Interference from HONO in the measurement of ambient air NO₂ via photolytic conversion and quantification of NO

The reference method to quantify mixing ratios of the criteria air pollutant nitrogen dioxide (NO₂) is NO-O₃ chemiluminescence (CL), in which mixing ratios of nitric oxide (NO) are measured by sampling ambient air directly, and mixing ratios of NO_x (= sum of NO and NO₂) are measured by converting NO₂ to NO using, for example, heated molybdenum catalyst or, more selectively, photolytic conversion (P-CL). In this work, the nitrous acid (HONO) interference in the measurement of NO₂ by P-CL was investigated. Results with two photolytic NO₂ converters are presented. The first used radiation centered at 395 nm, a wavelength region commonly utilized in P-CL. The second used light at 415 nm, where the overlap with the HONO absorption spectrum and hence its photolysis rate are less. Mixing ratios of NO₂, NO_x and HONO entering and exiting the converters were quantified by Thermal Dissociation Cavity Ring-down Spectroscopy (TD-CRDS). Both converters exhibited high NO₂ conversion efficiency (CF_NO2; > 90%) and partial conversion of HONO. Plots of CF against flow rate were consistent with photolysis frequencies of 4.2 s^-1 and 2.9 s^-1 for NO₂ and 0.25 s^-1 and 0.10 s^-1 for HONO at 395 nm and 415 nm, respectively. CF_HONO was larger than predicted from the overlap of the emission and HONO absorption spectra. The results imply that measurements of NO₂ by P-CL marginally but systematically overestimate true NO₂ concentrations, and that this interference should be considered in environments with high HONO:NO₂ ratios such as the marine boundary layer or in biomass burning plumes.