Microwave Studies of Chemistry of the Middle Atmosphere

The purpose of this study has been to investigate O_3 chemistry in Earth's middle atmosphere. The NRAO 12-meter radio telescope at Kitt Peak, AZ was used to observe lambda = 1 mm emission spectra of trace species at altitudes 50 -70 km. Brightness of the emission lines was used to determine abundance of the emitting species, and shapes of the pressure broadened lines were used to obtain altitude resolution of these abundances. Observations of ^{18}O^{16}O, CO, and O_3 were used to establish a calibration appropriate for atmospheric observations with a telescope primarily used for astronomical work. Diurnal variation of O_2(^1 Delta_{g}) was observed and compared with photochemical model results. Observed O_2(^1Delta_ {g}) abundances were 20% higher than model abundances, and model results can be brought into agreement with observations by reducing the rate coefficient for O_2(^1Delta_ {g}) quenching by 20% below the accepted value. The behavior of O_2(^1Delta _{g}) through the afternoon and evening was observed to agree with model calculations. Symmetric and asymmetric isotopomers of ^{50}O_3 were observed. Previous workers have found large, highly variable, and unexplained enhancements of ^{50}O _3 in the stratosphere. We extend the range of observations to the mesosphere. Significant variability in the abundance of the asymmetric isotopomer was observed. Diurnal variations of HO_2 were observed in conjunction with H_2O and O_3. Comparisons were made with photochemical model results. At mid-day HO _2 abundances were observed to be ~40% higher than model predictions. Model results for this time period can be brought into agreement with observations by reducing the rate coefficient for rm HO_2 + O--> OH + O _2 by 40%. Observed HO_2 altitude profiles in the early morning, late afternoon, and early evening are very different from model predictions.