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Thermodynamic constraints on limestone-based arsenic removal from water

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Abstract

Limestone-based material is effective for reducing arsenic concentrations below the current US limit of 0.010 mg/L for drinking water, typically resulting in final concentrations of about 0.004–0.006 mg/L (4–6 parts per billion). However, in laboratory and field testing, reductions to the 1 ppb range are difficult to achieve with limestone unless other material such as iron is added. Scanning electron microscopy and energy-dispersive X-ray analysis show the formation of calcium arsenate on limestone after arsenic removal. The arsenic removal mechanism with untreated limestone appears to be the formation of a low-solubility precipitate of calcium arsenate hydroxide, in the form of Ca5(AsO4)3OH (arsenate apatite). Likely reactions and thermodynamic data show strongly negative Gibbs free energy changes and indicate a theoretical removal limit of about 4 ppb for arsenic using native limestone. Impurities in limestone, such as iron, also could enhance the removal process. The solubility product of arsenate apatite is approximately 10−40. This low solubility appears to account for the stability of the waste product after arsenic removal with limestone.

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Acknowledgements

We thank Dr. Edward F. Duke, Director of the Engineering and Mining Experiment Station at South Dakota School of Mines and Technology, for his assistance with scanning electron microscopy and energy-dispersive X-ray microanalysis.

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Authors and Affiliations

  1. South Dakota School of Mines and Technology, Rapid City, SD, USA

    Arden D. Davis & David J. Dixon

  2. Western Kentucky University, Bowling Green, KY, USA

    Cathleen J. Webb

  3. Minnesota Department of Natural Resources, St. Paul, MN, USA

    Jenifer L. Sorensen

Authors
  1. Arden D. Davis
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  2. Cathleen J. Webb
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  3. Jenifer L. Sorensen
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  4. David J. Dixon
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Correspondence to Arden D. Davis.

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Davis, A.D., Webb, C.J., Sorensen, J.L. et al. Thermodynamic constraints on limestone-based arsenic removal from water. Environ Earth Sci 77, 33 (2018). https://doi.org/10.1007/s12665-017-7204-6

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