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At least 253 records · Page 14

The atmosphere of the primitive earth and the prebiotic synthesis of organic compounds

The prebiotic synthesis of organic compounds is investigated using a spark discharge on various simulated prebiotic atmospheres at 25 C. It is found that glycine is almost the only amino acid produced from the model atmospheres containing CO and CO2. These results show that the maximum yield is about the same for the three carbon sources (CO, CO2, and CH4) at high H2/carbon ratios, but that CH4 is superior at low H2/carbon ratios. CH4 is found to yield a much greater variety of amino acids than either CO or CO2. If it is assumed that amino acids more complex than glycine were required for the origin of life, then these findings indicate the need for CH4 in the primitive atmosphere. The yields of cyanide and formaldehyde are shown to parallel the amino acid results, with yields of HCN and H2CO as high as 13 percent based on carbon. Ammonia is also found to be produced from N2 in experiments with no added NH3 in yields as high as 4.9 percent. These results indicate that large amounts of NH3 would have been synthesized on the primitive earth by electric discharges.

Miller, S. L.↗

Photodeposition of Nitride Insulators on 3-5 Substrates

Laser assisted chemical vapor deposition (LCVD) of nitride insulators, using an excimer laser operating on either KrF or ArF transitions (248 nm or 193 nm respectively) was explored. The properties of silicon nitride films Deposited with 193 nm photons on quartz and silicon substrates in a SiH4, NH3, N2 and He mixture are discussed. Aluminum films were deposited at substrate temperatures from room temperature to 200 C using 248 nm or 193 nm photons to dissociate trimethylaluminum (TMA). Deposition of Al films were investigated to isolate problems associated with TMA such as C and O contamination during AlN depositions. The Al film properties were evaluated on SiO2 and Si substrates. Preliminary results were obtained for aluminum nitride films using TMA and NH3 as the gas phase Al and N donors. The properties of Cr films deposited over areas 5 square cm using 193 nm or 248 nm photons to dissociate Cr(CO) were investigated.

Collins, G. J.↗

Tunable diode laser optogalvanic spectroscopy of molecules

The laser optogalvanic (LOG) technique for studying molecular spectra has been extended for the first time to the infrared wavelength region. Portions of the NH3 nu-2 band at 9.5 microns and the NO2 nu-3 band at 6.2 microns have been recorded at Doppler-limited resolution using CW tunable diode lasers to probe dc electrical discharges in pure NH3 and an NO2/He gas mixture. Using adjustable electrode positions and an orthogonal geometry between the probe laser and the discharge axis, two contributions to the optogalvanic signal are identified: one which corresponds to an increase in discharge impedance and is seen only for irradiation of the negative glow region; and a second which corresponds to a decrease in discharge impedance and is seen for irradiation of all other discharge regions.

Webster, C. R.↗

Composition, Structure and Evolution of Uranian and Neptunian Satellites

Large uncertainties in the current estimated densities of all of these satellites prevent detailed modeling or predictions. Nevertheless, current evidence suggests that at least Titania and Oberon might have anomalously high densities of 2-39 cm(-3), possibly requiring almost ice-free hydrated silicates or formation in a CO-rich environment, implying presence of CO-clathrate and a small ice/rock ratio. Trition and the four largest satellites of Uranus are massive enough to have undergone significant accretional heating and early differentiation; NH3-H2O volcanism; partial outgassing of CO, N2, Ch4; formation of dark surficial deposits of carbon-rich material obtained by UV irradiation of outgassed material; and, at least in the cases of Ariel and Triton, a possibility of weak ongoing icy volcanic activity. Triton may be the largest captured body in the solar system, with an unusual history and composition, including the possibility of substantial liquid or solid nitrogen obtained from either primordial NH3 photolysis or clathrate decomposition.

Stevenson, D. J.↗

High pressure cosmochemistry applied to major planetary interiors: Experimental studies

Progress is reported on a project to determine the properties and boundaries of high pressure phases of the H2-He-H2O-NH3-CH4 system that are needed to constrain theoretical models of the interiors of the major planets. This project is one of the first attempts to measure phase equilibria in binary fluid-solid systems in diamond anvil cells. Vibrational spectroscopy, direct visual observations, and X-ray diffraction crystallography of materials confined in externally heated cells are the primary experimental probes. Adiabats of these materials are also measured in order to constrain models of heat flow in these bodies and to detect phase transitions by thermal anomalies. Initial efforts involve the NH3-H2O binary. This system is especially relevant to models for surface reconstruction of the icy satellites of Jupiter and Saturn. Thermal analysis experiments were completed for the P-X space, p4GPa:0 or = 0.50, near room temperature. The cryostat, sample handling equipment, and optics needed to extend the optical P-T-X work below room temperature was completed.

Nicol, M. F.↗

Basis set limit geometries for ammonia at the SCF and MP2 levels of theory

The controversy over the Hartree-Fock bond angle of NH3 is resolved and the convergence of the geometry for the molecule as the basis set is systematically improved with both SCF and correlated MP2 wave functions. The results of the geometrical optimizations, carried out in four stages with a series of uncontracted bases sets, are shown. The obtained structure for NH3 supports the results of Radom and Rodwell (1980) that the Hartree-Fock limit angle is significantly greater than was previously believed.

Defrees, D. J.↗

Prebiotic syntheses of purines and pyrimidines

The results of experimental and theoretical investigations of the prebiotic synthesis of purines and pyramidines are surveyed. Topics examined include the synthesis of purines from HCN via 4,5-disubstituted imidazole derivatives in aqueous solutions or liquid NH3, simultaneous formation of amino acids and purines by electron irradiation of CH4-NH3-H2O mixtures, synthesis of pyrimadines from cynoacetylene, energetics, formation of bases under anhydrous or concentrated conditions, formation of bases under dilute conditions, Fischer-Tropsch-type reactions, and the role of activated intermediates. It is pointed out that the precursor compounds have been detected in the interstellar medium, on Titan, and in other solar-system bodies, and that solar-nebula HCN concentrations of the order of 1-10 mM have been estimated on the basis of meteorite measurements.

Basile, B.↗

The photochemistry of the early atmosphere

The composition of the earth's present atmosphere is described. The formation of the earth from the coalescence and accretion of the refractory elements of the solar nebula is examined. Two possible compositions of the prebiological paleoatmosphere, which are a reducing atmosphere of CH4, NH3, and H2 or a mildly reducing atmosphere of H2O, CO2, and N2, and their photochemistry are analyzed. General photochemical and chemical processes are reviewed. The use of the coupled continuity-transport equation to calculate the vertical distribution of each species is discussed. A study of the photochemical process of CH4 and NH3 reveals that the reducing atmosphere could not possibly exist. An analysis of the photochemistry and chemistry of the H2O, CO2, and N2 atmosphere reveals that the photodissociation of H2O and CO2 results in a prebiotic source of O2, H2CO, and HCN, which are the components for the evolution of photosynthetic organisms and a strongly oxidizing atmosphere. The reactions which produce O2 and H2CO from H2O and CO2, and the relation between H2O and CO2 concentrations and O2 levels are investigated. The formation of O3 photochemically from O2 is explained.

Levine, J. S.↗

The ammonia-water phase diagram and its implications for icy satellites

A Holzapfel-type diamond anvil cell is used to determine the NH3 - H2O phase diagram in the region from 0 to 33 mole percent NH3, 240 to 370 K, and 0 to 5 GPa. The following phases were identified: liquid; water ices Ih, III, V, VI, VII, and VIII; ammonia monohydrate, NH3.H2O; and ammonia dihydrate NH3.2H2O. Ammonia dihydrate becomes prominent at moderate pressures (less than 1 GPa), with planetologically significant implications, including the possibility of layering in Titan's magma ocean.

Johnson, M. L.↗

Vertical cloud structure models for the NTRZ EQZ, SEB and STRZ of Jupiter

Latitude-dependent models of the vertically inhomogeneous Jovian cloud structure are presented. The models assume an atmospheric composition with (CH4)/(H2) = 2.0 x .003, (He)/(H2) = 0.11 and (NH3)/(H2) = 2.0 x .0004 consistent with the Voyager IRIS measurements and employ refractive indices appropriate for ammonia ice particles and a photochemical stratospheric aerosol layer. The free parameters of the models are determined by fitting the results of multiple, scratching calculations to the near-infrared center and limb spectra of Clark and McCord and the center-to-limb 6190, 6350, 7250, 7500, 8900 and 9500 A photometric measurements of West. The resulting synthetic center-to-limb profiles are in excellent agreement with the observations. Of the regions studied the tropical zones are the most similar, with the observed differences explained by variations in the vertical extent of the cloudy layers. The Equatorial Zone is a unique region with denser NH3 clouds than either of the tropical zones. At visible and near-infrared wavelengths the belt-zone contrasts can be explained by opacity differences. The optical depth of the stratospheric aerosol layer is larger in a belt, while the tropospheric clouds are deeper and thinner.

Carlson, B. E.↗

The ammonia-water phase diagram and its implications for icy satellites

A Holzapfel-type diamond anvil cell is used to determine the NH3 - H2O phase diagram in the region from 0 to 33 mole percent NH3, 240 to 370 K, and 0 to 5 GPa. The following phases were identified: liquid; water ices Ih, III, V, VI, VII, and VIII; ammonia monohydrate, NH3.H2O; and ammonia dihydrate NH3.2H2O. Ammonia dihydrate becomes prominent at moderate pressures (less than 1 GPa), with planetologically significant implications, including the possibility of layering in Titan's magma ocean.

Johnson, Mary L.↗

Cloud chemistry on Jupiter

Chemical equilibrium models used currently to interpret observations of Jupiter are reexamined using new data defining thermal profiles, which are substantially different from those used in the previous models. A model is developed for the chemical reactions controlling the composition of the upper troposphere on Jupiter, specifically the cloud-forming region from 10 bar to 0.1 bar, which includes, for the first time, the effects of aqueous chemistry on the composition and the vertical distribution of many measurable species in the atmosphere, identifying the factors influencing their abundances above the H2O cloud. The thermodynamic data for potential condensates on Jupiter, i.e., NH3(s), NH4SH(s), (NH4)2S(s), and H2S(s), are reexamined, recognizing the lack of data on sulfides for the temperature range of interest on Jupiter. Vertical profiles of mixing ratios for CO2, H2S, NH3, and H2, obtained for several assumed bulk abundances with respect to solar, are presented.

Carlson, Barbara E.↗

Abundances in Comet Halley at the time of the spacecraft encounters

Spectrophotometric observations of Comet Halley obtained in March 1986 at the time of the spacecraft encounters with the comet are described, and the column densities derived from the integrated emission band fluxes are presented. The scale lengths are determined from the spatial profiles of the observed species. Production rates are derived and the parent identities and abundance ratios of the studied species are discussed. The data indicate that the abundance of the primordial condensate NH3 comprises about 0.2 percent of the total volatile fraction of the comet nucleus. The ratio of production rates Q(NH2)/Q(H2O) = 0.003 indicates that Q(NH3)/Q(H2O) is roughly 0.3 percent, which is nearly 10 times lower than the value determined from Giotto ion mass spectrometer data. The production rate Q(CH)/Q(H2O) of 0.007 and the CH spatial profile indicate that CH cannot derive entirely from direct photodissociation of CH4.

Wyckoff, Susan↗

Nitric acid and ammonia emissions from a mid-latitude prescribed wetlands fire

The first simultaneous measurements of gaseous nitric acid and ammonia in the smoke plume of a wetlands biomass burn were obtained. The measurements were made using tungsten oxide-coated diffusion denuder tubes from a helicopter during a prescribed burn on November 9, 1987, at the Merritt Island National Wildlife Refuge, located at the NASA John F. Kennedy Space Center, Florida. The mean NH3 and HNO3 mixing ratios measured in the smoke plume were 19 ppbv and 14 ppbv, respectively, both significantly higher than background mixing ratios. Nitric acid correlated well with carbon dioxide produced by the combustion. The mean CO2-normalized emission ratio for HNO3 was found to be 0.00012. Ammonia, however, dit not correlate well with CO2, suggesting a more complex relationship between combustion and production/release of NH3.

Lebel, P. J.↗

CO observations of L1582

In this paper, the bright-rimmed cloud L1582 is mapped in (C-12)O and (C-13)O, and the embedded NH3 core is mapped in the CS(3 - 2) line. The optical bright rim coincides with the cloud edge seen in CO. Both the kinetic temperature and column density maps show elongated features along the bright rim, and the NH3 core is located right near the edge of the cloud inside a column density plateau region corresponding to an optical extinction patch. The density enhancement in the CS core is about a factor of three over the ambient cloud and the core mass is estimated at eight solar. The dust luminosity can be supplied by radiation from the Gamma Ori OB association. The most plausible heating source for the cloud gas is the photoelectric ejection of energetic electrons from grains induced by the far-UV flux from the Gamma Ori OB association.

Zhou, Shudong↗

Constraints on the microwave opacity of gaseous methane and water vapor in the Jovian atmosphere

Gaseous NH3's microwave absorption in the Jovian atmosphere appears too great to be due to a solar abundance of this gas. The additional capacity of microwave absorption is presently sought in measurements of the microwave absorption of CH4 and H2O under simulated Jovian conditions at 2.25 GHz, 8.5 GHz, 21.7 GHz; due to large error bars, measurements represent upper limits on the microwave opacity generated by H2O and CH4. The results obtained are consistent with theoretical expressions for microwave opacity in a Jovian atmosphere at the specified frequencies. The presence of an NH3 abundance exceeding the solar level by a factor of 1.5 is indicated by test results.

Jenkins, Jon M.↗

Infrared absorption features for tetrahedral ammonia ice crystals

An effort has been made to ascertain how particle shape and composition affect the strength and shape of resonant absorption features at 9.4 and 26 microns. A shifting of the peak of the resonance relative to that for spherical particles is noted in the computational results obtained for the extinction cross-sections of 0.5- and 1-micron, volume-equivalent radius tetrahedral NH3 ice crystals that either possessed or lacked foreign cores. It it judged unlikely that small, (less than 5-micron) NH3 particles could be the principal component of the haze in the 300-500 mbar region of Jupiter.

West, Robert A.↗

The evolution of organic mantles on interstellar grains

By laboratory simulation of the chemical processes on dust grains it was investigated how solid organic materials can be produced in the interstellar medium. The ice mantles that accrete on grains in molecular clouds, consisting primarily of H2O, CO, H2CO, NH3, and O2, are irradiated by the internal UV field, resulting in the storage of radicals upon photodissociation of the original molecules. Transient heating events lead to the production of oxygen-rich organic species by recombination reactions. The experiments indicated that in this way the observed amount of organic material can be produced if a grain passes a few times through a molecular cloud during its life. After the destruction of the cloud the grains enter a more diffuse medium. Here they are subjected to the interstellar UV field as well as to collisions with atomic hydrogen. Experiments show that the intense photoprocessing results in the removal of small species like H2O and NH3 as well as in carbonization of the organic molecules. Contrary to this, the atomic H flux will maintain a certain hydrogen level in the mantle. These processes likely convert the original, oxygen-rich organics into an unsaturated hydrocarbon type material such as that observed towards IRS 7 and in Comet Halley grains.

Schutte, Willem A.↗