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

Berndt, Torsten; Hoffmann, Erik H; Tilgner, Andreas; Herrmann, Hartmut · Nat Commun · 2025

basic_science · Level V

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Abstract

Isoprene (C<sub>5</sub>H<sub>8</sub>) 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 RO<sub>2</sub> radicals. Subsequent product formation is not conclusively understood yet. Here we report the observation of C<sub>4</sub>- and C<sub>5</sub>-products from OH + isoprene bearing at least two functional groups. Their production is initiated either by the reaction of initially formed δ-RO<sub>2</sub> radicals with NO or by 1,6 H-shift isomerization of Z-δ-RO<sub>2</sub> radicals. Both reaction channels also form highly oxygenated molecules (HOMs), which could be important for the generation of secondary organic aerosol. C<sub>5</sub>H<sub>9</sub>O<sub>8</sub> and C<sub>5</sub>H<sub>9</sub>O<sub>9</sub> radicals represent the main precursors of closed-shell HOMs. Global simulations revealed that the isoprene-derived HOM-RO<sub>2</sub> 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.