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The dislocation etch pits formed on the cleavage surfaces of lithium fluoride in an aqueous solution containing varying concentrations of ferric ions are investigated by electron microscopy. The results obtained reveal the powerful influence of the inhibitor in the stabilisation of kinks and macroledges. There is some evidence for the nucleation of disso­lution at imperfections other than the dislocations. Dissolution spirals are observed in some cases suggesting the presence of helical dislocations in lithium fluoride. / Thesis / Master of Science (MS)

The Giant Mine near Yellowknife, NWT generated 237 000 tonnes of arsenic-trioxide (As₂O₃)-rich dust as a by-product of gold mining during its years of operation (1948 - 2004). Arsenic trioxide is a relatively soluble form of arsenic (As) and is currently stored in the mine, posing a threat of contamination to the adjacent Great Slave Lake. This research investigates the potential for permanent remediation of the As₂O₃ using sulfidation to transform it to arsenic trisulfide (As₂S₃). Knowing that aqueous As₂O₃ readily reacts with sulfide (Ostermeyer, 2021), it was determined that the most practical and effective method to achieve sulfidation of the Giant Mine dust is to first dissolve the As₂O₃ and then conduct the reaction with sulfide. The optimal conditions at which to dissolve As₂O₃ were investigated. The solubility and dissolution rate in water were shown to increase with temperature, with solubility increasing from 185.7 g As₂O₃/kg water at 140 °C to 250.6 g As₂O₃/kg water at 180 °C. Qualitative demonstrations of the rate of dissolution show that ≥ 90 % of the As₂O₃ dissolved within 5 minutes at 140 °C, and 4 minutes at 180 °C; previous research indicates that time to equilibrium is > 24 hours at 60 °C (CANMET, 2000). Reaction of Giant-Mine material in water at elevated temperatures (140 °C - 200 °C) for 10 to 30 minutes consistently resulted in dissolution of approximately 80 wt. % of the initial solid-phase As concentrations, representing almost all the As₂O₃, yielding undissolved residues (≈ 40 wt. % of initial mass). The persistence of As in these residues is likely due to it being hosted in As₂O₃ - Sb₂O₃ solid solutions and low-solubility Fe-oxide phases in the initial sample (CANMET, 2000; Poirier, 2004).

Intrinsic to the many nano-enabled products are atomic-size multifunctional engineered nanomaterials, which upon release contaminate the environments, raising considerable health and safety concerns. This Ph.D. dissertation is designed to investigate (i) whether metals or oxide nanoparticles are more toxic than ions, and if MetPLATETM bioassay is applicable as a rapid nanotoxicity screening tool; (ii) how variable water chemistry (dissolved organic carbon (DOC), pH, and hardness) and organic compounds (cysteine, humic acid, and trolox) modulate colloidal stability, ion release, and aquatic toxicity of silver nanoparticles (AgNP); and (iii) the developmental responses of crop plants exposed to Ag- or ZnO- (zinc oxide) nanoparticles. Results suggest that the MetPLATEcan be considered a high-throughput screening tool for rapid nanotoxicity evaluation. Detectable changes in the colloidal diameter, surface charge, and plasmonic resonance revealed modulating effects of variable water chemistry and organic ligands on the particle stability, dissolution, and toxicity of AgNPs against Escherichia coli or Daphnia magna. Silver dissolution increased as a function of DOC concentrations but decreased with increasing hardness, pH, cysteine, or trolox levels. Notably, the dissociated Ag+ was inadequate to explain AgNP toxicity, and that the combined effect of AgNPs and dissolved Ag+ under each ligand treatment was lower than of AgNO3. Significant attenuation by trolox signifies an oxidative stress-mediated AgNP toxicity; its inability to attenuate AgNO3 toxicity, however, negates oxidative stress as Ag+ toxicity mechanism, and that cysteine could effectively quench free Ag+ to alleviate AgNO3 toxicity in D. magna. Surprisingly, DOC-AgNPs complex that apparently formed at higher DOC levels might have led daphnids filter-feed on aggregates, potentially elevating internal dose, and thus higher mortality. Maize root anatomy showed differential alterations upon exposure to AgNPs, ZnONPs, or their ions. Overall, various metal-based nanoparticles revealed lower toxicity than their ions against multiple organisms. This study showed that particle size, surface properties, and ion release kinetics of AgNPs modify following release into aquatic environment, suggesting potential implications to ecosystem health and functions, and that caution be applied when extending one species toxicity results to another because obvious differences in organism biology—supporting species sensitivity paradigm—can significantly alter nanoparticle or ionic toxicity.

Ooids of Great Salt Lake, Utah (GSL) have been studied periodically by geologists since the 1960's. These studies have documented the locations of ooid deposits, bulk composition, mineralogy, and internal structural variations of GSL ooids. Ooids have also been identified in sediment cores from lakes predating the Great Salt Lake, but similar descriptions have not been made for these ooids. Samples of ooids from cores in Pilot Valley, UT/NV and Knolls, UT have been obtained, along with samples from the Great Salt Lake at Bridger Bay and Rozel Point. The cortical fabrics and crystal morphologies of these ooids were studied in thin section and under scanning electron microscopy. Examples of cortex morphologies previously documented in GSL ooids were observed, to some degree, in ooids from Pilot Valley and Knolls. Knolls ooids had unique cortical layers that were resistive to acid and appeared to be dominantly comprised of clays. Bulk dissolution ages were obtained for ooids from each location. Ooids form both Pilot Valley and Knolls had average ages that pre-date Lake Bonneville, whereas GSL ooids from Bridger Bay had an average age of roughly 3,500 years before present (yr BP) and Rozel Point ooids had an average age of 500 yr BP. Along with a bulk age, ooids from Bridger Bay at the Great Salt Lake were subjected to serial dissolutions during which a split of gas was taken from each stage and an age was obtained. Ages spanned 7,000 years with the final dissolution stage delivering an average age of 9,000 yr BP. Based on this data it is likely that GSL ooids at Bridger Bay have been forming since the cessation of Lake Bonneville and that many of the nuclei in Bridger Bay ooids are remnant peloids from the Gilbert level of Lake Bonneville.

Although the self is central to human beings and has been pondered on for thousands and thousands of years, its nature remains unknown to us. Many want to solve the question of self but where does one even begin? Philosophers have investigated the self for hundreds if not thousands of years, and many theories and concepts exist. In more recent years it has become possible for science to investigate the self through the use of psychoactive substances. Most notably is the use of drug-induced ego-dissolution, where individuals report a state of self devoid of many of the characteristics that would normally be considered crucial for our everyday lives. This has created new circumstances, it is no longer solely philosophy that can investigate the self, but also science. By measuring the brain activity of participants who are experiencing this ego-dissolution, information about a disrupted self can be gathered. And by using this data more can be known about the normal state of self than ever before. Even though current research is young, it has still revealed certain elements of the self, such as the importance of connectivity between multiple brain regions. These findings strongly support the materialist network approach to the self, which philosophers are taking note of. Although many of the findings are of interest, they can still be underwhelming due to the vagueness of the exact nature of ego disruption being investigated and the lack of sophistication regarding the conceptualization of self.

Deep geological repository has been investigated as a solution for long term storage of spent nuclear fuel in Sweden for more than 40 years now. The Swedish nuclear fuel and waste management company (SKB) are commissioning the deep repository and they must ensure that nuclear waste is isolated from the environment for thousands of years. During this time the containment must withstand physical stress and corrosion. It is important for a safety analysis to determine the different reactions that could occur during this time. If the physical barriers break down, radiolysis of water will occur. Hydrogen peroxide formed during the radiolysis can oxidize the exposed surface of the fuel, which increases the dissolution of radiotoxic products. Hydrogen peroxide can also catalytically decompose on the surfaces of the fuel. This project set out to figure out the selectivity for catalytic decomposition of hydrogen peroxide. This was to be done analytically with coumarin as a scavenger for detecting hydroxyl radicals formed when hydrogen peroxide decomposes. This produces the fluorescent 7-hydroxycoumarin that with high precision could be measured using spectrofluorometry. The results were giving approximately 0.16% ratio between •OH-production and hydrogen peroxide consumption. Similar experiments were done with ZrO2 for comparison, but the results were largely inconclusive. The effect of bicarbonate (a groundwater constituent) was also investigated. Adding bicarbonate increased the reproducibility of the experiments and increased the dissolution of uranium. Both the uranium and the bicarbonate increased the screening effects which minimized the fluorescent signal output by the 7-hydroxycoumarin. / Geologiskt djupförvar av förbrukat kärnbränsle har undersökts som lösning i Sverige i över 40 år nu. Svensk kärnbränslehantering (SKB) driftsätter det geologiska djupförvaret och måste säkerställa att det förbrukade kärnbränslet hålls isolerat från omgivningen i tusentals år. Under denna tid måste förseglingen stå emot fysikalisk stress och korrosion. Det är därför viktigt för en säkerhetsanalys att undersöka de olika reaktioner som kommer ske. Om förseglingen bryts ned kommer kärnbränslet i kontakt med vattnet i berggrunden vilket leder till radiolys av vatten. Väteperoxid som skapas under radiolysen kan sedan oxidera den exponerade ytan av kärnbränslet, detta ökar upplösningen av radiotoxiska produkter. Väteperoxiden kan även katalytisk sönderdelas på kärnbränslets yta. Syftet med arbetet var att få fram selektiviteten för katalytisk sönderdelning av väteperoxid. Detta skulle uppnås analytiskt med kumarin som avskiljare för detektion av hydroxylradikaler som bildas när väteperoxid sönderdelas. Detta producerade det fluorescerande 7-hydroxykumarinet som med hög precision kunde mätas spektrofluorometriskt. Resultaten gav en ca 0,16% förhållande mellan •OH-produktion och väteperoxidkonsumtion. Likartade experiment gjordes med ZrO2 för jämförelse men resultaten var ofullständiga. Effekten av bikarbonat (en beståndsdel i grundvatten) undersöktes också. Genom addition av bikarbonat ökade experimentens reproducerbarhet och ökade även upplösningen av uran. Både uranet och bikarbonaten minskade den utgående fluorescerande signalen från 7-hydroxykumarinet.

The present thesis work is focused on the low-temperature transformation of food industry wastes like mussel shells into nanocrystalline ions-substituted hydroxyapatite powder, having similarities with natural bone apatite, on the consolidation of such powder by cold sintering, and on the physicochemical characterization of the raw materials, synthesised powders and sintered pellets. Nonetheless the evaluation of the mechanical and biological properties was carried out to address cold sintered bodies to possible scaffolds for bone tissue engineering applications. Mussel shells, like other biogenic source of calcium carbonate/phosphate, have the attractive of being a “zero”-cost raw material because they are a waste, but also of having trace elements (Mg, Na, Sr, etc.) which, if found in a bioceramic, have a positive effect on the biological properties. Therefore, mussel shell-derived hydroxyapatite could resemble the mineralized bone tissue, being natural apatite nanometric, ion substituted and with low crystalline tenor. In the first part of the manuscript, two production methods were explored: mechanochemistry and dissolution-precipitation synthesis. Mechanochemistry was carried out at room temperature by directly mixing crushed mussel shells with phosphoric acid in a ball mill. Nanocrystalline multi-ions substituted hydroxyapatite was produced after 4 h of milling and drying at 150°C. Conversely, dissolution-precipitation synthesis was carried out in two steps: the dissolution of crushed mussel shells by adding phosphoric and chloric acid occurred at room temperature, whereas the precipitation of calcium phosphates induced by soda solution, occurred at 45°C. Dissolution-precipitation was further implemented to produce a homogeneous composite material in a single-step by introducing chitosan (in a 2/5/10 wt%) during the dissolution step. The idea was to produce a composite material able to mimic the natural bone tissue composition. In the second part of the manuscript, cold sintering was investigated for the consolidation of the synthesised hydroxyapatite and hydroxyapatite-based composites at a maximum temperature of 200 °C to avoid phase transformation, limit grain growth and preserve the osteoconduction of the bioceramic materials. The effect of the main process parameters such as solvent amount, pressure, temperature and holding time was discussed. Pressure-solution creep and plastic deformation were pointed out as the fundamental consolidation mechanisms in cold sintering, the pressure playing the major role. With a synergistic combination of pressure (600 MPa), temperature (200°C) and liquid phase (20 wt%) it was possible to consolidate hydroxyapatite above 80% relative density in only 15 min. Furthermore, pressure and temperature act a complementary agent during cold sintering. In fact, it was possible to consolidate nanometric HAp and HAp/chitosan composites above 90% relative density by increasing the applied pressure up to 1.5 GPa at room temperature. The mechanical properties of cold sintered pellets were investigated, and resulted in a flexural bending strength and Vickers microhardness, respectively, of 45 MPa and 1.1 GPa for pure hydroxyapatite and of 55 MPa and 0.8 GPa for HAp/chitosan composite. In the frame of bone tissue engineering applications, cold sintered bodies were also preliminarily tested in vitro to establish their bioactivity, their cellular viability through cytotoxicity assessment, and the ability to sustain cells adhesion, osteogenic differentiation. And extracellular matrix mineralization.

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The invention of Li-ion batteries (LIBs) marks a new era of energy storage and allows for the large-scale industrialization of electric vehicles. However, the flammable organic electrolyte in LIBs raises significant safety concerns and has resulted in numerous fires and explosion accidents. In the pursuit of more reliable and stable battery solutions, interests in aqueous batteries composed of high-energy cathodes and water-based electrolytes are surging. Limited by the narrow electrochemical stability window (ESW) of water, conventional aqueous batteries only achieve inferior energy densities. Current development mainly focuses on manipulating the properties of aqueous electrolytes through introducing excessive salts or secondary solvents, which enables an unprecedentedly broad ESW and more selections of electrode materials while also resulting in some compromises. On the other hand, the interaction between electrodes and aqueous electrolytes and associated electrode failure mechanism, as the key factors that govern cell performance, are of vital importance yet not fully understood. Owing to the high-temperature calcination synthesis, most electrode materials are intrinsically moisture-free and sensitive to the water-rich environment. Therefore, compared to the degradation behaviors in conventional LIBs, such as cracking and structure collapse, the electrode may suffer more severe damage during cycling and lead to rapid capacity decay. Herein, we adopted multi-scale characterization techniques to identify the failure modes at cathode–electrolyte interface and provide strategies for improving the cell capacity and life during prolonged cycling. In Chapter 1, we first provide a background introduction of conventional non-aqueous and aqueous batteries. We then show the current development of modern aqueous batteries through electrolyte modification and their merits and drawbacks. Finally, we present typical electrode failure mechanism in non-aqueous electrolytes and discuss how water can further impact the degradation behaviors. In Chapter 2, we prepare three types of aqueous electrolytes and systematically evaluate the electrochemical performance of LiNixMnyCo1-x-yO2, LiMn2O4 and LiFePO4 in the aqueous electrolytes. Combing surface- and bulk-sensitive techniques, we identify the roles played by surface exfoliation, structure degradation, transition metal dissolution and interface formation in terms of the capacity decay in different cathode materials. We also provide fundamental insights into the materials selection and electrolyte design in the aqueous batteries. In Chapter 3, we select LiMn2O4 as the material platform to study the transition metal dissolution behavior. Relying on the spatially resolved X-ray fluorescence microscopy, we discover a voltage-dependent Mn dissolution/redeposition (D/R) process during electrochemical cycling, which is confirmed to be related to the Jahn–Teller distortion and surface reconstruction at different voltages. Inspired by the findings, we propose an approach to stabilize the material performance through coating sulfonated tetrafluoroethylene (i.e., Nafion) on the particle, which can regulate the proton diffusion and Mn dissolution behavior. Our study discovers the dynamic Mn D/R process and highlights the impact of coating strategy in the performance of aqueous batteries. In Chapter 4, we investigate the diffusion layer formed by transition metals at the electrode–electrolyte interface. With the help of customized cells and XFM technique, we successfully track the spatiotemporal evolution of the diffusion layer during soaking and electrochemical cycling. The thickness of diffusion layer is determined to be at micron level, which can be readily diminished when gas is generated on the electrode surface. Our approach can be further expanded to study the phase transformation and particle agglomeration at the interfacial region and provide insights into the reactive complexes. In Chapter 5, we reveal the correlation between the electrolytic water decomposition and ion intercalation behaviors in aqueous batteries. In the Na-deficient system, we discover that overcharging in the formation process can introduce more cyclable Na ions into the full cell and allows for a boosted performance from 58 mAh/g to 124 mAh/g. The mechanism can be attributed to the water oxidation on the cathode and Na-ion intercalation on the anode when the charging voltage exceeds the normal oxidation potential of cathode. We emphasize the importance of unique formation process in terms of the cell performance and cycle life of aqueous batteries. In Chapter 6, we summarize the results of our work and propose perspectives of future research directions. / Doctor of Philosophy / Li-ion batteries (LIBs) have dominated the market for portable devices and electric vehicles owing to their high energy density and good cycle life. However, frequent battery explosion accidents have raised significant safety concerns for all customers. The root cause can be attributed to the flammable organic electrolytes in conventional LIBs. To address this issue, aqueous batteries based on water-rich electrolytes attract intensive attention recently. Recent research progress has dramatically improved the energy density of aqueous batteries dramatically by modifying the properties of electrolytes. However, most electrode materials are incompatible with water, leading to severe side reactions and an unstable cycle life. Therefore, understanding the failure mechanism of electrode materials in the presence of water is crucial while not fully studied yet. Our projects systematically evaluate the degradation behavior of various electrodes in aqueous electrolytes and uncover the root cause of transition metal dissolution in the electrodes. Our studies shed light on improving battery capacity and cycle life through a specialized formation cycle and polymer coating process. Furthermore, we also provide new approaches to investigate the dynamic process occurring at electrode–electrolyte interface, which is applicable to other solid–liquid systems. In summary, our research reveals the correlation between the failure mechanism and the capacity decay in various electrode materials, proposing effective approaches to enhance the battery performance.