Environmental Chemistry Letters

, Volume 12, Issue 3, pp 413–417 | Cite as

High-valent iron-based oxidants to treat perfluorooctanesulfonate and perfluorooctanoic acid in water

  • Brian J. Yates
  • Ramona Darlington
  • Radek Zboril
  • Virender K. Sharma
Original Paper


Perfluoroalkyl and polyfluoroalkyl substances are occurring in consumer and industrial products. They have been found globally in the aquatic environment including drinking water sources and treated wastewater effluents, which has raised concern of potential human health effects because these substances may be bioaccumulative and extremely persistent. The saturated carbon–fluorine bonds of the substances make them resistant to degradation by physical, chemical, and biological processes. There is therefore a need for advanced remediation methods. Iron-based methods involving high-valent compounds are appealing to degrade these substances due to their high oxidation potentials and capability to generate environmentally friendly by-products. This article presents for the first time the oxidation ability of tetraoxy anions of iron(V) (FeVO4 3−, Fe(V)), and iron(IV) (FeIVO4 4−, Fe(IV)), commonly called ferrates, in neutral and alkaline solutions. Solid compounds of Fe(V) (K3FeO4) and Fe(IV) (Na4FeO4) were added directly into buffered solution containing perfluorooctansulfonate and perfluorooctanoic acid at pH 7.0 and 9.0, and mixed solutions were subjected to analysis for remaining fluoro compounds after 5 days. The analysis was performed by liquid chromatography–mass spectrometry/mass spectrometry technique. Fe(IV) showed the highest ability to oxidize the studied contaminants; the maximum removals were 34 % for perfluorooctansulfonate and 23 % for perfluorooctanoic acid. Both Fe(V) and Fe(IV) had slightly higher tendency to oxidize contaminants at alkaline pH than at neutral pH. Results were described by invoking reactions involved in oxidation of perfluorooctansulfonate and perfluorooctanoic acid by ferrates in aqueous solution. The results demonstrated potentials of Fe(V) and Fe(IV) to degrade perfluoroalkyl substances in contaminated water.


Ferrate Oxidation Degradation Perfluoroalkyl compounds Fe(V) Fe(IV) 



B.J. Yates and R. Darlington acknowledge support from Battelle’s Internal Research and Development funds. V. K. Sharma thanks United States National Science Foundation (CBET 1236331) for supporting ferrate research. The authors also acknowledge the support by the Operational Program Research and Development for Innovations–European Regional Development Fund (CZ.1.05/2.1.00/03.0058) and by Technological Agency of the Czech Republic—the project Environmental Friendly Nanotechnologies and Biotechnologies in Water and Soil Treatment (TE01020218).


  1. Appleman TD, Higgins CP, Quiñones O, Vanderford BJ, Kolstad C, Zeigler-Holady JC, Dickenson ERV (2014) Treatment of poly- and perfluoroalkyl substances in U.S. full-scale water treatment systems. Water Res 51:246–255CrossRefGoogle Scholar
  2. Butler EC, Chen L, Darlington R (2013) Transformation of trichloroethylene to predominantly non-regulated products under stimulated sulfate reducing conditions. Groundw Monit Remediat 33(3):52–60Google Scholar
  3. Crane RA, Scott TB (2012) Nanoscale zero-valent iron: future prospects for an emerging water treatment technology. J Hazard Mater 211–212:112–115CrossRefGoogle Scholar
  4. De la Cruz N, Giménez J, Esplugas S, Grandjean D, De Alencastro LF, PulgarÃn C (2012) Degradation of 32 emergent contaminants by UV and neutral photo-Fenton in domestic wastewater effluent previously treated by activated sludge. Water Res 46(6):1947–1957CrossRefGoogle Scholar
  5. Dedushenko SK, Perfilev YD, Tcheboukov DE, Pankratov DA, Kiselev YM (1999) A Mossbauer study of pentavalent iron in a vanadium(V) oxide matrix. Mendeleev Commun 5:171–172Google Scholar
  6. Dedushenko SK, Perfil’ev YD, Chuevb MA, Afanasev AM (2010) Identification of iron oxidation states in the products of interaction of Na2O2 and Fe2O3 by Mossbauer absorption spectroscopy. Russ J Inorg Chem 55(6):942–949CrossRefGoogle Scholar
  7. Dhakshinamoorthy A, Navalon S, Alvaro M, Garcia H (2012) Metal nanoparticles as heterogeneous Fenton catalysts. ChemSusChem 5(1):46–64CrossRefGoogle Scholar
  8. Filip J, Yngard RA, Siskova K, Marusak Z, Ettler V, Sajdl P, Sharma VK, Zboril R (2011) Mechanisms and efficiency of the simultaneous removal of metals and cyanides by using ferrate(VI): crucial roles of nanocrystalline iron(III) oxyhydroxides and metal carbonates. Chem Eur J 17(36):10097–10105CrossRefGoogle Scholar
  9. Horst C, Sharma VK, Clayton Baum J, Sohn M (2013) Organic matter source discrimination by humic acid characterization: synchronous scan fluorescence spectroscopy and Ferrate(VI). Chemosphere 90(6):2013–2019CrossRefGoogle Scholar
  10. Jeannot C, Malaman B, Gerardin R, Oulladiaf B (2002) Synthesis, crystal, and magnetic structures of the sodium ferrate(IV) Na4FeO4 studied by neutron diffraction and Mossbauer techniques. J Solid State Chem 165:266–277CrossRefGoogle Scholar
  11. Jiang JQ (2007) Research progress in the use of ferrate(VI) for the environmental remediation. J Hazard Mater 146:617–623CrossRefGoogle Scholar
  12. Jiang JQ (2014) Advances in the development and application of ferrate(VI) for water and wastewater treatment. J Chem Technol Biotechnol 89:165–177CrossRefGoogle Scholar
  13. Knepper TP, Lange FT (2012) Polyfluorinated chemicals and transformation productsGoogle Scholar
  14. Lee Y, von Gunten U (2012) Quantitative structure-activity relationships (QSARs) for the transformation of organic micropollutants during oxidative water treatment. Water Res 46(19):6177–6195CrossRefGoogle Scholar
  15. Lee Y, Zimmermann SG, Kieu AT, Gunten GV (2009) Ferrate (Fe(VI)) application for municipal wastewater treatment: a novel process for simultaneous micropollutant oxidation and phosphate removal. Environ Sci Technol 43:3831–3838CrossRefGoogle Scholar
  16. Lee YC, Lo SL, Kuo J, Huang C- (2013) Promoted degradation of perfluorooctanic acid by persulfate when adding activated carbon. J Hazard Mater 261:463–469CrossRefGoogle Scholar
  17. Luo Z, Strouse M, Jiang JQ, Sharma VK (2011) Methodologies for the analytical determination of ferrate(VI): a review. J Environ Sci Health, Part A Toxic/Hazard Subst Environ Eng 46(5):453–460Google Scholar
  18. Mitchell S, Mushtaque A, Teel AL, Watts RJ (2014) Degradation of perfluorooctanoic acid by reactive species generated through catalyzed H2O2 propagation reactions. Enviorn Sci Technol Lett 1:117–121CrossRefGoogle Scholar
  19. Noorhasan N, Patel B, Sharma VK (2010) Ferrate(VI) oxidation of glycine and glycylglycine: kinetics and products. Water Res 44:927–937CrossRefGoogle Scholar
  20. Prucek R, Tuček J, Kolařík J, Filip J, Marušák Z, Sharma VK, Zbořil R (2013) Ferrate(VI)-induced arsenite and arsenate removal by in situ structural incorporation into magnetic iron(III) oxide nanoparticles. Environ Sci Technol 43(7):3283–3292Google Scholar
  21. Rahman MF, Peldszus S, Anderson WB (2014) Behaviour and fate of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in drinking water treatment: a review. Water Res 50:18–340CrossRefGoogle Scholar
  22. Rush JD, Bielski BHJ (1989) Kinetics of ferrate(V) decay in aqueous solution. A pulse-radiolysis study. Inorg Chem 28:3947–3951CrossRefGoogle Scholar
  23. Sharma VK (2007) Disinfection performance of Fe(VI) in water and wastewater: a review. Water Sci Technol 55(1–2):225–232CrossRefGoogle Scholar
  24. Sharma VK (2011) Oxidation of inorganic contaminants by ferrates(Fe(VI), Fe(V), and Fe(IV))—kinetics and mechanisms—a review. J Environ Manage 92:1051–1073CrossRefGoogle Scholar
  25. Sharma VK, O’Connor DB, Cabelli DE (2001) Sequential one-electron reductions of Fe(V) to Fe(III) in alkaline solution. J Phys Chem B 105:11529–11532Google Scholar
  26. Sharma VK, Dutta PK, Ray AK (2007) Review of kinetics of chemical and photocatalytical oxidation of arsenic(III) as influenced by pH. J Environ Sci Health Part A Toxic/Hazard Subst Environ Eng 42(7):997–1004Google Scholar
  27. Sharma VK, Sohn M, Anquandah G, Nesnas N (2012) Kinetics of the oxidation of sucralose and related carbohydrates by ferrate(VI). Chemosphere 87:644–648CrossRefGoogle Scholar
  28. Sharma VK, Liu F, Tolan S, Sohn M, Kim H, Oturan MA (2013) Oxidation of β-lactam antibiotics by ferrate(VI). Chem Eng J 221:446–451CrossRefGoogle Scholar
  29. Sylvester P, Rutherford LA Jr, Gonzalez-Martin A, Kim J, Rapko BM, Lumetta GJ (2001) Ferrate treatment for removing chromium from high-level radioactive tank waste. Environ Sci Technol 35(1):216–221CrossRefGoogle Scholar
  30. United Nations Educational, Scientific, and Cultural Organization (2003) Water for people, water for life—the United Nations World Water Development Report, Edition 1 World Water Assessment Programme (WWAP)Google Scholar
  31. Yang B, Ying GG, Zhao J-, Liu S, Zhou LJ, Chen F (2012) Removal of selected endocrine disrupting chemicals (EDCs) and pharmaceuticals and personal care products (PPCPs) during ferrate(VI) treatment of secondary wastewater effluents. Water Res 46(7):2194–2204CrossRefGoogle Scholar
  32. Zboril R, Andrle M, Oplustil F, Machala L, Tucek J, Filip J, Marusak Z, Sharma VK (2012) Treatment of chemical warfare agents by zero-valent iron nanoparticles and ferrate(VI)/(III) composite. J Hazard Mater 211–212:126–130CrossRefGoogle Scholar

Copyright information

© Springer International Publishing Switzerland 2014

Authors and Affiliations

  • Brian J. Yates
    • 1
  • Ramona Darlington
    • 1
  • Radek Zboril
    • 2
  • Virender K. Sharma
    • 3
  1. 1.Energy and EnvironmentColumbusUSA
  2. 2.Department of Physical Chemistry, Regional Centre of Advanced Technologies and Materials, Faculty of SciencePalacky University in OlomoucOlomoucCzech Republic
  3. 3.Department of Environmental and Occupational Health, School of Public HealthTexas A&M UniversityCollege StationUSA

Personalised recommendations