Thallium(I) sequestration by jarosite and birnessite: Structural incorporation vs surface adsorption

Jarosite and birnessite secondary minerals play a pivotal role in the mobility, transport and fate of trace elements in the environment, although geochemical interactions of these compounds with extremely toxic thallium (Tl) remain poorly known. In this study, we investigated the sorption behavior of Tl(I) onto synthetic jarosite and birnessite, two minerals commonly found in soils and sediments as well as in mining-impacted areas where harsh conditions are involved. To achieve this, sorption and desorption experiments were carried out under two different acidic conditions and various Tl(I) concentrations to mimic natural scenarios. In addition, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and inductively coupled plasma (ICP) analyses were conducted to determine the performance of both minerals for Tl(I) sequestration. Our results indicate that both phases can effectively remove aqueous Tl by different sorption mechanisms. Jarosite preferentially incorporates Tl(I) into the structure to form Tl(I)-jarosite and eventually the mineral dorallcharite (TlFe₃(SO₄)₂(OH)₆) as increasing amounts of Tl are employed. Birnessite, however, favorably uptakes Tl(I) through an irreversible surface adsorption mechanism, underlining the affinity of Tl for this mineral in the entire concentration range studied (0.5–5 mmol L⁻¹). Lastly, the presence of Tl(I) in conditions where aqueous molar ratio Tl/Mn is ∼0.25 inhibits the formation of birnessite since oxidation of Tl(I) to Tl(III) followed by precipitation of avicennite (Tl₂O₃) take place. Thus, the present research may provide useful insights on the role of both jarosite and birnessite minerals in Tl environmental cycles.