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.