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Mechanism of secondary organic aerosol formation from the reaction of isoprene with sulfoxy radicals

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Abstract

Isoprene can react with sulfoxy radicals (SO4•− and SO3•−) to form organosulfur compounds in aqueous phase, and the organosulfur compounds are important compositions of secondary organic aerosols (SOAs). To make sure the specific configurations of the products and the role of SO4•− and SO3•− in the formation of organosulfur compounds, the reaction mechanisms are studied by theoretical calculations. The lowest Gibbs free energy barrier of addition of SO3•− onto isoprene is 24.06 kcal mol−1 at C4 site, and its rate constant is 1.30 × 10−11 M−1 s−1 at 298 K and 1 atm. And the Gibbs free energy barriers of addition of SO4•− onto isoprene at C1 and C4 sites are barrierless and 0.92 kcal mol−1; the rate constants of these two addition processes are 6.85 × 109 and 1.17 × 105 M−1 s−1 at 298 K and 1 atm. It elucidates that organosulfates are easier to be formed. As for the products P1 (with alcohol group) and P2 (with aldehyde group), the lowest Gibbs free energy barrier of the formation of P1 is 3.17 kcal mol−1, and that of the formation of P2 is 15.84 kcal mol−1, which means that the product with alcohol group is easier to be formed than that with aldehyde group. This work provides a reference for the formation of organosulfur compounds in aqueous phase, and it may help to understand the SOA formation.

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Data availability

All data generated or analyzed during this study are included in this published article and its supplementary information files. The data is available on request from corresponding author.

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Funding

This work was funded by the National Natural Science Foundation of China (21976109), the Natural Science Foundation of Shandong Province (ZR2018MB043), the Fundamental Research Funds of Shandong University (2018JC027), and Shandong Province Key Research and Development Program (2019GSF109037).

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Authors and Affiliations

  1. Environment Research Institute, Shandong University, Qingdao, 266237, China

    Wen Liu, Guochun Lv & Xiaomin Sun

  2. College of Biological and Environmental Engineering, Binzhou University, Binzhou, 256600, China

    Chenxi Zhang

Authors
  1. Wen Liu
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  2. Guochun Lv
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  3. Chenxi Zhang
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  4. Xiaomin Sun
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Contributions

Wen Liu: data curation, validation, and writing-original draft preparation; Guochun Lv: validation; Chenxi Zhang: methodology, reviewing, and editing; Xiaomin Sun: conceptualization, funding acquisition, reviewing, and editing

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Correspondence to Chenxi Zhang or Xiaomin Sun.

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Liu, W., Lv, G., Zhang, C. et al. Mechanism of secondary organic aerosol formation from the reaction of isoprene with sulfoxy radicals. Environ Sci Pollut Res 28, 42562–42569 (2021). https://doi.org/10.1007/s11356-021-13539-9

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  • DOI: https://doi.org/10.1007/s11356-021-13539-9

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