Preprints
https://doi.org/10.5194/acp-2022-13
https://doi.org/10.5194/acp-2022-13

  11 Jan 2022

11 Jan 2022

Review status: this preprint is currently under review for the journal ACP.

Formation of Organic Sulfur Compounds through SO2 Initiated Photochemistry of PAHs and DMSO at the Air-Water Interface

Haoyu Jiang1,2,3, Yingyao He4, Yiqun Wang1,2, Sheng Li5, Bin Jiang1,2, Luca Carena6, Xue Li7, Lihua Yang4, Tiangang Luan4, Davide Vione6, and Sasho Gligorovski1,2,3 Haoyu Jiang et al.
  • 1State Key Laboratory of Organic Geochemistry and Guangdong Provincial Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510 640, China
  • 2Guangdong-Hong Kong-Macao Joint Laboratory for Environmental Pollution and Control, Guangzhou Institute of Geochemistry, Chinese Academy of Science, Guangzhou 510640, China
  • 3Chinese Academy of Science, Center for Excellence in Deep Earth Science, Guangzhou, 510640
  • 4School of Marine Sciences, Sun Yat-sen University, Guangzhou 510006, China
  • 5Hunan Research Academy of Environmental sciences, Changsha, 410004, China
  • 6Dipartimento di Chimica, Università di Torino, Via Pietro Giuria 5, 10125 Torino, Italy
  • 7Institute of Mass Spectrometry and Atmospheric Environment, Jinan University, Guangzhou 510632, China

Abstract. The presence of organic sulfur compounds (OSs) at the water surface, acting as organic surfactants, may influence the air-water interaction and contribute to new particle formation in the atmosphere. However, the impact of ubiquitous anthropogenic pollutant emissions, such as SO2 and polycyclic aromatic hydrocarbons (PAHs) on the formation of OSs at the air-water interface still remains unknown. Here, we observe large amounts of OSs formation in presence of SO2, upon irradiation of aqueous solutions containing typical PAHs such as pyrene (PYR), fluoranthene (FLA), and phenanthrene (PHE), as well as dimethylsulfoxide (DMSO). We observe rapid formation of several gaseous OSs from light-induced heterogeneous reactions of SO2 with either DMSO or a mixture of PAHs/DMSO, and some of these OSs (e.g. methanesulfonic acid) are well established secondary organic aerosol (SOA) precursors. A myriad of OSs and unsaturated compounds are produced and detected in the aqueous phase. The tentative reaction pathways are supported by theoretical calculations of the reaction Gibbs energies. Our findings provide new insights into potential sources and formation pathways of OSs occurring at the water (sea, lake, river) surface, that should be considered in future model studies to better represent the air-water interaction and SOA formation processes.

Haoyu Jiang et al.

Status: open (until 22 Feb 2022)

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse

Haoyu Jiang et al.

Haoyu Jiang et al.

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Short summary
Heterogeneous oxidation of SO2 is suggested to be one of the most important pathways for sulfate formation during extreme haze events in China, yet the exact mechanism remains highly uncertain. Our study reveals that ubiquitous compounds at the sea surface PAHS and DMSO, when exposed to SO2 under simulated sunlight irradiation, generate abundant organic sulfur compounds, providing implications for air-sea interaction and secondary organic aerosols formation processes.
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