This thesis focuses on the geochemistry of secondary minerals, mainly calcite but also others such as fluorite and Ca/Al silicates, precipitated throughout the last 1.5 billion years in fractures of crystalline rock, SE Sweden. The work was based on previous reconnaissance studies and has been possible thanks to access to high-quality drill cores and associated mapping data provided by the Swedish Nuclear Fuel and Waste Management Co (SKB). Concentrations of rare earth elements (REEs) and occasionally other metals were determined in a variety of secondary minerals from fractures (mainly open systems) and veins (mainly sealed systems) and in primary minerals from the bedrock. Stable-isotope composition was measured in the secondary minerals. The overall aim was to define the sources, uptake and fractionation of REEs in calcite, and a few other co-genetic minerals, precipitated throughout the geological history under conditions ranging from hydrothermal to low temperatures. Collectively, the findings of the individual studies show that there is no easy and straightforward control of REE abundance and fractionation in calcite and other minerals in fractures and veins in crystalline bedrock settings. For example, the REE features in calcite vary extensively within sub-generations of single vein-precipitating events, on micro scale in transects across individual veins, and unsystematically over the geological history characterised by successively decreasing temperatures of mineral formation. Although the REE content in, and release from, the crystalline bedrock can have an influence on REE distribution in calcite and other minerals, it is of overall minor importance within a given bedrock domain. The main advantage of determining REEs in secondary minerals in fractures and veins in crystalline rock is therefore, as revealed in this work, to assess the character and evolution of the conditions (including features of the paleofluids) during confined mineral-precipitating events.

M.Sc. / Aspects of electron-electron correlations have for the past few decades been at the forefront of research in Solid State Physics. More traditional concepts under this topic have been phenomena such as superconductivity, and magnetic ordering in its many forms including long-range ordering and spin-glass freezing. The class of so-called strongly correlated electron systems has been a particularly active field of study, as witnessed by for instance the series of annual international conferences held under this topic since 1992. Compounds and alloys of strong electronic correlations have proved a very rich field of new and anomalous physical behaviours in metallic and semiconducting compounds and alloys of especially 4f- and 5f-electron systems, together with ceramics characterized as the so-called ¡§high-TC¡¨ superconductors. The f-electron systems have revealed a variety of behaviours such as ~ 1000-fold enhanced effective electron masses at low temperature, coexistence of superconductivity and magnetic ordering in systems where the magnetic interactions are far too strong to allow for Cooper-pair formation within the well-established BCS-interpretation, and electron transport and thermodynamic behaviour at low temperatures that completely defy our conventional Fermi-liquid paradigm of understanding the ground states of metals. The series of pseudo-ternary compounds Ce1-xLaxRu4Sn6 that were synthesized and characterized in this work for the first time are formed by substituting La for Ce in CeRu4Sn6, the parent compound. CeRu4Sn6 exhibits a number of properties which have been associated with a special class, the Kondo semiconductors of strongly correlated electron systems. CeRu4Sn6 has very recently been shown [A. M. Strydom et al. (2004)] to comprise an intriguing combination of characteristics that are thus far unique among the Kondo semiconductors: At low temperature (T 10 K) the specific heat proves the development of very strong electronic correlation out of an already low density of charge carriers (as shown by Hall-effect, resistivity, and the Sommerfeld coefficient of the specific heat). Furthermore, the specific heat follows a logarithmic increase as temperature is decreased below ~ 2 K, in a range where thermal transport shows the presence of an energy gap in the electronic density of states. The aim of this work was to investigate the intermediate and higher temperature (4.01 K „T T „T 300 K) behaviour of the electrical resistivity of the Ce1-xLaxRu4Sn6 series of compounds in which the concentration of the 4f-electron magnetic ion Ce is progressively being reduced. A steady but slow decrease of the energy gap with increasing La concentration was found in this work in contrast with what is usually the case in Kondo semiconductors. Both the presence of an energy gap and the low density of charge carriers are found to be connected to the presence of Ce in the unit cell, and are therefore not an artefact of the peculiar filledƒ{cageƒ{like tetragonal crystal structure of these compounds. An interesting strong anisotropy was found in the way in which the tetragonal unit cell expands preferentially within the aƒ{b plane, compared to the elongation along the cƒ{axis, upon moving from CeRu4Sn6 to LaRu4Sn6. / Prof. A.M. Strydom

Rare events play a crucial role in our society and a great effort has been dedicated to numerically study them in different contexts. This thesis proposes a numerical methodology based on Monte Carlo Metropolis-Hastings algorithm to efficiently sample rare events in chaotic systems. It starts by reviewing the relevance of rare events in chaotic systems, focusing in two types of rare events: states in closed systems with rare chaoticities, characterised by a finite-time Lyapunov exponent on a tail of its distribution, and states in transiently chaotic systems, characterised by a escape time on the tail of its distribution. This thesis argues that these two problems can be interpreted as a traditional problem of statistical physics: sampling exponentially rare states in the phase-space - states in the tail of the density of states - with an increasing parameter - the system size. This is used as the starting point to review Metropolis-Hastings algorithm, a traditional and flexible methodology of importance sampling in statistical physics. By an analytical argument, it is shown that the chaoticity of the system hinders direct application of Metropolis-Hastings techniques to efficiently sample these states because the acceptance is low. It is argued that a crucial step to overcome low acceptance rate is to construct a proposal distribution that uses information about the system to bound the acceptance rate. Using generic properties of chaotic systems, such as exponential divergence of initial conditions and fractals embedded in their phase-spaces, a proposal distribution that guarantees a bounded acceptance rate is derived for each type of rare events. This proposal is numerically tested in simple chaotic systems, and the efficiency of the resulting algorithm is measured in numerous examples in both types of rare events. The results confirm the dramatic improvement of using Monte Carlo importance sampling with the derived proposals against traditional methodologies: the number of samples required to sample an exponentially rare state increases polynomially, as opposed to an exponential increase observed in uniform sampling. This thesis then analyses the sub-optimal (polynomial) efficiency of this algorithm in a simple system and shows analytically how the correlations induced by the proposal distribution can be detrimental to the efficiency of the algorithm. This thesis also analyses the effect of high-dimensional chaos in the proposal distribution and concludes that an anisotropic proposal that takes advantage of the different rates of expansion along the different unstable directions, is able to efficiently find rare states. The applicability of this methodology is also discussed to sample rare states in non-hyperbolic systems, with focus on three systems: the logistic map, the Pomeau-Manneville map, and the standard map. Here, it is argued that the different origins of non-hyperbolicity require different proposal distributions. Overall, the results show that by incorporating specific information about the system in the proposal distribution of Metropolis-Hastings algorithm, it is possible to efficiently find and sample rare events of chaotic systems. This improved methodology should be useful to a large class of problems where the numerical characterisation of rare events is important.

Biosurfactants are compounds that exhibit surface activity (e.g., reduce surface and interfacial tension) and are derived from natural, biological sources. They are considered green substances due to their natural derivation, biodegradability, and relatively low toxicity. Biosurfactants from multiple classes have been shown to interact with metals, and a review of these interactions is provided. Rhamnolipids produced by Pseudomonas aeruginosa are attracting attention for metal remediation applications. The purpose of this dissertation is to evaluate rhamnolipids' ability to complex rare earth elements, determine the environmental compatibility of novel rhamnolipid diastereomers, and assess the efficacy of rhamnolipid as a collector in ion flotation. Previous research shows rhamnolipids selectively bind elements of environmental concern over common soil and water cations, but there had been no examination of transition metals from the f-block of the periodic table. The f-block elements include the rare earth elements, which are a vital component of nearly every modern technology and subject to supply risk. The interaction between monorhamnolipids and the rare earth elements was investigated by determining conditional stability constants using a resin-based ion exchange method. For the 27 metals examined, the conditional stability constants could be divided into three groups, albeit somewhat subjectively: weakly, moderately, and strongly bound. UO22+, Eu3+, Nd3+, Tb3+, Dy3+, La3+, Cu2+, Al3+, Pb2+, Y3+, Pr3+, and Lu3+are strongly bound with conditional stability constants ranging from 9.82 to 8.20; Cd2+, In3+, Zn2+, Fe3+, Hg2+, and Ca2+ are moderately bound with stability constants ranging from 7.17 to 4.10; and Sr2+, Co2+, Ni2+, UO22+, Cs+, Ba2+, Mn2+, Mg2+, Rb+, and K+ are weakly bound with stability constants ranging from 3.95 to 0.96. The uranyl ion is reported twice due to the ion demonstrating two distinct binding regions. The conditional stability constants were demonstrated to be an effective predictor of metal removal order. The metal parameters of enthalpy of hydration and ionic charge to radius ratio were shown to be determinants of complexation strength. Naturally produced rhamnolipids are a mixture of congeners. Synthetic rhamnolipid synthesis has recently enabled production of four monorhamnolipid diastereomers of a single congener. The biodegradability, acute toxicity (Microtox assay), embryo toxicity (Zebrafish assay), and metal binding capacity of the diastereomers was investigated and compared to natural monorhamnolipid. Biodegradability testing showed all the diastereomers were inherently biodegradable. By the Microtox assay, all of the monorhamnolipids were categorized as slightly toxic by Environmental Protection Agency ecotoxicity categories. Out of 22 parameters tested, the zebrafish toxicity assay showed only diastereomer toxicity for the mortality parameter, except for diastereomer R,R which showed no toxic effects. All the monorhamnolipids interacted with both Cd2+ and Pb2+. Ion flotation is one possible technology for metal recovery and remediation of metal contaminated waters. Ion flotation utilizes charged surfactants to collect and concentrate non-surface active ions at the surface of an aerated solution. Rhamnolipid's suitability as a collector in ion flotation was investigated. A flotation column was designed to test monorhamnolipid efficacy as a collector. Monorhamnolipids form foams and effectively remove Cs+, Cd2+, and La3+ from solution. The efficacy of the flotation process relies on the collector:colligend ratio and valency of the colligend. Flotation of metal solutions showed a removal order of Cd2+>La3+>>Cs+ when the metals were present individually and mixed at equimolar concentrations. When mixed at order of magnitude different concentrations, the flotation order was Cd2+>>Cs+>>La3+. These studies show rhamnolipid has potential to be used for environmentally-compatible metal recovery and metalliferous water remediation, especially for the rare earth elements.

Previous studies showed haploinsufficiency of RAI1 is the main cause of Smith-Magenis syndrome (SMS). SMS is a developmental neurobehavioral syndrome characterized by intellectual disability, congenital anomalies, obesity, neurobehavioral abnormalities, and disrupted circadian sleep-wake pattern. SMS is caused by deletion or mutation of chromosomal region 17p11.2 that includes RAI1. Studies in the Elsea lab have shown that RAI1 is a dosage-sensitive gene. Haploinsufficiency of RAI1 leads to dysregulation of CLOCK, NR1D2, POMC, and BDNF, which are responsible for circadian rhythm, metabolism, and cognitive development. Based on the data from Elsea’s recent study on zebrafish, rai1 gene expression in zebrafish is regulated by retinoic acid. Treatment with retinoic acid increases the expression of rai1. In this study, we focused on the effect of retinoic acid on human RAI1 expression. We found the expression of RAI1 was enhanced by the treatment with retinoic acid. The different concentrations of the retinoic acid affect the levels of increase in expression, but we found little evidence that RAI1 expression was affected by the length of treatment time. In this study, we were unable to find consistency in the pattern of changes in the expression level in respect to the different treatment concentrations. We identified nine strong retinoic acid response element (RARE) candidate sites upstream of the start codon in human RAI1. Since there are possible RARE sites present in the upstream sequence of RAI1, it is more likely that RAI1 is regulated by retinoic acid. However, further experimental evidence will be needed to confirm those sites selected in silico are able to bind RAR/RXR heterodimers, to prove the selected sites are real RARE sites and were not identified by chance.

This thesis presents two studies of charged charm meson decays using proton- proton collision data, corresponding to an integrated luminosity of 3 fb⁻¹, recorded by the LHCb experiment. A search for D_(s)^+ → π^+μ^+μ^- decays is performed. Rare decays of charged charm mesons have not previously been observed unlike their counterpart B meson and kaon decays. Such decays are c → u quark transitions and take place via loop diagrams within the Standard Model. Measurements of their branching fractions are an indirect test of New Physics, whose virtual contributions may enhance such quantities. No signals are observed and the 90% (95%) CL limits on the branching fractions, the most stringent to date, are found to be, B(D^+ → π^+μ^+μ^-) < 2.9 (3.3) × 10^-8, B(D_s^+ → π^+μ^+μ^-) < 1.76 (1.91) × 10^-7. The charge asymmetry measurement of D+ → π+π0 using π0 → e^+e^-γ decays is also described. Charge asymmetry in the Standard Model is expected to be small for charm meson decays. Any measured deviation from zero would be evidence of New Physics. This decay has not previously been observed at a hadron collider and the measurement acts as a 'proof of principle' study allowing a future analysis to examine the decay mode. No evidence of CP violation is found.

This Thesis describes the synthesis and characterisation of a series ofbisphenolate supported samarium borohydride, amide and zwitterionic rare earth complexes and their ability to effect the ring opening polymerisation (ROP) of cyclic esters and methylmethacrylate (MMA). Chapter 1 introduces ROP from both an industrial and an academic perspective and describes in detail the research in this area, with emphasis on rare earth initiators. The lanthanide elements and the bisphenolate ligand are also introduced. Chapter 2 describes the synthesis and characterisation ofbisphenolate supported samarium borohydride and silylamide complexes. Chapter 3 describes the ability of a selection of samarium borohydride and amide complexes to effect the ROP of the cyclic esters s-caprolactone (f-CL) and rac- lactide (rac-LA). Emphasis is placed on the effect that the nature of the bisphenolate pendant arm and the initiating moiety has on the polymerisation process. Chapter 4 describes the synthesis and characterisation of rare earth zwitterionic complexes and the ability ofa range of these complexes to effect the ROP of s-Cl. and rac-lactide. Mechanistic aspects ofthe ROP process will be discussed, as will the ability of these complexes to yield amide functionalised poly(rac-LA). Chapter 5 describes the ability ofbisphenolate samarium borohydride complexes to initiate the polymerisation of MMA. The experimental work conducted as part of this study is further supported computationally by calculations at the DFT level, both aspects will be described. Aspects concerning the synthesis and characterisation of the related borohydride derivative [Sm(N2siMe3NNPY)(BH4)2Li]oo will also be emphasised. Chapter 6 contains full experimental and characterising data for all 0 f the new compounds reported in this Thesis. Appendices A- T contain tables of selected crystallographic data for all new crystallographically characterised complexes described in this Thesis (partially on CD).

The present study is targeted on the optimization of the flotation conditions for the improvement of the industrial flotation practice. Part I is focused on the improvement of the flotation of Mountain Pass mine ore for the beneficiation of rare earth elements. The objective is to improve the rare earth recovery of Mountain Pass ore by developing a novel flotation reagents' scheme, meanwhile reducing the flotation temperature to a cost-efficient level and simplifying the flowsheet. Surface chemistry study by contact angle, zeta potential and microflotation tests indicate that a mixed collector consisting of oleic acid (OA) and sodium octanohydroxamate hydrate (OHA) is beneficial for rare earth flotation. More importantly, salicylhydroxamic acid (SHA) is also a promising collector due to the high selectivity. Lab-scale flotation tests using SHA as collector show that 80-90% REE recovery and <20% gangue recovery are achieved at 40°C~60°C, which yield a rougher concentrate of 30%~40% REO. A novel flotation scheme has been developed towards Mountain Pass rare earth mine. The new scheme is of both high selectivity and high recovery, meanwhile the dosage of reagent required is much less, and the flotation temperature is also significantly reduced. Interactive adsorption models are built up through FT-IR and AFM study. The interaction of collector with bastnaesite surface is illustrated. Hydroxamic acid collectors (OHA and SHA) adsorb on bastnaesite surface by forming stable chelating complex. The selectivity of collectors towards bastnaesite flotation is summarized as SHA>OHA>OA. Part II is focused on the improvement of the flotation of Resolution Copper's Superior mine ore at an elevated temperature for the beneficiation of chalcopyrite. Because the Resolution Copper ore is mined from a deep, hot, underground mine, the temperature of ROM (run of mine ore) is much higher than that of the ore usually processed in a typical open-pit copper mine. The ore temperature will still be high during flotation. It is therefore critical to carry out a systemic study on the flotation of Resolution Copper ore at elevated temperatures and clarify the impact on flotation. An overall beneficial effect is observed in high temperature flotation through a lab-scale flotation study. Further action of temperature control is not necessary. The contact angle results indicate that surface hydrophobicity is enhanced at elevated temperature, of which the surface morphology change (shown by AFM images) of xanthate adsorption species (dixanthogen) is the key factor.

In June 2009 I conducted a study of the habitat associated with Broadleaf Barbara's Buttons (Marshallia trinervia) along Bird's Creek in Vernon Parish, LA. Twenty two plots were sampled for all vascular plants. Of these, 17 samples were from the area where M. trinervia was present and 5 samples were from the area where M. trinervia was absent. From each sampling plot a soil sample was collected and analyzed. There were significant differences in the species richness of all plant groups (p=0.0075), herbaceous plants (p=0.056), and woody vines (p=0.083) between the two locations. The soil texture was also significantly different in the percentage of sand (p=0.021), silt (p=0.029), and clay (p=0.089) between the study locations. The study found that the samples associated with M. trinervia were higher in species richness for all plant groups and the soils from these locations had a higher mean percentage of silt and clay particles.

Ph.D. (Physics) / Please refer to full text to view abstract