Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
Accessory phases are important hosts of trace elements; allanite may contain >90% of the REE in a bulk rock. The mobility and redistribution of several trace elements, notably HREE, Th, U, and Y is thus controlled by reactions involving allanite and other REE phases, as well as several rock-forming minerals. As these elements are commonly concentrated in mature elastic sediments, a suite of impure quartzite was studied. Two eclogite facies samples from the Monometamorphic Cover Complex of the Sesia Zone (Western Italian Alps) are presented in some detail, as they reveal a remarkably rich spectrum of reaction relationships that involve REE phases.;Two allanite-forming reactions were inferred from textures and phase compositions;(1) monazite + Ca-silicate(?) + fluid -> allanite + apatite + thorite;;(2) monazite + thorite + Ca-silicate(?) + fluid -> Th-rich allanite + auerlite +/- apatite.;Petrographic observations and thermodynamic models suggest that allanite entered the HP assemblage at similar to 530 degrees C and 17-18 kbar during prograde metamorphism.;In one sample, allanite is rimmed by epidote rich in Y and HREE that grew at the expense of xenotime. Two net transfer reactions were derived;(3) xenotime + allanite + fluid -> Y-rich epidote + apatite + thorite;;(4) xenotime + allanite + fluid -> Y-rich epidote + aeschynite + thorite + (phosphate?).;Textural relationships and trace element analyses of coexisting allanite/monazite and xenotime/Y-rich epidote reveal systematic partitioning of the REE. Partition coefficients for the HREE are compatible with equilibrium fractionation, whereas those for the LREE show patterns that seem to be inherited from the precursor phases, in this case zircon with variable LREE composition.
ISSN: 0003-004X

hal-00745674
https://hal.archives-ouvertes.fr/hal-00745674
DOI : 10.2138/am.2012.3832

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
In situ mineralization of CO2 in ultramafic rock-hosted aquifers is one of the promising solutions for decreasing CO2 concentrations in the atmosphere. Naturally altered ultramafic rocks suggest that carbonation processes are controlled by local heterogeneities in the structure of the rock and fluid transport at the water-rock interfaces. We studied the role of rock crystallographic anisotropy relative to the global fluid flow direction on the mineralization of CO2 by means of electron microscope analyses from the macro- to the micrometer scale (EBSD-FIB). The sample used for the measurements was a hot pressed olivine core percolated by water enriched in CO2 (pCO2 = 10 MPa) at 180 °C. During the percolation experiment, olivine was dissolved and two types of carbonates, dolomite, and magnesite, were precipitated on olivine surfaces. The results showed that the dissolution of olivine is controlled by its crystallographic properties as shown by the development of etch-pits only on the (010)ol planes and with elongated shapes parallel to the [010]ol axes. In contrast, the precipitation of carbonates is governed by hydrodynamic properties. Carbonates are heterogeneously distributed in the percolated rock. They are mainly located along the moderate (for dolomite) and the minor (for magnesite) flow paths, both oriented parallel to the principal fluid flow direction, which allow carbonates to be supplied with divalent cations (e.g., Ca2+, Mg2+, and Fe2+). In these flow paths, carbonate growth is systematically oriented normal to the flow that facilitates the development of chemical gradients with cationic supersaturation conditions for carbonate precipitation near the walls.In natural systems, the (010)ol planes are parallel to the Moho and the (100)ol planes are vertical; our study suggests that flow of CO2-rich fluids will induce precipitation of carbonates localized along, and preferentially clogging, vertical flow paths while favoring olivine dissolution along horizontal fluid pathways. This dual control of structure and fluid flow on carbonation mechanisms could be an important parameter allowing sustainable CO2 storage in peridotites, while limiting the risks of leakage toward the surface.
ISSN: 0003-004X

hal-01143393
https://hal.archives-ouvertes.fr/hal-01143393
DOI : 10.2138/am-2015-4913

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
The effect of trace concentrations of Ti on the rate and mechanism of hydrogen diffusion in pure forsterite was investigated experimentally. Forsterite doped with 350–400 ppm Ti (predominantly octahedral Ti3+, minor tetrahedral Ti4+) was prepared by diffusing Ti into pure synthetic forsterite at high temperature (1500 °C), very low oxygen fugacity (~QFM-5) at atmospheric pressure. The Ti-doped forsterite was then diffusively hydroxylated in a piston-cylinder apparatus at much lower temperatures (650–1000 °C) and higher oxygen fugacities, at 1.5–2.5 GPa, with chemical activities buffered by forsterite-enstatite or forsterite-periclase and partial pressure of H2O equal to total pressure. This produced hydrogen concentration-distance profiles of several hundred micrometers in length. Diffusion of hydrogen through the Ti-doped forsterite, even at very high Embedded Image , does not lead to redox re-equilibration of the high Ti3+/ΣTi ratio set during the synthesis of the starting material at extremely reducing conditions—the metastable point defects are partially preserved.Three main hydroxylated point defects are observed; hydroxyl is associated with Ti4+ (titano-clinohumite point defects), Ti3+ (and possibly other trivalent cations), and M-site vacancies. Concentration-distance profiles represent an interplay between diffusion and reaction (i.e., site rearrangement) to form the observed point defects. In all experiments, the concentration-distance profiles of the hydroxylated Ti defects coincide with the concentration-distance profiles of the M-site vacancy substitution, with the same crystallographic anisotropy. This suggests that the macroscopic movement of hydrogen through the crystal is due to one diffusion mechanism (the diffusion of hydroxylated M-site vacancies). The net H diffusion coefficient [logD(ΣH)], between 650–1000 °C, is Embedded Image where the values of logD0(ΣH) parallel to [100] and [001] directions are −3.0 ± 0.4 and −2.2 ± 0.4, respectively; diffusion is therefore around one order of magnitude faster along the c axis than along the a axis. The diffusion of hydrogen is slightly faster in Ti-doped forsterite than in pure forsterite. There is no effect of chemical activity or oxygen fugacity on the rate of diffusion. Hydrogen diffusion profiles represent a complex interplay between the movement of H through the crystal lattice and point-defect reactions to maintain charge balance.
ISSN: 0003-004X

hal-01467402
https://hal.archives-ouvertes.fr/hal-01467402
DOI : 10.2138/am-2016-55681571

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
Hydrogen distribution between nominally anhydrous minerals (NAMs) of a garnet-lherzolite under subsolidus conditions has been investigated. Separated NAMs from a garnet-peridotite from Patagonia (Chile) are annealed together (olivine, orthopyroxene, clinopyroxene, and garnet) using a piston-cylinder at 3 GPa and 1100 °C using talc-pyrex cell assembly for 10, 25, and 100 h. The talc-pyrex assembly provides enough hydrogen in the system to re-equilibrate the hydrogen concentrations at high pressure. The three coexisting nominally anhydrous minerals (NAMs, i.e., olivine, orthopyroxene, and clinopyroxene) were successfully analyzed using FTIR. The resulting hydrogen concentrations exceed significantly the initial hydrogen concentration by a factor of 13 for olivine and a factor of 3 for both pyroxenes. Once mineral-specific infrared calibrations are applied, the average concentrations in NAMs are 115 ± 12 ppm wt H2O for olivine, 635 ± 75 ppm wt H2O for orthopyroxene, and 1214 ± 137 ppm wt H2O for clinopyroxene, garnet grains are dry. Since local equilibrium seems achieved over time (for 100 h), the calculated concentration ratios are interpreted as mineral-to-mineral hydrogen partition coefficients (i.e., Nernst’s law) for a garnet-peridotite assemblage. It yields, based on mineral-specific infrared calibrations, DOpx/Ol = 5 ± 1, DCpx/Ol = 10 ± 2, and DCpx/Opx = 1.9 ± 0.4. While DCpx/Opx is in agreement (within error) with previous results from experimental studies and concentration ratios observed in mantle-derived peridotites, the DPx/Ol from this study are significantly lower than the values reported from mantle-derived xenoliths and also at odd with several previous experimental studies where melt and/or hydrous minerals co-exists with NAMs. The results confirm the sensitivity of hydrogen incorporation in olivine regarding the amount of water-derived species (H) in the system and/or the amount of water in the coexisting silicate melt. The results are in agreement with an important but incomplete dehydration of mantle-derived olivine occurring at depth, during transport by the host magma or during slow lava flow cooling at the surface. The rapid concentration modification in mantle pyroxenes also points out that pyroxenes might not be a hydrogen recorder as reliable as previously thought.
ISSN: 0003-004X

hal-01622132
https://hal.archives-ouvertes.fr/hal-01622132
DOI : 10.2138/am-2017-6089

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
Wadsleyites with various iron contents were synthesized at ~12-14 GPa and 1400 °C under oxidizing and hydrous conditions in coexistence with enstatite. The samples were studied using micro-X-ray absorption near edge structure (XANES) and micro-Mössbauer spectroscopy to determine the ferric iron contents in polyphasic samples and secondary ion mass spectrometry (SIMS) to determine the water concentrations. XANES and Mössbauer analyses show that ferric iron content increases with increasing total iron content, and reaches a maximum of ~30% Fe3+/Fetotal. Two XANES results were cross-checked by Mössbauer analysis and both methods are in reasonable agreement. The use of Fourier transform infrared spectroscopy reveals a new protonation scheme in wadsleyite, with a significant proportion of protons associated with the high-frequency band at 3611 cm−1 and a new band located at 3500 cm−1. The intensity of these two bands is higher for Fe3+-rich wadsleyite. SIMS analyses show that water contents in wadsleyite vary from 4500 to 9400 ppm H2O by weight. Pyroxene water contents range from 790 to 1600 ppm wt H2O. The concentration of water in both phases decreases with increasing iron content. The partition coefficient of water between wadsleyite and pyroxene varies between 5 and 9 and increases with increasing Fe-number of wadsleyite [i.e., XFe/(XFe + XMg) × 100 ratio]. The divalent cation concentrations (i.e., Mg2+ + Fe2+), the Si as well as the H content in wadsleyite decrease with increasing Fe3+ content, indicating an incorporation mechanism via substitution into the metal (Me = Mg2+ and Fe2+) and Si sites with a ratio of 5/3 for (Fe3++H+):Me and of 5/1 for (Fe3++H+):Si, similarly as in the dry system. Thus, coupled substitution of Fe3+ and H+ does not affect the incorporation mechanism of Fe3+, but does affect the location of H+, which is partly incorporated at tetrahedral edges forming [FeSi′-(OH)o*]X neutral defects substituting for Si. In this model 25% of the ferric iron occupies the tetrahedral sites.
ISSN: 0003-004X

hal-00758071
https://hal.archives-ouvertes.fr/hal-00758071
DOI : 10.2138/am.2012.3869

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
To test if hydrogen incorporation by ionic diffusion can occur between a volatile-rich kimberlitic liquid and forsterite, results of high-pressure and high-temperature experiments using a piston-cylinder apparatus at 1200–1300 °C and 1 GPa for durations of 1 min, 5 h, and 23 h, are reported here. Kimberlitic liquid in the system CaO-MgO-Al2O3-SiO2-CO2-H2O and synthetic forsterite single crystals were chosen as a first simplification of the complex natural kimberlite composition. Unpolarized Fourier transform infrared spectroscopy was used to quantify the concentrations of OH in the crystallographically oriented forsterite. Scanning electron microscopy, electron backscattered diffraction, electron microprobe analyses, and transmission electron microscopy were performed to identify the run products. After 5 and 23 h, a forsterite overgrowth crystallized with the same orientation as the initial forsterite single crystal. The kimberlitic liquid has crystallized as micrometer-scale euhedral forsterite neocrystals with random crystallographic orientations, as well as a nanoscale aluminous phase and a calcic phase. Despite theoretical water-saturation of the system and long duration, none of the initial forsterite single crystals display signs of hydration such as hydrogen diffusion profile from the border toward the center of the crystal. Most likely, the presence of CO2 in the system has lowered the H2O fugacity to such an extent that there is no significant hydration of the starting forsterite single crystal or its overgrowth. Also, the presence of CO2 enhances rapid forsterite crystal growth. Forsterite growth rate is around 2 × 108 μm3/h at 1250 °C. These experimental results suggest a deep mantle origin of the high OH content found in natural mantle-derived xenoliths transported in kimberlites, as reported from the Kaapvaal craton. In agreement with previous studies, it also points out to the fact that significant hydration must take place in a CO2-poor environment.
ISSN: 0003-004X

hal-01217157
https://hal.archives-ouvertes.fr/hal-01217157
DOI : 10.2138/am-2015-5200

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
Pressure-temperature divariant melting phase relations of model carbonated peridotite in the system CaO-MgO-Al2O3-SiO2-CO2 from 8 to 12 GPa are reported. From 8 to 12 GPa, melting temperatures on the studied pressure-temperature divariant surface rise quite rapidly. Liquids, in equilibrium with forsterite, orthopyroxene, clinopyroxene, and garnet, on the low-temperature side of the divariant surface are magnesiocarbonatitic in composition. With increasing temperature along an isobar on the pressure-temperature divariant surface, and with the same crystalline phase assemblage, liquids gradually become kimberlitic in their composition. Given the model system data reported here, Group IB kimberlites and perhaps some kimberlites from Greenland, Canada, and South Africa could be generated from direct melting of carbonated peridotite in the pressure range of approximately 6-8 GPa. Some kimberlites from Canada and Russia could have formed by partial melting of carbonated mantle peridotite at pressures of about 10-12 GPa. From 8 to 12 GPa, liquid compositions on the studied divariant surface show a limited compositional range, which implies that the divariant surface is essentially flat. The implied flatness of the divariant surface, and so long as the liquid is in equilibrium with the crystalline assemblage of forsterite + orthopyroxene + clinopyroxene + garnet on the divariant surface, indicate that kimberlites belonging to Group IA and those more magnesian than Group IA cannot have their origin in only being a melting product of carbonated mantle peridotite. The absence of topography of the studied pressure-temperature divariant surface in all likelihood limits the generation of kimberlites in the Earth's upper mantle only.
ISSN: 0003-004X

hal-01053915
https://hal.archives-ouvertes.fr/hal-01053915
DOI : 10.2138/am.2014.4826

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
To constrain the crystallization of alkaline and volatile-rich lavas present in intraplate settings, we studied the petrological features and the geochemical composition of major, trace, and volatile elements of mineral and bulk-rock of two sodalite-bearing phonolites: (1) haüyne-plagioclase-bearing Si-K-rich phonolite from Laacher See (Germany) and (2) nosean-nepheline-bearing Si-poor phonolite from Saghro (Morocco). In haüyne-bearing phonolites (55–59 wt% SiO2, K > Na, Na+K/Al = 0.96–1.08), we found that the low silica and low sodium activity promoted the early crystallization of S-rich haüyne (13.7–13.9 wt% SO3, 0.4 wt% Cl) + S-rich apatite (0.7–0.9 wt% SO3), titanite, and rare pyrrhotite followed by clinopyroxene-plagioclase-sanidine at relatively low pressure and temperature (P = 250 MPa and T = 850 °C) and oxidized condition (ΔNNO-NNO+1, where NNO is nickel-nickel oxide buffer). The crystallization of haüyne occurred at fluid-undersaturated conditions from a silicate melt with 6 wt% H2O, 0.17–0.23 wt% Cl, 0.11–0.4 wt% S, and 0.07–0.14 wt% F. Nosean-bearing phonolites from Saghro are silica-poor and peralkaline (52–54 wt% SiO2, Na > K, Na+K/Al = 1.2) and crystallized at higher P and T (300 MPa and 950 °C) and more reduced conditions (NNO) compared to haüyne-bearing phonolites. The incongruent reaction to form nosean requires high silica and Na2O activity. The mineral assemblage and composition suggest early crystallization of nepheline followed by nosean (7.8–8.8 wt% SO3; 1–1.1 wt% Cl). The sequence of crystallization is: clinopyroxene + nepheline + S-poor apatite (<0.04 wt% SO3) + pyrrhotite followed by nosean and titanite. Nosean-bearing magmas are fluid-undersaturated with relatively low volatile content (4 wt% H2O, <0.25 wt% Cl, <0.056 wt% S, 0.08–0.1 wt% F), although Cl may have exsolved during ascent and formed a fluid phase (NaCl-bearing).Both haüyne- and nosean-bearing phonolites are last equilibrated at relatively low pressure and high temperature. Haüyne and nosean crystallized at oxidized and volatile-rich pre-eruptive conditions. They record the volatile concentrations at depth and may be used as oxybarometer. The incongruent reactions involved to form haüyne and nosean suggest that phonolitic magmas became more oxidized during crystallization. The initial volatile concentrations in basanite/nephelinite magmas, from partial melting of volatile-bearing K2O-rich mantle rock, should have been one important factor influencing the crystallization of haüyne-bearing Si-K-rich phonolite and nosean-bearing Si-poor phonolite in intracontinental setting.
ISSN: 0003-004X

hal-01278067
https://hal.archives-ouvertes.fr/hal-01278067
DOI : 10.2138/am-2015-5318

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
Crystallization experiments were conducted at 200 MPa to determine the effect of small amounts of H2O on the liquidus temperature of basaltic melts in which plagioclase is the liquidus phase. The H2O concentrations in the quenched glasses, determined by infrared spectroscopy and Karl-Fischer titration, ranged from 0.02 to 4.2 wt% H2O. The dry liquidus temperature at 200 MPa was estimated from experiments at 1 atm (H2O-free) and from the known pressure dependence of plagioclase crystallization temperature. The effect of water (expressed as wt% H2O) on the plagioclase liquidus temperature is nonlinear and diminishing with increasing melt H2O concentrations. According to our new experimental data, it can be empirically predicted with following equation: Formula where CH2O is the water concentration in the melt (wt%), TDRY, and TWET are plagioclase crystallization temperatures in water-free and water-bearing systems, respectively. The relationship between CH2O and liquidus temperature worked out in this study is valid for a range of basaltic compositions, ranging from high-alumina basalts to basaltic andesites. The combination of the empirical equation predicting the liquidus depression of plagioclase with previous models predicting the olivine liquidus curve is useful to determine the liquidus temperature in various H2O-bearing basaltic systems in which either plagioclase or olivine is the liquidus phase.
ISSN: 0003-004X

hal-00757600
https://hal.archives-ouvertes.fr/hal-00757600
DOI : 10.2138/am.2012.4100