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.