The coupling of sulfide and Fe-Mn mineral promotes the migration of lead and zinc in the redox cycle of high pH floodplain soils

In this study, we investigated the impact of fluctuating water levels on the distribution of lead (Pb) and zinc (Zn) in soil and sediments at a historical Pb-Zn smelting site along the Xiangjiang River. Despite the high pH levels (7 to 11) in the study area, which generally inhibits heavy metal solubility, we found that regular changes in water levels still affect Pb-Zn movement. Soil analysis revealed distinct redox zones within the unconfined aquifer, as shown by the variable Fe/Mn and Ce/Ce* ratios. Advanced techniques such as Mn K-edge XAFS, Mössbauer spectroscopy, and TOF-SIMS indicated persistent Fe-Mn redox cycling and highlighted the presence of Pb and Zn-rich manganese oxides near sulfur-bearing minerals. These findings suggest that acidic microzones produced by the oxidation of sulfur-bearing minerals become "refuges" for microbial and heavy metal activity. Considering that sulfur-containing minerals are widespread waste types in nonferrous metal smelting sites, these findings are instructive for a better understanding of the transformation mechanisms of heavy metal ions in nonferrous metal smelting-polluted environments and for guiding pollution remediation strategies.