Volcanic soils affected by different numbers of polluted river flooding events were investigated. Chromium and Cu were the major soil contaminants. Nickel, Fe, Zn and Mn total content never exceeded the Italian mandatory limits. The distribution of Cr and Cu total contents among studied soils indicated that only Cr contamination was related to overflowing events. In polluted soils, sequential chemical extractions revealed a preferential association of Cr and Cu with organic forms. A progressive Cr insolubilization with ageing was observed. Significant amounts of Cr and Cu were extracted by NH(4)-oxalate, suggesting metals association with short-range-order aluminosilicates and organo-mineral complexes. Possible methodological drawbacks in the use of the EU-BCR chemical speciation protocol on volcanic soils are discussed. Micromorphology and SEM/WDS analyses revealed Cr and Cu enriched silt and clay coatings in surface and subsurface soil horizons, suggesting a transfer of metal-rich sediments along the soil pore network with water movement.