Solid solubility in the CeTi2O6–CeTiNbO6 system: a multi-element X-ray spectroscopic study

In order to investigate the limits of solid solubility between Ce-brannerite (CeTi2O6) and Ce-aeschynite (CeTiNbO6), materials in the system CeTi2–xNbxO6 have been produced by a solid state route and characterised by XRD and XANES at the Ce L3-, Ti K- and Nb K-edges, including Rietveld method refinements and linear combination fitting. Significant solid solubility was observed at the brannerite end, with near-single-phase brannerite observed for x = 0.2, 0.4, and only minor aeschynite observed where x = 0.6 which was identified as exceeding the limit of solubility of Nb. All Nb was present as Nb5+, with the substitution of Nb5+ into the brannerite structure permitted by the reduction of the same fraction of Ce4+ to Ce3+. This work expands the crystal chemistry of the titanate brannerites, with Ce-site oxidation states of less than 4+ being possible where sufficient charge-balancing species are available on the Ti-site

Impact of rare earth ion size on the phase evolution of MoO3-containing aluminoborosilicate glass-ceramics

Transition metal and rare earth (RE) elements are important fission products present in used nuclear fuel, which in high concentrations tend to precipitate crystalline phases in vitreous nuclear waste forms. Two phases of particular interest are powellite (CaMoO4) and oxyapatite (Ca2RE8(SiO4)6O2). The glass compositional dependencies controlling crystallization of these phases on cooling from the melt are poorly understood. In the present study, the effect of rare earth identity and modifier cation field strength on powellite and apatite crystallization were studied in a model MoO3-containing alkali/alkaline-earth aluminoborosilicate glass with focus on (1) influence of rare earth cation size (for RE3+: Ce, La, Nd, Sm, Er, Yb) and (2) influence of non-framework cations (RE3+, Mo6+, Na+, Ca2+). Quenched glasses and glass-ceramics (obtained by slow cooling) were characterized by X-ray diffraction (XRD), Raman spectroscopy, X-ray absorption spectroscopy (XAS), and electron probe microanalysis (EPMA). All samples were X-ray amorphous upon quenching, except the Ce-containing composition which crystallized ceria (CeO2), and the sample devoid of any rare earth cations which crystallized powellite. On heat treatment, powellite and oxyapatite crystallized in the majority of the samples, with the former crystallizing in the volume and the latter on the surface. The EPMA results confirmed a small concentration of boron in the oxyapatite crystal structure. RE cations were incorporated in the glass, as well as in powellite, oxyapatite, and in the case of Yb3+, keiviite (Yb2Si2O7). Raman spectroscopy showed that the primary vibration band for molybdate MoO42−in the glasses was strongly affected by the ionic field strength of the modifying cations (alkali, alkaline earth, and RE), suggesting their proximity to the MoO42−ions in the glass, though the Mo–O bond length and coordination according to XAS suggested little local change

Compositional Dependence of Solubility/Retention of Molybdenum Oxides in Aluminoborosilicate-Based Model Nuclear Waste Glasses

Molybdenum oxides are an integral component of the high-level waste streams being generated from the nuclear reactors in several countries. Although borosilicate glass has been chosen as the baseline waste form by most of the countries to immobilize these waste streams, molybdate oxyanions (MoO42–) exhibit very low solubility (∼1 mol %) in these glass matrices. In the past three to four decades, several studies describing the compositional and structural dependence of molybdate anions in borosilicate and aluminoborosilicate glasses have been reported in the literature, providing a basis for our understanding of fundamental science that governs the solubility and retention of these species in the nuclear waste glasses. However, there are still several open questions that need to be answered to gain an in-depth understanding of the mechanisms that control the solubility and retention of these oxyanions in glassy waste forms. This article is focused on finding answers to two such questions: (1) What are the solubility and retention limits of MoO3 in aluminoborosilicate glasses as a function of chemical composition? (2) Why is there a considerable increase in the solubility of MoO3 with incorporation of rare-earth oxides (for example, Nd2O3) in aluminoborosilicate glasses? Accordingly, three different series of aluminoborosilicate glasses (compositional complexity being added in a tiered approach) with varying MoO3 concentrations have been synthesized and characterized for their ability to accommodate molybdate ions in their structure (solubility) and as a glass-ceramic (retention). The contradictory viewpoints (between different research groups) pertaining to the impact of rare-earth cations on the structure of aluminoborosilicate glasses are discussed, and their implications on the solubility of MoO3 in these glasses are evaluated. A novel hypothesis explaining the mechanism governing the solubility of MoO3 in rare-earth containing aluminoborosilicate glasses has been proposed

Viscosity bounds in liquids with different structure and bonding types

Recently, it was realized that liquid viscosity has a lower bound which is nearly constant for all liquids and is governed by fundamental physical constants. This was supported by experimental data in noble and molecular liquids. Here, we perform large-scale molecular dynamics simulations to ascertain this bound in two other important liquid types: the ionic molten salt system LiF and metallic Pb. We find that these ionic and metallic systems similarly have lower viscosity bounds corresponding to the minimum of kinematic viscosity of ∼10-7m2/s. We show that this agrees with experimental data in other systems with different structures and bonding types, including noble, molecular, metallic, and covalent liquids. This expands the universality of viscosity bounds into the main system types known

Attribution of divergent northern vegetation growth responses to lengthening non-frozen seasons using satellite optical-NIR and microwave remote sensing

The non-frozen (NF) season duration strongly influences the northern carbon cycle where frozen (FR) temperatures are a major constraint to biological processes. The landscape freeze-thaw (FT) signal from satellite microwave remote sensing provides a surrogate measure of FR temperature constraints to ecosystem productivity, trace gas exchange, and surface water mobility. We analysed a new global satellite data record of daily landscape FT dynamics derived from temporal classification of overlapping SMMR and SSM/I 37 GHz frequency brightness temperatures (Tb). The FT record was used to quantify regional patterns, annual variability, and trends in the NF season over northern (≥45°N) vegetated land areas. The ecological significance of these changes was evaluated against satellite normalized difference vegetation index (NDVI) anomalies, estimated moisture and temperature constraints to productivity determined from meteorological reanalysis, and atmospheric CO2 records. The FT record shows a lengthening (2.4 days decade-1; p < 0.005) mean annual NF season trend (1979-2010) for the high northern latitudes that is 26% larger than the Northern Hemisphere trend. The NDVI summer growth response to these changes is spatially complex and coincides with local dominance of cold temperature or moisture constraints to productivity. Longer NF seasons are predominantly enhancing productivity in cold temperature-constrained areas, whereas these effects are reduced or reversed in more moisture-constrained areas. Longer NF seasons also increase the atmospheric CO2 seasonal amplitude by enhancing both regional carbon uptake and emissions. We find that cold temperature constraints to northern growing seasons are relaxing, whereas potential benefits for productivity and carbon sink activity are becoming more dependent on the terrestrial water balance and supply of plant-available moisture needed to meet additional water use demands under a warming climate. © 2014 Taylor & Francis

Applying laboratory methods for durability assessment of vitrified material to archaeological samples

Laboratory testing used to assess the long-term chemical durability of nuclear waste forms may not be applicable to disposal because the accelerated conditions may not represent disposal conditions. To address this, we examine the corrosion of vitrified archeological materials excavated from the near surface of a ~1500-year old Iron Age Swedish hillfort, Broborg, as an analog for the disposal of vitrified nuclear waste. We compare characterized site samples with corrosion characteristics generated by standard laboratory durability test methods including the product consistency test (PCT), the vapor hydration test (VHT), and the EPA Method 1313 test. Results show that the surficial layer of the Broborg samples resulting from VHT displays some similarities to the morphology of the surficial layer formed over longer timescales in the environment. This work provides improved understanding of long-term glass corrosion behavior in terms of the thickness, morphology, and chemistry of the surficial features that are formed

Metabolic response to a ketogenic breakfast in the healthy elderly.

OBJECTIVE: To determine whether the metabolism of glucose or ketones differs in the healthy elderly compared to young or middle-aged adults during mild, short-term ketosis induced by a ketogenic breakfast. DESIGN AND PARTICIPANTS: Healthy subjects in three age groups (23 +/- 1, 50 +/- 1 and 76 +/- 2 y old) were given a ketogenic meal and plasma beta -hydroxybutyrate, glucose, insulin, triacylglycerols, total cholesterol, non-esterified fatty acids and breath acetone were measured over the subsequent 6 h. Each subject completed the protocol twice in order to determine the oxidation of a tracer dose of both carbon-13 (13C) glucose and 13C-beta-hydroxybutyrate. The tracers were given separately in random order. Apolipoprotein E genotype was also determined in all subjects. RESULTS: Plasma glucose decreased and beta-hydroxybutyrate, acetone and insulin increased similarly over 6 h in all three groups after the ketogenic meal. There was no significant change in cholesterol, triacylglycerols or non-esterified fatty acids over the 6 h. 13C-glucose and 13C-beta-hydroxybutyrate oxidation peaked at 2-3 h postdose for all age groups. Cumulative 13C-glucose oxidation over 24 h was significantly higher in the elderly but only versus the middle-aged group. There was no difference in cumulative 13C-beta-hydroxybutyrate oxidation between the three groups. Apolipoprotein E (epsilon 4) was associated with elevated fasting cholesterol but was unrelated to the other plasma metabolites. CONCLUSION: Elderly people in relatively good health have a similar capacity to produce ketones and to oxidize 13C-beta-hydroxybutyrate as middle-aged or young adults, but oxidize 13C-glucose a little more rapidly than healthy middle-aged adult

Glass-bonded iodosodalite waste form for immobilization of 129I

Immobilization of radioiodine is an important requirement for current and future nuclear fuel cycles. Iodosodalite [Na8(AlSiO4)6I2] was synthesized hydrothermally from metakaolin, NaI, and NaOH. Dried unwashed sodalite powders were used to synthesize glass-bonded iodosodalite waste forms (glass composite materials) by heating pressed pellets at 650, 750, or 850 °C with two types of sodium borosilicate glass binders. These heat-treated specimens were characterized with X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, thermal analysis, porosity and density measurements, neutron activation analysis, and inductively-coupled plasma mass spectrometry. For the best waste form produced (pellets mixed with 10 mass% of glass binder and heat-treated at 750 °C), the maximum possible elemental iodine loading was 19.8 mass%, but only ∼8–9 mass% waste loading of iodine was retained in the waste form after thermal processing. Other pellets with higher iodine retention either contained higher porosity or were incompletely sintered. ASTM C1308 and C1285 (product consistency test, PCT) experiments were performed to understand chemical durability under diffusive and static conditions. The C1308 test resulted in significantly higher normalized loss compared to the C1285 test, most likely because of the strong effect of neutral pH solution renewal and prevention of ion saturation in solution. Both experiments indicated that release rates of Na and Si were higher than for Al and I, probably due to a poorly durable Na-Si-O phase from the glass bonding matrix or from initial sodalite synthesis; however the C1308 test result indicated that congruent dissolution of iodosodalite occurred. The average release rates of iodine obtained from C1308 were 0.17 and 1.29 g m-2 d-1 for 80 or 8 m−1, respectively, and the C1285 analysis gave a value of 2 × 10−5 g m-2 d-1, which is comparable to or better than the durability of other iodine waste forms

Effect of Ti4+ on the structure of nepheline (NaAlSiO4) glass

In this study, the effect of Ti4+ on the structure of nepheline glass (NaAlSiO4) is investigated as SiO2 is systematically replaced with TiO2. Traditionally, TiO2 is considered to be a nucleating agent for silicate crystallization but can also be incorporated into the glass network in relatively large amounts as either a network former or modifier depending on its coordination with oxygen. To determine the effect of Ti4+ on the structure of nepheline glass, X-ray and neutron pair distribution function (PDF) analysis paired with Empirical Potential Structure Refinement (EPSR) were conducted and are supplemented with Raman spectroscopy, electron probe microanalysis, and X-ray absorption spectroscopy (including Extended X-ray Absorption Fine Structure, EXAFS). Through these methods, it has been found that up to 15 mol% (16 wt%) TiO2 can incorporate into the glass network as a four-fold coordinated species, with a minor contribution of higher coordinated Ti. Between NaAlTi0.1Si0.9O4 and NaAlTi0.2Si0.8O4, EXAFS suggests a local structure change in the second coordination sphere of Ti, which changes from Ti-Ti to Ti-Al. Raman spectroscopy also suggests that as Ti content increases, the Na environment becomes more ordered. These results suggest that the Ti activity coefficient and its isotopic fractionation for magnetite and other Ti-bearing minerals should be fairly constant in polymerized melts, such as metaluminous and peraluminous rhyolites