Environmental controls over methanol emission from leaves

Methanol is found throughout the troposphere, with average concentrations second only to methane among atmospheric hydrocarbons. Proposed global methanol budgets are highly uncertain, but all agree that at least 60% of the total source arises from the terrestrial biosphere and primary emissions from plants. However, the magnitude of these emissions is also highly uncertain, and the environmental factors which control them require further elucidation. Using a temperature-controlled leaf enclosure, we measured methanol emissions from leaves of six plant species by proton transfer reaction mass spectrometry, with simultaneous measurements of leaf evapotranspiration and stomatal conductance. Rates of emission at 30 degrees C varied from 0.2 to 38 mu g g (dry mass)(-1) h(-1), with higher rates measured on young leaves, consistent with the production of methanol via pectin demethylation in expanding foliage. On average, emissions increased by a factor of 2.3 for each 10 degrees C increase in leaf temperature. At constant temperature, emissions were also correlated with co-varying incident photosynthetic photon flux density and rates of stomatal conductance. The data were analyzed using the emission model developed by Niinemets and Reichstein (2003a, b), with the incorporation of a methanol production term that increased exponentially with temperature. It was concluded that control of emissions, during daytime, was shared by leaf temperature and stomatal conductance, although rates of production may also vary diurnally in response to variations in leaf growth rate in expanding leaves. The model, which generally provided reasonable simulations of the measured data during the day, significantly overestimated emissions on two sets of measurements made through the night, suggesting that production rates of methanol were reduced at night, perhaps because leaf growth was reduced or possibly through a direct effect of light on production. Although the short-term dynamics of methanol emissions can be successfully modeled only if stomatal conductance and compound solubility are taken into account, emissions on longer time scales will be determined by rates of methanol production, controls over which remain to be investigated.