Atmospheric Measurement Techniques www.atmos-meas-tech.net 1867-1381 1867-8548 3 4 2010 10.5194/amt-3-1039-2010 http://www.atmos-meas-tech.net/3/1039/2010/ http://www.atmos-meas-tech.net/3/1039/2010/amt-3-1039-2010.html http://www.atmos-meas-tech.net/3/1039/2010/amt-3-1039-2010.pdf 1039 1053 2010-08-17 A high-resolution mass spectrometer to measure atmospheric ion composition H. Junninen heikki.junninen@helsinki.fi M. Ehn T. Petäjä L. Luosujärvi T. Kotiaho R. Kostiainen U. Rohner M. Gonin K. Fuhrer M. Kulmala D. R. Worsnop Department of Physics, P.O. Box 64, 00014, University of Helsinki, Helsinki, Finland Department of Chemistry, P.O. Box 55, 00014, University of Helsinki, Helsinki, Finland Division of Pharmaceutical Chemistry, P.O. Box 56, 00014, University of Helsinki, Helsinki, Finland Tofwerk AG, 3600 Thun, Switzerland Aerodyne Research Inc, Billerica, MA 01821, USA In this paper we present recent achievements on developing and testing a tool to detect the composition of ambient ions in the mass/charge range up to 2000 Th. The instrument is an Atmospheric Pressure Interface Time-of-Flight Mass Spectrometer (APi-TOF, Tofwerk AG). Its mass accuracy is better than 0.002%, and the mass resolving power is 3000 Th/Th. In the data analysis, a new efficient Matlab based set of programs (tofTools) were developed, tested and used. The APi-TOF was tested both in laboratory conditions and applied to outdoor air sampling in Helsinki at the SMEAR III station. Transmission efficiency calibrations showed a throughput of 0.1–0.5% in the range 100–1300 Th for positive ions, and linearity over 3 orders of magnitude in concentration was determined. In the laboratory tests the APi-TOF detected sulphuric acid-ammonia clusters in high concentration from a nebulised sample illustrating the potential of the instrument in revealing the role of sulphuric acid clusters in atmospheric new particle formation. The APi-TOF features a high enough accuracy, resolution and sensitivity for the determination of the composition of atmospheric small ions although the total concentration of those ions is typically only 400–2000 cm⁻³. The atmospheric ions were identified based on their exact masses, utilizing Kendrick analysis and correlograms as well as narrowing down the potential candidates based on their proton affinities as well isotopic patterns. In Helsinki during day-time the main negative ambient small ions were inorganic acids and their clusters. The positive ions were more complex, the main compounds were (poly)alkyl pyridines and – amines. 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