Sources and migration of heavy metals in a karst water system under the threats of an abandoned Pb-Zn mine, Southwest China

Water quality is of great concern under the threats of an abandoned Pb-Zn mine within a vulnerable karst area. This study focuses on tracing the sources, migration and relevant geochemical controls of heavy metals along with surface- and groundwater flow, and assessing their hazards posed to the environment by indexes of heavy metal pollution (HPI) and ecological risks (ERI). We analyzed the concentrations of lead (Pb), zinc (Zn), cadmium (Cd) and copper (Cu) in filtered and digested surface water (SW) and groundwater (GW) samples. Whilst sulfate concentrations, δ³⁴S_SO4 isotope, and other physical-chemical parameters were measured in filtered SW and GW. Clearly elevated concentrations of Zn and Cd have been observed in the upstream of the Sidi River (max. 1540.3/1676.7, and 19.9/19.4 μg/L, for filtered/digested contents, respectively), and that of digested Pb and Cu (max. 17.8 and 114.6 μg/L, respectively) in the downstream karst groundwater. Zn and Cd are likely introduced by the Sidi River which is found mostly in the dissolved phase. While Pb and Cu are sourced from the remobilization of upper lying polluted soil which mostly existed in the particulate phase. Zn and Cd concentrations in the karst groundwater peak at the losing section while Pb and Cu in the river peaks at the gaining section as a result of metals transport with SW-GW exchange. Dilution significantly decreases total metals concentration in the non-karst area. Due to the buffer effect caused by carbonates dissolution and bacterial sulfate reduction, a steady neutral pH can reduce the concentrations of the dissolved metals in the karst area. The ERI and HPI assessments show an acceptable level for surface- and groundwater. A long-term observation on the contents of undissolved metals needs to be conducted in karst areas which are threatened by metal(s) mines.