Pollution of carbonate soils in a Mediterranean climate due to a tailings spill

The retention walls in a pond containing the residues from the pyrite mine of Aznalcóllar (southern Spain) broke open on 25 April 1998, spilling approximately 6 × 10⁶ m³ of polluted water and toxic tailings, which affected some 55 km². Drying and aeration of the tailings resulted in oxidation, forming an acidic solution with high pollutant contents, the effects of which were studied in a calcareous soil. The infiltration of this solution markedly affected only the first 12 mm of the soil, where strong acidification caused the weathering of the carbonates, and where the fine mineral particles were hydrolysed. The SO₄^2? ions in the acidic solution precipitated almost entirely at this depth, forming gypsum, hydroxysulphates and complex sulphates. The Fe³⁺ ions also precipitated there, mainly in amorphous or poorly crystallized forms, adsorbing to As, Sb, Tl and Pb dissolved in the acidic solution. The Al³⁺ ions, though partly precipitating in the acidic layer, accumulated mostly where the soil pH exceeded 5.5 (12–14 mm in depth). They did so primarily as amorphous or poorly crystallized forms, adsorbing to Cu dissolved in the acidic solution. The Zn²⁺ and Cd²⁺ ions accumulated mainly at pH > 7.0 (19–21 mm in depth), being adsorbed chiefly by clay mineral. After 15 months, only the first 20 mm of the soil were acidified by the oxidation of the tailings and most of the pollutants did not penetrate deeper than 100 mm. Consequently, the speed of the cleanup of the toxic spill is not as important as a thorough removal of tailings together with the upper 10 cm of the soil.