Abstract
The spatial distribution and ecological risk of potentially toxic elements (PTEs) were investigated in the topsoil of a peri-urban area surrounding a historical industrial complex in the Scarlino Plain in southwestern Tuscany, Italy. Superficial (0-5 cm) soil samples from 44 sites within a 1.5-km radius of the industrial district were analysed for As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sb, Sn, Tl, V and Zn concentrations after microwave-assisted acid digestion with HNO(3) and H(2)O(2). The results revealed significant contamination exceeding regulatory thresholds, predominantly caused by historical pyrite roasting and natural geochemical anomalies. The enrichment of As, Mn, Cu and Zn compared to European baselines was widespread, with As and Zn levels exceeding the Italian screening values in several samples. Principal component analysis identified distinct contamination patterns linked to land use, with the first component (PC1, 49.2% of the variance) associated with pyrite-derived PTEs (As, Cu, Cd, Pb and Zn), whereas PC2 represented geogenic inputs. Despite their combined contribution to soil contamination, this analysis effectively differentiated industrial signatures from those of natural sources. Ecological risk assessment indicated that As and Cd are major concerns in agricultural soils, where anthropogenic and natural sources overlap. These findings underscore the importance of distinguishing between natural and anthropogenic contributions to inform realistic mitigation targets and protect environmental and human health in historically impacted peri-urban areas.