Combining zinc desorption with EXAFS speciation analysis to understand Zn mobility in mining and smelting affected soils in Minas Gerais, Brazil

Abstract

Zinc contents exceeding regulatory levels have been documented in several areas in Brazil and elsewhere, especially in sites surrounding mining and smelting sites. Studies involving Zn release and speciation are keys to assess the mobility and bioavailability and thus the potential ecological risk of this element. This study evaluated Zn desorption and speciation from soils affected by mining (soils from a mine area, classified as Technosols) and smelting (mine tailing) activities in Brazil with high total Zn contents, ranging from 1.8 to 8.2%, using a stirred-flow approach and synchrotron-based X-ray absorption spectroscopy (XAS), in order to better assess Zn availability and mobility in these environments. The exchangeable fraction, extracted by 0.1 M CaCl2 solution, represented only a small (<0.5%) portion of the total Zn from soils of the mining site, while accounting for ~80% from tailings of the smelting site. In the mine area, X-ray absorption fine structure (XAFS) showed that Zn was associated with hemimorphite, Zn-ferrihydrite, Zn-phyllosilicates (Zn-kerolite), and Zn-layered double hydroxides (Zn-LDH); this is the first time these Zn precipitate/sorbed forms have been detected in Brazilian mining soils, which have been exposed to tropical conditions. The formation of these insoluble phases of Zn could explain the low Zn desorption from these soils, taking into consideration that Zn-ferrihydrite, Zn-kerolite, and Zn-LDH can lead to a significant decrease of the exchangeable/mobile fraction of Zn in soils. The higher amount of Zn desorbed (⁓80%) from the tailing material located in the smelting site could be attributed to the predominance of weakly bound forms of Zn (~70%). These findings were also seen by analyzing the Fourier Transform (FT) and Wavelet Transform (WT). This study has shown that combining EXAFS analyses with desorption extraction is relevant to better understand Zn mobility and how it is related to Zn speciation.