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Discussion papers
https://doi.org/10.5194/acp-2019-532
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-2019-532
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.

Submitted as: research article 12 Jul 2019

Submitted as: research article | 12 Jul 2019

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This discussion paper is a preprint. It is a manuscript under review for the journal Atmospheric Chemistry and Physics (ACP).

Effects of NO2 and C3H6 on the heterogeneous oxidation of SO2 on TiO2 in the presence or absence of UV irradiation

Biwu Chu1,2,3, Yali Wang1,3, Weiwei Yang1,3,4, Jinzhu Ma1,2,3, Qingxin Ma1,2,3, Peng Zhang1, Yongchun Liu1,5, and Hong He1,2,3 Biwu Chu et al.
  • 1State Key Joint Laboratory of Environment Simulation and Pollution Control, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
  • 2Center for Excellence in Regional Atmospheric Environment, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021, China
  • 3University of Chinese Academy of Sciences, Beijing 100049, China
  • 4Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, Institute of Environmental and Applied Chemistry, College of Chemistry, Central China Normal University, Wuhan 430079, China
  • 5Aerosol and Haze Laboratory, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Abstract. The heterogeneous reactions of SO2 in the presence of NO2 and C3H6 on TiO2 were investigated with the aid of in situ DRIFTS under dark conditions or with UV irradiation. Sulfate formation with or without the coexistence of NO2 and/or C3H6 was analyzed with IC. Under dark conditions, SO2 reacting alone resulted in sulfite formation on TiO2, while the presence of ppb levels of NO2 promoted the oxidation of SO2 to sulfate. The presence of C3H6 had little effect on sulfate formation in the heterogeneous reaction of SO2 but suppressed sulfate formation in the heterogeneous reaction of SO2 and NO2. UV irradiation could significantly enhance the heterogeneous oxidation of SO2 on TiO2, leading to a copious generation of sulfate, while the coexistence of NO2 and/or C3H6 significantly suppressed sulfate formation in experiments with UV lights. Step-by-step exposure experiments indicated that C3H6 mainly competes for reactive oxygen species (ROS), while NO2 competes with SO2 for both surface active sites and ROS. Meanwhile, the coexistence of NO2 with C3H6 further resulted in less sulfate formation compared to introducing either one of them separately to the SO2-TiO2 reaction system. The results of this study highlighted the complex heterogeneous reaction processes that take place due to the ubiquitous interactions between organic and inorganic species, and the requirement to consider the influence of coexisting VOCs and other inorganic gases in the heterogeneous oxidation kinetics of SO2.

Biwu Chu et al.
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Short summary
This study found that the coexisting NO2 and/or C3H6 had significant influences on heterogeneous oxidation of SO2 due to the ubiquitous interactions between organic and inorganic species, and their effects were different under dark conditions or with UV irradiation. The experimental results of this study highlighted the requirement to consider the influence of coexisting organics and other inorganic gases in the heterogeneous oxidation kinetics of SO2.
This study found that the coexisting NO2 and/or C3H6 had significant influences on heterogeneous...
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