光照对柠檬烯臭氧氧化产生二次有机气溶胶的影响

大气与环境光学学报 ›› 2012, Vol. ›› Issue (5): 348-357.

光照对柠檬烯臭氧氧化产生二次有机气溶胶的影响

刘志，胡长进，程跃，潘刚，郑晓宏，顾学军，赵卫雄，张为俊*

(中国科学院安徽光学精密机械研究所大气物理化学研究室，安徽合肥 230031)

收稿日期:2012-03-06 修回日期:2012-03-20 发布日期:2012-10-21
通讯作者: 刘志（1988-），男，河南信阳人，硕士研究生，主要从事大气光化学和二次有机气溶胶研究. E-mail:wjzhang@aiofm.ac.cn
作者简介:刘志（1988-），男，河南信阳人，硕士研究生，主要从事大气光化学和二次有机气溶胶研究.
基金资助:
国家自然科学基金（10979061，40975080）、中科院安徽光学精密机械研究所所长基金（YO3AG31147）、中国科学院知识创新工程重要方向性项目（KJCX2-YW-N24）资助

Effect of Illumination on Secondary Organic Aerosol Formation from Ozonolysis of Limonene

LIU Zhi, HU Chang-jin, CHENG Yue, PAN Gang, ZHENG Xiao-hong, GU Xue-jun, ZHAO Wei-xiong, ZHANG Wei-jun*

(Laboratory of Atmospheric Physico-Chemistry, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei 230031, China)

Received:2012-03-06 Revised:2012-03-20 Online:2012-10-21

摘要/Abstract

摘要：

作为一种重要的生物源挥发性有机物，柠檬烯的臭氧氧化是大气环境中二次有机气溶胶（SOA）的重要来源之一。基于实验室烟雾箱模拟系统，研究了紫外光照对柠檬烯臭氧氧化形成SOA的影响。实验分别对无光照（即“暗反应”）和有光照条件下反应前体物的消耗、SOA的质量浓度以及SOA的粒径分布随时间的变化等进行了实时探测，并结合气粒分配模型对产率进行了分析。研究结果表明在相应的实验条件下，紫外光照会导致SOA产率下降10-16%，而气相氧化阶段相关中间产物或者最终产物的光化学反应可能是导致产率下降的重要原因之一。

关键词: 光照, 柠檬烯, 臭氧氧化, 二次有机气溶胶, 烟雾箱

Abstract:

As an important biogenic volatile organic compound, ozonolysis of limonene is a significant source of atmospheric secondary organic aerosol (SOA). Quantitative research on ozonolysis of limonene was reported under both dark and UV-illuminated conditions in the self-made smog chamber. The time evolutions of limonene precursor, SOA mass concentration as well as SOA particle size distributions were investigated continuously, and the yield of SOA was analyzed according to the gas/particle partitioning theory. It is shown that exposure to UV light reduces SOA yield by 10%~16% under corresponding conditions, and it is proposed that gas-phase photolysis of some intermediate or final products may play a key role in the decline of yields in the presence of UV light.

Key words: illumination, limonene, ozonolysis, secondary organic aerosol, smog chamber

中图分类号:

X513

刘志胡长进程跃潘刚郑晓宏顾学军赵卫雄张为俊. 光照对柠檬烯臭氧氧化产生二次有机气溶胶的影响[J]. 大气与环境光学学报, 2012, (5): 348-357.

LIU Zhi, HU Chang-Jin, CHENG Yue, PAN Gang, ZHENG Xiao-Hong, GU Xue-Jun, ZHAO Wei-Xiong, ZHANG Wei-Jun. Effect of Illumination on Secondary Organic Aerosol Formation from Ozonolysis of Limonene[J]. Journal of Atmospheric and Environmental Optics, 2012, (5): 348-357.

参考文献

[1] Seinfeld J H, Pandis S N. Atmospheric Chemistry and Physics: From Air Pollution to Climate Change [M]. 2nd edition, New York: John Wiley & Sons, 2006.
[2] Hallquist M, Wenger J C, Baltensperger U, et al. The formation, properties and impact of secondary organic aerosol: current and emerging issures [J]. Atmos. Chem. Phys., 2009, 9(14): 5155-5236.
[3] Guenther A, Hewitt C N, Erickson D, et al. A global model of natural volatile organic compound emissions [J]. J. Geophys. Res., 1995, 100(D5): 8873-8892.
[4] Stroud C, Makar P, Karl T, et al. Role of canopy-scale photochemistry in modifying biogenic-atmosphere exchange of reactive terpene species: results from the CELTIC field study [J]. J. Geophys. Res., 2005, 110(D17): D17303.
[5] Weschler C J, Shields H C. Indoor ozone/terpene reactions as a source of indoor particles [J]. Atmos. Environ., 1999, 33(15): 2301-2312.
[6] Leungsakul S, Jaoui M, Kamens R M. Kinetic mechanism for predicting secondary organic aerosol formation from the reaction of d-limonene with ozone [J]. Environ. Sci. Technol., 2005, 39(24): 9583-9594. [7] Maksymiuk C S, Gayahtri C, Gil R R, et al. Secondary organic aerosol formation from multiphase oxidation of limonene by ozone: mechanistic constraints via two-dimensional heteronuclear NMR spectroscopy [J]. Phys. Chem. Chem. Phys., 2009, 11(36): 7810-7818.
[8] Walser M L, Desyaterik Y, Laskin J, et al. High-resolution mass spectrometric analysis of secondary organic aerosol produced by ozonation of limonene [J]. Phys. Chem. Chem. Phys., 2008, 10(7): 1009-1022.
[9] Pan X, Underwood J S, Xing J H, et al. Photodegradation of secondary organic aerosol generated from limonene oxidation by ozone studied with chemical ionization mass spectrometry [J]. Atmos. Chem. Phys., 2009, 9(12): 3851-3865.
[10] N?jgaard J K, Bilde M, Stengy C, et al. The effect of nitrogen dioxide on particle formation during ozonolysis of two abundant monoterpenes indoors [J]. Atmos. Environ., 2006, 40(6): 1030-1042.
[11] Zhang J Y, Hartz K E H, Pandis S N, et al. Secondary organic aerosol formation from limonene ozonolysis: homogeneous and heterogeneous influences as a function of NOx [J]. J. Phys. Chem. A., 2006, 110(38): 11053-11063.
[12] Saathoff H, Naumann K H, Moehler O, et al. Temperature dependence of yields of secondary organic aerosols from the ozonolysis of α-pinene and limonene [J]. Atmos. Chem. Phys., 2009, 9(5): 3851-3865.
[13] Jonsson ? M, Hallquist M, Ljungstr?m E. The effect of temperature and water on secondary organic aerosol formation from ozonolysis of limonene, Δ3-carene and α-pinene [J]. Atmos. Chem. Phys., 2008, 8(21): 6541-6549.
[14] Griffin R J, Cocker D R, Flagan R C, et al. Organic aerosol formation from oxidation of biogenic hydrocarbons [J]. J. Geophys. Res., 1999, 104(D3): 3555-3567.
[15] Presto A A, Hartz K E H, Donahue N M. Secondary organic aerosol production from terpene ozonolysis. 1. effect of UV radiation [J]. Environ. Sci. Technol., 2005, 39(18): 7028-7037.
[16] http://www.eurochamp.org/ [OL].
[17] Wang Wenxing, Shu Yonghui, Li Jinhua. Photochemical degradation of PAH_S on smoke particles in atmosphere [J]. China Environmental Science, 1997, 17(2): 97-102(in Chinese).
王文兴, 束用辉, 李金花. 煤烟粒子中PAH_S光化学降解的动力学 [J]. 中国环境科学, 1997, 17(2): 97-102.
[18] Zhang Yuanhang, Shao Kesheng, Tang Xiaoyan. The study of urban photochemical smog pollution in China [J]. Acta Scientiarum Naturalium Universitatis Pekinensis, 1998, 34(2-3): 392-400(in Chinese). 张远航, 邵可声, 唐孝炎. 中国城市光化学烟雾污染研究 [J]. 北京大学学报(自然科学版), 1998, 34(2-3): 392-400.
[19] Wu Shan, Hao Jiming, Lu Zifeng, et al. Effect of ammonium sulfate aerosol on the photochemical reaction of toluene/NOx/air mixture [J]. Environmental Science, 2007, 28(6): 1183-1187(in Chinese).
武山, 郝吉明, 吕子峰, 等. 硫酸铵气溶胶对甲苯-NOx-空气体系光化学反应的影响 [J]. 环境科学, 2007, 28(6): 1183-1187.
[20] Wu H, Mou Y J. Rate constant and products for the reaction of Cl atom with n-butyaldehyde [J]. Int. J. Chem. Kinet., 2007, 39(3): 168-174.
[21] Du L, Xu Y F, Ge M F, et al. Rate constant for the reaction of ozone with diethyl sulfide [J]. Atmos. Environ., 2007, 41(35): 7434-7439.
[22] Pan G, Hu C J, Wang Z Y, et al. Direct detection of isoprene photooxidation products by using synchrotron radiation photoionization mass spectrometry [J]. Rapid Commun. Mass Spectrom., 2012, 26(2): 189-194.
[23] Liu X Y, Zhang W J, Huang M Q, et al. Effect of illumination intensity and light application time on secondary organic aerosol formation from the photooxidation of α-pinene [J]. J. Environ. Sci., 2009, 21(4): 447-451.
[24] Odum J R, Hoffmann T, Bowman F, et al. Gas/particle partitioning and secondary organic aerosol yields [J]. Environ. Sci. Technol., 1996, 30(8): 2580-2585.
[25] Wirtz K, Martin-Reviejo M. Density of secondary organic aerosols [J]. J. Aerosol. Sci., 2003, 34: S223-S224.
[26] Cocker D R, Flagan R C, Seinfeld J H. State-of-the-art chamber facility for studying atmospheric aerosol chemistry [J]. Environ. Sci. Technol., 2001, 35(12): 2594-2601.
[27] Takekawa H, Minoura H, Yamazaki S. Temperature dependence of secondary organic aerosol formation by photo-oxidation of hydrocarbons [J]. Atmos. Environ., 2003, 37(24): 3413-3424.
[28] Pankow J F. An absorption model of the gas/aerosol partitioning involved in the formation of secondary organic aerosol [J]. Atmos. Environ., 1994, 28(2): 189-193. [29] Cao G, Jang M. Effects of particle acidity and UV light on secondary organic aerosol formation from oxidation of aromatics in the absence of NOx [J]. Atmospheric Environment, 2007, 41(35): 7603-7613.