A comparative study of ozone production in five U.S. metropolitan areas

Abstract

We present observations of O 3 and O 3 precursors measured at mid boundary layer altitude during field campaigns in Nashville, Tennessee (1995), New York City, New York (1996), Phoenix, Arizona (1998), Philadelphia, Pennsylvania (1999), and Houston, Texas (2000). Ozone production rates P(O 3 ) and their sensitivity to NO x and volatile organic carbons (VOCs) are calculated using observed concentrations as inputs to a steady state box model. City to city comparisons are made to illustrate common features of urban photochemistry and features that are unique to specific cities. Ozone production rates vary from nearly zero to 155 ppb h −1 . Differences in P(O 3 ) depend on precursor concentrations, namely, radical sources, NO x and VOCs. Under conditions where P(O 3 ) is greater than 25 ppb h −1 , there is a potential to produce enough same‐day O 3 to transform a typical regional background into a severe O 3 episode. Six such cases were observed, in Nashville, Philadelphia, and Houston, with elevated O 3 concentrations in the afternoon (130–211 ppb) following a morning in which P(O 3 ) was 25–140 ppb h −1 . High P(O 3 ) occurs when NO x concentrations are 5–25 ppb and OH‐VOC reactivity is above 5 s −1 . These conditions are infrequent, and aside from a common dependence on calm winds, reasons vary from city to city. In Nashville, high P(O 3 ) was observed during a stagnation event over downtown and under the circumstance that an air mass with a high concentration of isoprene encountered a NO x source. In Houston, NO x and light olefins are coemitted from petrochemical facilities leading to the highest P(O 3 )s of the five cities studied. High values of P(O 3 ) did not occur in Phoenix because of low radical production, caused mainly by a dry atmosphere, and a low VOC to NO x ratio. The sensitivity of P(O 3 ) to its precursors varied from NO x limited in rural samples to VOC limited near emission sources. In Philadelphia, and especially Phoenix, the highest O 3 production rates occurred under VOC‐limited conditions. In Nashville, New York City, and Houston the high‐P(O 3 ) samples were near the ridge line where P(O 3 ) responds somewhat to VOC reductions but is insensitive to NO x changes.