Chemodiversity of a Scots pine stand and implications for terpene air concentrations

Atmospheric chemistry in background areas is strongly influenced by natural vegetation. Coniferous forests are known to produce large quantities of volatile vapors, especially terpenes. These compounds are reactive in the atmosphere, and contribute to the formation and growth of atmospheric new particles. Our aim was to analyze the variability of mono-and sesquiterpene emissions between Scots pine trees, in order to clarify the potential errors caused by using emission data obtained from only a few trees in atmospheric chemistry models. We also aimed at testing if stand history and seed origin has an influence on the chemotypic diversity. The inherited, chemotypic variability in mono-and sesquiterpene emission was studied in a seemingly homogeneous 48 yr-old stand in Southern Finland, where two areas differing in their stand regeneration history could be distinguished. Sampling was conducted in August 2009. Terpene concentrations in the air had been measured at the same site for seven years prior to branch sampling for chemotypes. Two main compounds, alpha-pinene and Delta(3)-carene formed together 40-97% of the monoterpene proportions in both the branch emissions and in the air concentrations. The data showed a bimodal distribution in emission composition, in particular in Delta(3)-carene emission within the studied population. 10% of the trees emitted mainly alpha-pinene and no Delta(3)-carene at all, whereas 20% of the trees where characterized as high Delta(3)-carene emitters (Delta(3)-carene forming >80% of total emitted monoterpene spectrum). An intermediate group of trees emitted equal amounts of both alpha-pinene and Delta(3)-carene. The emission pattern of trees at the area established using seeding as the artificial regeneration method differed from the naturally regenerated or planted trees, being mainly high Delta(3)-carene emitters. Some differences were also seen in e. g. camphene and limonene emissions between chemotypes, but sesquiterpene emissions did not differ significantly between trees. The atmospheric concentrations at the site were found to reflect the species and/or chemodiversity rather than the emissions measured from any single tree, and were strongly dominated by alpha-pinene. We also tested the effect of chemodiversity on modeled monoterpene concentrations at the site and found out that since it significantly influences the distributions and hence the chemical reactions in the atmosphere, it should be taken into account in atmospheric modeling.