Trace elements may present an environmental hazard in the vicinity of mining and smelting activities. However, the factors controlling trace element distribution in soils around ancient and modern mining and smelting areas are not always clear. Tharsis, Ríotinto and Huelva are located in the Iberian Pyrite Belt in SW Spain. Tharsis and Ríotinto mines have been exploited since 2500 B.C., with intensive smelting taking place. Huelva, established in 1970 and using the Flash Furnace Outokumpu process, is currently one of the largest smelter in the world. Pyrite and chalcopyrite ore have been intensively smelted for Cu. However, unusually for smelters and mines of a similar size, the elevated trace element concentrations in soils were found to be restricted to the immediate vicinity of the mines and smelters, being found up to a maximum of 2 km from the mines and smelters at Tharsis, Ríotinto and Huelva. Trace element partitioning (over 2/3 of trace elements found in the residual immobile fraction of soils at Tharsis) and soil particles examination by SEM-EDX showed that trace elements were not adsorbed onto soil particles, but were included within the matrix of large trace element-rich Fe silicate slag particles (i.e. 1 mm Ø at least 1 wt.% As, Cu and Zn, and 2 wt.% Pb). Slag particle large size (1 mm Ø) was found to control the geographically restricted trace element distribution in soils at Tharsis, Ríotinto and Huelva, since large heavy particles could not have been transported long distances. Distribution and partitioning indicated that impacts to the environment as a result of mining and smelting should remain minimal in the region.