我国典型城市环境大气挥发性有机物特征比值

城市环境大气挥发性有机物(VOCs)比值能够提供有用信息.基于在我国典型城市进行的7次VOCs观测数据,利用正交最小二乘法(ODR)、线性拟合法等4种方法计算了VOCs组分比值,并探讨其在监测数据质量评估、来源诊断和光化学过程研究中的应用.结果显示:间,对-二甲苯与邻-二甲苯浓度在7次观测中均呈现非常好的相关性(r为0.975~0.997),且不同观测中比值接近(2.78~3.05),这一比值可以用来对城市大气VOCs(尤其是芳香烃)测量数据的可靠性进行评估.以甲苯/苯(T/B)和丙烷/乙烷(P/E)为例初步分析了我国不同城市大气VOCs来源的差异.上海和广州T/B最高,分别为2.37和1.78,高于隧道实验中T/B比值(1.52),说明还受到溶剂涂料等富含甲苯的排放源影响,北京夏季T/B与隧道实验接近,而成都、北京冬季和重庆T/B较低(0.744~1.36),说明受到生物质燃烧、煤燃烧等其他富含苯的排放源影响.P/E分析结果显示,广州P/E(1.27)显著高于其他数据集(0.270~0.645),与2010年广州部分公交车和出租车仍利用液化石油气(LPG)作为燃料有关.另外,基于邻-二甲苯/乙苯变化特征表征光化学反应程度,并初步估算出典型城市大气上午·OH暴露量为(2.70~4.45)×10~(10)molecule·cm~(-3)·s.

Ratios of Volatile Organic Compounds in Ambient Air of Various Cities of China

Volatile organic compounds (VOC) ratios in urban atmosphere could provide important information on VOC data quality, sources, and options for removal processes. Based on seven VOC measurement datasets, useful VOC ratios were calculated using four methods, including orthogonal distance(ODR), linear regression, geometric mean, mean, and frequency distribution. Ambient levels of m,p-xylene and o-xylene from the seven datasets showed good correlation with r ranging from 0.975 to 0.997, and their ratios (m,p-xylene/o-xylene) were close, with values of 2.78-3.05, indicating therefore that the ratio of m,p-xylene/o-xylene could be used to evaluate the quality of ambient measurement data in urban atmospheres. In addition, ratios of toluene versus benzene (T/B) and propane versus ethane (P/E) in different cities were compared, to investigate VOC sources in China. The highest T/B ratios were found in Shanghai and Guangzhou City, with values of 2.37 and 1.78, respectively, higher than the result from a tunnel study (1.52), suggesting the important influence of paint and solvent use. The T/B value for Beijing City during summer was close to that from the tunnel study, while the T/B ratios for Chengdu, Beijing during winter, and Chongqing were lower, with values ranging from 0.744 to 1.36, suggesting possible influences from biomass burning and coal combustion. The P/E value in Guangzhou was 1.27, significantly higher than the range of 0.270 to 0.645 found in other cities. The OH exposure in different cities were calculated based on o-xylene/ethylbenzene (X/E), with values ranging from 2.70×10¹⁰ to 4.45×10¹⁰ molecule·cm^-3·s.