Heavy metal concentrations and Pb isotopic composition were determined in the soils, slags, scums and landfill materials from a shut down industrial (brownfield) site. This was the second largest integrated steelworks in Italy, and is now under remediation by a Government project. It is located in the outskirts of Napoli on the Bagnoli–Fuorigrotta plain (BFP), which is part of the Campi Flegrei (CF) volcanic caldera, where many spas and geothermal springs occur. The purpose of this work is to distinguish the natural (geogenic) component, originated by hydrothermal activity, from anthropogenic contamination owing to industrial activity. ‘In-situ sediments’ (soils), slags, scums and landfill materials from 20 drill-cores were selected from a network of 197 drills carried out on a 100 × 100 m grid, covering the entire brownfield site. In general, heavy metal enrichments in the upper 3 m of the cores strongly suggest mixing between natural (geogenic) and anthropogenic components. Pb isotopic data are suggestive of three potential end members, and confirm the existence of a strong natural component in addition to contamination from anthropogenic activities. The slags, scums and landfill materials have been proved, through mineralogy and leachate experiments, to be geochemically stable; this shows that metal pollutants are not bio-available and, hence, do not pose a risk to future developments on this site. The natural contribution of hydrothermal fluids to soil pollution, in addition to the non-bio-availability of metal pollutants from industrial materials, indicate that heavy metal remediation of soils in this area would be of little use. Continuous discharge from mineralized hydrothermal solutions would cancel out any remediation effort.