Compact, Fast Cavity Ring-Down Spectroscopy Monitor for Simultaneous Measurement of Ozone and Nitrogen Dioxide in the Atmosphere

Abstract

A sensitive, compact detector for the simultaneous measurement of O3 and NO2 is presented in this work. There are two channels in the detector, namely the Ox channel and the NO2 channel. In the presence of excess NO, ambient O3 is converted to NO2 in the Ox measurement channel. In both channels, NO2 is directly detected via cavity ring-down spectroscopy (CRDS) at 409 nm. At a 10 s integration time, the Ox and NO2 channels have a 1σ precision of 14.5 and 13.5 pptv, respectively. The Allan deviation plot shows that the optimal sensitivity of O3 and NO2 occurs at an integration time of ~60 s, with values of 10.2 and 8.5 pptv, respectively. The accuracy is 6% for the O3 channel and 5% for the NO2 channel, and the largest uncertainty comes from the effective NO2 absorption cross-section. Intercomparison of the NO2 detection between the NO2 and Ox channels shows good agreement within their uncertainties, with an absolute shift of 0.31 ppbv, a correlation coefficient of R2 = 0.99 and a slope of 0.98. Further intercomparison for ambient O3 measurement between the O3/NO2-CRDS developed in this work and a commercial UV O3 monitor also shows excellent agreement, with linear regression slopes close to unity and an R2 value of 0.99 for 1 min averaged data. The system was deployed to measure O3 and NO2 concentrations in Hefei, China, and the observation results show obvious diurnal variation characteristics. The successful deployment of the system has demonstrated that the instrument can provide a new method for retrieving fast variations in ambient O3 and NO2.