The Chemical Landscape of Leaf Surfaces and Its Interaction with the Atmosphere.

Atmospheric chemists have historically treated leaves as inert surfaces that merely emit volatile hydrocarbons. However, a growing body of evidence suggests that leaves are ubiquitous substrates for multiphase reactions-implying the presence of chemicals on their surfaces. This Review provides an overview of the chemistry and reactivity of the leaf surface's "chemical landscape", the dynamic ensemble of compounds covering plant leaves. We classified chemicals as endogenous (originating from the plant and its biome) or exogenous (delivered from the environment), highlighting the biological, geographical, and meteorological factors driving their contributions. Based on available data, we predicted ≫2 μg cm -2 of organics on a typical leaf, leading to a global estimate of ≫3 Tg for multiphase reactions. Our work also highlighted three major knowledge gaps: (i) the overlooked role of ambient water in enabling the leaching of endogenous substances and mediating aqueous chemistry; (ii) the importance of phyllosphere biofilms in shaping leaf surface chemistry and reactivity; (iii) the paucity of studies on the multiphase reactivity of atmospheric oxidants with leaf-adsorbed chemicals. Although biased toward available data, we hope this Review will spark a renewed interest in the leaf surface's chemical landscape and encourage multidisciplinary collaborations to move the field forward.