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A grating monochromator infrared spectrometer and a curve of growth technique were used to obtain the absolute integrated intensity for the 3.44 micron NO2 vibration-rotation band at very small NO2 partial pressures. The intensity was found to be 78.9 plus or minus 1.6/cm/(atm cm) at 296 K at the 95% confidence level. The study has relevance to the infrared spectral measurement of atmospheric NO2.
Exhaust plane measurements of NO and NO2 emissions from a methane-fueled swirl-stabilized combustor are reported. Samples were obtained by water-cooled probes and analyzed by chemiluminescent and UV absorption techniques. The combustor consists of two confined concentric jets having swirl. The inner jet flows premixed fuel and air, the outer jet is air. Variable outer jet swirl allows operation with jets swirling either in the same or opposite directions (co- or counter-swirl), and the combustion is stabilized by the resulting recirculation zone formed on the combustor centerline. Swirl conditions strongly affect the NOx emissions because of the influence of swirl on the combustion process. In the co-swirl conditions, the inner flow reaches high temperatures, and the correspondingly high NOx emissions are primarily NO. Under counter-swirl conditions much lower values of total NO are found, and these emissions are almost entirely NO2. In this case vigorous mixing in the inter-jet shear layer leads to severe flame quenching and lower temperatures. Formation of NO2 is associated with quenching processes in the combustor and is thought to be formed via NO oxidation by HO2 free radicals.
CCl2FO2 radicals are produced in the stratosphere from the oxidation of CCl2F radicals produced from the photodissociation of CCl3F. The reactions of CCl2FO2 with NO and NO2 were studied by steady state photolysis at 1 atm and 286-305 K. The reactions were CCl2FO2 + NO yields CCl2FO + NO2 and CCl2FO2 + NO2 (+M) yields CCl2FO2NO2 (+M) with k3/k4 = 0.58 plus or minus 0.10 over this temperature range.
Simultaneous stratospheric vertical profiles of NO and NO2 at sunset were derived from an analysis of infrared solar absorption spectra recorded from a float altitude of 33 km with an interferometer system during a balloon flight. A nonlinear least squares procedure was used to analyze the spectral data in regions of absorption by NO and NO2 lines. Normalized factors, determined from calculations of time dependent altitude profiles with a detailed photochemical model, were included in the onion peeling analysis to correct for the rapid diurnal changes in NO and NO2 concentrations with time near sunset. The CO2 profile was also derived from the analysis and is reported.
The oxidation of SO2 to sulfate in air at 65 percent relative humidity on carbon particles was investigated gravimetrically in the presence of NO2 and O3. Approximately 1 mg samples of carbon black were exposed to continuously flowing ppbv mixtures of SO2, SO2 + NO2 and SO2 + O3 for prescribed periods of time before desorption into dry N2. Wet chemical analysis of the particles followed desorption. NO2 and O3 were found to have little, if any, effect relative to air on sulfate yields at the concentrations studied.
An experiment was operated on several Space Shuttle missions to provide spatial and spectral distributions of a ram glow associated with the Orbiter. The most recent data featured resolved spectrum and imagery of the glow with spectroscopic resolution of 34 A FWHM between 4000 and 8000 A. The spectrum of the glow on the Shuttle tail pod could be clearly separated from spectrum of the reflected light from the Orbiter. Analysis and comparison have been performed which strongly suggest the emission originates from recombination continuum of NO2. Both fast recombination (high temperature) and the spectral dependence in lifetime can describe the spectral difference. If the recombined NO2 retains 25 percent of the kinetic energy of the ram OI, the thickness of the glow layer can be explained by the lifetime of NO2 (2B1) recombination emission.
As a part of the Japanese activities of MAP in the Antarctica, balloon-borne measurements of the stratospheric NO2 profile were planned and carried out by the JARE 23rd and 24th wintering parties. Few results have been reported so far as the stratospheric NO2 profile at high latitude. There were no reported balloon measurements carried out in the Southern Hemisphere. Profiles are presented for the first balloon-borne measurement of the stratospheric NO2 in the Antarctica. Three balloons named JA21, JA25 and JA26 were launched from Syowa Station (69 deg S, 35.6 deg E) using 5000 cu. cm plastic balloons. JA21 balloon was launched on November 24, 1982, and JA25 and JA26 balloons on November 12 and 20, 1983, respectively.
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.
In February 1985 the NO2 concentration over Goeteborg, a major Swedish city, was monitored during two inversion situations. The differential absorption technique was employed and the results show the build-up of the concentration. In this experiment the laser beam was scanned horizontally over Goeteborg. The results were presented as maps over the NO2 concentration distribution. For security reasons the beam was not parallel to the ground, which gives a height gradient in some measurements. During the measurement period the NO2 concentration variation build-up from the morning to the afternoon was monitored. Great concentration variations were seen. Later the mixing below the inversion layer, resulting in a more uniform, high concentration was seen. The breakdown of the inversion when stronger winds start was also seen. Comparisons with a traditional point-measuring chemiluminiscence instrument and an optical method DOAS (Differential Optical Absorption Spectroscopy), were made. The results are discussed. Strong spatial concentration variations are shown by the lidar measurements. For a point-measuring system, the instrument must be very carefully placed since its location will strongly influence the values it gives.
Zonal mean mixing ratios of ozone and NO2 measured by SAGE II on several days in March and April, 1985 are compared against zonal means for this time of year previously measured by SAGE I, SBUV, and LIMS. After allowing for calculated diurnal variations of these gases, agreement within 15 percent is found for ozone and 20 percent for NO2. It is noted that the profile error bars given on the SAGE II data tapes need to be carefully interpreted and that the measured tropical variances suggest that these error bars are being somewhat overestimated. Planetary waves in both ozone and NO2 in the middle stratosphere should be derivable from the SAGE II measurements.
After a brief review of observations of the global distribution of stratospheric NO2, the possibiliy of combining different data sets to construct a NO2 reference model is discussed. It is shown that difficulties mainly arise from the diversity of techniques and variability of NO2 in the stratosphere. The diurnal variation and possibly a long term trend present special problems.
During the period of Feb. 28 to Mar. 2, 1986, 19 high resolution atmospheric spectra have been recorded during the night using the moon or during the day using the sun as a source with the Fourier transform spectrometer at the McMath Solar telescope on Kitt Peak. The NO2 absorption peak located at 2914.65/cm has been used to derive from the spectra the total vertical column densities of atmospheric NO2. A rather rapid decrease of the NO2 amount during the night has been observed, and its daytime increase from sunrise to sunset has been confirmed. A comparison with the predictions of a photochemical model is given.
Direct determinations of the equilibrium constant for the reaction N2O5 = NO2 + NO3 were carried out by measuring NO2, NO3, and N2O5 using long-path visible and infrared absorption spectroscopy as a function of temperature from 243 to 397 K. The first-order decay rate constant of N2O5 was experimentally measured as a function of temperature. These results are in turn used to derive a value for the rate coefficient for the NO-forming channel in the reaction of NO3 with NO2. The implications of the results for atmospheric chemistry, the thermodynamics of NO3, and for laboratory kinetics studies are discussed.
During the 1982 and 1983 Balloon Intercomparison Campaigns, the vertical profile of stratospheric NO2 was measured remotely by nine instruments and that of NO by two. Total overhead columns were measured by two more instruments. Between 30 and 35 km, where measurements overlapped, agreement between NO profiles was within + or - 30 percent, which is better than the accuracies claimed by the experimenters. Between 35 and 40 km, there was similarly good agreement between NO2 profiles, but below 30 km, differences of greater than a factor of 3 were found. In the second campaign, NO2 values from most instruments agreed within their quoted errors, except that the Oxford radiometer gave much lower values; the first campaign and the column measurements show a more uniform spread of results.
The validity of NO2 measurements from the stratospheric aerosol and gas experiment (SAGE) II is examined by comparing the data with climatological distributions of NO2 and by examining the consistency of the observations themselves. The precision at high altitudes is found to be 5 percent, which is also the case at specific low altitudes for certain latitudes where the mixing ratio is 4 ppbv, and the precision is 0.2 ppbv at low altitudes. The autocorrelation distance of the smoothed profile measurement noise is 3-5 km and 10 km for 1-km and 5-km smoothing, respectively. The SAGE II measurements agree with spectroscopic measurements to within 10 percent, and the SAGE measurements are about 20 percent smaller than average limb monitor measurements at the mixing ratio peak. SAGE I and SAGE II measurements are slightly different, but the difference is not attributed to changes in atmospheric NO2.
The present study compares the diurnal variation of NO2 measured near 30 km by the BLISS in situ laser spectrometer with calculations from a photochemical model that includes a detailed description of multiple scattering. Even better agreement is found between the data and the model, both at sunset and during the day. The conclusions of an earlier study that the high-resolution in situ measurements of NO2 facilitated validation of the understanding of the diurnal chemistry of NO2 are confirmed.
The MIESR method consists of two steps (1) collection of the radicals present in the ambient air at 77K in a polycrystalline D2O matrix and (2) identification and quantification of the different radicals in the laboratory by Electron Spin Resonance spectroscopy. In step (1), the sampling efficiency for sampling NO2 and RO2 was determined to be greater than or equal to 95 percent, with a measured accuracy of plus or minus 5 percent. In step (2), after collection, the samples are maintained at 77 K and spectra are recorded in the laboratory using a standard 9.5 GHz ESR system (Varian E-line). About 50 individual scans of each spectrum are recorded and digitally averaged in order to improve the signal-to-noise ratio. The ESR-spectra are analyzed with a recently developed numerical procedure which was demonstrated to allow speciation of NO2, NO3, HO2, CH3C(O)O2, and the sum of the alkylperoxy radicals. The detection limit is 5ppt for HO2, RO2, and NO2 and 3ppt for NO3 due to its narrower ESR-linewidth.
Simultaneous in situ measurements of stratospheric NO2, HNO3, HCl, and CH4 from 34 to 24 km were made in August 1992 from Palestine, Texas, using the Balloon-borne Laser In-Situ Sensor (BLISS) tunable diode laser spectrometer. Although the measurements of NO2, HNO3, and NO2/HNO3 agree well with gas-phase model calculations near 34 km where Stratospheric Aerosol and Gas Experiment (SAGE) 2 data show little sulfate aerosol, this is not true at the lower altitudes where SAGE 2 shows high aerosol loadings. At 24 km the BLISS NO2 and HNO3 measurements are 70% lower and 50% higher, respectively, than the gas phase model predictions, with a measured NO2/HNO3 ratio 5 times smaller. When the heterogeneous hydrolysis of N2O5 and ClONO2 on sulfate aerosol of surface area densities matching the SAGE 2 measurements is added to the model, good agreement with the BLISS measurements is found over the whole altitude range.