Supplementary material to "The Important Contribution of Secondary Formation and Biomass Burning to Oxidized Organic Nitrogen (OON) in a Polluted Urban Area: Insights from In Situ FIGAERO-CIMS Measurements"

Abstract. To investigate the sources and formation mechanism of oxidized organic nitrogen (OON), field measurements of OON were conducted using an iodide-adduct chemical ionization mass spectrometer equipped with a Filter Inlet for Gases and AEROsols (FIGAERO-CIMS) during fall of 2018 in the megacity of Guangzhou, China. Using levoglucosan as tracer of biomass burning emissions, the results show that biomass burning (49 %) and secondary formation (51 %) accounted for comparable fractions to the total particle-phase OON (pOON), while 24 % and 76 % to the gas-phase OON (gOON), respectively, signifying the important contribution of biomass burning to pOON and secondary formation to gOON in this urban area. Calculations of production rates of gas-phase organic nitrates (gON) indicated that hydroxyl radical (42 %) and nitrate radical (NO3) (49 %) oxidation pathways potentially dominated the secondary formation of gON. High concentration of NO3 radical during the afternoon daytime was observed, demonstrating that the daytime NO3 oxidation might be more important than the previous recognition. Monoterpenes, found to be major precursor of secondary gON, were mainly from anthropogenic emissions in this urban area. The ratio of secondary pOON to Ox ([Ox] = [O3] + [NO2]) increased as a function of relative humidity and aerosol surface area, indicating that heterogeneous reaction might be an important formation pathway for secondary pOON. Finally, the highly oxidized gOON and pOON with 6 to 11 oxygen atoms were observed, highlighting the complex secondary reaction processes of OON in the ambient air. Overall, our results can improve the understanding of the sources and dynamic variation of OON in urban atmosphere.