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NASA NTRS1991

Ozone depletion in the high latitude lower stratosphere - 1979-1990

Archived Stratospheric Aerosol and Gas Experiment (SAGE, SAGE II) and Solar and Backscattered Ultraviolet (SBUV) data are used to examine lower stratospheric O3 variations at 50 deg latitude in both hemispheres. These data indicate that from 1979 to 1985, 73-90 percent of the total O3 changes have occurred below approximately 25 km in altitude. Significant O3 depletions (up to 15 percent) have occurred in the partial column (127-15.8 mbar) in both hemispheres with indications of a recovery after 1985. Two-dimensional model simulations of O3 changes from 1979 to 1990 have been carried out. Comparisons with O3 data are presented. Model results suggest that by 1985, significant declines in global O3 were caused by destruction by odd nitrogen associated with long-term variations in the flux of precipitating relativistic electrons (2.6 percent); solar UV flux changes (1.8 percent); the dilution effect associated with the Antarctic O3 hole (1.2 percent); and atmospheric increases in CH4, N2O, and chlorofluorocarbons (0.4 percent). Analyses of drift-corrected SBUV and Total Ozone Mapping Spectrometer data and model calculations indicate that between 1979 and 1985, reductions of 4.3 to 4.8 percent in total column O3 averaged between 65 deg S and 65 deg N have occurred. Calculations indicate a full global O3 decline of 5.2 percent (peak-to-peak) or 6 percent (annual average) between 1979 and 1985 with a partial recovery between 1985 and 1989.

Callis, Linwood B.↗

NASA NTRS1990

Hydrogen-silicon carbide interactions

A study of the thermochemistry and kinetics of hydrogen environmental attack of silicon carbide was conducted for temperatures in the range from 1100 C to 1400 C. Thermodynamics maps based on the parameters of pressure and oxygen/moisture content were constructed. With increasing moisture levels, four distinct regions of attack were identified. Each region is defined by the thermodynamically stable solid phases. The theoretically stable solid phases of region 1 are silicon carbide and silicon. Experimental evidence is provided to support this thermodynamic prediction. Silicone carbide is the single stable solid phase in region 2. Active attack of the silicon carbide in this region occurs by the formation of gases of SiO, CO, CH4, SiH4 and SiH. Analyses of the kinetics of reaction for region 2 at 1300 C show the attack of the silicon carbide to be controlled by gas phase diffusion of H2O to the sample. Silicon carbide and silica are the stable phases common to regions 3 and 4. These two regions are characterized by the passive oxidation of silicon carbide and formation of a protective silica layer.

Eckel, Andrew J.↗

NASA NTRS1990

The strange gases of Jupiter and Saturn

The various gases found in the atmospheres of Jupiter and Saturn are discussed. A history of scientific investigation of these planets is outlined and results of these discoveries are considered. The molecular species found in these two planets are classified into several groups. The first group consists of H2, He, CH4, NH3, and H2O while the second group contains gases formed as the chemical byproducts of solar radiation, including simple hydrocarbons such as C2H2 and C2H6 and charged particles such as H3(+). The last group contains compounds which are chemically unstable in parts of Jupiter's atmosphere that have been probed and include Ge and As; two elements usually found in minerals on earth. An investigation of origin of these elements which are currently part of the upper reaches of the atmosphere of Jupiter and Saturn has led to discoveries about much deeper and hotter parts of atmospheres that can never be observed directly. A number of hypotheses are presented to account for the presence of various unexpected compounds, such as carbon monoxide.

Noll, Keith S.↗

NASA NTRS1991

Chemical models of interstellar gas-grain processes. II - The effect of grain-catalysed methane on gas phase evolution

The effects on gas phase chemistry which result from the continuous desorption of methane molecules from grain surfaces are studied. Significant and sustained enhancements in the abundances of several complex hydrocarbon molecules are found, in good agreement with their observed values in TMC-1. The overall agreement is, however, just as good for the case of zero CH4 desorption efficiency. It is thus impossible to determine from the models whether or not the grain-surface production of methane is responsible for the observed abundances of some hydrocarbon molecules.

Brown, Paul D.↗

NASA NTRS1991

Thermal maps of Jupiter - Spatial organization and time dependence of stratospheric temperatures, 1980 to 1990

The spatial organization and time dependence of Jupiter's stratospheric temperatures have been measured by observing thermal emission from the 7.8-micrometer CH4 band. These temperatures, observed through the greater part of a Jovian year, exhibit the influence of seasonal radiative forcing. Distinct bands of high temperature are located at the poles and midlatitudes, while the equator alternates between warm and cold with a period of approximately 4 years. Substantial longitudinal variability is often observed within the warm midlatitude bands, and occasionally elsewhere on the planet. This variability includes small, localized structures, as well as large-scale waves with wavelengths longer than about 30,000 kilometers. The amplitudes of the waves vary on a time scale of about 1 month; structures on a smaller scale may have lifetimes of only days. Waves observed in 1985, 1987, and 1988 propagated with group velocities less than + or - 30 meters/sec.

Orton, Glenn S.↗

NASA NTRS1991

The 2-micron polar haze of Jupiter

Model spectra have been constructed for the CH4 lines of the polar regions of Jupiter in such as way as to encompass the hydrogen pressure-induced opacity and haze layers revealed by high-resolution spectroscopy. Comparisons between observation and model spectra indicate that, for optically thin haze models, the polar haze is primarily located between the 70 and 5 mbar pressure levels; for opaque haze models, the top of the haze layers lies in the vicinity of the 15-mbar level. It is concluded that the polar haze is widely distributed over both polar regions and exhibits no strong correlation with auroral activities.

Kim, Sang J.↗

NASA NTRS1991

A study of photopolarimeter system UV absorption data on Jupiter, Saturn, Uranus, and Neptune - Implications for auroral haze formation

The present investigation of the dark hazes of Jupiter, Saturn, Uranus, and Neptune on the basis of Voyager 2 UV data notes a geographic correlation between the auroral zones of Jupiter and Saturn and UV-dark polar regions. While the auroral fluxes and penetration depths on Jupiter and Saturn may suffice for a darkening of the polar regions by auroras' action on methane, Uranus and Neptune are found to be bright at all latitudes. In the former case, this brightness is in keeping with auroral electron energies too small to reach the CH4 homopause at which haze production occurs; in the latter case, a UV-dark band exists from 30 deg S to 5 deg N which is probably unrelated to auroral processes.

Pryor, Wayne R.↗

NASA NTRS1990

Silicon carbon alloy thin film depositions using electron cyclotron resonance microwave plasmas

Amorphous and microcrystalline silicon carbon films (a-SiC:H, micro-c-SiC:H) have been deposited using SiH4, CH4 and H2 mixed gas ECR (electron cyclotron resonance) plasmas. The optical bandgap of a-SiC:H films is not dependent on the hydrogen dilution in the ECR plasma. The deposition rate of a-SiC:H films is found to be strongly dependent on the ECR magnetic field and the hydrogen dilution. The hydrogen dilution effect on the deposition rate indicates that the etching in ECR hydrogen plasmas plays an important role in the deposition of a-SiC:H films. The optical constants n and k of ECR-deposited a-SiC:H films in the wavelength region of 0.4 to 1.0 micron are determined to be 2.03-1.90 and 0.04-0.00, respectively. The microstructures of ECR-deposited micro-c-SiC:H films are shown by X-ray diffraction and SEM (scanning electron microscopy) to be composed of 1000-A alpha-SiC microcrystallites and amorphous network structures.

Shing, Y. H.↗

NASA NTRS1991

The greenhouse and antigreenhouse effects on Titan

The parallels between the atmospheric thermal structure of the Saturnian satellite Titan and the hypothesized terrestrial greenhouse effect can serve as bases for the evaluation of competing greenhouse theories. Attention is presently drawn to the similarity between the roles of H2 and CH4 on Titan and CO2 and H2O on earth. Titan also has an antigreenhouse effect due to a high-altitude haze layer which absorbs at solar wavelengths, while remaining transparent in the thermal IR; if this haze layer were removed, the antigreenhouse effect would be greatly reduced, exacerbating the greenhouse effect and raising surface temperature by over 20 K.

Mckay, Christopher P.↗

NASA NTRS1991

Theoretical study of the bonding of Nb(2+) to CH2, C2H2, and C2H4

The bonding of Nb(2+) with CH2, C2H2, and C2H4 is studied by using electronic structure calculations that include high levels of electron correlation. The binding energy for NbCH2(2+) is in good agreement with the lower bound determined from the reaction with CH4 but is significantly smaller than the value determined from the binding energy and ionization potential of NbCH2(+). The calculations and a new interpretation of the experiment indicate that the larger value is in error primarily because the ionization potential of NbCH2(+) determined from bracketing charge-exchange reactions is too small. The computed binding energy of NbC2H2(2+) is in good agreement with experiment. The calculations show that the bonding is predominantly covalent in character for both NbCH2(2+) and NbC2H2(2+), whereas for NbC2H4(2+) the electronic states that are predominantly ionic and covalent are nearly degenerate. The trend in binding energies, CH2 greater than C2H2 greater than C2H4, is consistent with the energy required to prepare the ligands for bonding.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1991

Optical constants of solid methane and ethane from 10,000 to 450/cm

Near- and mid-IR spectra of thin films of crystalling phase I and phase II C2H6 are presented using a combined least squares and Kramers-Kronig analysis. Complex refractive indices derived from these data are also presented. To obtain material in phase I, samples are annealed at 33 K for about 30 min; phase II is obtained by recooling below the transition temperature of 20.4 K. The derived optical parameters are shown. The infrared spectrum of phase I CH4 exhibits broad structureless absorptions at about 1300 and 2600/cm. On cooling the sample below 20.4 K (phase II), the absorptions are sharpened, and each band develops fine structure. The present results and those of Roux et al. (1979) are compared. The agreement with the real parts is found to be excellent; given the difference in resolution, the agreement with the imaginary parts is also good.

Pearl, J.↗

NASA NTRS1991

Properties of planetary fluids at high pressures and temperatures

Observational data obtained by the Voyager space probes to the giant planets Jupiter, Saturn, Uranus, and Neptune have provided valuable information, which is used to refine the picture of the nature of the interiors of these planets. Major results from the Voyager missions include observations of substantial magnetic fields and improved models of internal density distributions. The goal is to obtain equations of state and electrical conductivity data for planetary gases (H2 and He) and the ices (H2O, CH4, and NH3, and their mixtures), which are considered to be the major constituents of the giant planets. These data are needed to test theoretical data bases used to construct models of the chemical composition of planetary interiors, models which are consistent with observables such as mass, diameter, gravitational moments, rotation rate, and magnetic field. The 100 GPa (1 Mbar) pressures and several 1000 K temperatures in the giant planets can be achieved in the lab by the shock compression of liquid specimens. Results are briefly examined.

Nellis, W. J.↗

NASA NTRS1991

Spectroscopy of comets

Observations of NH2, OI, CH, CO(+), CO2(+), H2O(+), and N2(+) in optical spectra of comets represent ionization and dissociation product abundances of N2, NH3, H2O, CH4, CO2, and CO. The primary objectives are to determine: (1) accurate production rates for the observed species, and (2) accurate relative abundances of condensates in a sample of comet nuclei. The ultimate goal is to constrain models of comet formation and chemical processing in the outer primordial solar nebula.

Wyckoff, Susan↗

NASA NTRS1991

Production of organic compounds in plasmas: A comparison among electric sparks, laser-induced plasmas and UV light

In order to study the production of organic compounds in plasmas (and shocks), various mixtures of N2, CH4, and H2, modeling the atmosphere of Titan, were exposed to discrete sparks, laser-induced plasmas (LIP) and ultraviolet light. The yields of HCN and simple hydrocarbons were measured and compared to those calculated from a simple quenched thermodynamic equilibrium model. The agreement between experiment and theory was fair for HCN and C2H2. However, the yields of C2H6 and other hydrocarbons were much higher than those predicted by the model. Our experiments suggest that photolysis by ultraviolet light from the plasma is an important process in the synthesis. This was confirmed by the photolysis of gas samples exposed to the light, but not to the plasma or shock waves. The results of these experiments demonstrate that, in addition to the well-known efficient synthesis of organic compounds in plasmas, the yields of saturated species, e.g., ethane, may be higher than predicted by theory and that LIP provide a convenient and clean way of simulating planetary lightning and impact plasmas in the laboratory.

Scattergood, T. W.↗

NASA NTRS1991

The relative importance of prebiotic synthesis on the Earth and input from comets and meteorites

The prebiotic synthesis of hydrogen cyanide and formaldehyde was studied by the action of electric discharges on various model primitive atmospheres containing CH4, CO, and CO2. Photochemical production rates would also have been important and were calculated for HCN and H2CO. A reasonable rate of synthesis of amino acids from these sources is about 10 n moles/(sq cm yr) or 0.10 moles/sq cm in 10(exp 7) yrs. This would give a concentration of 3 x 10(exp -4) M in an ocean of the present size (300 liters/sq cm). The amino acids cannot accumulate over a longer period because the entire ocean passes through the 350 C submarine vents in 10(exp 7) yrs, which decomposes all the organic compounds. A number of workers have calculated the influx of comets and meteorites on the primitive earth, both as a destructive process for organic compounds and for any life that was present, as well as a source of organic compounds. Some of the amino acids from the meteorite proposed to have hit the earth 65 x 10(exp 6) yrs ago were detected at the Cretaceous/Tertiary boundary sediments. The problem with proposing a large scale input of organic compounds from meteorites and comets is that they must survive passage through the atmosphere and impact. There are some processes that would allow survival such as showers of centimeter to meter sized meteorites and various aerodynamic braking processes for larger objects. Even if a significant amount of the organic material survived impact, the destructive processes in the hydrothermal vents would remove these compounds on the average in 10(exp 7) yrs or less. If it is assumed that the input rate was sufficient to overcome these destructive processes, then too much carbon and water, especially from comets, would have been added to the surface of the earth. It was concluded that while some organic material was added to the earth from comets and meteorites, the amount available from these sources at a given time was only a few percent of that from earth based syntheses.

Miller, S. L.↗

NASA NTRS1991

Seals Research at Texas A/M University

The Turbomachinery Laboratory at Texas A&M has been providing experimental data and computational codes for the design seals for many years. The program began with the development of a Halon based seal test rig. This facility provided information about the effective stiffness and damping in whirling seals. The Halon effectively simulated cryogenic fluids. Another test facility was developed (using air as the working fluid) where the stiffness and damping matrices can be determined. This data was used to develop bulk flow models of the seal's effect upon rotating machinery; in conjunction with this research, a bulk flow model for calculation of performance and rotordynamic coefficients of annular pressure seals of arbitrary non-uniform clearance for barotropic fluids such as LH2, LOX, LN2, and CH4 was developed. This program is very efficient (fast) and converges for very large eccentricities. Currently, work is being performed on a bulk flow analysis of the effects of the impeller-shroud interaction upon the stability of pumps. The data was used along with data from other researchers to develop an empirical leakage prediction code for MSFC. Presently, the flow field inside labyrinth and annular seals are being studied in detail. An advanced 3-D Doppler anemometer system is being used to measure the mean velocity and entire Reynolds stress tensor distribution throughout the seals. Concentric and statically eccentric seals were studied; presently, whirling seals are being studied. The data obtained are providing valuable information about the flow phenomena occurring inside the seals, as well as a data base for comparison with numerical predictions and for turbulence model development. A finite difference computer code was developed for solving the Reynolds averaged Navier Stokes equation inside labyrinth seals. A multi-scale k-epsilon turbulence model is currently being evaluated. A new seal geometry was designed and patented using a computer code. A large scale, 2-D seal flow visualization facility is also being developed.

Morrison, Gerald L.↗

NASA NTRS1990

Evaluated rate constants for selected HCFC's and HFC's with OH and O((sup)1D)

The chemistry of HCFC's and HFC's in the troposphere is controlled by reactions with OH in which a hydrogen atom is abstracted from the halocarbon to form water and a halo-alkyl radical. The halo-alkyl radical subsequently reacts with molecular oxygen to form a peroxy radical. The reactions of HCFC's and HFC's with O(exp1D) atoms are unimportant in the troposphere, but may be important in producing active chlorine of OH in the stratosphere. Here, the rate constants for the reactions of OH and O(exp1D) with many HFC's and HCFC's are evaluated. Recommendations are given for the five HCFC's and three HFC's specified by AFEAS as primary alternatives as well as for all other isomers of C1 and C2 HCFC's and HFC's where rate data exist. In addition, recommendations are included for CH3CCl3, CH2Cl2, and CH4.

Hampson, Robert F.↗

NASA NTRS1989

Theory and observations: Model simulations of the period 1955-1985

The main objective of the theoretical studies presented here is to apply models of stratospheric chemistry and transport in order to understand the processes that control stratospheric ozone and that are responsible for the observed variations. The model calculations are intended to simulate the observed behavior of atmospheric ozone over the past three decades (1955-1985), for which there exists a substantial record of both ground-based and, more recently, satellite measurements. Ozone concentrations in the atmosphere vary on different time scales and for several different causes. The models described here were designed to simulate the effect on ozone of changes in the concentration of such trace gases as CFC, CH4, N2O, and CO2. Changes from year to year in ultraviolet radiation associated with the solar cycle are also included in the models. A third source of variability explicitly considered is the sporadic introduction of large amounts of NO sub x into the stratosphere during atmospheric nuclear tests.

Isaksen, Ivar S. A.↗