Measurement report: Important contributions of oxygenated compounds to emissions and chemistry of volatile organic compounds in urban air

Abstract

Abstract. Volatile organic compounds (VOCs) play important roles in the tropospheric atmosphere. In this study, VOCs were measured at an urban site in Guangzhou, one of the megacities in the Pearl River Delta (PRD), using a gas chromatograph–mass spectrometer/flame ionization detection (GC–MS/FID) and a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS). Diurnal profile analyses show that stronger chemical removal by OH radicals for more reactive hydrocarbons occurs during the daytime, which is used to estimate the daytime average OH radical concentration. In comparison, diurnal profiles of oxygenated volatile organic compounds (OVOCs) indicate evidence of contributions from secondary formation. Detailed source analyses of OVOCs, using a photochemical age-based parameterization method, suggest important contributions from both primary emissions and secondary formation for measured OVOCs. During the campaign, around 1700 ions were detected in PTR-ToF-MS mass spectra, among which there were 462 ions with noticeable concentrations. VOC signals from these ions are quantified based on the sensitivities of available VOC species. OVOC-related ions dominated PTR-ToF-MS mass spectra, with an average contribution of 73 % ± 9 %. Combining measurements from PTR-ToF-MS and GC–MS/FID, OVOCs contribute 57 % ± 10 % to the total concentration of VOCs. Using concurrent measurements of OH reactivity, OVOCs measured by PTR-ToF-MS contribute greatly to the OH reactivity (19 % ± 10 %). In comparison, hydrocarbons account for 21 % ± 11 % of OH reactivity. Adding up the contributions from inorganic gases (48 % ± 15 %), ∼ 11 % (range of 0 %–19 %) of the OH reactivity remains `missing”, which is well within the combined uncertainties between the measured and calculated OH reactivity. Our results demonstrate the important roles of OVOCs in the emission and evolution budget of VOCs in the urban atmosphere.