Total mercury, chromium, nickel and other trace chemical element contents in soils at an old cinnabar mine site (Merník, Slovakia): anthropogenic versus natural sources of soil contamination.

The aims of this study were to investigate the occurrence and distribution of total mercury (Hg) and other trace elements of environmental concern, such as arsenic (As), copper (Cu), chromium (Cr), manganese (Mn), nickel (Ni), lead (Pb), zinc (Zn) and vanadium (V), in soils from the abandoned Merník cinnabar mine in eastern Slovakia. For this purpose, thirty soil samples from two depth intervals within the mine area (n = 60 soil samples) and additional sixteen soil samples from adjacent areas (n = 25 soil samples) were collected. Total Hg was measured by atomic absorption spectrometry, while As and other metals were analyzed using inductively coupled plasma atomic emission spectrometry. High mercury concentrations (> 100 mg/kg with a maximum of 951 mg/kg) were observed only in surface soils close to mine waste heaps and adits. Otherwise, Hg concentrations in the majority of surface soils were lower (0.14-19.7 mg/kg), however, higher than Hg in soils collected from sites outside the mine area (0.19-6.92 mg/kg) and even considerably higher than Hg in soils at sites not influenced by the Merník mine. Elevated Cr and Ni concentrations in soils regardless of their sampling sites (mean of 276 mg/kg and median of 132 mg/kg for Cr and 168 mg/kg and 81 mg/kg for Ni, respectively) were attributed to the lithology of the area; the soils are underlain by the sediments of the Central Carpathian Palaeogene, containing a detritus of ultrabasic rocks. As our geochemical data are compositional in nature, they were further treated by compositional data analysis (CoDA). Robust principal component analysis (RPCA) applied on centred (clr) log-ratio-transformed data and correlation analysis of compositional parts based on symmetric balances distinguished very well different sources of origin for the chemical elements. The following three element associations were identified: Hg association with the main source in mining/roasting, Cr-Ni association derived from bedrock and As-Cu-Mn-Pb-Zn-V association (natural background and minor sulphides/sulfosalts in mineralized rocks). The values of geoaccumulation index and enrichment factor suggested that concentrations of Hg in the soils were influenced by human industrial activities.

Occurrence of selected trace metals and their oral bioaccessibility in urban soils of kindergartens and parks in Bratislava (Slovak Republic) as evaluated by simple in vitro digestion procedure.

A total of eighty surface soil samples were collected from public kindergartens and urban parks in the city of Bratislava, and the <150µm soil fraction was evaluated for total concentrations of five metals, Cd, Cu, Hg, Pb and Zn, their oral bioaccessibilities, non-carcinogenic and carcinogenic health risks to children, and lead isotopic composition. The mean metal concentrations in urban soils (0.29, 36.1, 0.13, 30.9 and 113mg/kg for Cd, Cu, Hg, Pb and Zn, respectively) were about two times higher compared with background soil concentrations. The order of bioaccessible metal fractions determined by Simple Bioaccessibility Extraction Test was: Pb (59.9%) > Cu (43.8%) > Cd (40.8%) > Zn (33.6%) > Hg (12.8%). Variations in the bioaccessible metal fractions were mainly related to the total metal concentrations in urban soils. A relatively wide range of lead isotopic ratios in urban soils (1.1598-1.2088 for 206Pb/207Pb isotopic ratio) indicated a combination of anthropogenic and geogenic sources of metals in the soils. Lower values of 206Pb/207Pb isotopic ratio in the city centre and similar spatial distribution of total metal concentrations, together with their increasing total concentrations in soils towards the city centre, showed that traffic and coal combustion in former times were likely the major sources of soil contamination. The non-carcinogenic and carcinogenic health risks to children due to exposure to metals in kindergarten and urban park soils were low, with hazard index and cancer risk values below the threshold values at all studied sites.