泰山夏季PM2.5中生物源SOA的分子组成及影响因素

衣雅男; 姚蒸蒸; 侯战方; 周瑞文; 李政; 刘晓迪; 王亚晨; 伏梦璇; 魏本杰; 燕丽; 孟静静

PDF(494 KB)

中国环境科学 ›› 2020, Vol. 40 ›› Issue (8) : 3352-3359.

大气污染与控制

泰山夏季PM_2.5中生物源SOA的分子组成及影响因素

衣雅男¹, 姚蒸蒸², 侯战方¹, 周瑞文¹, 李政¹, 刘晓迪¹, 王亚晨¹, 伏梦璇¹, 魏本杰¹, 燕丽³, 孟静静¹

作者信息 +

Molecular compositions and affecting factors of biogenic SOA in PM_2.5 from Mount Taishan during the summer

YI Ya-nan¹, YAO Zheng-zheng², HOU Zhan-fang¹, ZHOU Rui-wen¹, LI Zheng¹, LIU Xiao-di¹, WANG Ya-chen¹, FU Meng-xuan¹, WEI Ben-jie¹, Yan Li³, MENG Jing-jing¹

Author information +

文章历史 +

摘要

为探究泰山夏季PM_2.5中生物源二次有机气溶胶（BSOA）的分子组成、昼夜变化特征、及影响因素，于2016年7~8月在泰山山顶进行PM_2.5样品采集，并对碳质组分、无机离子和BSOA示踪物进行分析.结果表明，元素碳（EC）和左旋葡聚糖质量浓度处于较低水平且昼夜差异较小（t检验，P < 0.05），表明采样期间泰山山顶气溶胶受人为污染排放的影响较小.BSOA示踪物的总质量浓度呈昼高夜低的变化特征，表明白天较强的温度和太阳辐射使得气溶胶的氧化程度比夜间强.其中，异戊二烯类SOA示踪物的质量浓度最高达（77.64±51.79）ng/m³，其次为单萜烯类和倍半萜烯类SOA示踪物，分别为（33.68±21.29）和（6.97±3.28）ng/m³.基于示踪物-产率法估算得出SOC_异戊二烯对有机碳（OC）的贡献率（15.3%）最高.由BSOA示踪物与RH（R￡-0.45）和pH_is（R￡-0.53）的负相关性可知，高湿条件可以降低气溶胶的酸度进而抑制BSOA通过酸催化氧化反应的形成.由BSOA与温度和人为源指示物（左旋葡聚糖和EC）的相关性分析得出，采样期间泰山地区BSOA主要受当地BVOCs氧化反应的影响，而受长距离传输人为污染源的影响较小.

Abstract

To investigate the molecular composition, diurnal variation, and influencing factors of biogenic secondary organic aerosols (BSOA) in PM_2.5 from Mt. Tai during summer time, PM_2.5 samples were collected during July and August of 2016. The samples were determined for molecular distributions of carbonaceous compounds, inorganic ions and the tracers of BSOA (isoprene, monoterpene and sesquiterpene derived SOA). The results showed that the mass concentrations of elemental carbon (EC) and levoglucosan were in lower level and did not exhibit significant diurnal variations, suggesting that the effect of anthropogenic pollution during the sampling period was minor. The concentrations of BSOA tracers were higher in daytime than those in nighttime, indicating that the daytime aerosols were more photochemically aged than those in night time due to the higher temperature and stronger solar radiation. Isoprene SOA tracers [(77.64±51.79)ng/m³] was the dominant species, followed by monoterpene [(33.68±21.29)ng/m³] and sesquiterpene [(6.97±3.28)ng/m³] SOA tracers. Based on tracer-yield method, the contribution rate (15.3%) of isoprene derived secondary organic carbon (SOC) to OC was the highest. The BSOA tracers presented significant negative correlations with relative humidity (RH) (R￡-0.45) and particle in-situ pH (pH_is) (R￡-0.53), suggesting that higher RH can suppress the acid-catalyzed formation of BSOA because of the lower aerosol acidity due to dilution. The correlations of BSOA with temperature and anthropogenic pollutants (e.g., levoglucosan and EC) suggested that BSOA were largely derived from the local oxidation of biogenic VOCs rather than long-range transport.

导出引用

衣雅男, 姚蒸蒸, 侯战方, 周瑞文, 李政, 刘晓迪, 王亚晨, 伏梦璇, 魏本杰, 燕丽, 孟静静. 泰山夏季PM_2.5中生物源SOA的分子组成及影响因素[J]. 中国环境科学. 2020, 40(8): 3352-3359

YI Ya-nan, YAO Zheng-zheng, HOU Zhan-fang, ZHOU Rui-wen, LI Zheng, LIU Xiao-di, WANG Ya-chen, FU Meng-xuan, WEI Ben-jie, Yan Li, MENG Jing-jing. Molecular compositions and affecting factors of biogenic SOA in PM_2.5 from Mount Taishan during the summer[J]. China Environmental Science. 2020, 40(8): 3352-3359

中图分类号： X513

参考文献

[1] Li L, Lai W, Pu J G, et al. Polar organic tracers in PM_2.5 aerosols from an inland background area in Southwest China:Correlations between secondary organic aerosol tracers and source apportionment[J]. Journal of Environmental Science, 2018,69:281-293.
[2] Yuan Q, Lai S C, Song J W, et al. Seasonal cycles of secondary organic aerosol tracers in rural Guangzhou, Southern China:The importance of atmospheric oxidants[J]. Environmental Pollution, 2018,240:884-893.
[3] Guenther A, Karl T, Harley P, et al. Estimates of global terrestrial isoprene emissions using MEGAN (model of emissions of gases and aerosols from nature)[J]. Atmospheric Chemistry and Physics, 2006, 6:3181-3210.
[4] Chen Q, Farmer D K, Schneider J, et al. Mass spectral characterization of submicron biogenic organic particles in the Amazon Basin[J]. Geophysical Research Letters, 2009,36(20):L20806,doi:10.1029/2009GL039880.
[5] Carlton A G, Pinder R W, Bhave P V, et al. To what extent can biogenic SOA be Controlled?[J]. Environmental Science & Technology, 2010,44:3376-3380.
[6] Zhang Y J, Tang L L, Sun Y L, et al. Limited formation of isoprene epoxydiols-derived secondary organic aerosol under NO_x-rich environments in Eastern China[J]. Geophysical Research Letters, 2017,44(4):2035-2043.
[7] Kristensen K, Cui T, Zhang H, et al. Dimers in apinene secondary organic aerosol effect of hydroxyl radical, ozone, relative humidity and aerosol acidity[J]. Atmospheric Chemistry and Physics, 2014, 14(8):4201-4218.
[8] Hallquist M, Wenger J C, Baltensperger U, et al. The formation, properties and impact of secondary organic aerosol current and emerging issues[J]. Atmospheric Chemistry and Physics, 2009,9:5155-5236.
[9] Zhu C M, Kawamura K, Fu P Q. Seasonal variations of biogenic secondary organic aerosol tracers in Cape Hedo, Okinawa[J]. Atmospheric Environment, 2016,130:113-119.
[10] Stone E A, Nguyen T T, Pradhan B B, et al. Assessment of biogenic secondary organic aerosol in the Himalayas[J]. Environmental Chemistry, 2012,9(3):263-272.
[11] Li J J, Wang G H, Cao J J, et al. Observation of biogenic secondary organic aerosols in the atmosphere of a mountain site in central China:temperature and relative humidity effects[J]. Atmospheric Chemistry and Physics, 2013,13(22):11535-11549.
[12] Ren Y Q, Wang G H, Tao J, et al. Seasonal characteristics of biogenic secondary organic aerosols at Mt. Wuyi in Southeastern China:Influence of anthropogenic pollutants[J]. Environmental Pollution, 2019,252:493-500.
[13] Meng J J, Wang G H, Hou Z F,et al. Molecular distribution and stable carbon isotopic compositions of dicarboxylic acids and related SOA from biogenic sources in the summertime atmosphere of Mt. Tai in the North China Plain[J]. Atmospheric Chemistry and Physics, 2018, 18(20):15069-15086.
[14] Fu P Q, Kawamura K, Kanaya Y, et al. Contributions of biogenic volatile organic compounds to the formation of secondary organic aerosols over Mt. Tai, Central East China[J]. Atmospheric Environment, 2010,44(38):4817-4826.
[15] Zhu Y H, Yang L X, Kawamura K, et al. Contributions and source identification of biogenic and anthropogenic hydrocarbons to secondary organic aerosols at Mt. Tai in 2014[J]. Environmental Pollution, 2017,220:863-872.
[16] Meng J J, Liu X D, Hou Z F, et al. Molecular characteristics and stable carbon isotope compositions of dicarboxylic acids and related compounds in the urban atmosphere of the North China Plain:Implications for aqueous phase formation of SOA during the haze periods[J]. Science of The Total Environment, 2020,705:135256, doi:10.1016/j.scitotenv.
[17] Xue J, Lau A K H, Yu J Z. A study of acidity on PM_2.5 in Hong Kong using online ionic chemical composition measurements[J]. Atmospheric Environment, 2011,45(39):7081-7088.
[18] Kleindienst T E, Jaoui M, Lewandowski M, et al. Estimates of the contributions of biogenic and anthropogenic hydrocarbons to secondary organic aerosol at a southeastern US location[J]. Atmospheric Environment, 2007,41(37):8288-8300.
[19] Cao J J, Lee S C, Chow J C, et al. Spatial and seasonal distributions of carbonaceous aerosols over China[J]. Journal of Geophysical Research:Atmospheres, 2007,112(D22):D22S11,doi:10.1029/2006JD008205.
[20] Pio C, Cerqueira M, Harrison R M, et al. OC/EC ratio observations in Europe:Re-thinking the approach for apportionment between primary and secondary organic carbon[J]. Atmospheric Environment, 2011, 45(34):6121-6132.
[21] Zhang R, Wang G, Guo S, et al. Formation of urban fine particulate matter[J]. Chemical Reviews, 2015,115(10):3803-3855.
[22] 刘晓迪,孟静静,侯战方,等.济南市夏、冬季PM_2.5中化学组分的季节变化特征及来源解析[J].环境科学, 2018,39(9):4014-4025. Liu X D, Meng J J, Hou Z F, et al. Seasonal variation and source analysis of chemical characteristic in PM_2.5 during the summer and winter in Ji'nan City[J]. Environmental Science, 2018,39(9):4014-4025.
[23] Zhang R Y, Wang G H, Guo S, et al. Formation of urban fine particulate matter[J]. Chemical Reviews, 2015,115(10):3803-3855.
[24] Wang G H, Zhang F, Peng J F, et al. Particle acidity and sulfate production during severe haze events in China cannot be reliably inferred by assuming a mixture of inorganic salts[J]. Atmospheric Chemistry Physics, 2018,18(14):10123-10132.
[25] Wu Z J, Wang Y, Tan T Y, et al. Aerosol liquid water driven by anthropogenic inorganic salts:Implying its key role in haze formation over the North China Plain[J]. Environmental Science & Technology Letters, 2018,5(3):160-166.
[26] 孟静静,刘晓迪,侯战方,等.菏泽市冬季PM_2.5中二元羧酸类SOA的昼夜变化特征[J].环境科学, 2018,39(11):4876-4884. Meng J J, Liu X D, Hou Z F, et al. Diurnal variation of dicarboxylic acids and related SOA in PM_2.5 from Heze City in winter[J]. Environmental Science, 2018,39(9):4014-4025.
[27] Surratt J D, Murphy S M, Kroll J H, et al. Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene[J]. The Journal of Physical Chemistry A, 2006,110(31):9665-9690.
[28] Surratt J D, Chan A W, Eddingsaas N C,et al. Reactive intermediates revealed in secondary organic aerosol formation from isoprene[J]. Proceedings of the National Academy of Sciences of the United States of America, 2010,107(15):6640-6645.
[29] Szmigielski R, Surratt J D, Gómez-González Y,et al. 3-methyl-1, 2,3-butanetricarboxylic acid:An atmospheric tracer for terpene secondary organic aerosol[J]. Geophysical Research Letters, 2007, 34(24),L24811(1-6),doi:10.1029/2007GL031338.
[30] Haque M M, Kawamura K, Kim Y. Seasonal variations of biogenic secondary organic aerosol tracers in ambient aerosols from Alaska[J]. Atmospheric Environment, 2016,130:95-104.
[31] Ding X, Wang X M, Zheng M. The influence of temperature and aerosol acidity on biogenic secondary organic aerosol tracers:Observations at a rural site in the central Pearl River Delta region, South China[J]. Atmospheric Environment, 2011,45(6):1303-1311.
[32] Ren Y Q, Wang G H, Li J J,et al. Seasonal variation and size distribution of biogenic secondary organic aerosols at urban and continental background sites of China[J]. Journal of Environmental Sciences (China), 2018,71:32-44.
[33] Fu P Q, Kawamura K, Chen J,et al. Isoprene, monoterpene, and sesquiterpene oxidation products in the high Arctic aerosols during late winter to early summer[J]. Environment Science and Technology, 2009,43:4022-4028.
[34] Liu Y S, Li X R, Tang G Q,et al. Secondary organic aerosols in Jinan, an urban site in North China:Significant anthropogenic contributions to heavy pollution[J]. Journal of Environmental Science (China), 2019,80:107-115.
[35] Li J J, Wang G H, Zhang Q,et al. Molecular characteristics and diurnal variations of organic aerosols at a rural site in the North China Plain with implications for the influence of regional biomass burning[J]. Atmospheric Chemistry and Physics, 2019,19(16):10481-10496.
[36] Wang W Z, Wu M H, Li L,et al. Polar organic tracers in PM_2.5 aerosols from forests in eastern China[J]. Atmospheric Chemistry and Physics, 2008,8:7507-7518.
[37] Fu P Q, Kawamura K, Chen J, et al. Secondary production of organic aerosols from biogenic VOCs over Mt. Fuji, Japan[J]. Environmental Science & Technology, 2014,48(15):8491-8497.
[38] Hong Z, Zhang H, Zhang Y,et al. Secondary organic aerosol of PM_2.5in a mountainous forest area in southeastern China:Molecular compositions and tracers implication[J]. Science of the Total Environment, 2019,653:496-503.
[39] Ding X, Wang X M, Gao B, et al. Tracer-based estimation of secondary organic carbon in the Pearl River Delta, south China[J]. Journal of Geophysical Research:Atmospheres, 2012,117,D05313, doi:10.1029/2011JD016596.
[40] Zhu W F, Luo L N, Cheng Z,et al. Characteristics and contributions of biogenic secondary organic aerosol tracers to PM_2.5 in Shanghai, China[J]. Atmospheric Pollution Research, 2018,9(2):179-188.
[41] Ervens B, Turpin B J, Weber R J. Secondary organic aerosol formation in cloud droplets and aqueous particles (aqSOA):A review of laboratory, field and model studies[J]. Atmospheric Chemistry and Physics Discussions, 2011,11(8):22301-22383.
[42] Riva M, Bell D M, Hansen AM K,et al. Effect of organic coatings, humidity and aerosol acidity on multiphase chemistry of isoprene epoxydiols[J]. Environmental Science & Technology, 2016,50(11):5580-5588.