A powerful tool for assessing distribution and fate of potentially toxic metals (PTMs) in soils: integration of laser ablation spectrometry (LA-ICP-MS) on thin sections with soil micromorphology and geochemistry.

The dynamic behavior and inherent spatial heterogeneity, at different hierarchic levels, of the soil system often make the spatial distribution of potentially toxic metals (PTMs) quite complex and difficult to assess correctly. This work demonstrates that the application of laser ablation spectrometry (LA-ICP-MS) to soil thin sections constitutes an ancillary powerful tool to well-established analytical methods for tracing the behavior and fate of potential soil contaminants at the microsite level. It allowed to discriminate the contribution of PTMs in distinct soil sub-components, such as parent rock fragments, neoformed, clay-enriched or humified matrix, and specific pedogenetic features of illuvial origin (unstained or iron-stained clay coatings) even at very low contents. PTMs were analyzed in three soil profiles located in the Muravera area (Sardinia, Italy), where several, now abandoned mines were exploited. Recurrent trends of increase of many PTMs from rock to pedogenic matrix and to illuvial clay coatings, traced by LA-ICP-MS compositional data, revealed a pedogenetic control on metal fractionation and distribution, based on adsorption properties of clay minerals, iron oxyhydroxides or organic matter, and downprofile illuviation processes. The main PTMs patterns coupled with SEM-EDS analyses suggest that heavy metal-bearing mineral grains were sourced from the mine plants, in addition to the natural sedimentary input. The interplay between soil-forming processes and geomorphic dynamics significantly contributed to the PTMs spatial distribution detected in the different pedogenetic horizons and soil features.