| Popis: |
The photochemical box model (PBM) developed in the present study is based on the principle of mass conservation. It has a horizontal domain of the size of a typical city and a vertical dimension defined by the mixed-layer height. The concentration of any pollutant is determined by horizontal advection, vertical entrainment, source emissions and chemical reactions. A one-dimensional high resolution boundary layer model by Blackadar (Preprints, Third Symp. on Atmospheric Turbulence, Diffusion, and Air Quality, Raleigh, Am. Met. Soc., pp. 443–447, 1976; Advances in Environmental Sciences and Engineering, Vol. 1, No. 1 (edited by Pfafflin J. and Ziegler E.), pp. 50–85. Gordon and Breach, New York, 1979) has been incorporated in the PBM and further developed to consider the effect of urban heat islands in the simulation of mixed layer height. The predicted mixed-layer heights compare very well with observations. The gas phase chemical kinetic mechanism used in the Regional Acid Deposition Model II (RADM2) and that of an earlier version of PBM have been used to calculate the contributions of chemical reactions to the changes of pollutant concentrations. Detailed analysis and comparisons of the two chemical mechanisms have been made. The simulated pollutant concentrations using both chemical mechanisms are in very good agreement with available observations for CO, NO, NO2 and O3. A radiative transfer model developed by Madronich (J. geophys. Res.92, 9740–9752, 1987) has been incorporated in the PBM for the calculation of actinic flux and photolytic rate constants. Height-averaged and radiation-corrected photolytic rate constants are used for the photochemical reactions. Budget analyses conducted for CO, NO, NO2 and O3 have enhanced our understanding of the relative contributions of horizontal advection, vertical entrainment, source emissions and chemical reactions to the overall rate of change of their concentrations. Model predictions are not sensitive to the large number of peroxy radical-peroxy radical reactions in the RADM2 chemical mechanism under urban conditions. |
