Chromium transformation driven by iron redox cycling in basalt-derived paddy soil with high geological background values

The flooding and drainage of paddy fields has great effects on the transformation of heavy metals, however, the transformation of Cr in basalt-derived paddy soil with high geological background values was less recognized. The typical basalt-derived paddy soil was incubated under alternating redox conditions. The Cr fractions and the dynamics of Fe/N/S/C were examined. The HCl-extractable Cr increased under anaerobic condition and then decreased during aerobic stage. The UV-vis spectra of the supernatant showed that amounts of colloids were released under anaerobic condition, and then re-aggregated during aerobic phase. The scanning transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) revealed that Fe oxides were reduced and became dispersed during anaerobic stage, whereas Fe(II) was oxidized and recrystallized under aerobic condition. Based on these results, a kinetic model was established to further distinguish the relationship between the transformation of Cr and Fe. During anaerobic phase, the reduction of Fe(III) oxides not only directly released the structurally bound Cr, but also enhanced the breakdown of soil aggregation and dissolution of organic matter causing indirect mobilization of Cr. During aerobic phase, the oxidation of Fe(II) and further recrystallization of newly formed Fe(III) oxides might induce the re-aggregation of soil colloids and further incorporation of Cr. In addition, the kinetic model of Cr and Fe transformation was further verified in the pot experiment. The model-based findings demonstrated that the Cr transformation in the basalt-derived paddy soil with high geological background values was highly driven by redox sensitive iron cycling.