Using back trajectories and process analysis to investigate photochemical ozone production in the Puget Sound region

A photochemical Eulerian grid modeling system, consisting of MM5/CALMET/CALGRID, was modified to include a process analysis scheme, and a back trajectory method using the CALPUFF model in a reverse diffusion mode was implemented to define the air mass transport path reaching a downwind receptor from urban Seattle, WA. Process analysis was used to determine the relative importance of chemical production, advection, diffusion and deposition within the receptor grid cell and also along the air mass transport path from the urban source area to the receptor. This analysis was applied to an ozone episode occurring during 11–14 July 1996, in the Puget Sound region of Washington State. Within the receptor grid, the process analysis showed that ozone concentrations increase during the day as chemical production exceeds the net effects of deposition and vertical diffusion. Concentrations decrease after mid-afternoon when horizontal advection begins to dominate the other processes. When applied along the air mass transport path, process analysis shows that during most of the day, chemical production is larger than the other processes and causes the air mass ozone concentration to steadily increase during transport downwind of the urban core. Maximum ozone production rates equaled 20–25 ppb/h along the trajectory to the rural monitoring site where peak ozone levels occurred approximately 40 km downwind of urban Seattle, WA. The chemical production rates during this ozone evolution process play an important role in the peak ozone values. Higher peak ozone concentrations that occurred on Sunday, 14 July 1996 (118 ppbv), compared to those on Friday, 12 July 1996 (80 ppbv), were due, in part, to the higher ozone production rates along the trajectory to the rural monitoring site on 14 July compared to 12 July. These differences in chemical production appear to be related to differences in VOC/NOx ratios within the urban air mass for each day. The importance of VOC/NOx effects on the 2 days versus differences in meteorology was confirmed by running the simulation for Friday with Sunday emissions and using Sunday meteorological fields with Friday emissions. Differences in emissions for the 2 days produced almost twice the effect on peak ozone concentrations at the downwind receptor compared to the effects of differences in meteorology for these 2 days.