Measurements of the HONO photodissociation constant

Measurements of the photodissociation constant for nitrous acid (j _HONO) were made at an urban site in Toronto, Canada, during the months of May–July 2005, using an optically thin actinometer. Operating details of the j _HONO monitor are reported, along with laboratory tests. Measurements of j _HONO were obtained for solar zenith angles ranging from 20–75^∘, under clear and cloudy skies. Maximum error estimates on j _HONO under clear skies range from 11% at sunrise, to 4% at solar noon, with a minimum detection limit of 5.7 × 10⁻⁴/sec for our actinometer. Measured clear-sky values of j _HONO were compared with values calculated by a four-stream discrete ordinate radiative transfer (RT) model (ACD TUV version 4.1), and were found to be within better than 10% agreement for solar zenith angles < 65^∘. For conditions of scattered cloud, enhancement and suppression of the j _HONO values occurred by as much as 16%–70%, and 59%–80%, respectively. The integrated band area of the nπ^∗ transition for gas-phase nitrous acid yields an oscillator strength, f = (1.06 ± 0.044)×10⁻³ (based on clear-sky data), 19.1% higher than the value reported by Bongartz et al. (1991).