Tritium is an important environmental radionuclide whose reactivity with ligands and solids in aquatic systems is assumed to be limited. We studied the fractionation and sorption of tritium (added as tritiated water) in river water and seawater, and found that its distribution appears to be influenced by its affinity for organic matter. Tritium rapidly equilibrates with dissolved organic ligands that are retained by a reverse-phase C18 column, and with suspended sediment particles. Significantly, a measurable fraction of sorbed tritium associates with proteinaceous material that is potentially available to sediment-feeding organisms. These characteristics have not been reported previously and cannot be accounted for solely by isotopic exchange with hydrogen. Nevertheless, they are in qualitative agreement with available measurements of tritium in estuarine and coastal waters where its principal discharge is as tritiated water. Further research into the estuarine biogeochemical behaviour of tritium is required and radiological distribution coefficients and concentration factors that are assumed for this radionuclide may require reconsideration.