Environmental impact of ancient small-scale mercury ore processing at Pšenk on soil (Idrija area, Slovenia)

The Idrija mine was the second largest Hg mine in the world surpassed only by the Almaden mine in Spain. It has been estimated that almost 145,000 tons of Hg was produced during operation (1490-1995) of the mine. In the first decade of Hg mining in Idrija the ore was roasted in piles; after that it was roasted for 150 years, until 1652, in earthen vessels at various sites in the woods around Idrija. Pšenk is one out of 21 localities of ancient roasting sites established on the hills surrounding Idrija and one of the largest localities of roasting vessel fragments. The unique way of roasting very rich Hg ore at this site has resulted in soil contamination and considerable amounts of waste material that potentially leach Hg into the surrounding environment. The main aim of this study was to determine the distribution and the forms of Hg in contaminated soils in order to evaluate potential environmental risk. Detailed soil sampling was performed on 37,800 m² area to establish the extent of Hg pollution and to investigate Hg transformations and transport characteristics through the 400 a-long period. A total of 156 soil (0-15 cm and 15-30 cm) and SOM (soil organic matter) samples were collected from 73 sampling points. Three soil profiles were sampled to determine vertical distribution of Hg. The main Hg phases were determined by the Hg-thermo-desorption technique. The measured Hg contents in soil samples in the study area vary from 5.5 to almost 9000 mg/kg with a median of 200 mg/kg. In SOM, Hg contents range from 1.4 to 4200 mg/kg with a median of 20 mg/kg. Extremely high Hg contents were found in soil profiles where the metal reaches 37,020 mg/kg. In general, Hg concentrations in all three profiles show a gradual decrease with depth with the minimum values between 140 mg/kg and 1080 mg/kg. The Hg-thermo-desorption curves indicate the presence of Hg in the form of cinnabar and that of Hg bound to organic or mineral soil matter. The distribution of Hg species in soil and SOM samples show almost equal distribution of cinnabar and non-cinnabar Hg compounds. The non-cinnabar fraction shows a little increase with depth, but cinnabar represents a high portion of total Hg (about 40%). Large amounts of potentially mobile and transformable non-cinnabar Hg compounds exist at the roasting site, which are potentially bioavailable.