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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.↗

NASA NTRS1990

Deformation and fracture of aluminum-lithium alloys: The effect of dissolved hydrogen

The effects of dissolved hydrogen on the mechanical properties of 2090 and 2219 alloys are studied. The work done during this semi-annual period consists of the hydrogen charging study and some preliminary mechanical tests. Prior to SIMS analysis, several potentiostatic and galvanostatic experiments were performed for various times (going from 10 minutes to several hours) in the cathodic zone, and for the two aqueous solutions: 0.04N of HCl and 0.1N NaOH both combined with a small amount of As2O3. A study of the surface damage was conducted in parallel with the charging experiments. Those tests were performed to choose the best charging conditions without surface damage. Disk rupture tests and tensile tests are part of the study designed to investigate the effect of temperature, surface roughness, strain rate, and environment on the fracture behavior. The importance of the roughness and environment were shown using the disk rupture test as well as the importance of the strain rate under hydrogen environment. The tensile tests, without hydrogen effects, have not shown significant differences between low and room temperature.

Rivet, F. C.↗

NASA NTRS1989

Cryogenic Limb Array Etalon Spectrometer (CLAES) - Experiment overview

The Cryogenic Limb Array Etalon Spectrometer (CLAES) is one of a complement of instruments on the NASA Upper Atmosphere Research Satellite which is expected to study atmospheric photochemistry, energy input, and dynamics following a 1991 launch. CLAES measures stratospheric altitude profiles of temperature, pressure, O3, H2O, CH4, N2O, NO, NO2, N2O5, HNO3, ClONO2, HCl, CFC-11, and CFC-12. These data are obtained typically between 10 and 60 km, with 2.5-km vertical resolution and 500-km horizontal grid size. Coverage is obtained between latitudes 80 deg north and south, thereby providing substantial coverage of the Antarctic spring polar ozone-hole region. CLAES derives the listed geophysical parameters from measurement of earth-limb spectral emissions between 3.5 and 13 microns. Brief discussions of the measurement concept, instrument design, and performance are presented, followed by a more detailed discussion of scientific capabilities and measurement modes.

Roche, Aidan E.↗

NASA NTRS1989

Nitrogen and chlorine species in the spring Antarctic stratosphere - Comparison of models with Airborne Antarctic Ozone Experiment observations

The concentrations and the time development of chlorine and nitrogen trace gases in the Antarctic stratosphere before, during, and after the Airborne Antractic Ozone Experiment (AAOE) were simulated using photochemical models of the Antractic stratosphere during winter/spring. The initial conditions in the calculations were constrained using observations by the AAOE instrument. The comparison of calculated results with the AAOE measurements of HCl and ClO suggest that heterogeneous chemistry was maintained throughout the month of September 1987.

Rodriguez, J. M.↗

NASA NTRS1990

Measurement of threshold temperature effects in dissociative electron attachment to HI and DI

From accurate spectroscopic constants it is found that the thermal dissociative-attachment process (DA) in DI should be exothermic only for rotational levels J greater than 8 in v = O. Here, measurement of an enhancement of DA with rotational temperature T in the range 298-468 K is reported. The effect is easily accounted for by the increase in total fractional population of excited J levels in DI relative to HI. The effect affords a rotational analog to the use of vibrationally excited molecules (e.g., HCl) in a plasma to control electron conduction.

Chutjian, A.↗

NASA NTRS1990

Incorporation of stratospheric acids into water ice

Hydrochloric and hydrofluoric acids are absorbed within the water ice lattice at mole fractions maximizing below 0.00001 and 0.0001 in a variety of solid impurity studies. The absorption mechanism may be substitutional or interstitial, leading in either case to a weak permeation of stratospheric ices by the acids at equilibrium. Impurities could also inhabit grain boundaries, and the acid content of atmospheric ice crystals will then depend on details of their surface and internal microstructures. Limited evidence indicates similar properties for the absorption of HNO3. Water ice lattices saturated with acid cannot be a significant local reservoir for HCl in the polar stratosphere.

Elliott, Scott↗

NASA NTRS1990

Heterogeneous conversion of COF2 to HF in polar stratospheric clouds

It is argued that the reaction COF2 + H2O - 2HF + CO2 should proceed on surfaces of polar stratospheric clouds, based on laboratory evidence for this reaction in condensed phase and on analysis of column observations of HF during the Airborne Arctic Stratospheric Expedition. If the hypothesis is confirmed, observations of COF2 and HF could provide unambiguous indication of heterogeneous processing of polar air, and could help elucidate the influence of heterogeneous chemistry on concentrations of HCl, ClNO3, and chlorine oxide radicals.

Wofsy, Steven C.↗

NASA NTRS1990

The polar stratospheric cloud event of January 24. II - Photochemistry

During the 1988/89 Airborne Arctic Stratospheric Expedition (AASE), observations of the chemical composition, aerosol characteristics and atmospheric state were obtained from two aircraft, a NASA ER-2 and a DC-8. This paper presents a diagnosis of observations obtained using the ER-2 on January 24, 1989, using a Lagrangian coupled microphysical-photochemical model. The high chlorine monoxide mixing ratios observed from the ER-2 on the afternoon of January 24, 1989 are interpreted as a result of in situ heterogeneous release of reactive chlorine from the reservoirs HCl and CIONO2 on type-1 polar stratospheric cloud particles observed to be present at that time. This essential element in theories of polar ozone depletion has never before been observed directly in the stratosphere.

Jones, R. L.↗

NASA NTRS1990

The Balloon Intercomparison Campaigns - An introduction and overview

The Balloon Intercomparison Campaigns of 1982 and 1983 involved a comparison of measurements by 21 instruments from seven countries, assembled on four gondolas, assigned to collect data on the vertical profiles of HCl, HNO3, NO2, NO, O3, and many other stratospheric constituents. Most of these sensors supplied data on more than two constituents. This paper describes the instruments and the constituents measured by each of the sensor and the parameters of each balloon flight, together with some results.

Watson, R. T.↗

NASA NTRS1990

Heterogeneous reactions on nitric acid trihydrate

The first direct measurements are reported of the reaction probabilities at stratospheric temperatures for two important heterogeneous reactions on nitric acid trihydrate (NAT), the compound which makes up the predominant, type I form of polar stratospheric cloud (PSC). Sticking coefficients and solubilities of HCl and NAT, which are important in modeling physicochemical processes in the stratosphere, are also reported. The results show that the conversion of the chlorine reservoir species in the stratosphere to photochemically active forms can occur within a few days of the first appearance of type I PSCs during the polar winter.

Moore, S. B.↗

NASA NTRS1990

Tracking atmospheric trace gases by spectroscopy from Kitt Peak

Researchers analyzed solar spectra obtained with the 1-m Fourier Transfer Spectrometer (FTS) for absorption by CO2, CH4, N2, CO, HF, and HCl. During the period 1979 to 1985, they found that the CO2 total column amount was increasing 0.4 percent/year, CH4 was up 1.1 percent/year, while N2O shows no detectable trend. CO undergoes a large seasonal variation that masks any long-term trend within the observational time span. Stratospheric HF doubles in strength, displaying a conspicuous single-point increase that coincided with the mystery volcanic event of that era. Researchers are now attempting to resume the observations as resources permit.

Wallace, Lloyd↗

NASA NTRS1990

Electrochemical impedance spectroscopy of metal alloys in the space transportation system launch environment

AC impedance measurements were performed to investigate the corrosion resistance of 18 alloys under conditions similar to the Space Transportation System (STS) launch environment. The alloys were: (1) zirconium 702; (2) Hastelloy C-22, C-276, C-4, and B-2; (3) Inconel 600 and 825; (4) Ferralium 255; (5) Inco Alloy G-3; (6) 20Cb-3; (7) SS 904L, 304LN, 316L, 317L, and 304L; (8) ES 2205; and (9) Monel 400. AC impedance data were gathered for each alloy at various immersion times in 3.55 percent NaCl-0.1N HCl. Polarization resistance values were obtained for the Nyguist plots at each immersion time using the EQUIVALENT CIRCUIT software package available with the 388 electrochemical impedance software. Hastelloy C-22 showed the highest overall values for polarization resistance while Monel 400 and Inconel 600 had the lowest overall values. There was good general correlation between the corrosion performance of the alloys at the beach corrosion testing site, and the expected rate of corrosion as predicted based on the polarization resistance values obtained. The data indicate that electrochemical impedance spectroscopy can be used to predict the corrosion performance of metal alloys.

Calle, Luz↗

NASA NTRS1991

Sources of volcanic aerosols: Petrologic and volcanological constraints

Global climatic effects brought about by volcanism are related to the impact of volcanic gases and their derivative aerosols on the atmosphere, rather than the effects of volcanic ash. Evidence from both historic eruptions and polar ice cores indicate that volcanic sulfur gases are the dominant aerosol-forming component, resulting in produciton of a sulfuric acid-rich stratosphere aerosol that can have profound effects on the earth radiation budget over periods of a few years. Due to highly variable sulfur content of different magma types, the climatic effects do not relate simply to total erupted mass. There is a close relationship between volcanic sulfur yield to the atmospheric and hemispheric surface temperature decrease following an eruption, with up to 1 C surface temperature decrease indicated following a major volcanic event such as the 1815 Tambora eruption. While the erupted mass of HCl and HF is equal to or greater than that of sulfur gases in some volcanic events, the halogens do not form known aerosols nor are they abundant in ice core acidity layers. The early removal of halogens from eruption columns occurs by rain flushing and adsorption onto tephra particles, but the fate of halogens in the atmosphere following very large explosive eruptions is unknown. The CO2 flux to the atmosphere from volcanic eruptions is volumetrically one of the most important of the gas species, but owing to the huge size of the atmospheric reservoir of this gas, the volcanic contribution is likely to have negligible effects.

Sigurdsson, Haraldur↗