A mechanism for biogenic production and emission of MEK from MVK decoupled from isoprene biosynthesis

Methyl ethyl ketone (MEK) is an important compound in atmospheric chemistry. While attention has been paid mostly to anthropogenic sources of MEK, recently it has been shown that biogenic sources are globally as important as anthropogenic ones. However, the origin of biogenic MEK has yet to be completely elucidated. We present the full mechanism by which within-plant transformation of methyl vinyl ketone (MVK) and, to a minor extent, of 2-butanol and 3-buten-2-ol, is a source of biogenic MEK. Such transformation is observed in red oak for both exogenous MVK, taken up from the atmosphere, and endogenous MVK generated within a plant when it experiences stress (e.g. heat stress). Endogenous MVK emitted by plants is typically explained by within-plant oxidation of isoprene caused by oxidative stress. In this study we show that MVK and MEK emissions caused by heat stress are not related to isoprene in isoprene-emitting plants, implying that the massive carbon investment that plants commit to isoprene production is not explained by a direct antioxidant role. The presented mechanism can be important for inclusion in plant emission and in plant-atmosphere interaction models.