Natural arsenic attenuation via metal arsenate precipitation in soils contaminated with metallurgical wastes: II. Cumulative evidence and identification of minor processes

Accurate identification of individual As species in contaminated environments is critical because the toxicology, mobility and adsorptive properties of this element may vary substantially with its chemical forms and oxidation states. The goal of this work was to relate the geochemical behavior of As in soils contaminated by a lead smelter in Mexico, with its chemical speciation, and to achieve direct identification of low-solubility poorly-crystalline metal arsenates. Arsenic was identified as the most mobile trace element in the wastes from the smelting plant. Arsenic solubility in soils was significantly lower than its solubility in wastes, showing natural attenuation of this element. Its solubility in soil was quantitatively described in selected samples through thermodynamic equilibrium modeling. The results indicated that As solubility is controlled by solid Pb and Cu arsenate formation. The behaviors of the sequential chemical extractions were consistent with the presence of the predicted arsenates. Microscopic evidence of the formation of solid metal arsenates were obtained in fine soil fractions of selected samples with high As contents, by using the following complementary techniques: X-ray diffraction, scanning electron microscopy and transmission electron microscopy, both coupled with energy dispersive X-ray spectroscopy, and the latter with a high angle annular dark field detector. All results supported the formation of low-solubility Pb arsenates as controlling As mobility in the samples studied, in which As(V) adsorption to Fe (hydr)oxides was not the dominant process of natural attenuation.