基于气团老化程度对挥发性有机物分类改善PMF源解析效果

VOCs作为臭氧与二次有机气溶胶的关键前体物,其来源解析对臭氧和颗粒物的协同控制至关重要.但多数VOCs具有反应性,不能完全满足受体模式对污染源排放化学物质组成稳定的假设要求,导致受体模式解析结果不能精准反映实际源贡献.为解决因不同VOCs反应活性不同而导致的组分相对变化与模型假设不符的问题,引入VOCs老化程度来表征其光化学反应的状态.将乌海市超级观测站监测的VOCs依据乙苯与间/对-二甲苯的比值分为高、中和低这3种老化状态.结果表明,分类后解析结果的模拟值与实测值的回归方程参数(斜率和截距)、标准误差、决定系数和残差合格率等模型诊断参数改善明显.因为老化程度与气团在大气中的传输时间和大气氧化性密切相关,在一定程度上也反映了气团的不同来源信息.在高老化态样品中焦化源贡献率最高,达47.20%;在低老化态样品中燃烧源和焦化源均较高,分别为28.67%和24.39%.按老化程度进行分类后,PMF对VOCs源解析的结果更符合实际排放源的贡献.

Improved Performance of PMF Source Apportionment for Volatile Organic Compounds Based on Classification of VOCs' Aging Degree in Air Mass

VOCs are the key precursors of ozone and secondary organic aerosols. The results of source apportionment for VOCs are very important for the coordinated control of ozone and second organic particulate matter. However, VOCs do not fully meet the assumption of the receptor model because the VOCs released from each source are relatively unstable in the transmission process for their reactivity. As a result, we do not accurately obtain the actual source contribution when the receptor model is used for the source apportionment of VOCs. In order to solve the problem that the relative changes in the components caused by VOCs reactivity are not consistent with the PMF model hypothesis, the aging degree of VOCs was introduced to distinguish the state characteristics after their photochemical reactions in the ambient air. According to the ratio of ethylbenzene to m/p-xylene, VOCs monitored at Wuhai were divided into three aging states:high, medium, and low. The results showed that the model parameters, such as regression equation parameters (slope and intercept), standard error, determination coefficient, and pass rate of residual error, were improved obviously compared to the sample set after classification. Because the degree of aging is closely related to the transport time of air mass and the atmospheric oxidation in the atmosphere, it also reflects the different sources of air mass to some extent. In the high-aging VOCs samples, the coking source occupied a high proportion (up to 47.20%). In the low-aging VOCs samples, the combustion source and coking source accounted for a higher proportion, 28.67% and 24.39%, respectively. After the classification according to the aging degree, the results of VOCs source apportionment by PMF are more consistent with the actual contribution of emission sources.