二次有机气溶胶估算方法比较研究
收稿日期: 2014-04-14
网络出版日期: 2014-05-11
基金资助
项目受国家重点基础研究发展计划（No.2013CB228503）和国家自然科学基金（Nos.21025728，21190052，GZ663，41121004）资助.
Comparison of Secondary Organic Aerosol Estimation Methods
Received date: 2014-04-14
Online published: 2014-05-11
Supported by
Project supported by the National Basic Research Program of China (No.2013CB228503) and the National Natural Science Foundation of China (Nos.21025728, 21190052, GZ663, 41121004).
为研究北京夏季二次有机气溶胶（SOA）浓度，比较多种SOA估算方法的不确定性和在我国的适用性，在CAREBEIJING 2008大型观测期间在城市点北大点和郊区点榆垡点采集大气颗粒物PM2.5样品，利用多种方法对二次有机碳（SOC）的浓度进行了估算，估算方法包括二次有机示踪物产率法、非一次源OC法、非生物质燃烧水溶性有机碳法（WSOC）和元素碳示踪有机碳/元素碳比值法.估算结果表明，二次有机气溶胶已经成为北京颗粒有机物的重要组成部分，夏季SOC可以占总有机碳（OC）的50%甚至更高。通过模拟我国典型的生物质燃烧，实测建立适合我国的获得了非生物质燃烧WSOC方法中的重要参数，即获得方法中重要参数生物质燃烧排放颗粒物中WSOC/OC的比值，我国生物质燃烧颗粒物中该比值平均为0.48±0.04.多种方法结果均表明，SOA已经成为北京颗粒有机物的重要组成部分，所占比例可以达到50%甚至更高.利用化学质量守恒模型（CMB）和示踪物产率法对颗粒有机物来源进行闭合发现，依靠目前的示踪物技术北京大气颗粒有机物中仍然有20%～27%的来源不清楚.通过综合比较了多种SOC估算方法，确定了各方法在我国的适用性： 示踪物产率法、非一次源OC法和EC示踪OC/EC比值法可适用于我国大气中SOC的估算，但是非生物质燃烧WSOC方法仅适用于我国大气中水溶性SOC的估算，但是不同方法之间存在的系统误差.本研究还对这几种方法的不确定性做了初步的分析，为其他研究者选择估算方法提供参考和依据.示踪物产率法仅估算了几种特定VOCs前体物对SOC贡献，因此低估了总的SOC，但是这种方法是目前唯一一种可以估算特定VOCs前体物对SOC贡献的方法；同样地，非生物质燃烧WSOC法仅估算了水溶性的SOC，因此也低估了总的SOC；非一次源OC法高估了SOC，这主要是由于未能解析出的一次源OC造成的.而且这种高估在城市地区更为显著，主要是因为城市地区一次源相对比较复杂造成的；非生物质燃烧WSOC法低估了总的SOC，而且这种方法仅适用于我国水溶性SOC的估算；EC示踪OC/EC比值法的主要不确定性来自于一次源OC/EC比值的确定，由于这个比值造成的单点误差最高可高估54%或低估64%.
郭松 , 胡敏 , 郭庆丰 , 尚冬杰 . 二次有机气溶胶估算方法比较研究[J]. 化学学报, 2014 , 72(6) : 658 -666 . DOI: 10.6023/A14040254
To investigate the secondary organic aerosol (SOA) formation in Beijing, fine particle (PM2.5) samples were collected at an urban site (Peking University, PKU) and a rural site (Yufa) during CAREBEIJING 2008 summer intensive field campaign.Several approaches were used to estimate ambient secondary organic aerosolsSOA concentrations, including tracer-yield method, non-primary organic carbon method (receptor model, Chemical Mass Balance model), non-biomass burning water soluble organic carbon (WSOC) method and EC tracer OC/EC ratio method.The results indicated secondary formation has become major contributor to organic aerosols in Beijing, accounting for 50% or more of the total OC during the campaign.To develop non-biomass burning WSOC method, simulation of typical Chinese biomass burning was conducted to obtain the important parameters.The average WSOC/OC ratio in Chinese biomass burning is 0.48±0.04.This ratio can be used in non-biomass burning WSOC method to estimate SOC of China.The results from different methods all indicated secondary formation has become major contributor to organic aerosols in Beijing, accounting for 50% or more of the total OC.A closure study was made by combination of CMB model and tracer-yield method.Five primary sources, including vegetative detritus, biomass burning, coal burning, gasoline engines and diesel engines, and four secondary organic aerosols derived from isoprene, α-pinene, β-caryophyllene and toluene were apportioned.To the current knowledge, about 20%～27% of the OC sources still remain unknown.Applicability of these SOC methods in China was tested by comparing the different methods.Tracer-yield method, CMB model and EC tracer OC/EC ratio method can be used to estimate SOC in China.However, non-biomass burning WSOC method can only be used to estimate water-soluble SOC.Uncertainty analysis was conducted to help researchers to choose determine the proper method to estimate SOC in China.Tracer-yield method underestimates total SOC, but it is the only approach thatbecause it can only estimate SOCs from several specific precursors.Similarly, non-biomass burning WSOC method also underestimate SOC.Non-primary OC method overestimates SOC due to unapportioned primary OC, especially in urban area where the particle sources are complicated.Non-biomass burning WSOC method underestimate SOC, and can only be used to estimate water soluble SOC in China.The uncertainty of EC-tracer OC/EC ratio method is mainly from the primary OC/EC ratio.The largest overestimation and underestimation of single point value can be 54% and 64%.
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