Influence of ship emissions on NOx, SO2, O3 and PM concentrations in a North-Sea harbor in France

The influence of in-port ship emissions on gases and PM10 concentrations has been estimated in the port city of Calais, northern France, one of the busiest harbor in Europe, with numerous rotations of ferries or roll-on/roll-off cargo in average per day. NOx, SO2, O3 and PM10 concentrations were continuously measured over a three-month period, as well as real-time particle size distribution. A rural site located at Cape Gris-Nez, 20 km from Calais, was considered to deduce intrinsic contribution of ship emissions at the harbor city. The average concentrations of the studied species as well as the pattern of the conditional bivariate probability function at the two sites evidenced that in-port shipping, especially during the maneuvering operations, has an important influence on the NOx and SO2 concentrations. The impact of shipping in the harbor of Calais on average concentrations was estimated to 5l% for SO2, 35% for NO, 15% for NO2 and 2% for PM10 in the studied period. Concentration peaks of SO2 and NOx associated with an 03 depletion appeared synchronized with departures and arrivals of ferries. For winds blowing from the harbor, when compared to the background level, the number of particles appeared 10 times higher, with the highest differences in the 30-67 nm and the 109-167 nm size ranges. The average impact of in-port ships on PM10 concentrations was estimated to ＋28.9 μg/m^3 and concerned mainly the PM1 size fraction （40%）. Punctually, PM10 can potentially reach a concentration value close to 100μg/m^3.

Chemical characterization of fine and ultrafine PM, direct and indirect genotoxicity of PM and their organic extracts on pulmonary cells

Particulate matter in ambient air constitutes a complex mixture of fine and ultrafine particles composed of various chemical compounds including metals, ions, and organics. A multidisciplinary approach was developed by studying physico-chemical characteristics and mechanisms involved in the toxicity of particulate atmospheric pollution. PM0.3-2.s and PM2.5 including ultrafine particles were sampled in Dunkerque, a French industrialized seaside city. PM samples were characterized from a chemical and toxicological point of view. Physico-chemical characterization evidenced that PM2.5 comes from several sources： natural ones, such as soil resuspension and marine sea-salt emissions, as well as anthropogenic ones, such as shipping traffic, road traffic, and industrial activities. Human BEAS-2B tung cells were exposed to PM0.3-2.5, or to the Extractable Organic Matter （EOM） of PM0.3-2.5 and PM2.s. These exposures induced several mechanisms of action implied in the genotoxicity, such as oxidative DNA adducts and DNA Damage Response. The toxicity of PM-EOM was higher for the sample including the ultrafine fraction （PM2.5） containing also higher concentrations of polycyclic aromatic hydrocarbons. These results evidenced the major role of organic compounds in the toxicity of PM.

Characterisation and seasonal variations of particles in the atmosphere of rural, urban and industrial areas：Organic compounds

Atmospheric aerosol samples（PM2.5–0.3, i.e., atmospheric particles ranging from 0.3 to2.5 μm） were collected during two periods： spring–summer 2008 and autumn–winter 2008–2009, using high volume samplers equipped with cascade impactors. Two sites located in the Northern France were compared in this study： a highly industrialised city（Dunkirk） and a rural site（Rubrouck）. Physicochemical analysis of particulate matter（PM） was undertaken to propose parameters that could be used to distinguish the various sources and to exhibit seasonal variations but also to provide knowledge of chemical element composition for the interpretation of future toxicological studies. The study showed that PM2.5–0.3concentration in the atmosphere of the rural area remains stable along the year and was significantly lower than in the urban or industrial ones, for which concentrations increase during winter.High concentrations of polycyclic aromatic hydrocarbons（PAHs）, dioxins, furans and dioxin like polychlorinated biphenyls（DL-PCBs）, generated by industrial activities, traffic and municipal wastes incineration were detected in the samples. Specific criteria like Carbon Preference Index（CPI） and Combustion PAHs/Total PAHs ratio（CPAHs/TPAHs） were used to identify the possible sources of atmospheric pollution. They revealed that paraffins are mainly emitted by biogenic sources in spring–summer whereas as in the case of PAHs, they have numerous anthropogenic emission sources in autumn-winter（mainly from traffic and domestic heating）.