Studies of heavy metals are concentrate on clay fractions, but coarser fractions of the soil can constitute significant sources of structural forms of heavy metals. The aim of this study was to evaluate the occurrence of heavy metals in the structure of minerals of the sand and silt fractions of soils from three different parent materials (metamorphic rocks and granite) in southern Brazil using SEM/EDS -Scanning Electron Microscopy with Energy Dispersive Spectroscopy and with WD-EPMA -with Wavelength Dispersive-Electron Probe Microanalysis. We sampled soils from two areas naturally rich in heavy metals, with high mineral deposits (galena -PbS) hosted in carbonate rocks and phyllite/mica schist. The main form of Ba in the sand and silt fractions was as barite (BaSO 4 ). The precipitation of Ba and S from the soil solution occurred on the surface of silicate mineral particles. Due to the proximity of ionic radius of Ba-Pb, there was isomorphic substitution of Ba for Pb in the barite structure. The only primary mineral source of Pb in the coarse soil fractions was trioctahedral mica. Several secondary minerals in the silt and sand are sources of structural Pb: plumbogummite, plumboferrite, magnetoplumbite, and cerussite. There was a strong geochemical association of Pb-Fe-Mn. Zinc was also associated with Fe. The SEM/EDS/WD-EPMA techniques are important analyses to complement standard procedures, such as X-ray diffraction and total chemical digestion, in geochemical studies.