Th. doct.-ing.--Trait. et prod. de matières prem. vég.--Toulouse--I.N.P., 1983. N°: 256.

Th.--Sci. phys.--Toulouse--I.N.P., 1984. N°: 81.

Th. 3e cycle--Physico-chim. des matér.--Toulouse--I.N.P., 1982. N°: 129.

Th. 3e cycle--Physico-chim. des matér.--Toulouse--I.N.P., 1982. N°: 122.

Th.--Sci. phys.--Toulouse--I.N.P., 1982. N°: 62.

Les cellules osseuses évoluent in vivo sur des matrices extracellulaires principalement formées de collagène de type I, dont le degré de minéralisation varie au cours du remodelage osseux. Le minéral de l'os, de structure apatitique, a été montré comme potentialisant les activités et modifiant la forme des cellules ostéoblastiques. Dans le but de comprendre les effets du micro-environnement matriciel sur les évènements précurseurs à la phase de formation, nous avons émis l'hypothèse que ces modifications morphologiques pouvaient expliquer en elles-mêmes l'augmentation de l'activité descellules ostéoblastiques, par augmentation de leur mécano-sensibilité, et que ce changement de préhension environnementale pouvait moduler la réponse aux stimulations mécaniques les plus fréquemment observées in vivo, à savoir les micro-vibrations. Nous avons montré que sur les matériaux de collagène minéralisé ACC (Apatite Collagen Complex), les pré-ostéoblastes de la lignée MC3T3-E1 synthétisaient une matrice riche en ostéopontine, fibronectine et facteurs angiogéniques, de façon concomitante à une augmentation dépendante de la quantité de minéral de leur adhérence et de leur migration. Nous avons de plus observé une augmentation de la mécano-sensibilité (expression et turn-over augmentés des adhésions focales) des pré-ostéoblastes sur ACC. Finalement, nous avons établi que la réponse aux stimuli vibratoires était positive sur des matériaux non minéralisés (information) et négative sur ACC (stress) par rapports aux supports non stimulés, ce que nous avons interprété comme une hypersensibilité mécanique cellulairelors de la culture sur ACC. L'ensemble de ces données nous a montré que les modifications de mécanique cellulaire de préostéoblastes cultivés sur ACC engendraient une fonctionalisation spécifique ressemblant à celle observée in vivo dans la ligne cémentante, indispensable à la formation osseuse. D'autre part, les modifications de mécano-sensibilité observées sur ACC, en faisant un support mécano-mimétique et nous amenant à la comparaison du comportement cellulaire observé avec les ostéocytes, pourraient en elles-mêmes expliquer le dépôt matriciel spécifique et la réception modifiée aux signaux vibratoires. Dans notre but ultime de création d'un modèle de remodelage osseux in vitro, les paramètres physicochimiques matriciels osseux et l'établissement de cocultures seront à prendre en compte / Bone cells interact in vivo with extracellular matrices mainly formed of type-I collagen, for which the mineral content changes during the bone remodeling cycle. Bone mineral, which is apatitic in nature, was shown to respectively increase and alter the activity and form of osteoblasts. In order to study the micro-environmental effects of the matrix on the preliminary steps of bone formation, it was hypothesized that these morphological alterations could explain the increased activity of the osteoblastic cells by enhancing their mecano-sensibility. This altered mechano-sensibility could in turn modify the osteoblastic cells’ response to the widely perceived micro-vibrations in vivo. It was demonstrated that, on the collagen-mineralized materials ACC (Apatite Collagen Complex), MC3T3-E1 pre-osteoblastic cells formed a matrix rich in osteopontin, fibronectin and angiogenic factors. At the same time, an increase in cell adhesion and migration dependent on the mineral content was seen. We also observed an enhanced mechano-sensibility (increased focal adhesion gene expression and turn-over) when cells were cultured on ACC. Furthermore, it was found that the vibratory stimuli response was up-regulated on non-mineralized materials (information) and downregulated on ACC (stress) vs. non-stimulated substrates. This observation was interpreted as a hypersensitization to environmental cues on ACC. Taken together, these data have demonstrated that pre-osteoblastic cell mechanic alterations on ACC give rise to a specific functionalization mimicking what is observed in vivo in the cement line required for bone-formation. ACC-related mechano-sensibility changes, which render ACC a mechanomimetic substrate and lead us to compare the observed cell behavior with osteocytes, could explain the specific matrix deposition and altered response to vibrations. The final goal of establishing a model for in vitro bone remodeling can only be fulfill by considering physico-chemical parameters of the bonematrix and cocultures

The apatite crystal structure-A5(TO4)3X-allows for complex substitutions of various minor and trace elements including volatile constituents, rare earth elements, and redox sensitive elements (e.g., As, Mn, Fe, S) (Piccoli and Candela, 1994; Piccoli and Candela, 2002; Pan and Fleet, 2002; Teiber et al., 2015; Harlov, 2015). In this study, apatite grains from 19 intrusions across northeastern Nevada with varied petrogenetic and metallogenic properties were analyzed by electron probe microanalysis (EPMA) to obtain major and trace element abundances. Systematic variations in Sr and REE concentrations in apatite grains from granitic host rocks are the result of competition with pre-existing and coexisting minerals in silicate melts. The presence of zoning in cathodoluminescence colors combined with high Sr concentrations in apatite from many of the Eocene granodiorite rocks suggest magma mixing affected the geochemical evolution in many of the Eocene igneous systems. In addition, high Sr concentrations in apatite grains from Late Cretaceous two-mica granites may reflect significant magmatic input from lower crustal and/or mantle sources despite the felsic nature of these intrusive rocks.A new EPMA analytical routine to measure arsenic down to detection limits of approximately 20 ppm allowed a more extensive characterization of As concentration in igneous apatite than has previously been published. Still, correlations between As and other trace-element concentrations are not evident, which may reflect the simple substitution of As5+ for P5+ in the apatite structure. Petrologic controls on As content include redox state, indicated by the high Asapat/Asbulk-rock in relatively oxidized intrusive rocks. An additional control is competition among other magmatic phases, exsolving aqueous fluids, or sulfide melts, indicated by enrichment of As in apatite cores relative to apatite rims. Past studies on redox-sensitive elements in igneous apatite have focused on Mn and S, but with further investigation, As may also prove to be a key redox-sensitive trace element in apatite for interpreting igneous and hydrothermal processes.

Constraining the depositional age of Neoproterozoic stratigraphy in western North America has implications for correlating global glaciation and tectonic events. The depositional ages of the Neoproterozoic Mutual and Browns Hole formations of northern Utah are controlled by two conflicting datapoints. However, new U-Pb geochronological data from 95 detrital apatite grains refines the maximum depositional age of the volcanic member of the Browns Hole Formation to 613 ± 12 Ma (2σ). This places new restrictions on the time available for the deposition of underlying units. Due to debate regarding the age models for underlying stratigraphy, two scenarios for sediment accumulation rates are explored. These results highlight a need for further exploring regional unconformities. Evidence for several post-depositional fluid-rock interaction events are observed in the Mutual and Browns Hole formations. Cross-cutting relationships identified via petrography, scanning electron microscopy, and electron microprobe analysis show at least seven fluid mediated events: (1) early grain-rimming hematite cement, (2) quartz overgrowth and cement development, (3) feldspar dissolution, (4) phosphate dissolution, (5) partial quartz dissolution, (6) authigenic mineral precipitation in cluding clays, sericite, monazite, and apatite cement, and (7) later hematite cementation. Constraining the timing of these events is challenging due to a limited of datable material. Using basic geochemical modeling and consideration of expected mineral formation conditions, a paragenetic sequence is placed into context of the known geologic history.

Calcium phosphates are important compounds as they exist in natural aqueous systems such as rivers, lakes, ocean, and soil. These calcium phosphates are widely used to provide information on paleotemperatures as well as many anthropological features, such as paleodiets. One of the most ubiquitous forms of calcium phosphate is hydroxyapatite (Ca10(PO4)6(OH)2) which is a major component of hard tissue such as bones, fossils, and tooth enamel. The oxygen isotope systematics in the hydroxyapatite associated with carbonate-water system will provide further information to allow for the reconstruction of terrestrial and marine environments. For example, Fricke et al. (1998) used oxygen isotope analysis of the carbonate components of hydroxyapatite in tooth enamel of mammals to investigate changes in terrestrial climate. Therefore, the purpose of this research study was to examine the oxygen isotope systematics in inorganic carbonate-bearing hydroxyapatite and water at low temperatures. This Master’s thesis followed and modified the methods described in Lécuyer et al. (2010) in an attempt to synthesize hydroxyapatite crystals and carbonate-bearing hydroxyapatite. The crystals synthesized were characterized in terms of several conditions (i.e., influence of mixing rate and maturations, pH, and concentrations of NaHCO3). Methods to produce hydroxyapatite were developed and analyzed using X-Ray diffraction analysis. The results demonstrated a strong dependence of pH in the hydroxyapatite solutions. Moreover, the effect of concentrations of NaHCO3 was deemed to be essential in order to obtain the desired amount of structural carbonates in the hydroxyapatite crystals. Furthermore, this research evaluated the temperature dependence of oxygen isotopic fractionation between HAP-bound carbonate and water at 10, 25, and 40 oC. Our study is the first to assess the two mixing-rates experiments with different maturations (7 and 14 days) on the oxygen isotope effects and fractionation behaviour between HAP-bound carbonate and water. Both maturation time and the effect of initial concentration of NaHCO3 were found to be the most important in determining the equilibrium conditions in our experiments. / Dissertation / Master of Science (MSc)

Les oxynitrures dopés terre rare présentent des propriétés intéressantes pour un usage en tant que luminophore pour LEDs blanches. Une nouvelle famille de luminophores dopés Eu2+ ou Ce3+ avec un réseau hôte oxynitrure de structure apatite a été étudiée : La8+xSr2-x(Si/Ge)6NyO26+x/2-3/2y. L’ammonolyse d’un précurseur oxyde de structure apatite a été utilisée comme technique générale de nitruration. Elle a permis de diminuer substantiellement la température de nitruration en comparaison avec la méthode classique par réaction à l’état solide sous atmosphère mixte N2/H2. Les différentes luminescences des luminophores obtenus ont été étudiées et corrélées à la structure cristalline à l’aide de différentes techniques de caractérisation.La structure apatite présente notamment la particularité de proposer plusieurs sites anioniques pour l’introduction de l’azote ainsi que deux sites cationiques pour les ions terre rare activateurs. L’utilisation de nombreuses techniques de caractérisation (IR, Raman, RMN, diffraction des neutrons) a permis d’obtenir des informations sur la position de l’azote. En parallèle, la comparaison des propriétés optiques avec celles de composés réduits sous Ar/H2 a permis d’attribuer les émissions aux différents sites cristallins disponibles dans la structure. Des mesures de rendement quantique ainsi que des tentatives d’optimisation des propriétés de luminescence ont été effectuées. / Rare-earth doped oxynitrides have attracted much attention as phosphors for white LEDs. A new family of Ce3+ or Eu2+-doped oxynitride phosphors with the apatite structure has been studied: La8+xSr2-x(Si/Ge)6NyO26+x/2-3/2y. The ammonolysis of an apatite oxide precursor has been used as a general method of synthesis, allowing decreasing the nitriding temperature respective to the classical solid state reaction in N2/H2 atmosphere. The luminescence properties of the obtained phosphors have been studied and relationships with the crystalline structure have been drawn.The apatite structure shows several crystallographic sites available for nitrogen as well as two cationic sites for optically active rare-earth ions. Several structural characterization technique have been used (IR, Raman, NMR, Neutron diffraction) and important information has been obtained concerning the nitrogen distribution in the available positions of the crystal structure. Comparison of the luminescent properties with those of compounds reduced under Ar/H2 allowed attributing emissions to the different crystallographic sites available in the structure.Quantum efficiency measurements have been carried out as well as trials for improving the intensity of the luminescent properties.