1Aix-Marseille Université, CNRS, LCE FRE 3416, 13331 Marseille, France
2Université Lyon 1, CNRS, UMR5256, IRCELYON, Institut de Recherches sur la Catalyse et l'Environnement de Lyon, 69626 Villeurbanne, France
3Universités Joseph Fourier-Grenoble 1-CNRS, UMR5183, Laboratoire de Glaciologie et Géophysique de l'Environnement, 38402 Saint Martin d'Hères, France
4Laboratoire des Sciences du Climat et de l'Environnement, CEA-CNRS-UVSQ-IPSL, 91191 Gif sur Yvette, France
5Laboratory of Atmospheric Chemistry, Paul Scherrer Institut, 5232 Villigen PSI, Switzerland
*now at: INERIS, Parc Technologique Alata, BP2, 60550 Verneuil-en-Halatte, France
Received: 06 Jul 2012 – Discussion started: 09 Aug 2012
Abstract. As part of the FORMES summer 2008 experiment, an Aerodyne compact time-of-flight aerosol mass spectrometer (cToF-AMS) was deployed at an urban background site in Marseille to investigate the sources and aging of organic aerosols (OA). France's second largest city and the largest port in the Mediterranean, Marseille, provides a locale that is influenced by significant urban industrialized emissions and an active photochemistry with very high ozone concentrations. Particle mass spectra were analyzed by positive matrix factorization (PMF2) and the results were in very good agreement with previous apportionments obtained using a chemical mass balance (CMB) approach coupled to organic markers and metals (El Haddad et al., 2011a). AMS/PMF2 was able to identify for the first time, to the best of our knowledge, the organic aerosol emitted by industrial processes. Even with significant industries in the region, industrial OA was estimated to contribute only ~ 5% of the total OA mass. Both source apportionment techniques suggest that oxygenated OA (OOA) constitutes the major fraction, contributing ~ 80% of OA mass. A novel approach combining AMS/PMF2 data with 14C measurements was applied to identify and quantify the fossil and non-fossil precursors of this fraction and to explicitly assess the related uncertainties. Results show with high statistical confidence that, despite extensive urban and industrial emissions, OOA is overwhelmingly non-fossil, formed via the oxidation of biogenic precursors, including monoterpenes. AMS/PMF2 results strongly suggest that the variability observed in the OOA chemical composition is mainly driven in our case by the aerosol photochemical age. This paper presents the impact of photochemistry on the increase of OOA oxygenation levels, formation of humic-like substances (HULIS) and the evolution of α-pinene SOA (secondary OA) components.
Revised: 28 Jun 2013 – Accepted: 01 Jul 2013 – Published: 15 Aug 2013
El Haddad, I., D'Anna, B., Temime-Roussel, B., Nicolas, M., Boreave, A., Favez, O., Voisin, D., Sciare, J., George, C., Jaffrezo, J.-L., Wortham, H., and Marchand, N.: Towards a better understanding of the origins, chemical composition and aging of oxygenated organic aerosols: case study of a Mediterranean industrialized environment, Marseille, Atmos. Chem. Phys., 13, 7875-7894, doi:10.5194/acp-13-7875-2013, 2013.