Soils in the vicinity of nonferrous metal smelters are often highly polluted by inorganic contaminants released from particulate emissions. We used a technique with double polyamide experimental bags (1-μm mesh) to study the in situ transformation of fly ash (FA) from a secondary Pb smelter in acidic soil profiles. Between 62 and 66% of the FA dissolved after one year's exposure in the soils, leading to complete dissolution of primary caracolite (Na(3)Pb(2)(SO(4))(3)Cl) and KPb(2)Cl(5), with formation of secondary anglesite (PbSO(4)), minor PbSO(3), and trace carbonates. Release of Pb was pH-dependent, whereas not for Cd and Zn. Significant amounts of metals (mainly Cd and Zn) partitioned into labile soil fractions. The field data agreed with laboratory pH-static leaching tests performed on FA, which was washed before the experiment to remove soluble salts. This indicates that appropriate laboratory leaching can accurately predict FA behavior in real-life scenarios (e.g., exposure in soil).