Articles | Volume 5, issue 6
Atmos. Meas. Tech., 5, 1459–1489, 2012
Atmos. Meas. Tech., 5, 1459–1489, 2012

Research article 27 Jun 2012

Research article | 27 Jun 2012

Development of a parallel sampling and analysis method for the elucidation of gas/particle partitioning of oxygenated semi-volatile organics: a limonene ozonolysis study

S. Rossignol1,2, L. Chiappini1, E. Perraudin2,*, C. Rio1, S. Fable1, R. Valorso2, and J. F. Doussin2 S. Rossignol et al.
  • 1Institut National de l'Environnement Industriel et des Risques, Parc Technologique ALATA, 60550 Verneuil-en-Halatte, France
  • 2LISA, Universités Paris-Est-Créteil et Paris Diderot, CNRS UMR7583, 61 Av. du Général de Gaulle, 94010 Créteil, France
  • *now at: EPOC, University of Bordeaux, CNRS UMR5805, 351 Cours de la Libération, 33400 Talence, France

Abstract. The gas/particle partitioning behaviour of the semi-volatile fraction of secondary organic matter and the associated multiphase chemistry are key features to accurately evaluate climate and health impacts of secondary organic aerosol (SOA). However, today, the partitioning of oxygenated secondary species is rarely assessed in experimental SOA studies and SOA modelling is still largely based on estimated partitioning data. This paper describes a new analytical approach, solvent-free and easy to use, to explore the chemical composition of the secondary organic matter at a molecular scale in both gas and particulate phases. The method is based on thermal desorption (TD) of gas and particulate samples, coupled with gas chromatography (GC) and mass spectrometry (MS), with derivatisation on sampling supports. Gaseous compounds were trapped on Tenax TA adsorbent tubes pre-coated with pentafluorobenzylhydroxylamine (PFBHA) or N-Methyl-N-(t-butyldimethylsilyl)trifluoroacetamide (MTBSTFA). Particulate samples were collected onto quartz or Teflon-quartz filters and subsequently subjected to derivatisation with PFBHA or MTBSTFA before TD-GC/MS analysis. Method development and validation are presented for an atmospherically relevant range of organic acids and carbonyl and hydroxyl compounds. Application of the method to a limonene ozonolysis experiment conducted in the EUPHORE simulation chamber under simulated atmospheric conditions of low concentrations of limonene precursor and relative humidity, provides an overview of the method capabilities. Twenty-five compounds were positively or tentatively identified, nine being in both gaseous and particulate phases; and twelve, among them tricarboxylic acids, hydroxyl dicarboxylic acids and oxodicarboxylic acids, being detected for the first time.