Investigation of HO2 uptake mechanisms onto multiple-component ambient aerosols collected in summer and winter time in Yokohama, Japan

Abstract

The heterogeneous loss of HO2 radicals onto ambient aerosols plays an important role in tropospheric chemistry. However, sparse investigation of the dominating parameters controlling the HO2 uptake coefficients onto ambient aerosols (γHO2) has largely hindered the application of the measured γHO2 to the global spatial prediction. Here we induced an offline method using LFP-LIF technique to measure the kinetics of HO2 uptake onto ambient aerosols collected in summertime and wintertime in Yokohama city, a regional urban site near Tokyo, Japan. By controlling the dominating parameters which influence γHO2, we were able to investigate the detailed HO2 uptake mechanism. We characterized the chemical composition of the collected ambient aerosols, including organics, inorganics, transition metals ions, etc. and modeled γHO2 using different mechanisms. Results show that γHO2 increased with the increase in RH, and the aerosol states (“dry” or wet/aqueous) have large effects on γHO2. With fixed RH and aerosol chemical composition, γHO2was highly dependent on pH and inversely correlated with [HO2]0. By combing the measured γHO2 values with the modeled ones, we found that both the HO2 self-reaction and transition metal-catalyzed reactions should be accounted for to yield a single parameterization to predict γHO2, and different chemical compositions may have collective effects on γHO2. Results may serve for extending the γHO2 values measured at one observation site to different environmental conditions, which will help us to achieve more accurate modeling results concerning secondary pollutant formation (i.e., ozone).