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Photolysis Rate Coefficient Calculations in Support of SOLVE II

A quantitative understanding of photolysis rate coefficients (or "j-values") is essential to determining the photochemical reaction rates that define ozone loss and other crucial processes in the atmosphere. j-Values can be calculated with radiative transfer models, derived from actinic flux observations, or inferred from trace gas measurements. The primary objective of the present effort was the accurate calculation of j-values in the Arctic twilight along NASA DC-8 flight tracks during the second SAGE III Ozone Loss and Validation Experiment (SOLVE II), based in Kiruna, Sweden (68 degrees N, 20 degrees E) during January-February 2003. The JHU/APL radiative transfer model was utilized to produce a large suite of j-values for photolysis processes (over 70 reactions) relevant to the upper troposphere and lower stratosphere. The calculations take into account the actual changes in ozone abundance and apparent albedo of clouds and the Earth surface along the aircraft flight tracks as observed by in situ and remote sensing platforms (e.g., EP-TOMS). A secondary objective was to analyze solar irradiance data from NCAR s Direct beam Irradiance Atmospheric Spectrometer (DIAS) on-board the NASA DC-8 and to start the development of a flexible, multi-species spectral fitting technique for the independent retrieval of O3,O2.02, and aerosol optical properties.

Swartz, William H.↗

Sensitivity of Photolysis Frequencies and Key Tropospheric Oxidants in a Global Model to Cloud Vertical Distributions and Optical Properties

Clouds affect tropospheric photochemistry through modification of solar radiation that determines photolysis frequencies. As a follow-up study to our recent assessment of the radiative effects of clouds on tropospheric chemistry, this paper presents an analysis of the sensitivity of such effects to cloud vertical distributions and optical properties (cloud optical depths (CODs) and cloud single scattering albedo), in a global 3-D chemical transport model (GEOS-Chem). GEOS-Chem was driven with a series of meteorological archives (GEOS1- STRAT, GEOS-3 and GEOS-4) generated by the NASA Goddard Earth Observing System data assimilation system. Clouds in GEOS1-STRAT and GEOS-3 have more similar vertical distributions (with substantially smaller CODs in GEOS1-STRAT) while those in GEOS-4 are optically much thinner in the tropical upper troposphere. We find that the radiative impact of clouds on global photolysis frequencies and hydroxyl radical (OH) is more sensitive to the vertical distribution of clouds than to the magnitude of column CODs. With random vertical overlap for clouds, the model calculated changes in global mean OH (J(O1D), J(NO2)) due to the radiative effects of clouds in June are about 0.0% (0.4%, 0.9%), 0.8% (1.7%, 3.1%), and 7.3% (4.1%, 6.0%), for GEOS1-STRAT, GEOS-3 and GEOS-4, respectively; the geographic distributions of these quantities show much larger changes, with maximum decrease in OH concentrations of approx.15-35% near the midlatitude surface. The much larger global impact of clouds in GEOS-4 reflects the fact that more solar radiation is able to penetrate through the optically thin upper-tropospheric clouds, increasing backscattering from low-level clouds. Model simulations with each of the three cloud distributions all show that the change in the global burden of ozone due to clouds is less than 5%. Model perturbation experiments with GEOS-3, where the magnitude of 3-D CODs are progressively varied from -100% to 100%, predict only modest changes (<5%) in global mean OH concentrations. J(O1D), J(NO2) and OH3 concentrations show the strongest sensitivity for small CODs and become insensitive at large CODs due to saturation effects. Caution should be exercised not to use in photochemical models a value for cloud single scattering albedo lower than about 0.999 in order to be consistent with the current knowledge of cloud absorption at the ultraviolet wavelengths.

Liu, Hongyu↗