Combining metal and sulfate isotopes measurements to identify different anthropogenic impacts on dissolved heavy metals levels in river water

Dissolved heavy metals (DHMs) contamination has raised global concern for ecological and human health development. Weathering of sulfide-bearing ore metals can produce acidic, sulfate-rich solutions in the presence of water and oxygen (O-2), and DHMs are released to deprave the river water quality. Sulfur and oxygen isotope signatures (S-delta 34(SO4) and O-delta 18(SO4)) could identify this pyrite-derived sulfate; however, it is yet not well known whether the S-delta 34(SO4) and O-delta 18(SO4) values could limit the DHMs sources and illustrate anthropogenic impacts on DHMs along the river corridor. We tried to solve this problem through field works in the Luohe River and Yihe River, two tributaries of the Yellow River, China, where metal sulfide mine activities mostly occurred upstream, but agricultural and domestic behaviors concentrated in the lower plain reaches. In the Luohe River upper areas, S-delta 34(SO4) values had negative correlations with concentrations of cadmium (Cd) (p < 0.01), nickel (Ni) (p < 0.05), molybdenum (Mo) (p < 0.01), uranium (U) (p < 0.01), and SO42-(p < 0.01). However, as the S-delta 34(SO4) values increased downstream in the Luohe River, concentrations of copper (Cu) (p < 0.05), mercury (Hg) (p < 0.05), Ni (p < 0.05), and SO42- (p < 0.01) simultaneously elevated. The Bayesian Isotope Mixing Model (BIMM) results via S-delta 34(SO4) values demonstrated 64.3%-65.3% of SO(4)(2-)from acid mine drainage (AMD) in the Luohe River's upper reaches and 63.5%-67.7% in the Yihe River's upper reaches, and about 33% from sewage and industrial effluents in the Luohe River's lower reaches and 27% in Yihe River's lower reaches. Our results confirmed the different anthropogenic impacts on the DHMs concentrations in Luohe River and Yihe River and provided a robust method for DHMs sources appointment and pollution management in river systems.