苯乙烯-臭氧反应产生的二次有机气溶胶的吸湿性研究

大气与环境光学学报 ›› 2012, Vol. ›› Issue (4): 254-.

苯乙烯-臭氧反应产生的二次有机气溶胶的吸湿性研究

（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）

（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:2012-03-16 修回日期:2012-03-29 出版日期:2012-07-28 发布日期:2012-07-19
通讯作者: 郑晓宏（1985-）男, 广东汕头人, 研究生, 主要从事大气物理化学研究. E-mail:wjzhang@aiofm.ac.cn
作者简介:郑晓宏（1985-）男, 广东汕头人, 研究生, 主要从事大气物理化学研究.
基金资助:
国家自然科学基金（10979061、40975080）、中国科学院知识创新工程重要方向性项目（KJCX2-YW-N24）、中科院安徽光学精密机械研究所所长基金（YO3AG31147）资助

Hygroscopicity of SOA Formed by Ozonolysis of Styrene

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

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

Received:2012-03-16 Revised:2012-03-29 Published:2012-07-28 Online:2012-07-19

摘要/Abstract

摘要：

基于自主搭建的加湿串联差分迁移率分析仪(hygroscopic tandem differential mobility analyzer, H-TDMA)和实验室烟雾箱模拟系统，分别对有无种子气溶胶（硫酸铵）存在的条件下，苯乙烯臭氧氧化反应体系产生的二次有机气溶胶(secondary organic aerosol, SOA)的吸湿性进行了研究。通过对反应产生的不同粒径的SOA粒子(70 nm, 85 nm, 100 nm)的吸湿性测量，发现无论有无种子气溶胶的存在，产生的SOA粒子的吸湿生长因子(growth factor, GF)（相对湿度为85%）都随着反应时间的继续而逐渐增大；并且在有硫酸铵种子气溶胶存在的条件下产生的SOA的吸湿性比无种子气溶胶情况下产生的粒子的吸湿性更强，但比纯的硫酸铵无机气溶胶的吸湿性要小。分析表明随着氧化反应的进行，更多的吸湿性较大的高极性氧化产物分配到SOA粒子中，导致这些粒子的GF由反应初始阶段的<1逐渐增大到>1；而在有种子气溶胶存在的条件下产生的SOA粒子，由于受硫酸铵种子气溶胶较强吸湿性的影响，因此比没有种子气溶胶时产生的纯SOA相对要强，但这种影响受限于外层包裹的有机组分的较低的吸湿性（相对于硫酸铵），因此远小于纯硫酸铵气溶胶的吸湿生长因子。而不同粒径的SOA粒子的吸湿性生长因子随时间的演化关系所表现出来的一致性，也表明了在本实验条件下，产生的SOA气溶胶粒子的化学组成不依赖于粒子的粒径。

关键词: 苯乙烯, 臭氧氧化, 二次有机气溶胶, 吸湿性

Abstract:

The hygroscopic property of secondary organic aerosols (SOA) formed by ozonolysis of styrene has been comprehensively studied on the basis of self-assembled hygroscopic-tandem differential mobility analyzer (H-TDMA) and the homemade smog chamber. SOA was produced in the dry chamber (RH<5%) in the presence and absence of ammonium sulfate seed particles, and the diameter-based (70 nm, 85 nm, 100 nm) hygroscopic growth factor (GF) of the SOA as a function of time has been measured by using H-TDMA. It is found that the aerosol water uptake increases with reaction time in the experiment for all the SOA with or without seed particles, which indicates that more highly oxidized polar compounds (more hygroscopic) are partitioned into particles according to the reaction time. The effect of seed particles on the hygroscopicity of the aerosols, although limited by the wrap of organic components, is also investigated. And different classified diameters of SOA exhibit similar hygroscopic growth factors, suggesting that the aerosol composition is independent of particle size.

Key words: styrene, ozonolysis, secondary organic aerosols, hygroscopicity

中图分类号:

X513

郑晓宏胡长进潘刚程跃刘志赵卫雄顾学军张为俊. 苯乙烯-臭氧反应产生的二次有机气溶胶的吸湿性研究[J]. 大气与环境光学学报, 2012, (4): 254-.

ZHENG Xiao-Hong, HU Chang-Jin, Pan Gang, CHENG Yue, LIU Zhi, ZHAO Wei-Xiong, GU Xue-Jun, ZHANG Wei-Jun. Hygroscopicity of SOA Formed by Ozonolysis of Styrene[J]. Journal of Atmospheric and Environmental Optics, 2012, (4): 254-.

参考文献

[1] Sisler J F, Malm W C. The relative importance of soluble aerosols to spatial and seasonal trends of impaired visibility in the United States [J]. Atmos. Environ., 1994, 28(5): 851-862.
[2] Charlson R J, Schwartz S E, Hales J M, et al. Climate forcing by anthropogenic aerosol [J]. Science, 1992, 255(5043): 423-430.
[3] Dusek U, Frank G P, Hildebrandt L. Size matters more than chemistry for cloud-nucleating ability of aerosol particles [J]. Science, 2006, 312(5778): 1375-1378.
[4] IPCC, 2007. Climate change 2007: the physical science basis [C]. In Contribution of Working Group I to the fourth assessment report of the Intergovernmental Panel on Climate Change [M]. Cambridge: Cambridge University Press, United Kingdom and New York, NY, USA.
[5] Chan H K, Eberl S, Daviskas E, et al. Changes in lung deposition of aerosols due to hygroscopic growth: a fast SPECT study [J]. Journal of Aerosol Medicine, 2002, 15(3): 307-311.
[6] Tang I N. Water transformation and growth of aerosol particles composed of mixed salts [J]. J. Aerosol Sci., 1976, 7(5): 361-371.
[7] Tang I N, Munkelwitz H R. Water activities, densities, and refractive-indices of aqueous sulfates and sodium-nitrate droplets of atmospheric importance [J]. J. Geophys. Res.-Atmos., 1994, 99(D9): 18801-18808.
[8] Weis D D, Ewing G E. Water content and morphology of sodium chloride aerosol particles [J]. J. Geophys. Res. -Atmos., 1999, 104(D17): 21275-21285.
[9] Zhang Y, Seigneur C, Seinfeld J H, et al. A comparative review of inorganic aerosol thermodynamic equilibrium modules: similarities, differences, and their likely causes [J]. Atmospheric Environment, 2000, 34(1): 117-137.
[10] Topping D O, McFiggans G B, Coe H. A curved multi-component aerosol hygroscopicity model framework: part 1- inorganic compounds [J]. Atmos. Chem. Phys., 2005, 5(5): 1205-1222.
[11] Saxena P, Hildemann L M. Water-soluble organics in atmospheric particles: a critical review of the literature and application of thermodynamics to identify candidate compounds [J]. J. Atmos. Chem., 1996, 24(1): 57-109.
[12] Hallquist M, Wenger J C, Baltensperger U, et al. The formation, properties and impact of secondary organic aerosol: current and emerging issuers [J]. Atmos. Chem. Phys., 2009, 9(14): 5155-5236.
[13] Li W J, Zhang D Z, Shao L Y, et al. Individual particle analysis of aerosols collected under haze and non-haze conditions at a high-elevation mountain site in the North China Plain, Atmos. Chem. Phys., 2011, 11(8): 11733-11744.
[14] David R, Cocker III, Brian T, et al. The effect of water on gas–particle partitioning of secondary organic aerosol: II. m-xylene and 1,3,5-trimethylbenzene photooxidation systems [J]. Atmos. Environ., 2001, 35(35): 6073-6085.
[15] Varutbangkul V, Brechtel F J, Bahreini R, et al. Hygroscopicity of secondary organic aerosols formed by oxidation of cycloalkenes, monoterpenes, sesquiterpenes, and related compounds [J]. Atmos. Chem. Phys., 2006, 6: 2367-2388.
[16] Agency for Toxic Substances and Disease Registry (ATSDR), Toxicological Profile for Styrene [R]. U. S. Public Health Service, U. S. Department of Health and Human Services, Atlanta, GA, 1992.
[17] Bufalini J J, Altshuller A P. Kinetics of vapor-phase hydrocarbon-ozone reactions [J]. Can. J. Chem., 1965, 43: 2243-2251.
[18] Tuazon E C, Arey J, Atkinson R, et al. Gas-phase reactions of 2-vinylpyridine and styrene with OH and NO3 radicals and O3 [J]. Environ. Sci. Technol., 1993, 27(9): 1832-1841.
[19] Carter W P L, Luo D, Malkina I L. Final Report to the Styrene Information and Research Center [R]. 1999.
[20] Jia Long, Xu Yongfu. Formation of secondary organic aerosol from the styrene-NOx irradiation [J]. Acta Chimica Sinica, 2010, 68(23): 2429-2435.
贾龙, 徐永福. 苯乙烯-NOx光照的二次有机气溶胶生成 [J]. 化学学报, 2010, 68(23): 2429-2435.
[21] McMurry P H, Stolzenburg M R. On the sensitivity of particle size to relative humidity for Los Angeles aerosols [J]. Atmos. Environ., 1989, 23(2):497-507.
[22] Liu P Y H, Pui D Y H, Whiby K T, et al. The aerosol mobility chromatograph: a new detector for sulfuric acid aerosols [J]. Atmos. Environ., 1978, 12(1-3): 99-104. [23] 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.
[24] 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-China, 2009, 21(4): 447-451.
[25] Wang Xuan, Chen Jianhua, Chen Jianmin, et al. Characterization of hygroscopic properties of laboratory-generated nanometer aerosols [J]. Research of Environmental Sciences, 2011, 24(6): 621-631(in Chinese).
王轩, 陈建华, 陈建民, 等. 实验室发生纳米气溶胶吸湿性表征 [J]. 环境科学研究, 2011, 24(6): 621-631.
[26] Villani P, Picard D, Michaud V, et al. Design and validation of a volatility hygroscopic tandem differential mobility analyzer (VH-TDMA) to characterize the relationships between the thermal and hygroscopic properties of atmospheric aerosol particles [J]. Aerosol Science and Technology, 2008, 42(9): 729-741.