Suggested Citation:
Kleeman, Michael J., Qi Ying, Ajith Kaduwela (2005) Control Strategies for the Reduction of Airborne Particulate Nitrate in California's San Joaquin Valley. Atmospheric Environment 39 (29), 5325 - 5341

The effect of NO_x, volatile organic compound (VOC), and NH₃ emissions control programs on the formation of particulate ammonium nitrate in the San Joaquin Valley (SJV) was examined under the typical winter conditions that existed on 4–6 January, 1996. The UCD/CIT photochemical transport model was used for this study so that the source origin of primary particulate matter and secondary particulate matter could be identified. When averaged across the entire SJV, the model results predict that 13–18% of the reactive nitrogen (NO_y=NO_x+reaction products of NO_x) emitted from local sources within the SJV was converted to nitrate at the ground level. Each gram of NO_x emitted locally within the SJV (expressed as NO₂) produced 0.23–0.31 g of particulate ammonium nitrate (NH₄NO₃), which is much smaller than the maximum theoretical yield of 1.7 g of NH₄NO₃ per gram of NO₂. The fraction of reactive nitrogen converted to nitrate varied strongly as a function of location. Urban regions with large amounts of fresh NO emissions converted little reactive nitrogen to nitrate, while remote areas had up to 70% conversion (equivalent to approximately 1.2 g of NH₄NO₃ per gram of NO₂). The use of a single spatially averaged ratio of NH₄NO₃/NO_x as a predictor of how changes to NO_x emissions would affect particulate nitrate concentrations would not be accurate at all locations in the SJV under the conditions studied.

The largest local sources of particulate nitrate in the SJV were predicted to be diesel engines and catalyst equipped gasoline engines under the conditions experienced on 6 January, 1996. Together, these sources accounted for less than half of the ground-level nitrate aerosol in the SJV. The remaining fraction of the aerosol nitrate originated from reactive nitrogen originally released upwind of the SJV. The majority of this upwind reactive nitrogen was already transformed to nitrate by the time it entered the SJV. The effect of local emissions controls on this upwind material was small.

A 50% reduction in NO_x emissions applied to sources within the SJV reduced the predicted concentration of total nitrate by approximately 25% during the study episode. VOC emissions controls were less effective, while reasonable NH₃ emissions controls had the smallest effect on the amount of ammonium nitrate produced. A 50% reduction in VOC emissions lowered predicted concentrations of total nitrate by 17.5%, while a 50% reduction in NH₃ emissions lowered predicted concentrations of total nitrate by only 10%. This latter result is expected since the formation of ammonium nitrate aerosol is limited by the availability of gas-phase nitric acid, with large amounts of excess NH₃ available. NO_x emissions controls appear to be the most efficient method to reduce the concentration of locally generated particulate nitrate in the SJV under the conditions experienced on 4–6 January, 1996.