Kinetics of N2O5 Hydrolysis on Secondary Organic Aerosol and Mixed Ammonium Bisulfate-Secondary Organic Aerosol Particles

被引:37
作者
Escoreia, Egda N. [1 ]
Sjostedt, Steven J. [2 ]
Abbatt, Jonathan P. D. [1 ]
机构
[1] Univ Toronto, Dept Chem, Toronto, ON M5S 1A1, Canada
[2] Environm Canada, Sci & Technol Branch, N York, ON, Canada
基金
加拿大自然科学与工程研究理事会;
关键词
SUPERCOOLED SULFURIC-ACID; IN-SITU DETECTION; REACTIVE UPTAKE; HYGROSCOPIC GROWTH; AQUEOUS AEROSOLS; HETEROGENEOUS HYDROLYSIS; REACTION PROBABILITIES; THERMODYNAMIC MODEL; SULFATE AEROSOLS; BUTANOL FILMS;
D O I
10.1021/jp107721v
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The kinetics of the hydrolysis reaction of N2O5 on secondary organic aerosol (SOA) produced through the ozonolysis of alpha-pinene and on mixed ammonium bisulfate-SOA particles was investigated using an entrained aerosol flow tube coupled to a chemical ionization mass spectrometer. We report room temperature uptake coefficients, gamma, on ammonium bisulfate and SOA particles at 50% relative humidity of 1.5 x 10(-2) +/- 1.5 x 10(-3) and 1.5 x 10(-4) +/- 2 x 10(-5), respectively. For the mixed ammonium bisulfate-SOA particles, gamma decreased from 2.6 x 10(-3) +/- 4 x 10(-4) to 3.0 x 10(-4) +/- 3 x 10(-5) as the SOA mass fraction increased from 9 to 79, indicating a strong suppression in gamma with the addition of organic material. There is an order-of-magnitude reduction in the uptake coefficient with the smallest amount of SOA material present and smaller additional reductions with increasing aerosol organic content. This newly coated organic layer may either decrease the mass accommodation coefficient of N2O5 onto the particle or hinder the dissolution and diffusion of N2O5 into the remainder of the aerosol after it has been accommodated onto the surface. The former corresponds to a surface effect and the latter to bulk processes. The low value of the uptake coefficient on pure SOA particles will likely make N2O5 hydrolysis insignificant on such an aerosol, but atmospheric chemistry models need to account for the role that organics may play in suppressing the kinetics of this reaction on mixed organic-inorganic particles.
引用
收藏
页码:13113 / 13121
页数:9
相关论文
共 53 条
[1]  
[Anonymous], 2020, Gothenburg Protocol to reduce transboundary air pollution, DOI DOI 10.5860/CHOICE.44-4512
[2]  
[Anonymous], 2009, J AM CHEM SOC, DOI DOI 10.1021/JA906434C
[3]   On the reactive uptake of gaseous compounds by organic-coated aqueous aerosols:: Theoretical analysis and application to the heterogeneous hydrolysis of N2O5 [J].
Anttila, Tatu ;
Kiendler-Scharr, Astrid ;
Tillmann, Ralf ;
Mentel, Thomas F. .
JOURNAL OF PHYSICAL CHEMISTRY A, 2006, 110 (35) :10435-10443
[4]   Phase transitions and hygroscopic growth of aerosol particles containing humic acid and mixtures of humic acid and ammonium sulphate [J].
Badger, CL ;
George, I ;
Griffiths, PT ;
Braban, CF ;
Cox, RA ;
Abbatt, JPD .
ATMOSPHERIC CHEMISTRY AND PHYSICS, 2006, 6 :755-768
[5]   Reactive uptake of N2O5 by aerosol particles containing mixtures of humic acid and ammonium sulfate [J].
Badger, Claire L. ;
Griffiths, Paul T. ;
George, Ingrid ;
Abbatt, Jonathan P. D. ;
Cox, R. Anthony .
JOURNAL OF PHYSICAL CHEMISTRY A, 2006, 110 (21) :6986-6994
[6]   Measurements of secondary organic aerosol from oxidation of cycloalkenes, terpenes, and m-xylene using an Aerodyne aerosol mass spectrometer [J].
Bahreini, R ;
Keywood, MD ;
Ng, NL ;
Varutbangkul, V ;
Gao, S ;
Flagan, RC ;
Seinfeld, JH ;
Worsnop, DR ;
Jimenez, JL .
ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2005, 39 (15) :5674-5688
[7]   Production and decay of ClNO2, from the reaction of gaseous N2O5 with NaCl solution: Bulk and aerosol experiments [J].
Behnke, W ;
George, C ;
Scheer, V ;
Zetzsch, C .
JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 1997, 102 (D3) :3795-3804
[8]   Toward a general parameterization of N2O5 reactivity on aqueous particles: the competing effects of particle liquid water, nitrate and chloride [J].
Bertram, T. H. ;
Thornton, J. A. .
ATMOSPHERIC CHEMISTRY AND PHYSICS, 2009, 9 (21) :8351-8363
[9]   Direct observations of N2O5 reactivity on ambient aerosol particles [J].
Bertram, Timothy H. ;
Thornton, Joel A. ;
Riedel, Theran P. ;
Middlebrook, Ann M. ;
Bahreini, Roya ;
Bates, Timothy S. ;
Quinn, Patricia K. ;
Coffman, Derek J. .
GEOPHYSICAL RESEARCH LETTERS, 2009, 36
[10]   Water uptake by particles containing humic materials and mixtures of humic materials with ammonium sulfate [J].
Brooks, SD ;
DeMott, PJ ;
Kreidenweis, SM .
ATMOSPHERIC ENVIRONMENT, 2004, 38 (13) :1859-1868