Comparison of the SAPRC07 and SAPRC99 photochemical mechanisms during a high ozone episode in Texas: Differences in concentrations, OH budget and relative response factors

The latest SAPRC photochemical mechanism SAPRC07 (S07), an update from SAPRC99 (S99), is implemented into the Community Multi-scale Air Quality (CMAQ) model and applied to simulate a high ozone episode during the Texas Air Quality Study 2000 (TexAQS 2000). The results from the S07 mechanism are compared with those from the S99 mechanism. In general, the predicted 03 concentrations by S07 are lower than those of S99 with maximum difference as high as 20%. The two mechanisms also show significant differences in the predicted OH, HNO3, PAN and HCHO concentrations. S99 predicts higher OH concentration by 7-20%, higher PAN by approximately 20-25% and higher HCHO by approximately 15% than S07. OH budget analysis suggests that OH propagation factor (P-OH) is higher in urban and industrial areas but lower in rural areas. Although S07 generally predicts similar or higher P-OH, S99 predicts higher new OH formation rate from H2O + O(D-1) and leads to higher OH and thus higher O-3 in most part of the domain. OH reactions with VOCs and CO accounts for a majority part of reacted OH. Secondary VOCs photolysis is not a main path of regenerated OH. New OH mainly comes from H2O + O(D-1) reaction. Although the two mechanisms predict different ozone concentrations, the relative response factor (RRF) of ozone at rural, urban and industrial sites under emission controls of anthropogenic NO. and VOC controls by factors 0.6-1.4 predicted by the two mechanisms are very similar. This suggests that although the absolute predictions are different, both models will provide nearly identical attainment assessment in regulatory applications. (C) 2012 Elsevier Ltd. All rights reserved.