Sensitivity of Ozone to NOx and VOCs in a Street Canyon

The sensitivity of ozone to NOx and volatile organic compounds (VOCs) emission rates under different ventilation rates and NO2-to- NOx emission ratios in a street canyon is investigated using a chemistry box model. The carbon bond mechanism IV (CBM-IV) with 36 gaseous species and 93 chemical reactions is incorporated. NOx and VOCs emission rates considered range from 0.01 to 0.30 ppb s(-1) with intervals of 0.01 ppb s(-1). Three different ventilation rates and three different NO2-to-NOx emission ratios are considered. The simulation results show that the ozone concentration decreases with increasing NOx emission rate but increases with increasing VOCs emission rate. When the emission ratio of VOCs to NOx is smaller than about 4, the ozone concentration is lower in the street canyon than in the background. On average, the magnitude of the sensitivity of ozone to NOx emission rate is significantly larger than that to VOCs emission rate. As the NOx emission rate increases, the magnitude of the sensitivity of ozone to NOx and VOCs emission rates decreases. Because the ozone concentration is lower in the street canyon than in the background, the increased ventilation rate enhances ozone inflow from the background. Therefore, the increase in ventilation rate results in the increase in ozone concentration and the decrease in the magnitude of the sensitivity of ozone to NOx and VOCs emission rates when the emission ratio of VOCs to NOx is smaller than about 4. On the other hand, the increase in NO2-to- NOx emission ratio results in the increase in ozone concentration because the chemical ozone production due to the NO2 photolysis is enhanced. In the present experimental setup, the contribution of the change in NO2-to- NOx emission ratio to the change in the sensitivity of ozone to NOx emission rate is larger than that of the change in ventilation rate.