An industrial site, polluted with As and heavy metals, was investigated by combining chemical (sequential extractions and pHstat leaching tests), physical and mineralogical characterization of soil samples and slag fragments, and by the analysis of soil porewater aimed at assessing the distribution, speciation and mobility of heavy metals and As. On the site itself, arsenic concentrations up to 3.6% in surficial soil samples and up to 22% in slag fragments were found, together with elevated concentrations (percentage level) of Cu, Co, Ni, Zn and Pb. High concentrations of arsenic (up to 38,000 microg/l) and heavy metals (up to 1700 microg/l Cu and 4700 microg/l Zn) were also found in the in situ sampled soil porewater, highlighting the considerable availability of As, Zn and Cu for uptake by plants and leaching to the ground water. Sequential extractions also indicated a high availability of arsenic and copper in most samples and slag fragments of the industrial site, although poorly reactive phases were encountered as well. pHstat leaching tests confirmed that the present leaching of contaminants is alarming. Moreover, soil acidification will enhance the leaching of contaminants, emphasizing that remediation of the industrial site is urgent. Small scale variability of total metal concentrations and metal speciation, both in the horizontal and vertical direction, and the occurrence of a camouflage layer underline the importance of elaborate sampling for pollution assessment on an industrial site.