Articles | Volume 16, issue 2
Atmos. Chem. Phys., 16, 675–689, 2016
Atmos. Chem. Phys., 16, 675–689, 2016

Research article 21 Jan 2016

Research article | 21 Jan 2016

Formation of secondary aerosols from gasoline vehicle exhaust when mixing with SO2

T. Liu1,2, X. Wang1, Q. Hu1, W. Deng1,2, Y. Zhang1, X. Ding1, X. Fu1,2, F. Bernard1,3, Z. Zhang1,2, S. Lü1,2, Q. He1,2, X. Bi1, J. Chen4, Y. Sun5, J. Yu6, P. Peng1, G. Sheng1, and J. Fu1 T. Liu et al.
  • 1State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
  • 2University of Chinese Academy of Sciences, Beijing 100049, China
  • 3Chemical Sciences Division, NOAA Earth System Research Laboratory, Boulder, Colorado 80305, USA
  • 4Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science & Engineering, Fudan University, Shanghai 200433, China
  • 5Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing 100029, China
  • 6Division of Environment, Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, China

Abstract. Sulfur dioxide (SO2) can enhance the formation of secondary aerosols from biogenic volatile organic compounds (VOCs), but its influence on secondary aerosol formation from anthropogenic VOCs, particularly complex mixtures like vehicle exhaust, remains uncertain. Gasoline vehicle exhaust (GVE) and SO2, a typical pollutant from coal burning, are directly co-introduced into a smog chamber, in this study, to investigate the formation of secondary organic aerosols (SOA) and sulfate aerosols through photooxidation. New particle formation was enhanced, while substantial sulfate was formed through the oxidation of SO2 in the presence of high concentration of SO2. Homogenous oxidation by OH radicals contributed a negligible fraction to the conversion of SO2 to sulfate, and instead the oxidation by stabilized Criegee intermediates (sCIs), formed from alkenes in the exhaust reacting with ozone, dominated the conversion of SO2. After 5 h of photochemical aging, GVE's SOA production factor revealed an increase by 60–200 % in the presence of high concentration of SO2. The increase could principally be attributed to acid-catalyzed SOA formation as evidenced by the strong positive linear correlation (R2 = 0.97) between the SOA production factor and in situ particle acidity calculated by the AIM-II model. A high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) resolved OA's relatively lower oxygen-to-carbon (O : C) (0.44 ± 0.02) and higher hydrogen-to-carbon (H : C) (1.40 ± 0.03) molar ratios for the GVE / SO2 mixture, with a significantly lower estimated average carbon oxidation state (OSc) of −0.51 ± 0.06 than −0.19 ± 0.08 for GVE alone. The relative higher mass loading of OA in the experiments with SO2 might be a significant explanation for the lower SOA oxidation degree.

Short summary
The formation of SOA and sulfate aerosols from the photooxidation of gasoline vehicle exhaust (GVE) when mixing with SO2 was investigated in a smog chamber. We found that the presence of GVE enhanced the conversion of SO2 to sulfate predominantly through reactions with stabilized Criegee intermediates. On the other hand, the elevated particle acidity enhanced the SOA production from GVE. This study indicated that SO2 and GVE could enhance each other in forming secondary aerosols.
Final-revised paper