Abstract. Forest soils are a significant source for the primary and secondary greenhouse gases N 2 O and NO. However, current estimates are still uncertain due to the still limited number of field measurements and the herein observed pronounced variability of N trace gas fluxes in space and time, which are due to the variation of environmental factors such as soil and vegetation properties or meteorological conditions. To overcome these problems we further developed a process-oriented model, the PnET-N-DNDC model, which simulates the N trace gas exchange on the basis of the processes involved in production, consumption and emission of N trace gases. This model was validated against field observations of N trace gas fluxes from 19 sites obtained within the EU project NOFRETETE, and shown to perform well for N 2 O (r 2 =0.68, slope=0.76) and NO (r 2 =0.78, slope=0.73). For the calculation of a European-wide emission inventory we linked the model to a detailed, regionally and temporally resolved database, comprising climatic properties (daily resolution), and soil parameters, and information on forest areas and types for the years 1990, 1995 and 2000. Our calculations show that N trace gas fluxes from forest soils may vary substantial from year to year and that distinct regional patterns can be observed. Our central estimate of NO emissions from forest soils in the EU amounts to 98.4, 84.9 and 99.2 kt N yr −1 , using meteorology from 1990, 1995 and year 2000, respectively. This is <1.0% of pyrogenic NO x emisCorrespondence to: K. Butterbach-Bahl (klaus.butterbach@imk.fzk.de) sions. For N 2 O emissions the central estimates were 86.8, 77.6 and 81.6 kt N yr −1 , respectively, which is approx. 14.5% of the source strength coming from agricultural soils. An extensive sensitivity analysis was conducted which showed a range in emissions from 44.4 to 254.0 kt N yr −1 for NO and 50.7 to 96.9 kt N yr −1 for N 2 O, for year 2000 meteorology.The results show that process-oriented models coupled to a GIS are useful tools for the calculation of regional, national, or global inventories of biogenic N trace gas emissions from soils. This work represents the most comprehensive effort to date to simulate NO and N 2 O emissions from European forest soils.

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The collisional deactivation of vibrationally highly excited benzyl radicals in the ground electronic state has been investigated. Vibrationally excited benzyl radicals have been generated using the fast dissociation of vibrationally excited ethylbenzene prepared from UV absorption followed by fast internal conversion. Subsequent to complete collisional deactivation the benzyl radicals have been reexcited by the absorption of a further UV‐photon also followed by fast internal conversion. Once again the collisional deactivation of the benzyl radicals has been monitored by time‐resolved UV absorption spectroscopy. Average energies transferred per collision have been determined by comparison of absorption‐time profiles with different initial vibrational energies. It was found that the rate of collisional deactivation of the open shell benzyl radical is almost identical to the rate of collisional deactivation of the closed shell hydrocarbons of similar size.