Abstract. 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 (heavy fuel oil combustion/shipping, coke production and steel manufacturing) as well as some primary biogenic emissions. This source apportionment exercise is well corroborated by 14C measurements. Primary OC estimated by the CMB accounts on average for 22% of total OC and is dominated by the vehicular emissions that contribute on average for 17% of OC mass concentration (vehicular PM contributes for 17% of PM2.5). Even though industrial emissions contribute only 2.3% of the total OC (7% of PM2.5), they are associated with ultrafine particles (Dp<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. 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 ill-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 artifacts 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.
Abstract. The properties of atmospheric aerosol particles in Marseille and Athens were investigated. The studies were performed in Marseille, France, during July 2002 and in Athens, Greece, during June 2003. The aerosol size distribution and the formation and growth rates of newly formed particles were characterized using Differential Mobility Particle Sizers. Hygroscopic properties were observed using a Hygroscopic Tandem Differential Mobility Analyzer setup. During both campaigns, the observations were performed at suburban, almost rural sites, and the sites can be considered to show general regional background behavior depending on the wind direction. At both sites there were clear pattern for both aerosol number concentration and hygroscopic properties. Nucleation mode number concentration increased during the morning hours indicating new particle formation, which was observed during more than 30% of the days. The observed formation rate was typically more than 1 cm−3 s−1, and the growth rate was between 1.2–9.9 nm h−1. Based on hygroscopicity measurements in Athens, the nucleation mode size increase was due to condensation of both water insoluble and water soluble material. However, during a period of less anthropogenic influence, the growth was to a larger extent due to water insoluble components. When urban pollution was more pronounced, growth due to condensation of water soluble material dominated.
Abstract. 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 14C 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 PM2.5). Even though, industrial emissions contribute for only 2.3% of the total OC (7% of PM2.5), they are associated with ultrafine particles (Dp<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.
