PM2.5 characterization of primary and secondary organic aerosols in two urban-industrial areas in the East Mediterranean.

Primary and secondary organic aerosols in PM2.5 were investigated over a one-year campaign at Zouk Mikael and Fiaa, Lebanon. The n-alkanes concentrations were quite similar at both sites (26-29 ng/m3) and mainly explained by anthropogenic emissions rather than natural ones. The concentrations of total Polycyclic Aromatic Hydrocarbons (PAHs) were nearly three times higher at Zouk Mikael (2.56 ng/m3) compared to Fiaa (0.95 ng/m3), especially for indeno[1,2,3-c,d]pyrene linked to the presence of the power plant. A characteristic indeno[1,2,3-c,d]pyrene/(indeno[1,2,3-c,d]pyrene + benzo[g,h,i]perylene) ratio in the range 0.8-1.0 was determined for heavy fuel oil combustion from the power plant. Fatty acids and hopanes were also investigated and were assigned to cooking activities and vehicular emissions respectively. Phthalates were identified for the first time in Lebanon with high concentrations at Zouk and Fiaa (106.88 and 97.68 ng/m3 respectively). Moreover, the biogenic secondary aerosols revealed higher concentrations in summer. The total terpene concentration varied between 131 ng/m3 at Zouk Mikael in winter to 469 ng/m3 at Fiaa in summer. Additionnally, the concentrations of the dicarboxylic acids especially for adipic and phthalic acids were more influenced by anthropogenic sources.The analysis of molecular markers and diagnostic ratios indicated that the sites were strongly affected by anthropogenic sources such as waste open burning, diesel private generators, cooking activities, road transport, power plant, and industrial emissions. Moreover, results showed different pattern during winter and summer seasons. Whereas, higher concentrations of biogenic markers were clearly encountered during the summer period.

Investigating the industrial origin of terpenoids in a coastal city in northern France: A source apportionment combining anthropogenic, biogenic, and oxygenated VOC.

Terpenoids have long been known to originate from natural sources. However, there is growing evidence for emissions from anthropogenic activities in cities, in particular from the production, manufacturing, and use of household solvents. Here, as part of the DATAbASE (Do Anthropogenic Terpenoids mAtter in AtmoSpheric chEmistry?) project, we investigate for the first time the potential role of industrial activities on the terpenoid burden in the urban atmosphere. This study is based on continuous VOC observations from an intensive field campaign conducted in July 2014 at an industrial-urban background site located in Dunkirk, Northern France. More than 80 VOCs including oxygenated and terpenoid compounds were measured by on-line Thermal Desorption Gas Chromatography with a Flame Ionization Detection (TD-GC-FID) and Proton Transfer Reaction-Time of Flight Mass Spectrometry (PTR-ToFMS). Isoprene, α-pinene, limonene and the sum of monoterpenes were the terpenoids detected at average mixing ratios of 0.02 ± 0.02 ppbv, 0.02 ± 0.02 ppbv, 0.01 ± 0.01 ppbv and 0.03 ± 0.05 ppbv, respectively. Like other anthropogenic VOCs, the mixing ratios of terpenoids significantly increase downwind the industrial plumes by one order of magnitude. Positive Matrix Factorization (PMF) was performed to identify the different emission sources of VOCs and their contribution. Six factors out of the eight factors extracted (r2 = 0.95) are related to industrial emissions such as solvent use, chemical and agrochemical storage, metallurgy, petrochemical, and coal-fired industrial activities. From the correlations between the industrial-type PMF factors, sulfur dioxide, and terpenoids, we determined their emissions ratios and we quantified for the first time their industrial emissions. The highest emission ratio is related to the alkene-dominated factor and is related to petrochemical, metallurgical and coal-fired industrial activities. The industrial emissions of monoterpenes equal 8.1 ± 4.3 tons/year. Those emissions are as significant as the non-industrialized anthropogenic ones estimated for the Paris megacity.