References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-11-3007-2011

The effect of H2SO4 – amine clustering on chemical ionization mass spectrometry (CIMS) measurements of gas-phase sulfuric acid

Kurtén

¹ ² Petäjä

¹ Smith

³ ⁴ Ortega

I. K.

¹ Sipilä

¹ Junninen

¹ Ehn

¹ Vehkamäki

¹ Mauldin

⁴ Worsnop

D. R.

¹ ³ ⁵ Kulmala

Division of Atmospheric Science, Department of Physics, P. O. Box 64, 00014 University of Helsinki, Finland

University of Copenhagen, Department of Chemistry, Universitetsparken 5, 2100 København Ø, Denmark

University of Eastern Finland, Yliopistonranta 1, P. O. Box 1627, 70211 Kuopio, Finland

National Center for Atmospheric Research, 1850 Table Mesa Drive, Boulder CO 80305, USA

Aerodyne Research, Inc. 45 Manning Rd, Billerica, MA 0182, USA

31 03 2011

11 6 3007 3019

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

This article is available from http://www.atmos-chem-phys.net/11/3007/2011/acp-11-3007-2011.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/3007/2011/acp-11-3007-2011.pdf

The state-of-the art method for measuring atmospheric gas-phase sulfuric acid is chemical ionization mass spectrometry (CIMS) based on nitrate reagent ions. We have assessed the possible effect of the sulfuric acid molecules clustering with base molecules on CIMS measurements using computational chemistry. From the computational data, three conclusions can be drawn. First, a significant fraction of the gas-phase sulfuric acid molecules are very likely clustered with amines if the amine concentration is around or above a few ppt. Second, some fraction of these acid-amine clusters may not be charged by the CIMS instrument, though the most reliable computational methods employed predict this fraction to be small; on the order of ten percent or less. Third, the amine molecules will evaporate practically immediately after charging, thus evading detection. These effects may need to be taken into account in the interpretation of atmospheric measurement data obtained using chemical ionization methods. The purpose of this study is not to criticize the CIMS method, but to help understand the implications of the measured results.

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