Heterogeneous oxidation of secondary organic tracers of isoprene by hydroxyl radicals
SHEN Ping, HU Qian, CAO Gang, ZHU Rong-shu
Shenzhen Key Laboratory of Organic Pollution Prevention and Control, School of Civil and Environmental Engineering, Harbin Institute of Technology, Guangdong Shenzhen 518055, China
Abstract：When the tracer-based method is applied to analyze the contribution of various gas precursors to secondary organic aerosols (SOA), the heterogeneous oxidation reactions between organic tracers and atmospheric oxidants (·OH, O3, NO3, etc.) will lead to uncertainty in source apportionment. In this paper, the secondary organic tracers of isoprene SOA, 2-methylerythritol (2-ME) and its analogue erythritol (AME) pure substance were studied by oxidation by ·OH under different experimental conditions in an atmospheric smog chamber. The experimental results show that the heterogeneous oxidation reaction effective rate constant of AME and ·OH is in the range of 3.64×10-11 ~ 4.15×10-11cm3/ (molecule·s) at 24.7 (±1.5) ℃.The effective lifetime of AME is about 4.46 ~ 5.09h when the average typical concentration of atmospheric ·OH is 1.5×106molecule/cm3. The effective rate constant of 2-ME ranges from 4.39×10-12 to 9.05×10-12cm3/(molecule·s), corresponding to the atmospheric lifetime of 0.85 ~ 1.76d. The ·OH oxidation reaction of isoprene organic tracer was significant, and tracer-based method would underestimate the contribution of isoprene to SOA.
Carlton A M, Wiedinmyer C, Kroll J. A review of Secondary Organic Aerosol (SOA) formation from isoprene [J]. Atmospheric Chemistry and Physics, 2009,9:4987-5005.
[2]
Kirkby J, Duplissy J, Sengupta K, et al. Ion-induced nucleation of pure biogenic particles [J]. Nature, 2016,533(7604):521-526.
[3]
Ng N, Chhabra P, Chan A, et al. Effect of NOx level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes [J]. Atmospheric Chemistry and Physics, 2007,7:5159-5174.
[4]
Docherty K, Wu W, Lim Y, et al. Contributions of organic peroxides to secondary aerosol formed from reactions of monoterpenes with O3 [J]. Environmental Science & Technology, 2005,39:4049-4059.
[5]
Vizuete W, Junquera V, Allen D. Sesquiterpene emissions and secondary organic aerosol formation potentials for southeast tex as special issue of aerosol science and technology on findings from the fine particulate matter supersites program [J]. Aerosol Science and Technology-Aerosol Sci Tech, 2004,38:167-181.
[6]
Weber R, Sullivan A, Peltier R, et al. A study of secondary organic aerosol formation in the anthropogenic-influenced Southeastern United States [J]. Journal of Geophysical Research-Atmospheres, 2007,112:D13302.
[7]
Volkamer R, Jimenez J, Martini F, et al. Secondary organic aerosol formation from anthropogenic air pollution: Rapid and higher than expected [J]. Geophysical Research Letters, 2006,33:L17811.
[8]
张 莉,王效科,欧阳志云,等.中国森林生态系统的异戊二烯排放研究 [J]. 环境科学, 2003,(1):8-15. Zhang Li, Wang Xiaoke, Ouyang Zhiyun, et al. Study on isoprene emissions in forest ecosystems in China [J]. Environmental Science, 2003,(1):8-15.
[9]
Fu Y, Liao H. Biogenic isoprene emissions over China: Sensitivity to the CO2 inhibition effect [J]. Atmospheric and Oceanic Science Letters, 2016,9:1-18.
[10]
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.
[11]
Lai C, Liu Y, Ma J, et al. Heterogeneous kinetics of cis-pinonic acid with hydroxyl radical under different environmental conditions [J]. The Journal of Physical Chemistry A, 2015,119(25):6583-6593.
[12]
王润华.甲苯SOA示踪物的羟基自由基非均相氧化研究 [D]. 哈尔滨:哈尔滨工业大学, 2021. Wang Runhua. Study on heterogeneous oxidation of hydroxyl radicals in toluene SOA tracer [D]. Harbin: Harbin Institute of Technology, 2021.
[13]
Chen Y, Zhang Y, Lambe A T, et al. Heterogeneous hydroxyl radical oxidation of isoprene-epoxydiol-derived methyltetrol sulfates: plausible formation mechanisms of previously unexplained organosulfates in ambient fine aerosols [J]. Environmental Science & Technology Letters, 2020,7(7):460-468.
[14]
Hu W, Palm B, Day D, et al. Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) [J]. Atmospheric Chemistry and Physics, 2016,16:11563-11580.
[15]
Xu R, Lam H K, Wilson K R, et al. Effect of inorganic-to-organic mass ratio on the heterogeneous OH reaction rates of erythritol: implications for atmospheric chemical stability of 2-methyltetrols [J]. Atmospheric Chemistry and Physics, 2020,20(6):3879-3893.
[16]
Kessler S H, Smith J D, Che D L, et al. Chemical sinks of organic aerosol: kinetics and products of the heterogeneous oxidation of erythritol and levoglucosan [J]. Environmental Science & Technology, 2010,44(18):7005-7010.
[17]
谢绍东,于 淼,姜 明.有机气溶胶的来源与形成研究现状 [J]. 环境科学学报, 2006,(12):1933-1939. Xie Shaodong, Yu Miao, Jiang Ming. Research status on the source and formation of organic aerosols [J]. Journal of Environmental Science, 2006,(12):1933-1939.
[18]
何凌燕,胡 敏,黄晓锋,等.北京大气气溶胶PM2.5中的有机示踪化合物 [J]. 环境科学学报, 2005,(1):23-29. He Lingyan, Hu Min, Huang Xiaofeng, et al. Organic tracer compounds in atmospheric aerosol PM2.5 in Beijing [J]. Journal of Environmental Science, 2005,(1):23-29.
[19]
Donahue N M. Competitive oxidation in atmospheric aerosols: The case for relative kinetics [J]. Geophysical Research Letters, 2005, 32(16).
[20]
Lai C, Liu Y, Ma J, et al. Degradation kinetics of levoglucosan initiated by hydroxyl radical under different environmental conditions [J]. Atmospheric Environment, 2014,91:32-39.
[21]
Liu C, Zeng C. Heterogeneous kinetics of methoxyphenols in the OH-initiated reactions under different experimental conditions [J]. Chemosphere, 2018,209:560-567.
[22]
Liu C, Zhang P, WEN X, et al. Heterogeneous kinetics, products, and mechanisms of ferulic acid particles in the reaction with NO3 radicals [J]. Atmospheric Environment, 2017,152:172-179.
[23]
Slade J H, Knopf D A. Heterogeneous OH oxidation of biomass burning organic aerosol surrogate compounds: assessment of volatilisation products and the role of OH concentration on the reactive uptake kinetics [J]. Physical chemistry chemical physics: PCCP, 2013,15(16):5898-5915.
[24]
Knopf D A, Forrester S M, Slade J H. Heterogeneous oxidation kinetics of organic biomass burning aerosol surrogates by O3, NO2, N2O5, and NO3 [J]. Physical chemistry chemical physics: PCCP, 2011,13(47):215-2162.
[25]
Liu C, He Y, Chen X E. Kinetic study on the heterogeneous degradation of coniferyl alcohol by OH radicals [J]. Chemosphere, 2020,241:125088.
[26]
Lam H K, Kwong K C, Poon H Y, et al. Heterogeneous OH oxidation of isoprene-epoxydiol-derived organosulfates: kinetics, chemistry and formation of inorganic sulfate [J]. Atmospheric Chemistry and Physics, 2019,19(4):2433-2440.
[27]
Claeys M, Graham B, Vas G, et al. Formation of secondary organic aerosols through photooxidation of isoprene [J]. Science (New York, N.Y.), 2004,303:1173-1176.
[28]
黄亚娟,曹 罡,朱荣淑,等.异戊二烯和甲苯二次有机示踪物的臭氧非均相氧化 [J]. 环境科学, 2019,40(3):1163-1171. Huang Yajuan, Cao Gang, Zhu Rongshu, et al. Heterogeneous oxidation of ozone by secondary organic tracers of isoprene and toluene [J]. Environmental Science, 2019,40(3):1163-1171.
[29]
胡 倩.异戊二烯SOA示踪物的非均相氧化研究 [D]. 哈尔滨:哈尔滨工业大学, 2021. Hu Qian. Heterogeneous oxidation of isoprene SOA tracers [D]. Harbin: Harbin Institute of Technology, 2021.
[30]
Wang R, Huang Y, Hu Q, et al. In-Situ FTIR study of heterogeneous oxidation of SOA tracers by ozone [J]. Frontiers in Environmental Chemistry, 2021,2:732219.
[31]
Wang R, Huang Y, Cao G. Heterogeneous oxidation of isoprene SOA and toluene SOA tracers by ozone [J]. Chemosphere, 2020,249: 126258.
[32]
Wang S, Tsona N T, Du L. Effect of NOx on secondary organic aerosol formation from the photochemical transformation of allyl acetate [J]. Atmospheric Environment, 2021,255:118426.
[33]
Chen L, Bao K, Li K, et al. Ozone and secondary organic aerosol formation of Toluene/NOx irradiations under complex pollution scenarios [J]. Aerosol and Air Quality Research, 2017,17(7):1760-1771.
[34]
Kroll J H, Ng N L, Murphy S M, et al. Secondary organic aerosol formation from isoprene photooxidation under high-NOx conditions [J]. Geophysical Research Letters, 2005,32:L18808.
[35]
Xu J, Griffin R J, Liu Y, et al. Simulated impact of NOx on SOA formation from oxidation of toluene and m-xylene [J]. Atmospheric Environment, 2015,101:217-225.
[36]
Qi X, Zhu S, Zhu C, et al. Smog chamber study of the effects of NOx and NH3 on the formation of secondary organic aerosols and optical properties from photo-oxidation of toluene [J]. Science of The Total Environment, 2020,727:138632.
[37]
Cheng X, Chen Q, Jie LI Y, et al. Highly oxygenated organic molecules produced by the oxidation of benzene and toluene in a wide range of OH exposure and NOx conditions [J]. Atmos. Chem. Phys., 2021,21(15):12005-12019.
[38]
Xu L, Kollman M S, Song C, et al. Effects of NOx on the volatility of secondary organic aerosol from isoprene photooxidation [J]. Environmental Science & Technology, 2014,48(4):2253-2262.
[39]
Ng N, Kroll J, Chan A, et al. Secondary organic aerosol formation from m-xylene, toluene, and benzene [J]. Atmospheric Chemistry and Physics Discussions, 2007,7:3909-3922.
[40]
Zhao D, Schmitt S H, Wang M, et al. Effects of NOx and SO2 on the secondary organic aerosol formation from photooxidation of α-pinene and limonene [J]. Atmospheric Chemistry and Physics, 2017,18:1611-1628.
[41]
Chapleski R C, Zhang Y, Troya D, et al. Heterogeneous chemistry and reaction dynamics of the atmospheric oxidants, O3, NO3, and OH, on organic surfaces [J]. Chemical Society reviews, 2016,45(13):3731-3746.
[42]
Bai J, Sun X, Zhang C, et al. The atmospheric degradation reaction of dehydroabietic acid (DHAA) initiated by OH radicals and O3 [J]. Chemosphere, 2013,92(8):933-940.
[43]
Docherty K S, Ziemann P J. Reaction of oleic acid particles with NO3 Radicals: Products, mechanism, and implications for radical-initiated organic aerosol oxidation [J]. The Journal of Physical Chemistry A, 2006,110(10):3567-3577.
[44]
Zhang H, Yang B, Wang Y, et al. Gas-phase reactions of methoxyphenols with NO3 radicals: Kinetics, products, and mechanisms [J]. The Journal of Physical Chemistry A, 2016,120(8): 1213-1221.
