Chromium cycle in Red Soil Critical Zone constrained by chromium isotopes.

Chromium (Cr) isotopic system has been used to trace Cr pollution in the modern surface environment and redox change in the paleoenvironment. However, the transformation mechanism of Cr in soil and the accompanied Cr isotopic fractionation have not been clarified clearly. Here we measured Cr isotopic compositions (δCr) of two paddy field profiles from the Red Soil Critical Zone Observatory in South China. The δCr values of the young paddy fields, which have been cultivated for about 20 years, range from -0.34 ‰ to -0.22 ‰. The old paddy fields have been cultivated for >100 years and have more positive Cr isotopic compositions than the young paddy fields, from -0.20 ‰ to -0.06 ‰. The results of three-step leaching experiments show that iron and manganese oxides are enriched in heavy Cr isotopes, while organic matters have much lower Cr isotopic compositions, likely resulting from back reduction of Cr(VI). Our results suggest that Cr isotopic fractionation during the oxidation of Cr(III) is not the only reason for the depletion of heavy isotopes during oxidative weathering, and the partial back-reduction of generated Cr(VI) by organic matter plays an important role in Cr isotopic fractionation during weathering. Comparison between the old and young paddy fields further indicates that cultivation can significantly affect the Cr cycle in red soils. Paddy fields could be a potential sink for the Cr(VI) contaminant, and soils with a long history of cultivation would be more susceptible.