Photochemical ageing of aerosols contributes significantly to the production of atmospheric formic acid

Abstract

Formic acid (HCOOH) is one of the most abundant organic acids in the atmosphere and affects atmospheric acidity and aqueous chemistry. However, the HCOOH sources are not well understood. In a recent field study, we measured atmospheric HCOOH concentrations at a coastal site in southern China. The average concentrations of HCOOH were 191 ± 167 ppt in marine air masses and 996 ± 433 ppt in coastal air masses. A strong linear correlation between HCOOH concentrations and the surface area densities of submicron particulate matter was observed in coastal air masses. Post-campaign laboratory experiments confirmed that the photochemical ageing of ambient aerosols promoted by heterogeneous reactions with ozone produced a high concentration of HCOOH at a rate of 0.185 ppb h−1 under typical ambient conditions at noon. HCOOH production was strongly affected by nitrate photolysis, as this efficiently produces OH radicals that oxidise organics to form HCOOH. We incorporated this particle-phase source into a photochemical model, and the net HCOOH production rate increased by about 3 times compared with the default Master Chemical Mechanism (MCM). These findings demonstrate that the photochemical ageing of aerosols is an important source of HCOOH that should be included in atmospheric chemistry–transport models.