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At least 721 records · Page 40
All sourcesNASA NTRSDOE OSTI
NASA NTRS1987

Heavy carbon in individual oxide grains from the Murchison meteorite

The carbon isotopic composition of individual oxide grains from Murchison HF-HCl acid residue CFOc has been measured in the ion microprobe. Many grains contain carbon with large C-13 excesses ranging to 7000 per mil. In most cases the carbon is present as micron-sized subgrains. The association of silicon with the anomalous carbon points towards SiC as carrier. If this tentative identification is correct, then the SIC grains most likely originated in the circumstellar atmospheres of red giants. Oxide grains in which the O-18/O-16 ratio has also been measured show variable O-16 excesses which are not correlated with the C-13 excesses. This indicates that the sources of the anomalous carbon and oxygen isotopic compositions of the oxide grains are unrelated.

Zinner, Ernst↗
NASA NTRS1987

Glass properties in the yttria-alumina-silica system

The glass formation region in the yttria-alumina-silica system was investigated. Properties of glasses containing 25 to 55 wt pct yttria were measured and the effect of the composition was determined. The density, refractive index, thermal-expansion coefficient, and microhardness increased with increasing yttria content. The dissolution rate in 1N HCl increased with increasing yttria content and temperature. These glasses were also found to have high electrical resistivity.

Hyatt, M. J.↗
NASA NTRS1987

Reaction of chlorine nitrate with hydrogen chloride and water at Antarctic stratospheric temperatures

Laboratory studies of heterogeneous reactions important for ozone depletion over Antarctica are reported. The reaction of chlorine nitrate (ClONO2) with H2O and HCl on surfacers that simulate polar stratospheric clouds are studied at temperatures relevant to the Antarctic stratosphere. The gaseous products of the resulting reactions, HOCl, Cl2O, and Cl2, could readily photolyze in the Antarctic spring to produce active chlorine for ozone depletion. Furthermore, the additional formation of condensed-phase HNO3 could serve as a sink for odd nitrogen species that would otherwise scavenge the active chlorine.

Tolbert, Margaret A.↗
NASA NTRS1988

Simultaneous measurement of minor stratospheric constituents with emission far-infrared spectroscopy

The vertical mixing ratio profiles of H2O, HDO, O3, heavy ozone, HF, HCl, HCN, and OH in the stratosphere are retrieved from high-resolution far-infrared emission spectra. These spectra were obtained with a balloon-borne Fourier transform spectrometer in the spring of 1979 at 32 deg N. The nonlinear least squares fit method is used in the analysis. The results are obtained relative to the O2 mixing ratio, whose emission features can be found in the same spectra. The retrieval of OH together with other species should be particularly significant for the study of upper stratospheric photochemistry, although the errors are relatively large: 28 percent for OH and 16-19 percent for other species.

Carli, Bruno↗
NASA NTRS1988

Infrared measurements of column abundances of several trace gases in the Antarctic atmosphere

Atmospheric emission measurements were made in 1978 from an LC 130 aircraft from Point Mugu, CA, to McMurdo Station, Antarctica, and from McMurdo over the Antarctic continent on several different flights. These included a number of flights over the South Pole. In December 1980, infrared solar spectra were obtained from the ground at South Pole Station. Infrared solar spectra were also obtained from South Pole during late November and early December of 1986. These latter measurements were extended to cover additional spectral regions to obtain column densities of a number of additional constituents. The results obtained from these measurement series are reviewed and, where measurements were made during both periods, compared. Spectral absorption or emission features due to HNO3, NO, NO2, HCl, (H-16)2O, (H-18)2O, HDO, CH4, and N2O were used to obtain data on the total column abundances for these compounds.

Murcray, F. J.↗
NASA NTRS1988

Isotopic anomalies of Ne, Xe, and C in meteorites. I - Separation of carriers by density and chemical resistance

The carriers of presolar noble gases were studied by isotopically analyzing 19 separates from the Murray and Murchison C2 chondrites for Ne, Xe, C, and N. It is found that the carriers of Ne-E(H) and Xe-S are resistant to HCl, HF, boiling HClO4, and CrO3-H2SO4, and thus must be either diamond or some resistant carbide or oxide. The carrier of Ne-E(L) may be some form of amorphous carbon with delta C13 of about +340 percent. A new carbon component, C theta, found as 0.2-2-micron inclusions in Murchison spinel, is amorphous and contains little or no noble gas. A new heavy nitrogen component is found which has an abundance of about 1 ppm in the bulk meteorite, combusts at 450-500 C, and may be associated wtih isotopically normal carbon or with C-alpha.

Ming, Tang↗
NASA NTRS1988

Formation of polar stratospheric clouds simulated in a two dimensional model of the atmosphere

A microphysics code has been implemented in a two dimensional model of the atmosphere to study formation of polar stratospheric clouds containing HCl or HNO3. The model range is from pole to pole in latitude and from the ground to about 20 km in altitude. Resolution in latitude is 10 deg and about 0.8 km in altitude. This is an Eulerian model with prescribed eddy diffusion coefficients and the circulation obtained from observations. The chemistry of the model follows the family approach for NO(x), Cl(x) and HO(x) while the ozone is fixed and changed seasonally. The aerosol code is based on an assigned population of condensation, coagulation and sedimentation. Aerosol growth is simulated in nine different size bins ranging between 0.01u and 2.56u. The model has been built to study aerosol layers formation in the upper troposphere and lower stratosphere and has been validated for sulfate aerosol resulting from a rather complex sulfur chemistry.

Visconti, Guido↗
NASA NTRS1988

Laboratory studies of sticking coefficients and heterogeneous reactions important in the stratosphere

The discovery of ozone depletion during spring in the Antarctic stratosphere has received wide spread attention. Both meteorological and chemical mechanisms have been used in attempts to explain this observation. The chemical theory focused on the chlorofluoromethanes released into the atmosphere. However, gas-phase, homogeneous reactions alone in the model can not adequately explain such a depletion. Heterogeneous reactions on ice surfaces could be important in the Antarctic stratosphere. These reactions are thought to convert ClONO2 and N2O5 into HNO3 in the solid phase while Cl2, HOCl, and ClNO2 are released into the stratosphere as gas-phase products. The photolysis of Cl2, HOCl, and ClNO2, then produces active chlorine which subsequently removes ozone through several catalytic cycles, including the Cl2O2 mechanism. The polar stratospheric clouds are thought to consist of mixtures of water ice, nitric acid, and sulfuric acid. Condensation of HCl onto the PSC's could provide active surfaces for heterogeneous reactions.

Leu, Ming-Taun↗
NASA NTRS1988

Photochemical modeling of the Antarctic stratosphere: Observational constraints from the airborne Antarctic ozone experiment and implications for ozone behavior

The rapid decrease in O3 column densities observed during Antarctic spring has been attributed to several chemical mechanisms involving nitrogen, bromine, or chlorine species, to dynamical mechanisms, or to a combination of the above. Chlorine-related theories, in particular, predict greatly elevated concentrations of ClO and OClO and suppressed abundances of NO2 below 22 km. The heterogeneous reactions and phase transitions proposed by these theories could also impact the concentrations of HCl, ClNO3 and HNO3 in this region. Observations of the above species have been carried out from the ground by the National Ozone Expedition (NOZE-I, 1986, and NOZE-II, 1987), and from aircrafts by the Airborne Antarctic Ozone Experiment (AAOE) during the austral spring of 1987. Observations of aerosol concentrations, size distribution and backscattering ratio from AAOE, and of aerosol extinction coefficients from the SAM-II satellite can also be used to deduce the altitude and temporal behavior of surfaces which catalyze heterogeneous mechanisms. All these observations provide important constraints on the photochemical processes suggested for the spring Antarctic stratosphere. Results are presented for the concentrations and time development of key trace gases in the Antarctic stratosphere, utilizing the AER photochemical model. This model includes complete gas-phase photochemistry, as well as heterogeneous reactions. Heterogeneous chemistry is parameterized in terms of surface concentrations of aerosols, collision frequencies between gas molecules and aerosol surfaces, concentrations of HCl/H2O in the frozen particles, and probability of reaction per collision (gamma). Values of gamma are taken from the latest laboratory measurements. The heterogeneous chemistry and phase transitions are assumed to occur between 12 and 22 km. The behavior of trace species at higher altitudes is calculated by the AER 2-D model without heterogeneous chemistry. Calculations are performed for solar illumination conditions typical of 60, 70, and 80 S, from July 15 to October 31.

Rodriguez, Jose M.↗
NASA NTRS1988

Chemistry of chlorinated species in the Antarctic stratosphere

The chemistry of Cl sub 2 O sub 2, the chlorine monoxide dimer, has been further investigated in order to better asses its potential role in catalytic ozone destruction cycles. The dimer has been generated in a flow system, in the 200 to 250 K temperature range, by using ozone and chlorine atoms as ClO precursors. The Cl-atoms are produced by a microwave discharge of either Cl sub 2, or of F sub 2 with subsequent addition of HCl. With this later scheme the dimer can be generated in the absence of Cl sub 2. The Fourier transform infrared spectra of the products clearly indicates the presence of two isomers, in agreement with earlier results (J. Phys. Shen., 91, 433, 1987). None of the observed IR bands can be attributed to a ClO-OClO adduct, since they all appear in the absence of any detectable amount of OCl. It is likely that the particles in the polar stratospheric clouds will have a relatively dilute nitric acid outer layer, even if the core is the nitric acid monohydrate, since the particles are in equilibrium with the ambient water vapor, which is present at levels of a few parts per million.

Molina, Mario J.↗
NASA NTRS1988

Modelling the Antarctic lower stratosphere

Results form modeling studies of the Antarctic lower stratosphere which have attempted to simulate the large springtime ozone losses and corresponding changes in other trace constituents are given. These studies were carried out in a photochemical box model, a one-dimensional model without transport and in a two-dimensional photochemical-dynamical-radiation model. The photochemical studies have investigated inter alia the sensitivity of ozone to inclusion in the model of heterogeneous chemistry, and to the inclusion of the ClO dimer. When both of these are incorporated in the model, ozone depletions resembling whose found in Halley Bay in 1987 (J.C. Farman, Nature, 329, 1987) can be reproduced. The temporal variations (both diurnal and during the August to October period) of a number of important tracers including HCl, ClONO2, OClO and BrO are discussed. The two-dimensional study concentrated on the difficulty of establishing in the model the dynamical preconditioning of the lower polar stratosphere - low temperatures, low N2O, etc., high ClOx. Calculations are presented to show: (1) the depletion of ozone during the springtime season, (2) the effect of large ozone losses on lower latitudes, and (3) the longer term (multi-year) variations of ozone in Antarctica, assuming realistic increases in the atmospheric halogen burden.

Chipperfield, M. P.↗
NASA NTRS1988

Modelling the Antarctic ozone hole

Researchers performed model calculations of the ozone depletions taking place in the Antarctic lower stratosphere. Making the assumption that odd nitrogen is frozen out on stratospheric haze particles, an analysis is given of how much homogeneous reactions can contribute to ozone loss during September-October. Comparisons with observations indicate the potential importance of reactions with HCl in the polar stratospheric cloud particles.

Crutzen, P. J.↗
NASA NTRS1989

Halogen Occultation Experiment (HALOE) optical filter characterization

The Halogen Occultation Experiment (HALOE) is a solar occultation experiment that will fly on the Upper Atmosphere Research Satellite to measure mixing ratio profiles of O3, H2O, NO2, NO, CH4, HCl, and HF. The inversion of the HALOE data will be critically dependent on a detailed knowledge of eight optical filters. A filter characterization program was undertaken to measure in-band transmissions, out-of-band transmissions, in-band transmission shifts with temperature, reflectivities, and age stability. Fourier Transform Infrared Spectrometers were used to perform measurements over the spectral interval 400/cm to 6300/cm (25 micrometers to 1.6 micrometers). Very high precision (0.1 percent T) in-band measurements and very high resolution (0.0001 percent T) out-of-band measurements have been made. The measurements revealed several conventional leaks at 0.01 percent transmission and greatly enhanced (1,000) leaks to the 2-element filters when placed in a Fabry-Perot cavity. Filter throughput changes by 5 percent for a 25 C change in filter temperature.

Harvey, Gale A.↗
NASA NTRS1988

Crystallization of supercooled solutions

Crystallization of uniformly supercooled solutions (Na2SO4, NaCl, H2SO4, HNO3, HCl) was studied. It is shown how crystal growth velocity and habit depend on solution and concentration. The segregation coefficient for the solute in ice is measured by analysis of ice and solution, separated immediately after initial freezing, at different supercoolings. Subsequent solidification gives ion rejection at a varying rate depending on the geometry of the freezing, and may result in separation of hydrates, particularly when the initial concentration is high, as in haze (inactivated) droplets and low temperatures found in the Antarctic stratosphere. Electrical effects associated with rapid freezing are also investigated. Results suggest that more extensive measurements need to be made in solutions at different supercoolings, and that substantial electrical effects may be present for higher concentrations under these conditions. Damage to vegetation could occur under specific conditions as concentrated solutions (possibly H2SO4) are rejected in the freezing of rime or dew.

Harrison, K.↗
NASA NTRS1988

Chlorine-hydrocarbon photochemistry in the marine troposphere and lower stratosphere

The role of chlorine atoms in the oxidation of methane and nonmethane hydrocarbons (NMHCs) in the marine troposphere and lower stratosphere was investigated using a one-dimensional photochemical model that incorporated the chemistry of CH4, NMHCs, NO(x), O(x), and HO(x), as well as organic and inorganic halogens in the troposphere and lower stratosphere. The model predicted that chlorine atoms are present in the marine troposphere at the concentrations of about 1000/cu cm, mostly as a product of the reaction between OH and HCl released from sea spray. The results indicate that Cl atoms cause 20 to 40 percent of NMHC oxidation in the troposphere and 40 to 90 percent in the lower stratosphere. At 15 km, the NMHC-Cl reactions account for nearly 80 percent of the PAN produced. Where available, experimental data confirmed the model predictions.

Singh, H. B.↗
NASA NTRS1989

Impact of heterogeneous reactions on stratospheric chemistry of the Arctic

The possible depletion of ozone due to heterogeneous reactions occurring in Arctic polar stratospheric clouds (PSCs) is fundamentally different from the Antarctic situation. PSCs in the Arctic are relatively short-lived and occur over limited regions of the Arctic stratosphere. The Arctic situation is examined using a model which calculates photochemical processes as a function of longitude in air circulating with fixed velocity around the pole at fixed pressure level and latitude. The model allows sunlight to vary diurnally and PSCs to occur in specified subregions of the domain. Measurements of chemical species including HCl, ClO, NO2 and HNO3 downwind from a PSC should show obvious changes compared to measurements in air unaffected by clouds. These species concentrations are found to be sensitive to sticking coefficients, cloud characteristics including particle number density and surface area, and to the PSC exposure time.

Douglass, Anne R.↗
NASA NTRS1989

Ozone minimum occurs in Antarctica in the springtime

Observations on the formation of the Antarctic ozone hole in the upper atmosphere are summarized, and the mechanism responsible for the ozone depletion in the spring is examined. It is shown that the sequence of events begins with the absorption of H2O, N2O5, HCl, and ClONO2 on the cloud ice particles in the winter and chemical reactions among absorbed chemicals which release (HNO3)s, Cl2, HOCl, and ClNO2. With the return of sunlight in the spring, the clouds evaporate, and the Cl2, HOCl, and ClONO2 molecules are destroyed by sunlight to form Cl atoms. These attack ozone, producing a reduction of ozone that accounts for the bulk of the ozone decrease observed by the ground-based ozone monitors. Data on the ozone concentration for the period between 1957 through 1987 indicate that the southern ozone hole has been intensifying since 1975 as the amount of man-made chlorine increases.

Aikin, Arthur C.↗
NASA NTRS1990

A field study of solid rocket exhaust impacts on the near-field environment

Large solid rocket motors release large quantities of hydrogen chloride and aluminum oxide exhaust during launch and testing. Measurements and analysis of the interaction of this material with the deluge water spray and other environmental factors in the near field (within 1 km of the launch or test site) are summarized. Measurements of mixed solid and liquid deposition (typically 2 normal HCl) following space shuttle launches and 6.4 percent scale model tests are described. Hydrogen chloride gas concentrations measured in the hours after the launch of STS 41D and STS 51A are reported. Concentrations of 9 ppm, which are above the 5 ppm exposure limits for workers, were detected an hour after STS 51A. A simplified model which explains the primary features of the gas concentration profiles is included.

Anderson, B. J.↗