基于城市大气挥发性有机物特征分析的数据质量评估方法及案例
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摘要
城市大气挥发性有机物(VOCs)监测是空气质量监测网的重要组成部分,而数据质量控制和质量保证是VOCs监测的基础。基于8次中国城市大气VOCs外场监测,通过挖掘VOCs浓度、组成和化学活性的内在规律,对VOCs监测数据质量进行评估并总结方法。分析结果显示:城市大气乙烷和苯等长寿命组分具有明显的背景浓度,且区域背景值较为接近,可以用来诊断长寿命VOCs组分浓度异常偏低或偏高现象。而示踪组分的季节(日)变化规律可以用来识别VOCs组分定性问题(如夏季大气异戊二烯和烷基硝酸酯浓度日变化规律应反映植被排放和光化学反应特征)。另外,在气团混合均匀的情况下,VOCs浓度波动与其活性之间存在负相关,这一规律可以用来核查数据准确性或局地源影响。
Measurement of ambient VOCs in urban atmosphere is an important part of the air quality monitoring network,and data quality control and quality assurance is the basis of VOCs monitoring. Based on 8 ambient VOCs measurements in China,the quality of VOCs data was evaluated using internal consistency test on VOCs mixing ratios,chemical composition,and reactivity.Results showed that long-lived VOCs species ethane and benzene exhibited similar regional background concentration,which can be used to diagnose abnormal low mixing ratios of long-lived VOCs. The seasonal/diurnal variation of tracers can be used to identify qualitative problems of VOCs components. For example,the diurnal variations of ambient isoprene and alkyl nitrates in summer should reflect the characteristics of biogenic emissions and photochemical reactions,respectively. In addition,a negative correlation between fluctuation of VOCs mixing ratios and their reactivity were found for well-mixed air masses,which can be used to check VOCs data quality or influences of local sources.
Measurement of ambient VOCs in urban atmosphere is an important part of the air quality monitoring network,and data quality control and quality assurance is the basis of VOCs monitoring. Based on 8 ambient VOCs measurements in China,the quality of VOCs data was evaluated using internal consistency test on VOCs mixing ratios,chemical composition,and reactivity.Results showed that long-lived VOCs species ethane and benzene exhibited similar regional background concentration,which can be used to diagnose abnormal low mixing ratios of long-lived VOCs. The seasonal/diurnal variation of tracers can be used to identify qualitative problems of VOCs components. For example,the diurnal variations of ambient isoprene and alkyl nitrates in summer should reflect the characteristics of biogenic emissions and photochemical reactions,respectively. In addition,a negative correlation between fluctuation of VOCs mixing ratios and their reactivity were found for well-mixed air masses,which can be used to check VOCs data quality or influences of local sources.
引文
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[22]WANG C,SHAO M,HUANG D,et al.Estimating Halocarbon Emissions Using Measured Ratio Relative to Tracers in China[J].Atmospheric Environment,2014(89):816-826.
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[25]LIU Y,SHAO M,FU L,et al.Source Profiles of Volatile Organic Compounds(VOCs)Measured in China:Part I[J].Atmospheric Environment,2008,42(25):6 247-6 260.
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[27]JOBSON B,PARRISH D,GOLDAN P,et al.Spatial and Temporal Variability of Nonmethane Hydrocarbon Mixing Ratios and Their Relation to Photochemical Lifetime[J].Journal of Geophysical Research,1998,103(D11).
[2]HOERGER C,CLAUDE A,PLASS-DUELMER C,et al.ACTRIS Non-methane Hydrocarbon Intercomparison Experiment in Europe to Support WMO,GAW and EMEP Observation Networks[J].Atmospheric Measurement Techniques,2015,8(7):2715-2 736.
[3]师耀龙,柴文轩,李成,等.美国光化学污染监测的经验与启示[J].中国环境监测,2017,33(5):49-56.SHI Yaolong,CHAI Wenxuan,LI Cheng,et al.Experience and Illumination of Photochemical Pollution Monitoring in United States[J].Environmental Monitoring in China,2017,33(5):49-56.
[4]陆思华,邵敏,王鸣.城市大气挥发性有机化合物(VOCs)测量技术[M].北京:中国环境科学出版社,2012.
[5]高闽光,刘文清,张天舒,等.傅立叶变换红外光谱法被动遥测大气中VOC[J].光谱学与光谱分析,2005,25(7):1 042-1 044.GAO Minguang,LIU Wenqing,ZHANG Tianshu,et al.Passive Remote Sensing of VOC in Atmosphere by FTIR Spectrometry[J].Spectroscopy and Spectral Analysis,2005,25(7):1 042-1 044.
[6]李悦,邵敏,陆思华.城市大气中挥发性有机化合物监测技术进展[J].中国环境监测,2015,31(4):1-7.LI Yue,SHAO Min,LU Sihua.Review on Technologies of Ambient Volatile Organic Compounds Measurement[J].Environmental Monitoring in China,2015,31(4):1-7.
[7]APEL E,CALVERT J,GILPIN T,et al.Nonmethane Hydrocarbon Intercomparison Experiment(NOMHICE):Task 4,Ambient Air[J].Journal of Geophysical Research,2003,108(D9).
[8]WANG M,ZENG L,LU S,et al.Development and Validation of a Cryogen-Free Automatic Gas Chromatograph System(GC-MS/FID)for Online Measurements of Volatile Organic Compounds[J].Analytical Methods,2014,6(23):9 424-9 434.
[9]PARRISH D,TRAINER M,YOUNG V,et al.Internal Consistency Tests for Evaluation of Measurements of Anthropogenic Hydrocarbons in the Troposphere[J].Journal of Geophysical Research:Atmospheres,1998,103(D17):22 339-22 359.
[10]WANG M,SHAO M,CHEN W,et al.A Temporally and Spatially Resolved Validation of Emission Inventories by Measurements of Ambient Volatile Organic Compounds in Beijing,China[J].Atmospheric Chemistry and Physics,2014,14(12):5 871-5 891.
[11]YUAN B,HU W,SHAO M,et al.VOC Emissions,Evolutions and Contributions to SOA Formation at a Receptor Site in Eastern China[J].Atmospheric Chemistry and Physics,2013,13(17):8 815-8 832.
[12]WANG B,LIU Y,SHAO M,et al.The Contributions of Biomass Burning to Primary and Secondary Organics:A Case Study in Pearl River Delta(PRD),China[J].Science of the Total Environment,2016(569/570):548-556.
[13]YUAN B,LIU Y,SHAO M,et al.Biomass Burning Contributions to Ambient VOCs Species at a Receptor Site in the Pearl River Delta(PRD),China[J].Environmental Science&Technology,2010,44(12):4 577-4 582.
[14]WANG M,CHEN W,SHAO M,et al.Investigation of Carbonyl Compound Sources at a Rural Site in the Yangtze River Delta Region of China[J].Journal of Environmental Sciences,2015,28:128-136.
[15]XIE X,SHAO M,LIU Y,et al.Estimate of Initial Isoprene Contribution to Ozone Formation Potential in Beijing,China[J].Atmospheric Environment,2008,42(24):6 000-6 010.
[16]WANG B,SHAO M,LU S,et al.Variation of Ambient Non-methane Hydrocarbons in Beijing City in Summer2008[J].Atmospheric Chemistry and Physics,2010,10(13):5 911-5 923.
[17]WANG M,SHAO M,CHEN W,et al.Trends of Nonmethane Hydrocarbons(NMHC)Emissions in Beijing During 2002-2013[J].Atmospheric Chemistry and Physics,2015,15(3):1 489-1 502.
[18]LOUIE P,HO J,TSANG R,et al.VOCs and OVOCs Distribution and Control Policy Implications in Pearl River Delta Region,China[J].Atmospheric Environment,2013(76):125-135.
[19]WANG H,CHEN C,WANG Q,et al.Chemical Loss of Volatile Organic Compounds and Its Impact on the Source Analysis Through a Two-Year Continuous Measurement[J].Atmospheric Environment,2013(80):488-498.
[20]LI L,CHEN Y,ZENG L,et al.Biomass Burning Contribution to Ambient Volatile Organic Compounds(VOCs)in the Chengdu-Chongqing Region(CCR),China[J].Atmospheric Environment,2014(99):403-410.
[21]GUO H,SO K,SIMPSON I,et al.C1-C8 Volatile Organic Compounds in the Atmosphere of Hong Kong:Overview of Atmospheric Processing and Source Apportionment[J].Atmospheric Environment,2007,41(7):1 456-1 472.
[22]WANG C,SHAO M,HUANG D,et al.Estimating Halocarbon Emissions Using Measured Ratio Relative to Tracers in China[J].Atmospheric Environment,2014(89):816-826.
[23]BAKER A,BEYERSDORF A,DOEZEMA L,et al.Measurements of Nonmethane Hydrocarbons in 28United States Cities[J].Atmospheric Environment,2008,42(1):170-182.
[24]MONOD A,SIVE B,AVINO P,et al.Monoaromatic Compounds in Ambient Air of Various Cities:A Focus on Correlations Between the Xylenes and Ethylbenzene[J].Atmospheric Environment,2001,35(1):135-149.
[25]LIU Y,SHAO M,FU L,et al.Source Profiles of Volatile Organic Compounds(VOCs)Measured in China:Part I[J].Atmospheric Environment,2008,42(25):6 247-6 260.
[26]HELMIG D,TANNER D,HONRATH R,et al.Nonmethane Hydrocarbons at Pico Mountain,Azores:1.Oxidation Chemistry in the North Atlantic Region[J].Journal of Geophysical Research,2008,113(D20).
[27]JOBSON B,PARRISH D,GOLDAN P,et al.Spatial and Temporal Variability of Nonmethane Hydrocarbon Mixing Ratios and Their Relation to Photochemical Lifetime[J].Journal of Geophysical Research,1998,103(D11).