Solubility controls on plutonium and americium release in subsurface environments exposed to acidic processing wastes

To identify the role of waste composition and sediment interactions in controlling Pu and Am mobility in contaminated sediments at Hanford, a legacy nuclear site, Pu and Am concentrations in solutions equilibrated with contaminated sediments from beneath the 216-Z-9 (Z-9) Trench were compared to the solubilities of PuO2 materials, synthesized by methods representative of the disposed wastes, in the absence of sediments. This work shows that the solubilities of PuO2 materials synthesized by different methods, and with varying particle sizes, agree with PuO2(am,hyd), although dissolution kinetics differed between materials. According to saturation index (SI) calculations, PuO2(am,hyd) is likely also controlling Pu release from sediments under conditions where phosphate concentrations are low. However, both Pu-phosphate and Am-phosphate phases, identified in SI calculations and by high resolution transmission electron microscopy, play roles in controlling release in low pH, high phosphate, shallow sediments just below the Z-9 Trench. The elevated phosphate is likely due to decomposition of tributyl phosphate from waste solutions over time. Sediments from deeper in the subsurface beneath the Z-9 Trench are less acidic and contain less phosphate, with Pu solubility likely controlled by PuO2(am,hyd) that precipitated following neutralization of the acidic waste stream. Controls on Am concentrations in deeper sediments are more complex and potentially involve sediment adsorption and/or release from Pu(1-x)AmxO2 following Am in-growth. The concentrations of both Pu and Am were elevated in the colloidal fraction associated with shallow sediments, but not in PuO2 experiments, suggesting the presence of Pu/Am pseudocolloids (e.g., Pu/Am associated with mineral colloids). However, Pu and Am association with the colloidal size fraction was not observed in deeper sediments, suggesting transport of Pu and Am to these depths beneath the Z-9 Trench was not due to colloidal transport. [Display omitted] •Pu solubility in contaminated Hanford sediments compared with PuO2 without sediments.•Solubility controlling phases revealed by thermodynamically derived saturation indices.•PuO2 solubility matches PuO2(am,hyd) regardless of synthesis or particle size.•PuO2(am,hyd), Am/Pu-phosphate and adsorbed Am control solubility as a function of depth.•Trace Pu/Am concentrations in deeper sediments are not due to colloidal transport.