Plutonium(IV) sorption during ferrihydrite nanoparticle formation

Kurt F Smith, Katherine Morris, Gareth T.w. Law, Ellen Winstanley, Francis R. Livens, Joshua Simon Weatherill, Liam Abrahamsen-mills, Nicholas Bryan, J. Frederick Willem Mosselmans, Giannantonio Cibin, Stephen Parry, Richard Blackham, Kathleen Law, Samuel Shaw

Research output: Contribution to journalArticlepeer-review


Understanding interactions between iron (oxyhydr)oxide nanoparticles and plutonium is essential to underpin technology to treat radioactive effluents, in clean-up of land contaminated with radionuclides, and to ensure the safe disposal of radioactive wastes. These interactions include a range of adsorption, precipitation and incorporation processes. Here, we explore the mechanisms of plutonium sequestration during ferrihydrite precipitation from an acidic solution. The initial 1 M HNO3 solution with Fe(III)(aq) and 242Pu(IV)(aq) underwent controlled hydrolysis via the addition of NaOH to pH 9. The majority of Fe(III)(aq) and Pu(IV)(aq) was removed from solution between pH 2 and 3 during ferrihydrite formation. Analysis of Pu-ferrihydrite by Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy showed that Pu(IV) formed an inner sphere tetradentate complex on the ferrihydrite surface, with minor amounts of PuO2 present. Best fits to the EXAFS data collected from Pu-ferrihydrite samples aged for two- and six- months showed no statistically significant change in the Pu(IV)-Fe oxyhydroxide surface complex despite the ferrihydrite undergoing extensive recrystallisation to hematite. This suggests the Pu remains strongly sorbed to the iron (oxyhydr)oxide surface and could be retained over extended time periods.
Original languageEnglish
Pages (from-to)2437-2442
JournalACS Earth and Space Chemistry
Issue number11
Early online date16 Sept 2019
Publication statusPublished - 16 Sept 2019


  • plutonium
  • ferrihydrite
  • hematite
  • nanoparticle
  • XAS
  • sorption

Research Beacons, Institutes and Platforms

  • Dalton Nuclear Institute


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