Microscale Zn and Pb distribution patterns in subsurface soil horizons: an indication for metal transport dynamics

In many studies on soil pollution, authors conclude that there is no downward migration of metal elements if no evidence for enrichment can be inferred from profiles of total metal contents. We assessed possible transfer of mobile and less mobile metal pollutants to depth in subsurface horizons of a heavy metal contaminated soil, by a study of specific pedofeatures in thin sections by optical microscopy, and their corresponding Zn and Pb distribution patterns by synchrotron‐based X‐ray microfluorescence. In the B horizon (70 cm depth), Zn accumulation was predominantly associated with clay–iron coatings. Strong correlation was found between Zn and Fe (r = 0.94), Zn and Mn (r = 0.75), Zn and Ti (r = 0.84), and Zn and K (r = 0.88), but significant correlation was absent between Zn and Pb. In the C horizon (100 cm depth), clear Pb accumulation was observed in distinct iron coatings, with large correlation coefficients found between Pb and Fe (r = 0.94–0.75), whereas correlation between Zn and Fe was absent. Detected Zn concentrations were small and attributed to the local natural geochemical background. These results were then compared with data of the composition of gravitational soil water collected in other soils from the same study area. Thus, Zn accumulation in the B horizon was ascribed to interception of dissolved Zn²⁺ by negatively charged constituents of clay–iron coatings. In contrast, Pb accumulation in C horizons was related to precipitation of Pb‐bearing iron colloids leading to neoformed, optically pure iron oxyhydroxide crystals and coatings. We demonstrate very localized accumulation of almost immobile Pb which occurs at greater depth than the more mobile Zn. The common, but strongly localized, occurrence of Pb‐bearing iron coatings in the soil groundmass explained the absence of changes in the total Pb concentrations of the C horizon compared with the concentrations in the B horizon.