Natural attenuation of zinc pollution in smelter-affected soil.

Previous synchrotron X-ray microprobe measurements of Zn speciation in contaminated and uncontaminated soils have identified phyllosilicate as the main sequestration phase. The emphasis now is focused on comparing the nature and properties of neoformed and geogenic phyllosilicate species to understand natural attenuation processes. Refined structural characterization of the two types of Zn-containing phyllosilicate in slightly basic smelter-affected agricultural soils were obtained using a so far unprecedented combination of X-ray microscopic techniques, including fluorescence (μ-XRF), absorption (μ-EXAFS), and diffraction (μ-XRD), and X-ray bulk-sensitive techniques, including powder and polarized EXAFS spectroscopy. The unpolluted and polluted species are both dioctahedral smectites, but the first which contains minor Zn (ca. 150 mg/kg) is aluminous and Fe-free, and the second, which contains several hundreds to a few thousands mg/kg Zn depending on the distance to the smelter and wind direction, is ferruginous with an average Fe/Al atomic ratio of 1.1 ± 0.5. The Zn(2+) and Fe(3+) in the neoformed smectite are derived from the weathering of ZnS, ZnO, FeS(2), and ZnFe(2)O(4) particles from the smelter. These cations diffuse away from their particulate mineral sources and coprecipitate with Al and Si in the soil clay matrix. Zinc sequestration in the octahedral sheet of dioctahedral smectite is potentially irreversible, because this type of phyllosilicate is stable over a large pH range, and the neoformed species is analogous to the native species which formed over time during pedogenesis.