Lead, zinc and arsenic mobilization/attenuation processes during interactions between smelter slag and water show differences depending on the origin of the slag. The studied samples, waste from ore and car-battery processing, were submitted to long-term (365 days) batch leaching at two different initial pH values. The leachate analyses were input to the EQ3NR speciation-solubility code to speciate the solutions and determine the degree of saturation with respect to different phases, and a mineralogical investigation was made of the newly formed phases. An ‘oxidizing’ scenario can be proposed for slag waste disposal, considering that cerussite (PbCO3) at pH >6 becomes a major solubility-controlling phase for Pb, and newly formed hydrous ferric oxides (HFO –common secondary phases under oxidizing conditions) efficiently adsorb As. No efficient scavenging mechanism was found for Zn, which was progressively leached from the slag and in particular from the ore-processing slag. Quenched glass-rich slag from old car-battery processing was found to release significant amounts of Pb, especially in acidic environments. Neither slag would therefore be suitable for recycling for civil engineering purposes. Conversely, extremely low releases of Pb, Zn and As were observed for recent car-battery processing slag, which could therefore be considered for road construction.