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At least 253 records · Page 14

Some aspects of stratospheric chemical response to solar particle precipitations. I - Potential roles of N2/A3Sigma/ and ion-chemistry

Large amounts of long lived N2(A3Sigma) are created by the energy degradation of precipitating solar particles. Laboratory data suggest that in the stratosphere N2(A3Sigma) are efficiently converted into N2O. Through reactions with O(1D), N2O may gradually release NO and thereby influence the long term aspects of stratospheric chemical response. During the daytime, negative ions may transform an active NO(x) into an inactive HNO3. At night both negative and positive ion chemistry generate HO(x). Omission of ionic chemistry results in considerable underestimation of O3 depletion during the initial phases of solar particle events, and thereby introduces significant error in the estimation of the nature of the prompt response.

Prasad, S. S.↗

Temperature and composition measurements from the l.r.i.r. and l.i.m.s. experiments on Nimbus 6 and 7

The limb radiance inversion radiometer (LRIR) on Nimbus 6 was the first orbiting infrared limb scanner; it has four channels with which to determine temperature, O3, and H2O in the stratosphere and low mesosphere. The limb infrared monitor of the stratosphere (LIMS) is a similar six-channel instrument which was launched on Nimbus 7 in October 1978 in order to measure O3, H2O, NO2, and HNO3. The instrumentation and inversion techniques are briefly described, and the application of limb scanner data to the study of photochemical, dynamical, and transport problems is discussed.

Gille, J. C.↗

An experiment concept to measure stratospheric trace constituents by Laser Heterodyne Spectroscopy

The concept and techniques of a Laser Heterodyne Spectrometer experiment for measuring the vertical profiles of several stratospheric trace gases are discussed. The goal of the experiment is to develop a laser heterodyne receiver capable of measuring 2-4 gases simultaneously from Spacelab and, ultimately, from free-flying platforms. Sensitivity analyses are currently being performed for tenuous molecules such as ClO, ClONO2, NOCl, HO2, H2O2, and N2O5, although the capability exists for measuring more abundant gases, such as O3, HNO3, N2O, NO2, and CH4. Results indicate that O3 and ClO vertical profiles can be measured with an accuracy equal to or better than 95% and 80%, respectively, over the total profile. Laboratory measurements of the performance characteristics of the local oscillator and heterodyne detector are discussed with reference to 'excess-noise' and Doppler-shift effects.

Allario, F.↗

AFGL trace gas compilation - 1980 version

A new edition of the AFGL trace gas compilation is now available. Absorption line parameters of positions, intensities, and half-widths are given for the major bands of thirteen gases covering the spectral region from 0 to 10,000/cm. In addition to updating the original gases (NO, SO2, NO2, and NH3), the molecules HNO3, OH, HF, HCl, HBr, HI, ClO, OCS, and H2CO have been added to the compilation. The sources for the additions and modifications are described.

Rothman, L. S.↗

Tropospheric chemistry - A global perspective

Processes that affect the concentration of tropospheric OH are considered, taking into account linkages between the chemistry of OH and the chemistry of H, HO2, and H2O2. A review is presented of observational data of special relevance to OH, notably the distributions of CO, CH4, O3, H2O, HNO3, NO, and NO2. Most of the results presented in connection with the description of the model were obtained by solving time-dependent continuity equations. Rates for photolytic processes were allowed to vary diurnally with insolation. It is found that a well-calibrated and reliable model for OH places important constraints on global budgets for a variety of gases including CH4, H2, and CH3Cl in addition to CO. Accurate measurements of species such as CH3CCl3 can provide valuable checks on global models that must integrate over a variety of atmospheric conditions. However, emission rates for the relevant gases must be adequately quantified.

Logan, J. A.↗

A fast and accurate radiance algorithm for application to inversion of limb measurements

A method is devised to accurately calculate broad band limb radiance based on a precalculated data base consisting of homogeneous path emissivity as a function of mass path data for various temperatures and pressures. Accurately estimating limb radiance by splicing together interpolated information from the emissivity curves requires no temperature or pressure weighting, and only two interpolations per layer path. The emissivity growth approximation (EGA) technique is applied in a simulated inversion study to the inference of O3, H2O, NO2 and HNO3, and it is found to have comparable accuracies to more sophisticated many-degree band models. The EGA technique is also found to be two orders of magnitude faster, while requiring one second per inversion for one constituent at one-km resolution, allowing a completely nonlinear relaxation time inversion to be done at linear speeds. The technique is also expected to work well for nadir calculations, and prove adequate for estimating occultation radiances.

Gordley, L. L.↗

Atlas of absorption lines from 0 to 17 900 cm(-1)

Plots of absorption line strength versus line position for wavenumbers from 0 to 17,900 cm(-1) are shown for 20 atmospheric gases (H2O, CO2, O3, N2O, CO, CH4, O2, NO, SO2, NO2, NH3, HNO3, OH, HF, HCl, HBr, HI, ClO, OCS, H2CO). Also shown are similar plots of lower-state energy values for adsorption lines for the strongly adsorbing atmospheric gases (H2O, CO2, O3, and CH4) for wavenumbers from 0 to 5000 cm(-1).

Park, J. H.↗

Friction and Wear of Iron in Corrosive Media

Friction and wear experiments were conducted with elemental iron exposed to various corrosive media including two acids, base, and a salt. Studies involved various concentrations of nitric and sulfuric acids, sodium hydroxide, and sodium chloride. Load and reciprocating sliding speed were kept constant. With the base NaOH an increase in normality beyond 0.01 N resulted in a decrease in both friction and wear. X-ray photoelectron spectroscopy (XPS) analysis of the surface showed a decreasing concentration of ferric oxide (Fe2O3) on the iron surface with increasing NaOH concentration. With nitric acid (HNO3) friction decreased in solutions to 0.05 N, beyond which no further change in friction was observed. The concentration of Fe2O3 on the surface continued to increase with increasing normality. XPS analysis revealed the presence of sulfates in addition of Fe2O3 on surfaces exposed to sulfuric acid and iron chlorides but no sodium on surfaces exposed to NaCl.

Rengstorff, G. W. P.↗

Atmospheric cycles of nitrogen oxides and ammonia

The atmospheric cycles of nitrogenous trace compounds for the Northern and Southern Hemispheres are discussed. Source strengths and destruction rates for the nitrogen oxides: NO, NO2 and HNO3 -(NOX) and ammonia (NH3) are given as a function of latitude over continents and oceans. The global amounts of NOX-N and NH3-N produced annually in the period 1950 to 1975 (34 + 5 x one trillion g NOx-N/yr and 29 + or - 6 x one trillion g NH3-N/yr) are much less than previously assumed. Globally, natural and anthropogenic emissions are of similar magnitude. The NOx emission from anthropogenic sources is 1.5 times that from natural processes in the Northern Hemisphere, whereas in the Southern Hemisphere, it is a factor of 3 or 4 less. More than 80% of atmospheric ammonia seems to be derived from excrements of domestic animals, mostly by bulk deposition: 24 + or - 9 x one trillion g NO3 -N/yr and 21 + or - 9 x one trillion g NH4+-N/yr. Another fraction may be removed by absorption on vegetation and soils.

Bottger, A.↗

Tropospheric passive remote sensing: Introduction

Measurement needs regarding chemical and transport parameters were identified. Measurement of those gases involved in tropospheric photochemistry (O3, CO, CH4, NOx, HNO3, SO2, NH3, and CH3CCl3) and quantification of their sources and sinks, as well as a fundamental understanding of atmospheric chemical transformations were discussed. The photochemistry of OH and its role as a sink are summarized. The concentrations and lifetimes of the tropospheric gases were considered. Major concerns in tropospheric transport are the making of representative remote measurements of trace gases and aerosols and the dependence of these measurements on structural differences in the atmosphere.

Source record↗

Is there any chlorine monoxide in the stratosphere?

A ground based search for the 856.50137/cm R(9.5) and for the 859.76765 R(12.5) transitions of stratospheric (Cl-35)O was made in the solar absorption mode using an infrared heterodyne spectrometer. Lines due to stratospheric HNO3 and tropospheric OCS were detected, at about 0.3% absorption levels. The expected lines of ClO in this same region were not detected, even though the optical depth of the ClO lines should be on the order of 0.2% using currently accepted ClO abundances. These infrared measurements suggest that stratospheric ClO is at least a factor of 7 less abundant than is indicated by indirect in situ fluorescence measurements, and the upper limit of 2.4x10 to the 13th power molecules/sq cm to the integrated column density of ClO is a factor of over 4 less than is indicted by microwave measurements. Results imply that the release of fluorocarbon precursors of ClO may be significantly less important for the destruction of stratospheric ozone than was previously thought.

Rogers, J. D.↗

Influence of corrosive solutions on microhardness and chemistry of magnesium oxide /001/ surfaces

X-ray photoelectron spectroscopy analyses and hardness experiments were conducted on cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved to specimen size along the /001/ surface, and indentations were made on the cleaved surface in corrosive solutions containing HCl, NaOH, or HNO3 and in water without exposing the specimen to any other environment. The results indicated that chloride (such as MgCl2) and sodium films are formed on the magnesium oxide surface as a result of interactions between an HCl-containing solution and a cleaved magnesium oxide surface. The chloride films soften the magnesium oxide surface. In this case microhardness is strongly influenced by the pH value of the solution. The lower the pH, the lower the microhardness. Sodium films, which are formed on the magnesium oxide surface exposed to an NaOH containing solution, do not soften the magnesium oxide surface.

Ishigaki, H.↗

Results from the July 1981 Workshop on Passive Remote Sensing of the Troposphere

Potential roles of passive remote sensors in the study of the chemistry and related dynamics of the lower atmosphere were defined by a Tropospheric Passive Remote Sensing Workshop, and technology advances required to implement these roles were identified. A promising role is in making global-scale, multilayer measurements of the more abundant trace tropospheric gaseous species (e.g., O3, CO, CH4, HNO3) and of aerosol thickness and size distribution. It includes both nadirand limb-viewing measurements. Technology advances focus on both scanning- and fixed-spectra, nadir-viewing techniques with resolutions of 0.1 kaysers or better. Balloon- and Shuttle-borne experiments should be performed to study the effects of instrument noise and background fluctuations on data inversion and to determine the utility of simultaneously obtained nadir- and limb-viewing data.

Keafer, L. S., Jr.↗

Noble gases in E-chondrites

The combination of noble gas data for 12 E-chondrites with literature data shows K-Ar ages greater than 4 AE for 14 out of 18 meteorites, while U, Th-He ages are often shorter. Cosmic ray exposure ages are found to differ systematically between types E4 and E6, with the respective, below-16 Myr and above-30 Myr values implying that the E-chondrite parent body predominantly contains a single petrologic type on the 1 km scale of individual impacts in contrast to the mixed parent bodies of the ordinary chondrites. Amounts of planetary gas in E4-E6 chondrites fall in the range for ordinary chondrites of types 4-6, but fail to correlate with petrologic type or volatile trace element contents, in contrast to the ordinary chondrites. Analyses of mineral separates show that the planetary gases are concentrated in an HFand HCl-insoluble mineral, similar to phase Q. The subsolar gases are located in an HCl- and HNO3-resistant phase.

Crabb, J.↗

High resolution atmospheric spectroscopy using a diode laser heterodyne spectrometer

Ultrahigh resolution (0.007 per cm) atmospheric solar absorption spectra that have been obtained from a tunable infrared heterodyne radiometer are discussed. The radiometer was developed for ground based observations in the 8-12 micron region, and tunability is achieved through the use of Pb-salt semiconductor laser local oscillators. Spectra have been obtained in a piecewise fashion from 9.1 to 11.1 microns using laser emission modes that exhibit characteristics suitable for local-oscillator operation. Spectra showing absorption features of HNO3, O3, CO2, and H2O are presented along with comparisons of experimental and synthetic spectra calculated using a line-by-line atmospheric transmission model.

Hoell, J. M., Jr.↗

Radiation and chemistry in the stratosphere - Sensitivity to O2 absorption cross sections in the Herzberg continuum

It is suggested that the discrepancies between observed and modeled vertical profiles of such halocarbons as CFCl3, as well as the problem of simultaneously fitting N2O, CH4, CF2Cl2 and CFCl3 profiles with a single eddy diffusion model, are due to an overestimation of the molecular oxygen absorption cross sections in the 200-220 nm spectral region. The replacement of current O2 cross sections in this range with values that are in better agreement with results for the compounds cited leads to N2O, CF2Cl2 and CFCl3 concentration reductions of factors 0.70, 0.62 and 0.19, respectively. Profiles of CH4, H2 and CO remain unchanged, and the predicted concentration of HNO3 above 30 km is reduced by about 50% for yet another improved fit with observations. It is noted that the correction proposed produces a 30% ozone increase near the 20-25 km peak.

Froidevaux, L.↗

Clouds and wet removal as causes of variability in the trace-gas composition of the marine troposphere

A modeling study of the effects of clouds and wet removal on the chemistry of the remote marine troposphere is described. Using a time-dependent model with parameterized vertical transport to calculate trace-gas concentrations, it is found that large variations in key species (e.g., HNO3, H2CO, and H2O2) result from simulations of sporadic rainfall, changes in cloud cover, and external inputs such as surface NO sources. Depending on the frequency and intensity of an event, the effects of these perturbations may persist for several days, thereby invalidating assumptions of photochemical equilibrium in the interpretation of measurements. Long-term integrations with fixed boundary conditions and regularly occurring cloud and rain episodes demonstrate a strong sensitivity of the mean concentration of longer-lived soluble gases to precipitation frequency but also confirm the validity of using properly chosen parameterizations of wet removal in steady state calculations.

Thompson, A. M.↗

Precursor gases of aerosols in the Mount St. Helens eruption plumes at stratospheric altitudes

Nineteen stratospheric samples from the eruption plumes of Mount St. Helens were collected in five flight experiments. The plume samples were collected at various altitudes from 13.1 to 20.7 km by using the Ames cryogenic sampling system on board the NASA U-2 aircraft. The enriched, cryogenically collected samples were analyzed by chromatography. The concentrations of aerosols precursor gases (OCS, SO2, and CS2), CH3Cl, N2O, CF2Cl2, and CFCl3 were measured by gas chromatography. Large enhancement of the mixing ratio of SO2 and moderate enhancement of CS2 and OCS were found in the plume samples compared with similar measurement under pre-volcanic conditions. A fast decay rate of the SO2 mixing ratio in the plume was observed. Measurement of Cl(-), SO2(2-), and NO3(-) by ion chromatography was also carried out on water solutions prepared from the plume samples. The results obtained with this technique imply large mixing ratios of HCl, (NO + NO2 + HNO3), and SO2, in which these constituents are the respective sources of the anions. Measurement of the Rn222 concentration in the plume was made. Other stratospheric constituents in the plume samples, such as H2O, CO2, CH4, and CO, were also observed.

Inn, E. C. Y.↗