Understanding interactions between iron (oxyhydr)oxide nanoparticles and plutonium is essential to underpin technology to treat radioactive effluents, in cleanup 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 HNO 3 solution with Fe(III) (aq) and 242 Pu(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 PuO 2 present. Best fits to the EXAFS data collected from Pu−ferrihydrite samples aged for 2 and 6 months showed no statistically significant change in the Pu(IV)−Fe oxyhydroxide surface complex despite the ferrihydrite undergoing extensive recrystallization to hematite. This suggests the Pu remains strongly sorbed to the iron (oxyhydr)oxide surface and could be retained over extended time periods.

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Analysis of a radioactive, coated concrete core from the decommissioned, spent nuclear fuel cooling pond at the Hunterston-A nuclear site (UK) has provided a unique opportunity to study radionuclides within a real-world system. The core, obtained from a dividing wall and sampled at the fill level of the pond, exhibited radioactivity (dominantly (137)Cs and (90)Sr) heterogeneously distributed across both painted faces. Chemical analysis of the core was undertaken using microfocus spectroscopy at Diamond Light Source, UK. Mapping of Sr across the surface coatings using microfocus X-ray fluorescence (μXRF) combined with X-ray absorption spectroscopy showed that Sr was bound to TiO2 particles in the paint layers, suggesting an association between TiO2 and radiostrontium. Stable Sr and Cs sorption experiments using concrete coupons were also undertaken to assess their interactions with the bulk concrete in case of a breach in the coating layers. μXRF and scanning electron microscopy showed that Sr was immobilized by the cement phases, whilst at the elevated experimental concentrations, Cs was associated with clay minerals in the aggregates. This study provides a crucial insight into poorly understood infrastructural contamination in complex systems and is directly applicable to the UK's nuclear decommissioning efforts.

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