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Highly oxidized products from the atmospheric reaction of hydroxyl radicals with isoprene

Author

Listed:
  • Torsten Berndt

    (Leibniz Institute for Tropospheric Research (TROPOS))

  • Erik H. Hoffmann

    (Leibniz Institute for Tropospheric Research (TROPOS))

  • Andreas Tilgner

    (Leibniz Institute for Tropospheric Research (TROPOS))

  • Hartmut Herrmann

    (Leibniz Institute for Tropospheric Research (TROPOS))

Abstract

Isoprene (C5H8) globally accounts for half of the non-methane hydrocarbon flux into Earth´s atmosphere. Its degradation is mainly initiated by the gas-phase reaction with OH radicals yielding a complex system of RO2 radicals. Subsequent product formation is not conclusively understood yet. Here we report the observation of C4- and C5-products from OH + isoprene bearing at least two functional groups. Their production is initiated either by the reaction of initially formed δ-RO2 radicals with NO or by 1,6 H-shift isomerization of Z-δ-RO2 radicals. Both reaction channels also form highly oxygenated molecules (HOMs), which could be important for the generation of secondary organic aerosol. C5H9O8 and C5H9O9 radicals represent the main precursors of closed-shell HOMs. Global simulations revealed that the isoprene-derived HOM-RO2 production is comparable with that of α-pinene, currently regarded as very important HOM source. This study provides a more complete insight into isoprene´s degradation process including the HOM formation.

Suggested Citation

  • Torsten Berndt & Erik H. Hoffmann & Andreas Tilgner & Hartmut Herrmann, 2025. "Highly oxidized products from the atmospheric reaction of hydroxyl radicals with isoprene," Nature Communications, Nature, vol. 16(1), pages 1-12, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-57336-1
    DOI: 10.1038/s41467-025-57336-1
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    References listed on IDEAS

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    1. Siddharth Iyer & Matti P. Rissanen & Rashid Valiev & Shawon Barua & Jordan E. Krechmer & Joel Thornton & Mikael Ehn & Theo Kurtén, 2021. "Molecular mechanism for rapid autoxidation in α-pinene ozonolysis," Nature Communications, Nature, vol. 12(1), pages 1-6, December.
    2. Torsten Berndt & Stefanie Richters & Tuija Jokinen & Noora Hyttinen & Theo Kurtén & Rasmus V. Otkjær & Henrik G. Kjaergaard & Frank Stratmann & Hartmut Herrmann & Mikko Sipilä & Markku Kulmala & Mikae, 2016. "Hydroxyl radical-induced formation of highly oxidized organic compounds," Nature Communications, Nature, vol. 7(1), pages 1-8, December.
    3. Mikael Ehn & Joel A. Thornton & Einhard Kleist & Mikko Sipilä & Heikki Junninen & Iida Pullinen & Monika Springer & Florian Rubach & Ralf Tillmann & Ben Lee & Felipe Lopez-Hilfiker & Stefanie Andres &, 2014. "A large source of low-volatility secondary organic aerosol," Nature, Nature, vol. 506(7489), pages 476-479, February.
    4. Torsten Berndt & Erik H. Hoffmann & Andreas Tilgner & Frank Stratmann & Hartmut Herrmann, 2023. "Direct sulfuric acid formation from the gas-phase oxidation of reduced-sulfur compounds," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
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