Spatial Distribution of Mercury and Potentially Toxic Elements in Soils from an Agricultural and Grazing Area Affected by Historical Mining

Historical mining districts are long-term sources of environmental contamination, especially where agriculture and grazing occur near mining areas. This study evaluates mercury (Hg) and other potentially toxic elements (PTEs) in soils from Solana de Peñarrubia, within the Almadén mining district (Spain). Thirty-four soil samples collected using a regular staggered grid were analyzed for total Hg and major oxides and selected trace elements. Spatial patterns were evaluated using Kriging interpolation, hierarchical clustering, PCA, and the geoaccumulation index, after standardizing variables to minimize differences in magnitude among them. Thermal desorption and microscopy were performed on three selected high-Hg samples, with thermal assignments interpreted as operational rather than definitive mineralogical identifications. Hg concentrations ranged from 10 to 994 mg kg−1, with the highest values in the northern sector. The PCA separated cropland soils, associated mainly with lithological variables, from soils with anthropogenic inputs related to Hg, Pb, SO3, and SiO2. The geoaccumulation index indicated Hg enrichment, reaching the extremely polluted category at the maximum concentration. Thermal desorption profiles were dominated by fractions within the reference range of α-HgS, accounting for 78.27–87.44% of the estimated relative abundance, while microscopic examination revealed particles consistent with cinnabar in high-Hg samples. The Hg anomaly showed no straightforward relationship with the mapped local lithology and may partly reflect, as a working hypothesis, the possible redistribution of Hg-bearing mineralized materials associated with historical mining or metallurgical activities.