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. Volatile organic compounds (VOCs) regulate atmospheric oxidationcapacity, and the reactions of VOCs are key in understanding ozone formationand its mitigation strategies. When evaluating their impact, most previousstudies did not fully consider the role of oxygenated VOCs due tolimitations of measurement technology. By using a proton-transfer-reactiontime-of-flight mass spectrometer (PTR-ToF-MS) combined with a gaschromatograph–mass spectrometer (GC–MS), a large number of oxygenated VOCs (OVOCs)have been quantified in Guangzhou city, China. Based on the new dataset, wedemonstrate that constraints using OVOC observations are essential inmodeling radical and ozone production, as modeled OVOCs can besubstantially lower than measurements, potentially due to primary emissionsand/or missing secondary sources. Non-formaldehyde (HCHO) OVOCs cancontribute large fractions (22 %–44 %) of total ROx radical production,which are comparable to or larger than the contributions from nitrous acidand formaldehyde. Our results show that models without OVOC constraintsusing ambient measurements will underestimate the production rates ofROx and ozone, and they may also affect the determination of sensitivityregime in ozone formation. Therefore, a thorough quantification ofphotodegradable OVOC species is in urgent need to understand accurately the ozone chemistry and to develop effective control strategies.

atmospheric chemistry and physics

Direct observations indicate photodegradable oxygenated volatile organic compounds (OVOCs) as larger contributors to radicals and ozone production in the atmosphere