Abstract Two air-pollution-control (APC) residues – one from flue gas cooling with alkaline water and one from deionised water cooling – from secondary lead metallurgy were submitted to two different standardized short-term leaching protocols: US EPA toxicity characteristic leaching procedure (TCLP) and static leaching according to Czech/European norm EN 12457-2. The experimental procedure was coupled with detailed mineralogical investigation of the solid material (SEM, XRPD) and speciation-solubility calculations using the PHREEQC-2 geochemical code. Both types of residues were considered as hazardous materials exhibiting substantial leaching of Pb (up to 7130 mg/l) and other inorganic contaminants. However, the APC residue produced by flue gas cooling with alkaline water (sample B) exhibits more favourable leaching and environmental characteristics than that produced by simple deionised water cooling (sample A). At pH < 5, primary caracolite (Na 3Pb 2(SO 4) 3Cl) and potassium lead chloride (KCl·2PbCl 2) are completely or partially dissolved and transformed to residual anglesite (PbSO 4), cotunnite (PbCl 2) and laurionite (Pb(OH)Cl). At pH 5–6, anglesite is still the principal residual product, whereas at pH >6, phosgenite (PbCl 2·PbCO 3) became the dominant secondary phase. The results are consistent with the mineralogical and geochemical studies focused on acidic forest soils highly polluted by smelter emissions, where anglesite, as a unique Pb-bearing phase, has been detected. From the technological point of view, the mixing of APC residue with alkaline water, followed by an increase in the suspension pH and equilibration with atmospheric CO 2, may be used to ensure the precipitation of less soluble Pb carbonates, which are more easily recycled in the Pb recovery process in the metallurgical plant.