Mobility of Cd and Zn in polluted and unpolluted Spodosols

Leaching of Cd and Zn in polluted acid, well-drained soils is a critical pathway for groundwater pollution. Models predicting future groundwater contamination with these metals have rarely been validated at the field scale. Spodosol profiles (pH 3.2-4.5) were sampled in an unpolluted (reference) field and in a field contaminated with Cd and Zn through atmospheric deposition near a zinc smelter. Average metal concentrations in the upper horizons were 0.2 mg Cd kg(-1) and 9 mg Zn kg(-1) in the unpolluted field, and 0.8 mg Cd kg(-1) and 71 mg Zn kg(-1) in the contaminated field. Isotopic dilution was used to measure the labile concentration of Cd and Zn, and the metal transport was modelled using measured sorption parameters that describe the distribution between the labile metal pool (instead of the total metal pool) and the solution phase obtained by centrifugation. Solutions were also collected by wick samplers in two polluted and one unpolluted profile at a depth of 70 cm. Concentrations in these solutions were in the order of 15 mu g Cd litre(-1) and 0.8 mg Zn litre(-1) for the polluted profiles, and 1 mu g Cd litre(-1) and 0.04 mg Zn litre(-1) for the unpolluted profile. The concentrations in these solutions agreed well with those in soil solutions obtained by centrifugation, which supported the use of the local equilibrium assumption (LEA). Present-day Cd profiles in the polluted field were calculated with the LEA, based on the emission history of the nearby smelter and taking spatial variability into account. Observed and predicted depth profiles agreed reasonably well, but total Cd concentrations in the topsoil were generally underestimated by the model. This may be attributed to the presence of non-labile Cd in the atmospheric deposition, which was not accounted for in the retrospective modelling. The large concentrations of non-labile Zn in the topsoil of the polluted field were also indicative that metals in the atmospheric deposition were (partly) in a sparingly soluble form, and that release of these non-labile metals is a slow process. The presence of non-labile metals should be taken into account when evaluating metal mobility or predicting their transport.