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Interaction mechanism and kinetics of ferrous sulfide and manganese oxides in aqueous system

  • Soils, Sec 3 • Remediation and Management of Contaminated or Degraded Lands • Research Article
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An Erratum to this article was published on 08 August 2017

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Abstract

Purpose

The oxidation of ferrous sulfide (FeS) causes soil acidification and the release of toxic heavy metal ions. Manganese oxides usually participate in the oxidation of FeS and affect the geochemical cycling of elemental Fe and S. Here, we studied the mechanism and influencing factors of FeS oxidation by oxygen and manganese oxides including birnessite, todorokite, and manganite. Metallic cavity electrode was used to study the kinetics of the electron transfer between FeS and manganese oxides.

Materials and methods

Manganese oxide minerals, including birnessite, todorokite, and manganite, were synthesized and used for the oxidation of FeS. The oxidation products were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, spectroscopy, high-performance liquid chromatography, and ion chromatography. The effects of pH and Fe(II) concentration on the oxidation rate of FeS were investigated. Metallic cavity electrodes filled with manganese oxides and FeS were respectively used as cathode and anode electrodes to study their reaction kinetics and the influence of crystal structure on the oxidation activity of manganese oxides.

Results and discussion

Elemental sulfur, SO4 2−, and lepidocrocite were formed as the intermediates during the oxidation of FeS by todorokite and oxygen in air. Low pH facilitated the dissolution of manganese oxides and the oxidation of FeS. When FeS suspension was oxidized by oxygen in air, the participation of todorokite decreased the degree of crystallinity of the newly formed ferric (hydr)oxides and accelerated the oxidation of polysulfide to S0 and S0 to SO4 2− via rapid adsorption and oxidation of Fe(II). The formation of Fe(II)/Fe(III) redox couple promoted electron transfer and resulted in increased oxidation rate of FeS. Fe(III) worked as the dominant oxidant under acidic conditions (pH < 4.0) and oxygen in air was the dominant oxidant at higher pH (pH > 4.0) in ambient atmosphere.

Conclusions

Todorokite accelerates FeS oxidation via adsorption and oxidation of Fe(II). Electrons are mainly transported by Fe(II)/Fe(III) shuttle at lower pH, and oxygen accepts electrons when pH is higher than 4.0. The oxidation activity follows the order of birnessite>todorokite>manganite. This work expands the understanding of the interactions and geochemical processes of FeS and manganese oxides, and provides a new technique to study the redox kinetics between soil mineral particles.

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Change history

  • 08 August 2017

    An erratum to this article has been published.

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Acknowledgements

This work was supported by the Fundamental Research Funds for the Central Universities (Program no. 2662015JQ002), the National Natural Science Foundation of China (Grant nos. 41171375, 41571228, 41425006, and 41330852), and the Fok Ying-Tong Education Foundation (Grant no. 141024).

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Authors and Affiliations

  1. Key Laboratory of Arable Land Conservation (Middle and Lower Reaches of Yangtse River), Ministry of Agriculture, College of Resources and Environment, Huazhong Agricultural University, Wuhan, 430070, China

    Yao Luo, Jiayu Ding, Yougang Shen, Wenfeng Tan, Fan Liu & Guohong Qiu

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  1. Yao Luo
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  2. Jiayu Ding
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  3. Yougang Shen
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  4. Wenfeng Tan
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  5. Fan Liu
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  6. Guohong Qiu
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Correspondence to Guohong Qiu.

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Responsible editor: Daniel C. W. Tsang

An erratum to this article is available at https://doi.org/10.1007/s11368-017-1801-6.

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Luo, Y., Ding, J., Shen, Y. et al. Interaction mechanism and kinetics of ferrous sulfide and manganese oxides in aqueous system. J Soils Sediments 18, 564–575 (2018). https://doi.org/10.1007/s11368-017-1774-5

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  • DOI: https://doi.org/10.1007/s11368-017-1774-5

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