Emission from plants is a major source of atmospheric methanol. Growing tissues contribute most to plant-generated methanol in the atmosphere, but there is still controversy over biological and physico-chemical controls of methanol emission. Methanol as a water-soluble compound is thought to be strongly controlled by gas-phase diffusion (stomatal conductance), but growth rate can follow a different diurnal rhythm from that of stomatal conductance, and the extent to which the emission control is shared between diffusion and growth is unclear. Growth and methanol emissions from Gossypium hirsutum, Populus deltoides, and Fagus sylvatica were measured simultaneously. Methanol emission from growing leaves was several-fold higher than that from adult leaves. A pronounced diurnal rhythm of methanol emission was observed; however, this diurnal rhythm was not predominantly determined by the diurnal rhythm of leaf growth. Large methanol emission peaks in the morning when the stomata opened were observed in all species and were explained by release of methanol that had accumulated in the intercellular air space and leaf liquid pool at night in leaves with closed stomata. Cumulative daily methanol emissions were strongly correlated with the total daily leaf growth, but the diurnal rhythm of methanol emission was modified by growth rate and stomatal conductance in a complex manner. While in G. hirsutum and in F. sylvatica maxima in methanol emission and growth coincided, maximum growth rates of P. deltoides were observed at night, while maximum methanol emissions occurred in the morning. This interspecific variation was explained by differences in the share of emission control by growth processes, by stomatal conductance, and methanol solubilization in tissue water.

Leaf isoprene emission scales positively with light intensity, is inhibited by high carbon dioxide (CO 2 ) concentrations, and may be enhanced or inhibited by low oxygen (O 2 ) concentrations, but the mechanisms of environmental regulation of isoprene emission are still not fully understood. Emission controls by isoprene synthase, availability of carbon intermediates, or energetic cofactors have been suggested previously. In this study, we asked whether the short-term (tens of minutes) environmental control of isoprene synthesis results from alterations in the immediate isoprene precursor dimethylallyldiphosphate (DMADP) pool size, and to what extent DMADP concentrations are affected by the supply of carbon and energetic metabolites. A novel in vivo method based on postillumination isoprene release was employed to measure the pool size of DMADP simultaneously with the rates of isoprene emission and net assimilation at different light intensities and CO 2 and O 2 concentrations. Both net assimilation and isoprene emission rates increased hyperbolically with light intensity. The photosynthetic response to CO 2 concentration was also hyperbolic, while the CO 2 response curve of isoprene emission exhibited a maximum at close to CO 2 compensation point. Low O 2 positively affected both net assimilation and isoprene emission. In all cases, the variation in isoprene emission was matched with changes in DMADP pool size. The results of these experiments suggest that DMADP pool size controls the response of isoprene emission to light intensity and to CO 2 and O 2 concentrations and that the pool size is determined by the level of energetic metabolites generated in photosynthesis.

The responses of isoprene emission rate to temperature are characterized by complex time-dependent behaviors that are currently not entirely understood. To gain insight into the temperature dependencies of isoprene emission, we studied steadystate and transient responses of isoprene emission from hybrid aspen (Populus tremula 3 Populus tremuloides) leaves using a fast-response gas-exchange system coupled to a proton-transfer reaction mass spectrometer. A method based on postillumination isoprene release after rapid temperature transients was developed to determine the rate constant of isoprene synthase (IspS), the pool size of its substrate dimethylallyldiphosphate (DMADP), and to separate the component processes of the temperature dependence of isoprene emission. Temperature transients indicated that over the temperature range 25°C to 45°C, IspS was thermally stable and operated in the linear range of its substrate DMADP concentration. The in vivo rate constant of IspS obeyed the Arrhenius law, with an activation energy of 42.8 kJ mol 21 . In contrast, steady-state isoprene emission had a significantly lower temperature optimum than IspS and higher activation energy. The reversible temperature-dependent decrease in the rate of isoprene emission between 35°C and 44°C was caused by decreases in DMADP concentration, possibly reflecting reduced pools of energetic metabolites generated in photosynthesis, particularly of ATP. Strong control of isoprene temperature responses by the DMADP pool implies that transient temperature responses under fluctuating conditions in the field are driven by initial DMADP pool size as well as temperature-dependent modifications in DMADP pool size during temperature transients. These results have important implications for the development of process-based models of isoprene emission.