1National Space Institute, Technical University of Denmark, 2100, Copenhagen Ø, Denmark
2Division of Atmospheric Science, Department of Physics, P.O. Box 64, 00014 University of Helsinki, Finland
3Department of Environmental Science and Technology, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Yokohama, 226-8502, Japan
4University of Copenhagen, Department of Chemistry, 2100, Copenhagen Ø, Denmark
5Department of Environmental Chemistry and Engineering, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Yokohama, 226-8502, Japan
6Department of Earth and Planetary Science, Tokyo Institute of Technology, Meguro-ku, Tokyo, 152-8551, Japan
Received: 17 Nov 2011 – Discussion started: 13 Feb 2012
Abstract. Sulphuric acid is an important factor in aerosol nucleation and growth. It has been shown that ions enhance the formation of sulphuric acid aerosols, but the exact mechanism has remained undetermined. Furthermore some studies have found a deficiency in the sulphuric acid budget, suggesting a missing source. In this study the production of sulphuric acid from SO2 through a number of different pathways is investigated. The production methods are standard gas phase oxidation by OH radicals produced by ozone photolysis with UV light, liquid phase oxidation by ozone, and gas phase oxidation initiated by gamma rays. The distributions of stable sulphur isotopes in the products and substrate were measured using isotope ratio mass spectrometry. All methods produced sulphate enriched in 34S and we find an enrichment factor (δ34S) of 8.7 ± 0.4‰ (1 standard deviation) for the UV-initiated OH reaction. Only UV light (Hg emission at 253.65 nm) produced a clear non-mass-dependent excess of 33S. The pattern of isotopic enrichment produced by gamma rays is similar, but not equal, to that produced by aqueous oxidation of SO2 by ozone. This, combined with the relative yields of the experiments, suggests a mechanism in which ionising radiation may lead to hydrated ion clusters that serve as nanoreactors for S(IV) to S(VI) conversion.
Revised: 24 May 2012 – Accepted: 02 Jun 2012 – Published: 19 Jun 2012
Enghoff, M. B., Bork, N., Hattori, S., Meusinger, C., Nakagawa, M., Pedersen, J. O. P., Danielache, S., Ueno, Y., Johnson, M. S., Yoshida, N., and Svensmark, H.: An isotopic analysis of ionising radiation as a source of sulphuric acid, Atmos. Chem. Phys., 12, 5319-5327, doi:10.5194/acp-12-5319-2012, 2012.