Modeling of daytime HONO vertical gradients during SHARP 2009

Abstract. Nitrous acid (HONO) acts as a major precursor of the hydroxyl radical (OH) in the urban atmospheric boundary layer in the morning and throughout the day. Despite its importance, HONO formation mechanisms are not yet completely understood. It is generally accepted that conversion of NO₂ on surfaces in the presence of water is responsible for the formation of HONO in the nocturnal boundary layer, although the type of surface on which the mechanism occurs is still under debate. Recent observations of higher than expected daytime HONO concentrations in both urban and rural areas indicate the presence of unknown daytime HONO source(s). Various formation pathways in the gas phase, and on aerosol and ground surfaces have been proposed to explain the presence of daytime HONO. However, it is unclear which mechanism dominates and, in the cases of heterogeneous mechanisms, on which surfaces they occur.

Vertical concentration profiles of HONO and its precursors can help in identifying the dominant HONO formation pathways. In this study, daytime HONO and NO₂ vertical profiles, measured in three different height intervals (20–70, 70–130, and 130–300 m) in Houston, TX, during the 2009 Study of Houston Atmospheric Radical Precursors (SHARP) are analyzed using a one-dimensional (1-D) chemistry and transport model. Model results with various HONO formation pathways suggested in the literature are compared to the the daytime HONO and HONO/NO₂ ratios observed during SHARP. The best agreement of HONO and HONO/NO₂ ratios between model and observations is achieved by including both a photolytic source of HONO at the ground and on the aerosol. Model sensitivity studies show that the observed diurnal variations of the HONO/NO₂ ratio are not reproduced by the model if there is only a photolytic HONO source on aerosol or in the gas phase from NO₂^* + H₂O. Further analysis of the formation and loss pathways of HONO shows a vertical dependence of HONO chemistry during the day. Photolytic HONO formation at the ground is the major formation pathway in the lowest 20 m, while a combination of gas-phase, photolytic formation on aerosol, and vertical transport is responsible for daytime HONO between 200–300 m a.g.l. HONO removal is dominated by vertical transport below 20 m and photolysis between 200–300 m a.g.l.