ABSTRACT Mercury can travel over long distances, and bioaccumulate in the trophic chain thereby posing a threat to not only humans but also animals and plants. Mercury also causes neurological problems such as the Minamata diseases. Pollution and toxicity of mercury have become a global problem that requires immediate attention. In this study, a thermal-desorption technique using a Zeeman direct mercury (Hg) analyser (DMA) was employed for the quantification of Hg in river sediments as well as for Hg thermo-scanning to investigate the behaviour of Hg release from sediments. Thermal speciation was based on comparison of the temperatures at which Hg species in sediments were thermally released to the temperatures at which Hg in known standards were released. Moreover, total Hg concentrations in river sediments were measured using a DMA. The accuracy of the method for total Hg quantification was confirmed by the analysis of several standard reference materials of sediment (SRM2709a, NCS DC 73325, NCS DC 73374, NCS DC 73316 and NCS DC 73322) and quantitative percentage recoveries ranging from 84 to 99% were obtained. The total Hg concentrations in sediments ranged from 7.4 to 35.2 ng/g and 2.1 to 21.2 ng/g in the low and high flow seasons, respectively. Different forms of Hg associated with river sediments were successfully identified by thermo-desorption technique. The concentrations of Hg in the sediment samples were all below 200 ng/g which is the sediment quality guideline set by the United States Environmental Protection Agency (US EPA). Different species of Hg were present in the sediment samples, with humic acid and/or iron oxide being the most predominant forms of Hg associated with the sediments.