Abstract
High levels of Iron (Fe) and manganese (Mn) in soils may contribute to secondary contamination of groundwater. However, there is limited understanding of the cycling mechanisms of Fe and Mn in groundwater and soil. This study aimed to investigate the biogeochemical processes constituting the Fe and Mn cycle by combining hydrochemistry, sequential extraction and microbiological techniques. The results indicated a similar vertical distribution pattern of Fe and Mn, with lower levels of the effective form (EFC-Fe/Mn) observed at the oxygenated surface, increasing near the groundwater table and decreasing below it. Generally, there was a tendency for accumulation above the water table, with Mn exhibiting a higher release potential compared to Fe. Iron‑manganese oxides (Ox-Fe/Mn) dominated the effective forms, with Fe and Mn in the soil entering groundwater through the reduction dissolution of Ox-Fe/Mn and the oxidative degradation of organic matter or sulfide (OM-Fe/Mn). Correlation analysis revealed that Fe and Mn tend to accumulate in media with fine particles and high organic carbon (TOC) contents. 16S rRNA sequencing analysis disclosed significant variation in the abundance of microorganisms associated with Fe and Mn transformations among unsaturated zone soils, saturated zone media and groundwater, with Fe/Mn content exerting an influence on microbial communities. Furthermore, functional bacterial identification results from the FAPROTAX database show a higher abundance of iron-oxidizing bacteria (9.3 %) in groundwater, while iron and manganese-reducing bacteria are scarce in both groundwater and soil environments. Finally, a conceptual model of Fe and Mn cycling was constructed, elucidating the biogeochemical processes in groundwater and soil environments. This study provides a new perspective for a deeper understanding of the environmental fate of Fe and Mn, which is crucial for mitigating Fe and Mn pollution in groundwater.
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