Protonation and Oligomerization of Gaseous Isoprene on Mildly Acidic Surfaces: Implications for Atmospheric Chemistry

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)(2)H+ and (ISOP)(3)H+ on the surface of pH < 4 water jets. We estimate uptake coefficients, gamma(ISOP) = (0.5 - 2.0) X 10(-6) on pH = 3 water, which translate into the significant reuptake of leaf-level ISOP emissions in typical (surface-to-volume 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.