Selenate removal by zero-valent iron under anoxic conditions: effects of nitrate and sulfate

  • Soumya DasEmail author
  • Matthew B. J. Lindsay
  • M. Jim Hendry
Original Article


Batch experiments were conducted to examine aqueous Se(VI) removal by zero-valent iron (ZVI) under anoxic conditions in the presence and absence of NO3 and SO42−. Initial concentrations for Se(VI), SO4, and NO3–N of 5 mg L−1, 1800 mg L−1, and 13 mg L−1, respectively, were employed to mimic mine waters. In the control experiment, 90% Se(VI) removal occurred within 1.5 h without SO42− and NO3 (B1). This removal threshold was reached after 3 h with NO3 added (B3) and after 33 h with SO42− added (B2). Removal reached 90% after 42 h with both SO42− and NO3 added (B4). Modeled Se(VI) removal rates consistently followed first-order kinetics and revealed that the presence of SO42− and, to a lesser extent, NO3 inhibited Se(VI) removal. Increases in pH and Fe coupled with decreasing Eh are consistent with ZVI corrosion under anoxic conditions. Transmission electron microscopy, Raman spectroscopy, and X-ray diffraction revealed magnetite [Fe3O4] and lepidocrocite [γ-FeOOH] formed at ZVI surfaces during the experiments. X-ray absorption near edge structure spectroscopy indicated that Se(VI) was predominantly reduced to Se(0) (70–80%), but Se(IV) (10–13%) and Se(-II) (2–13%) were also detected at reacted ZVI surfaces. Overall, the results show that although SO42− and NO3 present in mine wastes can reduce reaction rates, Se(VI) removal by ZVI under anoxic conditions is associated with extensive reduction to insoluble Se(0).


Zero-valent iron Selenate Removal Reduction Sulfate Nitrate 



The authors acknowledge funding provided by the Natural Sciences and Engineering Research Council of Canada (NSERC) IRC program (MJH; Grant No. 184573) and Discovery Grant program (MBJL; Grant No. RGPIN-2014-06589). The authors also acknowledge the Canadian Light Source, whose operations are supported by the University of Saskatchewan, the Government of Saskatchewan, Western Economic Diversification Canada, the National Research Council Canada, and the Canadian Institutes of Health Research. The authors also thank Ms. Fina Nelson and Dr. Jared Robertson for assistance provided during batch and XAS experiments, respectively.

Supplementary material

12665_2019_8538_MOESM1_ESM.doc (2.4 mb)
Supplementary material Comparison of measured aqueous Se(VI) concentrations (C/C0) with time for B1, B2, B3, and B4 batches under anoxic and oxic (Das et al., 2017) conditions. pH, Eh, Fe(T), and sulfate concentrations of respective batches along with tem images of un-reacted and reacted ZVI surfaces. detailed linear combination fitting of Se K-edge XANES spectra, absorption energy values for the Se K-edge of E0 (first inflection point), and the most intense peak (white line) for se reference standards (seven figures and two tables) (DOC 2492 kb)


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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Soumya Das
    • 1
    Email author
  • Matthew B. J. Lindsay
    • 1
  • M. Jim Hendry
    • 1
  1. 1.Department of Geological SciencesUniversity of SaskatchewanSaskatoonCanada

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