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At least 73 records · Page 4

Examination of wintertime latitudinal gradients in stratospheric NO2 using theory and LIMS observations

Nimbus 7 LIMS data and a photochemical model are used to show that the observed sharp latitudinal gradients in stratospheric wintertime NO2 are consistent with the conversion of NO2 to N2O5 at high latitudes. This conversion, and the sharp gradients, are brought about by the interaction between transport and photochemistry. Calculated variations show good agreement with observations.

Callis, L. B.↗

MAP/GLOBUS campaign 1983

The major scientific objectives of the campaign are the accurate measurement of ozone and its short-term variability together with the determination of members of the NO sub x family as NO, NO2, NO3, N2O5, and HNO3. Related important solar fluxes (including scattered fluxes) shall be measured as much as possible. Other important trace species (as H2O) shall be determined simultaneously. The detailed scientific objectives for the ozone and NO sub x measurements are given. A further scientific objective is the study of atmospheric dynamics, especially of the meteorological background. Therefore special analysis will be performed of the data of respective network stations and satellites. Local wind and turbulence measurements will also be performed.

Offerman, D.↗

High atmospheric NO(x) levels and multiple photochemical steady states

The rate of removal of atmospheric NO(x) compounds at different NO(x) levels is estimated using a one-dimensional photochemical model. NO(x) removal by wet deposition, surface deposition, and thermochemical processes is examined. NO(x) removal rates at different surface NO mixing ratios are calculated and the data are analyzed. It is revealed that at low NO(x) levels NO(x) is photochemically converted to HNO3 by either wet or dry deposition; however, at high NO(x) levels formation of HNO3 is inhibited due to the disappearance of tropospheric ozone and OH, and the NO(x) is removed by rainout of N2O4 and N2O5, surface deposition of NO and NO2, and direct dissolution of NO and NO2 in rainwater. The effects of NO(x) mixing ratios greater than 10 to the -7th on the ozone and climate are investigated.

Kasting, J. F.↗

Short-term variability of nitrogen dioxide in the winter stratosphere

Measurements of limb radiance from the Solar Mesosphere Explorer (SME) satellite are used to infer the NO2 density at the 10- and 16-mbar pressure levels from January 1 to March 31 of 1982. A photochemical-dynamical model is developed using the presently accepted chemistry of the NO(x) family. The dynamical model produces isentropic trajectories which simulate the history of air parcels. From the trajectories the photochemical model calculates NO2 densities, which are compared to those observed by SME. Although the model generally reproduces the spatial and temporal variations rather well, some disagreement was noted for conditions of exceptionally low temperatures. Further analysis indicates that the temperature sensitivity of the N2O5 photolysis cross sections may be overestimated at low temperatures.

Zawodny, J. M.↗

Seasonal behavior of NO2 in the winter stratosphere - Inferred NO(x)

An analysis is performed of Solar Mesosphere Explorer (SME) data for the first 90 days of 1982, when a trend of increasing NO2 content in the stratosphere near the 10 mbar pressure level was detected. A photochemical-dynamical model is developed to account for the observed densities, which were also detected with ground-based instrumentation. The model calculations indicated that partitioning of the NO(x) family from N2O5 to NO2 was responsible for the trend. The new partitioning requires a lowering of the mixing ratio of NO(x), which was also observed. Finally, the SME data also confirmed that the enhanced NO2 concentrations were dependent on the solar zenith angle.

Zawodny, J. M.↗

Observations of the diurnal variation of nitrogen dioxide in the stratosphere

Observations of NO2 from the limb infrared monitor of the stratosphere (LIMS) experiment in high-latitude summer are presented. Appropriate selection of latitude and days during the month of May yields NO2 observations obtained during the afternoon and evening at solar zenith angles ranging from about 35-110 deg. These data show that the NO2 abundances in the stratosphere become strongly dependent on the solar zenith angle for angles exceeding about 80 deg. Model calculations and other observations suggest that from about 80-95 deg this dependence probably reflects variations in the propagation of the visible radiation that photodissociates NO2. The data obtained at zenith angles greater than about 95 deg provide clear evidence for the night decay of NO2 to form N2O5, and the observed decay rate is shown to be consistent with present theory.

Solomon, S.↗

Condensation of HNO3 and HCl in the winter polar stratospheres

Nitric acid and hydrochloric acid vapors may condense in the winter polar stratospheres. Nitric acid clouds, unlike water ice clouds, would form at the temperatures at which polar stratospheric clouds (PSCs) are observed and would have optical depths of the magnitude observed suggesting that HNO3 is a dominant component of PSCs. ClO, N2O5 and ClNO3 may react on cloud particle surfaces yielding additional HNO3, HCl, and HOCL. In the vicinity of PSCs these reactions could deplete the stratosphere of photochemically active NO(x) species. The sedimentation of PSCs may remove these materials from the stratosphere. The loss of vapor phase NO(x) might allow halogen-based chemistry to create the ozone hole.

Toon, Owen B.↗

Simultaneous in situ measurements and diurnal variations of NO, NO2, O3, jNO2, CH4, H2O, and CO2 in the 40- to 26-km region using an open path tunable diode laser spectrometer

Simultaneous in situ measurements of temperature, pressure, and the NO, NO2, O3, jNO2, CH4, H2O, and CO2 concentrations were conducted in the 40- to 26-km region of the stratosphere using the JPL Balloon-borne Laser In Situ Sensor, a tunable diode laser absorption spectrometer. The NO, NO2, CH4, H2O, and CO2 concentration measurements generally show good agreement with previous observations, with a tendency for somewhat lower NO2 amounts. Measured O3 concentrations at 38 km agree well with comparable measurements from in situ UV photometers, but at 28 km they are lower by about 10 percent and agree more closely with the solar backscattered UV data. A decline was found in NO2 during the night over a 5-km altitude range, which implies either lower NO2 postsunset profiles, or an NO2 decay rate that is significantly higher than current model predictions that use N2O5 chemistry.

Webster, Christopher R.↗

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↗

Visible and near-ultraviolet spectroscopy at Thule AFB (76.5 N) from January 28 - February 15, 1988

Near-ultraviolet and visible spectrographs identical to those employed at McMurdo Station, Antarctica (77.8 S) during the austral spring seasons of 1986 and 1987 were used to study the stratosphere above Thule, Greenland (76.5 N) during early spring, 1988. Observations were carried out both at night using the direct moon as a light source, and during the day by collecting the scattered light from the zenith sky when solar zenith angles were less than about 94.5 degrees. Excellent meteorological conditions prevailed in the troposphere and stratosphere at Thule. Surface weather was extremely clear over most of the period, facilitating measurements of the direct light from the moon. The lower stratospheric arctic polar vortex was located very near Thule throughout the observing period, and temperature at the 30 mbar level were typically below -80 C above Thule, according to the National Meteorological Center daily analyses. Thus conditions were favorable for polar stratospheric cloud formation above Thule. Total column ozone abundances were about 350 to 400 Dobson units, and did not suggest a clear temporal trend over the observing period. Stratospheric nitrogen dioxide measurements were complicated by the presence of a large component of tropospheric pollution on many occasions. Stratospheric nitrogen dioxide could be identified on most days using the absorption in the scattered light from the zenith sky, which greatly enhances the stratospheric airmass while suppressing the tropospheric contribution. These measurements suggest that the total vertical column abundance of nitrogen dioxide present over Thule in February was extremely low, sometimes as low as 3 x 10 to the 14th per sq cm. The abundance of nitrogen dioxide increased systemically from about 3 x 10 to the 14th in late January to 1.0 x 10 to the 15th per sq cm in mid-February, perhaps because of photolysis of N2O5 in the upper part of the stratosphere, near 25 to 35 km.

Mount, G. H.↗

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.↗

Comparison of model results transporting the odd nitrogen family with results transporting separate odd nitrogen species

A fast two-dimensional residual circulation stratospheric family transport model, designed to minimize computer requirements, is developed. The model was used to calculate the ambient and perturbed atmospheres in which odd nitrogen species are transported as a family, and the results were compared with calculations in which HNO3, N2O5, ClONO2, and HO2NO2 are transported separately. It was found that ozone distributions computed by the two models for a present-day atmosphere are nearly identical. Good agreement was also found between calculated species concentrations and the ozone response, indicating the general applicability of the odd-nitrogen family approximations.

Douglass, Anne R.↗

High resolution infrared spectroscopy of the sun and the earth's atmosphere from space

The FFT spectrometer used in the atmospheric trace molecule spectroscopy (ATMOS) experiment, flown for the first time aboard the Shuttle Spacelab 3 mission (in April 1985), is described together with the instrument's design parameters, the ATMOS's science objectives, and observational techniques used. The ATMOS experiment acquired more than 1000 atmospheric spectra with an equal number of 'solar only' scans, yielding absorption spectra of some 400 different atmospheric constituents. Data were obtained on such key reservoir species as COF2, HNO4, and N2O5; simultaneous vertical distributions of the minor gases from 5 to 140 km; the entire odd-nitrogen family in the stratosphere; and on most of the halogen-source gases with their corresponding reservoir and sink species.

Farmer, Crofton B.↗

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.↗

Measurements of nitric oxide and total reactive nitrogen in the Antarctic stratosphere - Observations and chemical implications

Results are presented on measurements of NO and the sum of reactive nitrogen species, NO(y), which include NO, NO2, NO3, N2O5, HNO3, and ClONO2 (in addition to ClO, O3, H2O, and N2O measurements), obtained aboard the NASA ER-2 aircraft flying over the Antarctica between the latitudes of 53 and 72 deg S during the Airborne Antarctic Ozone Experiment. The boundary of the chemically perturbed region (CPR), as indicated by a sharp increase in the level of ClO, occurred near 66 deg S; outside or equatorward of the CPR, the NO(y) mixing ratios ranged between 6 and 12 ppbv, with values decreasing poleward and reaching total NO(y) levels of 4 ppbv or less within 5-deg poleward of the boundary. Data presented in this paper clearly associate the Antarctic ozone decrease with perturbed conditions of ClO, NO(y), and H2O, which are in turn associated with processes defined as nonstandard heterogeneous chemistry, denitrification, and dehydration, respectively.

Fahey, D. W.↗

Stratospheric ozone - Impact of human activity

The current knowledge of the chemistry of the stratosphere is reviewed, with particular consideration given to the measurements from the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment and from the Airborne Antarctic Ozone Experiment. Analysis of the ATMOS data at 30 deg N suggests that the current understanding of the contemporary-stratosphere chemistry at mid-latitudes is relatively complete, except for possible problems with the diurnal variations of N2O5 at low altitudes, and with ClNO3 at higher altitudes. Except for some difficulties with these two compounds, the data from ATMOS agree well with the gas phase models for nitrogen and chlorine species at 30 deg N in spring. It is emphasized that, in addition to the HOCl mechanism proposed by Solomon et al. (1986), the ClO-BrO scheme proposed by McElroy et al. (1986), and the ClO dimer mechanism introduced by Molina and Molina (1987), other processes exist that are responsible for ozone removal.

Mcelroy, Michael B.↗

Nitric oxide measurements in the Arctic winter stratosphere

Measurements of NO from five flights of the NASA ER-2 aircraft during the Airborne Arctic Stratospheric Expedition are presented. The NO values and vertical gradient near 60 deg N latitude are similar to previous measurements near 50 deg N in winter (Ridley et al., 1984, 1987). The NO latitudinal gradient is distinctly negative outside of the polar vortex, approaching zero at the boundary of the vortex, and remaining below the 20 pptv detection limit inside the vortex. Steady state NO2 and NO(x) (NO + NO2) are calculated from measured NO, O3, and ClO, and modeled photodissociation rates. NO(x) outside the vortex shows a negative dependence on latitude and solar zenith angle. Low NO(x) and NO(x)/NO(y), inside and near the vortex boundary may be indications of heterogeneous removal of ClONO2 and N2O5.

Fahey, D. W.↗

Heterogeneous reactions with NaCl in the El Chichon volcanic aerosols

Previous investigations of the effects of the 1982 eruption of the El Chichon volcano could not explain all the observations of changes in O3, HCl, NO and NO2 simultaneously without proposing unproven chemical reactions. Since reactions between solid NaCl and gaseous ClNO3 and N2O5 rapidly produce photochemically active chlorine species and solid NaNO3 in laboratory experiments, it is suggested that these reactions could have occurred with the NaCl observed to be present in the El Chichon sulfuric acid areosols. As a consequence, it is predicted that HCl should increase substantially, while NO(x) should decrease, in agreement with the measurements after the eruption. Ozone should be only slightly affected by these reactions. Reactions between solid NaCl and the acids H2SO4 and HNO3 might prove to be important, but sufficient evidence regarding their efficiency and the pressure of HNO3 in the aerosols is lacking.

Michelangeli, Diane V.↗