Atmos. Chem. Phys. Discuss., 10, 14897-14946, 2010
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This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Composition and temporal behavior of ambient ions in the boreal forest
M. Ehn1, H. Junninen1, T. Petäjä1, T. Kurtén1, V.-M. Kerminen1,2, S. Schobesberger1, H. E. Manninen1, I. K. Ortega1, H. Vehkamäki1, M. Kulmala1, and D. R. Worsnop1,2,3
1Department of Physics, P.O. Box 64, 00014, University of Helsinki, Finland
2Finnish Meteorological Institute, Research and Development, P.O. Box 503, 00101 Helsinki, Finland
3Aerodyne Research Inc, Billerica, MA 01821, USA

Abstract. A recently developed atmospheric pressure interface mass spectrometer (APi-TOF) measured the negative and positive ambient ion composition at a boreal forest site. As observed in previous studies, the negative ions were dominated by strong organic and inorganic acids (e.g. malonic, nitric and sulfuric acid), whereas the positive ions consisted of strong bases (e.g. alkyl pyridines and quinolines). Several new ions and clusters of ions were identified based on their exact masses, made possible by the high resolution, mass accuracy and sensitivity of the APi-TOF. Time series correlograms aided in peak identification and assigning the atomic compositions to molecules. Quantum chemical calculations of proton affinities and cluster stabilities were also used to confirm the plausibility of the assignments. Acids in the gas phase are predominantly formed by oxidation in the gas phase, and thus the concentrations are expected to vary strongly between day and night. This was also the case in this study, where the negative ions showed strong diurnal behavior, whereas the daily changes in the positive ions were considerably smaller. A special focus in this work was the changes in the ion distributions occurring during new particle formation events. We found that sulfuric acid, together with its clusters, dominated the negative ion spectrum during these events. The monomer (HSO4) was the largest peak, together with the dimer (H2SO4·HSO4) and trimer ((H2SO4)2·HSO4). SO5 also tracked HSO4 at around 20% of the HSO4 concentration at all times. During the strongest events, also the tetramer and a cluster with the tetramer and ammonia were detected. Quantum chemical calculations predict that sulfuric acid clusters containing ammonia are much more stable when neutral, thus the detection of a single ion cluster implies that ammonia can be an important compound in the nucleation process. We also believe to have made the first observations of an organosulfate (glycolic acid sulfate) in the gas phase. This ion, and its cluster with sulfuric acid, correlates with the HSO4, but peaks in the early afternoon, some hours later than HSO4 itself. A list of all identified ions is presented in the supplementary material, and also a list of all detected masses not yet identified.

Citation: Ehn, M., Junninen, H., Petäjä, T., Kurtén, T., Kerminen, V.-M., Schobesberger, S., Manninen, H. E., Ortega, I. K., Vehkamäki, H., Kulmala, M., and Worsnop, D. R.: Composition and temporal behavior of ambient ions in the boreal forest, Atmos. Chem. Phys. Discuss., 10, 14897-14946, doi:10.5194/acpd-10-14897-2010, 2010.
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