Two main subjects are addressed in this study. The ability of a bright red material with metallic behaviour to be used as a visible light photocatalyst for hydrogen evolution and the feasibility of visible light photocatalytic water splitting using Z-schemes constituted from different kinds of photocatalysts and materials used as mediators. Strontium niobate (Sr₁₋ₓNbO₃) is an A-site deficient perovskite with intense red colour. It is an unusual material that displays both metallic type conduction and- as we present- photocatalytic activity. Specifically, photocatalytic visible light hydrogen production with oxalic acid as a sacrificial reagent is achieved from this material even without the need for a co-catalyst or other alteration. This photocatalytic activity is screened with time and related to different parameters that might influence it, like crystal structure, surface area and surface chemistry. The crystal structure of strontium niobate is A site stoichiometry dependant and the materials acquires a cubic symmetry for Sr≤ 0.92 and orthorhombic for 0.92≤ Sr≤ 0.97. The change of crystal structure from cubic to orthorhombic symmetry seems to have a negative effect on the photocatalytic activity, as the NbO₆ octahedra become distorted and unfavourable for d-orbital overlapping. The highest photocatalytic activity is exhibited at the turning point of one structure to the other. Increase in the photocatalytic activity is also exhibited by enlarging the surface area through ball milling, nevertheless, a clear trend for surface area effect on activity is not obtained among samples with different Sr content. Additionally, an enrichment of Sr on the surface of strontium niobate is observed by XPS, which apart from the fact that seems to be a governing factor improving stability it is also considered a key point for the exhibited photocatalytic activity altogether. Full water splitting under visible light from Z-schemes is studied by fabricating three general categories of systems. These three different categories depend on the mediator used to fabricate the Z-schemes and are: redox couple Z-schemes (with Fe⁺³/Fe⁺²), solid mediator Z-schemes (with GO) and no mediator Z-schemes. The materials used as photocatalysts for the fabrication of the Z-schemes are: Sr₀.₉₂NbO₃ for hydrogen production and both WO₃ and BiVO₄ independently for oxygen production. The photocatalytic activity for water splitting is evaluated in production of hydrogen and oxygen with time and the ratio of their production rates is frequently checked to see whether the ideal hydrogen to oxygen 2:1 is achieved. The general idea acquired from the results of all the three types of systems is that, water splitting with Z-schemes is a complicated process and in most cases governed by many subreactions. More specifically, in all cases of redox couple Z-schemes we got hydrogen to oxygen ratio imbalances and with the most prominent one being the lack of hydrogen production. Thankful is the fact that a certain type of system, the one consisting of WO₃ as oxygen photocatalyst and Fe⁺² as initial mediator species gives results very close to the ideal one and with a high degree of reproducibility indicating this way the probable formation of a Z-scheme that has overcome more of the imbalances. In between the two other categories, solid mediator and no mediator Z-schemes, subreactions seem to be the governing factor hence imbalances are always present. A case study in the no mediator Z-schemes on an attempt to investigate sources of imbalances, reveals that a big source of imbalance is most probably from the trapping of protons from WO₃.

M.Sc. / The strontium isotope ratio 87Sr/86Sr in the wine and soil of four wine-producing regions in South Africa has been determined using quadrupole ICP-MS. Isotope ratio measurements with fairly good precision had been obtained and 87Sr/86Sr ratio values in wine and soil samples were statistically evaluated to determine whether the regions investigated could be distinguished. Statistical interpretation of data revealed that the Robertson wine-producing region could be distinguished from Stellenbosch, Swartland and Walker Bay wine regions on the basis of their 87Sr/86Sr ratio. By using a combination of 87Sr/86Sr and multielement data, canonical discriminant functions with very good classification abilities could be obtained to correctly distinguish between wine and soil samples originating from a specific production region. Due to the isobaric overlap of strontium and rubidium at mass 87, a very good strontium-rubidium separation method had to be developed. The chelating properties of EDTA and DCTA in combination with ion exchange chromatography were explored in order to achieve such a separation. Due to the advanced rubidium separation ability of the developed DCTA elution method, it has been employed in all wine and soil sample preparations. Since chromatographic ion exchange procedures are not capable of removing all the rubidium from the sample matrices, 87Sr/86Sr ratio values were mathematically corrected for residual rubidium using an 88Sr correction. Since strontium isotope ratio measurements require very good precision, it is traditionally determined using TIMS. However, due to the ease of operation, shorter analysis time and widespread availability of quadrupole ICP-MS, the technique was evaluated for its merit for determining strontium isotope ratios. The optimization of acquisition parameters for the determination of the 87Sr/86Sr ratio in wine and soil samples with good precision of below 0.1% RSD has been conducted. Furthermore, selected sample matrix components were assessed as possible matrix interferences as well as for their ability to affect the precision of measurements. It was concluded that with adequate optimization of acquisition parameters, proper sample preparation and reliable mathematical correction of data, 87Sr/86Sr ratio measurements with reasonable precision could be obtained using quadrupole ICP-MS.

Cette thèse vise à avancer dans la compréhension de la formation récemment découverte de carbonates amorphes intracellulaires par des cyanobactéries. Des synthèses abiotiques ont permis de produire des carbonates similaires aux inclusions intracellulaires en termes de morphologie, structure et composition chimique. Ceci a permis notamment de discuter les conditions chimiques présentes dans le milieu intracellulaire de ces bactéries, qui semblent incompatibles avec les connaissances actuelles de l’intérieur des cyanobactéries. Plusieurs souches de cyanobactéries formant ou non des carbonates intracellulaires ont été cultivées en laboratoire. Des études de chimie des solutions sur le milieu extracellulaire ont montré que la précipitation intracellulaire est un processus actif pour la cellule, c’est-à-dire nécessitant de l’énergie. De plus, les cyanobactéries formant des carbonates de calcium intracellulaires imposent de faibles concentrations en calcium dans leur milieu de vie. Le suivi de la formation de carbonates intracellulaires dans des milieux contrôlés a aussi permis de démontrer qu’une espèce formait spécifiquement des carbonates de baryum et de strontium grâce à une affinité pour le baryum supérieure à celle pour le strontium, elle-même supérieure à celle pour le calcium. Ceci ouvre des perspectives intéressantes pour la dépollution et questionne l’utilisation des rapports Sr/Ca comme proxy des paléo-environnements. / In this thesis we study the recently discovered formation of intracellular amorphous carbonates by cyanobacteria. Abiotic syntheses produced carbonates with a morphology, structure and composition similar as intracellular inclusions. The intracellular chemical conditions in the cyanobacteria can be discussed; they seem inconsistent with our current knowledge about cyanobacteria. Several cyanobacterial strains, forming intracellular carbonates or not, were cultured in the laboratory. Analyses of the chemical composition of extracellular solutions showed that intracellular precipitation is an active process, i.e., it needs energy. Also, cyanobacteria forming intracellular calcium carbonates imposed low concentrations in calcium in their living environment. Monitoring the formation of intracellular carbonates in controlled environments also demonstrated that one species formed carbonates of barium and strontium owing to an affinity for barium higher than for strontium and higher for strontium than calcium. This feature opens interesting perspectives on bioremediation and questions the use of Sr/Ca ratios as a proxy for paleo-environments.

Zeolites were used in this study to remove two types of non-radioactive ions (Cobalt-59 and Strontium-89) from wastewater. This was designed to model the use of ion-exchange technique to remove radioactive Co-60 and Sr-90 from low level wastewater from Al-Tuwaitha site. Al-Tuwaitha site is a nuclear research in Iraq was used for radio-medical and radio-chemical purposes before 1990. In this study, hierarchical microporous/macroporous structures were developed to overcome the diffusivity problem using zeolite. Diatomite and carbon were used to prepare the composite adsorbents by incorporating them with three types of zeolites (A, Y and clinoptilolite). From the XRD, SEM and EDAX measurement it was confirmed that successfully prepared of Iraqi palm tree leafs-Clinoptlolite (IPClinp) and Tamarind stones-Clinoptilolite (TSClinp) composites were obtained in this study as there is no evidence in literature of this being carried out before. The carbons were prepared successfully through the Pyrolysis method for 2h at 900°C in an inert atmosphere from two types of raw waste plant materials of Iraqi Palm Tree leafs (IP) and Tamarind stones (TS). For both types of carbons, the SEM images show organised porosities in different shapes. A third material used as a zeolite scaffold was diatomite (Celatom FW-14) a readily available natural material (dead algae).A hydrothermal treatment was used to build the hierarchical structure of zeolite onto carbon and diatomite materials, the scaffolds were seeded with nano-zeolite crystals prior to the treatment and thereafter mixed with the zeolite gel composition mixture in a stainless steel autoclave. Zeolite seeds were prepared using ball mill method to reduce the particle size of the commercial zeolite to sub-micron range for each type of zeolite. The surface area, morphology, element compositions and structure for each type of zeolite and composite material were characterised using BET method, SEM, EDAX and XRD. The amounts of each type of zeolite on the carbon composites were determined using TGA while that of the diatomite composite was determined by gravimetric analysis. The results show that each type of zeolite was successfully deposited and uniformly organised onto the surface of all support materials. All pure zeolites and composite materials were successfully tested to remove Co2+ and Sr2+ ions from aqueous solutions. It was found that the composite materials had higher ability to remove both ions relative to the pure zeolites. This increase is attributed to the deposition of zeolite (microporous) onto the macroporous structure (carbon and diatomite) which increased the flow accessibility within zeolite in the hierarchical structured composites. Comparison of the removal between the two metal ions indicates that all of the materials had higher uptake for Sr2+ than Co2+ ions. The highest adsorption capacities were realised with Tamarind Stone–ZeoliteA (TSA) in the order 120mg.gz-1and 290mg.gz-1 for Co2+ and Sr2+ ions, respectively. The effect of the experimental variables shows increasing uptake with increasing pH and initial ion concentrations while it decreased with increasing the solution temperature. The Co2+ loaded composites was subjected to vitrification process at 12000C for 2h. The encapsulated composites were leached for 90 and 120 days and no significant Co2+ was recorded in the leached solution. The results show that the composite materials can be used effectively to remove the radioactive ion of Co-60 and Sr-90 ion as they display the same chemical behaviour as Co-59 and Sr-89 studied in this work.

Two aluminum spherical mirrors with radii of 203.2 mm and radii of curvature also of 203.2 mm have been used to construct a tunable Fabry-Perót type resonator operational at frequencies as low as 500 MHz. The resonator has been incorporated into a pulsed nozzle, Fourier transform, Balle-Flygare spectrometer. The spectrometer is of use in recording low J transitions of large asymmetric molecules where the spectra are often greatly simplified compared to higher frequency regions. The resonators use is illustrated by recording the rotational spectra of bromobenzene and iodobenzene. In related experiments, using similar equipment, the pure rotational spectra of four isotopomers of SrS and all three naturally occurring isotopomers of the actinide-containing compound thorium monoxide have been recorded between 6 and 26 GHz. The data have been thoroughly analyzed to produce information pertaining to bond lengths and electronic structures.

The efforts of my research have led to the successful construction of several instruments that have helped expand the field of microwave spectroscopy. The classic Balle-Flygare spectrometer has been modified to include two different sets of antenna to operate in the frequency ranges 6-18 GHz and 18-26 GHz, allowing it to function for a large range without having to break vacuum. This modified FTMW instrument houses two low noise amplifiers in the vacuum chamber to allow for the LNAs to be as close to the antenna as physically possible, improving sensitivity. A new innovative Balle-Flygare type spectrometer, the efficient low frequency FTMW, was conceived and built to operate at frequencies as low as 500 MHz through the use of highly curved mirrors. This is new for FTMW techniques that normally operate at 4 GHz or higher with only a few exceptions around 2 GHz. The chirped pulse FTMW spectrometer uses horn antennas to observe spectra that span 2 GHz versus the standard 1 MHz of a cavity technique. This instrument decreases the amount of time to obtain a large spectral region of relative correct intensity molecular transitions. A Nd:YAG laser ablation apparatus was attached to the classic Balle-Flygare and chirped pulse FTMW spectrometers. This allowed the study of heavy metal containing compounds. The instruments I constructed and the techniques I used have allowed the discovery of further insights into molecular chemistry. I have seen the effects of fluorinating an alkyl halide by determining the geometry of the carbon backbone of trans-1-iodoperfluoropropane and observing a ΔJ = 3 forbidden transition caused by a strong quadrupole coupling constant on this heavy molecule. The quadrupole coupling tensors of butyronitrile, a molecule observed in space, have been improved. The nuclear quadrupole coupling tensor of difluoroiodomethane was added to a list of variably fluorinated methyl halides upholding a trend for the magnitude of χzz. The study of SrS led to the determination of the Born-Oppenheimer breakdown terms and improving the precision of the SrS internuclear distance. I have also conducted the first pure rotational spectroscopic investigation on an actinide containing molecule, ThO.

京都大学 / 0048 / 新制・課程博士 / 博士(医学) / 甲第22370号 / 医博第4611号 / 新制||医||1043(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 別所 和久, 教授 戸口田 淳也, 教授 妻木 範行 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22425号 / 工博第4686号 / 新制||工||1731(附属図書館) / 京都大学大学院工学研究科都市社会工学専攻 / (主査)教授 小池 克明, 教授 立川 康人, 准教授 柏谷 公希 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

This diploma thesis deals with non-traditional binder, which is strontium aluminate, with his preparation and hydration. The behaviour of binary and ternary mixtures of strontium-calcium-barium aluminates was also studied. These aluminates were prepared by firing an equimolar mixture of aluminum oxide and the appropriate carbonate. Samples prepared this way, including their mixtures, were characterized by analytical methods such as X-ray diffraction analysis (XRD), thermal analysis with evolved gas analysis (TG-DTA and EGA), scanning electron microscopy (SEM), infrared spectroscopy (IR) and calorimetry, with the greatest importance for the study of the hydration process.

Strontium isotope (87Sr/86Sr) analyses have been used effectively to reconstruct the origin of osteological remains that have not been exposed to increasing temperatures (Bentley, 2006; Juarez, 2008; Knudson et al., 2005). However, previous research has shown that no thermally induced changes occur to original strontium isotope values (87Sr/86Sr) of bone and teeth specimens that have been subjected to temperatures between 212 and 1832 degrees Fahrenheit (Beard and Johnson, 2000; Grupe and Hummel, 1991; Harbeck et al., 2011), though the published literature regarding strontium isotope ratio stability and survivorship in thermally altered bone and teeth is limited. This is surprising given the potential implications for geolocation inquiries of cremains (or severely burnt remains) in both forensic and archaeological contexts. This research will focus on the latter context by using strontium isotope analyses, via thermal ionization mass spectrometry, to reconstruct the origins of human remains from a unique late Woodland period (A.D. 600-850) archaeological burial site known as the Perrins Ledge crematory, located in the lower Illinois River valley. Strontium isotope signatures derived from the Perrins Ledge cremains will be compared with values obtained from osteological faunal remains from three contemporary neighboring sites (Carlin, Apple Creek, and Newbridge). It is expected that the Perrins Ledge values will mirror those derived from the neighboring contemporary habitation sites suggesting local groups used the crematorium.