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At least 379 records · Page 21

Proton irradiation of SiH4-Fe(CO)5-H2O ices - Production of refractory silicates and implications for the solar nebula

The results of a number of experiments are reported in which SiH4-Fe(CO)5-H2O ice mixtures were irradiated by 1 MeV protons at 15 K and then warmed to room temperature in approximately 50 K steps. The properties of a sample were monitored by observing its infrared absorption spectrum as a function of its processing history. In each experiment in which ice samples containing SiH4 were irradiated, a refractory amorphous silicate residue remained after warming to room temperature. In addition to the usual broad silicate features at 10 and 20 microns, features due to water or hydroxyl at 3 and 6.2 microns, and a feature due to CO at 5 microns, a surprisingly stable infrared feature at 4.6 microns, attributed to the SiH stretching fundamental, was observed.

Nuth, J. A.↗

OH-asterisk (7-5) Meinel band dayglow and nightglow measured by the SME limb scanning near infrared spectrometer - Comparison of the observed seasonal variability with two-dimensional model simulations

Seasonal variations of the OH-asterisk (7-5) mesospheric hydroxyl emission at 1.89 microns observed by the SME near-IR spectrometer are compared with the theoretical predictions of a two-dimensional dynamical/chemical model. The good agreement found at low latitudes for both dayglow and nightglow provides support for the model assumption that breaking gravity waves induce seasonal and latitudinal variations in diffusion. The seasonal behavior of atomic hydrogen in the upper mesosphere (related to vertical transport) and/or uncertainties in the OH Meinel band parameters are proposed as possible explanations for the discrepancy noted between model and observational data for the middle latitudes.

Le Texier, H.↗

Diurnal and seasonal variation of the nighttime OH (8-3) emission at low latitudes

Nighttime morphological maps of the hydroxyl emission (8-3 band) measured by the Visible Airglow Experiment on board the Atmosphere Explorer E satellite are presented for solstice and equinox conditions. The volume emission rate profile of the emission was determined by inverting satellite perigee observations. This profile was later used to convert limb measurements into zenith intensities of the emission. A theoretical model has been used to correct twilight observations for the presence of the thermospheric O(+)(2P) emission at 7320-7330 A. The derived morphology agrees well with ground based measurements and theoretical simulations.

Abreu, Vincent J.↗

Enhancement of Pt/SnO2 Catalysts by Addition of H2O

Water vapor in pretreatment gas restores essential hydroxyl groups. Platinum on tin oxide (Pt/SnO2) is good catalyst for oxidation of carbon monoxide (CO) at temperatures from about 25 degrees C to 100 degress C. Activity of Pt/SnO2 for CO oxidation significantly enhanced by pretreating it at approximately 225 degrees C with reducing gas such as CO. Technique useful in manufacture of high-power CO2 lasers for industrial and scientific uses.

Schryer, David R.↗

Faults in the Mojave Desert, California, as revealed on enhanced Landsat images

Landsat TM images, subjected to four-component processing through which lithologies can be discriminated by their contrasting absorption and reflection at IR wavelengths, have revealed previously unsuspected strike-slip and normal faults in the central and eastern Mojave Desert. These discriminations, which extend to ferric and ferrous iron and to hydroxyl content without compromise of landform depiction, represent a novel type of geophysical display for geologic mapping in regions of well-exposed bedrock; the faults thus discovered form part of an extensive regional network of right shear which connects Death Valley region faults with those in the San Andreas system.

Ford, J. P.↗

F.T. spectroscopy of OH produced in a microwave surface plasma

Emission spectra of the hydroxyl radical have been recorded between 450 and 4200/cm at 0.0027/cm unapodized resolution from an air+oxygen+water vapor plasma, using a surface microwave discharge. The characteristics of the source are described. The emission spectra were recorded with the F.T. spectrometer using a GeCu detector and KCl beams plitter. High J values were observed both for the pure rotational transition in v=0 and v=1 vibrational levels, and for the rovibrational transition in the 0-1 and 1-2 bands. The set of line intensity data will be used to compute the electric dipole moment function of OH.

Benidar, A.↗

A photochemical model of ozone interference effects in laser detection of tropospheric OH

Laser-generated interference in the laser-induced fluorescence detection of tropospheric hydroxyl is addressed by a detailed photochemical model. This phenomenon arises through photolysis of ozone by the detection laser and subsequent reaction of O(1D) with H2O to form OH. The approach is direct time integration of the coupled differential equations describing the pertinent chemical reactions, collisional energy transfer, and photolytic and spectroscopic processes, including an assessment of limitations due to uncertainties in the input parameters. The goal is to use the model to quantitatively design OH detection methods so that the experimental results need not rely on such a model for interpretation. Previously reported measurements of tropospheric OH appear to have been contaminated by ozone interference effects and by optical saturation of the monitoring transition. However, suggested improvements can reduce the problem to interference levels below 200,000 OH molecules/cu cm, permitting measurements useful for testing theories of fast tropospheric photochemistry.

Smith, Gregory P.↗

OH vertical column abundance - Tropical measurements

Measurements of the vertical column abundance of atmospheric hydroxyl (OH) have been made during the period 1987-1989 at the National Weather Service (NWS) station at Moen, Truk, Federated States of Micronesia (7 deg N, 152 deg E). A total of 384 independent data sets was obtained. Tropical OH abundance levels average about 22 percent above corresponding mid-latitude values, with OH levels during late winter and early spring up to 50 percent above those observed at 40 deg N. Stratospheric wind and temperature data obtained from the daily NWS radiosonde data are examined for correlations with the OH results.

Burnett, Clyde R.↗

Amazon Basin ozone and aerosol - Wet season observations

The ozone and aerosol number density data obtained from aircraft flights over the Amazon Basin (AB) during April and May of 1987 are summarized with particular attention given to the general characteristics of ozone and aerosol for wet season (WS), compared to dry season (DS), meteorology. It is concluded that the AB provides favorable conditions for the production of hydroxyl radical and subsequent chemical and photochemical reactions which generate or consume key atmospheric trace species. It is determined that a negative ozone gradient exists within the mixed layer (ML). WSML ozone is about 7 ppbv lower than that of DS. The net sink characteristics of the WSML are seen throughout the troposphere of the AB in that the ozone at 3-4 km altitude is typically 15-25 ppbv as compared to DS values of 30-35 ppbv. In terms of aerosol source characteristics of the AB, ML aerosols are 5-10 times higher than observed in the troposphere with ML values of 100-200 aerosols/cu cm. An analysis of aerosol size distribution data is presented.

Gregory, Gerald L.↗

Hybrid propulsion technology program: Phase 1, volume 4

The use of a liquid oxidizer-solid fuel hybrid propellant combination in booster rocket motors appears extremely attractive due to the integration of the best features of liquid and solid propulsion systems. The hybrid rocket combines the high performance, clean exhaust, and safety of liquid propellant engines with the low cost and simplicity of solid propellant motors. Additionally, the hybrid rocket has unique advantages such as an inert fuel grain and a relative insensitivity to fuel grain and oxidizer injection anomalies. The advantages mark the hybrid rocket as a potential replacement or alternative for current and future solid propellant booster systems. The issues are addressed and recommendations are made concerning oxidizer feed systems, injectors, and ignition systems as related to hybrid rocket propulsion. Early in the program a baseline hybrid configuration was established in which liquid oxygen would be injected through ports in a solid fuel whose composition is based on hydroxyl terminated polybutadiene (HTPB). Liquid oxygen remained the recommended oxidizer and thus all of the injector concepts which were evaluated assumed only liquid would be used as the oxidizer.

Claflin, S. E.↗

Derivation of mid-infrared (5-25 microns) optical constants of some silicates and palagonite

Recent reports concerning the mid-infrared reflectance properties of silicates coupled with recent observations of the Earth and other planets in the mid-infrared and the planned Thermal Emission Spectrometer scheduled as an instrument to be included on the Mars Observer all illustrate the increasing interest in the optical properties of materials in the mid-infrared and their direct application to remote sensing observations of other planetary surfaces. As the laboratory and observational data increase they will ultimately be modeled to aid in the understanding of the composition mineralogy, and distribution of the surface and atmospheric constituents on these bodies. In order to facilitate such quantitative analyses, knowledge regarding the optical constants (real (n) and imaginary (k) indices of refraction) of a wide variety of pertinent materials is required. Examples of the application of such quantitative analyses to the interpretation of Martian surface and atmospheric constituents, based on the optical constants of minerals, are presented. This study was initially conceived in order to aid in the interpretation of Martian surface and atmospheric aerosol mineralogy. As a result, the minerals included are biased toward samples which represent hydrated and hydroxylated silicates. These include the Al and Mg end members of the 1:1 layer lattice silicates, kaolinite and serpentine, respectively; an Al-bearing 2:1 layer lattice silicate, pyrophyllite; the Mg and Al smectite clays saponite and montmorillonite, respectively; and a palagonite, typically a poorly characterized alteration product of basaltic glass. The reflectivities of all samples were determined by placing them at the focus of a near-normal reflective attachment located in a Fourier transform spectrometer. To derive the optical constants of a material as a function of wavelength, researchers used the commonly employed technique of dispersion analysis.

Roush, T. L.↗

Dissolution of quartz in aqueous basic solution, 106-236 C - Surface kinetics of 'perfect' crystallographic faces

A highly accurate method, called the negative crystal method, for determining the rate of dissolution on specific crystallographic faces of crystals was developed, in which the dissolution rates of nominally perfect crystal faces are obtained by measuring the size of individual negative crystals during a sequence of dissolution steps. The method was applied to determine the apparent activation energy and rate constants for the dissolution of quartz in 0.01 M KOH solutions at temperatures from 106 to 236 C. Also investigated were the effects of hydroxyl activity and ionic strength. The apparent activation energies for the dissolution of the prism and of the rhomb were determined.

Gratz, Andrew J.↗

Selection of Landsat TM band and band-ratio combinations to maximize lithologic information in color composite displays

Correlation analyses of Landsat TM data for arid areas and laboratory spectral data for various combinations of minerals indicate that band combination 1-4-7 maximally differentiates lithologic materials in most scenes, but that band combination 1-5-7 is preferable for scenes in which hydroxyl-rich minerals are prominent or of specific interest. Among band ratio combinations, 3/1 - 5/4 - 5/7 ranks high for optimal information display.

Crippen, Robert E.↗

Derivation of mid-infrared (5-25 microns) optical constraints of some silicates and palagonite

This study was initially conceived in order to aid in the interpretation of Martian surface and atmospheric aerosol mineralogy. As a result, the minerals included are biased toward samples which represent hydrated and hydroxylated silicates. Due to their physical particle size, clays and other materials, such as palagonite, cannot be prepared using typical preparation techniques. Yet in some cases, such as for Mars, these are the materials of perhaps the greatest interest. In order to obtain a suitable sample of these less cohesive materials for the laboratory measurements, a KBr pellet die was used and a pellet of the pure sample was prepared. For all clays and the palagonite, a pellet with highly reflective surfaces at visible wavelengths was produced. The reflectivities of all samples were determined, and to derive the optical constants of a materials as a function of wavelength, dispersion analysis was used which describes the real and imaginary indices of refraction as the contributions due to a sum of classical oscillators and relates them via Frensel's equations for non-normal incidence, the the measured near-normal reflectivity. The final values that were determined represent averages of several model fits to each data set using the same number of oscillators by varying the high frequency dielectric constant.

Roush, T. L.↗

Catalytic RNA and synthesis of the peptide bond

We are studying whether the L-19 IVS ribozyme from Tetrahymena thermophila can catalyze the formation of the peptide bond when it is supplied with synthetic aminoacyl oligonucleotides. If this reaction works, it could give us some insight into the mechanism of peptide bond formation and the origin of coded protein synthesis. Two short oligoribonucleotides, CCCCC and a protected form of CCCCU were prepared; the former was made by the controlled hydrolysis of Poly(C), and the later by multistep chemical synthesis from the protected monomers. The homopentamer was then aminocylated using C-14 labelled Boc-protected glycine imidazolide. This aminoacylated oligo-nucleotide has now been shown to enter the active site of the L-19 IVS, and aminoacyl transfer, and peptide bond formation reactions are being sought. Our synthesis of CCCCU made us aware of the inadequacy of many of the 2'- hydroxyl protecting groups that are in use today and we therefore designed a new 2'- protecting group that is presently being tested.

Usher, D. A.↗

Halocarbon ozone depletion and global warming potentials

Concern over the global environmental consequences of fully halogenated chlorofluorocarbons (CFCs) has created a need to determine the potential impacts of other halogenated organic compounds on stratospheric ozone and climate. The CFCs, which do not contain an H atom, are not oxidized or photolyzed in the troposphere. These compounds are transported into the stratosphere where they decompose and can lead to chlorine catalyzed ozone depletion. The hydrochlorofluorocarbons (HCFCs or HFCs), in particular those proposed as substitutes for CFCs, contain at least one hydrogen atom in the molecule, which confers on these compounds a much greater sensitivity toward oxidation by hydroxyl radicals in the troposphere, resulting in much shorter atmospheric lifetimes than CFCs, and consequently lower potential for depleting ozone. The available information is reviewed which relates to the lifetime of these compounds (HCFCs and HFCs) in the troposphere, and up-to-date assessments are reported of the potential relative effects of CFCs, HCFCs, HFCs, and halons on stratospheric ozone and global climate (through 'greenhouse' global warming).

Cox, Richard A.↗

Review of ultraviolet absorption cross sections of a series of alternative fluorocarbons

Solar photolysis is likely to contribute to the stratospheric destruction of those alternative fluorocarbons (HFC's) which have two or more chlorine atoms bonded to the same carbon atom. Two of the eight HFC's considered here fall into this category, namely HFC-123 and HFC141b. For these two species there is good agreement among the various measurements of the ultraviolet cross sections in the wavelength region which is important for atmospheric photodissociation, that is, around 200 nm. There is also good agreement for HFC-124, HFC-22 and HFC-142b. These are the three species which contain one chlorine atom per molecule. The agreement in the measurements is poor for the other species, i.e., those that do not contain chlorine, except in so far as to corroborate that solar photolysis should be negligible relative to destruction by hydroxyl radicals.

Molina, Mario J.↗

An assessment of potential degradation products in the gas-phase reactions of alternative fluorocarbons in the troposphere

Tropospheric chemical transformations of alternative hydrofluorocarbons (HCF's) and hydrochlorofluorocarbons (HCFC's) are governed by hydroxyl radical initiated oxidation processes, which are likely to be analogous to those known for alkanes and chloroalkanes. A schematic diagram is used to illustrate plausible reaction mechanisms for their atmospheric degradation, where R, R', and R'' denote the F- and/or Cl-substituted alkyl groups derived from HCF's and HCFC's subsequent th the initial H atom abstraction by HO radicals. At present, virtually no kinetic data exist for the majority of these reactions, particularly for those involving RO. Potential degradation intermediates and final products include a large variety of fluorine- and/or chlorine-containing carbonyls, acids, peroxy acids, alcohols, hydrogen peroxides, nitrates and peroxy nitrates, as summarized in the attached table. Probably atmospheric lifetimes of these compounds were also estimated. For some carbonyl and nitrate products shown in this table, there seem to be no significant gas-phase removal mechanisms. Further chemical kinetics and photochemical data are needed to quantitatively assess the atmospheric fate of HCF's and HCFC's, and of the degradation products postulated in this report.

Niki, Hiromi↗