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Methylmercury Degradation by Trivalent Manganese

  • Shuang Zhang
    Shuang Zhang
    Key Laboratory of Arable Land Conservation (Middle and Lower Reaches of Yangtse River), Ministry of Agriculture and Rural Affairs, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, P.R. China
    Department of Criminal Science and Technology, Henan Police College, Zhengzhou 450046, P.R. China
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  • Baohui Li
    Baohui Li
    Key Laboratory of Arable Land Conservation (Middle and Lower Reaches of Yangtse River), Ministry of Agriculture and Rural Affairs, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, P.R. China
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  • Yi Chen
    Yi Chen
    Key Laboratory of Arable Land Conservation (Middle and Lower Reaches of Yangtse River), Ministry of Agriculture and Rural Affairs, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, P.R. China
    More by Yi Chen
  • Mengqiang Zhu
    Mengqiang Zhu
    Department of Ecosystem Science and Management, University of Wyoming, 1000 E. University Ave., Laramie, Wyoming 82071, United States
  • Joel A. Pedersen
    Joel A. Pedersen
    Department of Environmental Health and Engineering, Johns Hopkins University, Baltimore, Maryland 21218, United States
  • Baohua Gu
    Baohua Gu
    Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
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  • Zimeng Wang
    Zimeng Wang
    Department of Environmental Science and Engineering, Fudan University, Shanghai 200433, P.R. China
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  • Hui Li
    Hui Li
    Department of Crop and Soil Sciences, North Carolina State University, Raleigh, North Carolina 27695, United States
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  • Jinling Liu
    Jinling Liu
    School of Earth Sciences, China University of Geosciences, Wuhan 430074, P.R. China
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  • Xin-Quan Zhou
    Xin-Quan Zhou
    Key Laboratory of Arable Land Conservation (Middle and Lower Reaches of Yangtse River), Ministry of Agriculture and Rural Affairs, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, P.R. China
  • Yun-Yun Hao
    Yun-Yun Hao
    Key Laboratory of Arable Land Conservation (Middle and Lower Reaches of Yangtse River), Ministry of Agriculture and Rural Affairs, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, P.R. China
    More by Yun-Yun Hao
  • Hong Jiang
    Hong Jiang
    College of Science, Huazhong Agricultural University, Wuhan 430070, P.R. China
    More by Hong Jiang
  • Fan Liu
    Fan Liu
    Key Laboratory of Arable Land Conservation (Middle and Lower Reaches of Yangtse River), Ministry of Agriculture and Rural Affairs, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, P.R. China
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  • Yu-Rong Liu*
    Yu-Rong Liu
    Key Laboratory of Arable Land Conservation (Middle and Lower Reaches of Yangtse River), Ministry of Agriculture and Rural Affairs, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, P.R. China
    *Email: [email protected]. Tel.: +86 27 87280271. Fax: +86 27 87288618.
    More by Yu-Rong Liu
  • , and 
  • Hui Yin*
    Hui Yin
    Key Laboratory of Arable Land Conservation (Middle and Lower Reaches of Yangtse River), Ministry of Agriculture and Rural Affairs, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, P.R. China
    *Email: [email protected]. Tel.: +86 27 87280271. Fax: +86 27 87288618.
    More by Hui Yin
Cite this: Environ. Sci. Technol. 2023, 57, 14, 5988–5998
Publication Date (Web):March 30, 2023
https://doi.org/10.1021/acs.est.3c00532
Copyright © 2023 American Chemical Society

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    Supporting Info (1)»

    Abstract

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    Methylmercury (MeHg) is a potent neurotoxin and has great adverse health impacts on humans. Organisms and sunlight-mediated demethylation are well-known detoxification pathways of MeHg, yet whether abiotic environmental components contribute to MeHg degradation remains poorly known. Here, we report that MeHg can be degraded by trivalent manganese (Mn(III)), a naturally occurring and widespread oxidant. We found that 28 ± 4% MeHg could be degraded by Mn(III) located on synthesized Mn dioxide (MnO2–x) surfaces during the reaction of 0.91 μg·L–1 MeHg and 5 g·L–1 mineral at an initial pH of 6.0 for 12 h in 10 mM NaNO3 at 25 °C. The presence of low-molecular-weight organic acids (e.g., oxalate and citrate) substantially enhances MeHg degradation by MnO2–x via the formation of soluble Mn(III)-ligand complexes, leading to the cleavage of the carbon–Hg bond. MeHg can also be degraded by reactions with Mn(III)-pyrophosphate complexes, with apparent degradation rate constants comparable to those by biotic and photolytic degradation. Thiol ligands (cysteine and glutathione) show negligible effects on MeHg demethylation by Mn(III). This research demonstrates potential roles of Mn(III) in degrading MeHg in natural environments, which may be further explored for remediating heavily polluted soils and engineered systems containing MeHg.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.est.3c00532.

    • Details on the synthesis and characterization of various Mn oxides; HPLC-ICP-MS spectra of MeHg degradation products; linear correlation analysis of the demethylation extent and the basic physicochemical properties of minerals or the Mn(III)-ligand stability constant; proportions of various Hg species during the reactions of MeHgSR or MeHg with birnessite or Mn(III) complexes; changes in pH during the reactions of birnessite with different concentrations of oxalate; UV–vis spectra of Mn(III)-oxalate complexes and related solid particles; pseudo-first-order kinetic analysis of MeHg degradation by Mn(III)-PP complexes at pH 7.1; comparison of the apparent rate constants of MeHg degradation by MnO2–x and Mn(III)-PP complexes with those by biotic and photo processes; and experimental details and the results of MeHg degradation in artificial MeHg-polluted soils treated with birnessite and oxalate mixtures (PDF)

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