Protonation and oligomerization of gaseous isoprene on mildly acidic surfaces: Implications for atmospheric chemistry

Shinichi Enami, Himanshu Mishra, Michael R. Hoffmann, Agustín J. Colussi*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

55 Scopus citations

Abstract

In a global process linking the Earth's climate with its ecosystems, massive photosynthetic isoprene (ISOP) emissions are converted to light-scattering haze. This phenomenon is imperfectly captured by atmospheric chemistry models: predicted ISOP emissions atop forest canopies would deplete the oxidizing capacity of the overhead atmosphere, at variance with field observations. Here we address this key issue in novel laboratory experiments where we apply electrospray mass spectrometry to detect online the products of the reactive uptake of gaseous ISOP on the surface of aqueous jets as a function of acidity. We found that ISOP is already protonated to ISOPH + and undergoes cationic oligomerization to (ISOP) 2H + and (ISOP) 3H + on the surface of pH < 4 water jets. We estimate uptake coefficients, γ ISOP = (0.5 - 2.0) × 10 -6 on pH = 3 water, which translate into the significant reuptake of leaf-level ISOP emissions in typical (surface-to-volume ∼5 m -1) forests during realistic (a few minutes) in-canopy residence times. Our findings may also account for the rapid decay of ISOP in forests after sunset and help bring the global budget of volatile organic compounds closer to balance.

Original languageEnglish (US)
Pages (from-to)6027-6032
Number of pages6
JournalJournal of Physical Chemistry A
Volume116
Issue number24
DOIs
StatePublished - Jun 21 2012

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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