Within the framework of Migr’Hycar research project, the fate of oil spill was studied with the aim to characterize their physical-chemical behaviour. For this purpose, seven petroleum oils commercially available were tested and the distributions of the water soluble components were determined according to two experimental devices; laboratory conditions and pilot conditions in Polludrome. In the dissolved fraction, 41 polycyclic aromatic hydrocarbons and their derivates were quantified, among them are 16 EPA priority pollutants. A coupling of the stir bar sorptive extraction method and high performance gas chromatography mass spectrometry were used. Analyses showed that naphthalenes series constitute the major part of the water soluble fraction from fresh oils. In fact, light and heavy molecules have different contributions to solubilization kinetics. From the results, a linear correlation was established between the density of oils and the times of maximum solubilization. Moreover, the effect of 10% ethanol in gasoline was observed on the profile of solubilized PAHs in water. Kinetic patterns obtained with Polludrome showed the influence of surface water/oil ratio (WOR) on the volatilization process. Compared to laboratory conditions, the dynamic conditions of Polludrome led to an enhanced evaporation process, thus shifting the solubility peak.