Modeling of photolysis rates over Europe: impact on chemical gaseous species and aerosols

Abstract. This paper evaluates the impact of photolysis rate calculation on simulated European air composition and air quality. In particular, the impact of the cloud parametrisation and the impact of aerosols on photolysis rates are analysed. Photolysis rates are simulated using the Fast-JX photolysis scheme and gas and aerosol concentrations over Europe are simulated with the regional chemistry-transport model Polair3D of the Polyphemus platform. The photolysis scheme is first used to update the clear-sky tabulation of photolysis rates used in the previous Polair3D version. Important differences in photolysis rates are simulated, mainly due to updated cross-sections and quantum yields in the Fast-JX scheme. In the previous Polair3D version, clouds were taken into account by multiplying the clear-sky photolysis rates by a correction factor. In the new version, clouds are taken into account more accurately by simulating them directly in the photolysis scheme. Differences in photolysis rates inside clouds can be large but outside clouds, and especially at the ground, differences are small.

To take into account the impact of aerosols on photolysis rates, Polair3D and Fast-JX are coupled. Photolysis rates are updated every hour. Large impact on photolysis rates is observed at the ground, decreasing with altitude. The aerosol specie that impact the most photolysis rates is dust especially in south Europe. Strong impact is also observed over anthropogenic emission regions (Paris, The Po and the Ruhr Valley) where mainly nitrate and sulphate reduce the incoming radiation. Differences in photolysis rates lead to changes in gas concentrations, with the largest impact simulated on OH and NO concentrations. At the ground, monthly mean concentrations of both species are reduced over Europe by around 10 to 14% and their tropospheric burden by around 10%. The decrease in OH leads to an increase of the life-time of several species such as VOC. NO₂ concentrations are not strongly impacted and O₃ concentrations are mostly reduced at the ground (−3%). O₃ peaks are systematically decreased because of the NO₂ photolysis rate coefficient decrease. Not only gas are impacted but also secondary aerosols, due to changes in gas precursors concentrations. However changes in aerosol species concentrations often compensate each other resulting in a low impact on PM₁₀ and PM_2.5 concentrations (lower than 2%).

The changes in gas concentrations at the ground induced by the modification of photolysis rates (by aerosols and clouds) are compared to changes induced by 29 different model parametrisations in Roustan et al. (2010). Among the 31 model parametrisations, "including aerosols on photolysis rates calculation" has the strongest impact on OH concentrations and on O₃ bias in July.

In terms of air quality, ground concentrations (NO₂, O₃, PM₁₀) are compared with measurements. Changes arising from cloud parametrisation are small. Simulation performances are often slightly better when including aerosol in photolysis rates calculation. The systematic O₃ peak reduction leads to large differences in the exceedances of the European O₃ standard as calculated by the model, in better agreement with measurements. The number of exceedances of the information and the alert threshold is divided by 2 when the aerosol impact on photochemistry is simulated. This shows the importance of taking into account aerosols impact on photolysis rates in air quality studies.