The sources, distribution, levels and sinks of perfluorooctane sulfonate (PFOS) estimated to be released from areas of high population density, have been explored using the river Rhine as a case study. A comparison between modelled and measured data is presented, along with analysis of the importance of PFOS sorption in riverine systems. PFOS releases into the Rhine were estimated to be 325-690 kg/yr based on per capita emission rates of 27-57 [small mu ]g day-1 from a population of 33 million living within a 50 km zone either side of the river. Sorption of PFOS to suspended particles and sediments may alter its fate in the aquatic environment. Therefore available measured and modelled partitioning data was assessed, and Kd values (sorption coefficient) of 7.5 and 20 were selected. This resulted in sediment-water ratios of 23-76 : 1, which are similar to ratios reported in the literature, and resulted in modelled estimates that