The elemental composition of soils is governed by geogenic processes and anthropogenic activities. A comprehensive soil study was conducted on a national level, in which the elemental composition of soils from two different layers was compared with the intention to differentiate between natural and anthropogenic sources of elemental enrichments. Topsoil (0-5 cm) and subsoil (20-30 cm) samples were collected from 249 different locations on a national scale (Slovenia). Elemental composition for 55 major, minor, and trace elements (ICP-MS, aqua regia digestion) was determined on the fraction <0.063 mm. By calculating the enrichment ratios in different lithological units, it was determined that levels of Ti are higher in soils overlying metamorphic and igneous rocks, Zr and Ca are more abundant over carbonates, while levels of Ni are higher in soils overlying marlstones. Elevated levels of Hg were detected in subsoils in the historical Hg mining area in Idrija, which indicates the presence of nearby orebodies as a potential source for the geochemical anomaly. Spatial distribution of elements showed that higher levels of Pb, Zn, Cu, and Hg were detected in topsoils of urban areas, indicating that anthropogenic sources could be the potential cause of soil contamination. Pb, Zn, Cu, and Hg levels were up to four times higher in topsoils compared to subsoils sampled at historical mining areas (e.g., Mezica, Idrija, Litija), which shows that historical mining left a significant environmental impact. Although mining and smelting activities ended a few decades ago, soils in some areas are still heavily enriched with various metals. Some other potential anthropogenic sources of elements were identified, such as farming and ironworks. Based on the results of this study, we can conclude that by comparing elemental compositions of soils from different layers, we can recognise the origin of elemental enrichments.
