Simultaneous detection of atmospheric HONO and NO₂ utilising an IBBCEAS system based on an iterative algorithm

We present an improved incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) system based on an iterative retrieval algorithm for the simultaneous detection of atmospheric nitrous acid (HONO) and nitrogen dioxide (NO2). The conventional IBBCEAS retrieval algorithm depends on the absolute change in the light intensity, which requires high light source stability and the stable transmission of the light intensity of all optical components. The new algorithm has an iterative module to obtain the effective absorption optical path length, and the concentrations of HONO and NO2 are then determined by differential optical absorption spectroscopy (DOAS) retrieval; thus, the method is insensitive to the fluctuation in the absolute light intensity. The robustness of the system is verified by simulating the influence of the relative change in the light intensity on the spectral retrieval results. The effect of nitrogen purging in front of the cavity mirrors on shortening the actual cavity length was measured and corrected using NO2 gas samples. Allan deviation analysis was conducted to determine the system stability, and it indicated that the detection limits (2 sigma) of HONO and NO2 are 0.08 and 0.14 ppbv at an integration time of 60 s respectively. Furthermore, Kalman filtering was used to improve the measurement precision of the system. The measurement precision at an integration time of 3 s can be improved 4.5-fold by applying Kalman filtering, which is equivalent to the measurement precision at an integration time of 60 s without applying Kalman filtering. The atmospheric HONO and NO2 concentrations were observed by the IBBCEAS system based on an iterative algorithm and were compared with values measured by conventional IBBCEAS.