Thermal desorption technique to speciate mercury in carbonate, silicate, and organic-rich soils

Thermal desorption is a well-assessed technique to speciate mercury (Hg) in soils and sediments. However, the effects related to the different matrices are still not properly assessed. In this study, thermal desorption was applied to Hg-free calcite mixed with Hg standard and soils rich in carbonate and silicate minerals, as well as organic matter. Hg⁰, H_gCl₂, H_gO, α-HgS, β-HgS and organo-mercuric compounds were recognized, pointing out that the soil matrix operates notable differences in terms of breakdown temperatures of the Hg-compounds and suggesting that the mineralogical composition of soil has to be investigated before applying the thermal desorption technique. Furthermore, the presence of ^Hg0 was carefully evaluated since, as already observed, it forms Hg²⁺, which increases mercury mobility in the pedological cover with important consequences for those soils contaminated and located close to decommissioned or active mining areas and/or industrial sites (e.g. chloro-alkali industries). Experimental runs were thus carried out by using carbonate-, silicate- and organic-rich soils doped with liquid Hg. It was observed that Hg⁰ tends to be oxidized to form Hg⁺ and then Hg²⁺ as a function of soil matrix and reaction time. Surprisingly, the oxidation rate is rather fast, since after 42 days the initial content of Hg⁰ is halved, thus following an exponential decay. This implies that in Hg⁰-polluted areas, the fate of the resulting Hg²⁺ can be that to: i) be adsorbed by organic matter and/or Fe-Mn-Al oxides and/or ii) feed shallow aquifers. This study is a further step ahead to understand the behavior of Hg in contaminated soils from industrial and mining areas where liquid Hg is occurring in different soil matrices and may provide useful indications for remediation operations.