The Use of Photochemical Indicators to Evaluate Ozone-NO_x-Hydrocarbon Sensitivity: Case Studies from Atlanta, New York, and Los Angeles

ABSTRACT

This study examines the use of ambient measurements of a number of "photochemical indicators" as a basis for determining ozone-NO_x-hydrocarbon sensitivity and for evaluating the performance of ozone models. The successful photochemical indicators are: 0₃/NO , 0₃/NO_z (where NO_z = NO_y-NO_x), 0₃/HN0₃, H₂0₂/HN0₃, and H₂0₂/NO_z. Results of Urban Airshed Model (UAM-IV) simulations for Atlanta, GA, New York, NY, and Los Angeles, CA, show that high values of these species ratios are correlated with NO_x-sensitive chemistry and low values are associated with reactive organic gases (ROG)-sen-sitive chemistry. Correlations between measured 0₃ and NO in Atlanta and between 0₃ and NO_z in Los Angeles are consistent with theory and reflect the difference between likely NO_x-sensitive chemistry in Atlanta and hydrocarbon-sensitive chemistry in Los Angeles. Measured 0₃, NO_x and NO are used to evaluate model performance during two air pollution events in Atlanta and Los Angeles. The performance evaluation includes model scenarios for each city with different anthropogenic and biogenic emission rates and different NO_x-ROG sensitivity predictions. Simulations with different NO_x-ROG chemistry are found to give similar predictions for peak ozone but different values for photochemical indicators. Comparison with measured values of photochemical indicators provides a more stringent test of model performance than evaluation versus observed ozone.