Kinetics Study of OH Uptake onto Deliquesced NaCl Particles by Combining Laser Photolysis and Laser-Induced Fluorescence.

Abstract

Despite the role of hydroxyl radical (OH) uptake onto sea-salt particles as a daytime chlorine source, affecting the chemical processes in the marine boundary layer, its uptake coefficient has not yet been confirmed by direct measurement methods. This study reports the application of a combination technique of laser flash photolysis generation and laser-induced fluorescence detection for the direct kinetic measurement of OH uptake onto deliquesced NaCl particles. The uptake coefficient was not constant and inversely depended on the initial OH concentration, indicating that the first uptake step is Langmuir-type adsorption. The resistance model, including surface processes, well reproduced the observed uptake coefficient. The model predicted an uptake coefficient for the atmospheric relevant OH concentration within the range from 0.77 to 0.95. Such values may lead to emissions of Cl2 higher than those predicted in previous studies based on other values. Hence, the proposed value may provide more reliable estimations of ozone formation, oxidation of volatile organic compounds, secondary organic aerosol formation, and lifetime of methane and elemental mercury in the marine boundary layer.