Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 6 6 2006 10.5194/acpd-6-13165-2006 http://www.atmos-chem-phys-discuss.net/6/13165/2006/ http://www.atmos-chem-phys-discuss.net/6/13165/2006/acpd-6-13165-2006.html http://www.atmos-chem-phys-discuss.net/6/13165/2006/acpd-6-13165-2006.pdf 13165 13224 2006-12-15 Ambient sesquiterpene concentration and its link to air ion measurements B. Bonn boris.bonn@helsinki.fi A. Hirsikko H. Hakola T. Kurtén L. Laakso M. Boy M. Dal Maso J. M. Mäkelä M. Kulmala Department of Physical Sciences, University of Helsinki, Helsinki, Finland Finnish Meteorological Institute, Helsinki, Finland National Center of Atmospheric Research, Boulder, CO, USA Tampere University of Technology, Institute of Physics, Tampere, Finland Ambient air ion size distributions have been measured continuously at the Finnish boreal forest site in Hyytiälä since spring 2003. In general, these measurements show a maximum of air ions below 1.0 nm in diameter. But this physical characterization does not provide any information about the ion's chemical composition, which is one key question regarding the explanation of nucleation events observed. In this study we propose a link of the observed maximum of negative air ions between 0.56 and 0.75 nm to the so-called stabilised Criegee biradical, formed in the reaction of biogenic sesquiterpenes with ozone and predominantly destroyed by its reaction with ambient water vapour. Calculations of the electron and proton affinities of 120 kJ mol^−1 (1.24 eV) and of 960 kJ mol^−1 support this link. Other possible candidates such as sulphuric acid derived clusters are unable to explain the observations made. By using this approach, we are able to calculate the ambient concentration of sesquiterpenes at the air ion instrument inlet with a high time resolution on the daily and seasonal scale. 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