Photochemical Aging of Atmospheric Fine Particles as a Potential Source for Gas-Phase Hydrogen Peroxide

Atmospheric hydrogen peroxide (H₂O₂), as an important oxidant, plays a key role in atmospheric sulfate formation, affecting the global radiation budget and causing acid rain deposition. The disproportionation reactions of hydroperoxyl radicals (HO₂) in both gas and aqueous phases have long been considered as dominant sources for atmospheric H₂O₂. However, these known sources cannot explain the significant formation of H₂O₂ in polluted areas under the conditions of high NO levels and low ambient relative humidity (RH). Here, we show that under relatively dry conditions during daytime, atmospheric fine particles directly produce abundant gas-phase H₂O₂. The formation of H₂O₂ is verified to be by a reaction between the particle surface -OH group and HO₂ radicals formed by photooxidation of chromophoric dissolved organic matters (CDOMs), which is slightly influenced by the presence of high NO levels but remarkably accelerated by water vapor and O₂. In contrast to aqueous-phase chemistry, transition metal ions (TMIs) are found to significantly suppress H₂O₂ formation from the atmospheric fine particles. The H₂O₂ formed from relatively dry particles can be directly involved in in situ SO₂ oxidation, leading to sulfate formation. As CDOMs are ubiquitous in atmospheric fine particles, their daytime photochemistry is expected to play important roles in formation of H₂O₂ and sulfate worldwide.