Diferentes estratégias de flotação (reagentes, pH e rota) têm sido utilizadas na separação entre apatita e carbonatos em todo o mundo. Há evidências na literatura de que a cristalinidade afeta a flotação de apatitas e calcitas com oleato de sódio. Além disso, a dissolução dos sais semi-solúveis pode influenciar a interação entre a superfície dos minerais e os reagentes de flotação, uma vez que o mecanismo de adsorção mais importante é a precipitação de oleato de cálcio na interface sólido/líquido. Portanto, o objetivo deste trabalho é investigar a relação entre cristalinidade, cinética de dissolução e resposta à flotação de apatitas e calcitas de diferentes gêneses (ígnea, metamórfica e sedimentar) e origens. Quatro tipos de minerais foram utilizados: purificados a partir de minérios, previamente purificados, naturalmente puros e amostras de coleção. As amostras foram caracterizadas por fluorescência de raios-X e microanálise (WDS/EDS). Características físicas como densidade (d), área superficial (S) e porosidade (P) também foram determinadas. O método de Rietveld aplicado à difração de raios-X foi usado tanto para comprovar a pureza das amostras como para estudar a cristalinidade dos minerais por meio da determinação dos parâmetros de rede (distâncias a e c, e volume da cela unitária- VCU), além do grau de cristalinidade (GC), tamanho de cristalito (TC) e microdeformação (MD). Ensaios de dissolução, conduzidos na ausência de CO2, forneceram a quantidade (mol) de íons Ca2+ (nCa2+) dissolvidos em função do tempo (t) e normalizada em relação à área superficial. Os resultados se ajustam a um modelo de primeira ordem: nCa2+ = Ca2+MAX(1- e-kt). Este procedimento permitiu calcular os valores da quantidade máxima de íons Ca2+ dissolvidos (Ca2+MAX), bem como da constante cinética (k). Além disso, a velocidade de dissolução foi determinada para a etapa rápida (VR), que caracteriza o início da reação, e para a etapa lenta (VL), que ocorre nas proximidades do estado estacionário. A resposta à flotação com oleato de sódio foi determinada por meio de experimentos de microflotação. Várias relações de causa e efeito são encontradas: flotabilidade (F) versus VR, e VR versus características intrínsecas (parâmetros de rede, de cristalinidade e físicos). VR foi selecionado para participar de tais modelos, pois, caracteriza o intervalo de tempo em que o condicionamento (1 minuto) e a microflotação (1 minuto) ocorrem. Observa-se que a flotabilidade dos minerais aumenta com o aumento de VR, sugerindo que apatitas e calcitas que disponibilizam mais íons Ca2+ em solução para interagir com o oleato, exibem mais elevada flotabilidade. Equações lineares de F em função de VR em pH 8 (R = 0,97 para apatitas e R = 0,66 para calcitas) e pH 10 (R = 0,95 para apatitas e R = 0,63 para calcitas) foram encontradas. Correlações lineares múltiplas foram utilizadas para relacionar VR (em pH 8 e 10) com as características intrínsecas que exercem maior influência sobre este parâmetro. Para as apatitas, VR foi equacionado em função de GC, TC e c, enquanto para as calcitas, os parâmetros GC, TC, d e P foram selecionados para compor o modelo. Os valores de VR calculados se ajustam aos observados dentro de um intervalo de confiança de 95%. As equações lineares propostas para as apatitas foram usadas para se estimar F das amostras de Anitápolis-SC e Tapira-MG, que não foram submetidas aos ensaios de dissolução. Os valores de F calculados estão em concordância com aqueles experimentalmente determinados. / Different flotation strategies (reagents, pH and route) have been adopted to separate apatite from carbonates around the world. Literature provides evidences that crystallinity affects flotation response of apatite and calcite with sodium oleate. Furthermore, dissolution of salt-type minerals influences the interaction between mineral surface and flotation reagents, because the most important adsorption mechanism is the surface precipitation of calcium oleate onto mineral/water interface. Therefore, the objective of this research is to investigate the relationship between crystallinity, dissolution kinetics and flotation response of apatites and calcites from different genesis (igneous, metamorphic and sedimentary) and origins. Four sorts of minerals were utilized: minerals purified from ores, minerals previously purified, naturally pure minerals and collection samples. They were characterized by X-ray fluorescence and X-ray microanalysis (WDS/EDS). Physical characteristics, as specific gravity (d), surface area (S) and porosity (P), were also determined. The Rietveld method applied to X-ray diffraction data was used either to probe the purity of samples or to study the crystallinity of the minerals by means of determining their lattice parameters (a and c dimensions plus lattice volume-VCU), in addition to crystallinity degree (GC), crystallite size (TC) and microstrain (MD). Dissolution experiments, conducted in the absence of CO2, yielded curves which relate the amount (mol) of dissolved Ca2+ ions (nCa2+) versus time (t), normalized by the surface area. They fit a first order model: nCa2+ = Ca2+MAX(1- e-kt). Curve fitting via exponential adjustment was accomplished to calculate values of the maximum amount of dissolved Ca2+ ions (Ca2+MAX) and the kinetic constant (k). In addition, the dissolution rate was determined for the fast step (VR), which characterizes the beginning of the reaction, and for the slow step (VL), as it tends to the steady state. Flotation response with sodium oleate was determined by microflotation experiments. Several cause-effect relationships are found: floatability (F) versus VR, and VR versus intrinsic characteristics of minerals (lattice, crystallinity and physical parameters). VR was selected to participate in the model because it characterizes the length of time along which reagent conditioning (1 minute) plus microflotation (1 minute) take place. It is observed that F increases as VR becomes greater, suggesting that samples of apatites and calcites which place more Ca2+ ions in solution to interact with oleate exhibit higher flotation performance. Linear equations of F versus VR at pH 8 (R = 0,97 for apatites and R = 0,66 for calcites) and pH 10 (R = 0,95 for apatites and R = 0,63 for calcites) were found. Likewise, multiple linear correlations were used to relate VR (at pH 8 and 10) with the intrinsic characteristics of apatites and calcites that affect VR to a greater extent. For apatites, VR was modeled as a function of GC, TC and c, while for calcites, the parameters GC, TC d and P were selected to compose the model. The calculated VR values fit the experimental ones within 95% of confidence. The linear equations developed for apatites were used to estimate floatability of the samples from Anitápolis-SC and Tapira-MG, which were not submitted to dissolution experiments. The values of calculated floatability are in agreement with the experimental ones.

Este trabalho aborda a molhabilidade de apatita por água em temperatura ambiente (20-25°C) objetivando contribuir para um melhor entendimento de seu comportamento em sistemas de flotação. Água, devido às fortes forças atrativas entre suas moléculas, não espalha completamente sobre sólidos de baixa energia como apatita pré-tratada com surfatantes aniônicos de cadeia longa. Este comportamento é explorado por engenheiros de processamento mineral para separar apatita de minerais de ganga via flotação aniônica direta em circuitos industriais ao redor do mundo. Nesta tese, a molhabilidade de apatita (tratada ou não com oleato de sódio-NaOl em pH=10,5) foi caracterizada pelo ângulo de contato de avanço da água (TETAa), trabalho de adesão (Wa) da água sobre apatita e coeficiente de espalhamento (S) de água sobre o sólido. Medidas diretas de TETAa sobre os planos frontal (010) e basal (001) de um cristal de apatita bem definido proveniente de Ipirá- BA (apatita-Ipirá) foram executadas pelo Método da Bolha Cativa (MBC), enquanto determinações indiretas de TETAa foram realizadas pelo Método da Ascensão Capilar (MAC) através da percolação de líquidos (água e/ou metanol) através de leitos partículas de apatita-Ipirá ou apatita-Cajati (proveniente de Cajati-SP). No MAC, o uso de hexano foi adequado para determinar a magnitude da constante de empacotamento (c) para partículas de apatita de baixa molhabilidade (TETAa>>0°), enquanto que a água se mostrou mais apropriada para ser usada na determinação da constante c para partículas de apatita não tratadas com surfatantes (TETAa~0o). Ensaios de microflotação foram conduzidos com apatita-Ipirá em pH=10,5 e com NaOl (0-75mg/L) enquanto ensaios de flotação gama foram executados com minério de fosfato proveniente de Cajati-SP previamente tratado com amido (37,5mg/L) e alquil sarcosinato de sódio-Berol®867 (25mg/L) em pH=10,6. Os resultados das medidas de TETAa e dos ensaios de microflotação indicaram uma relação de causa-efeito entre a concentração de NaOl (0-75mg/L), molhabilidade de apatita-Ipirá e sua resposta à microflotação: as maiores recuperações foram obtidas com as maiores concentrações do coletor NaOl, maiores valores de TETAa, menores valores de Wa e valores mais negativos de S. Os valores de TETAa diretamente medidos sobre as faces de um cristal de apatita-Ipirá pelo MBC mostrou que NaOl adsorve preferencialmente sobre o plano (010) comparado ao plano (001). Além disso, a tensão superficial crítica de molhabilidade (GAMAc) da apatita-Ipirá, pré-tratada com 75mg/L de NaOl, foi de 30,2erg/cm2 para o plano (001) versus 29,6erg/cm2 para o plano (010). Após serem condicionadas com reagentes de flotação (amido=37,5mg/L e Berol®867=25mg/L em pH=10,6) e flotadas em estágio rougher, partículas de apatita-Cajati exibiram TETAa=64.2°±1.1°. O valor de GAMAc, determinado via experimentos de flotação gama foi GAMAc~34,5erg/cm2; enquanto GAMAc determinado por diagramas cosTETA x GAMALV foi de GAMAc~33,9erg/cm2. Os resultados de flotação gama com o minério de fosfato de Cajati mostrou um platô de máxima recuperação de apatita (95-98%) quando 52,7erg/cm2<GAMALV<72,9erg/cm2. Ao contrário da apatita, a recuperação dos minerais de ganga (silicatos e carbonatos) foi estritamente ascendente com o aumento de GAMALV. A maior Eficiência de Separação apatita/ganga (E.S. = recuperação de apatita menos a recuperação de ganga) foi obtida em GAMALV=50,5erg/cm2 para apatita/silicatos e em GAMALV=51,4erg/cm2 para apatita/carbonatos. Os resultados dos experimentos de flotação gama indicaram que, no circuito industrial de Cajati-SP, GAMALV pode ser modulada pela dosagem do coletor, e sua magnitude pode guiar engenheiros na tomada de decisões a respeito da dosagem de coletor que promova a maior seletividade de separação apatita/ganga. Entretanto, a falta de instrumentos apropriados para realizar medidas on-line confiáveis de GAMALV tem impedido a execução destas medidas em circuitos industriais. Deste modo, decisões a respeito da dosagem do coletor feitas pelos engenheiros continuam a ser baseadas em uma abordagem empírica ao invés de científica. / This work approaches the wetting of apatite by water at room temperature (20-25°C) aiming at to contribute towards a better understanding of its behavior in flotation systems. Water, because of its powerful attractive forces, does not readily spread over the surface of low energy solids as apatite pre-treated with anionic long chain surfactants. This behavior is exploited by mineral processing engineers to separate apatite from gangue minerals via direct anionic flotation in industrial plants around the world. In this thesis, the wettability of apatite (treated or not with sodium oleate- NaOl at pH=10.5) was characterized by the advancing water contact angle (TETAa), work of adhesion (Wa) of water to apatite and the spreading coefficient (S) of water over the solid. Direct measurements of TETAa on either frontal-(010) or basal-(001) planes of a well formed apatite crystal from Ipirá-BA (apatite-Ipirá) were carried out via Captive Bubble (CB) method, whereas indirect determinations of TETAa were accomplished via Capillary Rise (CR) method by means of percolation of liquids (water and/or methanol) through particle beds of apatite-Ipirá and apatite-Cajati (from Cajati-SP). At CR method, the use of hexane was adequate to determine the magnitude of packing constant (c) for apatite particles of low wettability (TETAa>>0o), whereas water proved to be more appropriate to be used in the determination constant c for apatite particles non-treated with surfactants (TETAa~0o). Microflotation tests were conducted with apatite-Ipirá at pH=10.5 with NaOl (0-75mg/L) whereas gamma flotation tests were carried out with phosphate ore from Cajati-SP previously treated with starch (37.5mg/L) and sodium alkyl sarcosinate-Berol®867 (25mg/L) at pH=10.6. Results from measurements of TETAa and microflotation experiments indicated a cause-effect relationship between concentration of NaOl (0-75mg/L), wettability of apatite-Ipirá and its microflotation response: the highest recoveries were yielded at higher concentration of collector NaOl, higher values of TETAa, lower values of Wa and more negative the values of S. Values of TETAa directly measured on the faces of a crystal of apatite-Ipirá by CB method showed that NaOl adsorbs preferentially onto (010) plane compared to (001) plane. Moreover, the critical surface tension of wettability (GAMAc) of apatite-Ipirá, pre-treated with 75mg/L of NaOl, was 30.2erg/cm2 for (001)-plane versus 29.6erg/cm2 for (010)-plane. After being conditioned with flotation reagents (starch=37.5mg/L and Berol®867=25mg/L at pH=10.6) and floated at rougher stage, particles of apatite-Cajati exhibited TETAa=64.2o±1.1o. The value of GAMAc, determined via gamma flotation experiments was GAMAc~34.5erg/cm2; whereas GAMAc determined by cosTETA x GAMALV plots was GAMAc~33.9erg/cm2. Results from gamma flotation experiments with phosphate ore from Cajati showed a plateau of maximum apatite recovery (95-98%) when 52.7erg/cm2<GAMALV<72.9erg/cm2. Unlike apatite, the recovery of gangue minerals (silicates and carbonates) was strictly ascending when GAMALV was increased. The highest Efficiency of Separation apatite/gangue (E.S. = recovery of apatite minus recovery of gangue) was attained at GAMALV=50.5erg/cm2 for apatite/silicates and at GAMALV=51.4erg/cm2 for apatite/carbonates. The results from gamma flotation experiments indicate that, at the industrial plant of Cajati-SP, GAMALV can be modulated by collector dosage, and its magnitude can provide guidance to practitioners to make decision on collector dosage to achieve a desired value of GAMALV which promotes the best selectivity of the separation apatite/gangue. Notwithstanding, the lack of suitable instruments to accomplish on-line reliable measurements of GAMALV has been hindering the implementation of those measurements at industrial circuits. This way, decisions on collector dosage made by practitioners continue to be based rather on empirical than on scientific approach.

[pt] O principal método de beneficiamento da rocha fosfática para concentração da apatita é a flotação. A flotação da apatita com baixo teor costuma utilizar surfactantes sintéticos, que apesar de caros apresentam boa seletividade. A fim de reduzir custo sem perder eficiência, surgiram pesquisas com o intuito de substituir estes surfactantes convencionais por biossurfactantes. Esta rota de bioprocessamento mineral revela-se atrativa sob o aspecto comercial, visto que além de apresentar baixo custo é ambientalmente aceitável, pois ao utilizar microrganismos não patogênicos cria-se uma nova classe de reagentes biodegradáveis, modificando o cenário da flotação convencional. Este trabalho tem como objetivo avaliar o uso da estirpe bacteriana Rhodococcus erythropolis e do biossurfactante extraído desta na bioflotação da apatita. Foram realizados ensaios de bioflotação utilizando tubo de Hallimond, na faixa de pH entre 3 e 11, faixa granulométrica da apatita entre 75 e 106 micrômetros, com solução de 10(-3)M de NaCl, diferentes concentrações dos biorreagentes e tempo de flotação igual a 2, 5 e 7 minutos. O biossurfactante apresentou melhor desempenho, quando comparado com a biomassa. Em todos os casos, observou-se um incremento da flotabilidade em valores de pH menor que 7, no entanto, a maior flotabilidade apresentou-se em pH igual a 4 com a utilização de 140 mg/L de biossurfactante. / [en] The main method of processing phosphate rock, for apatite concentration, is flotation. The flotation of apatite with low content usually uses synthetic surfactants, which are expensive, but present good selectivity. In order to reduce costs without losing efficiency, research has emerged with the purpose of replacing these conventional surfactants by biosurfactants. This mineral bioprocessing route is attractive in the commercial aspect, since low cost and environmentally friendly, when using non-pathogenic microorganisms, creating a new class of biodegradable reagents and modifying the conventional flotation scenario. This work aims to evaluate the use of bacterial strain Rhodococcus erythropolis and the biosurfactant extracted from in apatite bioflotation. Bioflotation tests were performed using a Hallimond tube in the pH range of 3 to 11, apatite granulometric range between 75 and 106 micrometers in a solution of 10(-3)M NaCl, different concentrations of the bioreagents and flotation time equal to 2, 5 and 7 minutes. The biosurfactant presented better performance, recovering more apatite than the biomass. In all cases an increase in flotability was observed at pH bigger than 7, however, the highest flotability was at pH to be 4 with 140 mg/L of biosurfactant.

[pt] A hidroxiapatita (HA) é um constituinte natural dos ossos e rochas ígneas e tem grande importância na reserva de cálcio e fósforo dos vertebrados. Possui propriedades de biocompatibilidade e bioatividade, permitindo que haja substituições de seus átomos por outros. Neste trabalho são estudadas as substituições de Cd e Sr nos dois sítios cristalinos, 1 e 2, de Ca. São apresentados cálculos de estrutura eletrônica (ordem de ligação e carga atômica) em aglomerados de HA, Cd/HA e Sr/HA, utilizando o método de Huckel estendido (eHT), que se baseia na aproximação de ligações fortes (tight binding) em base não ortogonal. Os parâmetros empíricos utilizados foram ajustados de modo a reproduzir dados experimentais e cálculos ab initio nos óxidos CaO, CdO e SrO. Os resultados para os sistemas HA mostram que, em ambas as substituições, o sítio 2 é o preferencial. São feitas comparações com resultados encontrados na literatura, tanto experimentais quanto calculados através da Teoria do Funcional Densidade(DFT). O presente estudo corrobora trabalhos anteriores mostrando que o método semi-empírico eHT pode fornecer uma descrição qualitativa adequada das propriedades eletrônicas de sistemas envolvendo HA pura ou com substituições. / [en] Hydroxyapatite (HA) is a natural constituent of bones and igneous rocks. It plays important role in the storage of calcium and phosphorus of vertebrates. HA presents biocompatibility and bioactivity properties, allowing substitutions of its atoms for others. In this work, the substitutions of Cd and Sr in two crystal sites, 1 and 2, of Ca, are studied. Electronic structure calculations (bond order and atomic charge) are performed on pure and Cd/HA and Sr/HA clusters, by using the extended Hückel Theory (eHT), based on non orthogonal tight binding approximations. For a better description of the HA systems, it is used empirical parameters adjusted in order to reproduce known band structure and experimental data on CaO, CdO and SrO oxides. It is shown that site 2 is the preferred substitution site for both, Cd and Sr. This result is discussed in connection with previous experimental and DFT based calculations on the two substituted HA. The present study corroborates previous work which suggested that eHT may provide a reasonable qualitative description of basic electronic properties of both pure and substituted hydroxyapatite materials.

The weathering of apatite is the foundation of the phosphorus cycle and essential to life, yet little is known about the nanoscale mechanisms driving apatite weathering. Deciphering nanoscale dissolution in apatite is a significant step to understand phosphate weathering behavior, that was key to the development of life. Determining what controls apatite weathering can impact many areas of environmental and medical mineralogy such as dentistry, contaminant scavenging, geochronology, and paleoenvironment studies. The aim of this study was to characterize apatite dissolution across scales with an emphasis on the nanoscale mechanisms. Recent research on the weathering of silicate minerals at the nanoscale has provided telling evidence of a relatively new chemical weathering model referred to as coupled interfacial dissolution-precipitation (CIDR) mechanism. We hypothesize that this mechanism could be broadened to phosphate minerals. To investigate crystals of Durango fluorapatite (FAP) and hydroxyl-chlorapatite (HAP) were hydrolyzed in flow-through devices with pH 3 HNO3 solutions. Apatites used in the study were chemically and structurally characterized via Single Crystal-XRD, with particular emphasis on the anion composition and atomic arrangement. Determination of the mechanisms of dissolution was carried at multiple scales using ICP-OES chemical analysis (macroscale), SEM (microscale) and STEM-HAADF-EDS/EELS on FIB liftouts (nanoscale). At the macroscale, The anionic composition of the apatite controlled its weathering rate. As expected, HAP dissolution occurred at faster rates compared to FAP. SEM characterization of the crystal surfaces pre- and post-dissolution revealed the development of etch pits during dissolution, however, more pronounced for FAP than HAP. Observation of the mineral/solution interface at the nanoscale using STEM-HAADF revealed the development of a nanometric amorphous layer likely depleted in Ca compared to P. The observation of a sharp crystalline/amorphous transition and 5 to 15 nanometers thick amorphous surface altered layer, associated with a depletion in Ca suggests that similar to silicate, apatite is subject to a coupled interfacial dissolution-reprecipitation mechanism. This potential discovery could transform our understanding of phosphate behavior in medical and environmental mineralogy fields.

Apatite is one of the accessory minerals in the UHP metamorphosed eclogites at Northern Dulan belt, North Qaidam. It appears in three kinds of occurrences: (1) included in garnet which often shows cracks along the apatite grains, (2) coexisting with omphacite, rutile and/or clinozoisite in matrix and often surrounded by garnet, and (3) coexisting with retrograded minerals. The three eclogite samples examined in the present study are enriched in garnet. Two of them contain up to 80 vol.% garnet and the other is a porphyry of medium-grained garnet. They commonly show cracks and features of retrograde metamorphism, such as fissure-filling of secondary minerals including calcite or greenschist facies minerals. There are two size-ranges of well-oriented sulfide minerals included in apatite. One is nanometer-sized sulfide needles (50 ¡Ñ 20 ~ 870 ¡Ñ 120 nm) and particles (55 ~ 370 nm). The other is micrometer-sized sulfide needles (~20 ¡Ñ 0.5 £gm) and rods (~2.5 ¡Ñ 0.5£gm). Fluid inclusions and the micrometer-sized sulfide minerals commonly occur in the apatite grains that are near the cracks. Both nanometer- and micrometer-sized sulfide minerals are elongated with their long axes being normal or parallel to the c axis of the apatite. We used SEM-EDS and TEM-EDS to analyze and found that the sulfide minerals are troilite, pyrrhotite, Cu-bearing pyrrhotite and chalcopyrite. There are two sets of preferred crystallographic orientations for the dominated troilite and host apatite. The rod troilite is elongated along its a axis and <001>troilite // <001>apatite, <48-3>troilite ∡ <13-3>apatite = ~ 0.6º, (2-10)troilite // (3-10)apatite, <100>troilite ∡ <100>apatite = ~ 10º. The needle troilite is also elongated along its a axis and <001>troilite ¡æ <001>apatite, <-110>troilite ∡ <-12-2>apatite = ~ 1.3º, (11-2)troilite // (0-1-1)apatite. The preferred crystallographic orientation relationships, in terms of the c axis of troilite being parallel or normal to the c axis of host apatite, are similar to those for oriented quartz precipitates and omphacite hosts in the previous studies. According to the observations that only few sulfide minerals included in other minerals, the occurrences of apatites, and the microtextures of sulfide minerals, we suggest that the origin of sulfide minerals may relate to metasomatism during plate subduction. Metal ions such as iron, copper, cobalt and nickel were carried by chlorine- and sulfur-enriched fluids, which might be trapped as primary fluid inclusions in the apatite. The sulfide minerals then formed at the sites of fluid inclusions with the aid of fluids and available ions.

This research studies 6 eclogites from Qinglongshan Donghai in the Sulu ultrahigh-pressure (UHP) province, eastern China. Petrographic microscope, Ramam spectrometer, scanning electron microscope (SEM) and transmission electron microscope (TEM) are utilized to identify mineral compositions, microstructures and mineral precipitates. Optical observations show the eclogites with the following mineral assemblage: garnet + omphacite + amphibole + epidote + rutile ¡Ó quartz ¡Ó phengite ¡Ó kyanite ¡Ó coesite pseudomorph ¡Ó apatite ¡Ó talc. Oriented mineral precipitates are found within omphacite and within apatites. The parallel precipitates in omphacite are quartz rods confirmed by electron probe microanalysis (EPMA) and TEM diffraction patterns. The direction of the long axes of the quartz rods seem to have relation with the cleavage and with the parting of omphacite. The direction of the long axis of quartz is not necessarily the c axis direction of quartz. Pargasite is intergrown with quartz and the amounts of both minerals seem to have a positive relation. Pargasite contain element K which is not found in omphacite and there is no obvious crystallographic relation between quartz, pargasite, and omphacite. There is amphibole exsolved from the omphacite and the crystallographic axes of tht exsolved amphibole parallel to those of omphacite. The a and c parameters for the two phases are equal while the b parameter of the amphibole is almost twice that of omphacite. A two-stage growth mechanism for quartz and amphibole intergrown within omphacite is proposed: (1) very fine quartz rods exsolved (or aided with infilling fluids) from a supersilicic clinopyroxene during decompression, creating grain boundaries between quartz rods and host, (2) growth of amphibole and quartz along the grain boundaries with fluid participation and an expense of omphacite during retrograde metamorphism. There are two different precipitates within apatites in different eclogites. One of the precipitates is calcium sulfate (anhydrite or gypsum) and the other is ferrous sulfide (pyrrhotite?). There was no report about calcium sulfate within apatite in UHP rocks before. The formation of sulfide (reduced) or sulfate (oxidized) is controlled by the fugacity of oxygen. According to the previous reports and the discoveries of this research, there are many different kinds of precipitates containing silicate incompatible elements in apatites. It can¡¦t be ruled out that the precipitates exsolved from apapites but apatites are more likely to act as sinks of silicate incompatible elements and different minerals precipitated within apatites under different redox conditions rather than exsolution processes.

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Texte traduit de: Th. Etat--Sci. nat.--Strasbourg 1, 1988. Titre de soutenance : Géochimie et pétrographie de la formation à phosphate des Ganntour, Maroc ; utilisation pour une explication de la genèse des phosphorites crétacé-éocènes. / Résumé en français. Bibliogr. p. 210-218.

Thesis (Ph. D.)--West Virginia University, 2007. / Title from document title page. Document formatted into pages; contains xvii, 189 p. : ill. (some col.). Vita. Includes abstract. Includes bibliographical references (p. 150-162).