Humins (HU) are the most insoluble fraction of humic substances. Chemically, they can be considered as humic macromolecules bonded to the mineral matter of soil. The HU have a marked colloidal character and they are extremely important in retention of pollutants in soils. The aim of this work is to combine adsorption data with spectroscopic techniques in order to study the adsorption and precipitation processes of Cu(II) on HU. Analysis of sorption isotherms by means of several single-adsorption-process-based models makes it possible to obtain the speciation diagrams of Cu(II) species on HU surfaces. Further, FTIR (which provides information about the changes in the surface groups of the HU) and DRX (which shows the formation of possible crystalline phases on the HU surface) were used to determine the specific interactions of Cu(II) cations with the surface reactive groups of HU. The shape of the isotherms at constant pH varies with pH from L1-type (pH 2-4) to L3-type (pH 5-6) and S-type (pH 8), which indicates a change in the retention mechanism. When pH is 2 the retention of Cu(II), as [Cu(H2O)(6)](2+), is the preferred retention mechanism. The retained quantity of Cu(II) as [Cu(OH)(H2O)(5)](+) increases with pH. Starting from pH 4 the Cu(II) begins its precipitation, which is the preferred retention mechanism at pH 8. The presence of HU has a great influence on the precipitation process of Cu(II), giving rise to botalackite, which reveals epitaxial growth of crystals. (C) 2004 Elsevier Inc. All rights reserved.