Garnets are major silicates from the upper mantle to the transition zone. Elastic properties of garnets are essential to interpret the variation of seismic velocities at different depths and construct a model of the Earth’s composition. Due to the chemical flexibility at octahedron sites of the crystal structures, garnets usually exist with multiple components and have many composition variations. Pyrope is an important member in the garnet group. Fe2+-Mg2+ substitution in pyrope is one of the common solid solutions. We have synthesized and measured three synthetic solid solutions samples (Py83Alm17, Py54Alm46 and Py30Alm70). Equations of state yielded their isothermal bulk moduli K0 to be 172(4)GPa, 174(2)GPa, and 183(2)GPa, respectively, which confirmed that almandine content (Fe2+ substitution) increased the bulk modulus of the garnet. A relation between the bulk modulus and the almandine mole fraction (n) was derived to be K0 = 170 + 15 n, showing it is a nearly ideal mixing model. Another factor that also significantly influences the elasticity of pyrope is water. Water is transported to the deep Earth by subduction slabs and mainly exists in nominally anhydrous minerals (NAM) as hydroxyl (OH-). Its content in minerals varies as depth increases. We therefore investigated pressure influence on water solubility in pyrope. A suite of pyrope single crystals was synthesized in a water-saturated environment at 6, 7, 9 and 12GPa and water was characterized by FTIR. IR spectra showed a typical peak at 3630 cm-1. At 9 and 12GPa, new peaks at 3572 cm-1 and 3504 cm-1 appeared and indicated that a new substitution mechanism, other than hydrogarnet substitution SiO4=(OH)4, was adopted in the pyrope crystal structure. Water solubility in pyrope reached 0.2wt% at 7GPa. From 4-7GPa, water solubility increased. At 9GPa, water content dropped to 0.07wt% and increased to 0.3wt% at 12GPa, where a cubic to tetragonal phase transition was observed. Water showed a weakening effect on the bulk moduli of hydrous pyrope. Their bulk moduli were 166GPa, 173GPa and 161GPa with water contents of 0.07wt%, 0.1wt% and 0.2wt%, respectively. An approximate linear relationship was proposed about the bulk modulus as a function of water content.

La mobilisation des REE et de l’Hf par un fluide aqueux durant les processus métamorphiques HP-BT peut entraîner des perturbations dans la signature des protolithes et/ou dans les datations obtenues par les systèmes isotopiques Sm-Nd et Lu-Hf. L’étude couplée de la transition éclogite - amphibolite de la localité de Vårdalsneset (WGR, Norvège) et des coefficients de partage des REE et de l’Hf entre un fluide aqueux à NaCl ou à CO2 et le grenat pyrope (P = 3 GPa, T = 800°C) déterminés expérimentalement conduit à deux résultats majeurs. Tout d’abord, une différence d’échelle de mobilité entre les REE (mobiles à l’échelle décimétrique) et l’Hf (mobile à l’échelle du grain) est démontrée. Les signatures des protolithes restent cependant identifiables et les âges modèles Sm-Nd et Lu-Hf des métabasites ne sont pas perturbés, arguant d’une mobilité restreinte des REE. Ensuite; cette étude montre l’influence du CO2 dissous dans le fluide aqueux sur le partage fluide-roche des HREE. L'étude expérimentale indique que les HREE sont incompatibles dans le pyrope en présence d'un fluide à CO2. Ces résultats permettent d’expliquer l’appauvrissement en HREE sous l'effet de fluides à H2O-CO2 ou à CO2 des métabasites de Vårdalsneset. / REE and Hf mobility in aqueous fluids during HP-BT metamorphism can disturb magmatic signatures of protoliths and Sm-Nd and Lu-Hf dating. This study performed on both natural samples from Vårdalsneset (WGR, Norway) and experimental estimates of REE and Hf partition coefficients between aqueous fluid with NaCl or CO2 and pyrope (P = 3 GPa, T = 800°C) highlights two main results. Firstly, REE can be mobilized at the sample scale (tens of centimetres) whereas Hf is only mobilized at the grain scale. Magmatic signatures of protoliths are nevertheless recognizable and Nd and Hf model ages are not disturbed, that suggests slight mobility of REE. Secondly, an aqueous fluid with CO2 induces an incompatible behaviour of HREE in pyrope, which can explain the depletion in HREE of the metabasites of Vårdalsneset in presence of a H2O-CO2 or CO2 fluid.

L'étude des métapelites de haute pression des Alpes occidentales révéle une grande variété de degrés métamorphiques, depuis un domaine a Fe-Mg-carpholite, un domaine intermédiaire à chloritoïde magnesien-talc-phengite, jusqu'à un domaine ou sont stables la coesite, le pyrope et l'ellenbergerite, nouveau mineral du systeme pelitique. L'etude expérimentale du système MgO-Al(2)O(3)-SiO(2)-H(2)O a permis la synthèse de Mg-carpholite, Mg-chloritoide et pyrope, et la determination de leur stabilitè et relations de phase entre 400 et 800°C, 15 et 40 kbar. Appliquées aux systèmes naturels et associées à de nouvelles datations (39Ar-40Ar), ces données sont intégrées dans un schéma évolutif de la chaine alpine impliquant l'enfouissement de la croûte continentale à près de 100 km de profondeur

Elastic properties of the major constituent minerals in the Earth’s upper mantle at relevant high pressure-temperature (P-T) conditions are crucial for understanding the composition and seismic velocity structures of the region. In this study, we have measured the single-crystal elasticity of natural Fe-bearing pyrope, Mg2.04Fe0.74Ca0.16Mn0.05Al2Si3O12, using in situ Brillouin spectroscopy and X-ray diffraction at simultaneous high P-T conditions up to 20 GPa and 750 K in an externally-heated diamond anvil cell. The derived aggregate adiabatic bulk and shear modulus (KS0, G0) at ambient conditions are 168.2 (±1.8) GPa and 92.1 (±1.1) GPa, respectively, consistent with literature results. Using the third-order Eulerian finite-strain equation to fit the high P-T data, the derived pressure derivative of the bulk and shear moduli at constant temperature are (∂KS/∂P)T=4.4 (±0.1) and (∂G/∂P)T=1.2 (±0.1), respectively. Applying these pressure derivatives, the temperature derivative of these moduli at constant pressure are also calculated, yielding (∂KS/∂T)P=-18.5(±1.3) MPa/K and (∂G/∂T)P=-5.2(±1.1) MPa/K, respectively. Compared to literature values, our results show that addition of 25% Fe in pyrope increases the pressure derivative of the bulk modulus by 7%, but has a negligible effect on other elastic parameters. Extrapolation of our results shows that Fe-bearing pyrope remains almost elastically isotropic at relevant P-T conditions of the upper mantle, indicating that it may not have a significant contribution to seismic Vp and Vs anisotropy in the upper mantle. Together with the elasticity of olivine and pyroxene minerals in the upper mantle, we have constructed new velocity profiles for two representative compositional models, pyrolite and piclogite, along Earth’s upper mantle geotherm. These velocity models show Vs profiles consistent with seismic observations, although Vp profiles are slightly lower than in seismic models. / text

Bohemian garnets have been known as a jewellery stone for many centuries. There is still a lot of interest in them, however, the reserves in traditional locations are getting smaller. That is why search for alternative source of similar garnets in gem quality started. Shavaryn Tsaram deposit in Mongolia is considered as one of the potential sources. Pyrope samples from eight Bohemian localities of two areas (České středohoří [The Central Bohemian Uplands] and Podkrkonoší [The Giant Mountains]) and from Shavaryn Tsaram deposit in Mongolia were analysed using electron microprobe, LA-ICP-MS, ICP-OES, Mössbauer spectroscopy and x-ray powder diffraction. The data were compared with the conclusion that the Mongolian garnets from Shavaryn Tsaram deposit are so different from the Bohemian ones that it will not be possible to use them as a gem material of similar qualities. Bohemian garnet can be characterised as a red garnet with refraction index 1.747 (+/- 0.001) with dominant pyrope component of the average composition Py78Alm17Gr5 and Cr2O3 content above 1 wt.%. The data were also evaluated from two classification schemes point of view. The schemes by Schulze (2003) and Grütter (2004) are used in determining source materials and in diamond prospection. According to them source rocks of Bohemian garnets...