杭州市城区挥发性有机物污染特征及反应活性

使用Summa罐在杭州市城区朝晖站点离线采样,利用GCMS分析122种挥发性有机物（VOCs）.通过2018年5月至2019年4月连续1a的观测,结果发现,观测期间大气VOCs平均体积分数为（59.4±23.6）×10^-9,浓度高值出现在12月而低值出现在2月,含氧有机物（OVOC）,尤其是醛酮类化合物是占比最高的组分,在夏季尤甚.朝晖站点VOCs浓度没有明显的周末效应,但节假日的VOCs浓度有明显下降.其大气VOCs浓度与空气质量指数（AQI）值呈现正相关性,首要污染物为PM_2.5时观测到的VOCs浓度最高.运用·OH消耗速率（L^·OH）和臭氧生成潜势（OFP）做大气反应活性评估,观测期间L^·OH均值为7.5 s^-1,OFP均值为152.1×10^-9,醛酮类化合物、芳烃和烯烃是活性最高的组分,该站点整体大气活性水平与2-甲基戊烷相当.观测期间甲苯/苯（T/B）均值为1.95,说明杭州市城区受到较明显的机动车排放影响.使用正定矩阵因子分析法（PMF）解析出杭州全年VOCs污染的6个因子,分别为二次生成（17.6%）、燃烧源（11.8%）、工艺过程（12.3%）、溶剂使用（18.1%）、天然源（4.5%）和机动车尾气（35.7%）.

Characteristics and Reactivity of Ambient VOCs in Urban Hangzhou, China

The ambient concentration of 122 volatile organic compound (VOC) species were continuously measured in urban Hangzhou, China from May 2018 to April 2019. The average mixing ratio of VOCs was (59.4±23.6)×10^-9 and the oxygenated VOCs (OVOC) were the largest component. There was no clear "weekend effect" in urban Hangzhou, while the concentration of VOCs had a sharp decrease during long holidays. The concentration of VOCs had a positive correlation with air quality index (AQI) and reached the highest level when the primary pollutant was PM_2.5. The assessment results of atmospheric chemical reactivity with·OH radical loss rate (L^·OH) and ozone formation potential (OFP) showed the average value of L^·OH was 7.5 s^-1 and that of OFP was 152.1×10^-9, among which carbonyl compounds, aromatics, and alkenes were the most abundant components. The overall chemical reactivity level of VOCs in Hangzhou was equivalent to 2-methylpentane. The average value of toluene/benzene (T/B) was 1.95, which implied the ambient VOCs in Hangzhou were influenced by vehicle exhaust. Secondary formation (17.6%), combustion (11.8%), industrial processing (12.3%), solvent use (18.1%), biogenic source (4.5%), and vehicle exhaust (35.7%) were identified as six major sources of VOCs in Hangzhou through the positive matrix factorization (PMF) model.