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Experimental Study of the Formation of Organosulfates from α-Pinene Oxidation. 2. Time Evolution and Effect of Particle Acidity

  • G. Duporté
    G. Duporté
    Université de Bordeaux, EPOC, UMR 5805, F-33405 Talence Cedex, France
    CNRS, EPOC, UMR 5805, F-33405 Talence Cedex, France
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  • P.-M. Flaud
    P.-M. Flaud
    Université de Bordeaux, EPOC, UMR 5805, F-33405 Talence Cedex, France
    CNRS, EPOC, UMR 5805, F-33405 Talence Cedex, France
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  • J. Kammer
    J. Kammer
    Université de Bordeaux, EPOC, UMR 5805, F-33405 Talence Cedex, France
    CNRS, EPOC, UMR 5805, F-33405 Talence Cedex, France
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  • E. Geneste
    E. Geneste
    Université de Bordeaux, EPOC, UMR 5805, F-33405 Talence Cedex, France
    CNRS, EPOC, UMR 5805, F-33405 Talence Cedex, France
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  • S. Augagneur
    S. Augagneur
    Université de Bordeaux, EPOC, UMR 5805, F-33405 Talence Cedex, France
    CNRS, EPOC, UMR 5805, F-33405 Talence Cedex, France
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  • E. Pangui
    E. Pangui
    Université Paris-Est-Créteil (UPEC) and Université Paris Diderot (UPD), LISA, UMR 7583, F-94010 Créteil, France
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  • H. Lamkaddam
    H. Lamkaddam
    Université Paris-Est-Créteil (UPEC) and Université Paris Diderot (UPD), LISA, UMR 7583, F-94010 Créteil, France
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  • A. Gratien
    A. Gratien
    Université Paris-Est-Créteil (UPEC) and Université Paris Diderot (UPD), LISA, UMR 7583, F-94010 Créteil, France
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  • J.-F. Doussin
    J.-F. Doussin
    Université Paris-Est-Créteil (UPEC) and Université Paris Diderot (UPD), LISA, UMR 7583, F-94010 Créteil, France
  • H. Budzinski
    H. Budzinski
    Université de Bordeaux, EPOC, UMR 5805, F-33405 Talence Cedex, France
    CNRS, EPOC, UMR 5805, F-33405 Talence Cedex, France
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  • E. Villenave
    E. Villenave
    Université de Bordeaux, EPOC, UMR 5805, F-33405 Talence Cedex, France
    CNRS, EPOC, UMR 5805, F-33405 Talence Cedex, France
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  • E. Perraudin*
    E. Perraudin
    Université de Bordeaux, EPOC, UMR 5805, F-33405 Talence Cedex, France
    CNRS, EPOC, UMR 5805, F-33405 Talence Cedex, France
    *Tel: +33 5 4000 2868. E-mail: [email protected]
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Cite this: J. Phys. Chem. A 2020, 124, 2, 409–421
Publication Date (Web):December 18, 2019
https://doi.org/10.1021/acs.jpca.9b07156
Copyright © 2019 American Chemical Society

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    Abstract

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    The present work is an extensive laboratory study of organosulfate (OS) formation from the reaction of α-pinene oxidation products or proxies with acidified ammonium sulfate aerosols in three different acidity conditions ((NH4)2SO4 0.06 M; (NH4)2SO4/H2SO4 0.06 M/0.005 M; (NH4)2SO4/H2SO4 0.03 M/0.05 M). The kinetics of the reactions of α-pinene, α-pinene oxide, isopinocampheol, pinanediol, and myrtenal with ammonium sulfate particles were studied using a quasi-static reactor. The reaction of α-pinene oxide with the highly acidic ammonium sulfate particles was determined to be 7, 10, 21, and 24 times faster than for isopinocampheol, α-pinene, pinanedial, and myrtenal, respectively, for an OS precursor concentration of 1 ppm and after 1 h reaction time. The effective rate coefficients for OS formation from α-pinene oxide were determined to be 2 orders of magnitude higher in highly acidic conditions than for the two other acidity conditions. For α-pinene oxide reactions with highly acidic ammonium sulfate particles, OS formation was observed to increase linearly with (i) the time of reaction up to 400 min (r2 > 0.95) and (ii) α-pinene oxide gas-phase concentration. However, OS formation from α-pinene oxide reactions with slightly acidic or pure ammonium sulfate particles was limited, with a plateau ([OS]max = 0.62 ± 0.03 μg) reached after around 15–20 min. Organosulfate dimers (m/z 401 and m/z 481) were detected not only with highly acidic particles but also with slightly acidic and pure ammonium sulfate particles, indicating that oligomerization processes do not require strong acidity conditions. Dehydration products of organosulfates (m/z 231 and m/z 383) were observed only under highly acidic conditions, indicating the key role of H2SO4 on the dehydration of organosulfates and the formation of olefins in the atmosphere. Finally, this kinetic study was completed with simulation chamber experiments in which the mass concentration of organosulfates was shown to depend on the available sulfate amount present in the particle phase (r2 = 0.96). In conclusion, this relative comparison between five organosulfate precursors shows that epoxide was the most efficient reactant to form organosulfates via heterogeneous gas–particle reactions and illustrates how gas–particle reactions may play an important role in OS formation and hence in the atmospheric fate of organic carbon. The kinetic data presented in this work provide strong support to organosulfate formation mechanisms proposed in part 1 ( J. Phys. Chem. A 2016, 120, 7909−7923).

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.9b07156.

    • Figure S1, mass spectra from PTR-TOF-MS for α-pinene oxide and campholenic aldehyde; Figure S2, proposed organosulfate formation mechanism from α-pinene oxide; Figure S3, temporal mass profiles of m/z 249 (1), m/z 401, and m/z 481 organosulfate formation in the particulate phase; Figure S4, aerosol particle concentration in the CESAM chamber measured during the C4 experiment; Figure S5, temporal variations of OS 249 (1), OS 249 (2), and OS 249 (CA) from α-pinene oxide under nonacidified sulfate conditions in the CESAM chamber; Figure S6, temporal mass profile of OS 233 (3) from experiments between acidic sulfated aerosols (NH4)2SO4/H2SO4(0.03/0.05 M) and isopinocampheol; Table S1, structure of the organosulfates detected in α-pinene oxide experiments (PDF)

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    Cited By

    This article is cited by 11 publications.

    1. Cynthia Wong, Sijia Liu, Sergey A. Nizkorodov. Highly Acidic Conditions Drastically Alter the Chemical Composition and Absorption Coefficient of α-Pinene Secondary Organic Aerosol. ACS Earth and Space Chemistry 2022, 6 (12) , 2983-2994. https://doi.org/10.1021/acsearthspacechem.2c00249
    2. Eshani Hettiarachchi, Vicki H. Grassian. Heterogeneous Formation of Organonitrates (ON) and Nitroxy-Organosulfates (NOS) from Adsorbed α-Pinene-Derived Organosulfates (OS) on Mineral Surfaces. ACS Earth and Space Chemistry 2022, 6 (12) , 3017-3030. https://doi.org/10.1021/acsearthspacechem.2c00259
    3. Eshani Hettiarachchi, Vicki H. Grassian. Heterogeneous Reactions of α-Pinene on Mineral Surfaces: Formation of Organonitrates and α-Pinene Oxidation Products. The Journal of Physical Chemistry A 2022, 126 (25) , 4068-4079. https://doi.org/10.1021/acs.jpca.2c02663
    4. Li Xu, Narcisse T. Tsona, Lin Du. Relative Humidity Changes the Role of SO2 in Biogenic Secondary Organic Aerosol Formation. The Journal of Physical Chemistry Letters 2021, 12 (30) , 7365-7372. https://doi.org/10.1021/acs.jpclett.1c01550
    5. Zaeem Bin Babar, Fawad Ashraf, Jun-Hyun Park, Pham Duy Quang Dao, Chan Sik Cho, Ho-Jin Lim. Exploring Volatility Properties of Discrete Secondary Organic Aerosol Constituents of α-Pinene and Polycyclic Aromatic Hydrocarbons. ACS Earth and Space Chemistry 2020, 4 (12) , 2299-2311. https://doi.org/10.1021/acsearthspacechem.0c00210
    6. Martin Brüggemann, Rongshuang Xu, Andreas Tilgner, Kai Chung Kwong, Anke Mutzel, Hon Yin Poon, Tobias Otto, Thomas Schaefer, Laurent Poulain, Man Nin Chan, Hartmut Herrmann. Organosulfates in Ambient Aerosol: State of Knowledge and Future Research Directions on Formation, Abundance, Fate, and Importance. Environmental Science & Technology 2020, 54 (7) , 3767-3782. https://doi.org/10.1021/acs.est.9b06751
    7. Cuiping Ning, Yuan Gao, Haiming Yang, Xuyan Hao. Molecular characteristics and potential source of urban PM2.5-bound water-soluble organic matter in Shanghai during springtime. Atmospheric Environment 2023, 311 , 120025. https://doi.org/10.1016/j.atmosenv.2023.120025
    8. L. Poulain, A. Tilgner, M. Brüggemann, P. Mettke, L. He, J. Anders, O. Böge, A. Mutzel, H. Herrmann. Particle‐Phase Uptake and Chemistry of Highly Oxygenated Organic Molecules (HOMs) From α ‐Pinene OH Oxidation. Journal of Geophysical Research: Atmospheres 2022, 127 (16) https://doi.org/10.1029/2021JD036414
    9. Hongxing Jiang, Jun Li, Jiao Tang, Min Cui, Shizhen Zhao, Yangzhi Mo, Chongguo Tian, Xiangyun Zhang, Bin Jiang, Yuhong Liao, Yingjun Chen, Gan Zhang. Molecular characteristics, sources, and formation pathways of organosulfur compounds in ambient aerosol in Guangzhou, South China. Atmospheric Chemistry and Physics 2022, 22 (10) , 6919-6935. https://doi.org/10.5194/acp-22-6919-2022
    10. Andreas Tilgner, Thomas Schaefer, Becky Alexander, Mary Barth, Jeffrey L. Collett Jr., Kathleen M. Fahey, Athanasios Nenes, Havala O. T. Pye, Hartmut Herrmann, V. Faye McNeill. Acidity and the multiphase chemistry of atmospheric aqueous particles and clouds. Atmospheric Chemistry and Physics 2021, 21 (17) , 13483-13536. https://doi.org/10.5194/acp-21-13483-2021
    11. Yange Deng, Satoshi Inomata, Kei Sato, Sathiyamurthi Ramasamy, Yu Morino, Shinichi Enami, Hiroshi Tanimoto. Temperature and acidity dependence of secondary organic aerosol formation from α-pinene ozonolysis with a compact chamber system. Atmospheric Chemistry and Physics 2021, 21 (8) , 5983-6003. https://doi.org/10.5194/acp-21-5983-2021

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