The emission of volatile compounds from leaf litter

Abstract

Leaf litter is available at the Earth’s surface in large quantities. During the decomposition of leaf litter, volatile compounds can be released into the atmosphere, where they potentially influence local air quality, atmospheric chemistry or the global climate. In this thesis the focus was on the emission of C2-C5 hydrocarbons, molecular hydrogen (H2), carbon monoxide (CO) and methyl chloride (CH3Cl) from leaf litter and the factors that control the emissions were investigated. For different plant species, the emission rates of several C2-C5 hydrocarbons increased with temperature between 20 and 100°C according to the Arrhenius relation. When leaf litter was irradiated with UV, the emission increased linearly with the intensity of the UV. UVB radiation was more efficient in the generation of hydrocarbons from leaf litter than UVA. A simple upscaling showed that C2–C5 hydrocarbon emissions from leaf litter are likely insignificant for their global budgets, but may have a small influence on atmospheric chemistry on the local scale. Senescent and dead plant material releases carbon monoxide (CO), methane and larger hydrocarbons upon heating or irradiation with UV, but emissions of hydrogen (H2) have not been reported. In this study, H2 was released from leaf litter of Sequoiadendron giganteum in detectable amounts at temperatures above 45°C, whereas CO was also emitted at ambient temperature. Leaf litter has been identified as a potentially important source of CH3Cl. However, the factors controlling the emissions are unclear. Laboratory experiments have been performed in which CH3Cl emissions were measured from leaf litter of different plant species. For each investigated plant species, the CH3Cl emission rate strongly increased with temperature according to the Arrhenius relation. However, at constant temperature, large differences between different plants were observed. Therefore, CH3Cl emissions were measured from halophyte leaf litter with a varying chloride content, but no significant correlation between the CH3Cl emission rate and the chloride content of the plant material was observed. A limited set of field experiments was performed in which CH3Cl emissions were measured. Leaf litter emitted CH3Cl, but only in periods with fresh leaf litter fall. Outside these periods, the flux from leaf litter was zero or even slightly negative. The CH3Cl emission rate increased with temperature, but the temperature increase did not follow the Arrhenius relation as was observed in the laboratory experiments. The global importance of leaf litter as a source of CH3Cl was investigated using the global chemistry transport model TM5. Forward simulations with different emission scenarios indicated that at station Trinidad Head (mid-latitudes of North America), a substantial seasonal emission from leaf litter was required to match the measured CH3Cl mixing ratios at this station. Inversions performed with the TM4-4D-Var system indicated that the main CH3Cl sources were located in the Tropics, whereas the mid- and high latitudes were only a minor source. Sensitivity studies performed to investigate the robustness of the optimized emissions indicated that more than 90% of the global net emissions was located in the Tropics.