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Zirconolite is considered to be a suitable wasteform material for the immobilization of Pu and other minor actinide species produced through advanced nuclear separations. Here, we present a comprehensive investigation of Dy3+ incorporation within the self-charge balancing zirconolite Ca1–xZr1–xDy2xTi2O7 solid solution, with the view to simulate trivalent minor actinide immobilization. Compositions in the substitution range 0.10 ≤ x ≤ 1.00 (Δx = 0.10) were fabricated by a conventional mixed oxide synthesis, with a two-step sintering regime at 1400 °C in air for 48 h. Three distinct coexisting phase fields were identified, with single-phase zirconolite-2M identified only for x = 0.10. A structural transformation from zirconolite-2M to zirconolite-4M occurred in the range 0.20 ≤ x ≤ 0.30, while a mixed-phase assemblage of zirconolite-4M and cubic pyrochlore was evident at Dy concentrations 0.40 ≤ x ≤ 0.50. Compositions for which x ≥ 0.60 were consistent with single-phase pyrochlore. The formation of zirconolite-4M and pyrochlore polytype phases, with increasing Dy content, was confirmed by high-resolution transmission electron microscopy, coupled with selected area electron diffraction. Analysis of the Dy L3-edge XANES region confirmed that Dy was present uniformly as Dy3+, remaining analogous to Am3+. Fitting of the EXAFS region was consistent with Dy3+ cations distributed across both Ca2+ and Zr4+ sites in both zirconolite-2M and 4M, in agreement with the targeted self-compensating substitution scheme, whereas Dy3+ was 8-fold coordinated in the pyrochlore structure. The observed phase fields were contextualized within the existing literature, demonstrating that phase transitions in CaZrTi2O7–REE3+Ti2O7 binary solid solutions are fundamentally controlled by the ratio of ionic radius of REE3+ cations.

Reactive spark plasma sintering has been utilised as a high-throughput processing route for the synthesis of two simulant zirconolite wasteform materials, targeting Ca0.80Ce0.20ZrTi1.60M0.40O7 (M = Fe3+ and Al3+). Materials were processed under 15 MPa uniaxial pressure, with heating/cooling rates of 100 °C/min to 1320 °C, maintained under vacuum. Despite moderate yield (> 80 wt%) of zirconolite-2M, a considerable Ce-rich perovskite phase was formed in both formulations, attributed to complete reduction of the Ce inventory to Ce3+, as determined by Ce L3-edge XANES analysis. The composition charge balanced with Al3+ was favoured on the basis of lower accompanying perovskite fraction.

A series of zirconolite ceramics with stoichiometry Ca1-xCexZrTi2-2xAl2xO7 (x = 0–0.35), considered as a host phase for the immobilisation of separated plutonium, were prepared from a mixture of oxide precursors by sintering in air at 1450 °C. Ce was utilised as a structural surrogate for Pu, with Al added to provide charge compensation. XRD and electron diffraction analyses indicated crystallisation of the zirconolite-2M polytype for all compositions, accompanied by various secondary phases contingent on the doping level, consistent with microstructure observation. The relative yield of zirconolite phases remained above 94 wt.% for 0.05 < x < 0.20. It was determined that Ce was partially reduced to the Ce3+ oxidation state and Al occupied mainly octahedral Ti sites. The incorporation rate of CeO2 was calculated to be 9.27 wt.% in Ca0.80Ce0.20ZrTi1.60Al0.40O7 with a comparatively high yield of 94.7 wt.%, which is representative of a PuO2 incorporation rate of 14.86 wt.%.

Low-temperature soft chemical synthesis routes to transition-metal nitrides are of interest as an alternative to conventional high-temperature ammonolysis reactions involving large volumes of chemotoxic NH3 gas. One such method is the reaction between metal oxides and NaNH2 at ca. 200 °C to yield the counterpart nitrides; however, there remains uncertainty regarding the reaction mechanism and product phase assemblage (in particular, noncrystalline components). Here, we extend the chemical tool box and mechanistic understanding of such reactions, demonstrating the nitridation of Fe3O4 by reaction with NaNH2 at 170–190 °C, via a pseudomorphic reaction. The more reduced Fe3O4 precursor enabled nitride formation at lower temperatures than the previously reported equivalent reaction with Fe2O3. The product phase assemblage, characterized by X-ray diffraction, thermogravimetric analysis, and 57Fe Mössbauer spectroscopy, comprised 49–59 mol % ε-Fe2+xN, accompanied by 29–39 mol % FeO1–xNx and 8–14 mol % γ″-FeN. The oxynitride phase was apparently noncrystalline in the recovered product but could be crystallized by heating at 180 °C. Although synthesis of transition-metal nitrides is achieved by reaction of the counterpart oxide with NaNH2, it is evident from this investigation that the product phase assemblage may be complex, which could prove a limitation if the objective is to produce a single-phase product with well-defined electrical, magnetic, or other physical properties for applications. However, the significant yield of the FeO1–xNx oxynitride phase identified in this study opens the possibility for the synthesis of metastable oxynitride phases in high yield, by reaction of a metal oxide substrate with NaNH2, with either careful control of H2O concentration in the system or postsynthetic hydrolysis and crystallization.

High-entropy boride-silicon carbide (HEB-SiC) ceramics were fabricated using boride-based powders prepared from borothermal and boro/carbothermal reduction methods. The effects of processing routes (borothermal reduction and boro/carbothermal reduction) on the HEB powders were examined. HEB-SiC ceramics with > 98% theoretical density were prepared by spark plasma sintering at 2000 °C. It was demonstrated that the addition of SiC led to slight coarsening of the microstructure. The HEB-SiC ceramics prepared from boro/carbothermal reduction powders showed a fine-grained microstructure and higher Vickers’ hardness but lower fracture toughness value as compared with the same composition prepared from borothermal reduction powders. These results indicated that the selection of the powder processing method and the addition of SiC phase could contribute to the optimal preparation of high-entropy boride-based ceramics.

Praseodymium-doped zirconolite ceramics targeting nominal composition Ca1-xPrxZrTi2-5x/3Al5x/3O7 (x ≤ 0.20, Δx = 0.05) were fabricated by a mixed oxide solid state reaction, at 1350 °C in air for 20 h. Praseodymium (Pr) was employed as a surrogate for neptunium (Np), with Al3+ co-accommodated to provide charge balance. High-resolution transmission electron microscopy and electron diffraction analyses confirmed that zirconolite crystallised as the 2 M monoclinic polytype throughout the phase evolution, with no evidence of transformation to other polytype structures. Phase assemblage and microstructural data were consistent with zirconolite occupying a high fraction of the phase assemblage (>ca. 93 wt %), alongside a minor secondary perovskite phase at all levels of targeted Pr incorporation. Despite this, it was demonstrated near theoretical density formed through a solid-state fabrication route, and we therefore propose that, through analogy with the corresponding Pr solid solution, zirconolite may be a suitable candidate for the immobilisation of Np-bearing wastes.

The synthesis, structure, and thermal stability of the periodate double perovskites A2NaIO6 (A= Ba, Sr, Ca) were investigated in the context of potential application for the immobilization of radioiodine. A combination of X-ray diffraction and neutron diffraction, Raman spectroscopy, and DFT simulations were applied to determine accurate crystal structures of these compounds and understand their relative stability. The compounds were found to exhibit rock-salt ordering of Na and I on the perovskite B-site; Ba2NaIO6 was found to adopt the Fm-3m aristotype structure, whereas Sr2NaIO6 and Ca2NaIO6 adopt the P21/n hettotype structure, characterized by cooperative octahedral tilting. DFT simulations determined the Fm-3m and P21/n structures of Ba2NaIO6 to be energetically degenerate at room temperature, whereas diffraction and spectroscopy data evidence only the presence of the Fm-3m phase at room temperature, which may imply an incipient phase transition for this compound. The periodate double perovskites were found to exhibit remarkable thermal stability, with Ba2NaIO6 only decomposing above 1050 °C in air, which is apparently the highest recorded decomposition temperature so far recorded for any iodine bearing compound. As such, these compounds offer some potential for application in the immobilization of iodine-129, from nuclear fuel reprocessing, with an iodine incorporation rate of 25–40 wt%. The synthesis of these compounds, elaborated here, is also compatible with both current conventional and future advanced processes for iodine recovery from the dissolver off-gas.

A series of Ca1-xCexZrTi2-2xCr2xO7 zirconolite ceramics (0 ≤ x ≤ 0.35) were reactively sintered in air at 1350 °C for 20 h. Single phase zirconolite-2M was formed for x ≤ 0.15, with Cr2O3 and an undesirable Ce-bearing perovskite phase present above x = 0.20. Electron diffraction analysis confirmed that the zirconolite-2M polytype was maintained over the solid solution. X-ray absorption near edge structure (XANES) data determined that between 10–20% Ce was speciated as Ce3+, and Cr was present uniformly as Cr3+ with near edge features consistent with occupation of octahedral sites within the zirconolite-2M structure. A sample corresponding to x = 0.20 was processed by reactive spark plasma sintering (RSPS), with a rapid processing time of less than 1 h. XANES data confirmed complete reduction to Ce3+ during RSPS, promoting the formation of a Ce-bearing perovskite, comprising 19.3 ± 0.4 wt. % of the phase assemblage.

Ion-specific media (ISM) have played an integral role in the clean-up and remediation efforts at the Fukushima Dai-ichi disaster site, through the processing of contaminated wastewaters. The use of these materials generates a secondary nuclear waste stream, presenting its own series of engineering problems arising from stringent handling and long-term storage requirements. A reactive spark plasma sintering (SPS) method was investigated for conditioning of the spent cesium exchanged zeolite, chabazite. A natural form of the zeolite was used as an analogue to the engineered ISM used at the Fukushima NPP site. Simulant wasteforms were sintered using different temperature and pressure parameters followed by analysis of phase assemblage, density, and durability (using the product consistency test (PCT)). The results indicated that zeolite structure had collapsed completely, with the exchanged cesium partitioned primarily into a durable feldspar to assure stability of the sintered material for passively safe storage or geological disposal.

The potential impacts of climate change are expected to reshape the patterns of demand and supply of water for agriculture, therefore the assessment of the impacts of climate change on agricultural water consumption will be essential. The water footprint provides a new approach to the assessment of agricultural water consumption under climate change. This paper provides an analysis of the impacts of climate changes on the water footprint of spring wheat in Hetao Irrigation District, China during 1980-2009. Results indicate that: 1) crop evapotranspiration and irrigation water requirements of spring wheat presented a downtrend owing to the climate factors variation in the study period; 2) under the combined influence of increasing crop yield and decreasing crop evapotranspiration, the water footprint decreased during the study period, exhibiting a trend of 0.025 m3 kg-1 yr-1; 3) the total contribution rate of the climatic factors for the decline of water footprint of spring wheat during the study period was only 10.45%. These results suggest that the water footprint of a crop, to a large extent, is determined by agricultural management rather than by the regional agro-climate and its variation. Nevertheless, we should pay attention to the adaptation of effective strategies for minimizing the agricultural production risk caused by climate change., Es de esperar que los impactos potenciales del cambio climático redefinan los patrones de oferta y demanda de agua para la agricultura. Por ello es esencial la evaluación del impacto del cambio climático sobre este consumo y en esta evaluación el estudio de la huella hídrica ofrece nuevas alternativas. Este trabajo analiza los impactos del cambio climático sobre la huella hídrica de trigo de primavera en el Distrito de Riego Hetao, China, entre 1980 y 2009. Los resultados indican que: 1) la necesidad de agua de los cultivos y el requerimiento de agua de riego del trigo de primavera presentó una tendencia a la baja, debido a la variación de los factores climáticos en el período de estudio; 2) bajo la influencia combinada del aumento de rendimiento de los cultivos y la disminución en la evapotranspiración del cultivo, la huella hídrica disminuyó durante el período de estudio, tendiendo a 0,025 m3 kg-1 año-1, 3) la tasa de contribución total de los factores climáticos en la disminución de la huella hídrica de trigo de primavera durante el período de estudio fue sólo -10,45%. Estos resultados sugieren que, en gran medida, la huella hídrica de un cultivo está más determinada por la gestión agrícola que por el agro-clima de la región y sus variaciones. Sin embargo, debemos prestar atención a la adaptación de estrategias eficaces para minimizar el riesgo provocado por el cambio climático en la producción agrícola.

The potential impacts of climate change are expected to reshape the patterns of demand and supply of water for agriculture, therefore the assessment of the impacts of climate change on agricultural water consumption will be essential. The water footprint provides a new approach to the assessment of agricultural water consumption under climate change. This paper provides an analysis of the impacts of climate changes on the water footprint of spring wheat in Hetao Irrigation District, China during 1980-2009. Results indicate that: 1) crop evapotranspiration and irrigation water requirements of spring wheat presented a downtrend owing to the climate factors variation in the study period; 2) under the combined influence of increasing crop yield and decreasing crop evapotranspiration, the water footprint decreased during the study period, exhibiting a trend of 0.025 m3 kg-1 yr-1; 3) the total contribution rate of the climatic factors for the decline of water footprint of spring wheat during the study period was only 10.45%. These results suggest that the water footprint of a crop, to a large extent, is determined by agricultural management rather than by the regional agro-climate and its variation. Nevertheless, we should pay attention to the adaptation of effective strategies for minimizing the agricultural production risk caused by climate change. Es de esperar que los impactos potenciales del cambio climático redefinan los patrones de oferta y demanda de agua para la agricultura. Por ello es esencial la evaluación del impacto del cambio climático sobre este consumo y en esta evaluación el estudio de la huella hídrica ofrece nuevas alternativas. Este trabajo analiza los impactos del cambio climático sobre la huella hídrica de trigo de primavera en el Distrito de Riego Hetao, China, entre 1980 y 2009. Los resultados indican que: 1) la necesidad de agua de los cultivos y el requerimiento de agua de riego del trigo de primavera presentó una tendencia a la baja, debido a la variación de los factores climáticos en el período de estudio; 2) bajo la influencia combinada del aumento de rendimiento de los cultivos y la disminución en la evapotranspiración del cultivo, la huella hídrica disminuyó durante el período de estudio, tendiendo a 0,025 m3 kg-1 año-1, 3) la tasa de contribución total de los factores climáticos en la disminución de la huella hídrica de trigo de primavera durante el período de estudio fue sólo -10,45%. Estos resultados sugieren que, en gran medida, la huella hídrica de un cultivo está más determinada por la gestión agrícola que por el agro-clima de la región y sus variaciones. Sin embargo, debemos prestar atención a la adaptación de estrategias eficaces para minimizar el riesgo provocado por el cambio climático en la producción agrícola.