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At least 343 records · Page 19

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NASA NTRS1985

The rainout parameterization in a photochemical model

Photochemical models of tropospheric trace species typically simulate the effects of wet removal of soluble species from the atmosphere through a first-order rainout parameterization, which is independent of the species solubility and constant in time. In this work a modified first-order rainout parameterization is proposed that is a function of the species' solubility and takes into account the intermittent nature of atmospheric wet removal. In the case of a highly soluble species, such as HNO3, the inclusion of the effects of intermittent rainout in the parameterization leads to averaged rainout lifetimes considerably higher than ones used in most photochemical models. For illustrative purposes this parameterization is applied to a one-dimensional steady state model with parameterized eddy diffusion, although in principle it can be used in more sophisticated multidimensional models. The model results are compared to analagous calculations obtained with a 3-D tracer transport model.

Giorgi, F.↗

NASA NTRS1985

Microwave limb sounder for stratospheric measurements

The balloon-borne Microwave Limb Sounder (BMLS) measures atmospheric thermal emission from millimeter wavelength spectral lines to determine vertical profiles of stratospheric species. The instrument flown to data operates at 205 BHz to measure ClO, O3, and H2O2. A 63 GHz radiometer is added to test the technique for determining tangent point pressure from the MLS experiment on the Upper Atmosphere Research Satellite (UARS). Many additional species is also measured by the BLMS. A radiometer at 270 GHz would provide measurements of HO2, NO2, HNO3, N2O, 16O18O16O, and HCN. With this addition the BMLS can test the current theory of O3 heavy ozone photochemical balance in the upper stratosphere.

Waters, J. W.↗

NASA NTRS1986

Boron determination in steels by Inductively-Coupled Plasma spectometry (ICP)

The sample is treated with 5N H2SO4 followed by concentrated HNO3 and the diluted mixture is filtered. Soluble B is determined in the filtrate by Inductively-Coupled Plasma (ICP) spectrometry after addition HCl and extraction of Fe with ethyl-ether. The residue is fused with Na2CO3 and, after treatment with HCl, the insoluble B is determined by ICP spectrometry as before. The method permits determination of ppm amounts of B in steel.

Coedo, A. G.↗

NASA NTRS1985

Surface effects of corrosive media on hardness, friction, and wear of materials

Hardness, friction, and wear experiments were conducted with magnesium oxide exposed to various corrosive media and also with elemental iron and nickel exposed to water and NaOH. Chlorides such as MgCl2 and sodium containing films were formed on cleaved magnesium oxide surfaces. The MgCl2 films softened the magnesium oxide surfaces and caused high friction and great deformation. Hardness was strongly influenced by the pH value of the HCl-containing solution. The lower the pH, the lower the microhardness. Neither the pH value of nor the immersion time in NaOH containing, NaCl containing, and HNO3 containing solutions influenced the microhardness of magnesium oxide. NaOH formed a protective and low friction film on iron surfaces. The coefficient of friction and the wear for iron were low at concentrations of NaOH higher than 0.01 N. An increase in NaOH concentration resulted in a decrease in the concentration of ferric oxide on the iron surface. It took less NaOH to form a protective, low friction film on nickel than on iron.

Miyoshi, K.↗

NASA NTRS1985

An upper limit to the rate of the HCl + ClONO2 reaction

The reaction HCl + ClONO2 yields Cl2 + HNO3 has been studied by Fourier transform infrared spectroscopy and by a static wall-less UV absorption technique. An upper limit to the homogeneous bimolecular rate constant of 10 to the -19th cu cm/molecule per sec was established, making the reaction unimportant in the stratosphere.

Molina, L. T.↗

NASA NTRS1985

Synopsis of the Fifth Conference on the Meteorology of the Stratosphere and Mesosphere

The papers presented at the Fifth Conference on the Meteorology of the Stratosphere and Mesosphere held on April 23-26, 1985, are reviewed. The observational aspects of large-scale circulation, such as summer and winter circulation in the Southern Hemisphere, and analysis schemes, like the multivariate statistical analysis scheme, are discussed. The topics of numerical simulations of the general circulation and sudden-warming are examined. Papers concerning processes of O3, NO2, H2, and HNO3 are described. Research on large-scale mixing processes in the stratosphere is presented. The topic of equatorial dynamics and stability is analyzed. Papers focusing on the effect of gravity waves on the general circulation are studied.

Schoeberl, M. R.↗

NASA NTRS1986

Inversion of limb radiance measurements - An operational algorithm

The limb radiance inversion radiometer (LRIR) and limb infrared monitor of the stratosphere (LIMS) experiments aboard the Nimbus 6 and 7 spacecraft have made observations of infrared emission by CO2, O3, H2O, HNO3, and NO2 at the earth's limb. This paper describes a method by which such measurements can be inverted to give vertical distributions of temperature and mixing ratios as functions of pressure. The simple and efficient approach was successfully applied to the LRIR data and subsequently in the initial assessment of the LIMS data. Inversion of synthetic data indicates the size of the errors to be expected as a result of the assumptions and instrumental errors. Retrievals of measured LIMS radiances are shown as examples and compared to in situ observations. The differences are comparable to those obtained with the more complex retrieval scheme used to process the LIMS archival products. Some problems are noted.

Bailey, P. L.↗

NASA NTRS1985

Evaluation of a catalytic reduction technique for the measurement of total reactive odd-nitrogen NOy in the atmosphere

The suitability of a technique for the measurement of total reactive odd-nitrogen NOy-containing species in the atmosphere has been examined. In the technique, an NOy component species, which may include NO, NO2, NO3, HNO3, peroxyacetyl nitrate, and particulate nitrate, are catalytically reduced by CO to form NO molecules on the surface of a metal converter tube, and the NO product is detected by chemiluminescence produced in reaction with O3. Among the catalysts tested in the temperature range of 25-500 C, Au was the preferred catalyst. The results of laboratory tests investigating the effects of pressure, O3, and H2O on NOy conversion, and the possible sources of interference, have shown that the technique is suitable for atmospheric analyses. The results of a test in ambient air at a remote ground-based field site are included.

Fahey, D. W.↗

NASA NTRS1986

Global distribution of peroxyacetyl nitrate

Peroxyacetyl nitrate (PAN) atmospheric concentration samples were collected hourly from an ocean vessel 50 mi off the continental coast traveling from Seattle to Chile in 1984. Air concentration data for PAN and light hydrocarbons (LHC) were also taken by aircraft in the same period over Wyoming and Colorado and over the eastern Pacific. The PAN concentrations were higher and more variable in the Northern Hemisphere than in the Southern Hemisphere, increased with altitude, and were higher in the winter than in summer. The summer PAN concentrations were higher in the continental troposphere than in the marine troposphere. The results show that photochemical models of the atmosphere which do not account for the reaction between nonmethane hydrocarbons and PAN will probably overestimate the abundances of NO(x) and HNO3. The collection of further PAN concentration data is recommended as a means to characterizing the moderating role of PAN in the photochemistry of the troposphere.

Singh, H. B.↗

NASA NTRS1985

LIMS data - Inferred stratospheric distribution of NOx and HOx trace constituents and the calculated odd nitrogen budget

LIMS, SAMS, SBUV and in-situ data have been used to infer species not measured but which are of photochemical interest, e.g., O(3P), O(1D), NO, N2O5, OH, HO2, ClO and HCl. (LIMS = limb infrared monitor of the stratosphere; SAMS = stratospheric and mesospheric sounder; and SBUV = solar backscattered ultraviolet instrument.) Production and loss of odd nitrogen have been calculated and estimates have been made of the odd nitrogen transport due to adiabatically driven circulation derived from LIMS data. Data used from LIMS include O3, NO2, HNO3, H2O and T. CH4 and N2O were taken from SAMS and the UV solar flux from the SBUV instrument. Species were inferred for periods in October, December, March and May. Results for December are discussed. Results indicate: (1) maximum stratospheric odd nitrogen levels of 25 ppbv; (2) evidence of odd nitrogen transport from the mesosphere appearing at 25 km in the wintertime polar latitudes; (3) the polar night build-up of high levels of N2O5 beginning after the autumnal equinox; and (4) the possibility of large downward fluxes of odd nitrogen into the troposphere during the winter at latitudes poleward of 60 degrees.

Callis, L. B.↗

NASA NTRS1987

Atlas of Absorption Lines from 0 to 17900 Cm (sup)-1

Plots of logarithm (base 10) of absorption line strength versus wavenumber from 0 to 17900/cm(sup)-1 are shown for the 28 atmospheric gases (H2O, CO2, O3, N2O, CO, CH4, O2, NO, SO2, NO2, NH3, HNO3, OH, HF, HCl, HBr, HI, ClO, OCS, H2CO, HOCl, N2, HCN, CH3Cl, H2O2, C2H2, C2H6, PH3), which appear in the 1986 Air Force Geophysics Laboratory high-resolution transmission molecular absorption data base (HITRAN) compilation, and for O(P-3), O-18 isotopic ozone, and HO2 from the 1984 JPL compilation in the 0- to 200/cm(sup)-1 region, and infrared solar CO lines at 4500 K. Also shown are plots of logarithm (base 10) of approximate infrared absorption cross sections of 11 heavy molecules versus wavenumber. The cross-section data cover 700 to 1800/cm(sup)-1 and are included as a separate data file in the 1986 HITRAN database.

Park, J. H.↗

NASA NTRS1986

Pressure and temperature dependences of the reaction of OH with nitric acid

Rate constants for the reaction of OH with HNO3 have been measured by using a laser flash photolysis resonance absorption technique at 298 and 248 K in the presence of 10-730 Torr of He, N2, and SF6. A dependence on total pressure was observed with rate constant values increasing at 298 K from 1.11 x 10 to the -13th cu cm/molecule/s at 10 Torr to 1.45 x 10 to the -13th cu cm/molecule/s at 730 Torr, and at 248 K from 1.87 x 10 to the -13th cu cm/molecule/s at 10 Torr to 3.07 x 10 to the -13th cu cm/molecule/s at 730 Torr with helium as the diluent gas. Falloff behavior occurred at lower pressures with SF6 or N2 as the diluent gas. Extrapolated zero pressure rate constants were determined and correspond to an Arrhenius activation energy of E/R = -710 K.

Stachnik, R. A.↗

NASA NTRS1986

Antarctic O3 - Chemical mechanisms for the spring decrease

Chemical explanations for the spring decline of Antarctic O3 involve reactions of ClO or interactions between BrO and ClO. Reaction schemes involving Br radicals have the highest efficiency for removal of O3. The chemical mechanisms require low levels of NO(x). Recent cooling of the stratosphere may have triggered formation of HNO3 monohydrate, removing NO(x) and setting the stage for enhanced loss of ozone over Antarctica.

Mcelroy, Michael B.↗

NASA NTRS1986

Reactions of chlorine nitrate with HCl and H2O

The kinetics of the reactions of chlorine nitrate with HCl and H2O are characterized using a static photolysis/Fourier transform infrared spectrophotometer apparatus. For the homogeneous gas-phase reaction with HCl, an upper limit for the rate constant of less than 8.4 x 10 to the -21st, and for the reaction with H2O, a limit of less than 3.4 x 10 to the -21st cu cm/molecule per s, were obtained at 296 + or - 2 K. The yield of HNO3 is almost unity in both cases, and no synergistic effect is noted between HCl and H2O. The kinetic behavior of the reaction with H2O is well described by simple first-order kinetics, while the behavior of the reaction with HCl is described in terms of the Langmuir adsorption isotherm.

Hatakeyama, Shiro↗

NASA NTRS1986

A kinetics study of the homogeneous and heterogeneous components of the HCl + ClONO2 reaction

The kinetics of the reaction HCl + ClONO2 to Cl2 + HNO3 were investigated at 298 K using a flow reactor with FTIR analysis to assess the importance of this reaction for stratospheric chemistry. The observed reaction was characteristic of a heterogeneous process; an upper limit of 5 x 10 to the -18th cu cm/molecule per s was obtained for the homogeneous gas phase rate constant. From calculations of the first order wall rate constant, estimates were made of the reaction rate on stratospheric aerosols. Because both HCl and ClONO2 need to be adsorbed on the particle surface, the reaction will be of negligible importance under most stratospheric conditions.

Friedl, Randall R.↗

NASA NTRS1986

Balloon-borne cryogenic spectrometer for measurement of lower stratospheric trace constituents

A liquid-nitrogen cooled, multidetector Fourier transform spectrometer has been constructed to measure minor stratospheric constituents via high resolution, earth-limb emission spectroscopy from a balloon-borne platform. Cryogenic cooling, combined with the use of extrinsic silicon photoconductor detectors cooled to liquid-helium temperature, allows the detection of weak emission features of gaseous species. The spectrometer has two basic scan modes: the first mode records the continuous spectrum from 650-2100/cm with 0.2/cm resolution; the second simultaneously records four preselected narrow intervals (about 175/cm bandpass each) with 0.02/cm resolution, unapodized. Filtering of the interferogram signal is done by real-time, digital signal processing. The most important feature of this flat mirror Michelson system, with respect to remote balloon-borne operation, is the dynamic alignment system which maintains the relative parallelism of the two flat reflectors of the interferometer. Species identified to date in data obtained during a Nov. 6, 1984, flight include: CO2, O3, H2O, CH4, HNO3, N2O, NO2, NO, CCl3F (Freon-11) and CF2Cl2 (Freon-12).

Brasunas, J. C.↗

NASA NTRS1987

Infrared spectroscopy of the lower stratosphere with a balloon-borne cryogenic Fourier spectrometer

The IR limb emission of the lower stratosphere has been measured using a balloon-borne liquid nitrogen-cooled Michelson interferometer with liquid helium-cooled Si:Ga detectors. Portions of the thermal emission spectrum have been recorded between 650 and 2000/cm with an unapodized spectral resolution of 0.03/cm. This is the highest spectral resolution limb emission thus far obtained. A preliminary description is given of these data along with a discussion of the significant features. Species identified to date include CO2, O3, CFCl3, CF2Cl2, H2O, CH4, HNO3, N2O, NO2, and ClONO2. A tentative identification is made for NO, representing the first direct spectroscopic detection of NO in emission.

Kunde, Virgil G.↗

NASA NTRS1987

The use of atmospheric measurements to constrain model predictions of ozone change from chlorine perturbations

Atmospheric photochemistry models have been used to predict the sensitivity of the ozone layer to various perturbations. These same models also predict concentrations of chemical species in the present day atmosphere which can be compared to observations. Model results for both present day values and sensitivity to perturbation depend upon input data for reaction rates, photodissociation rates, and boundary conditions. A method of combining the results of a Monte Carlo uncertainty analysis with the existing set of present atmospheric species measurements is developed. The method is used to examine the range of values for the sensitivity of ozone to chlorine perturbations that is possible within the currently accepted ranges for input data. It is found that model runs which predict ozone column losses much greater than 10 percent as a result of present fluorocarbon fluxes produce concentrations and column amounts in the present atmosphere which are inconsistent with the measurements for ClO, HCl, NO, NO2, and HNO3.

Douglass, Anne R.↗