Nature and coordination geometry of geologically relevant aqueous Uranium(VI) complexes up to 400 ºC: A review and new data.

The structure of the uranyl aqua ion (UO22+) and a number of its inorganic complexes (specifically, UO2Cl+, UO2Cl20, UO2SO40, [Formula: see text] , [Formula: see text] and UO2OH42-) have been characterised using X-Ray absorption spectroscopy/extended X-Ray absorption fine structure (XAS/EXAFS) at temperatures ranging from 25 to 326 ºC. Results of ab initio molecular dynamics (MD) calculations are also reported for uranyl in chloride and sulfate-bearing fluids from 25 to 400 ºC and 600 bar to 20 kilobar (kb). These results are reported alongside a comprehensive review of prior structural characterisation work with particular focus given to EXAFS works to provide a consistent and up-to-date view of the structure of these complexes under conditions relevant to U mobility in ore-forming systems and around high-grade nuclear waste repositories. Regarding reported EXAFS results, average equatorial coordination was found to decrease in uranyl and its sulfate and chloride complexes as temperature rose - the extent of this decrease differed between species and solution compositions but typically resulted in an equatorial coordination number of ∼3-4 at temperatures above 200 ºC. The [Formula: see text] complex was observed at temperatures from 25 to 247 ºC and exhibited no major structural changes over this temperature range. UO2OH42- exhibited only minor structural changes over a temperature range from 88 to 326 ºC and was suggested to manifest fivefold coordination with four hydroxyl molecules and one water molecule around its equator. Average coordination values derived from fits of the reported EXAFS data were compared to average coordination values calculated using the experimentally derived thermodynamic data for chloride complexes reported by Dargent et al. (2013) and Migdisov et al. (2018b), and for sulfate complexes reported by Alcorn et al. (2019) and Kalintsev et al. (2019). Sulfate EXAFS data were well described by available thermodynamic data, and chloride EXAFS data were described well by the thermodynamic data of Migdisov et al. (2018b), but not by the data of Dargent et al. (2013). The ab initio molecular dynamics calculations confirmed the trends in equatorial coordination observed with EXAFS and were also able to provide an insight into the effect of pressure in equatorial water coordination - for a given temperature, higher pressures appear to lead to a greater number of equatorially bound waters counteracting the temperature effect.

Ingenious Fabrication of Ag-Filled Porous Anodic Alumina Films as Powerful SERS Substrates for Efficient Detection of Biological and Organic Molecules.

Surface-enhanced Raman scattering (SERS) has been widely used to effectively detect various biological and organic molecules. This detection method needs analytes adsorbed onto a specific metal nanostructure, e.g., Ag-nanoparticles. A substrate containing such a structure (called SERS substrate) is user-friendly for people implementing the adsorption and subsequent SERS detection. Here, we report on powerful SERS substrates based on efficient fabrication of Ag-filled anodic aluminum oxide (AAO) films. The films contain many nanopores with small as-grown inter-pore gap of 15 nm. The substrates are created by electrochemically depositing silver into nanopores without an additional pore widening process, which is usually needed for conventional two-step AAO fabrication. The created substrates contain well-separated Ag-nanoparticles with quite a small inter-particle gap and a high number density (2.5 × 1010 cm-2). We use one-step anodization together with omitting additional pore widening to improve the throughput of substrate fabrication. Such substrates provide a low concentration detection limit of 10-11 M and high SERS enhancement factor of 1 × 106 for rhodamine 6G (R6G). The effective detection of biological and organic molecules by the substrate is demonstrated with analytes of adenine, glucose, R6G, eosin Y, and methylene blue. These results allow us to take one step further toward the successful commercialization of AAO-based SERS substrates.

Kinetically driven successive sodic and potassic alteration of feldspar.

The dynamic evolutions of fluid-mineral systems driving large-scale geochemical transformations in the Earth's crust remain poorly understood. We observed experimentally that successive sodic and potassic alterations of feldspar can occur via a single self-evolved, originally Na-only, hydrothermal fluid. At 600 °C, 2 kbar, sanidine ((K,Na)AlSi3O8) reacted rapidly with a NaCl fluid to form albite (NaAlSi3O8); over time, some of this albite was replaced by K-feldspar (KAlSi3O8), in contrast to predictions from equilibrium reaction modelling. Fluorine accelerated the process, resulting in near-complete back-replacement of albite within 1 day. These findings reveal that potassic alteration can be triggered by Na-rich fluids, indicating that pervasive sequential sodic and potassic alterations associated with mineralization in some of the world's largest ore deposits may not necessarily reflect externally-driven changes in fluid alkali contents. Here, we show that these reactions are promoted at the micro-scale by a self-evolving, kinetically-driven process; such positive feedbacks between equilibrium and kinetic factors may be essential in driving pervasive mineral transformations.

The nature of Pu-bearing particles from the Maralinga nuclear testing site, Australia.

The high-energy release of plutonium (Pu) and uranium (U) during the Maralinga nuclear trials (1955-1963) in Australia, designed to simulate high temperature, non-critical nuclear accidents, resulted in wide dispersion µm-sized, radioactive, Pu-U-bearing 'hot' particles that persist in soils. By combining non-destructive, multi-technique synchrotron-based micro-characterization with the first nano-scale imagining of the composition and textures of six Maralinga particles, we find that all particles display intricate physical and chemical make-ups consistent with formation via condensation and cooling of polymetallic melts (immiscible Fe-Al-Pu-U; and Pb ± Pu-U) within the detonation plumes. Plutonium and U are present predominantly in micro- to nano-particulate forms, and most hot particles contain low valence Pu-U-C compounds; these chemically reactive phases are protected by their inclusion in metallic alloys. Plutonium reworking was observed within an oxidised rim in a Pb-rich particle; however overall Pu remained immobile in the studied particles, while small-scale oxidation and mobility of U is widespread. It is notoriously difficult to predict the long-term environmental behaviour of hot particles. Nano-scale characterization of the hot particles suggests that long-term, slow release of Pu from the hot particles may take place via a range of chemical and physical processes, likely contributing to on-going Pu uptake by wildlife at Maralinga.

Selective radionuclide co-sorption onto natural minerals in environmental and anthropogenic conditions.

Anthropogenic activities can redistribute the constituents of naturally occurring radioactive materials (NORM), posing potential hazards to populations and ecosystems. In the present study, the co-sorption of several RN from the U decay chain- 238U, 230Th, 226Ra, 210Pb and 210Po, onto common minerals associated with mining activities (chalcopyrite, bornite, pyrite and barite) was investigated, in order to identify the various factors that control long-term NORM mobility and retentivity in environmental acid-mine drainage systems and hydrometallurgical processing. The results show selective RN co-sorption to the various natural minerals, suggesting that mineral-specific mechanisms govern the variability in NORM mobility and retentivity. Both 226Ra and 210Po underwent significant sorption onto the natural minerals investigated in this study. The order of co-sorption in sulfate media for chalcopyrite and bornite was 210Po>226Ra>206Pb>210Pb>238U/230Th. Conversely, both pyrite and barite showed increased affinity for 226Ra; the order of co-sorption in sulfate media was 226Ra>210Po>206Pb/210Pb>238U/230Th for pyrite and 226Ra>206Pb/210Pb>230Th/238U/210Po for barite. Similar orders of co-sorption were observed in the nitrate media: for chalcopyrite and bornite the order was 210Po>226Ra/206Pb/210Pb/238U/230Th compared to 226Ra>210Po/206Pb/210Pb/238U/230Th for pyrite and barite. The behavior of 210Po was found to the anomalous: in both sulfate and nitrate solutions, 210Po had little affinity for barite compared to the sulfides. Thermodynamic modeling indicated the formation of a reduced PoS(s) phase at the surface of sulfide minerals, leading to the suggestion that 210Po likely undergoes reductive precipitation on the surface of sulfide minerals. The high sorption of both 206Pb and 210Pb observed in the sulfate systems were likely as a result of co-precipitation as insoluble anglesite compared to nitrate where they mainly remained in solution. Overall, barite showed the highest affinity for 226Ra, given its propensity to sorb 226Ra (similar ionic size). Both 238U and 230Th were highly mobile in acidic sulfate and nitrate solutions. The results highlighted here identify the various constraints on the natural variability and fractionation of NORM in the environment, as well as the mineral-specific mechanisms that control co-sorption of RN. This information provides a framework for predicting RN transport within soils and ground waters with variable geochemical conditions and in metallurgical extraction processes, in order to develop effective strategies towards NORM mitigation.

Localised solution environments drive radionuclide fractionation in uraninite.

We explore the role of various solution environments - chloride brines, acid mine drainage (sulfate) and groundwater (carbonate), as well as pore pressure in producing secular disequilibrium among the various radionuclides (RN) in the U-decay series upon leaching of uraninite - the most abundant U-ore and a widespread accessory mineral in U-rich rocks. We observed that the end products of the U-decay chain, 206Pb and 207Pb, exist primarily at the surface/edges of grains or within large pores in the uraninite. In contrast, the intermediate daughters 226Ra, 210Pb, 210Po, and 234/230Th, exist primarily within the bulk of uraninite, requiring breakdown by leaching for subsequent mobility to occur. Overall, pore pressure had little effect on RN mobility, with solution environment being the primary factor in creating significant mobility and disequilibrium among the RN, as it drives the initial breakdown of uraninite and influences the subsequent differential solubility of individual RNs. This was particularly the case for carbonate-bearing fluids, leading to significant fractionation of the various daughter RN arising from variable complexation and sorption phenomena. Understanding the geochemical behaviour of the RN in the U-decay series is important for predicting and managing the risks associated with RN in both environmental (acid-mine drainage) and engineered (metallurgical extraction) processes. Effective modelling of long-term RN behaviour should incorporate this strong relative fractionation caused by contrasting geochemical behaviour of individual RN during and after their release into the water from uraninite and subsequent interaction with the surrounding aquifer host rocks.

A comparative bio-oxidative leaching study of synthetic U-bearing minerals: Implications for mobility and retention.

In this study, the effects of bio-oxidative leaching on several synthetic uranium minerals - Uraninite [UO2], Pitchblende [U3O8], Coffinite [USiO4], Brannerite [UTi2O6] and Betafite [(U,Ca)2(Ti,Nb,Ta)2O7]) compared to chemical leaching in the presence of pyrite was investigated. In all cases, bio-oxidative leaching was faster and increased overall %U extraction compared to chemical leaching. The results indicated that the bio-oxidative leachability of the uranium minerals was in the order: pitchblende≈ uraninite > coffinite>> brannerite > betafite. The leaching of pitchblende and uraninite was fast and complete; U extraction from coffinite was slower over 28 days' during the bioleaching. The use of thermophiles doubled the recovery of U from refractory brannerite. The results highlight the significant capability of bio-leaching in the recovery of U from brannerite; both mesophilic and thermophilic bacteria was found to enhance U recovery likely through enhanced breakdown of the titanate structure. Brannerite is often found in significant quantities within ore tailings due to its refractory nature, which can lead to subsequent release of U into the environment. Conversely, betafite is highly stable in the presence of mesophile and moderate thermophiles, which suggested that betafite materials can be a viable future host for long term storage for spent nuclear fuels.

Understanding the mobility and retention of uranium and its daughter products.

Knowledge of the behavior of technologically enhanced naturally occurring radioactive materials derived through the decay of U and its daughter products, and their subsequent fractionation, mobilization and retention, is essential to develop effective mitigation strategies and long-term radiological risk prediction. In the present study, multiple state-of-the-art, spatially resolved micro-analytical characterization techniques were combined to systematically track the liberation and migration of radionuclides (RN) from U-bearing phases in an Olympic Dam Cu flotation concentrate following sulfuric-acid-leach processing. The results highlighted the progressive dissolution of U-bearing minerals (mainly uraninite) leading to the release, disequilibrium and ultimately upgrade of daughter RN from the parent U. This occurred in conjunction with primary Cu-Fe-sulfide minerals undergoing coupled-dissolution reprecipitation to the porous secondary Cu-mineral, covellite. The budget of RN remaining in the leached concentrate was split between RN still hosted in the original U-bearing minerals, and RN that were mobilized and subsequently sorbed/precipitated onto porous covellite and auxiliary gangue mineral phases (e.g. barite). Further grinding of the flotation concentrate prior to sulfuric-acid-leach led to dissolution of U-bearing minerals previously encapsulated within Cu-Fe-sulfide minerals, resulting in increased release and disequilibrium of daughter RN, and causing further RN upgrade. The various processes that affect RN (mobility, sorption, precipitation) and sulfide minerals (coupled-dissolution reprecipitation and associated porosity generation) occur continuously within the hydrometallurgical circuit, and their interplay controls the rapid and highly localized enrichment of RN. The innovative combination of tools developed here reveal the heterogeneous distribution and fractionation of the RN in the ores following hydrometallurgical treatment at nm to cm-scales in exquisite detail. This approach provides an effective blueprint for understanding of the mobility and retention of U and its daughter products in complex anthropogenic and natural processes in the mining and energy industries.

The aqueous chemistry of polonium (Po) in environmental and anthropogenic processes.

The longest-lived naturally occurring isotope of polonium is polonium-210, one of the daughters of uranium-238 (138 days half-life). As a daughter radionuclide of radon-222, polonium-210 can become enriched in pore fluids in U-bearing rocks, leading to contents in excess of 100 Bq.g-1 in some products from the mineral, coal, oil and gas industries (e.g., anode slimes in copper refinement; sludge from the oil and gas industry). Since 2006, IAEA recommendation limits require polonium and other radionuclides from the U- and Th-series decay to be regulated for products and wastes that contain >1 Bq.g-1, which results in the classification of large amounts of industrial products and waste as radioactive. To develop effective methods for polonium removal and/or control, it is necessary to acquire an understanding of its aqueous chemistry. Based on a review of available experimental data, we developed a self-consistent thermochemical model for polonium in inorganic aqueous solutions. Polonium exists mainly in two oxidation states in aqueous solutions: Po(IV) and Po(II). The importance of Po(II) is unique, as Te(II) or Se(II) complexes do not appear to play a significant role in aqueous solution at room temperature. The model is used to discuss polonium speciation in some environmental and process waters.

Radionuclide disposal using the pyrochlore supergroup of minerals as a host matrix-A review.

Since the first large scale commercial nuclear power plant became operational in 1958, the nuclear power industry has been faced with the growing problem of disposal of radionuclides produced from nuclear fission. The current global production of high level nuclear waste is approximately 10,000 metric tons p.a., consisting predominantly of uranium, plutonium, actinides and other minor radionuclides. Developing a safe and cost-effective method for long term storage and disposal of nuclear waste is a key issue of concern to the nuclear power industry. A promising approach to radionuclide disposal is incorporation of the nuclear waste into refractory oxide host minerals or mineral matrices. This technique offers lower leaching rates when compared to the commonly used glass-based vitrification approaches. The refractory pyrochlore supergroup of minerals are particularly attractive for this purpose as they can incorporate considerable amounts of the radionuclides: 93Zr, 133Ba, 135Cs, Th, U, 238Pu, and 244Cm, while demonstrating very low leachability. This review examines the structural, compositional and chemical properties of radionuclide-containing pyrochlore supergroup minerals. Compiled leaching data for radionuclides hosted in pyrochlores demonstrates that these materials offer a high degree of aqueous durability making them strong candidates for radionuclide disposal, offering a viable storage alternative to traditional vitrification methods.

Zeolitic intralayer microchannels of magadiite, a natural layered silicate, to boost green organic synthesis.

Despite the considerable attention given to the applications of magadiite in previous research, the properties of this natural layered silicate have remained mysterious due to the lack of crystal structure information. On the other hand, no one has doubted the intercalation capability between the layers. Here we succeed in determining the structure of magadiite using X-ray pair distribution functions and synchrotron powder diffractometry. We discover unexpected zeolitic microchannels within the layers. We describe efficient synthesis of 100% pure benzoic acid from toluene by using magadiite as an additive in a TiO2 photocatalytic system oxidizing toluene. Based on the uncovered structure of magadiite, we clarify the mechanism of this unique photocatalytic system: the microchannels of magadiite not only separate/accommodate the desired partially oxidized product formed on TiO2 but also prevent the accumulation of the overoxidized products on the TiO2 surface that deactivates the photocatalytic activity.

Synthesis and characterisation of the uranium pyrochlore betafite [(Ca,U)2(Ti,Nb,Ta)2O7].

Betafite of composition [(Ca,U)2(Ti,Nb,Ta)2O7] was prepared via a solid state synthesis route. The synthesis was shown to be sensitive to initial reactant ratios, the atmosphere used (oxidising, neutral, reducing) and time. The optimum conditions for the synthesis of betafite were found to be heating the reactants required at 1150°C for 48 h under an inert gas atmosphere. XRD characterisation revealed that the synthesised betafite contained minor impurities. EPMA analysis of a sectioned surface showed very small regions of Ca-free betafite on grain boundaries as well as minor rutile impurities. Some heterogeneity between the Nb:Ta ratio was observed by quantitative EPMA but was generally within the nomenclature requirements stated for betafite. SEM analysis revealed the synthesised betafite was comprised mostly of hexaoctohedral crystals of ∼ 3 µm in diameter. XPS analysis of the sample showed that the uranium in the synthesised betafite was predominately present in the U(5+) oxidation state. A minor amount of U(6+) was also detected which was possibly due to surface oxidation.