Total and leached Arsenic, Mercury and Antimony were determined in the topsoils developed on the mining waste dumping area of Le Lame (Mt. Amiata, central Italy) where the post-processing Hg-rich ore deposits from the mining area of Abbadia San Salvatore were stored. The concentrations of As, Hg and Sb were up to 610, 1910 and 1610 mg kg⁻¹, respectively, while those in the leachates (carried out with CO₂-saturated MilliQ water to simulate the meteoric water conditions) were up to 102, 7 and 661 μg·L⁻¹, respectively. Most aqueous solutions were characterized by Hg content <0.1 μg·L⁻¹. This is likely suggesting that the mine wastes (locally named “rosticci”) were possibly resulting from an efficient roasting process that favored either the removal or inertization of Hg operated by the Gould furnaces and located in the southern sector of Le Lame. The highest values of total and leachate mercury were indeed mostly found in the northern portion where the “rosticci”, derived by the less efficient and older Spirek-Cermak furnaces, was accumulated. The saturation index was positive for the great majority of leachate samples in Fe-oxy-hydroxides, e.g., ferrihydrite, hematite, magnetite, goethite, and Al-hydroxides (boehmite and gibbsite). On the other hand, As- and Hg-compounds were shown to be systematically undersaturated, whereas oversaturation in tripuhyte (FeSbO₄) and romeite (Ca₂Sb₂O₇) was evidenced. The Eh-pH diagrams for the three chalcophile elements were also constructed and computed and updated according to the recent literature data.

The distribution of heavy metals in plants (Castanea sativa, Sambucus nigra, Verbascum thapsus, Popolus spp., Salix spp., Acer pseudoplatanus, Robinia pseudoacacia) growing in soils from active and abandoned mining areas is of scientific significance as it allows to recognize their ability to survive in a hostile environment and provide useful indications for phytoremediation operations. In this work, soils from the former Hg-mining area of Abbadia San Salvatore (Tuscany, Central Italy) were analyzed for total, leached Hg, % of organic and inorganic-related Hg. The dehydrogenase enzyme activity (DHA) was also measured with the aim to evaluate the status of the soil, being characterized by high Hg contents (up to 1068 mg kg⁻¹). Eventually, the concentration of Hg in the different parts of the plants growing on these soils was also determined. Most studied soils were dominated by inorganic Hg (up to 92%) while the DHA concentrations were < 151 µg TPF g⁻¹ day⁻¹, suggesting that the presence of Hg is not significantly affecting the enzymatic soil activity. This is also supported by the bioaccumulation factor (BF), being predominantly characterized by values < 1. Sambucus nigra and Verbascum thapsus had the highest Hg contents (39.42 and 54.54 mg kg⁻¹, respectively). The plant leaves appear to be the main pathways of Hg uptake, as also observed in other mining areas, e.g., Almadèn (Spain), indicating that particulate-Hg and Hg⁰ are the main forms entering the plant system, the latter derived by the GEM emitted by both the edifices hosting the roasting furnaces and the soils themselves.

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.

The Galleria Italia waters drain the complex tunnel system of the former Hg-mining area of Abbadia San Salvatore (Tuscany, central Italia) and feed the 2.5 km-long Fosso della Chiusa creek. The mining exploitation was active for more than one century and more than 100,000 tons of liquid mercury were produced by roasting processes of cinnabar (HgS). In this work, a discontinuous geochemical monitoring of the Galleria Italia circumneutral waters was carried out from February 2009 to October 2020, during which the main physicochemical parameters, main and minor dissolved species and trace elements (including Hg) were determined. In the observation period, significant variations in the water chemistry were recorded, particularly when flooding waves, due to intense precipitations, occurred, with the two main events being recorded in February 2009 and January 2010. The chemical composition of the Galleria Italia waters was Ca(Mg)-SO₄ and related to congruent dissolution of gypsum/anhydrite at which a contribution from carbonatic and silicatic minerals and partial solubilization of CO₂ and and H₂S oxidation is to be added. Regarding the trace elements, Al, Mn and Fe were up to 1500, 768 and 39520 μg L⁻¹, with these elements also showing high contents in the sediment precipitating by the Galleria Italia waters. In most cases, dissolved mercury was below the instrumental detection limit (1 μg L⁻¹. Considering a mean flow rate of 40 L s⁻¹ of the discharged water, the amount of dissolved mercury released from Galleria Italia was computed, although most mercury was occurring in the sediment (1.2 mg kg⁻¹). A more realistic computation of mercury released from Galleria Italia should involve a sampling network along the Fosso della Chiusa before entering the riverine system of the Tiber basin, into which dissolved and suspended mercury are to be determined along with that occurring in the sediments.