Abstract

The nonlinear chemical processes involved in ozone production (P(O-3)) have necessitated using proxy indicators to convey information about the primary dependence of P(O-3) on volatile organic compounds (VOCs) or nitrogen oxides (NOx). In particular, the ratio of remotely sensed columns of formal... Show moreThe nonlinear chemical processes involved in ozone production (P(O-3)) have necessitated using proxy indicators to convey information about the primary dependence of P(O-3) on volatile organic compounds (VOCs) or nitrogen oxides (NOx). In particular, the ratio of remotely sensed columns of formaldehyde (HCHO) to nitrogen dioxide (NO2) has been widely used for studying O-3 sensitivity. Previous studies found that the errors in retrievals and the incoherent relationship between the column and the near-surface concentrations are a barrier in applying the ratio in a robust way. In addition to these obstacles, we provide calculational-observational evidence, using an ensemble of 0-D photochemical box models constrained by DC-8 aircraft measurements on an ozone event during the Korea-United States Air Quality (KORUS-AQ) campaign over Seoul, to demonstrate the chemical feedback of NO2 on the formation of HCHO is a controlling factor for the transition line between NOx-sensitive and NOx-saturated regimes. A fixed value (similar to 2.7) of the ratio of the chemical loss of NOx (LNOx) to the chemical loss of HO2+RO2 (LROx) perceptibly differentiates the regimes. Following this value, data points with a ratio of HCHO/ NO2 less than 1 can be safely classified as NOx-saturated regime, whereas points with ratios between 1 and 4 fall into one or the other regime. We attribute this mainly to the HCHO-NO2 chemical relationship causing the transition line to occur at larger (smaller) HCHO/NO2 ratios in VOC-rich (VOC-poor) environments. We then redefine the transition line to LNOx/LROx similar to 2.7 that accounts for the HCHO-NO2 chemical relationship leading to HCHO = 3.7 x (NO2 - 1.14 x 10(16) molec.cm(-2)). Although the revised formula is locally calibrated (i.e., requires for readjustment for other regions), its mathematical format removes the need for having a wide range of thresholds used in HCHO/NO2 ratios that is a result of the chemical feedback. Therefore, to be able to properly take the chemical feedback into consideration, the use of HCHO = a x (NO2 - b) formula should be preferred to the ratio in future works. We then use the Geostationary Trace gas and Aerosol Sensor Optimization (GeoTASO) airborne instrument to study O-3 sensitivity in Seoul. The unprecedented spatial (250 x 250 m(2)) and temporal (similar to every 2 h) resolutions of HCHO and NO2 observations form the sensor enhance our understanding of P(O-3) in Seoul; rather than providing a crude label for the entire city, more in-depth variabilities in chemical regimes are observed that should be able to inform mitigation strategies correspondingly. Show less