We studied soils exposed to emissions from the Ventanas copper smelter in central Chile. Values of pH, free Cu2+ activity, and total dissolved copper were determined in the saturated paste extracts and the soil solutions collected by means of perforated plastic bottles installed in situ. Soil solutions were collected based on the periodicity of the rain. The topsoils (up to 30 cm) exhibited pH values in the saturated paste extracts of 4.6-5.5 and total soil copper concentrations of 310-640 mg/kg. In contrast, subsoils exhibited pH values in the saturated paste extracts of 6.4-7.2 and total soil copper concentrations of 30-60 mg/kg. These data suggest that the anthropogenic inputs of the Ventanas smelter, with respect to increase in Cu concentrations and acidification, are restricted to the topsoil while the subsoil remains unaffected. The above observations are probably due to sandy loam texture of the topsoils that allowed rapid water infiltration that did not allow the equilibrium between the rain water and the soil constituents to be reached. Consistent with this argument, soil solutions were not as acid as saturated paste extracts. Likewise, free Cu2+ activities and total dissolved copper concentrations in the soil solutions were lower in the saturated paste extracts. Thus, saturated paste extracts were not a good proxy of soil solutions for short-duration and intense rain events. In situ soil solution sampling by simple and low-cost devices, such as perforated plastic bottles used in this study, is a better mean for assessment of metal mobility in contaminated soils than saturated paste extracts. In solutions percolating through the soil during rain events, dissolved organic carbon was the major factor controlling total dissolved copper concentrations while soil pH was the major factor controlling the free Cu2+ activity.