Mercury (Hg) solubility and reactivity in soils at two extremely contaminated ancient small scale cinnabar roasting sites in the surroundings of the Hg mining area of Idrija (Slovenia) were determined in order to assess the mobility of Hg in the aqueous phase and to evaluate the extent of leaching of Hg into Idrijca River and further downstream. Water leaching experiments were performed on soil and SOM (soil organic matter) samples from historical roasting sites Pšenk and Frbejžene trate. The determined concentrations of leachable Hg in soil samples from the studied areas range from 16 to exceptionally high concentration of 18,000μg/kg, representing 0.0002 to 1.1% of total Hg in these samples, while in SOM samples leachable Hg concentrations range between 13.3 and 6000μg/kg, which corresponds to 0.0017–0.074% of total Hg determined in SOM. The soluble Hg concentrations in investigated soil profiles range from 183 to 18,000μg/kg (0.038–1.7% of total Hg). On the average, more than 90% of soluble Hg occurs in a non-reactive complex bound form, suggesting the preferential binding of Hg to humic matter. Soluble Hg in studied soil profiles generally increases with depth. The obtained results show that Hg is effectively transported to deeper soil layers, mainly as soluble organic complexes. It is estimated that there is still about 10kg of soluble Hg stored in soils of the investigated roasting sites, which is continuously leached to surface waters and deeper into the soil. •Water leaching experiments were performed on soil and SOM samples.•Total soluble, complex-bound and reactive Hg was defined.•Extremely high concentrations (up to 18,000μg/kg) of soluble Hg were determined.•More than 90% of soluble Hg occurs in a non-reactive complex bound form.•We estimate that soluble Hg stored in soils is mobilized to the groundwater.