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Impact of δ-MnO2 on the chemical speciation and fractionation of Cr(III) in contaminated soils

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Abstract

Oxidation of Cr(III) by birnessite (δ-MnO2) was an important geochemical reaction determining the toxicity and mobility of dissolved Cr(III) in soils. Herein, changes of Cr speciation and fractionation were systematically studied in Cr(III)-contaminated soils with δ-MnO2 in soil aging process. The results showed that Cr(III) could be rapidly oxidized to Cr (VI) by δ-MnO2, and the coating of Fe and Al oxides on δ-MnO2 had a strong hindering effect on the oxidation of Cr(III). The Cr(III) oxidation process by δ-MnO2 followed a two-phase model of pseudo first-order kinetics. The rapid decrease of oxidation rate constant in second phase was due to the coverage of adsorbed Cr(III) and newly generated Cr(VI) and Mn(II) on the active sites of δ-MnO2. X-ray photoelectron spectroscopy analysis further confirmed that the diffusion and adsorption of Cr(III) on the electron-accepting sites were important factors affecting the Cr(III) oxidation by δ-MnO2. Compared with the soils without δ-MnO2, high contents of Cr(VI) were generated in silt (22.30 mg/kg) and sandy soil (70.95 mg/kg) with 2 wt% δ-MnO2 after the addition of Cr(III) wastewater within 2 days, and the Cr(VI) contents were above 1 mg/kg in these two soils during the whole incubation process. Moreover, the total Cr proportion of the exchangeable fraction increased by 12.8% in silt and 5.2% in sandy soil with 2 wt% δ-MnO2 after soil aging for 120 days. The presence of δ-MnO2 markedly increased the oxidation potential and mobility of exogenous Cr(III) in soils.

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All data generated or analyzed during this study are included in this published article and its supplementary information files.

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Acknowledgements

We thank the editors and reviewers for their valuable comments and suggestions for greatly improving the quality of the manuscript.

Funding

This study is financially supported jointly by Natural Science Foundation of Hebei Province (D2020504003) and Fundamental Research Funds of Chinese Academy of Geological Sciences (CAGS) (SK202113).

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Authors and Affiliations

  1. Institute of Hydrogeology & Environmental Geology, Chinese Academy of Geological Sciences, Shijiazhuang, 050061, China

    Xiangke Kong, Yanyan Wang, Lisha Ma & Hui Li

  2. Key Laboratory of Groundwater Remediation of Hebei Province and China Geological Survey, Shijiazhuang, 050061, China

    Xiangke Kong, Yanyan Wang, Lisha Ma & Hui Li

  3. Technical Centre for Soil, Agriculture and Rural Ecology and Environment, Ministry of Ecology and Environment, Beijing, 100012, China

    Zhantao Han

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  1. Xiangke Kong
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  4. Hui Li
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Contributions

XK contributed significantly to analysis and manuscript preparation. HL helped perform the analysis with constructive discussions. YW and LM performed the experiment. ZH contributed to the conception of the study. All authors read and approved the final manuscript.

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Correspondence to Hui Li.

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Highlights

1. Aqueous Cr(III) was rapidly oxidized to Cr(VI) by δ-MnO2 in soils, and the coating of Fe/Al oxides on δ-MnO2 resulted in the coverage of the available active sites of δ-MnO2 and inhibited the electron transfer between Cr(III) and Mn(IV).

2. The Cr(III) oxidation process by δ-MnO2 followed a two-phase model of pseudo first-order kinetics.

3. The diffusion and adsorption of Cr(III) on the electron-accepting sites of δ-MnO2 were important factors affecting the Cr(III) oxidation.

4. The presence of δ-MnO2 markedly increased the oxidation potential and mobility of exogenous Cr(III) in soils.

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Kong, X., Wang, Y., Ma, L. et al. Impact of δ-MnO2 on the chemical speciation and fractionation of Cr(III) in contaminated soils. Environ Sci Pollut Res 29, 45328–45337 (2022). https://doi.org/10.1007/s11356-022-18798-8

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  • DOI: https://doi.org/10.1007/s11356-022-18798-8

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