Direct observations indicate photodegradable oxygenated VOCs as larger contributors to radicals and ozone production in the atmosphere

Abstract. Volatile organic compounds (VOCs) regulate atmospheric oxidation capacity, and the reactions of VOCs are key in understanding ozone formation and its mitigation strategies. When evaluating its impact, most previous studies did not fully consider the role of oxygenated VOCs due to limitations of measurement technology. By using a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) combined with gas chromatography mass spectrometer (GC-MS) technology, we are able to quantify a large number of oxygenated VOCs in a representative urban environment in southern China. Based on the new dataset, we find that non – formaldehyde (HCHO) OVOCs can contribute large fractions (22–44 %) of total ROX radical production, comparable or larger than the contributions from nitrous acid and formaldehyde. We demonstrate that constraints using OVOCs observations are essential in modeling radical and ozone production, as modelled OVOCs can be substantially lower than measurements, potentially due to primary emissions and/or missing secondary sources. Our results show that models without OVOC constraints using ambient measurements will underestimate P(ROX) and ozone production rate, and may also affect the determination of sensitivity regime in ozone formation. Therefore, a thorough quantification of photodegradable OVOCs species is in urgent need to understand accurately the ozone chemistry and to develop effective control strategies.