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At least 73 records · Page 4

The photolysis of ozone

Ozone was photolyzed at 25 C with steady illumination at several wavelengths from 2288 to 2850 A, at O3 pressures from 0.1 to 2.7 torr, and at absorbed intensities from 0.15 to 65 microns/min. Experiments were done in pure dry O3, and in the presence of He, CO2, N2, H2O, H2, N2O, He-CO2, He-H2O, CO2-H2O, O2-N2O, CO2-O2, and N2O5-O2-CO2 mixtures. The results show that in the absence of added gases or in the presence of He, the quantum yield of O3 consumption is 5.5 independent of conditions, except at pressures below 0.4 torr. In the presence of CO2 or N2, ozone consumption falls toward 4.0. The primary photolytic act produces O(1 D) and siglet O2, presumably O2(1 delta), at all wavelengths below 3000 A. Relative quenching constants O(1 D) removal by various gases were measured at 2288, 2537, and 2800 A. For O3, CO2, and N2, the relative rates are 1.0/0.4 to 0.5/0.08 to 0.11 at all wavelengths. For H2O the constant at 2537 A is 1.5 relative to that for O3. With N2O, a noticeable wavelength effect is observed and the relative rate constants are 1.5, 2 to 3, 4.0 for O3 compared to N2O at 2800, 2537, and 2288 A, respectively.

Lissi, E.↗

Photochemistry of nitrogen in the Martian atmosphere

Models are developed for the photochemistry of a CO2-H2O-N2 atmosphere on Mars. Estimates are given for the concentrations of N, NO, NO2, NO3, N2O5, HNO2, HNO3, and N2O as a function of altitude. Nitric oxide is the most abundant form of odd nitrogen, present with a mixing ratio relative to CO2 of the order of 1 hundred-millionth. Deposition rates for nitrite and nitrate minerals could be as large as 300,000 N equivalent atoms per sq cm/sec under present conditions and may have been higher in the past.

Yung, Y. L.↗

Inorganic chemistry: Direct syntheses from pure liquid SO3 and from trivalent and pentavalent nitrogen derivatives

From pure liquid SO3 direct synthesis reactions were carried out with N2O5, NO2Cl, NOCl which yielded N2O54SO3, 3SO3, 2SO3-NO2Cl2SO3-NOCl2SO3 and NOCl2SO3, the latter being obtained for the first time in the pure state. In all cases the crystallized product was obtained by separating the constituents of the mixture and then going through a single viscous liquid phase.

Vandorpe, B.↗

An experiment concept to measure stratospheric trace constituents by laser heterodyne spectroscopy

Laser heterodyne spectroscopy (LHS) techniques were used to measure radical gases from Spacelab. Major emphasis was placed on the measurement of ClO, ClOnO2, HO2, H2O2, N2O5, and HOCl in solar occultation with vertical resolution less than or equal to 2-km and vertical range from 1O to 70-km. Sensitivity analyses were performed on ClO and O3 to determine design criteria for the LHS instrument. Results indicate that O3 and ClO vertical profiles can be measured with an accuracy more than or equal to 95% and more than or equal to 80%, respectively, over the total profile.

Allario, F.↗

The problem of nighttime stratospheric NO3

Detailed calculations of the behavior of the NO3 column content as a function of time after sunset show that it takes nearly 2 hours to increase from daytime values of approximately 10 to the 11th/sq cm to nighttime values of 10 to the 14th/sq cm. These results appear to be in conflict with the measured NO3-concentration rise time of 40 min after sunset obtained from the 662-nm absorption data of Noxon et al. (1978). Changes in the rate constants affecting the NO, NO2, NO3, N2O5 system, the atmospheric temperature, and the amount of NO2 are not able to bring the calculated rise time for the NO3 column content into agreement with observations.

Herman, J. R.↗

Heterogeneous atmospheric reactions - Sulfuric acid aerosols as tropospheric sinks

The reaction probabilities of various atmospheric species incident on a bulk sulfuric acid surface are measured in order to determine the role of sulfuric acid aerosols as pollutant sinks. Reaction products and unreacted starting materials leaving a Knudsen cell flow reactor after collision at 300 K with a H2SO4 surface or a soot surface were detected by mass spectrometry. Significant collision reaction probabilities are observed on a H2SO4 surface for H2O2, HNO3, HO2NO2, ClONO2, N2O5, H2O and NH3, and on soot for NH3. Estimates of the contribution of heterogeneous reactions to pollutant removal under atmospheric conditions indicate that while aerosol removal in the stratosphere is insignificant (loss rate constants approximately 10 to the -10th/sec), heterogeneous reactions may be the dominant loss process for several tropospheric species (loss rate constant approximately 10 to the -5th/sec, comparable to photolysis rate constants).

Baldwin, A. C.↗

Integrated band intensities of gaseous N/2/O/5/

Values for mid-IR integrated band intensities of gaseous N2O5 were determined at room temperature. The absorptions studied were at 1720, 1246, 743, and 557/cm. The integrated intensities were 2204, 581, 685, and 699/atm cm, respectively. Implications of these results for the stratospheric detection of N(2)O(5) are discussed.

Lovejoy, R. W.↗

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.↗

Precision of NO2 photolysis rate measurements

Gas-phase kinetic calculations indicate that actinometric measurements of the rate of solar photolysis of NO2 in nitrogen can be in error by +5 to -15% or more, unless odd oxygen N2O5 chemistry, and trace oxygen content are considered. A field experiment confirms that the effect of the quartz tube on the measured photolysis rate is less than 1.7%.

Dickerson, R. R.↗

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↗