1Johannes Gutenberg-Universität, Institute for inorganic Chemistry and analytical Chemistry, Duesbergweg 10–14, 55128 Mainz, Germany
2Karlsruhe Institute of Technology Institute for Meteorology and Climate Research (IMK-AAF), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
3Forschungszentrum Jülich GmbH, ICG-2: Troposphäre, 52425 Jülich, Germany
4Carnegie Mellon University Department of Chemical Engineering, 5000 Forbes Avenue, Pittsburgh, PA 15213-3890, USA
Received: 15 Jun 2011 – Discussion started: 06 Jul 2011
Abstract. This paper presents the results of mass spectrometric investigations of the OH-initiated oxidative aging of α-pinene SOA under simulated tropospheric conditions at the large aerosol chamber facility AIDA, Karlsruhe Institute of Technology. In particular, the OH-initiated oxidation of pure pinic and pinonic acid, two well-known oxidation products of α-pinene, was investigated. Two complementary analytical techniques were used, on-line atmospheric pressure chemical ionization/mass spectrometry (APCI/MS) and filter sampling followed by liquid chromatography/mass spectrometry (LC/ESI-MS). The results show that 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a very low volatile α-pinene SOA product and a tracer compound for terpene SOA, is formed from the oxidation of pinonic acid and that this oxidation takes place in the gas phase. This finding is confirmed by temperature-dependent aging experiments on whole SOA formed from α-pinene, in which the yield of MBTCA scales with the pinonic acid fraction in the gas phase. Based on the results, several feasible gas-phase radical mechanisms are discussed to explain the formation of MBTCA from OH-initiated pinonic acid oxidation.
Revised: 08 Jan 2012 – Accepted: 18 Jan 2012 – Published: 08 Feb 2012
Müller, L., Reinnig, M.-C., Naumann, K. H., Saathoff, H., Mentel, T. F., Donahue, N. M., and Hoffmann, T.: Formation of 3-methyl-1,2,3-butanetricarboxylic acid via gas phase oxidation of pinonic acid – a mass spectrometric study of SOA aging, Atmos. Chem. Phys., 12, 1483-1496, doi:10.5194/acp-12-1483-2012, 2012.