Development of a net ozone production rate detection system based on dual-channel cavity ring-down spectroscopy

A novel system for measuring net photochemical ozone production rates in the atmosphere based on cavity ring-down spectroscopy (OPR-CRDS) was developed. The system consists of two chambers (a reaction chamber and a reference chamber) and a dual-channel O_x-CRDS detector. To minimize the wall loss of O_x in the chambers, the inner surfaces of both chambers are coated with Teflon film. The performance of the OPR-CRDS system was characterized. It was found that even though the photolysis frequency (J value) decreased by 10%, the decrease in the P(O₃) caused by the ultraviolet-blocking film coating was less than 3%. The two chambers had a good consistency in the mean residence time and the measurement of NO₂ and O_x under the condition of no sunlight. The detection limit of the OPR-CRDS was determined to be 0.20 ppbv/hr. To further verify the accuracy of the system, the direct measurement values of the OPR-CRDS system were compared with the calculation results based on radical (OH, HO₂, and RO₂) reactions, and a good correlation was obtained between the measured and calculated values. Finally, the developed instrument was applied to obtain the comprehensive field observations at an urban site in the Yangtze River Delta (China) for 40 days, the time series and change characteristics of the P(O₃) were obtained directly, and the good environmental adaptability and stability of the OPR-CRDS system were demonstrated. It is expected that the new instrument will be beneficial to investigations of the relationship between P(O₃) and its precursors.