The ozone decomposition onto mineral surfaces prepared with traces of solid TiO2 in a matrix of SiO2 in order to mimic mineral dust particles has been investigated using a coated-wall flow-tube system at room temperature and atmospheric pressure. The ozone uptake coefficients were measured both under dark conditions and irradiation using near UV-light. While uptake in the dark was negligible, a large photoenhanced ozone uptake was observed. For TiO2/SiO2 mixtures under irradiation, the uptake coefficients increased with increasing TiO2 mass fraction (from 1 to 3 wt %), and the corresponding uptake coefficient based on the geometric surfaces ranged from 3 x 10(-6) to 3 x 10(-5). The uptake kinetics was also observed to increase with decreasing ozone concentration between 290 and 50 ppbv. Relative humidity influenced the ozone uptake on the film, and a reduced ozone loss was observed for relative humidity above 30%. The experimental results suggest that under atmospherically relevant conditions the photochemistry of dust can represent an important sink of ozone inside the dust plume.

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.