Emission fluxes and atmospheric degradation of monoterpenes above a boreal forest. Field measurements and modelling

The contribution of monoterpenes to aerosol formation processes within and above forests is not well understood. This is also true for the particle formation events observed during the BIOFOR campaigns in Hyytiala, Finland. Therefore, the diurnal variation of the concentrations of several biogenic volatile organic compounds (BVOCs) and selected oxidation products in the gas and particle phase were measured on selected days during the campaigns in Hyytiala, Finland. alpha -pinene and Delta (3)-carene were found to represent the most important monoterpenes above the boreal forest. A clear vertical gradient of their concentrations was observed together with a change of the relative monoterpene composition with height. Based on concentration profile measurements of monoterpenes, their fluxes above the forest canopy were calculated using the gradient approach. Most of the time, the BVOC fluxes show a clear diurnal variation with a maximum around noon. The highest fluxes were observed for alpha -pinene with values up to 20 ng m(-2) s(-1) in summer time and almost 100 ng m(-2) s(-1) during the spring campaign. Furthermore, the main oxidation products from a-pinene, pinonaldehyde, and from beta -pinene, nopinone, were detected in the atmosphere above the forest. In addition to these more volatile oxidation products, pinic and pinonic acid were identified in the particle phase in a concentration range between 1 and 4 ng m(-3). Beside these direct measurement of known oxidation products, the chemical sink term in the flux calculations was used to estimate the amount of product formation of the major terpenes (alpha -pinene, beta -pinene, Delta (3)-carene). A production rate of very low volatile oxidation products (e.g., multifunctional carboxylic) from . OH- and O-3-reaction of monoterpenes of about 1.3 (.) 10(4) molecules cm(-3) s(-1) was estimated for daylight conditions during summer time. Additionally, model calculations with the one-dimensional multilayer model CACHE were carried out to investigate the diurnal course of BVOC fluxes and chemical degradation of terpenes.