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International audience; Rare earth element (REE) enrichments in carbonatites are often described as resulting from late magmatic-hydrothermal or supergene processes. However, magmatic pre-enrichment linked to the igneous processes at the origin of carbonatites are likely to contribute to the REE fertilisation. Experimental constraints reveals that immiscibility processes between carbonate and silicate melts can lead to both REE enrichments and depletions in carbonatites making the magmatic processes controlling REE enrichments unclear.We link REE contents of carbonatites to the magmatic stage at which carbonatites are separated from silicate magma in their course of differentiation. We present results of experiments made at pressure and temperature conditions of alkaline magmas and associated carbonatites differentiation (0.2 to 1.5 GPa; 725 to 975 °C; FMQ to FMQ +2.5), simultaneously addressing crystal fractionation of alkaline magmas and immiscibility between carbonate (calcio-carbonate type) and silicate melts (nephelinite to phonolite type). The experimental data shows that the degree of differentiation, controlling the chemical composition of alkaline melts, is a key factor ruling the REE concentration of the coexisting immiscible carbonate melts. In order to predict carbonate melt REE enrichments during alkaline magma differentiation, we performed a parameterisation of experimental data on immiscible silicate and carbonate melts, based exclusively on the silica content, the alumina saturation index and the alkali/alkaline-earth elements ratio of silicate melts. This parameterisation is applied to more than 1600 geochemical data of silicate magmas from various alkaline provinces (East African Rift, Canary and Cape Verde Islands) and show that REE concentrations of their potential coeval carbonatite melts can reach concentration ranges similar to those of highly REE enriched carbonatites (∑REE > 30 000 ppm) by immiscibility with phonolitic/phono-trachytic melt compositions, while more primitive alkaline magmas can only be immiscible with carbonatites that are not significantly enriched in REE.

The modelling of peatland functioning, in particular the impact of anthropogenic warming and direct human disturbance on CO2, CH4 and N2O, requires detailed knowledge of the peat structure and of both water and gas flow with respect to the groundwater table level. To this end, freezing is nowadays increasingly used to obtain small size peat samples for X-ray micro computed tomography (X-ray μ-CT) as required by the need to increase the resolution of the 3D X-ray CT images of the peat structure recorded. The aim of this study was to analyze the structure of a peat material before and after freezing using X-ray μ-CT and to look for possible alterations in the structure by investigating looking at the air-filled porosity. A highly decomposed peat material close to water saturation was selected for study and collected between 25 and 40 cm depth. Two samples 4 × 4 × 7 cm3 in volume were analyzed before and after freezing using an X-ray μ-CT Nanotom 180NF (GE Phoenix X-ray, Wunstorf, Germany) with a 180 kV nanofocus X-ray tube and a digital detector array (2304 × 1152 pixels Hamamatsu detector). Results showed that the continuity and cross section of the air-filled tubular pores several hundreds to about one thousand micrometers in diameter were altered after freezing. Many much smaller air-filled pores not detected before freezing were also recorded after freezing with 470 and 474 pores higher than one voxel in volume (60 × 60 × 60 μm3 in volume each) before freezing, and 4792 and 4371 air-filled pores higher than one voxel in volume after freezing for the two samples studied. Detailed analysis showed that this increase resulted from a difference in the whole range of pore size studied and particularly from a dramatic increase in the number of air-filled pores ranging between 1 voxel (216 103 μm3) and 50 voxels (10.8 106 μm3) in volume. Theoretical calculation of the consequences of the increase in the specific volume of water by 8.7 % when it turns from liquid to solid because of freezing led to the creation of a pore volume in the organic matrix which remains saturated by water when returning to room temperature and consequently to the desaturation of the largest pores of the organic matrix as well as the finest tubular pores which were water-filled before freezing. These new air-filled pores are those measured after freezing using X-ray μ-CT and their volume is consistent with the one calculated theoretically. They correspond to small air-filled ovoid pores several voxels in volume to several dozen voxels in volume and to discontinuous air-filled fine tubular pores which were both detected after freezing. Finally, the increase in the specific volume of water because of freezing appears also be also responsible for the alteration of the already air-filled tubular pores before freezing as shown by the 3D binary images and the pore volume distribution.

Whether seismic rupture propagates over large distances to generate mega-earthquakes or is rapidly arrested mainly depends on the slip processing within the fault core, including in particular frictional melting or intense grain-size reduction and amorphization. The record of seismic slip in exhumed fault zones consists in many instances in Black Faults Rocks, dark and glass-like-filled aphanitic veins that have been interpreted as resulting from quenching of frictional melts, i.e., pseudotachylytes. Such interpretation has nevertheless been questioned as similar macro to nano-textures have been observed either on intensely comminuted natural fault rocks or on slow creep experiments on crustal rocks, where melting is absent. Here, we report a new dataset of Raman Spectroscopy of Carbonaceous Material analyses, aimed at discriminating the slip weakening processes operating in the fault core during slip. Using high spatial resolution profiles on natural Black Fault Rocks from accretionary complexes and an experimentally calibrated modelling of Raman intensity ratio evolution with temperature, we assessed different scenarios of temperature evolution during fault slip. In the three studied Black Fault Rocks interpreted so far as natural pseudotachylytes, Raman Spectroscopy of Carbonaceous Material results are not consistent with a molten origin and therefore should reflect a mechanical wear during deformation. These results bear major consequences on the dynamics of faulting, as the slip-weakening processes that occur during seismic slip rely on the extreme grain-size reduction and fluidization rather than melting.

Whether seismic rupture propagates over large distances to generate mega-earthquakes or on the contrary slows down quickly, is heavily dependent on the slip processes operating within the fault core, such as frictional melting or intense grain-size reduction and amorphization. The record, in fossil fault zones, of seismic slip, consists in many instances in Black Faults Rocks (BFR), that consists in a generally thin dark and aphanitic veins similar to volcanic glasses, which cross-cuts sharply a weakly foliated tectonic mélange, and have been interpreted as resulting from quenching of a melt (i.e. pseudotachylytes). Such interpretation has nevertheless been questioned because identical (micro- and nano-) textures have been observed on intensely comminuted natural fault rocks and on slow creep experiments on crustal rocks.In this study, we report a new dataset of high spatial-resolution Raman Spectroscopy of Carbonaceous Materials (RSCM) profiles across natural BFR from two accretionary complexes. RSCM is sensitive to both temperature and deformation. We have carried out analyses on Okitsu and Nobeoka BFR from the Shimanto Belt and Kodiak BFR from the Kodiak Accretionary Complex to discriminate the slip weakening process. The Raman Intensity Ratio (i.e. R1 in Beyssac et al., 2002) and the Area ratio (RA1 in Lahfid et al., 2010) show a drastic and discontinuous stepped increase along profiles across the BFR, revealing a higher crystallinity. Moreover, in spite of scattering, highest values have been measured on the rim between the BFR and the host-rock. Fluidization structures, interpreted as injection veins, show similar values to the ones in the host rock. Additionally, using an experimentally calibrated kinetics 1D modelling of Intensity ratio evolution with temperature, we compared the natural Raman spectroscopy profiles to different scenarios of temperature increase during seismic slip. In the three examples of BFR from accretionary complexes interpreted as natural pseudotachylytes, RSCM profiles are not consistent with a molten origin and must reflect mechanical wear during deformation.Consequently, these results bear major consequences on the dynamics of faulting in accretionary complexes, as the slip-weakening processes that occur during seismic slip rely on extreme grain-size reduction and fluidization rather than melting.

International audience; Magma ascending from the storage region toward the surface may crystallize small and rapidly-grown crystals, designated as microlites. Upon decompression, the rapid changes of the microlite textures, such as number density and crystal size, directly impact the rheology of the magma in the volcanic conduit, and eventually control the effusive vs. explosive style of the subaerial eruption. This is of prime importance for volcanic risk assessment involving highly viscous silica-rich magmas that are prone to fragmentation. To this aim, we present a theoretical modeling of plagioclase nucleation and growth in rhyolitic-like melts, based on previous decompression experiments. Thus, the modeling is valid for plagioclase crystallization in rhyolitic melts decompressed at 875 • C from 200 MPa to final pressures of 50, 75, or 100 MPa, which represents effective undercooling (T eff) of 110, 80 and 55 • C, respectively. Our results of nucleation-rate calculation using the Classical Nucleation Theory (CNT; case of homogeneous nucleation) and values of crystal-melt interfacial energy (σ) either from literature or empirically calculated, strongly disagree with previously-determined experimental nucleation rates. By inverting the CNT calculation using the experimentally-determined nucleation rates, we propose plagioclase-liquid interfacial energies from 0.041 to 0.059 J.m −2 with T eff increasing from 55 to 110 • C, which is about 2-3 times lower than σ determined empirically and macroscopically. We modeled plagioclase growth rates by atom diffusion in melt (following Fick's second law adapted to multicomponent systems), considering a crystal-melt interface advancing over time (as crystal grows) and a chemically-closed finite reservoir (no component supply). The component limiting plagioclase growth has been determined to be CaO, for which we calculated diffusion coefficients from 10 −14 to 10 −15 m 2 /s (conditions of a silicic melt, 875 • C, and H 2 O saturation pressures from 50 to 100 MPa). The overall good agreement between the model and the experimental growth laws validates diffusion as the main process controlling isothermal decompression-induced plagioclase growth under moderate T eff < 110 • C. Combining both calculations, crystal number density and size, may be relevant to predict plagioclase microlite textures in ascending rhyolitic magmas, which may now be incorporated in conduit flow models to assess the magma rheological behavior that controls eruption dynamics.

International audience; Decompression melting of the upper mantle produces magmas and volcanism at the Earth's surface. Experimental petrology demonstrates that the presence of CO2 and H2O enhances peridotite melting anywhere within the upper mantle down to approximately 200–300 km depth. The presence of mantle melts with compositions ranging from carbonate-rich to silicate-rich unavoidably affects the geophysical signals retrieved from Earth's mantle. Geochemical investigations of erupted intraplate magmas along with geophysical surveys allow for constraining the nature and volume of primary melts, and a sound formalism is required to integrate these diverse datasets into a realistic model for the upper mantle including melting processes. Here, we introduce MAGLAB, a model developed to calculate the composition and volume fraction of melts in the upper mantle, together with the corresponding electrical conductivity of partially molten mantle peridotites at realistic pressure-temperature conditions and volatile contents. We use MAGLAB to show how the compositions of intraplate magmas relate to variations in lithosphere thickness. Progressive partial melting of a homogeneous peridotitic mantle source can in theory create the diversity of compositions observed among the spectrum of intraplate magma types, with kimberlite melts beneath thick continental shields, alkaline magmas such as melilitite, nephelinite and basanite beneath thinner continents and relatively old plus thick oceanic lithospheres, and ‘regular’ basalts beneath the youngest and thinnest oceanic lithospheres as well as beneath significantly thinned continental lithospheres. MAGLAB calculations support recent experimental findings about the role of H2O in the upper mantle on producing primary kimberlitic melts in addition to CO2. We demonstrate the robustness of MAGLAB calculations by reproducing the compositions of erupted melts as well as associated mantle electrical conductivities beneath the Society hotspot in the Pacific Ocean. A comparison of our simulations with magnetotelluric surveys at various oceanic settings shows that the heterogeneities in electrical conductivity of Earth's upper mantle are related to variations in volatile content via the presence of small (generally <

Understanding the assemblage of basic grains is essential for predicting many soil properties. X-ray synchrotron microtomography with a high resolution was used for visualisation and quantification of the assemblage of silt grains with a clay phase containing 20% of clays. The 3D computed image was analysed after appropriate segmentation by using: (i) autocorrelation functions which enables anisotropy discussion of the assemblage; (ii) chord distribution which gives information on the size distribution of the void and solid phases; and (iii) the Hoshen-Kopelman algorithm (6-connectivity) in order to label each void with a unique number and thus enabling discussion of the connectivity. Our results show that X-ray synchrotron microtomography enables a more accurate analysis of the assemblage of silt grains with a clay phase than with conventional methods. Thus, it showed the isotropy of the silt-clay assemblage in the studied soil material. The void and solid phase volumes were smaller than 80 and 120 μm in all directions, respectively. The mean distance between two interfaces was 6.9 and 13.4 μm for the void and solid phase, respectively. X-ray synchrotron microtomography of the soil material studied also showed that the voids resulting from the assemblage of the silt grains with the clay phase can be considered as fully connected in the studied dried materials.

Summary In many disciplines, binary numerical porous media are commonly generated as realizations of a random process characterized by a limited set of morphological measurements, e.g. the conditioning and truncated Gaussian random field (GRF) model or the Monte Carlo simulated annealing (SA) reconstruction. Whether the output microstructures of a model are quantitative or qualitative depends largely on the information carried by the constraints that are implemented. We focus on the standard two-point correlation function, also referred to as the covariance. The isotropic situation has been previously extensively studied. Here, we concentrate on a vector distance-dependent covariance. Relying on practical solutions to the phase-retrieval problem (retrieving an object from its Fourier modulus) encountered in general imaging, we show empirically that a finite binary two- or three-dimensional actual sample can be recovered systematically to within a pixel from its correlation integral (the volume average covariance to within a scale factor). In random modelling, this characteristic, describing uniquely a single sample of finite size, must be simplified, i.e. reduced to its statistical content, prior to be fitted in a random model (GRF, SA) as the characteristic of a series of realizations of a porous medium. We consider a common simplification, i.e. truncation, in which that part of the covariance relating to the small-scale features of the observed sample is preserved only. This arbitrary simplification is empirically supported by numerous published numerical experiments showing that the small-scale content of a volume-averaged covariance can be fairly well reproduced in realizations of various random models: its statistical nature is thus illustrated with the GRF model. The unique solution to the phase-retrieval problem confers an important sense to this numerical agreement: the correlation integral being the most complete descriptor, the actual sample and the model outputs are considered as true analogues over scales smaller or equal to the cutoff length attached to the truncation. Thus, awareness of the phase-retrieval problem supports on an empirical basis the generation of synthetic binary objects from a direct measurement on an available sample.

Predicting the physical properties of porous materials is difficult due to the complexity of the underlying microstructure that determines physics at the macroscopic scales of interest to the practitioner. The study of the relation between macroscopic physics and the microstructure can be largely facilitated if simplified and physically relevant representations of the microstructure are available. Herein, it is to reduce the structural complexity of a 3D digital image of an actual sample to the only rules describing the association of pore throat sizes and shapes to adjacent pores. Such rules, shown by a variety of independent approaches to govern the main part of flow and transport are measured by image analysis and expressed in the form of a pore network model. Relying on a random model of porous microstructures, the approach can be applied to isotropic porous materials whose observation by imagery is limited to 2D due to the small spatial resolution of the porosity.

International audience; In paleo-accretionary prisms and the shallow metamorphic domains of orogens, circulating fluids trapped in inclusions are commonly composed of a mixture of salt water and methane, producing two types of fluid inclusions: methane-bearing aqueous and methane-rich gaseous fluid inclusions. In such geological settings, where multiple stages of deformation, veining and fluid influx are prevalent, textural relationships between aqueous and gaseous inclusions are often ambiguous, preventing the microthermometric determination of fluid trapping pressure and temperature conditions. To assess the P-T conditions of deep circulating fluids from the Hyuga unit of the Shimanto paleo-accretionary prism on Kyushu, Japan, we have developed a new computational code, applicable to the H2O-CH4-NaCl system, which allows the characterization of CH4-bearing aqueous inclusions using only the temperatures of their phase transitions estimated by microthermometry: Tmi, the melting temperature of ice; Thyd, the melting temperature of gas hydrate and Th,aq, homogenization temperature. This thermodynamic modeling calculates the bulk density and composition of aqueous inclusions, as well as their P-T isochoric paths in a P-T diagram with an estimated precision of approximatively 10 %. We use this computational tool to reconstruct the entrapment P-T conditions of aqueous inclusions in the Hyuga unit, and we show that these aqueous inclusions cannot be cogenetic with methane gaseous inclusions present in the same rocks. As a result, we propose that pulses of a high-pressure, methane-rich fluid transiently percolated through a rock wetted by a lower-pressure aqueous fluid. By coupling microthermometric results with petrological data, we infer that the exhumation of the Hyuga unit from the peak metamorphic conditions was nearly isothermal and ended up under a very hot geothermal gradient. In subduction or collision zones, modeling aqueous fluid inclusions in the ternary H2O-CH4-NaCl system and not simply in the binary H2O-NaCl is necessary, as the addition of even a small amount of methane to the water raises significantly the isochores to higher pressures. Our new code provides therefore the possibility to estimate precisely the pressure conditions of fluids circulating at depth.

International audience; We present here new experimental data on H2O-CO2 solubility in mafic melts with variable chemical compositions (alkali basalt, lamproite and kamafugite) that extend the existing database. We show that potassium and calcium-rich melts can dissolve ∼ 1 wt% CO2 at 3500 bar (350 MPa) and 1200°C, whereas conventional models predict solubilities of 0.2-0.5 wt%, under similar P-T conditions. These new data, together with those in the literature, stress the fundamental control of melt chemical composition on CO2 solubility. We present a semi-empirical H2O-CO2 solubility model for mafic melts, which employs simplified concepts of gas-melt thermodynamics coupled with a parameterization of both chemical composition and structure of the silicate melt. The model is calibrated on a selected database consisting of 289 experiments with 44 different mafic compositions. Statistical analyses of the experimental data indicate that, in mafic melts, the chemical composition and therefore the structure of the melt plays a fundamental role in CO2 solubility. CO2 solubility strongly depends on the amount of non-bridging oxygen per oxygen (NBO/O) in the melt, but the nature of the cation bonded to NBO is also critical. Alkalis (Na+K) bonded to NBO result in a strong enhancement of CO2 solubility, whereas Ca has a more moderate effect. Mg and Fe bonded to NBO have the weakest effect on CO2 solubility. Finally, we modelled the effect of water and concluded that H2O dissolution in the melt enhances CO2 solubility most likely by triggering NBO formation. In contrast with CO2 but in agreement with earlier findings, H2O solubility in mafic melts is negligibly affected by melt composition and structure: it only shows a weak correlation with NBO/O.

International audience; A novel experimental setup was used to measure in-situ variations of electrical conductivity (EC) during deformation in torsion (simple shear) at 300 MPa confining pressure and temperatures between 873 and 1473 K. This setup is designed to test if deformation of partially molten systems can produce electrical anisotropy. The motivation for this study comes from the observation that the Lithosphere–Asthenosphere Boundary (LAB) at mid-ocean ridges and in particular at the East Pacific Rise is strongly electrically anisotropic. In an initial set of calibration experiments, the variation of EC with temperature (873–1473 K) was determined for Carrara marble, Åheim dunite and basalt-bearing olivine aggregates. EC was then monitored during deformation experiments at 1473 K and measured in the frequency range between 6 MHz and 1 Hz. The electrical response of the different materials tested as a function of frequency, changes significantly depending on the presence, absence, proportion and distribution of melt contained in the specimen. Melt-free samples show a single conduction mechanism whereas melt-bearing samples display two conduction mechanisms linked in series, reflecting the contribution of isolated and connected melt. Impedance was measured along the sample radius, in a direction parallel to the shear gradient inherent in torsion experiments. During the tests, increasing values of the impedance measured suggest that the long range melt connectivity decreases radially, and melt drains from low to high shear stress regions. The conductivity, calculated from impedance measurements, is low and comparable to values measured along mid-ocean ridges. We suggest that electrical anisotropy of the LAB reflects an alternation of melt-enriched and melt-depleted channels elongated in the spreading direction possibly induced by spreading velocity gradients along the ridge. This implies that the observed electrical anisotropy reveals larger scale processes than strain-induced generation of crystallographic preferred orientations. Such large-scale processes could influence the distribution of seamounts and chemical variations of mid-ocean ridge basalts.

The understanding of weathered processes and, more generally, of transfer properties of building stones, requires a detailed knowledge of porosity characteristics. This study aims to analyze two-dimensional (2-D) images of stones by using mathematical tools that enable the description of the pore and solid phase distribution. We selected two limestones that have been widely used for different types of buildings: a quarried and weathered Tuffeau stone (the latter being used in most châteaux of the Loire) and a quarried Sebastopol stone selected for numerous buildings in Paris. Backscattered electron scanning images obtained on thin sections of the stones were studied by using autocorrelation function analysis and chord distributions. Results showed that these mathematical tools are able to discuss, quantitatively and statistically, differences of pore and solid distributions between quarried limestones, and to discuss the degree of weathering of stones collected from buildings. Thus, very small differences of pore and solid phase distribution between the samples studied were revealed by chord distribution analysis and autocorrelation function analysis. Resulting characteristics obtained with such an analysis are promising information for a better understanding of weathering mechanisms.

International audience; Assessment of the weathering of a particular limestone, the tuffeau, used in historical monuments requires an accurate description of its microstructure. An efficient tools to obtain such a description is X-ray microtomography. However the segmentation of the images of this multiphasic material is not trivial. As the identification of pertinent markers of the structural components to extract is difficult, a two steps filtering approach is chosen. Alternate sequential filters are shown to efficiently remove the noise but, as they destroy the structural components smaller than the structuring element used, they cannot be carried out far enough. Hence as a second step in the filtering process, a mosaic operator, relying on a pragmatic yet efficient marker determination, is implemented to simplify further the images.