Cyclic Voltammetric Experiment - Simulation. Comparisons of the Complex Mechanism Associated with Electrochemical Reduction of Zr4+ in LiCl-KCl Eutectic Molten Salt

Nuclear energy increasingly represents an important option for generating largely clean CO2-free electricity and zirconium is a fission product that is expected to be present in irradiated fuels. The present investigation addresses the electrochemical reduction of Zr4+ to Zro in LiCl - KCl eutectic molten salt in the temperature range 425–550◦C using cyclic voltammetry (CV), square-wave voltammetry (SWV) and bulk electrolysis. Simulations of the CV data indicate that the initial reduction proceeds through surface confined steps: Zr4+* + 2e− ↔Zr2+* and Zr2+* + 2e− ↔Zr* processes (* adsorbed species) followed by a peak-shaped complex diffusion controlled step that consists of a combination of closely spaced processes associated with the reactions Zr4+ + 4e− →Zr and Zr4+ + 3e− →Zr+*. Zr+*, probably in the form of ZrCl* is then further reduced to Zro* at even more negative potentials. The simulations provide the first quantitative analysis of the thermodynamics and kinetics of the Zr4+ reduction in the LiCl-KCl eutectic

The Role of Th-U Minerals in Assessing the Performance of Nuclear Waste Forms

Materials designed for nuclear waste disposal include a range of ceramics, glass ceramics and glass waste forms. Those with crystalline phases have provided the momentum for studies of minerals as a means to understand aspects of waste-form crystal chemistry, behaviour in aqueous systems and radiation damage over geological periods of time. Although the utility of natural analogue studies varies, depending upon the degree of analogy to the proposed geological repository and other factors such as chemical composition, the available data suggest that Th-U host phases such as brannerite, monazite, pyrochlore, zircon and zirconolite are resistant generally to dissolution in aqueous fluids at low temperatures. Geochemical durability may or may not extend to hydrothermal systems depending on the specifics of fluid composition, temperature and pressure. At elevated temperatures, for example, davidite may break down to new phase assemblages including titanite, ilmenite and rutile. Perovskite is generally less resistant to dissolution at low temperatures and breaks down to TiO2, releasing A-site cations to the aqueous fluid. Studies of radiation damage indicate that the oxide and silicate phases become amorphous as a result of the gradual accumulation of alpha-recoil collision cascades. Monazite tends to remain crystalline on geological time scales, a very attractive property that potentially eliminates major changes in physical properties such as density and volume, thereby reducing the potential for cracking, which is a major concern for zircon. In spite of recent success in describing the behaviour of Th-U minerals in geological systems, considerable work remains in order to understand the P-T-X conditions during alteration and T-t history of the host rocks

Experimental and simulation study of the electrode reaction mechanism of La3+ in LiCl-KCl eutectic molten salt

Nuclear energy increasingly represents an important option for generating largely clean CO2-free electricity. The present investigation addressed the electrochemical reduction of La3+, a rare earth element, in LiCl - KCl eutectic molten salt in the temperature range 450–550°C using transient techniques such as cyclic voltammetry (CV) and square-wave voltammetry (SWV). Simulation of the CV data suggested a reaction mechanism in which lanthanum reduction occurred in a single three-electron step (La3+ + 3e− → La°). The rate constant, k° was determined to be 5.7 x 10−3, 14.6 x 10−3 and 31.7 x 10−3 cm/s and the Matsuda et al.1 dimensionless parameter Ʌ was 0.82, 1.52 and 2.89 for temperatures of 450, 500 and 550°C, respectively and therefore it was concluded that the was process quasi reversible

Radiation effects in Zr and Hf containing garnets

Garnets have been considered as host phases for the safe immobilisation of high-level nuclear waste, as they have been shown to accommodate a wide range of elements across three different cation sites, such as Ca, Y, Mn on the a-site, Fe, Al, U, Zr, and Ti on the b-site, and Si, Fe, Al on the c-site. Garnets, due to their ability to have variable composition, make ideal model materials for the examination of radiation damage and recovery in nuclear materials, including as potential waste forms. Kimzeyite, Ca3Zr2FeAlSiO12, has been shown naturally to contain up to 30 wt% Zr, and has previously been examined to elucidate both the structure and ordering within the lattice. This study examines the effects of radiation damage and recovery using in-situ ion beam irradiation with 1 MeV Kr ions at the IVEM-TANDEM facility, Argonne National Laboratory. The complementary Hf containing system Ca3Hf2FeAlSiO12 was also examined, and found to have a different response to irradiation damage. A sample of irradiated Ca3Zr2FeAlSiO12, at 1000 K, was characterised using aberration corrected (S)TEM and found to contain discreet, nano-sized, crystalline Fe rich particles, indicating a competing process during recovery is occurring

Retention of Actinides in Natural Pyrochlores and Zirconolites

Natural pyrochlore and zirconolite undergo a crystalline-aperi­odic transformation caused by alpha-decay of 232Th and 2380 at dose levels between 2 X 1014 and 3 X 1017 a/mg. The principal effects of the transformation are volume expansion and micro­fracturing, providing potential pathways for fluids. Geochemical alteration of the minerals may occur under hydrothermal conditions or in low temperature, near surface environments, but Th and U usually remain immobile and can be retained for time scales up to 109 years. However, the Th-U isotope systematics of a zirconolite-bearing vein and dolomite host rock may provide evidence for disequilibrium between 230Th, 234U and 238U

New insights into phase distribution, phase composition and disorder in Y2(Zr,Sn) 2O7 ceramics from NMR spectroscopy

A combination of 89Y and 119Sn NMR spectroscopy and DFT calculations are used to investigate phase evolution, local structure and disorder in Y2Zr2−xSnxO7 ceramics, where a phase change is predicted, from pyrochlore to defect fluorite, with increasing Zr content. The ability of NMR to effectively probe materials that exhibit positional and compositional disorder provides insight into the atomic-scale structure in both ordered and disordered phases and, by exploiting the quantitative nature of the technique, we are able to determine detailed information on the composition of the phase(s) present and the average coordination number (and next-nearest neighbour environment) of the cations. In contrast to previous studies, a more complex picture of the phase variation with composition emerges, with single-phase pyrochlore found only for the Sn end member, and a single defect fluorite phase only for x = 0 to 0.6. A broad two-phase region is observed, from x = 1.8 to 0.8, but the two phases present have very different composition, with a maximum of 13% Zr incorporated into the pyrochlore phase, whereas the composition of the defect fluorite phase varies throughout. Preferential ordering of the anion vacancies in the defect fluorite phase is observed, with Sn only ever found in a six-coordinate environment, while remaining vacancies are shown to be more likely to be associated with Zr than Y. Our findings are then discussed in the light of those from previous studies, many of which utilize diffraction-based approaches, where, in most cases, a single phase of fixed composition has been assumed for the refinement procedure. The significant and surprising differences encountered demonstrate the need for complementary approaches to be considered for a detailed and accurate picture of both the long- and short-range structure of a solid to be achieved

The Quantification of Radiation Damage in Orthophosphates Using Confocal μ-Luminescence Spectroscopy of Nd3+

In this study, we present a new concept based on the steady-state, laser-induced photoluminescence of Nd3+, which aims at a direct determination of the amorphous fraction fa in monazite- and xenotime-type orthophosphates on a micrometer scale. Polycrystalline, cold-pressed, sintered LaPO4, and YPO4 ceramics were exposed to quadruple Au-ion irradiation with ion energies 35 MeV (50% of the respective total fluence), 22 MeV (21%), 14 MeV (16%), and 7 MeV (13%). Total irradiation fluences were varied in the range 1.6 × 1013–6.5 × 1013 ions/cm2. Ion-irradiation resulted in amorphization and damage accumulation unto a depth of ~5 μm below the irradiated surfaces. The amorphous fraction created was quantified by means of surface-sensitive grazing-incidence X-ray diffraction and photoluminescence spectroscopy using state-of-the-art confocal spectrometers with spatial resolution in the μm range. Monazite-type LaPO4 was found to be more susceptible to ion-irradiation induced damage accumulation than xenotime-type YPO4. Transmission electron microscopy of lamella cut from irradiated surfaces with the focused-ion beam technique confirmed damage depth-profiles with those obtained from PL hyperspectral mapping. Potential analytical advantages that arise from an improved characterization and quantification of radiation damage (i.e., fa) on the μm-scale are discussed

Modulation of Equatorial Currents and Tropical Instability Waves During the 2021 Atlantic Niño

Every few years the eastern equatorial Atlantic Ocean is significantly warmer than usual during boreal summer. Such warm events are referred to as Atlantic Niño events, and share similarities with El Niño events in the Pacific. In 2021, the strongest Atlantic Niño in at least four decades was observed in the equatorial Atlantic. This study is the first that investigates the complex interaction between Atlantic Niño, tropical Atlantic upper-ocean currents, and equatorial waves based on various observational data sets. We show that the developing 2021 Atlantic Niño weakened both the background flow and the variability of near-surface currents in May, which in turn largely reduced the strength of intraseasonal (20–50 days) waves that are usually generated by instability of the upper-ocean zonal currents. As a consequence, the cooling effect that these waves usually have north of the equator and the warming effect along the equator vanished from May to July 2021. Interestingly, variability of chlorophyll concentration was enhanced, suggesting that enhanced meridional chlorophyll gradients compensated for reduced wave activity. Keywords: Equatorial upwelling, Tropical Instability Waves, Atlantic Niño, Equatorial currents, SST, Meridional Chl-a gradient