Linking Precursors and Volatility of Ambient Oxygenated Organic Aerosols Using Thermal Desorption Measurement and Machine Learning

Xinyu Wang, Yongyi Zhao, Ke Hu, Jian Wang, Qiongqiong Wang, Nan Chen, Bo Zhu, Hong-Hai Zhang and Huan Yu*, 
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Abstract

We conducted thermal desorption measurements and machine learning analysis to investigate the volatility and precursors of ambient oxygenated organic aerosols (OOA), with a focus on the link between them, in a variety of urban and marine locations. We found that the OOA species measured by an iodide-based Chemical Ionization Mass Spectrometer equipped with a Filter Inlet for Gases and AEROsol (FIGAERO-CIMS) accounted for 16 ± 13% of OA in those urban and marine locations and represented mostly the secondary and moderate-volatility portion of ambient OA. On average, 25.1% in species number and 26.8% in mass of the OOA species detected by the FIGAERO-CIMS in a winter campaign at an urban site in Wuhan, a megacity in central China, might be attributed to thermal decomposition fragments. Our results show that the volatility and precursor of ambient OOA differed systematically according to location, season, and pollution level. The OOA in the ocean atmosphere was characterized by high fractions of extremely low volatility organic compounds (ELVOC) and aliphatic species, while the inland urban OOA was characterized by aromatic species and fell primarily into the low volatility organic compounds (LVOCs) and semivolatile organic compounds (SVOCs) range. The volatilities of OOA in the inland urban atmosphere in summer, pollution days, and daytime were lower than those in winter, clean days, and nighttime. When the PM episode developed from clean to particle growth and then to pollution period, the OOA species shifted from Low-Mw OOA species to Median-Mw OOA species and then to highly nonvolatile species. The study of ambient OOA volatility in this work also provides important data for future closure studies of SOA formation and its precursors.

Abstract Image

利用热脱附测量和机器学习将环境含氧有机气溶胶的前体和挥发性联系起来
我们进行了热解吸测量和机器学习分析,以研究环境含氧有机气溶胶(OOA)的挥发性和前体,重点是它们之间在城市和海洋等不同地点的联系。我们发现,配备气体和含氧有机气溶胶过滤器入口的碘化化学电离质谱仪(FIGAERO-CIMS)测量到的含氧有机气溶胶物种占这些城市和海洋地区含氧有机气溶胶的 16 ± 13%,并且主要代表了环境含氧有机气溶胶的次级和中等挥发性部分。FIGAERO-CIMS 在武汉(中国中部的一个特大城市)的一次冬季活动中检测到的 OOA 物种中,平均有 25.1% 的物种数量和 26.8% 的质量可能归因于热分解碎片。我们的研究结果表明,不同地点、不同季节和不同污染程度的环境中 OOA 的挥发性和前体都存在系统性差异。海洋大气中的 OOA 以高比例的极低挥发性有机化合物(ELVOC)和脂肪族物种为特征,而内陆城市的 OOA 以芳香族物种为特征,主要属于低挥发性有机化合物(LVOC)和半挥发性有机化合物(SVOC)范围。夏季、污染日和白天内陆城市大气中的 OOA 挥发性低于冬季、清洁日和夜间。当可吸入颗粒物从清洁期发展到颗粒物增长期,再发展到污染期时,OOA 种类从低-Mw OOA 种类转变为中-Mw OOA 种类,再转变为高不挥发性种类。这项工作中对环境 OOA 挥发性的研究也为未来 SOA 形成及其前体的封闭研究提供了重要数据。
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