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<p>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.</p>

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

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2026年7月1日

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  • 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

摘要

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.