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Abstract. Organic nitrates are important atmospheric species that significantly affect the cycling of NOx and ozone production. However, characterization of particulate organic nitrates and their sources in polluted atmosphere is a big challenge and has not been comprehensively studied in Asia. In this study, an aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed at an urban site in China from 2015 to 2016 to characterize particulate organic nitrates in total nitrates with a high time resolution. Based on the cross-validation of two different data processing methods, organic nitrates were effectively quantified to contribute a notable fraction of organic aerosol (OA), namely 9 %–21 % in spring, 11 %–25 % in summer, and 9 %–20 % in autumn, while contributing a very small fraction in winter. The good correlation between organic nitrates and fresh secondary organic aerosol (SOA) at night, as well as the diurnal trend of size distribution of organic nitrates, indicated a key role of nighttime local secondary formation of organic nitrates. Furthermore, theoretical calculations of nighttime SOA production of NO3 reactions with volatile organic compounds (VOCs) measured during the spring campaign were performed, resulting in three biogenic VOCs (α-pinene, limonene, and camphene) and one anthropogenic VOC (styrene) identified as the possible key VOC precursors to particulate organic nitrates. The comparison with similar studies in the literature implied that nighttime particulate organic nitrate formation is highly relevant to NOx levels. This study proposes that unlike the documented cases in the United States and Europe, modeling nighttime particulate organic nitrate formation in China should incorporate not only biogenic VOCs but also anthropogenic VOCs for urban air pollution, which needs the support of relevant smog chamber studies in the future.

<p><strong>Abstract.</strong> Organic nitrates are important atmospheric species that significantly affect the cycling of NOx and ozone production. However, characterization of particulate organic nitrates and their sources in inorganic nitrate-abundant particles in polluted atmosphere is a big challenge, and has been little performed in the literature. In this study, an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed at an urban site in South China from 2015 to 2016 to characterize particulate organic nitrates with high time resolution. Based on two different data processing methods, 13–21 % of the total measured nitrates was identified to be organic nitrates in spring, 41–64 % in summer and 16%–25 % in autumn; however, in winter, most measured nitrates were inorganic. The good correlation between organic nitrates and fresh secondary organic aerosol identified by the positive matrix factorization method at night rather than in the daytime indicated a potentially important role of nighttime secondary formation. Therefore, we theoretically estimated nighttime NO<sub>3</sub> radical concentrations and SOA formation using the various VOCs measured simultaneously. Consequently, the calculated products of monoterpene reacting with NO<sub>3</sub> agreed well with the organic nitrates in terms of both concentration and variation, suggesting that the biogenic VOC reactions with NO<sub>3</sub> at night are the dominant formation pathway for particulate organic nitrates in polluted atmosphere, despite of much higher abundance of anthropogenic VOCs.</p>

Secondary organic aerosol (SOA) is a key component in atmospheric aerosols, strongly influencing air quality and climate. Most previous studies focused on SOA formation in the fine aerosol mode, and little is known about SOA formation across a broader size range, especially for the coarse aerosol mode. In this study, we coupled radiocarbon analysis and the offline aerosol mass spectrometric method to characterize water-soluble organic matter in size-segregated samples between 0.056 and 18 μm collected in urban Shenzhen, China. For the first time, detailed size distributions of different types of oxygenated organic aerosols (OOAs) are obtained. Fossil fuel OOA was mostly distributed in fine particles, and biogenic OOA occurred mostly in coarse particles. Organic composition and correlation analyses suggested that the major source of the coarse-mode OOA was more plausible to be heterogeneous reactions of biogenic volatile organic compounds (VOCs) on soil dust rather than primary biological materials. If so, this mechanism would complement the missing sinks of biogenic VOCs, significantly influence the regional and global organic aerosol budgets, and thus should be considered in air quality and climate models. This study highlights the urgent need for laboratory simulations of heterogeneous reactions of various VOCs on soil dust.