This study was conducted to compare the speciation and behavior of P in soils receiving either different biosolids or inorganic fertilizer, as assessed by sequential chemical extractions, phosphate desorption, and synchrotron X-ray absorption near edge structure (XANES) spectroscopy. The objectives of this study were to i) measure the total amount of organic and inorganic phosphorus removed by chemical extraction method ii) investigate how P desorption kinetics are influenced in biosolids amended soils compared to inorganic fertilizer amended soils; and iii) perform solid state speciation of soil samples before and after chemical extraction and desorption with P K-edge XANES spectroscopy. Soil samples were analyzed that received three different rates of biosolids (16.8, 33.6, and 67.2 Mg ha-1 yr-1) and one inorganic fertilizer application (336 kg N, 224 kg P, and 112 kg K ha-1 yr-1) for 32 years. Both sequential chemical extraction and XANES analysis showed that total amount of P increased in biosolids amended soils (from 5292 to 10945 mg P kg-1) and that it increased with increasing application rate. Sequential chemical extractions showed that the labile portion of total P in inorganic fertilized soil (40 %) was larger than in biosolids applied soils (39 to 27 %). Results from both sequential chemical extraction and XANES analysis showed that NaOH extraction removed the highest amount of P from all biosolids applied soils (from 1857 to 2600 mg P kg-1). <p>The amount of desorbed P decreased as the soil:solution ratio increased from 0.005 to 100 g L-1 for both soils and the desorption was typically higher in inorganic fertilizer applied soil than in biosolids applied soil. The effect of pH on P desorption was pronounced, and desorption was higher at pH 5 than pH 7.5 for both soils. A continuous flow desorption method was also used to measure cumulative P desorption over time. Cumulative P desorption in inorganic fertilizer applied soil (894.5 mg P kg-1) was higher than in the biosolids amended soils (572.9 mg P kg-1) over 20 hr period time. First-order and parabolic diffusion kinetic equations were used to model the desorption data from the continuous flow technique. This revealed that the P desorption rate was faster (and chemically-controlled) at initial stages and slower (and diffusion-limited) at later stages. The desorption rate was much faster in inorganic fertilizer applied soil than in biosolids applied soil.<p>XANES analysis of the fractions removed in sequential chemical extractions suggested that the predominant form of P was poorly crystalline dicalcium phosphate in biosolids applied soils, and labile, sorbed forms as well as some apatite-type calcium phosphate was present in inorganic fertilizer applied soil. The combined results from sequential chemical extraction and XANES analysis indicate that P in inorganic fertilizer and biosolids-applied soils behave differently. There were larger amounts of low crystallinity phosphates in the biosolids samples, and much higher apatite content in the inorganic fertilizer amended soil.

In the current research, oil derived from several Brassica species, and related oilseeds, was investigated for use as a lubricant base-oil. Oils obtained from B. rapa L. were selected because of their superior cold temperature performance over Sinapis alba L., B. carinata A., B. napus, and B. juncea L. The commercial antiwear additive zinc dialkyl dithiophosphate (ZDDP) was added (800 ppm) to B. rapa oils to determine the impact on oxidative stability and lubricity. It was found that the B. rapa oil ACS-C7 had a low cloud and pour point. B. rapa oils had poor oxidative stability at 97.8 °C when compared to a mineral oil (petroleum-based) standard. ZDDP had little effect on oxidative stability and cloud point. It was concluded that B. rapa oils have sufficient low temperature performance for use as a lubricant base oil. However, for continued use in a motor oil formulation, further modification of the oxidative stability will be necessary. All B. rapa oils with and without ZDDP were subjected to lubricity testing in a Plint High Frequency Wear Tester (TE-77). Lubricity testing simulates the high temperature and pressure in a motor system. The coefficient of friction and resultant wear scar width were measured. B. rapa oils lower coefficients of friction and decrease wear scar widths when compared with a mineral oil standard. Addition of ZDDP to B. rapa oils slightly increased lubricity performance of the oils. The wear scars produced on the polished stainless steel disk were subjected to X-ray Absorption Near Edge Structure (XANES) analysis using two synchrotron beamlines at the Canadian Light Source. XANES analysis confirmed the presence of a lubricating tribofilm on the surface of the stainless steel disks following B. rapa lubricity testing. These results indicate that B. rapa oils are suitable candidates as lubricant base oils for motor oil formulation.

This study was conducted to compare the speciation and behavior of P in soils receiving either different biosolids or inorganic fertilizer, as assessed by sequential chemical extractions, phosphate desorption, and synchrotron X-ray absorption near edge structure (XANES) spectroscopy. The objectives of this study were to i) measure the total amount of organic and inorganic phosphorus removed by chemical extraction method ii) investigate how P desorption kinetics are influenced in biosolids amended soils compared to inorganic fertilizer amended soils; and iii) perform solid state speciation of soil samples before and after chemical extraction and desorption with P K-edge XANES spectroscopy. Soil samples were analyzed that received three different rates of biosolids (16.8, 33.6, and 67.2 Mg ha-1 yr-1) and one inorganic fertilizer application (336 kg N, 224 kg P, and 112 kg K ha-1 yr-1) for 32 years. Both sequential chemical extraction and XANES analysis showed that total amount of P increased in biosolids amended soils (from 5292 to 10945 mg P kg-1) and that it increased with increasing application rate. Sequential chemical extractions showed that the labile portion of total P in inorganic fertilized soil (40 %) was larger than in biosolids applied soils (39 to 27 %). Results from both sequential chemical extraction and XANES analysis showed that NaOH extraction removed the highest amount of P from all biosolids applied soils (from 1857 to 2600 mg P kg-1). <p>The amount of desorbed P decreased as the soil:solution ratio increased from 0.005 to 100 g L-1 for both soils and the desorption was typically higher in inorganic fertilizer applied soil than in biosolids applied soil. The effect of pH on P desorption was pronounced, and desorption was higher at pH 5 than pH 7.5 for both soils. A continuous flow desorption method was also used to measure cumulative P desorption over time. Cumulative P desorption in inorganic fertilizer applied soil (894.5 mg P kg-1) was higher than in the biosolids amended soils (572.9 mg P kg-1) over 20 hr period time. First-order and parabolic diffusion kinetic equations were used to model the desorption data from the continuous flow technique. This revealed that the P desorption rate was faster (and chemically-controlled) at initial stages and slower (and diffusion-limited) at later stages. The desorption rate was much faster in inorganic fertilizer applied soil than in biosolids applied soil.<p>XANES analysis of the fractions removed in sequential chemical extractions suggested that the predominant form of P was poorly crystalline dicalcium phosphate in biosolids applied soils, and labile, sorbed forms as well as some apatite-type calcium phosphate was present in inorganic fertilizer applied soil. The combined results from sequential chemical extraction and XANES analysis indicate that P in inorganic fertilizer and biosolids-applied soils behave differently. There were larger amounts of low crystallinity phosphates in the biosolids samples, and much higher apatite content in the inorganic fertilizer amended soil.

Since discovering the anomaly of the La-based cuprates (La2-xSrxCuO4) at x~ , researches of stripe phase have been prevailing recently. Related vast experiments, like neutron scattering, Raman and infrared ray (IR) spectra, Hall effect, and magnetic susceptibility etc. have performed on this subject. These results indicate that a crossover from one- to two-dimensional charge transport happens at x~ . In this thesis, we synthesize p-type superconductors La2-xSrxCu0.995Zn0.005O4 by solid-state reaction. It has been well know there is a marked drop in Tc- x phase diagram at x~ of La2-xSrxCuO4. It is possible that this phenomenon is related to the formation of a stripe phase. The experimental work on x-ray absorption near edge spectroscopy (XANES) in La2-xSrxCuO4 and La2-x-ySrxNdyCuO4 have been done during these years in our laboratory. The results show that the absorption-spectroscopy diagrams of two systems have apparent differences in the region of upper Hubbard Band (UHB). The differences are due to that the stripe is observed in La2-x-ySrxNdyCuO4, but not in La2-xSrxCuO4. No observation of stripe phase in La2-xSrxCuO4 may be attributed to that the drop at x~ in Tc-x phase diagram of La2-xSrxCuO4 is smaller than that in La2-x-ySrxNdyCuO4. Therefore, thesis reports the comparison of spectroscopic diagram between La2-x-ySrxNdyCuO4 and La2-xSrxCu0.995Zn0.005O4, which show more a pronounced Tc-x drop than the La2-xSrxCuO4 system. Meanwhile, the effect on the thermoelectric power by the formation of stripe phase is also investigated and discussed as well.

Abstract The x~ 1/8anomaly in the La-based cuprates had been puzzling since the discovery of high-Tc superconductors. Recently, the stripe phase which has attracted considerable attention in connection with many experiments, like neutron scattering, Raman and infrared(IR) spectra, Hall effect, thermoelectric power and magnetic susceptibility, etc. These results indicate that a crossover from one- to two-dimensional charge transfer accurs at x~1/8 . In this thesis, we synthesize two series of p-type superconductors La2-xSrxCuO4 and La1.4-xSrxNd0.6CuO4 by solid-state reaction. It has been well known that there is a marked drop in Tc - x phase diagram at x~1/8 in both systems. It is possible that this phenomenon is related to the stripe phase. This interesting question has motivated us to initiate the experiment of x-ray absorption near edge spectroscopy (XANES) to investigate the possibility of the electronic structure change caused by the stripe phase. It is found that the spectral weight of the hole carriers scales with the doping level x rather than with Tc . However, the charge stripe was observed in La1.4-xSrxNd0.6CuO4, but not in La2-xSrxCuO4. Our results also suggest that the formation of the stripe phase is not related to the structural phase transition in La1.4-xSrxNd0.6CuO4 consistent with earlier results. Comparisons are made between our results and those reported on the basic of the stripe phase scenario.

Research into determining what intrinsic characteristics cause materials to be hard is imperative if one would like to design future materials with a hardness exceeding that of diamond. Measuring the hardness of materials in order to obtain a fundamental quantity independent of extrinsic factors is difficult, if not impossible. However, many theories have been proposed pertaining to the quantification of hardness as a fundamental property. While it is clear that the hardness of a material will strongly depend on its crystal structure, another fundamental quantity, the electronic band gap, has also been linked to the intrinsic hardness of materials. The electronic band gap is a seemingly simple quantity, but is difficult to de- termine for novel or complicated materials. Core-level spectroscopy techniques that probe the occupied and unoccupied density of states separately allow for an indirect determination of the electronic band gap. These methods have several advantages over conventional tech- niques in that they do not strongly depend on the extrinsic material properties such as defects and impurities. The electronic band gap has been determined in this way for several novel materials. These include group 14 nitrides with spinel structure that were recently studied over the last decade. The electronic band gap of three synthesized binary spinel nitrides γ-Si3N4, γ-Ge3N4 and γ-Sn3N4 are determined using core-level spectroscopy to be 4.8 ± 0.2 eV, 3.5 ± 0.2 and 1.6 ± 0.2 eV, respectively. These measurements agree with the calculated values of 4.97, 3.59 and 1.61 eV for γ-Si3N4, γ-Ge3N4 and γ-Sn3N4, respectively. We have also extended these measurements and calculations to include the solid solutions γ-(GexSi1−x)3N4 and γ-(SnxGe1−x)3N4 showing these spinel-structured nitrides form a multi-functional class of semiconductors. This band gap measurement technique has also been applied successfully to the phosphor converting light emitting diode material Ba3Si6O12N2 and the novel semicon- ductor MnNCN. This shows that using core-level spectroscopy is a very effective method to determine the electronic band gap where there are no other feasible techniques. Aside from the electronic band gap, core-level spectroscopy is also a complementary technique to deter- mine the crystal structure, which is also an important parameter with regard to hardness. The crystal structure, particularly aspects such as anion ordering and vacancy ordering, have been determined for the spinel-structured oxonitride Ga3O3N and a novel phase of calcium nitride Ca3N2. These results show that core-level spectroscopy is a powerful technique to determine the anion ordering in oxonitrides and was further applied to the material class β-sialons, allowing for the determination of the electronic band gap as well as ascertaining both the anion and cation ordering. Combining all of these aspects we show that the electronic band gap is not only useful for predicting the hardness of materials, but in some cases can be used to predict the existence of certain materials. We use theoretical methods, combined with experimental measurements, to calculate the hardness and electronic band gap of all possible binary and ternary group 14 spinel-structured nitrides. Through the correlation of the hardness and electronic band gap we show that only the three already synthesized binary group 14 spinel-structured nitrides are stable along with their solid solutions and that the elusive spinel-structured carbon nitride γ-C3N4 will be never synthesized.

La formation de patines noires riches en fer et/ou manganèse sur les édifices en grès est un phénomène observé pour une grande variété d’environnements mais qui n’est pas encore totalement compris. Le château de Lunéville, situé dans l’est de la France, est un cas d’étude intéressant puisqu'il présente des patines apparues pour différentes conditions : certaines semblent s’être formées naturellement alors que d’autres se sont développées sur des pierres ayant été exposées à un incendie. Ces dernières ont connu une élévation de leur température de surface, mais ont surtout été soumises à de grandes quantités d’eau lors de l’intervention des pompiers. Ce travail de thèse vise à mieux comprendre le phénomène de formation des patines en étudiant différents faciès de grès prélevés sur le château de Lunéville et en carrière. Afin d’appréhender l’influence des paramètres intrinsèques aux grès, des faciès patinés et non patinés ont été comparés d’un point de vue pétrophysique, chimique et minéralogique en s’appuyant sur des techniques d’analyse de laboratoire (microscopies optique et électronique avec sonde d’analyse dispersive en énergie, diffraction des rayons X, spectrométrie Raman, mesures de perméabilité, porosité et capillarité, ...), et sur de grands instruments (analyses par émission de rayons X induits par des particules (PIXE) sur l’accélérateur de proton AGLAE, analyses en micro-diffraction des rayons X et micro-spectrométrie d’absorption X (XANES) au synchrotron SOLEIL). En complément de cette caractérisation des blocs de pierre, les patines formées dans différents environnements ont également été comparées afin de dégager les paramètres extrinsèques dominants. Enfin, l’aspect dynamique de la libération du manganèse par les grès a été étudié, d’une part en menant des expériences de dissolution pour plusieurs pH, d’autre part en montrant qu’il était possible de recréer une patine de manganèse en laboratoire, par imbibition d’une éprouvette de grès. Les résultats obtenus permettent de proposer un modèle de formation des patines basé sur la dissolution des phases manganésifères initialement présentes dans les grès, puis la migration des ions libérés en solution dans le milieu poreux vers la surface des pierres / The formation of iron and/or manganese black patina on sandstone buildings is a phenomenon observed for various environments but which is not fully understood yet. The palace of Lunéville, in eastern France, is an interesting example because it has patinas that have developed in different conditions : some seem to have grown naturally while others have appeared on stones which were exposed to a fire. These stones experienced an increase of their surface temperature, but most of all, they were subjected to a substantial volume of water as part of attempts to extinguish the fire. The goal of this thesis is to understand the formation of the patinas by investigating different sandstone facies collected from the palace of Lunéville and from quarry. In order to understand the influence of the sandstones intrinsic parameters, the patinated and unpatinated facies were compared from petrophysical, chemical and mineralogical point of view, using laboratory techniques (optical and electron microscopy with energy dispersive X-ray spectroscopy, X-ray diffraction, Raman spectrometry, permeability, porosity and capillarity measurements, ...) and large instruments (Particle Induced X-ray Emission (PIXE) on the AGLAE proton accelerator, X-ray micro-diffraction analysis and X-ray absorption micro spectroscopy (XANES) at the SOLEIL synchrotron). In addition to this characterization, patinas coming from different environments were also compared in order to extract the main extrinsic parameters. Finally, the dynamical aspect of the release of manganese from the sandstones was investigated by conducting dissolution experiments at various pH, and by demonstrating the possibility to recreate a Mn patina in laboratory, using sandstone imbibition techniques. The results allow to propose a model for the patina formation based on the dissolution of the Mn-phases initially present in the sandstones’ bulks, followed by the migration through the porous network towards the surface of the ions released in the solution

L'altération hydrothermale d'une péridotite océanique conduit à une profonde transformation minéralogique qui correspond au « processus de serpentinisation ». Durant ce processus, le Fe2+ initialement contenu dans les olivines et/ou les pyroxènes peut s'oxyder en Fe3+ en incorporant des phases nouvellement formées comme la serpentine et la magnétite. L'hydrolyse de l'eau associée à cette réaction entraine la production de grandes quantités d'hydrogène. Au niveau des dorsales océaniques, de fortes concentrations en hydrogène et hydrocarbures ont été récemment mises en évidence sur quelques sites hydrothermaux d'un genre nouveau, tous situés dans un contexte ultrabasique. Dans le but de comprendre les processus contrôlant l'altération hydrothermale des péridotites, et en particulier la production d'hydrogène dans ce type de contexte, nous avons couplé des expériences de serpentinisation in-situ à des simulations thermodynamiques. Les produits de synthèse obtenus dans nos expériences ont été caractérisés à l'aide de différents outils spectroscopiques, principalement par absorption des rayons X en synchrotron. Nous avons ainsi développé plusieurs protocoles expérimentaux permettant d'une part de quantifier les proportions des phases minérales, mais aussi de déterminer la distribution et la spéciation du fer dans nos échantillons altérés. Nos expériences montrent que la cinétique de serpentinisation est fortement dépendante des conditions physico-chimiques (température, rapport eau/roche, état structurel et composition chimique de protolithe) présentes dans le milieu naturel. Parallèlement, ces travaux indiquent que les rôles joués par la serpentine et la magnétite dans la production d'hydrogène évoluent suivant la température mais changent également fortement au cours de la réaction. Ces résultats, affinés par des modélisations numériques, ont été replacés dans un cadre naturel, dans le but de déterminer les différents processus se produisant le long d'un trajet P-T hydrothermal. Il apparait ainsi que l'essentiel de la réaction de serpentinisation s'effectue sur le trajet « prograde » avec une production maximale d'hydrogène située autour de 275°C. Enfin, et grâce aux gradients de température estimés dans ce type de contexte, nous avons pu déterminer la taille et la géométrie probable d'un site hydrothermal comme celui de « Rainbow ». / The hydrothermal alteration of a natural peridotite leads to a strong mineralogical change, the so-called “serpentinization process”. During this process, the Fe2+ initially contained in olivines and/or pyroxenes is partially oxidized in Fe3+ incorporated in new mineral phases like serpentine or magnetite. This reaction conducts to the hydrolysis of water and therefore produces high amount of hydrogen. In the mid-ocean ridges, high concentrations of hydrogen and hydrocarbons have recently been measured on a new type of hydrothermal fields, always located on on ultramafic rocks. With the aim to better understand the processes controlling the hydrothermal alteration of peridodites, and in particular the related hydrogen production, numerous in-situ experiments of serpentinization were coupled with thermodynamic calculations. The altered products were characterized using different spectroscopic tools, particularly by X-ray absorption analysis in 3rd generation synchrotrons. Several experimental protocols were thus developed allowing to accurately quantify the phase proportions, the iron distribution, and the iron speciation in the altered samples. Experiments display that the serpentinization kinetic is highly dependent from the physico-chemical conditions (temperature, water-to-rock ratio, structural state and chemical composition of the protolith) inferred in the natural environment. In parallel, our work shows that the roles play by both serpentine and magnetite mineral phases evolve as function of temperature but as well change during the alteration process. These results were coupled with the numerical simulations to be replaced in a natural context determining the different processes encountered along a P-T hydrothermal pathway. As a result, the serpentinization reaction is mainly effective during the “prograde” pathway and the maximum hydrogen production occurs around 275°C. Finally and based on the thermal gradients inferred in such contexts, the size and the geometry of the “Rainbow” hydrothermal field were defined.

Concern over excess phosphorus (P) input and loading in some soils of the Canadian prairie region has led to a need for a better understanding of the fate of added manure and fertilizer P. Information on the effects of manure application over long term (i.e., years) and short term (i.e., weeks, months) as related to management practices and manure form is still lacking. Knowledge of the P forms and species present in soil following application of manure and inorganic P fertilizers, and linking this to potential P availability and mobility is needed to make sound P management recommendations. The objective of this thesis project was to assess the speciation of soil P in different manures and inorganic fertilizer-amended Saskatchewan soils as affected by time, presence and absence of plants, landscape position, soil type, and management practices including rate and placement. Three studies were conducted (growth chamber and field-based experiments) to study P behavior in soils. These studies closely followed a time scale, beginning with speciation and fate followed over the very short-term (i.e., days to weeks) to a short-term period (i.e., months to a year) following amendment application, and finally the effects of repeated annual manure additions made over the long term (i.e., 11 years). Soils used in this study were loamy textured Brown and Black Chernozems. Solid cattle manure (SCM) and liquid hog manure (LHM) were applied at low and high rates in the very short-term and long-term studies. The low rate of SCM and LHM application was 7.6 T ha-1 yr-1 (dry weight) and 37,000 L ha-1 yr-1, respectively which was equivalent to approximately 100 kg total N ha-1 yr-1 application (agronomic N rate). The high rate was four times this amount. Inorganic fertilizer (mono-ammonium phosphate blended with urea) at rate of 54 kg N ha-1 and 12 kg P ha-1 and SCM at rate of 60 T ha-1 were applied in the short-term study. A sequential chemical extraction procedure was used to fractionate P in very short-term and short-term studies and different soil test phosphorus (STP) methods were used to determine effects on the labile P in the long-term study. Changes in P speciation with time and their relative proportions in fertilizered soils were also assessed using the synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy in all studies. This study has revealed that manure, especially SCM elevates labile P over all time frames examined. Over the very short-term (i.e., weeks to a month), P was added as manure tends to remain in labile forms like brushite and adsorbed P that is accessible to plants for uptake. In the manure band (months to a year), manure P was relatively unchanged over a period of months while in the mono-ammonium phosphate (MAP) fertilizer band, adsorbed and Ca-P was readily formed from fertilizer P. Aging over several years (one to eleven years), along with high soil pH and high Ca:P ratio enhanced formation of more stable Ca-P minerals like apatite, especially in SCM amended soil. Overall, the unique combined use of wet chemical analysis and synchrotron-based techniques in this thesis research has improved our understanding of fate and transformation of P added to prairie soils. It is suggested that future studies of fate of applied P in soil also utilize a combination of wet chemical and spectroscopic techniques, as this was shown to be a rewarding approach.

Reproduction de : Thèse de 3e cycle : Chimie organique : Metz : 1972. / Titre provenant de l'écran-titre. Notes bibliogr.