ACPD Atmospheric Chemistry and Physics Discussions ACPD 1680-7375 Copernicus GmbH Göttingen, Germany 10.5194/acpd-10-25435-2010 Primary sources of PM<sub>2.5</sub> organic aerosol in an industrial Mediterranean city, Marseille El Haddad I. 1 Marchand N. 1 Wortham H. 1 Piot C. 2 3 Besombes J.-L. 2 Cozic J. 3 Chauvel C. 4 Armengaud A. 5 Robin D. 5 Jaffrezo J.-L. 3 Universités d'Aix-Marseille-CNRS, UMR 6264, Laboratoire Chimie Provence, Equipe Instrumentation et Réactivité Atmosphérique, Marseille, 13331, France Laboratoire de Chimie Moléculaire et Environnement, Université Savoie-Polytech'Savoie, Chambéry, France Université Joseph Fourier-Grenoble 1-CNRS, UMR 5183, Laboratoire de Glaciologie et Géophysique de l'Environnement, Saint Martin d'Hères, 38402, France Université Joseph Fourier-Grenoble 1-CNRS, UMR 5025, Laboratoire de Geodynamique des Chaines Alpines, BP 53, Grenoble, 38048, France Regional Network for Air Quality Monitoring (ATMO-PACA), 146 rue Paradis 13006 Marseille, France 01 11 2010 10 11 25435 25490 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-discuss.net/10/25435/2010/acpd-10-25435-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/10/25435/2010/acpd-10-25435-2010.pdf

Marseille, the most important port of the Mediterranean Sea, represents a challenging case study for source apportionment exercises, combining an active photochemistry and multiple emission sources, including fugitive emissions from industrial sources and shipping. This paper presents a Chemical Mass Balance (CMB) approach based on organic markers and metals to apportion the primary sources of organic aerosol in Marseille, with a special focus on industrial emissions. Overall, the CMB model accounts for the major primary anthropogenic sources including motor vehicles, biomass burning, and the aggregate emissions from three industrial processes (HFO combustion/shipping, coke production and steel manufacturing) as well as some primary biogenic emissions. This source apportionment exercise is well corroborated by <sup>14</sup>C measurements. Primary OC estimated by the CMB accounts on average for 22% and is dominated by the vehicular emissions that contribute on average for 17% of OC mass concentration (17% of PM<sub>2.5</sub>). Even though, industrial emissions contribute for only 2.3% of the total OC (7% of PM<sub>2.5</sub>), they are associated with ultrafine particles (<i>Dp</i><80 nm) and high concentrations of Polycyclic Aromatic Hydrocarbons (PAH) and heavy metals such as Pb, Ni and V. On one hand, given that industrial emissions governed key primary markers, their omission would lead to substantial uncertainties in the CMB analysis performed in areas heavily impacted by such sources, hindering accurate estimation of non-industrial primary sources and secondary sources. This result implies that CMB modelling should not be a straightforward exercise and one have to carefully investigate the marker behaviours and trends beforehand, especially in complex environments such as Marseille. On the other hand, being associated with bursts of submicron particles and carcinogenic and mutagenic components such as PAH, these emissions are most likely related with acute health outcomes and should be regulated despite their small contributions to OC. Another important result is the fact that 78% of OC mass cannot be attributed to the major primary sources and thus remains un-apportioned. We have consequently critically investigated the uncertainties underlying our CMB apportionments. While we have provided some evidence for photochemical decay of hopanes, this decay does not appear to significantly alter the CMB estimates of the total primary OC. Sampling artefacts and unaccounted primary sources also appear to marginally influence the amount of un-apportioned OC. Therefore, this significant amount of un-apportioned OC is mostly attributed to secondary organic carbon that appears to be the major component of OC, during the whole period of study.

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