Enhanced HONO Formation from Aqueous Nitrate Photochemistry in the Presence of Marine Relevant Organics: Impact of Marine-Dissolved Organic Matter (m-DOM) Concentration on HONO Yields and Potential Synergistic Effects of Compounds within m-DOM

Nitrous acid (HONO) is a key molecule in the reactive nitrogen cycle. However, sources and sinks for HONO are not fully understood. Particulate nitrate photochemistry has been suggested to play a role in the formation of HONO in the marine boundary layer (MBL). Here we investigate the impact of marine relevant organic compounds on HONO formation from aqueous nitrate photochemistry. In particular, steady-state, gas-phase HONO yields were measured from irradiated nitrate solutions at low pH containing marine-dissolved organic matter (m-DOM). m-DOM induces a nonlinear increase in HONO yield across all concentrations compared to that for pure nitrate solutions, with rates of HONO formation increasing by up to 3-fold when m-DOM is present. Furthermore, to understand the potential synergistic effects that may occur within complex samples such as m-DOM, mixtures of chromophoric (light-absorbing) and aliphatic (non-light-absorbing) molecular proxies were utilized. In particular, mixtures of 4-benzoylbenzoic acid (4-BBA) and ethylene glycol (EG) in acidic aqueous solutions containing nitrate showed more HONO upon irradiation compared to solutions containing only one of the molecular proxies. This suggests that synergistic effects in the HONO formation can occur in complex organic samples. Atmospheric implications of the results presented here are discussed.

This study examines how marine-dissolved organic matter enhances the photochemical conversion of nitrate into nitrous acid and uncovers synergistic effects in the formation of nitrous acid in the environment.