“…In the last decades, many studies [7,11,[13][14][15][16][17] have reported the performance of pXRF instruments based on QA/QC validation procedures using certified reference materials (CRMs), blank samples, and/or traditional laboratory analyses on site-specific samples, studying different groups of elements in various matrices. Moreover, pXRF analyses of soil, lato sensu, samples are usually performed on common elements such as base metal(loid)s (e.g., As, Cu, Fe, Mn, Pb, Zn), whereas, curiously, highly toxic elements such as Hg and Sb have not been considered or have not been found in concentrations high enough and were detected in a small number of studies, e.g., [18,19]. Thus, the main purpose of this research was to evaluate the advantages and disadvantages of the use of pXRF on samples collected from two different decommissioned mining areas in Italy characterised by Pb-Zn and (Hg-rich) Cu-Sb ore deposits found to have very low to very high concentrations of As, Cu, Hg, Pb, Sb, and Zn.…”