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Simon M Peacock - One of the best experts on this subject based on the ideXlab platform.
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subduction factory 1 theoretical mineralogy densities seismic wave speeds and h2o contents
Journal of Geophysical Research, 2003Co-Authors: Bradley R. Hacker, Geoffrey A Abers, Simon M PeacockAbstract:[1] We present a new compilation of physical properties of minerals relevant to subduction zones and new phase diagrams for mid-ocean ridge basalt, lherzolite, depleted lherzolite, harzburgite, and serpentinite. We use these data to calculate H2O content, density and seismic wave speeds of subduction zone rocks. These calculations provide a new basis for evaluating the subduction factory, including (1) the presence of hydrous phases and the distribution of H2O within a subduction zone; (2) the densification of the subducting slab and resultant effects on measured gravity and slab shape; and (3) the variations in seismic wave speeds resulting from thermal and Metamorphic processes at depth. In considering specific examples, we find that for ocean basins worldwide the lower oceanic crust is partially hydrated (<1.3 wt % H2O), and the uppermost mantle ranges from unhydrated to � 20% serpentinized (� 2.4 wt % H2O). Anhydrous eclogite cannot be distinguished from harzburgite on the basis of wave speeds, but its � 6% greater density may render it detectable through gravity measurements. Subducted hydrous crust in cold slabs can persist to several gigapascals at seismic velocities that are several percent slower than the surrounding mantle. Seismic velocities and VP/VS ratios indicate that mantle wedges locally reach 60–80% hydration. INDEX TERMS: 3040 Marine Geology and Geophysics: Plate tectonics (8150, 8155, 8157, 8158); 3660 Mineralogy and Petrology: Metamorphic Petrology; 3919 Mineral Physics: Equations of state; 5199 Physical Properties of Rocks: General or miscellaneous; 8123 Tectonophysics: Dynamics, seismotectonics; KEYWORDS: subduction, seismic velocities, mineral physics, H2O
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subduction factory 1 theoretical mineralogy densities seismic wave speeds and h 2 o contents
Journal of Geophysical Research, 2003Co-Authors: Bradley R. Hacker, Geoffrey A Abers, Simon M PeacockAbstract:[1] We present a new compilation of physical properties of minerals relevant to subduction zones and new phase diagrams for mid-ocean ridge basalt, lherzolite, depleted lherzolite, harzburgite, and serpentinite. We use these data to calculate H2O content, density and seismic wave speeds of subduction zone rocks. These calculations provide a new basis for evaluating the subduction factory, including (1) the presence of hydrous phases and the distribution of H2O within a subduction zone; (2) the densification of the subducting slab and resultant effects on measured gravity and slab shape; and (3) the variations in seismic wave speeds resulting from thermal and Metamorphic processes at depth. In considering specific examples, we find that for ocean basins worldwide the lower oceanic crust is partially hydrated (<1.3 wt % H2O), and the uppermost mantle ranges from unhydrated to � 20% serpentinized (� 2.4 wt % H2O). Anhydrous eclogite cannot be distinguished from harzburgite on the basis of wave speeds, but its � 6% greater density may render it detectable through gravity measurements. Subducted hydrous crust in cold slabs can persist to several gigapascals at seismic velocities that are several percent slower than the surrounding mantle. Seismic velocities and VP/VS ratios indicate that mantle wedges locally reach 60–80% hydration. INDEX TERMS: 3040 Marine Geology and Geophysics: Plate tectonics (8150, 8155, 8157, 8158); 3660 Mineralogy and Petrology: Metamorphic Petrology; 3919 Mineral Physics: Equations of state; 5199 Physical Properties of Rocks: General or miscellaneous; 8123 Tectonophysics: Dynamics, seismotectonics; KEYWORDS: subduction, seismic velocities, mineral physics, H2O
Bradley R. Hacker - One of the best experts on this subject based on the ideXlab platform.
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evolution of north himalayan gneiss domes structural and Metamorphic studies in mabja dome southern tibet
Journal of Structural Geology, 2004Co-Authors: Jeffrey Lee, Bradley R. Hacker, Yu WangAbstract:Field, structural, and Metamorphic Petrology investigations of Mabja gneiss dome, southern Tibet, suggest that contractional, extensional, and diapiric processes contributed to the structural evolution and formation of the domal geometry. The dome is cored by migmatites overlain by sillimanite-zone metasedimentary rocks and orthogneiss; Metamorphic grade diminishes upsection and is defined by a series of concentric isograds. Evidence for three major deformational events, two older penetrative contractional and extensional events and a younger doming event, is preserved. Metamorphism, migmitization, and emplacement of a leucocratic dike swarm were syntectonic with the extensional event at mid-crustal levels. Metamorphic temperatures and pressures range from , 500 8C and , 150‐ 450 MPa in chloritoid-zone rocks to 705 ^ 65 8C and 820 ^ 100 MPa in sillimanite-zone rocks. We suggest that adiabatic decompression during extensional collapse contributed to development of migmatites. Diapiric rise of low density migmatites was the driving force, at least in part, for the development of the domal geometry. The structural and Metamorphic histories documented in Mabja Dome are similar to Kangmar Dome, suggesting widespread occurrence of these events throughout southern Tibet. q 2004 Elsevier Ltd. All rights reserved.
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subduction factory 1 theoretical mineralogy densities seismic wave speeds and h2o contents
Journal of Geophysical Research, 2003Co-Authors: Bradley R. Hacker, Geoffrey A Abers, Simon M PeacockAbstract:[1] We present a new compilation of physical properties of minerals relevant to subduction zones and new phase diagrams for mid-ocean ridge basalt, lherzolite, depleted lherzolite, harzburgite, and serpentinite. We use these data to calculate H2O content, density and seismic wave speeds of subduction zone rocks. These calculations provide a new basis for evaluating the subduction factory, including (1) the presence of hydrous phases and the distribution of H2O within a subduction zone; (2) the densification of the subducting slab and resultant effects on measured gravity and slab shape; and (3) the variations in seismic wave speeds resulting from thermal and Metamorphic processes at depth. In considering specific examples, we find that for ocean basins worldwide the lower oceanic crust is partially hydrated (<1.3 wt % H2O), and the uppermost mantle ranges from unhydrated to � 20% serpentinized (� 2.4 wt % H2O). Anhydrous eclogite cannot be distinguished from harzburgite on the basis of wave speeds, but its � 6% greater density may render it detectable through gravity measurements. Subducted hydrous crust in cold slabs can persist to several gigapascals at seismic velocities that are several percent slower than the surrounding mantle. Seismic velocities and VP/VS ratios indicate that mantle wedges locally reach 60–80% hydration. INDEX TERMS: 3040 Marine Geology and Geophysics: Plate tectonics (8150, 8155, 8157, 8158); 3660 Mineralogy and Petrology: Metamorphic Petrology; 3919 Mineral Physics: Equations of state; 5199 Physical Properties of Rocks: General or miscellaneous; 8123 Tectonophysics: Dynamics, seismotectonics; KEYWORDS: subduction, seismic velocities, mineral physics, H2O
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subduction factory 1 theoretical mineralogy densities seismic wave speeds and h 2 o contents
Journal of Geophysical Research, 2003Co-Authors: Bradley R. Hacker, Geoffrey A Abers, Simon M PeacockAbstract:[1] We present a new compilation of physical properties of minerals relevant to subduction zones and new phase diagrams for mid-ocean ridge basalt, lherzolite, depleted lherzolite, harzburgite, and serpentinite. We use these data to calculate H2O content, density and seismic wave speeds of subduction zone rocks. These calculations provide a new basis for evaluating the subduction factory, including (1) the presence of hydrous phases and the distribution of H2O within a subduction zone; (2) the densification of the subducting slab and resultant effects on measured gravity and slab shape; and (3) the variations in seismic wave speeds resulting from thermal and Metamorphic processes at depth. In considering specific examples, we find that for ocean basins worldwide the lower oceanic crust is partially hydrated (<1.3 wt % H2O), and the uppermost mantle ranges from unhydrated to � 20% serpentinized (� 2.4 wt % H2O). Anhydrous eclogite cannot be distinguished from harzburgite on the basis of wave speeds, but its � 6% greater density may render it detectable through gravity measurements. Subducted hydrous crust in cold slabs can persist to several gigapascals at seismic velocities that are several percent slower than the surrounding mantle. Seismic velocities and VP/VS ratios indicate that mantle wedges locally reach 60–80% hydration. INDEX TERMS: 3040 Marine Geology and Geophysics: Plate tectonics (8150, 8155, 8157, 8158); 3660 Mineralogy and Petrology: Metamorphic Petrology; 3919 Mineral Physics: Equations of state; 5199 Physical Properties of Rocks: General or miscellaneous; 8123 Tectonophysics: Dynamics, seismotectonics; KEYWORDS: subduction, seismic velocities, mineral physics, H2O
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time and Metamorphic Petrology calcite to aragonite experiments
Science, 1992Co-Authors: Bradley R. Hacker, Stephen H Kirby, Steven R BohlenAbstract:Although the equilibrium phase relations of many mineral systems are generally well established, the rates of transformations, particularly in polycrystalline rocks, are not. The results of experiments on the calcite to aragonite transformation in polycrystalline marble are different from those for earlier experiments on powdered and single-crystal calcite. The transformation in the polycrystalline samples occurs by different mechanisms, with a different temperature dependence, and at a markedly slower rate. This work demonstrates the importance of kinetic studies on fully dense polycrystalline aggregates for understanding mineralogic phase changes in nature. Extrapolation of these results to geological time scales suggests that transformation of calcite to aragonite does not occur in the absence of volatiles at temperatures below 200°C. Kinetic hindrance is likely to extend to higher temperatures in more complex transformations.
Geoffrey A Abers - One of the best experts on this subject based on the ideXlab platform.
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subduction factory 1 theoretical mineralogy densities seismic wave speeds and h2o contents
Journal of Geophysical Research, 2003Co-Authors: Bradley R. Hacker, Geoffrey A Abers, Simon M PeacockAbstract:[1] We present a new compilation of physical properties of minerals relevant to subduction zones and new phase diagrams for mid-ocean ridge basalt, lherzolite, depleted lherzolite, harzburgite, and serpentinite. We use these data to calculate H2O content, density and seismic wave speeds of subduction zone rocks. These calculations provide a new basis for evaluating the subduction factory, including (1) the presence of hydrous phases and the distribution of H2O within a subduction zone; (2) the densification of the subducting slab and resultant effects on measured gravity and slab shape; and (3) the variations in seismic wave speeds resulting from thermal and Metamorphic processes at depth. In considering specific examples, we find that for ocean basins worldwide the lower oceanic crust is partially hydrated (<1.3 wt % H2O), and the uppermost mantle ranges from unhydrated to � 20% serpentinized (� 2.4 wt % H2O). Anhydrous eclogite cannot be distinguished from harzburgite on the basis of wave speeds, but its � 6% greater density may render it detectable through gravity measurements. Subducted hydrous crust in cold slabs can persist to several gigapascals at seismic velocities that are several percent slower than the surrounding mantle. Seismic velocities and VP/VS ratios indicate that mantle wedges locally reach 60–80% hydration. INDEX TERMS: 3040 Marine Geology and Geophysics: Plate tectonics (8150, 8155, 8157, 8158); 3660 Mineralogy and Petrology: Metamorphic Petrology; 3919 Mineral Physics: Equations of state; 5199 Physical Properties of Rocks: General or miscellaneous; 8123 Tectonophysics: Dynamics, seismotectonics; KEYWORDS: subduction, seismic velocities, mineral physics, H2O
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subduction factory 1 theoretical mineralogy densities seismic wave speeds and h 2 o contents
Journal of Geophysical Research, 2003Co-Authors: Bradley R. Hacker, Geoffrey A Abers, Simon M PeacockAbstract:[1] We present a new compilation of physical properties of minerals relevant to subduction zones and new phase diagrams for mid-ocean ridge basalt, lherzolite, depleted lherzolite, harzburgite, and serpentinite. We use these data to calculate H2O content, density and seismic wave speeds of subduction zone rocks. These calculations provide a new basis for evaluating the subduction factory, including (1) the presence of hydrous phases and the distribution of H2O within a subduction zone; (2) the densification of the subducting slab and resultant effects on measured gravity and slab shape; and (3) the variations in seismic wave speeds resulting from thermal and Metamorphic processes at depth. In considering specific examples, we find that for ocean basins worldwide the lower oceanic crust is partially hydrated (<1.3 wt % H2O), and the uppermost mantle ranges from unhydrated to � 20% serpentinized (� 2.4 wt % H2O). Anhydrous eclogite cannot be distinguished from harzburgite on the basis of wave speeds, but its � 6% greater density may render it detectable through gravity measurements. Subducted hydrous crust in cold slabs can persist to several gigapascals at seismic velocities that are several percent slower than the surrounding mantle. Seismic velocities and VP/VS ratios indicate that mantle wedges locally reach 60–80% hydration. INDEX TERMS: 3040 Marine Geology and Geophysics: Plate tectonics (8150, 8155, 8157, 8158); 3660 Mineralogy and Petrology: Metamorphic Petrology; 3919 Mineral Physics: Equations of state; 5199 Physical Properties of Rocks: General or miscellaneous; 8123 Tectonophysics: Dynamics, seismotectonics; KEYWORDS: subduction, seismic velocities, mineral physics, H2O
Masci Lorella - One of the best experts on this subject based on the ideXlab platform.
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Cristallochimie du fer dans les chlorites métamorphiques : approche analytique multiéchelle, expérimentale, et implications pétrologiques
HAL CCSD, 2019Co-Authors: Masci LorellaAbstract:Chorite is a phyllosilicate crystallizing in a wide range of pressure and temperature conditions, among a diversity of rocks : from diagenesis to Metamorphic conditions, typically in greenschist facies but also in blueschist and amphibolite facies. Chlorite is useful for Metamorphic Petrology as a geothermometer, as its composition is sensitive to the temperature of crystallization and chlorite is commonly found within mineral assemblages. Chlorite shows many solid solutions, among which Fe may be incorporated in large proportions in divalent (Fe2+) and/or trivalent (Fe3+) state. Unfortunately current models for geothermometry on chlorite either neglect Fe3+ or require evaluating the thermodynamic properties of Fe3+-rich chlorite for increased accuracy. This study aims at providing new crystal-chemistry data on ferric chlorite from a wide range of composition and origin, and to answer the following questions : (1) how much Fe3+ may be incorporated in chlorite ? (2) what are the cationic substitutions and end-members for Fe3+ incorporation ? (3) how is Fe3+ distributed within the chlorite structure ? and (4) what are the dependencies between Fe3+ in chlorite and the pressure-temperature conditions, and oxygen fugacity, at crystal and mineral scales ? This work investigates the speciation of iron in chlorite with different techniques; X-ray absorption near-edge spectroscopy at the Fe-K edge (K XANES), and electron energy-loss spectroscopy (EELS) combined with electron microprobe major element analyzes. X-ray diffraction investigation brings structural information on the structure of ferric chlorite. This analytical strategy is focused on chlorite from natural rock samples and experimental syntheses made at fixed pressure and temperature, and under buffered oxygen fugacity. A new database on ferric chlorite crystal-chemistry is the major output of this work, which highlights substitutions involving Fe3+. A Fe3+ -rich, vacant endmember is required to account for the di-trioctahedral substitution, and a magnesian end-member with 1 Fe3+ replacing Al for the homovalent Al - Fe3+ substitution. These results are observed in natural specimens and confirmed by experimental synthsesis of ferric chlorite. In addition, chlorite with Fe3+ > 1.5 p.f.u. shows systematic deviation from the ideal O10(OH)8 anionic basis, where proton deficit has been inferred from indirect measurements of H+ content. These results are consistent with the existence of an "oxychlorite" group within the classification of phyllosilicates. At mineral scale, the variations of the oxidation state take place at nanoscale and are unrelated to variations in the amount of Fe. Chlorite crystallized via experimental synthesis shows similar features. These results explain the poor success of geothermometry on some iron-rich chlorite, and allow us to propose improved cation distribution algorithms for geo thermometry. Our study paves the way for future experimental synthesis focused on oxychlorite.Les chlorites sont des phyllosilicates ayant la particularité de cristalliser sur une large gamme de conditions de pression et température, et dans une variété de roches et d’environnements géologiques pouvant aller du contexte diagénétique au contexte métamorphique de type schiste bleu à amphibolitique. La composition des chlorites est sensible à leur température de cristallisation, et avec leur présence récurrente au sein des paragénèses, celles-ci sont couramment utilisées pour l’estimation des conditions thermobarométriques par les pétrologues. Cependant la plupart des modèles thermobarométriques actuels ne permettent pas d’estimer de manière fiable des températures au sein de l’ensemble des compositions des chlorites. Les modèles thermodynamiques en particulier ne prennent pas en compte ou sous-estiment l’état d’oxydation du fer dans les chlorites qui peut être sous forme Fe2+ ou Fe3+. Ce travail de thèse a ainsi pour objectif d’apporter de nouvelles données cristallochimiques sur un large panel de chlorites ayant incorporé du fer trivalent de compositions et contextes variés, tout en répondant aux questions sur : (1) la quantité de Fe3+ qui peut être incorporée dans les chlorites, (2) les substitutions cationiques permettant l’incorporation du Fe3+ dans les chlorites et leurs pôles purs associés, (3) la localisation du Fe3+ et des autres cations dans les sites cristallographiques des chlorites et enfin, (4) sur le lien éventuel entre le Fe3+ dans les chlorites et les conditions thermodynamiques du milieu que sont la pression, température, et la fugacité en oxygène à l’échelle du cristal et du minéral. Ce travail de thèse utilise différentes méthodes de mesure du Fe3+/FeTOT ; la spectroscopie d’absorption du fer au seuil K (K XANES), et la spectroscopie par perte d’énergie des électrons (EELS) couplées à l’utilisation de la microsonde électronique. Ce volet analytique est complété par des analyses de diffraction des rayons X. L’approche utilisée repose sur l’étude de chlorites naturelles échantillonnées pour leur représentativité du domaine de composition, ainsi que sur des chlorites synthétisées expérimentalement sous pression, température, et fugacité en oxygène contrôlées. Une nouvelle base de données cristallochimiques sur les chlorites ferriques constitue l’apport principal de ce travail, et a permis en particulier de mettre en évidence les substitutions contrôlant l’incorporation du Fe3+ dans la structure. Ainsi la substitution di-trioctaédrique 3R2+ = 2Fe3+ + _ et l’échange Al = Fe3+ semblent expliquer le domaine de composition des chlorites ferriques jusqu’à Fe3+ ∼ 1.5 p.f.u., permettant de définir un ou plusieurs pôles purs de type ferri-sudoite en plus d’un pôle ferrique non lacunaire et magnésien, dans les chlorites naturelles et synthétiques. Mais l’analyse de l’oxygène dans les chlorites les plus ferriques montrent un déficit de protons interprété comme lié à l’oxydation du fer divalent, tel que : Fe2+ + H+ = Fe3+, mettant en évidence un composant "oxychlorite" à base anionique O12(OH)6. Une implication importante est que la présence de lacunes et la substitution di-trioctaédrique précédemment révélées sont largement un artefact de normalisation sur la base anionique O10(OH)8. A l’échelle du minéral la distribution du rapport Fe3+/FeTOT dans les chlorites montre des variations pouvant atteindre jusqu’à ∼ 30 %, sur une échelle de la centaine à dizaine de nanomètres. Cette hétérogénéité se retrouve également à l’échelle du micromètre mais n’est pas corrélée à la distribution du FeTOT et des autres éléments majeurs dans la lame. Enfin en plus de confirmer les substitutions des chlorites naturelles, les synthèses de chlorites ont permis d’identifier un probable contrôle de la fugacité en oxygène sur le rapport Fe3+/FeTOT mais pas sur la quantité de Fe3+ incorporée, indépendamment de la composition de départ
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Cristallochimie du fer dans les chlorites métamorphiques : approche analytique multiéchelle, expérimentale, et implications pétrologiques
HAL CCSD, 2019Co-Authors: Masci LorellaAbstract:Chorite is a phyllosilicate crystallizing in a wide range of pressure and temperature conditions, among a diversity of rocks : from diagenesis to Metamorphic conditions, typically in greenschist facies but also in blueschist and amphibolite facies. Chlorite is useful for Metamorphic Petrology as a geothermometer, as its composition is sensitive to the temperature of crystallization and chlorite is commonly found within mineral assemblages. Chlorite shows many solid solutions, among which Fe may be incorporated in large proportions in divalent (Fe2+) and/or trivalent (Fe3+) state. Unfortunately current models for geothermometry on chlorite either neglect Fe3+ or require evaluating the thermodynamic properties of Fe3+-rich chlorite for increased accuracy. This study aims at providing new crystal-chemistry data on ferric chlorite from a wide range of composition and origin, and to answer the following questions : (1) how much Fe3+ may be incorporated in chlorite ? (2) what are the cationic substitutions and end-members for Fe3+ incorporation ? (3) how is Fe3+ distributed within the chlorite structure ? and (4) what are the dependencies between Fe3+ in chlorite and the pressure-temperature conditions, and oxygen fugacity, at crystal and mineral scales ? This work investigates the speciation of iron in chlorite with different techniques; X-ray absorption near-edge spectroscopy at the Fe-K edge (K XANES), and electron energy-loss spectroscopy (EELS) combined with electron microprobe major element analyzes. X-ray diffraction investigation brings structural information on the structure of ferric chlorite. This analytical strategy is focused on chlorite from natural rock samples and experimental syntheses made at fixed pressure and temperature, and under buffered oxygen fugacity.A new database on ferric chlorite crystal-chemistry is the major output of this work, which highlights substitutions involving Fe3+. A Fe3+ -rich, vacant endmember is required to account for the di-trioctahedral substitution, and a magnesian end-member with 1 Fe3+ replacing Al for the homovalent Al - Fe3+ substitution. These results are observed in natural specimens and confirmed by experimental synthsesis of ferric chlorite. In addition, chlorite with Fe3+ > 1.5 p.f.u. shows systematic deviation from the ideal O10(OH)8 anionic basis, where proton deficit has been inferred from indirect measurements of H+ content. These results are consistent with the existence of an "oxychlorite" group within the classification of phyllosilicates. At mineral scale, the variations of the oxidation state take place at nanoscale and are unrelated to variations in the amount of Fe. Chlorite crystallized via experimental synthesis shows similar features. These results explain the poor success of geothermometry on some iron-rich chlorite, and allow us to propose improved cation distribution algorithms for geo thermometry. Our study paves the way for future experimental synthesis focused on oxychlorite.Les chlorites sont des phyllosilicates ayant la particularité de cristalliser sur une large gamme de conditions de pression et température, et dans une variété de roches et d’environnements géologiques pouvant aller du contexte diagénétique au contexte métamorphique de type schiste bleu à amphibolitique. La composition des chlorites est sensible à leur température de cristallisation, et avec leur présence récurrente au sein des paragénèses, celles-ci sont couramment utilisées pour l’estimation des conditions thermobarométriques par les pétrologues. Cependant la plupart des modèles thermobarométriques actuels ne permettent pas d’estimer de manière fiable des températures au sein de l’ensemble des compositions des chlorites. Les modèles thermodynamiques en particulier ne prennent pas en compte ou sous-estiment l’état d’oxydation du fer dans les chlorites qui peut être sous forme Fe2+ ou Fe3+. Ce travail de thèse a ainsi pour objectif d’apporter de nouvelles données cristallochimiques sur un large panel de chlorites ayant incorporé du fer trivalent de compositions et contextes variés, tout en répondant aux questions sur : (1) la quantité de Fe3+ qui peut être incorporée dans les chlorites, (2) les substitutions cationiques permettant l’incorporation du Fe3+ dans les chlorites et leurs pôles purs associés, (3) la localisation du Fe3+ et des autres cations dans les sites cristallographiques des chlorites et enfin, (4) sur le lien éventuel entre le Fe3+ dans les chlorites et les conditions thermodynamiques du milieu que sont la pression, température, et la fugacité en oxygène à l’échelle du cristal et du minéral.Ce travail de thèse utilise différentes méthodes de mesure du Fe3+/FeTOT ; la spectroscopie d’absorption du fer au seuil K (K XANES), et la spectroscopie par perte d’énergie des électrons (EELS) couplées à l’utilisation de la microsonde électronique. Ce volet analytique est complété par des analyses de diffraction des rayons X. L’approche utilisée repose sur l’étude de chlorites naturelles échantillonnées pour leur représentativité du domaine de composition, ainsi que sur des chlorites synthétisées expérimentalement sous pression, température, et fugacité en oxygène contrôlées.Une nouvelle base de données cristallochimiques sur les chlorites ferriques constitue l’apport principal de ce travail, et a permis en particulier de mettre en évidence les substitutions contrôlant l’incorporation du Fe3+ dans la structure. Ainsi la substitution di-trioctaédrique 3R2+ = 2Fe3+ + _ et l’échange Al = Fe3+ semblent expliquer le domaine de composition des chlorites ferriques jusqu’à Fe3+ ∼ 1.5 p.f.u., permettant de définir un ou plusieurs pôles purs de type ferri-sudoite en plus d’un pôle ferrique non lacunaire et magnésien, dans les chlorites naturelles et synthétiques. Mais l’analyse de l’oxygène dans les chlorites les plus ferriques montrent un déficit de protons interprété comme lié à l’oxydation du fer divalent, tel que : Fe2+ + H+ = Fe3+, mettant en évidence un composant "oxychlorite" à base anionique O12(OH)6. Une implication importante est que la présence de lacunes et la substitution di-trioctaédrique précédemment révélées sont largement un artefact de normalisation sur la base anionique O10(OH)8.A l’échelle du minéral la distribution du rapport Fe3+/FeTOT dans les chlorites montre des variations pouvant atteindre jusqu’à ∼ 30 %, sur une échelle de la centaine à dizaine de nanomètres. Cette hétérogénéité se retrouve également à l’échelle du micromètre mais n’est pas corrélée à la distribution du FeTOT et des autres éléments majeurs dans la lame. Enfin en plus de confirmer les substitutions des chlorites naturelles, les synthèses de chlorites ont permis d’identifier un probable contrôle de la fugacité en oxygène sur le rapport Fe3+/FeTOT mais pas sur la quantité de Fe3+ incorporée, indépendamment de la composition de départ.Ces résultats améliorent les connaissances cristallochimiques sur les chlorites ferriques et permettent de proposer un nouvel algorithme d’allocation des cations dans les sites, en vue de l’élaboration d’un modèle thermodynamique prenant en compte l’incorporation du Fe3+
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Crystal-chemistry of iron in Metamorphic chlorite : a multiscale analytical and experimental study, with petrological issues
2019Co-Authors: Masci LorellaAbstract:Les chlorites sont des phyllosilicates ayant la particularité de cristalliser sur une large gamme de conditions de pression et température, et dans une variété de roches et d’environnements géologiques pouvant aller du contexte diagénétique au contexte métamorphique de type schiste bleu à amphibolitique. La composition des chlorites est sensible à leur température de cristallisation, et avec leur présence récurrente au sein des paragénèses, celles-ci sont couramment utilisées pour l’estimation des conditions thermobarométriques par les pétrologues. Cependant la plupart des modèles thermobarométriques actuels ne permettent pas d’estimer de manière fiable des températures au sein de l’ensemble des compositions des chlorites. Les modèles thermodynamiques en particulier ne prennent pas en compte ou sous-estiment l’état d’oxydation du fer dans les chlorites qui peut être sous forme Fe2+ ou Fe3+. Ce travail de thèse a ainsi pour objectif d’apporter de nouvelles données cristallochimiques sur un large panel de chlorites ayant incorporé du fer trivalent de compositions et contextes variés, tout en répondant aux questions sur : (1) la quantité de Fe3+ qui peut être incorporée dans les chlorites, (2) les substitutions cationiques permettant l’incorporation du Fe3+ dans les chlorites et leurs pôles purs associés, (3) la localisation du Fe3+ et des autres cations dans les sites cristallographiques des chlorites et enfin, (4) sur le lien éventuel entre le Fe3+ dans les chlorites et les conditions thermodynamiques du milieu que sont la pression, température, et la fugacité en oxygène à l’échelle du cristal et du minéral. Ce travail de thèse utilise différentes méthodes de mesure du Fe3+/FeTOT ; la spectroscopie d’absorption du fer au seuil K (K XANES), et la spectroscopie par perte d’énergie des électrons (EELS) couplées à l’utilisation de la microsonde électronique. Ce volet analytique est complété par des analyses de diffraction des rayons X. L’approche utilisée repose sur l’étude de chlorites naturelles échantillonnées pour leur représentativité du domaine de composition, ainsi que sur des chlorites synthétisées expérimentalement sous pression, température, et fugacité en oxygène contrôlées. Une nouvelle base de données cristallochimiques sur les chlorites ferriques constitue l’apport principal de ce travail, et a permis en particulier de mettre en évidence les substitutions contrôlant l’incorporation du Fe3+ dans la structure. Ainsi la substitution di-trioctaédrique 3R2+ = 2Fe3+ + _ et l’échange Al = Fe3+ semblent expliquer le domaine de composition des chlorites ferriques jusqu’à Fe3+ ∼ 1.5 p.f.u., permettant de définir un ou plusieurs pôles purs de type ferri-sudoite en plus d’un pôle ferrique non lacunaire et magnésien, dans les chlorites naturelles et synthétiques. Mais l’analyse de l’oxygène dans les chlorites les plus ferriques montrent un déficit de protons interprété comme lié à l’oxydation du fer divalent, tel que : Fe2+ + H+ = Fe3+, mettant en évidence un composant "oxychlorite" à base anionique O12(OH)6. Une implication importante est que la présence de lacunes et la substitution di-trioctaédrique précédemment révélées sont largement un artefact de normalisation sur la base anionique O10(OH)8. A l’échelle du minéral la distribution du rapport Fe3+/FeTOT dans les chlorites montre des variations pouvant atteindre jusqu’à ∼ 30 %, sur une échelle de la centaine à dizaine de nanomètres. Cette hétérogénéité se retrouve également à l’échelle du micromètre mais n’est pas corrélée à la distribution du FeTOT et des autres éléments majeurs dans la lame. Enfin en plus de confirmer les substitutions des chlorites naturelles, les synthèses de chlorites ont permis d’identifier un probable contrôle de la fugacité en oxygène sur le rapport Fe3+/FeTOT mais pas sur la quantité de Fe3+ incorporée, indépendamment de la composition de départ.Chorite is a phyllosilicate crystallizing in a wide range of pressure and temperature conditions, among a diversity of rocks : from diagenesis to Metamorphic conditions, typically in greenschist facies but also in blueschist and amphibolite facies. Chlorite is useful for Metamorphic Petrology as a geothermometer, as its composition is sensitive to the temperature of crystallization and chlorite is commonly found within mineral assemblages. Chlorite shows many solid solutions, among which Fe may be incorporated in large proportions in divalent (Fe2+) and/or trivalent (Fe3+) state. Unfortunately current models for geothermometry on chlorite either neglect Fe3+ or require evaluating the thermodynamic properties of Fe3+-rich chlorite for increased accuracy. This study aims at providing new crystal-chemistry data on ferric chlorite from a wide range of composition and origin, and to answer the following questions : (1) how much Fe3+ may be incorporated in chlorite ? (2) what are the cationic substitutions and end-members for Fe3+ incorporation ? (3) how is Fe3+ distributed within the chlorite structure ? and (4) what are the dependencies between Fe3+ in chlorite and the pressure-temperature conditions, and oxygen fugacity, at crystal and mineral scales ? This work investigates the speciation of iron in chlorite with different techniques; X-ray absorption near-edge spectroscopy at the Fe-K edge (K XANES), and electron energy-loss spectroscopy (EELS) combined with electron microprobe major element analyzes. X-ray diffraction investigation brings structural information on the structure of ferric chlorite. This analytical strategy is focused on chlorite from natural rock samples and experimental syntheses made at fixed pressure and temperature, and under buffered oxygen fugacity. A new database on ferric chlorite crystal-chemistry is the major output of this work, which highlights substitutions involving Fe3+. A Fe3+ -rich, vacant endmember is required to account for the di-trioctahedral substitution, and a magnesian end-member with 1 Fe3+ replacing Al for the homovalent Al - Fe3+ substitution. These results are observed in natural specimens and confirmed by experimental synthsesis of ferric chlorite. In addition, chlorite with Fe3+ > 1.5 p.f.u. shows systematic deviation from the ideal O10(OH)8 anionic basis, where proton deficit has been inferred from indirect measurements of H+ content. These results are consistent with the existence of an "oxychlorite" group within the classification of phyllosilicates. At mineral scale, the variations of the oxidation state take place at nanoscale and are unrelated to variations in the amount of Fe. Chlorite crystallized via experimental synthesis shows similar features. These results explain the poor success of geothermometry on some iron-rich chlorite, and allow us to propose improved cation distribution algorithms for geo thermometry. Our study paves the way for future experimental synthesis focused on oxychlorite
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principles of igneous and Metamorphic Petrology metamorphism and Metamorphic facies
2009Co-Authors: Anthony R Philpotts, Jay J AgueAbstract:INTRODUCTION Metamorphism is the sum of all changes that take place in a rock as a result of changes in the rock's environment; that is, changes in temperature, pressure (directed as well as lithostatic), and composition of fluids. The changes in the rock may be textural, mineralogical, chemical, or isotopic. These changes proceed at varying rates, so time is an important factor in metamorphism. Any kind of rock can be metamorphosed; the starting rock is called the protolith . Common protoliths include the spectrum of igneous rocks from ultramafic to felsic, as well as sedimentary rocks such as sandstones, alumina-rich shale (pelite), and carbonate rocks (limestone and dolostone). In its broadest sense, metamorphism includes the entire range of changes that take place between the zone of weathering and the zone in which melting gives rise to magmas. Traditionally, however, the low-temperature changes associated with weathering and the lithification and diagenesis of sediments have been omitted from the study of metamorphism. Typical Metamorphic reactions take place at temperatures above 150 to 200 °C. At the highest temperatures, metamorphism gives way to magmatic processes where partial melting produces migmatites , mixed igneous–Metamorphic rocks. Average continental crust starts melting under water-saturated conditions around 1000 °C at low pressures, but this temperature decreases with increasing pressure, dropping to 650 °C at 0.5 GPa (Fig. 11.7). The water-saturated beginning of melting of granite marks the upper temperature limit of metamorphism in many regions, because the latent heat of fusion provides an enormous heat sink.
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principles of igneous and Metamorphic Petrology cooling of igneous bodies and other diffusion processes
2009Co-Authors: Anthony R Philpotts, Jay J AgueAbstract:INTRODUCTION Once magma has been intruded or extruded, it begins to cool and crystallize. To cool, the magma must lose heat to its surroundings, which it does mainly by conduction. Conduction can be thought of as the diffusion of heat. The loss of heat from the magma causes solidification and crystallization of the magma and the growth of Metamorphic minerals in rocks that are heated by the magma. The growth of crystals in the magma and in the Metamorphic rocks first involves the formation of nuclei, and then the components needed for crystal growth must diffuse to these nuclei. This occurs through the liquid in the case of magma and through solid rock or films of grain-boundary fluid in the case of Metamorphic rocks. As magma crystallizes, the composition of the residual liquid is continuously changing and the composition of crystals must change their composition if they are to remain in equilibrium with the melt. For early formed phenocrysts to adjust their composition, components need to diffuse in and out of the crystals. As the temperature of Metamorphic rocks changes, the minerals must adjust their compositions to remain in equilibrium and this again involves diffusion. Diffusion, consequently, is one of the most important processes in the formation of rocks. To appreciate diffusion processes, it is necessary to understand some simple mathematical relations. We will develop these relations by discussing the cooling of igneous bodies. The same mathematical relations will then be applied to the diffusion of chemical components.
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principles of igneous and Metamorphic Petrology igneous rock associations
2009Co-Authors: Anthony R Philpotts, Jay J AgueAbstract:INTRODUCTION Early in the development of Petrology, it was recognized that certain rock types are commonly associated, whereas others never occur together. Moreover, the common associations were seen to correlate with certain geologic settings. Today, with the insight provided by plate tectonic theory, most igneous rocks can be assigned to particular plate tectonic environments, each of which has its own distinctive thermal regime, magma source region, and crustal stress pattern. But not all rock associations can be explained through plate tectonics. Some magmatism in the Archean and even the Proterozoic was different from that of Phanerozoic time, and distinctive rock associations were formed that were never again repeated in later times. Seismic evidence indicates that the lithosphere and upper mantle are essentially solid, although a small amount of liquid may exist in the low velocity layer. The formation of large magma chambers and volcanic edifices is therefore a rare occurrence that requires special conditions. Yet, the majority of crustal rocks are of igneous origin, and thus these conditions must, on occasion, be met. The steady-state geotherm beneath a continent or ancient ocean floor (Section 1.6) does not come near the dry beginning of melting curve for mantle peridotite, at least not at the depths at which we believe magmas are generated. Therefore, either the geotherm must be raised or the beginning of melting curve lowered if magmas are to form.
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principles of igneous and Metamorphic Petrology introduction to thermodynamics
2009Co-Authors: Anthony R Philpotts, Jay J AgueAbstract:INTRODUCTION Thermodynamics, the study of energy, is one of the most important subjects in all of science. Historically, it evolved from the desire to understand the efficiency of machines, in particular of steam engines. Much of its terminology, therefore, centers around heat and work, especially work associated with expanding gas. Thermodynamics, however, deals with the transfer of other forms of energy, such as that associated with chemical reactions. Although heat and mechanical work done by expanding gas are important in geology, for example in the cooling of a magma or the explosion of a volcano, it is in the study of chemical energies that thermodynamics is of greatest value to Petrology. It is particularly useful in the study of processes that take place within the Earth, where they cannot be observed directly. The increased availability in recent years of thermodynamic data for the common minerals and magmas has resulted in a rapid growth in the application of thermodynamics to petrologic problems, and computer programs now use these data to calculate the compositions of minerals crystallizing from magmas and the mineral assemblages that can form in Metamorphic rocks under any given temperature and pressure. The general applicability of thermodynamics stems from the fundamental nature of the principles on which it is based, namely simple observations on the behavior of energy. For example, although energy can be converted from one form to another (kinetic to potential, chemical to thermal, etc.), it can never be destroyed.
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principles of igneous and Metamorphic Petrology origin of rocks
2009Co-Authors: Anthony R Philpotts, Jay J AgueAbstract:INTRODUCTION In previous chapters, we have dealt with the specific details of the formation of rocks. In this final chapter, we examine the broader question of their ultimate origin. What conditions in the Earth bring about the formation of rocks, and from where does the material come to form them? These are important questions, the answers to which are critical to interpreting Earth's history, for only in rocks is any record of the geologic past preserved. There is certainly no unanimity among petrologists on answers to all aspects of these questions, but the theory of plate tectonics has provided a unifying paradigm that has eliminated much controversy. Difficulty in answering the questions stems from the inaccessibility of the regions in which the controlling processes operate and our limited experimental and theoretical knowledge of the behavior of material under the pressures and temperatures that exist in such regions. Because of the rapid evolution of ideas on this topic, no attempt is made in this chapter to review all aspects of these questions. Instead, some basic principles are discussed which should be of help in evaluating these ideas. Ever since the formation of the Earth 4.567 Ga ago, heat generated by accretionary processes, radioactive decay, and gravitative differentiation – in particular of the core – has been transferred to the surface of the planet where it has been radiated into space. Conduction, advection, and radiation have all played roles in this transfer.