Relatively new techniques can help in determining the occurrence of mineral species and the distribution of contaminants on soil surfaces such as natural minerals and organic matter. The Bt horizon from an Endoleptic Luvisol was chosen because of its well-known sorption capability. The samples were contaminated with Cu2+ and/or Pb2+ and both sorption and desorption experiments were performed. The preferential distribution of the contaminant species (Cu-63 and Pb-208) to the main soil components and their associations were studied together with the effectiveness of the surface sorption and desorption processes. The results obtained were compared with non-contaminated samples as well as with previous results obtained by different analytical techniques and advanced statistical analysis. Pb2+ competes favorably for the sorption sites in this soil, mainly in oxides and the clay fraction. Cu2+ and Pb2+ were mainly associated with hematite, gibbsite, vermiculite and chlorite. This study will serve as a basis for further scientific research on the soil retention of heavy metals. New techniques such as spectroscopic imaging and transmission electron microscopy make it possible to check which soil components retain heavy metals, thereby contributing to propose effective measures for the remediation of contaminated soil. (C) 2011 Elsevier B.V. All rights reserved.