Geochemical distribution and speciation of thallium in groundwater impacted by acid mine drainage (Southern China).

Thallium (Tl) commonly occurs in shallow groundwater affected by acid mine drainage (AMD); however, our knowledge of the occurrence of Tl in shallow groundwater is limited. This study observes that the shallow groundwater in an AMD-impacted area in Southern China contains an elevated Tl concentration (22 μg/L) under the oxidizing conditions and a low Tl concentration (<1 μg/L) in the reducing environment. The groundwater Tl concentration is positively correlated with oxidation-reduction potential (Eh) and negatively correlated with Cl content. The modelling results of the Tl species demonstrate that Tl+, TlSO4-, TlCl, and TlNO3 are the main forms of Tl in groundwater. Tl may precipitate as Tl(OH)3 under weakly acidic to alkaline conditions. Drill-core analysis of wells indicates that the Tl content in the vadose zone is equal to the background soil Tl content under oxidizing conditions. However, under artificial reducing conditions, the Tl content at the 3-4 m depth below the groundwater level ranges from 1.6 to 3.5 μg/g. This finding demonstrates that Tl solute in groundwater migrates into the aquifer when redox conditions change. Mn-oxides and illite in the weak permeable aquifer are the key minerals for Tl adsorption; some major sites of illite start to uptake Tl from pH 8.0. This study highlights not only the geochemical distribution of Tl in groundwater but also the influences of changes in redox conditions caused by human activities on Tl enrichment in groundwater. Enhancing our understanding of the aqueous geochemistry of Tl is of significance for the prevention and control of Tl pollution.