The application of the Modified Band Approach for the calculation of on-line photodissociation rate constants in TM5: implications for oxidative capacity

A flexible and explicit on-line parameterization for the calculation of tropospheric photodissociation rate constants (J-values) has been integrated into the global Chemistry Transport Model TM5. Here we provide a comprehensive description of this Modified Band Approach (MBA) including details of the optimization procedure employed, the methodology applied for calculating actinic fluxes, the photochemical reaction data used for each chemical species, the aerosol climatology which is adopted and the parameterizations adopted for improving the description of scattering and absorption by clouds. The resulting J-values change markedly throughout the troposphere when compared to the offline approach used to date, with significant increases in the boundary layer and upper troposphere. Conversely, for the middle troposphere a reduction in the actinic flux results in a decrease in J-values. Integrating effects shows that application of the MBA introduces seasonal dependent differences in important trace gas oxidants. Tropospheric ozone (O-3) changes by +/- 10% in the seasonal mean mixing ratios throughout the troposphere, especially over land. These changes and the perturbations in the photolysis rate of O3 induce changes of +/- 15% in tropospheric OH. In part this is due to an increase in the re-cycling efficiency of nitrogen oxides. The overall increase in northern hemispheric tropospheric ozone strengthens the oxidizing capacity of the troposphere significantly and reduces the lifetime of CO and CH4 by similar to 5% and similar to 4 %, respectively. Changes in the tropospheric CO burden, however, are limited to a few percent due to competing effects. Comparing the distribution of tropospheric ozone in the boundary layer and middle troposphere against observations in Europe shows there are improvements in the model performance during boreal winter in the Northern Hemisphere near regions affected by high nitrogen oxide emissions. Monthly mean total columns of nitrogen dioxide and formaldehyde also compare more favorably against OMI and SCIAMACHY total column observations.