The sorptive behaviour of polycyclic aromatic hydrocarbons (PAHs) is critical to controlling their transport, fates and effects in the environment. Experiments are described which detail the behaviour of a model compound (benzo(a)pyrene) under simulated aquatic conditions. The kinetics of sorption were comparable to those of other PAH compounds. The sorption equilibrium was extensively studied and found to be affected by several key parameters, notably sediment concentration. The sorption coefficient decreased substantially with the sediment concentration, from 9580 ml g⁻¹ at a sediment concentration of 0.067 g l⁻¹ to 1110 ml g⁻¹ at a sediment concentration of 9.8 g l⁻¹. The results are consistent with previous reports and often explained by the presence of colloids. In this paper the dry weight concentration of colloids was determined and used for deriving the true sorption coefficient, which is up to an order of magnitude higher than the observed partition coefficient. The sorption of benzo(a)pyrene was also dependent on some of the particle properties, and the sorption coefficient was found to increase with the organic carbon content and specific surface area of sediment particles. The desorption of benzo(a)pyrene from sediment was shown to be relatively rapid, with implications for the potential remobilisation of benzo(a)pyrene and similar compounds.