Heterogeneous formation and partitioning of nitrous acid on water surfaces: dependency on the acidity

Hydrolysis of nitrogen dioxide (NO₂) has long been recognized as a major formation path of atmospheric nitrous acid (HONO), which is regarded as a dominant hydroxyl radical (OH) source, particularly in a polluted environment. Since HONO is moderately water soluble and its solubility can be highly dependent on the acidity of the water solution, the HONO formation rate and its ensuring fate may also be affected by the acidity of the water surfaces. In this work, we investigated the hydrolysis of NO₂ on dilute sulfuric acid water solutions with a pH value ranging from ~3 to ~6. Both the gaseous HONO and dissolved nitrous acid solution were quantified by a wet-chemistry based HONO analyzer and ion chromatography analyses, respectively. The results showed that significant amount of HONO can participate into the aqueous phase at low acidity and as the acidity increased gas-phase HONO also increased. These results indicated that liquid water on various surfaces may both provide a reaction site for HONO formation and serve as a reservoir of HONO that can be released when the liquid water was evaporated.