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Antimonite Binding to Natural Organic Matter: Spectroscopic Evidence from a Mine Water Impacted Peatland

  • Johannes Besold
    Johannes Besold
    Department of Environmental Geochemistry, Bayreuth Center for Ecology and Environmental Research (BAYCEER), Bayreuth University, 95440 Bayreuth, Germany
  • Anne Eberle
    Anne Eberle
    Department of Environmental Geochemistry, Bayreuth Center for Ecology and Environmental Research (BAYCEER), Bayreuth University, 95440 Bayreuth, Germany
    More by Anne Eberle
  • Vincent Noël
    Vincent Noël
    Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States
  • Katharina Kujala
    Katharina Kujala
    Water Resources and Environmental Engineering Research Unit, University of Oulu, FI-90014, Oulu, Finland
  • Naresh Kumar
    Naresh Kumar
    Department of Geological Sciences, School of Earth, Energy, and Environmental Sciences, Stanford University, Stanford, California 94305, United States
    Department of Environmental Geosciences, Centre for Microbiology and Environmental Systems Science, University of Vienna, 1090 Vienna, Austria
    More by Naresh Kumar
  • Andreas C. Scheinost
    Andreas C. Scheinost
    The Rossendorf Beamline (ROBL) at ESRF, 38043 Grenoble, France and Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Institute of Resource Ecology, Bautzner Landstraße 400, 01328 Dresden, Germany
  • Juan Lezama Pacheco
    Juan Lezama Pacheco
    Department of Earth System Science, School of Earth, Energy, and Environmental Sciences, Stanford University, Stanford, California 94305, United States
  • Scott Fendorf
    Scott Fendorf
    Department of Earth System Science, School of Earth, Energy, and Environmental Sciences, Stanford University, Stanford, California 94305, United States
  • , and 
  • Britta Planer-Friedrich*
    Britta Planer-Friedrich
    Department of Environmental Geochemistry, Bayreuth Center for Ecology and Environmental Research (BAYCEER), Bayreuth University, 95440 Bayreuth, Germany
    *Phone: +49-921-553999; fax: +49-921-552334; e-mail: [email protected]
Cite this: Environ. Sci. Technol. 2019, 53, 18, 10792–10802
Publication Date (Web):August 22, 2019
https://doi.org/10.1021/acs.est.9b03924
Copyright © 2019 American Chemical Society

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    Abstract

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    Peatlands and other wetlands are sinks for antimony (Sb), and solid natural organic matter (NOM) may play an important role in controlling Sb binding. However, direct evidence of Sb sequestration in natural peat samples is lacking. Here, we analyzed solid phase Sb, iron (Fe), and sulfur (S) as well as aqueous Sb speciation in three profiles up to a depth of 80 cm in a mine water impacted peatland in northern Finland. Linear combination fittings of extended X-ray absorption fine structure spectra showed that Sb binding to Fe phases was of minor importance and observed only in the uppermost layers of the peatland. Instead, the dominant (to almost exclusive) sequestration mechanism was Sb(III) binding to oxygen-containing functional groups, and at greater depths, increasingly Sb(III) binding to thiol groups of NOM. Aqueous Sb speciation was dominated by antimonate, while antimonite concentrations were low, further supporting our findings of much higher reactivity of Sb(III) than Sb(V) toward peat surfaces. Insufficient residence time for efficient reduction of antimonate to antimonite currently hinders higher Sb removal in the studied peatland. Overall, our findings imply that Sb(III) binding to solid NOM acts as an important sequestration mechanism under reducing conditions in peatlands and other high-organic matter environments.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.est.9b03924.

    • Field site characteristics and sampling, General geochemical characterization, Scanning Electron Microscopy/Energy Dispersive X-ray Spectroscopy analyses and results, Iron solid-phase speciation analyses and results, Sulfur solid-phase speciation analyses and results, Antimony solid-phase speciation analyses and results, Aqueous Sb speciation results (PDF)

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