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Published March 27, 2016 | Published + Supplemental Material
Journal Article Open

Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry


Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H_2SO_4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H_2SO_4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF (Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H_2SO_4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H_2SO_4 cluster distribution compared to binary (H_2SO_4-H_2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H_2SO_4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self-contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit.

Additional Information

© 2016 The Authors. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made. Received 9 JUL 2015; Accepted 9 NOV 2015; Accepted article online 6 FEB 2016; Published online 24 MAR 2016. We would like to thank CERN for supporting CLOUD with important technical and financial resources and for providing a particle beam from the CERN Proton Synchrotron. We also thank P. Carrie, L.-P. De Menezes, J. Dumollard, K. Ivanova, F. Josa, I. Krasin, R. Kristic, A. Laassiri, O. S. Maksumov, B. Marichy, H. Martinati, S. V. Mizin, R. Sitals, A. Wasem, and M. Wilhelmsson for their important contributions to the experiment. This research has received funding from the EC Seventh Framework Programme (Marie Curie Initial Training Network "CLOUD-ITN" 215072, MC-ITN "CLOUD-TRAIN" 316662, ERC-Starting "MOCAPAF" grant 57360 and ERC-Advanced "ATMNUCLE" grant 227463), PEGASOS project funded by the European Commission under the Framework Programme 7 (FP7-ENV-2010-265148), the German Federal Ministry of Education and Research (project 01LK0902A and 01LK1222A), the Swiss National Science Foundation (project 200020_135307 and 206620_141278), the Academy of Finland (Center of Excellence project 1118615 and 251007), the Academy of Finland (138951, 135054, 133872, 251427, 139656, 139995, 137749, 141217, and 141451), the Finnish Funding Agency for Technology and Innovation, the Väisälä Foundation, the Nessling Foundation, the Austrian Science Fund (FWF; project J3198-N21), the Portuguese Foundation for Science and Technology (project CERN/FP/116387/2010), the Swedish Research Council, Vetenskapsrådet (grant 2011-5120), the Presidium of the Russian Academy of Sciences and Russian Foundation for Basic Research (grants 08-02-91006-CERN and 12-02-91522-CERN), the U.S. National Science Foundation (grants AGS1447056 and AGS1439551), the U.S. Department of Energy (contract DE-SC0014469), and the Davidow Foundation. We thank the tofTools team for providing tools for mass spectrometry analysis. The data presented in this paper are available by contacting the corresponding author L.R. (l.rondo@iau.uni-frankfurt.de).

Attached Files

Published - Rondo_et_al-2016-Journal_of_Geophysical_Research__Atmospheres.pdf

Supplemental Material - jgrd52766-sup-0001-Supplementary.doc


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