The characteristics of wintertime volatile organic compounds(VOCs)in the North China Plain(NCP)region are complicated and remain obscure.VOC measurements were con-ducted by a proton transfer reaction time-of-flight mass spectrometer(PTR-ToF-MS)at a rural site in the NCP from November to December 2018.Uncalibrated ions measured by PTR-ToF-MS were quantified and the overall VOC compositions were investigated by combining the measurements of PTR-ToF-MS and gas chromatography-mass spectrometer/flame ion-ization detector(GC-MS/FID).The measurement showed that although atmospheric VOCs concentrations are often dominated by primary emissions,the secondary formation of oxy-genated VOCs(OVOCs)is non-negligible in the wintertime,i.e.,OVOCs accounts for 42％±7％in the total VOCs(151.3±75.6 ppbV).We demonstrated that PTR-MS measurements for isoprene are substantially overestimated due to the interferences of cycloalkanes.The chemical changes of organic carbon in a pollution accumulation period were investigated,which suggests an essential role of fragmentation reactions for large,chemically reduced compounds during the heavy-polluted stage in wintertime pollution.The changes of emis-sion ratios of VOCs between winter 2011 and winter 2018 in the NCP support the positive effect of"coal to gas"strategies in curbing air pollutants.The high abundances of some key species(e.g.oxygenated aromatics)indicate the strong emissions of coal combustion in wintertime of NCP.The ratio of naphthalene to C8 aromatics was proposed as a potential indicator of the influence of coal combustion on VOCs.

Xianjun He;Bin Yuan;Caihong Wu;Sihang Wang;Chaomin Wang;Yibo Huangfu;Jipeng Qi;Nan Ma;Wanyun Xu;Ming Wang;Wentai Chen;Hang Su;Yafang Cheng;Min Shao

Institute for Environmental and Climate Research,Jinan University,Guangzhou 511443,China;Guangdong-Hongkong-Macau Joint Laboratory of Collaborative Innovation for Environmental Quality,Guangzhou 511443,China;State Key Laboratory of Severe Weather&Key Laboratory for Atmospheric Chemistry of China Meteorology Administration,Chinese Academy of Meteorological Sciences,Beijing 100081,China;Collaborative Innovation Center of Atmospheric Environment and Equipment Technology,Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control,School of Environmental Science and Engineering,Nanjing University of Information Science&Technology,Nanjing 210044,China;Nanjing Intelligent Environmental Science and Technology Co.,Ltd.,Nanjing 211800,China;Max Planck Institute for Chemistry,Mainz 55128,Germany

环境科学学报（英文版）

[1]Xianjun He;Bin Yuan;Caihong Wu;Sihang Wang;Chaomin Wang;Yibo Huangfu;Jipeng Qi;Nan Ma;Wanyun Xu;Ming Wang;Wentai Chen;Hang Su;Yafang Cheng;Min Shao-.Volatile organic compounds in wintertime North China Plain:Insights from measurements of proton transfer reaction time-of-flight mass spectrometer(PTR-ToF-MS))[J].环境科学学报（英文版）,2022(04):98-114

Uncalibrated,ppbV,cycloalkanes

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