Radical-omics reveals the hydrogen-abstraction pathway of isoprene oxidation.

Authors

Huan Song, Hongyang Cui, Huabin Dong, Ce Chen, Wenyu Wei, Yang Li, Qindan Zhu, Bo Tang, Chongqin Zhu, Xuefei Ma, Zhaofeng Tan, Shiyi Chen, Yi Wan, Keding Lu

Published in

Nature communications. Jul 01, 2026. Epub Jul 01, 2026.

Abstract

Isoprene is the most abundant biogenic volatile organic compound (BVOC) and has far-reaching impacts on secondary organic aerosol (SOA) formation globally. Its atmospheric oxidation produces diverse isomeric radicals that drive subsequent chain propagation and mechanistic branching. However, high-throughput experimental characterization of these isomeric-resolved radicals remains unavailable, leaving critical gaps in the underlying molecular mechanisms. Here we establish a radical-omics approach for isomer-specific identification and detection of hundreds of radical species generated during VOCs oxidation. Applied to OH-initiated isoprene oxidation, this method enables experimental quantification of four OH-added allylic radicals and determination of their branching ratios. We further found hydrogen-abstraction to be an unexpectedly important pathway, contributing up to 8.78 ± 3.96% of total branching. Incorporating the updated mechanism into a global chemical transport model shows that this pathway contributes up to 13.5% of isoprene-derived low-volatility SOA over tropical rainforests. These results provide an experimental foundation for radical screening and targeted mechanistic validation, revealing hidden pathways in complex atmospheric conditions.

PMID:
42386779
Bibliographic data and abstract were imported from PubMed on 02 Jul 2026.

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