Direct identification of total and missing OH reactivities from light-duty gasoline vehicle exhaust in China based on LP-LIF measurement

Abstract

Considerable efforts have been devoted to characterising the chemical components of vehicle exhaust. However, these components may not accurately reflect the contribution of vehicle exhaust to atmospheric reactivity because of the presence of species not accounted for (“missing species”) given the limitations of analytical instruments. In this study, we improved the laser photolysis–laser-induced fluorescence (LP–LIF) technique and applied it to directly measure the total OH reactivity (TOR) in exhaust gas from light-duty gasoline vehicles in China. The TOR for China I to VI-a vehicles was 15.6, 16.3, 8.4, 2.6, 1.5, and 1.6 × 104 sec−1, respectively, reflecting a notable drop as emission standards were upgraded. The TOR was comparable between cold and warm starts. The missing OH reactivity (MOR) values for China I to IV vehicles were close to zero with a cold start but were much higher with a warm start. The variations in oxygenated volatile organic compounds (OVOCs) under different emission standards and for the two start conditions were similar to those of the MOR, indicating that OVOCs and the missing species may have similar production processes. Online measurement revealed that the duration of the stable driving stage was the primary factor leading to the production of OVOCs and missing species. Our findings underscore the importance of direct measurement of TOR from vehicle exhaust and highlight the necessity of adding OVOCs and other organic reactive gases in future upgrades of emission standards, such that the vehicular contribution to atmospheric reactivity can be more effectively controlled.