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Results for the solar heating rates in ambient air due to absorption by black-carbon (BC) containing particles and ozone are presented as calculated from airborne observations made in the tropical tropopause layer (TTL) in January-February 2006. The method uses airborne in situ observations of BC particles, ozone and actinic flux. Total BC mass is obtained along the flight track by summing the masses of individually detected BC particles in the range 90 to 600-nm volume-equivalent diameter, which includes most of the BC mass. Ozone mixing ratios and upwelling and partial downwelling solar actinic fluxes were measured concurrently with BC mass. Two estimates used for the BC wavelength-dependent absorption cross section yielded similar heating rates. For mean altitudes of 16.5, 17.5, and 18.5 km (0.5 km) in the tropics, average BC heating rates were near 0.0002 K/d. Observed BC coatings on individual particles approximately double derived BC heating rates. Ozone heating rates exceeded BC heating rates by approximately a factor of 100 on average and at least a factor of 4, suggesting that BC heating rates in this region are negligible in comparison.

The Gas and Aerosol Measurement Sensor (GAMS) was deployed aboard the NASA DC-8 aircraft during the second SAGE III Ozone Loss and Validation Experiment (SOLVE II). GAMS acquired line-of-sight (LOS) direct solar irradiance spectra during the sunlit portions of ten science flights of the DC-8 between 12 January and 4 February 2003. Differential line-of-sight (DLOS) optical depth spectra are produced from the GAMS raw solar irradiance spectra. Then, DLOS ozone number densities are retrieved from the GAMS spectra using a multiple linear regression spectral fitting technique. Both the DLOS optical depth spectra and retrieved ozone data are compared with coincident measurements from two other solar instruments aboard the DC-8 platform to demonstrate the robustness and stability of the GAMS data. The GAMS ozone measurements are then utilized to evaluate the quality of the Wulf band ozone cross sections, a critical component of the SAGE III aerosol, water vapor, and temperature/pressure retrievals. Results suggest the ozone cross section compilation of Shettle and Anderson currently used operationally in SAGE III data processing may be in error by as much as 10-20% in theWulf bands, and their lack of reported temperature dependence is a significant deficiency. A second, more recent, cross section database compiled for the SCIAMACHY satellite mission appears to be of much better quality in the Wulf bands, but still may have errors as large as 5% near the Wulf band absorption peaks, which is slightly larger than their stated uncertainty. Additional laboratory measurements of the Wulf band cross sections should be pursued to further reduce their uncertainty and better quantify their temperature dependence.

A redetermination of the temperature dependence of the absorption cross-section (sigma) of NO2 in the visible-ultraviolet region was made in order to provide a more reliable data base for the calculation of NO2 photolysis rates in the atmosphere. Experiments over a wide range of temperatures and NO2 concentrations were conducted. The integral of a plot of sigma versus the inverse of the wavelength was essentially independent of temperature. Increasing temperature produced a shift of the spectrum toward longer wavelengths, resulting in a small negative temperature dependence of sigma over the 264-400 nm range and a small positive dependence over the 450-649 nm range. Increasing temperature produced broadening of individual spectral features, resulting in a systematic lowering of peaks and filling of valleys. Recommended cross sections are presented for use in tropospheric NO2 photolysis rate calculations.

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.

The design and construction of a long path cell for absorption measurements at temperatures ranging from 215-470 K and at pressures from vacuum to 10 atm are described. The cell consists of three concentric stainless-steel tubes; the innermost tube is 6.5-in. in internal diameter, has a volume of about 47 l, and contains White-type optics, six thermocouples, and a gas input tube; and the outermost tube provides a vacuum Dewar around the inner assembly. The optical design and temperature control system for the long path temperature variable cell are examined. The long path cell is applicable for analyzing temperature and pressure dependence of spectra and reaction rates of gases, and the cell has flow and photolysis capabilities for studying transient species and photochemically initiated reactions. A diagram of the cell is provided.

The carbon kinetic isotope effect in the CH4 + HO reaction is measured experimentally and the use of carbon isotope ratios to diagnose atmospheric methane is examined. The chemical, photolysis, and analytical experimental conditions and procedures are described. It is determined that the CH4 + HO reaction has a carbon kinetic isotope effect of 1.010 + or 0.007 for k(12)k(13) (rate constants ratio) at 297 + or - 3 K. This value is compared with the data of Rust and Stevens (1980). Causes for the poor correlation between the data at high methane conversions are discussed. It is supposed that the difference between the k(12) and k(13) values is due to a difference in the activation energy of the two reactions.

Eight balloon-borne in situ measurements of ClO in the stratosphere are analyzed and are compared with recent model calculations. While the use of in situ stratospheric studies of free radicals to test models by comparing observed and predicted concentration profiles is essential for a prognosis of changes in stratospheric ozone, resulting from future changes in stratospheric ozone, such studies provide only limited insight into the nature of stratospheric photochemistry, because natural variability and the large number of fast reactions which compete in the coupling among the key radicals frustrate a detailed comparison between a mean distribution provided by the models and an instantaneous distribution provided by a single observation.