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Quenched Carbonaceous Composite: a laboratory analog for carbonaceous material in the interstellar medium.

We review the properties of Quenched Carbonaceous Composite (QCC), a residue produced from a hydrocarbon plasma, and the properties of its derivatives. A. Sakata and his colleagues have shown that QCC has a 220 nm absorption band, visible fluorescence matching the extended red emission seen in reflection nebulae, and infrared absorption bands that correspond to the infrared emission features in reflection nebulae, HII regions, and planetary nebulae. These properties make QCC a strong candidate material as a laboratory analog to the carbonaceous material in the interstellar medium. QCC is distinguished from the PAH hypothesis in that (1) it is a condensate composed of aromatic and aliphatic molecules, as well as radicals; (2) it exhibits a 220 nm absorption that is very similar in wavelength to the 217 nm absorption in the interstellar medium; (3) it exhibits visible fluorescence consistent with that seen in reflection nebulae; and (4) the bands at 7.7 and 8.6 microns are caused by ketone bands in oxidized QCC. The aromatic component in QCC is thought to be typically 1-4 rings, with the majority being about 1-2 rings.

Carbon↗

The sticking probability of a hydrogen atom on icy mantle.

In the present work, we investigate the sticking process of a hydrogen atom on the surface of dust grains. As a realistic model for the icy mantle of dust grains, we produced slab-shaped amorphous water ice with infinite area by classical molecular dynamics (MD) computational simulation using two-dimensional periodic boundary condition. The resulting amorphous water ice slabs at 10 K and 70 K were found to be in good agreement with the experimental high-density and low-density amorphous water ice, respectively. Then, we investigated the dynamical behaviors of an impinging H atom on the surface of it by MD simulations. The sticking probabilities of incident H atoms with several initial temperatures on 10 K and 70 K ice were obtained. It was found that most of H atoms colliding with the 10 K ice stuck on the surface of it. After having stuck, the impinging H atoms diffused on the surface of ice and became trapped in one of potential wells on the surface. The mobility of a H atom on the surface of the amorphous water ice was found to depend only upon the temperature of ice.

Computer Simulation↗

Spectroscopic properties of polycyclic aromatic hydrocarbons (PAHs) and astrophysical implications.

PAHs (polycyclic aromatic hydrocarbons) are probably present as a mixture of neutral and ionized species and are responsible for the set of infrared emission bands in the 2-15 microns regions, which are observed in many different objects like reflection and planetary nebulae and external galaxies. PAHs are suggested to be the most abundant free organic molecules and ubiquitous in space. PAHs might also exist in the solid phase, included in interstellar ices in dense clouds. A complex aromatic network is expected on interstellar grains in the diffuse interstellar medium. The existence of an aromatic kerogen-like structure in carbonaceous meteorites and its similarity with interstellar spectra suggests a link between interstellar matter and primitive Solar System bodies.

Extraterrestrial Environment↗

Fullerenes in space.

The discovery and synthesis of fullerenes led to the hypothesis that they may be present and stable in interstellar space. Fullerenes have been reported in an impact crater on the LDEF spacecraft. Investigations of fullerenes in carbonaceous meteorites have yielded only small upper limits. Fullerene compounds and their ions could be interesting carrier molecules for some of the "diffuse interstellar bands" (DIBs), a long standing mystery in astronomy. We have detected two new diffuse bands that are consistent with laboratory measurements of the C60+, as first evidence for the largest molecule ever detected in space. Criteria for this identification are discussed. The inferred abundance (up to 0.9 % of cosmic carbon locked in C60+) suggests that fullerenes may play an important role in interstellar chemistry. We present new observations on DIB substructures consistent with fullerene compounds, and the search for neutral C60 in the diffuse medium.

Carbon↗

Complex organics in meteorites.

Complex macromolecular organic matter is present in carbonaceous chondrites as the most abundant organic matter and may be present in interstellar dusts and comets. With this view, our studies of the complex organic matter isolated from six CM2 chondrites, namely Yamato-74662, Yamato-791198, Yamato-793321, Yamato-86720, Belgica-7904, and Murchison are introduced and discussed in the text. The complex organic matter is acid-insoluble and organic solvent-insoluble, and therefore, it was examined by heating experiments to obtain information on its chemical constituents and characteristics. Three chondrites, Yamato-74662, Yamato-791198, and Murchison which have solvent-extractable organic compounds, such as amino acids, carboxylic acid, hydrocarbons, etc. possess thermally labile organic fraction in the complex organic matter. Organic compounds detected in the pyrolyzate of the complex organic matter number over 130 of which aromatic hydrocarbons are dominant. They appeared around 300 degrees C, and disappeared at about 600 degrees C with a maximum at 400-500 degrees C during the heating. On the other hand, the other three chondrites do not have the extractable organic compounds nor a thermally labile organic fraction. The presence or absence of the fraction in the complex organic matter likely indicates the presence or absence of the solvent-extractable organic compounds and relates to thermal history of the chondrite.

Carbon↗

Abiogenic synthesis of pyrimidine nucleotides in solid state by vacuum ultraviolet radiation.

The abiogenic synthesis of pyrimidine nucleotides in solid state has been investigated. Our experiment indicates that natural nucleotides are produced in thin films prepared from nucleoside and inorganic phosphate by irradiating with vacuum ultraviolet light (VUV, lambda=100-200 nm). We have investigated the influence of the type of nucleic acids base (thymidine, cytosine, uracil) and the structure of sugar moiety (ribose or deoxyribose) on the course and yield of reaction. We compared the action of vacuum ultraviolet light with action of gamma-radiation, heat and biology significant UV (254 nm) which have been investigated earlier. The occurrence of these reaction in open space is discussed.

Cytidine↗

Ion irradiation: its relevance to the evolution of complex organics in the outer solar system.

Ion irradiation of carbon containing ices produces several effects among which the formation of complex molecules and even refractory organic materials whose spectral color and molecular complexity both depend on the amount of deposited energy. Here results from laboratory experiments are summarized. Their relevance for the formation and evolution of simple molecules and complex organic materials on planetary bodies in the external Solar System is outlined.

Carbon↗

Hydrogen cyanide polymers from the impact of comet P/Shoemaker-Levy 9 on Jupiter.

Hydrogen cyanide polymers--heterogeneous solids ranging in color from yellow to orange to brown to black--may be among the organic macromolecules most readily formed within the Solar System. The non-volatile black crust of comet Halley, for example, as well as the extensive orange-brown streaks in the atmosphere of Jupiter, might consist largely of such polymers synthesized from HCN formed by photolysis of methane and ammonia. Laboratory studies of these ubiquitous compounds point to the presence of polyamidine structures synthesized directly from hydrogen cyanide. These would be converted by water to polypeptides which can be further hydrolyzed to alpha-amino acids. Other polymers and multimers with ladder structures derived from HCN would also be present and might well be the source of the many nitrogen heterocycles, adenine included, detected by thermochemolytic analysis. The dark brown color arising from the impacts of comet P/Shoemaker-Levy 9 on Jupiter could therefore be mainly caused by the presence of HCN polymers, whether originally present, deposited by the impactor or synthesized from freshly formed HCN. Spectroscopic detection of these predicted macromolecules and their hydrolytic and pyrolytic by-products would strengthen significantly the hypothesis that cyanide polymerization is a preferred pathway for prebiotic and extraterrestrial chemistry.

Evolution, Chemical↗

Regioselectivity of the photochemical addition of phosphine to unsaturated hydrocarbons in the atmospheres of Jupiter and Saturn.

Phosphine (PH3) has been observed in the atmospheres of Jupiter and Saturn. We have studied the regioselectivity in the gaseous phase of the photochemical addition of PH3 to propene 1, propadiene 2, propyne 3, 1,3-butadiene 4 and 1,3-butadiyne 5. The photolysis were performed at 185 and 254 nm. The volatile products formed in these reactions were characterized by 1H and 31P NMR. The n-propylphosphine 6 and the isopropylphosphine 7 were the major products observed in the photolysis of PH3 with propene. The allylphosphine 8 was obtained when most of the light was absorbed by propene. This allylphosphine was the main product formed in the photolysis of PH3 in the presence of propadiene; the methylvinylphosphine 10 being not detected in these experiments, the reaction presents a very high regioselectivity. When most of the light was absorbed by propadiene, the propargylphosphine 9 was also observed. The photolysis of PH3 in the presence of propyne led to the E- and Z-1-propenylphosphines 12a,b and small amounts of methylvinylphosphine 10. Even when most of the light was absorbed by propyne, the propargylphosphine 9 was not observed. The Z-1-butene-3-ynylphosphine 13a and a mixture of primary phosphines containing the E-and Z-2-butenylphosphines 14a,b were obtained as major products when 1,3-butadiyne and 1,3-butadiene respectively where photolyzed with PH3. A high regioselectivity was thus observed in the photolysis of PH3 with an alkyne or an allene but alkenes led to mixtures of products.

Atmosphere↗

New planetary atmosphere simulations: application to the organic aerosols of Titan.

The atmosphere of Titan partly consists of hazes and aerosol particles. Experimental simulation is one of the powerful approaches to study the processes which yield these particles, and their chemical composition. It provides laboratory analogues, sometimes called tholins. Development and optimization of experimental tools were undertaken in order to perform chemical and physical analyses of analogues under conditions free from contamination. A "Titan aerosol generator" was developed in the frame of the Cassini-Huygens mission, in order to produce Titan's aerosol analogues within conditions closer to those of the titanian atmosphere: cold plasma simulation system, low pressure and low temperature. The direct current (DC) glow discharge is produced by applying a DC voltage between two conductive electrodes inserted into the gas mixture-model of the studied atmosphere- at low pressure. A high-impedance power supply is used to provide the electrical field. All the system is installed in a glove box, which protect samples from any contamination. Finally the research program expected with this new material is presented.

Aerosols↗

Corona discharge of Titan's troposphere.

The atmosphere of Titan is constantly bombarded by galactic cosmic rays and Saturnian magnetospheric electrons causing the formation of free electrons and primary ions, which are then stabilized by ion cluster formation and charging of aerosols. These charged particles accumulate in drops in cloud regions of the troposphere. Their abundance can substantially increase by friction, fragmentation or collisions during convective activity. Charge separation occurs with help of convection and gravitational settling leading to development of electric fields within the cloud and between the cloud and the ground. Neutralization of these charge particles leads to corona discharges which are characterized by low current densities. These electric discharges could induce a number of chemical reactions in the troposphere and hence it is of interest to explore such effects. We have therefore, experimentally studied the corona discharge of a simulated Titan's atmosphere (10% methane and 2% argon in nitrogen) at 500 Torr and 298 K by GC-FTIR-MS techniques. The main products have been identified as hydrocarbons (ethane, ethyne, ethene, propane, propene + propyne, cyclopropane, butane, 2-methylpropane, 2-methylpropene, n-butene, 2-butene, 2,2-dimethylpropane, 2-methylbutane, 2-methylbutene, n-pentane, 2,2-dimethylbutane, 2-methylpentane, 3-methylpentane, n-hexane, 2,2-dimethylhexane, 2,2-dimethylpentane, 2,2,3-trimethylbutane, 2,3-dimethylpentane and n-heptane), nitriles (hydrogen cyanide, cyanogen, ethanenitrile, propanenitrile, 2-methylpropanenitrile and butanenitrile) and an uncharacterized film deposit. We present their trends of formation as a function of discharge time in an ample interval and have derived their initial yields of formation. These results clearly demonstrate that a complex organic chemistry can be initiated by corona processes in the lower atmosphere. Although photochemistry and charged particle chemistry occurring in the stratosphere can account for many of the observed hydrocarbon species in Titan, the predicted abundance of ethene is to low by a factor of 10 to 40. While some ethene will be produced by charged-particle chemistry, its production by corona processes and subsequent diffusion into the stratosphere appears to be an adequate source. Because little UV penetrates to the lower atmosphere to destroy the molecules formed there, the corona-produced species may be long-lived and contribute significantly to the composition of the lower atmosphere and surface.

Argon↗

HCN formation under electron impact: experimental studies and application to Neptune's atmosphere.

Laboratory experiments simulating organic synthesis in Neptune's atmosphere have been performed. We have submitted to a spark discharge gaseous mixtures containing 9 mbar of molecular nitrogen and 3 mbar of methane (the p(N2)/p(CH4) ratio is compatible with upper limits in Neptune's stratosphere) with varying quantities of molecular hydrogen. The spark discharge is used to model the energetic electrons produced by the impact of cosmic rays on the high atmosphere of Neptune. HCN is synthesized in the described experimental conditions, even with a low mixing ratio of molecular nitrogen. Studying the variation of HCN production with the initial composition of the gas mixture and extrapolating to high mixing ratio of molecular hydrogen allows to estimate HCN production in Neptune's atmosphere. The computed HCN production flux is 7x10(7) m-2 s-1, which is two orders of magnitude lower than the value predicted by chemical models for an internal source of N atoms. The major uncertainty in our extrapolation is the energetic distribution of electrons, implicitly assumed comparable in the discharge and in Neptune's atmosphere. We note that this distribution is also a source of uncertainty in chemical models. The chemical mechanism responsible for the local formation of HCN in the stratosphere probably occurs in the reactor too. We propose a simple characterization of the spark discharge. We thus link the molecular nitrogen dissociation cross section by electron impact to the measured parameters of the experiments (current, voltage, initial partial pressures) and to the resulting HCN partial pressures. However, other laboratory experiments with larger hydrogen pressures, requiring a more powerful electric source, have to be performed to yield a value of the cross section.

Atmosphere↗

Variations of the radiation dose onboard Mir station.

Dose variations, associated with the 11-year solar activity cycle, seasonal variations of particle fluxes in the Earth's radiation belts at the station orbit, and solar proton events are studied, using prolonged measurements of radiation doses inside orbital station Mir. Daily averages of radiation doses during the declining phase of the 22nd solar cycle and during transition to the 23rd solar activity cycle reached very large values for astronauts and significantly exceed the values calculated according to existing models.

Cosmic Radiation↗

Using cross-correlation techniques to assess the validity of AP8 at low altitude.

Background effects, such as single event upsets, are used as proxy data sets to evaluate AP8 at low attitude. The approach is to use a 2-D (longitude and latitude) cross-correlation between the background data set and the current-epoch AP8 predicted fluxes. The technique can be used to determine the energy of the particle that is producing a particular effect. This cross-correlation technique shows that using AP8 with a present-epoch magnetic field model accurately predicts the present location of the South Atlantic Anomaly proton flux enhancement and that a dual-peaked intensity structure above 100 MeV in the model is an artifact of AP8 and its interpolation routines.

Atlantic Ocean↗

An investigation of the spatial variations of the energetic trapped electrons at low altitudes.

We have analyzed the trapped electron data (0.19-3.2 MeV) taken by the Japanese OHZORA satellite operated at 350-850 km altitude in polar orbit during 1984-1987 near solar minimum. The electron observations reveal all the global attributes of the quiet-time electron radiation belts, such is the South Atlantic Anomaly, the electron "slot", and the outer radiation belt regions. The electron data are in general agreement with the NASA AE-8 electron model, but there are differences, particularly with respect to distinctive local-time variations in the slot region. In this paper, we present results from analyses of variations of the electron pitch angle distributions with local time, L-shell and altitude.

Altitude↗

Sources of inner radiation zone energetic helium ions: cross-field transport versus in-situ nuclear reactions.

Radial transport theory for inner radiation zone MeV He ions has been extended by combining radial diffusive transport, losses due to Coulomb friction and charge exchange reaction with local generation of 3He and 4He ions due to nuclear reactions taking place on the inner edge of the inner radiation zone. From interactions between high energy trapped protons and upper atmospheric constituents we have included a nuclear reaction yield helium flux source that was numerically derived from a nuclear reaction model originally developed at the Institute of Nuclear Researches of Moscow, Russia and implemented in the computer system at the University of Campinas, Brazil. Magnetospheric transport computations have been made covering the L-shell range L=1.0 to 1.6 and the resulting MeV He ion flux distributions show a strong influence of the local nuclear source mechanism on the inner zone energetic He ion content.

Cosmic Radiation↗

Chemical composition measurements of the atmosphere of Jupiter with the Galileo Probe mass spectrometer.

The Galileo Probe entered the atmosphere of Jupiter on December 7, 1995. Measurements of the chemical and isotopic composition of the Jovian atmosphere were obtained by the mass spectrometer during the descent over the 0.5 to 21 bar pressure region over a time period of approximately 1 hour. The sampling was either of atmospheric gases directly introduced into the ion source of the mass spectrometer through capillary leaks or of gas, which had been chemically processed to enhance the sensitivity of the measurement to trace species or noble gases. The analysis of this data set continues to be refined based on supporting laboratory studies on an engineering unit. The mixing ratios of the major constituents of the atmosphere hydrogen and helium have been determined as well as mixing ratios or upper limits for several less abundant species including: methane, water, ammonia, ethane, ethylene, propane, hydrogen sulfide, neon, argon, krypton, and xenon. Analysis also suggests the presence of trace levels of other 3 and 4 carbon hydrocarbons, or carbon and nitrogen containing species, phosphine, hydrogen chloride, and of benzene. The data set also allows upper limits to be set for many species of interest which were not detected. Isotope ratios were measured for 3He/4He, D/H, 13C/12C, 20Ne/22Ne, 38Ar/36Ar and for isotopes of both Kr and Xe.

Atmosphere↗