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We report on original geochemical data, which combine the rainfall trace metal contents from three different areas of Mt. Etna, variably fumigated by the volcanic plume, and those from soils, collected over the whole volcano. Trace element contents in rainfall appear mostly related to acidic ash leaching, while only for the most volatile elements (Cu, Zn, Cd, Pb, As, Sb, Tl, Se) we suggest a derivation from magmatic degassing. We analyzed separately the labile fraction of soil samples, considered the fraction bioavailable to plants and soil organisms living in. The complexing medium used to extract the bioavailable fraction simulates the growth environment of plant roots.The contents of trace elements in the bioavailable fraction from soil samples showed peculiar patterns, apparently unrelated to the plume fumigation. The transition metal contents in the bioavailable fraction account for less than 15 % of the pseudo-total fraction and the highest contents were measured in the less acidic soil samples and farthest from the summit craters. In particular, high Fe, Mn, Co, Ni, Pb, Zn, Cd contents were paralleled by high soil organic carbon concentrations, which increased in the samples collected downwind the summit vents. Concerning immobile elements, their abundance in the bioavailable fraction was related to the degree of alteration of soils. Two elements, Se and Tl, were enriched in soil samples collected at closer distance from the summit vents. Their origin is probably related to the plume deposition.The study highlighted that the accessibility of plants to potentially harmful trace elements present in the soil is not simply related to the exposure to pollutants, but also to their fate in the pedogenetic environment.