上海城区典型污染过程VOCs特征及臭氧潜势分析

利用在线气相色谱-氢火焰离子化（GC-FID）监测系统对上海市城区典型污染前、污染中和污染后的55种挥发性有机物（VOCs）进行了自动连续监测,分析了各个阶段VOCs（C2～C12）体积分数、物种变化特征.结果表明上海市城区典型污染前VOCs平均体积分数为27×10-9;污染中VOCs体积分数迅速增加,比污染前高3倍,达到87×10-9;具体以烷烃最高（35.2×10-9）、芳香烃次之（30.0×10-9）、烯烃最低（21.6×10-9）;用最大臭氧生成潜势量（ΦOFP）对不同污染阶段污染VOCs大气活性进行了评估,结果表明不同污染阶段VOCs的ΦOFP均呈现污染前〈污染后〈污染中的变化特征.污染前期的ΦOFP依次是芳香烃（53.0%）〉烯烃（36.1%）〉烷烃（11.7%）;污染中期的ΦOFP依次是芳香烃（54.7%）〉烯烃（36.7%）〉烷烃（9.8%）;污染后期ΦOFP则依次是烯烃（52.7%）〉芳香烃（36.0%）〉烷烃（13.2%）.具体关键活性物种主要包括甲苯、间、对二甲苯、1,3-丁二烯、乙烯、丙烯等芳香烃和烯烃物种,具体以烯烃C2～C4为主,芳香烃C6～C8为主.不同污染阶段O3与ΦOFP之间存在典型的非线性负相关关系,并且ΦOFP转化为O3的量均小于20%,说明臭氧浓度仍有很大上升空间;这对定量评估大气中VOCs对臭氧的影响具有重要意义.

Characteristics of Ambient VOCs and Their Role in O3 Formation:A Typical Air Pollution Episode in Shanghai Urban Area

The concentration, speciation and chemical reactivity of ambient volatile organic compounds (VOCs) in shanghai city were analyzed and measured by using online gas chromatography with flame ionization detection systems (GC-FID) during a typical air pollution episode (from Oct. 30th to Nov. 2nd, 2010) and 55 kinds of VOCs were detected. The results show that averaged concentrations of VOCs was 27 x 10(-9) before the episode, and then dramatically increased by 3 times (87 x 10(-9)) in the episode than the former, the main components were alkanes (35.2 x 10(-9)), aromatics (30.0 x 10(-9)), alkenes (21.6 x 10(-9)). Furthermore, the maximum ozone formation potential (PhiOFP) is analyzed and showed that PhiOFP (in the episode) > PhiOFP (after the episode) PhiOFP (before the episode). Before the episode, the percent of PhiOFP for aromatics 53.0% , alkenes 36. 1% and alkanes 11.7%; in the episode, the percent of PhiOFP for aromatics 54.7%, alkenes 36.7% and alkanes 9.8%; after the episode, the percent of PhiOFP for alkenes 52.7%, aromatics 36.0% and alkanes 13.2%. Alkenes (C2-C4) and aromatics (C6-C8) are the main components for the ozone formation, namely toluene, m,p-xylene, 1,3-butadiene, propene, ethene et al. In addition, the relationship is negative and nonlinear between the O3 and PhiOFP. And efficiencies of PhiOFP formed into O3 are below 20. 0% in different stage of episode. This is very important and meaningful for the quantitative evaluate the influence of VOCs towards O3.