Measuring and modeling investigation of the net photochemical ozone production rate via an improved dual-channel reaction chamber technique

Current process-based research mainly uses box models to evaluate photochemical ozone production and destruction rates, and it is unclear to what extent the photochemical reaction mechanisms are elucidated. Here, we modified and improved a net photochemical ozone production rate (NPOPR, P(O3)net) detection system based on the current dual-channel reaction chamber technique, which makes the instrument applicable to different ambient environments, and its various operating indicators were characterized, i.e., "airtightness", light transmittance, wall losses of the reaction and reference chambers, conversion rate of O3 to NO2, air residence time, and performance of the reaction and reference chambers. The limits of detection of the NPOPR detection system were determined to be 0.07, 1.4, and 2.3 ppbv h-1 at sampling flow rates of 1.3, 3, and 5 L min-1, respectively. We further applied the NPOPR detection system to field observations at an urban site in the Pearl River Delta (China). During the observation period, the maximum value of P(O3)net was 34.1 ppbv h-1, which was similar to 0 ppbv h-1 at night within the system detection error and peaked at approximately noon local time. The daytime (from 06:00-18:00 LT) average value of P(O3)net was 12.8 (+/- 5.5) ppbv h-1. We investigated the detailed photochemical O3 formation mechanism in the reaction and reference chambers of the NPOPR detection system using a zero-dimensional box model. We found that the photochemical reactions in the reaction chamber were very close to those in ambient air, but there was not zero chemistry in the reference chamber because the reaction related to the production and destruction of RO2 (= HO2 + RO2) continued in the reference chamber, which led to a small amount of P(O3)net. Therefore, the P(O3)net measured here can be regarded as the lower limit of the real P(O3)net in the atmosphere; however, the measured P(O3)net was still similar to 7.5 to 9.3 ppbv h-1 higher than the modeled P(O3)net value depending on different modeling methods, which may be due to the inaccurate estimation of HO2 / RO2 radicals in the modeling study. Short-lived intermediate measurements coupled with direct P(O3)net measurements are needed in the future to better understand O3 photochemistry. Our results show that the NPOPR detection system can achieve high temporal resolution and continuous field observations, which helps us to better understand photochemical O3 formation and provides a key scientific basis for continuous improvement of air quality in China.