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When limed farmland is converted to forestry cadmium (Cd), copper (Cu) and other heavy metals can become mobile because of acidification and increased concentration of dissolved humic substances. The influence of pH and dissolved organic C on amounts and rates of Cd and Cu release was investigated in a cultivated soil by extraction with $ 1 mM hydrochloric acid at pH 3 with and without dissolved organic C in the batch mode with weekly replacement of the extraction solution. After 88 weeks, 35-50% of aqua regia-extractable Cd was extracted; addition of 10 mM dissolved organic C had no effect on the amount dissolved, but it increased the initial rate of release because the organic matter buffered the suspension at a lower pH. The solubility and release rate of Cd decreased as the geochemically active fraction was depleted. This suggests that Cd occurs in the soil in a continuum of binding strengths ranging from readily available to strongly bound forms. The repeated extractions resulted in distribution coefficients (K d dis ) that have log-linear relationships with pH. This allows prediction of Cd solubility during acidification of soil. Dissolved organic C enhanced the release of Cu from less than 8% (without) to more than 20% (with) of aqua regia-extractable Cu. Total contents of Cd and Cu cannot be used as measures of the metals' availability during acidification of former limed farmland. Predictions of availability should be based on the solubility as a function of pH and the degree of Cd or Cu depletion from the geochemically active fraction in soil.

Summary Afforestation of sandy arable soils in northern Europe is likely to lead to an increase in the soil's acidity and changes in the behaviour of the organic matter, and this might affect the ability of the soil to retain heavy metals. It is important to assess the impact of such a change in the land use on the solubility of the heavy metals and to assess the risk of leaching to surface‐ and groundwater and the possible entrapment of heavy metals in the tree canopy. The impact of afforestation was assessed by excavating soil profiles in adjacent 34‐year‐old Norway spruce stands and arable plots at four different sites. We found that after 34 years the pH had decreased and cations were depleted in the topsoil under forest. The aqua regia‐extractable heavy metals were determined, and the heavy metal binding within the soil was assessed using a modified version of the BCR (Community Bureau of Reference) sequential extraction procedure. Higher contents of heavy metal were found in the arable plots in the loamy sand soils. Cadmium was found only in the most mobile fractions. The content of Pb in the subsoil was strongly correlated with the clay content, but not in the topsoil, which suggested that Pb had been added to the topsoil. We found strong correlations between the clay content and the Cu, Ni and Zn in the residual fraction, leading us to conclude that much of the Cu, Ni and Zn is of geological origin. No significant differences in the heavy metal fractionation between forest and arable soil were found, presumably because 34 years of different land use is not long enough to produce such differences.

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