehydes and nebular and/or pre-solar CN could have served as substrates for synthesis of a wide range of prebiotic compounds in the early solar system.

L.Chimiak↗