Evaluation of historical atmospheric pollution in an industrial area by dendrochemical approaches.

We conducted a dendrochemical study in order to evaluate the exposure of territories and populations to different types of pollutants and to characterise the history of pollution in one of the most intensely industrialised areas of Europe: the industrial port zone of Fos, also heavily urbanised. To perform the study, two tree species have been selected, Pinus halepensis and Populus nigra, on a rural plot located roughly 20 km away from the industrial harbour, an urban plot located in the city of Fos-sur-Mer and an industrial plot. Our study indicated that poplar was a more relevant model for the dendrochemical studies, exhibiting a higher bioaccumulation capacity than pine except for Hg, Sb and Mn. Moreover, thanks to this work, we observed significant exposure of the trees in the urban and industrial areas to As, Cd, Co, Cu, Mo, Sb, Zn, Al, Ca, and Mg, highlighting the exposure of the territory and populations living in the vicinity of the industrial harbour. The temporal variability of the concentrations measured in the tree rings corresponds to the increasing industrialisation of the territory as well as to the evolution of the industrial processes. Thus, this project highlighted the exposure of the Gulf of Fos to atmospheric emissions (industrial, road and urban) of the industrial harbour as well as the changes over time. It also pointed out the relevance of using dendrochemistry to measure atmospheric exposure of metals and metalloids and its temporal variability.

Chlorination by-product concentration levels in seawater and fish of an industrialised bay (Gulf of Fos, France) exposed to multiple chlorinated effluents.

Chlorination is one of the most widely used techniques for biofouling control in large industrial units, leading to the formation of halogenated chlorination by-products (CBPs). This study was carried out to evaluate the distribution and the dispersion of these compounds within an industrialised bay hosting multiple chlorination discharges issued from various industrial processes. The water column was sampled at the surface and at 7 m depth (or bottom) in 24 stations for the analysis of CBPs, and muscle samples from 15 conger eel (Conger conger) were also investigated. Temperature and salinity profiles supported the identification of the chlorination releases, with potentially complex patterns. Chemical analyses showed that bromoform was the most abundant CBP, ranging from 0.5 to 2.2 µg L(-1) away from outlets (up to 10 km distance), and up to 18.6 µg L(-1) in a liquefied natural gas (LNG) regasification plume. However, CBP distributions were not homogeneous, halophenols being prominent in a power station outlet and dibromoacetonitrile in more remote stations. A seasonal effect was identified as fewer stations revealed CBPs in summer, probably due to the air and water temperatures increases favouring volatilisation and reactivity. A simple risk assessment of the 11 identified CBPs showed that 7 compounds concentrations were above the potential risk levels to the local marine environment. Finally, conger eel muscles presented relatively high levels of 2,4,6-tribromophenol, traducing a generalised impregnation of the Gulf of Fos to CBPs and a global bioconcentration factor of 25 was determined for this compound.

New method to determine the total carbonyl functional group content in extractable particulate organic matter by tandem mass spectrometry.

A functional group analysis method was developed to determine the quantitative content of carbonyl functional groups in atmospheric particulate organic matter (POM) using constant neutral loss scanning-tandem mass spectrometry (CNLS-MS/MS). The neutral loss method consists in monitoring the loss of a neutral fragment produced by the fragmentation of a precursor ion in a collision cell. The only ions detected are the daughter ions resulting from the loss of the neutral fragment under study. Then, scanning the loss of a neutral fragment characteristic of a functional group enables the selective detection of the compounds bearing the chemical function under study within a complex mixture. The selective detection of carbonyl functional groups was achieved after derivatization with pentafluorophenylhydrazine (PFPH) by monitoring the neutral loss of C(6)F(5)N (181 amu), which was characteristic of a large panel of derivatized carbonyl compounds. The method was tested on 25 reference mixtures of different composition, all containing 24 carbonyl compounds at randomly determined concentrations. The repeatability and calibration tests were satisfying as they resulted in a relative standard deviation below 5% and a linear range between 0.01 and 0.65 mM with a calculated detection limit of 0.0035 mM. Also, the relative deviation induced by changing the composition of the mixture while keeping the total concentration of carbonyl functional groups constant was less than 20%. These reliability experiments demonstrate the high robustness of the developed procedure for accurate carbonyl functional group measurement, which was applied to atmospheric POM samples.