Herein, an experimental study coupled with a model in order to assess the non-equilibrium and multi-compound dissolution behaviour of a coal tar containing PAHs and phenols into water, is presented. For this aim, two experimental studies has been carried out: (1) coal tar-water partition equilibrium and (2) dissolution dynamics of coal tar under controlled hydrodynamic conditions in percolation columns packed with glass beads. The dissolution amount of the three target constituents (i.e. phenol, naphthalene and phenanthrene) was monitored by UV detection. The dissolution behaviour was modelled using a predictive fraction approach. The partition coefficients have been estimated from experimental data and the obtained results show that the partition coefficient of each constituent between the aqueous phase and the tar depends on the activities of the constituent in both phases and cannot be estimated only from the solubility of the pure compound in water. The non-equilibrium dissolution model was established, applied, for the experimental conditions and validated for three target compounds adjusting the effective interfacial area between tar and water. This parameter is specific of the experimental set-up. The global behaviour of coal tar has been modelled taking into account four categories of compounds according to their water solubility and volatilities. The mass transfer parameters have been estimated using available correlations. The results of this paper indicate that a model based on component fractions can be used to assess the non-equilibrium dissolution behaviour of a coal tar. (c) 2005 Elsevier B.V. All rights reserved.