Over 2000 ha of agricultural soils were contaminated by a pyritic sludge and acidic waste waters coming from a spill from a mining exploitation. The affected soils were acidic with sandy-loam texture (SL), loamy with neutral pH W, and calcareous, saline, with clay texture (Cs). The Cs soils were contaminated only with acidic waste waters. Sorption and extraction tests were applied to examine the medium-term dynamics of the interaction of trace elements (As, Cd, Cu, Pb and Zn) in the soils. The solid-soil solution distribution coefficient (K-D) was determined in soil samples taken 3 months (initial stage, 3M samples) and then nearly 2 years (final stage, 21M samples) after the accident. Distribution coefficient values ranged from the lowest values in the SL samples (from 0.2 l kg(-1) for Cd and Zn to 25 l kg(-1) for As) to higher values in the L and Cs soils. Lead and As had the highest K-D in all soils (over 10(5) l kg(-1) in the L soils). No clear dynamics pattern could be derived from these data because of the low heavy metal concentrations in the soil solution. As a complementary approach, four single extractions (0.01 and 1 mol l(-1) CaCl2; 0.05 mol l(-1) EDTA; 0.43 mol l(-1) CH3COOH) were applied to soil and sludge samples. Samples derived from submitting field 3M samples to drying-wetting (DW) cycles were included to define a complete laboratory approach to predict field dynamics. Results from extraction tests indicated that changes of the trace element interaction over time depended on the soil pH and on the source of contamination. For those soils affected only by the acidic waste waters, where an increase in fixation occurred, natural processes such as diffusion controlled dynamics. For those soils contaminated by a mixed source, the dynamics of the interaction was the resultant process of the combination of the natural attenuation and the oxidation of the pyritic sludge. This latter process led to an increase in the remobilisation for those elements associated with soluble secondary minerals (Cd and Zn) and to an increase in the fixation for those elements coprecipitating with insoluble secondary minerals (Pb and As). Drying-wetting cycles were useful to predict the dynamics in the field at month-year scale. The CH,COOH was recommended as the best test among those studied here to derive conclusions about dynamics pattern because it provided significant desorption yields in most scenarios. Acidic soils with sludge contamination represented the scenarios with the highest risk, while calcareous soils better attenuated contamination. In a longer time scale, the depletion of calcareous components needs to be controlled. (C) 2004 Elsevier B.V. All rights reserved.
