Conversion of sea salt aerosol to NaNO3 and the production of HCl:: Analysis of temporal behavior of aerosol chloride/nitrate and gaseous HCl/HNO3 concentrations with AIM

被引:55
作者
Dasgupta, Purnendu K.
Campbell, Scott W.
Al-Horr, Rida S.
Ullah, S. M. Rahmat
Li, Jianzhong
Amalfitano, Carlo
Poor, Noreen D.
机构
[1] Texas Tech Univ, Dept Chem & Biochem, Lubbock, TX 79409 USA
[2] Univ S Florida, Dept Chem Engn, Tampa, FL 33620 USA
[3] Univ S Florida, Coll Publ Hlth, Tampa, FL 33612 USA
基金
美国国家科学基金会;
关键词
parallel plate wetted denuder; gas-to-particle phase partitioning; thermodynamic modeling; supermicron particles;
D O I
10.1016/j.atmosenv.2006.09.054
中图分类号
X [环境科学、安全科学];
学科分类号
08 ; 0830 ;
摘要
Equilibrium modeling predicts that atmospheric sea salt can partition gas-phase HNO(3) to solid- or aqueous-phase NaNO(3). One month of semi-continuous and simultaneous measurements of particulate chloride and nitrate and gaseous HCl and HNO(3) concentrations were made in the Tampa, Florida, as part of the Bay Region Atmospheric Chemistry Experiment (BRACE). Tampa's proximity to coastal and bay waters enriches its atmosphere with sea salt. To help explain and interpret the observed time-dependent concentration and gas-to-particle phase partitioning behavior for the NaCl HNO(3) reaction, we applied the Aerosol Inorganics Model III (AIM) to the measurement data. Good agreement between model predictions and observations was found. Measurement and modeling results suggested that coarse-mode sea salt particles from the Atlantic Ocean arrived in the morning at the monitoring site when relative humidity (RH) was high and the nature of the equilibrium least favored the outgassing of HCl from the particles. As the RH dropped in the afternoon, the equilibrium favored outgassing of HCl and the particulate nitrate concentration increased even as the concentration of coarse particles decreased. This effect was tied to the change in the ratio of nitrate to chloride activity coefficients gamma(-)(NO3) /gamma(-)(Cl) with RH. AIM simulations indicated that this ratio approached unity at high RH but could take on small values (similar to 0.05) at the lowest RH observed here. Thus, the particle phase slightly favored nitrate over chloride at high RH and greatly favored it at lower RH. Modeling revealed how diurnal changes in RH can rapidly shift HNO(3) concentrations from gas- to particle-phase and thus affect the distance over which nitrogen is transported. (c) 2007 Elsevier Ltd. All rights reserved.
引用
收藏
页码:4242 / 4257
页数:16
相关论文
共 76 条
[1]   Heterogeneous interactions of HOBr, HNO3, O3, and NO2 with deliquescent NaCl aerosols at room temperature [J].
Abbatt, JPD ;
Waschewsky, GCG .
JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (21) :3719-3725
[2]   A continuous analyzer for soluble anionic constituents and ammonium in atmospheric particulate matter [J].
Al-Horr, R ;
Samanta, G ;
Dasgupta, PK .
ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2003, 37 (24) :5711-5720
[3]   Minimizing transmission electron microscopy beam damage during the study of surface reactions on sodium chloride [J].
Allen, HC ;
Mecartney, ML ;
Hemminger, JC .
MICROSCOPY AND MICROANALYSIS, 1998, 4 (01) :23-33
[4]  
ALLEN HC, 1996, J PHYS CHEM-US, V100, P3719
[5]  
Andreas EL, 1998, J PHYS OCEANOGR, V28, P2175, DOI 10.1175/1520-0485(1998)028<2175:ANSSGF>2.0.CO
[6]  
2
[7]   Ionic composition and size characteristics of particles in the Lower Fraser Valley: Pacific 2001 Field Study [J].
Anlauf, K ;
Li, SM ;
Leaitch, R ;
Brook, J ;
Hayden, K ;
Toom-Sauntry, D ;
Wiebe, A .
ATMOSPHERIC ENVIRONMENT, 2006, 40 (15) :2662-2675
[8]  
[Anonymous], J AEROSOL SCI S1
[9]  
ARNOLD JR, 2006, IN PRESS ATMOSPHERIC, DOI DOI 10.1016/J.ATMOSENV.2006.07.058
[10]  
ATKESON T, 2007, IN PRESS ATMOSPHERIC, DOI DOI 10.1016/J.ATMOSENV.2006.12.035