The encapsulation and immobilization of intermediate level wastes are discussed within this article, which include liquids, sludges, flocs, resins and salts are routinely encapsulated within cementitious grouts or occasionally bitumen. There are many different techniques and technologies have been utilized, with no one process being universally favored. For more complex wastes containing solid materials, metals or organics advanced treatment options, such as thermal vitrification, gasification or wet oxidation may be required. There are many treatment technologies capable of conditioning the wide variety of intermediate level wastes, with treatment decisions highly dependent on national regulations and current technological maturity.

A fraction of the UK Pu inventory may be immobilised in a zirconolite ceramic matrix prior to disposal. Two zirconolite compositions, targeting CaZr 0.80 Ce 0.20 Ti 2 O 7 and CaZr 0.80 U 0.20 Ti 2 O 7 , were fabricated by hot isostatic pressing, alongside a reformulated composition, nominally Ca 0.80 Zr 0.90 Ce 0.30 Ti 1.60 Al 0.40 O 7 , with an excess of Ti and Zr added to preclude the formation of an accessory perovskite phase. Materials were subjected to accelerated leaching in a variety of acidic and alkaline media at 90 °C, over a cumulative period of 14 d. The greatest Ce release was measured from CaZr 0.80 Ce 0.20 Ti 2.00 O 7 exposed to 1 M H 2 SO 4 , for which 14.7 ± 0.2% of the original Ce inventory was released from the wasteform into solution. The extent of Ce leaching into the solution was correlated with the quantity of perovskite present in the wasteform, and associated with the incorporation and preferential dissolution of Ce 3+ . CaZr 0.80 U 0.20 Ti 2.00 O 7 exhibited improved leach resistance relative to CaZr 0.80 Ce 0.20 Ti 2.00 O 7 , attributed to the decreased proportion of accessory perovskite, with 7.1 ± 0.1% U released to in 8 M HNO 3 after 7 d. The Ca 0.80 Zr 0.90 Ce 0.30 Ti 1.60 Al 0.40 O 7 composition, with no accessory perovskite phase, presented significantly improved leaching characteristics, with < 0.4%Ce released in both 8 M HNO 3 and 1 M H 2 SO 4 . These data demonstrate the need for careful compositional design for zirconolite wasteforms with regard to accessory phase formation and surrogate choice.

Sulfate radical advance oxidation processes (SR-AOPs) have attracted a greater attention as a suitable alternative of the hydroxyl radical based advance oxidation process (HR-AOPs). In this study, for the first time we report liquid phase mineralization of nuclear grade cationic IRN-77 resin in Co2+/peroxymonosulfate (PMS) based SR-AOPs. After the dissolution of cationic IRN-77 resin, 30 volatile and 15 semi-volatile organic compounds were analyzed/detected using non-targeted GC-MS analysis. The optimal reaction parameters for the highest chemical oxygen demand (COD) removal (%) of IRN-77 resin were determined, and the initial pH, PMS dosage, and reaction temperature were found to be the most influential parameters for the resin degradation. We successfully achieved ∼90% COD removal (1000 mg/L; 1000 ppm) of dissolved spent resin for SR-AOPs by optimizing the reaction parameters as initial pH = 9, Co2+ = 4 mM (catalyst), PMS = 60 mM (as oxidant) at 60 °C temperature for 60 min reaction. The electron spin resonance spectroscopy (ESR) spectra confirmed the presence of SO4∙- and OH∙ as main reactive species in the Co2+/PMS resin system. In addition, Fourier transform infrared spectroscopy (FT-IR) analyses were used for structural characterization of solid and liquid phase resin samples. We believe that this work will offer a robust approach for the effective treatment of spent resin generated from nuclear industry.

Struvite-K (MgKPO4·6H2O) is a magnesium potassium phosphate mineral with naturally cementitious properties, which is finding increasing usage as an inorganic cement for niche applications including nuclear waste management and rapid road repair. Struvite-K is also of interest in sustainable phosphate recovery from wastewater and, as such, a detailed knowledge of the crystal chemistry and high-temperature behavior is required to support further laboratory investigations and industrial applications. In this study, the local chemical environments of synthetic struvite-K were investigated using high-field solid-state 25Mg and 39K MAS NMR techniques, alongside 31P MAS NMR and thermal analysis. A single resonance was present in each of the 25Mg and 39K MAS NMR spectra, reported here for the first time alongside the experimental and calculated isotropic chemical shifts, which were comparable to the available data for isostructural struvite (MgNH4PO4·6H2O). An in situ high-temperature XRD analysis of struvite-K revealed the presence of a crystalline-amorphous-crystalline transition that occurred between 30 and 350 °C, following the single dehydration step of struvite-K. Between 50 and 300 °C, struvite-K dehydration yielded a transient disordered (amorphous) phase identified here for the first time, denoted δ-MgKPO4. At 350 °C, recrystallization was observed, yielding β-MgKPO4, commensurate with an endothermic DTA event. A subsequent phase transition to γ-MgKPO4 was observed on further heating, which reversed on cooling, resulting in the α-MgKPO4 structure stabilized at room temperature. This behavior was dissimilar from that of struvite exposed to high temperature, where NH4 liberation occurs at temperatures >50 °C, indicating that struvite-K could potentially withstand high temperatures via a transition to MgKPO4.

We report a high-field in-situ solid-state NMR study of the hydration of CaAl2O4 (the most important hydraulic phase in calcium aluminate cement), based on time-resolved measurements of solid-state 27Al NMR spectra during the early stages of the reaction. A variant of the CLASSIC NMR methodology, involving alternate recording of direct-excitation and MQMAS 27Al NMR spectra, was used to monitor the 27Al species present in both the solid and liquid phases as a function of time. Our results provide quantitative information on the changes in the relative amounts of 27Al sites with tetrahedral coordination (the anhydrous reactant phase) and octahedral coordination (the hydrated product phases) as a function of time, and reveal significantly different kinetic and mechanistic behaviour of the hydration reaction at the different temperatures (20 °C and 60 °C) studied.

We recently reported the first comprehensive investigation of magnesium potassium phosphate cements (MKPCs) blended with supplementary cementitious materials (pulverized fuel ash and granulated blast furnace slag) for the encapsulation of radioactive wastes [Gardner et al., Cem. Concr. Res. 74 (2015) 78-87]. Using a combination of characterization techniques, we demonstrated the important role of the reaction of the supplementary cementitious materials in contributing to the development of the microstructure and strength of MKPC composites. Here, we clarify aspects of our experimental design, and elaborate on the interpretation of our data, following discussion by Ma and Li.

Magnesium potassium phosphate cements (MKPCs), blended with 50 wt.% fly ash (FA) or ground granulated blast furnace slag (GBFS) to reduce heat evolution, water demand and cost, were assessed using compressive strength, X-ray diffraction (XRD), scanning electron microscopy (SEM) and nuclear magnetic resonance (NMR) spectroscopy on 25Mg, 27Al, 29Si, 31P and 39K nuclei. We present the first definitive evidence that dissolution of the glassy aluminosilicate phases of both FA and GBFS occurred under the pH conditions of MKPC. In addition to the main binder phase, struvite-K, an amorphous orthophosphate phase was detected in FA/MKPC and GBFS/MKPC systems. It was postulated that an aluminium phosphate phase was formed, however, no significant Al–O–P interactions were identified. High-field NMR analysis of the GBFS/MKPC system indicated the potential formation of a potassium-aluminosilicate phase. This study demonstrates the need for further research on these binders, as both FA and GBFS are generally regarded as inert fillers within MKPC.