Nitrous acid measurements in urban Los Angeles using novel techniques

Nitrous acid (HONO) is an important player in tropospheric photochemistry, as it is a source of hydroxyl radicals. Thus, accurate measurements of HONO and its sources and sinks are critical to fully understand tropospheric oxidation processes. Differential optical absorption spectroscopy (DOAS) has been used to measure HONO in the field over the past two decades, yielding much of the current knowledge about the molecule and its sources. In situ measurements with high sensitivity, time resolution and minimal interferences can provide further information about HONO sources and sinks. One method that could satisfy these criteria is incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS). IBBCEAS combines the sensitivity of cavity-enhanced techniques with the specificity of spectral resolution. The application of IBBCEAS to laboratory HONO measurements has been demonstrated, but the technique has not yet been used to detect HONO in the field. A two-channel instrument was custom-built for field measurements of HONO, with the first channel a 365 nm-centred IBBCEAS to measure HONO and NO2 and the second channel a 403 nm cavity ring-down spectrometer for an independent measure of NO2. The instrument was successfully deployed at the CalNex Pasadena ground site in May and June, 2010. Measurements compared well with previously validated HONO instrumentation, including DOAS, negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS) and a wet-chemical, derivitization system with HPLC detection (NitroMAC).