Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
A reactive percolation experiment was conducted by injecting seawater into a permeable olivine aggregate at 190 °C and 19 MPa to explore the relationships between hydration reactions and hydrodynamic properties during the onset of serpentinization in the ultramafic lithosphere exposed at mid-ocean ridges. The experiment was stopped after 23 days when the sample became impermeable. The initial flow rate was 0.2 mL/h and then was decreased down to 0.06 mL/h after 8 days. Permeability decreased continuously throughout the experiment. The analyses of fluid chemistry time series and of the mineralogy and structure of the reacted sample showed olivine dissolution and precipitation of proto-serpentine, brucite and Fe-oxides. These reactions are controlled by coupled hydrodynamic and chemical processes interacting at different time and spatial scales. Their first characteristic is the production of silica rich outlet fluids in disequilibrium with the observed reacted mineral assemblages. These compositions are interpreted as resulting from a suite of coupled dissolution-precipitation reactions, controlled at the pore scale by surface kinetic processes, that rapidly reaches steady-state (constant fluid composition independent of fluid flux). Hence, the effective rate of serpentinization was controlled, to the first order, by the transport of reactants during the experiment. Mass balance calculations show that the rate of olivine conversion was fast (0.2-0.5 wt%/day), yet only ∼8 wt% of the olivine sample reacted, because the permeability drop limited fluid circulation. Porosity varied little during the experiment compared to permeability changes: the decrease of permeability was explained by the structure of the newly formed serpentine favouring the clogging of fluid paths. The rate at which permeability decreased was the fastest at low flux conditions. This suggests that permeability changes were not controlled simply by the kinetics of the serpentinization reactions, but mainly reflected the development of low Peclet pore scale zones forming micro-environments that control the serpentinization reaction-paths. These results outline the need to take into account the coupling of hydrodynamic and chemical processes when modelling the effects of reactive transport within the hydrating oceanic lithosphere.
ISSN: 0012-821X

hal-00855043
https://hal.archives-ouvertes.fr/hal-00855043
DOI : 10.1016/j.epsl.2013.03.052

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We explore the relations between deformation, annealing, and melt percolation during rifting and the effect of these processes on seismic anisotropy by analyzing the microstructures and crystal preferred orientations (CPO) in a suite of mantle xenoliths from Mega, in the southern end of the Ethiopian rift. Previous geochemical studies on these xenoliths showed evidence for interactions with variable melt types and volumes during the rifting process. The peridotites have dominantly coarse-porphyroclastic microstructures, but coarse granular or partially recrystallized microstructures also occur. The olivine CPO, characterized by orthorhombic to fiber-[100] patterns and moderate intensities, the common occurrence of (100) tilt walls, and the predominance of <0vw> rotation axes accommodating low angle misorientations in olivine support deformation by dislocation creep with dominant activation of the [100](010) system. Annealing (static recrystallization) of variable intensity followed this deformation. Modal enrichment in pyroxenes in > 60% of the studied peridotites corroborates extensive, but spatially heterogeneous reactive melt percolation leading to refertilization of the lithospheric mantle beneath the southern Ethiopian rift. The common interstitial shapes of the pyroxenes and lack of correlation between the pyroxenes and the olivine CPOs in many samples suggest that part of the refertilization is post-kinematic. However, there is no simple relation between reactive melt percolation and annealing of the olivine deformation microstructure. Comparison with data from other xenolith localities points to changes in the metasomatic imprint in the lithospheric mantle along the East African rift system correlated with the evolution in the rift maturity. Seismic properties averaged over all samples show typical lithospheric mantle patterns with fast propagation of P- and polarization of the fast S-waves parallel to the lineation. The anisotropy is moderate (< 6% for P-waves and < 4% for S-waves), implying that aligned melt must contribute to the strong seismic anisotropy measured in the Main Ethiopian rift, north of Mega.
ISSN: 0040-1951

hal-01355918
https://hal.archives-ouvertes.fr/hal-01355918
DOI : 10.1016/j.tecto.2016.05.027

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
A set of four reactive flow-through experiments at temperature T = 100 degrees C and total pressure P=12 MPa was performed in limestone reservoir samples. By using various ranging from 0.7 to 10 MPa, these experiments mimic mass transfers occurring (1) near the injection well, where the brine is almost saturated with CO2 (i.e. P-CO2 approximate to P), and (2) at increasing distances from the injection well, where the fluid displays lower values and higher divalent cation concentrations due rock dissolution along the fluid pathway. Results for P-CO2 = 10 MPa show non-uniform dissolution features associated with transport-controlled mass transfer, while reaction-controlled uniform dissolution is observed for P-CO2 = 2.5 MPa. The experiment with P-CO2 = 6 MPa allows investigating in detail the transition from transport-to reaction-controlled dissolution. Conversely, the experiment reproducing conditions far from the injection well (P-CO2 = 0.7 MPa), shows a decrease of porosity triggered by the precipitation of Mg-rich calcite. For all the dissolution experiments, the time-resolved porosity phi(t) can be modeled by a simple non-linear equation including parameters that characterise the dissolution regime triggered by the reactivity of the inlet fluid (measured by the Damkohler number, Da). Furthermore, all dissolution experiments display power scaling between permeability (k) and porosity (phi) with distinctly different scaling exponents characterising the reactivity of the fluid percolating the sample, independently from the decrease with time of the reactive surface area. It is shown also that dissolution at moderate positive values of Da seems the most efficient to increase permeability and promote a rapid spreading of the reaction front, while inducing minimal modification of the porosity in the vicinity of the CO2 injection well. These results can be used to parameterize the k-phi function for modeling the earliest dissolution processes occurring in the vicinity of the reaction front.
ISSN: 0009-2541

hal-00445277
https://hal.archives-ouvertes.fr/hal-00445277
DOI : 10.1016/j.chemgeo.2009.03.028

Éditeur(s) : HAL CCSD
Résumé : This work provides new constraints on the interactions between deformation and percolation of melt or fluids, as well as on the implications of these processes for the seismic properties of the mantle wedge. It is based on the analysis of spinel peridotites from the massif of Ronda (Spain) and two xenolith suites from active subduction zones (Kamchatka, Papua New Guinea). A coupled structural, petrological and geochemical study of these samples shows that they underwent a reactive percolation of melts or Si-rich fluids, which was synchronous to a deformation event occurring under high temperature and low stress conditions, consistent with the PT conditions at the base of the lithosphere or in the asthenosphere. This reactive percolation is responsible for enrichment in pyroxenes, mainly orthopyroxene, which is often localized in bands parallel to the high-temperature foliation. This enrichment is associated with grain size reduction and dispersion of the crystallographic orientation of olivine. The dominant slip system in olivine is {0kl}[100], which results in fast S-wave polarization parallel to the flow direction in the mantle. The decrease in the intensity of the olivine crystal preferred orientations associated with the enrichment in pyroxene results in significant decrease of the anisotropy that may induce an underestimation of the thickness of the anisotropic layer by up to 33%. The observed orthopyroxene enrichment also lowers the Vp/Vs ratio, but cannot explain Vp/Vs < 1.7 mapped locally in the fore-arc mantle in Japan and the Andes. Such low Vp/Vs ratios may however be explained by considering the intrinsic anisotropy of the peridotites, which is generally ignored in large-scale Vp/Vs ratio mapping of the mantle wedge. Infrared analyses show that olivine from the both xenolith collections contains less water than the theoretical saturation calculated for their estimated equilibrium temperature in the spinel stability field. These low water content are similar to those observed in spinel peridotites from other subduction zones and probably record both the low solubility of water in olivine at relatively low pressure and dehydration during exhumation of the xenoliths. These measured water contents as well as theoretical saturation estimations are not sufficient to change the dominant slip direction of in olivine from [100] to [001].
Ce travail apporte de nouvelles contraintes sur les interactions entre déformation et processus d'hydratation et de percolation de magma ou de fluides dans le manteau à l'aplomb d'une zone de subduction et leurs implications sur les propriétés sismiques dans le coin mantellique. Il se base sur l'analyse de péridotites à spinelle provenant du massif de Ronda (Espagne) et deux séries de xénolites issues de zones de subduction actives (Kamchatka, Papouasie-Nouvelle-Guinée). L'étude structurale, pétrologique et géochimique de ces échantillons montrent qu'ils ont subit une percolation réactive de magma ou de fluide synchrone d'une déformation de haute température basse contrainte cohérente avec les condition PT de la base de la lithosphère ou de l'asthénosphère. Cette percolation réactive est responsable d'un enrichissement en pyroxènes, qui est souvent localisé dans des bandes parallèles à la foliation. Cet enrichissement est associé à une dispersion de l'orientation cristallographique de l'olivine. Les systèmes de glissement dominant dans l'olivine sont dans tous les cas {0kl}[100], ce qui implique que la direction de polarisation rapide des ondes S dans la partie supérieure du coin mantellique est parallèle à la direction d'écoulement dans le manteau. La décroissance de l'intensité des OPR de l'olivine associée à l'enrichissement en pyroxènes a pour conséquence une réduction non négligeable de l'anisotropie sismique qui peut induire jusqu'à 33% d'erreur sur l'interprétation de l'épaisseur de la couche anisotrope. Un enrichissement en orthopyroxène peut aussi entraîner une baisse du rapport Vp/Vs, mais ne peut expliquer les rapports Vp/Vs <1,7 cartés dans certains avant-arcs. Cependant de telles valeurs peuvent être expliquées si l'anisotropie des péridotites du coin mantellique est prise en compte. Les analyses par spectroscopie infra-rouge montrent que les olivines des deux séries de xénolites étudiées contiennent moins d'eau que la saturation théorique calculée pour leurs températures d'équilibre dans le domaine du spinelle. Ces faibles concentrations en eau sont similaires à celles observées dans les olivines des péridotites à spinelle des autres zones de subduction. Elles enregistrent probablement la faible solubilité de l'eau dans l'olivine à des pressions relativement basses et la déshydratation au cours de l'exhumation des xénolites. Ces teneurs en eau mesurées ainsi que les estimations de la saturation théorique ne sont pas suffisantes pour changer la direction de glissement dominante dans l'olivine de [100] à [001].
https://tel.archives-ouvertes.fr/tel-00689832

tel-00689832
https://tel.archives-ouvertes.fr/tel-00689832
https://tel.archives-ouvertes.fr/tel-00689832/document
https://tel.archives-ouvertes.fr/tel-00689832/file/These-Soustelle2010.pdf

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This study analyses the interactions between deformation and reactive fluid and melt percolation, and their effects on sub-arc mantle seismic properties based on microstructural observations on mantle xenoliths extracted by the Tubaf and Edison seamounts close to the Lihir Island, in the Papua New Guinea archipelago. These xenoliths sample an oceanic lithosphere, which has experienced high-temperature deformation in the presence of fluids or melts. This was followed by metasomatism under static conditions. Syn-kinematic percolation of reactive Si-rich melts or fluids in peridotites has produced pyroxene-enrichment, grain size reduction, and dispersion of olivine crystal preferred orientation (CPO). Fourier transform infrared spectroscopy analyses show that olivine has very low water contents (1-4 wt. ppm H2O), similar to spinel peridotites from other subduction zones. These low values may record both low water solubility in olivine at low pressure and dehydration during transport and exhumation. Water contents in pyroxenes are highly variable and likely result from spatially heterogeneous melt or fluid percolation. Analysis of olivine CPO indicates dominant activation of both (010)[100] and (001)[100] slip systems, which are characteristic of deformation under high temperature, low stress, low pressure and low to moderate hydrous conditions. Fast S-wave polarization and P- and Rayleigh propagation directions are thus parallel to the mantle flow direction. The pyroxene enrichment by melt-rock reactions is accompanied by dispersion of olivine CPO and induces a significant decrease of the maximum S-wave and P-wave anisotropy in the peridotites. The calculated seismic properties also show that the lowest Vp/Vs ratios (< 1.7) mapped in fore-arc mantle may only be explained by taking in consideration the CPO-induced elastic anisotropy of the peridotites.
ISSN: 0040-1951

hal-00950058
https://hal.archives-ouvertes.fr/hal-00950058
DOI : 10.1016/j.tecto.2013.09.024

Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : International audience
The mantle above a subducting slab is the site of complex interactions between deformation, partial melting, fluid migration and magma transport. To constrain these interactions and their effects on olivine deformation, we analyze microstructures, crystal preferred orientations, and water contents of peridotite xenoliths entrained by andesites of the Avacha volcano, southern Kamchatka arc. These xenoliths are refractory spinel harzburgites that have coarse-grained microstructures with widely spaced subgrain boundaries and sinuous grain boundaries in olivine, consistent with deformation by dislocation creep under low deviatoric stress (< 13 MPa) and with a significant contribution from diffusional processes. Analysis of crystal preferred orientations (CPO) indicates dominant activation of high-temperature, low-stress {0kl}[100] slip systems in olivine and of(100)[001] in orthopyroxene. In most samples, coarse opx crystals, elongated parallel to the lineation, enclose small olivine grains in crystallographic continuity with neighbouring crystals, indicating crystallization of orthopyroxene at the expense of olivine as a result of reactive percolation of Si-rich fluids coeval with the high-temperature deformation. Secondary crystallization of interstitial orthopyroxene led locally to development of opx-rich lenses parallel to the foliation, characterized by a decrease in olivine grain size and dispersion of the olivine CPO without changing the dominant slip systems. Half of the samples also show acicular orthopyroxene aggregates with which is associated a fine-grained matrix composed of rounded strain-free olivine, orthopyroxene, spinel, and rare amphibole crystals. This matrix occurs pervasively along grain boundaries or forms millimeter-scale irregular lenses and anastomosing veinlets that crosscut the coarse crystals and their ductile deformation structures. Both acicular orthopyroxene and the fine-grained matrix are interpreted as resulting from reactive transport of H2O-rich fluids under static conditions, probably in the lithospheric mantle. Infrared analyses show that olivine contains 1-8 center dot 6 ppm by weight of water. These low water contents are similar to those observed in spinel peridotites from other subduction zones and probably record both the low solubility of water in olivine at low pressure and dehydration during exhumation of the xenoliths. Water contents in orthopyroxene are highly variable (25-506 ppm H2O), probably recording spatially heterogeneous interaction with fluids or melts and compositional disequilibrium in the studied samples. Change in the dominant percolation mechanism from porous flow to fracturing suggests cooling, consistent with the low temperatures estimated from pyroxene thermometry (< 800-900 degrees C). The Avacha xenoliths therefore record pervasive deformation of a region of the mantle under asthenospheric conditions, followed by its accretion to the base of the lithosphere, probably as a result of cooling of the mantle wedge. Percolation of Si-rich fluids or hydrous melts is recorded at all stages; this probably enhanced diffusion and lowered deviatoric stresses during ductile deformation, but did not change the dominant slip direction in olivine from [100] to [001].
ISSN: 0022-3530

hal-00456053
https://hal.archives-ouvertes.fr/hal-00456053
DOI : 10.1093/petrology/egp085

Éditeur(s) : HAL CCSD
Résumé : Geological storage of CO2 is one of diverse technologies being explored to reduce atmospheric carbon fromindustrial processes (i.e. fossil fuel combustion). One of the specific features of CO2 injection is the possibility ofgeochemical reactions (dissolution – precipitation) between mobile reactive brine (e.g. formation water enrichedin CO2) and the host rock during the spatial and temporal evolution of CO2. That leads to modifications in thepore structure, which in turn change the flow dynamics of the reservoir (e.g. the permeability k). Then, thesesstructural modifications can largely control the injectivity, so that the pressure field in the reservoir and also theCO2 propagation. Accordingly, it is crucial to explore the changes in the reservoir properties (e.g. structural andhydrodynamic) induced during a CO2 injection and specially the relationships between them (e.g. k or reactivesurface-Sr versus porosity-φ , k versus rock heterogeneity), for developing predictive modelling tools of thetransport and reaction processes occurring during a CO2 injection and reliable risk assessment. In the case ofcarbonate rocks, the application of the predictive models of transport and reaction is still challenging, because oftheir high heterogeneity so that the incertitude in the reaction kinetics of carbonate minerals.From this perspective, we realized brine-enriched in CO2 percolation experiments through carbonate rocksamples in thermodynamic conditions expected during CO2 injection in deep reservoirs (T = 100°C et P =12MPa). The permeability changes k(t) is monitored during the experiments and the porosity variationφ (t) iscalculated from chemical analyses of the sampled outlet fluids, using ICP-EAS. The pore structure modificationsare investigated from high resolution X ray micro tomography images acquired from the synchrotron ofGrenoble (ESRF). Depending to the dissolution regime, controlled by the reservoir rock fabric and the chemicalcomposition of the brine (e.g. PCO2), we observed that a modification of pore structure can either improve(atypical result in dissolution context) or impair the value of the permeability k.
Le stockage géologique du CO2 est l’une des diverses technologies étant explorées afin deréduire les émissions de carbone atmosphérique des processus industriels (i.e. combustion del’énergie fossile). L’une des spécifiques caractéristiques de l’injection du CO2 en profondeurreste la possibilité de réactions géochimiques (dissolution-précipitation) entre la saumureréactive mobile (e.g. eau de formation enrichie en CO2) et la roche encaissante durantl’évolution spatiale et temporelle du CO2, conduisant à des modifications dans la structure despores et par conséquent dans les propriétés d’écoulement du réservoir (e.g. la perméabilité k).Donc, ces changements structuraux peuvent largement contrôler l’injectivité, ainsi que lechamp de pression dans le réservoir et aussi la propagation du CO2. Il demeure ainsi cruciald’explorer les changement dans les propriétés de réservoirs (e.g. structurales ethydrodynamiques) induits durant une injection de CO2 et explicitement les relations existantesentre eux (e.g. k ou surface réactive-Sr versus porosité-φ , k versus hétérogénéité de la roche),afin de développer des outils de modélisation prédictive des processus de transport etréactionnels se produisant durant une injection de CO2 et d’évaluer de façon fiable les risques.Dans le cas des réservoirs carbonatés, l’application des modèles prédictifs de transport réactifdemeure toujours un enjeu, car contrainte par la forte hétérogénéité en leur sein ainsi que parl’incertitude dans la cinétique de réactions des minéraux carbonatés dans ce contexte. Danscette optique, nous avons réalisé des expériences de percolation à travers des échantillons deroches carbonatées dans les conditions thermodynamiques de stockage en profondeur (T =100°C et P =12 MPa). L’évolution de la perméabilité k(t) est suivie au cours desexpériences ; et la variation de la porosité φ (t) est calculée à partir des résultats d’analyseschimiques au ICP-AES des fluides de sortie échantillonnés. L’investigation des modificationsapportées à la structure des pores est réalisée par le biais de la Micro-Tomographie hauterésolution à rayon X, acquise au synchrotron de Grenoble (e.g. ESRF).Dépendant du régime de dissolution, contrôlé par la fabrique de la roche réservoir et lacomposition chimique de la saumuré chargée en CO2 (e.g. PCO2 engagée), on a observéqu’une modification de la structure de la roche peut soit améliorer soit détériorer (résultatatypique en contexte de dissolution) la valeur de la perméabilité k.
https://hal.archives-ouvertes.fr/tel-01142136

tel-01142136
https://hal.archives-ouvertes.fr/tel-01142136
https://hal.archives-ouvertes.fr/tel-01142136/document
https://hal.archives-ouvertes.fr/tel-01142136/file/thesemangane2013.pdf

Éditeur(s) : HAL CCSD American Geophysical Union
Résumé : International audience
This work presents seismic properties derived from a detailed microstructural study of supra-subduction mantle xenoliths extracted by the active Avacha volcano in the southern Kamchatka arc. These peridotites underwent low-stress deformation and syn- to late-kinematic reactive percolation of hydrous melts or fluids leading to local orthopyroxene enrichment and dispersion of the olivine CPO in the shallow mantle wedge. All samples show an axial [ 100] olivine CPO implying fast S-wave polarization parallel to the flow direction in the mantle. Orthopyroxene-enrichment by reactive fluids/melts percolation lowers the Vp/Vs ratio, but cannot explain the Vp/Vs ratios <1.7 mapped in the Japan and Andes forearc mantle. These low Vp/Vs ratios may however be explained by considering the intrinsic anisotropy of the peridotites.
ISSN: 0094-8276

hal-00512636
https://hal.archives-ouvertes.fr/hal-00512636
DOI : 10.1029/2010GL043450

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Most peridotite massifs and mantle xenoliths show a wide range of isotopic variations, often involving significant decoupling between Hf, Nd and Sr isotopes. These variations are generally ascribed either to mingling of individual components of contrasted isotopic compositions or to time integration of parent-element enrichment by percolating melts/fluids, superimposed onto previous depletion event(s). However, strong isotopic decoupling may also arise during porous flow as a result of daughter-elements fractionation during solid-liquid interaction. Although porous flow is recognized as an important process in mantle rocks, its effects on mantle isotopic variability have been barely investigated so far. The peridotites of the Lherz massif (French Pyrenees) display a frozen melt percolation front separating highly refractory harzburgites from refertilized lherzolites. Isotopic signatures observed at the melt percolation front show a strong decoupling of Hf from Nd and Sr isotopes that cannot be accounted for by simple mixing involving the harzburgite protolith and the percolating melt. Using one dimensional percolation-diffusion and percolation-reaction modeling, we show that these signatures represent transient isotopic compositions generated by porous flow. These signatures are governed by a few critical parameters such as daughter element concentrations in melt and peridotite, element diffusivity, and efficiency of isotopic homogenization rather than by the chromatographic effect of melt transport and the refertilization reaction. Subtle variations in these parameters may generate significant inter-isotopic decoupling and wide isotopic variations in mantle rocks. (C) 2009 Elsevier B.V. All rights reserved.
ISSN: 0012-821X

hal-00413135
https://hal.archives-ouvertes.fr/hal-00413135
DOI : 10.1016/j.epsl.2008.12.033

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
To test the impact of fluid flow on the reactivity of porous (ultra-)mafic rocks, reactive percolation experiments were realized during which CO2-enriched water was injected at two different injection rates (Q = 0.1 and 1 mL h−1) through sintered analogues of olivine-accumulation zones in basaltic flows at temperature and fluid composition conditions (T = 180 °C; NaHCO3 buffered solution) favorable for CO2-mineralization (carbonation).All experiments resulted in silicate dissolution, carbonate precipitation upstream and (proto-)serpentine formation downstream indicating a decrease in the fluid reactivity along flow paths. The measured bulk carbonation rates ranged from 4 to 7 × 10−8 s−1; these values were significantly lower than previously published values of olivine carbonation rate obtained on powders in closed batch and flow-through reactors. Our study show complex couplings, at pore scale, between fluid flow, localization of reaction zones, and chemical reaction kinetics which in turn control hydrodynamic properties, carbonation rate and efficiency and fluid reactivity. This results in carbonation rates being higher when injection rates are high and permeability ultimately controlling carbonation reactions by limiting fluid input. During experiments, notable changes in permeability occurred for only minor changes in porosity indicating a control by the geometry of the porous network: heterogeneities in the distribution of flow paths favored the localization of precipitated minerals which in turn resulted in the closure of flow paths. This mechanism was particularly efficient at low injection rates. These results imply that controlling the injection rate could allow enhancing/limiting the efficiency of in situ carbonation.
ISSN: 0883-2927

hal-01115284
https://hal.archives-ouvertes.fr/hal-01115284
DOI : 10.1016/j.apgeochem.2014.11.024

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Seismic tomography and high surface heat flow models indicate an anomalously thin and hot lithospheric mantle beneath the Canadian Cordillera. To understand the thermal and deformational history of the lithospheric mantle under these conditions, we performed a study of the microstructures, crystal preferred orientations (CPO), and seismic anisotropy of mantle xenoliths collected in the Summit Lake volcano in the southern Canadian Cordillera. The xenoliths vary in composition between spinel lherzolites, cpx-rich lherzolites, and wehrlites. All samples are coarse-grained and show clear evidence for annealing, but deformation microstructures are well-preserved in the spinel lherzolites. Olivine CPO is characterized by a strong point-maximum of [100] and by a girdle distribution of [010[ and [001] axes normal to it; CPO strength is variable, spinel-lherzolites have the strongest CPO. Some samples show a weak orthopyroxene CPO consistent with the olivine one. However most pyroxenes have random CPO, interstitial shapes and undeformed appearance, which suggest a secondary origin by reactive melt percolation under static conditions, leading to crystallization of cpx + sp +/- opx at the expenses of olivine, followed by crystallization of cpx + sp +/- ol at the expenses of opx to produce the wehrlites. The studied xenoliths have typical upper mantle seismic properties patterns with fastest propagation of P-waves and polarization of S-waves parallel to the olivine [100] maxima. Maximum P- and S-waves anisotropy for lherzolites are 8 and 5% respectively. Dispersion of the olivine CPO due to neocrystallization of olivine results in weaker anisotropies (6.5 and 3.5%) in wehrlites. Seismic velocities calculated using a geotherm consistent with the equilibrium temperatures of the Summit Lake xenoliths are 3-4% lower than those expected in a normal, 100 km-thick lithosphere, consistent with seismic tomography models for the region. This high geothermal gradient may be partially explained by considering the anisotropy of thermal conductivity of olivine and subhorizontal foliations in the lithospheric mantle, which result in a decrease by up to 15% of the thermal conductivity in the vertical direction.
ISSN: 0040-1951

hal-00618332
https://hal.archives-ouvertes.fr/hal-00618332
DOI : 10.1016/j.tecto.2011.04.014

Éditeur(s) : HAL CCSD
Résumé : Differentiation of the lithospheric mantle occurred principally through partial melting and extraction of melts. Harzburgites are generally considered as melting residues whereas lherzolites are regarded as pristine mantle weakly affected by melting. However, some orogenic peridotites show evidence of igneous refertilization. In this context, this work re-investigates the nature of the Lherz lherzolites (Pyrenees), type-locality of lherzolites, described as a piece of preserved fertile mantle. Structural and geochemical data show that these lherzolites are not pristine but formed through a refertilization reaction between MORB-like melts and refractory lithosphere. Moreover, the Lherz peridotites were partly used to infer the composition of the primitive upper mantle and these results may have important implications for the nature of the late veneer. Additionally, crystal-preferred orientations of minerals (CPO) highlight a strong feedback between melt percolation and finite strain in the percolated rocks. CPO variations are ruled by a subtle balance between instantaneous melt fraction and local strain rate. This work also investigated the effect of melt percolation on Hf, Nd and Sr isotopes. Isotope systematics in Lherz shows that strong isotopic decoupling may arise in a percolation front. The modelling suggests that decoupled isotopic signatures are generated during porous flow and governed by the melt/matrix elements concentrations, chemical diffusivities or efficiency of isotopic homogenization. Melt-rock interactions can generate “intraplate-like” isotopic signatures. This suggests that a part of isotopic signatures of mantle-related rocks could be generated by diffusional processes associated with melt transport.
La différenciation du manteau lithosphérique s'est principalement effectuée par fusion partielle et extraction de magmas. Les harzburgites sont généralement considérées comme des résidus de fusion tandis que les lherzolites représentent un manteau originel peu affecté par la fusion. Cependant, certaines péridotites orogéniques montrent des évidences de refertilisation magmatique. Dans ce contexte, ce travail remet en cause la nature primitive des lherzolites de Lherz (Pyrénées), lithotype de la lherzolite. Les données structurales et géochimiques montrent que ces lherzolites ne représentent pas du manteau préservé mais qu'elles se sont formées par une réaction de refertilisation entre un liquide de type MORB et une lithosphère réfractaire. De plus, les orientations préférentielles de réseau (OPR) des minéraux montrent une forte interdépendance entre la percolation magmatique et la déformation finie observée dans les roches percolées. Les variations d'OPR semblent contrôlées par un équilibre subtil entre fraction de liquide instantanée et taux de déformation local. Ce travail a également abordé les effets de la percolation magmatique sur la variabilité isotopique des roches mantelliques. Les résultats montrent qu'un fort découplage isotopique peut s'observer dans un front de percolation. Les modèles suggèrent que le découplage des signatures isotopiques se produit pendant la percolation, gouverné par le rapport des concentrations en éléments (magma/matrice), la diffusivité et le processus d'homogénéisation isotopique. Les réactions magma/roche peuvent générer des signatures isotopiques de type intraplaque. Ceci suggère qu'une part des signatures isotopiques des roches ou laves dérivées du manteau pourrait être produite par des processus diffusionnels associés à du transport de magma.
https://tel.archives-ouvertes.fr/tel-00431325

tel-00431325
https://tel.archives-ouvertes.fr/tel-00431325
https://tel.archives-ouvertes.fr/tel-00431325/document
https://tel.archives-ouvertes.fr/tel-00431325/file/theseleroux08.pdf

Éditeur(s) : HAL CCSD
Résumé : In order to minimize CO2 atmospheric concentration, a solution consists in sequestrating CO2 in geological reservoirs. To estimate long term risks, it is necessary to quantify the couplings between reaction processes as well as structural and hydrodynamical modifications. We realised two experimental benches enabling injecting CO2-enriched-brine in conditions corresponding to in situ storage (T < 200 oC and P < 200 bar) and developed
an experimental protocol using X-Ray microtomography and fluid and rock analyses in order to measure the variations of physical and chemical parameters.
The study of carbonated reservoirs near the injection well, allows quantifying different k-phi relationships depending on the dissolution processes and triggered by the local fluid chemical composition and initials conditions. Away from the injection well, we observe carbonate precipitation decreasing the permeability. The study of fracturated caprock samples shows that alternative percolation of CO2-enriched-brine and CO2 gas increases the fracture permeability.
The study of silicated rocks indicates carbonate precipitation in zeolite sandstone and sintered dunite grains. Nevertheless, in zeolite sandstone we also observe the precipitation of clay particles located in the uid pathways which decrease strongly the permeability.
Afin de minimiser la concentration en CO2 dans l'atmosphère une solution consiste à le séquestrer dans les réservoirs géologiques. Pour évaluer les risques à long terme, il est nécessaire de quantifier les couplages entre les processus réactionnels et les modifications structurales et hydrodynamiques. Dans cette optique, nous avons construit deux dispositifs expérimentaux permettant d'injecter des saumures chargées en CO2 dans les conditions de stockage (T < 200 °C et P < 200 bar) et mis en oeuvre un protocole expérimental utilisant la microtomographie RX et l'analyse des roches et des fuides pour quantifier les variations des paramètres physiques et chimiques. Dans le cas des réservoirs carbonatés, on observe, près du puits d'injection, une forte variabilité des relations k-phi en fonction du régime de dissolution contrôlé par la chimie locale du fluide, ainsi que par les conditions initiales. A plus grande distance, on observe des processus de précipitation diminuant fortement la perméabilité. L'étude des roches de couverture fracturées (argilite) a montré qu'une percolation alternée d'une saumure chargée en CO2 et de CO2 gaz augmentait la perméabilité de fracture. Dans le cas des roches silicatées, la précipitation de carbonates est mise en évidence aussi bien dans les grès à zéolites que dans les frittés de dunite de San Carlos. Cependant, dans les grès à zéolites, la précipitation d'une phase argileuse est observée dans les chemins d'écoulement et engendre une forte diminution de la perméabilité.
https://tel.archives-ouvertes.fr/tel-00416408

tel-00416408
https://tel.archives-ouvertes.fr/tel-00416408
https://tel.archives-ouvertes.fr/tel-00416408/document
https://tel.archives-ouvertes.fr/tel-00416408/file/These_Luquot.pdf

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Underground CO2 sequestration is highly recommended as an effective means of significantly decreasing CO2 concentration in the atmosphere. Mineral storage is the more secure technology, but requires the presence of high concentration of divalent cations in the pore-fluid. Results from CO2 percolation experiments through chlorite/zeolite-rich sandstone samples from the Pretty Hill Formation (Otway Basin, Australia) are presented. The dissolution of the laumontite (7 wt.%) and chamosite (7 wt.%) are the potential sources of calcium, iron and magnesium required for carbonate precipitation. The percolation experiment was setup to reproduce, at laboratory scale, the in situ temperature and pressure conditions (T = 95 degrees C and P = 10 MPa). The fluid injected at constant flow rate is a rock-equilibrated brine subsequently enriched in CO2 up to partial pressure of 6 MPa. We observe feldspars, laumontite and chamosite dissolution, kaolinite and silica precipitation and a noticeable sink of CO2 in the sample which is attributed to the precipitation of both amorphous carbon due to the reduction of CO2 and Fe-rich carbonate. Permeability decreases of about one order of magnitude due to the localization of the kaolinite precipitation in the main flow paths, while porosity increases. The high reactivity of this sandstone makes this reservoir a valuable target for CO2 mineralization, but the associated permeability decrease may limit the injection rate and the spreading of the CO2 in the reservoir.
ISSN: 0009-2541

hal-00712829
https://hal.archives-ouvertes.fr/hal-00712829
DOI : 10.1016/j.chemgeo.2011.11.018

Éditeur(s) : HAL CCSD
Résumé : This study provides additional constraints on the relations between deformation, hydration and percolation of fluids and melts in the subcontinental lithospheric mantle beneath a craton and a rift, as well as their implication on its geodynamical behaviour. I have analysed the microstructures, the CPOs, and the hydrogen content of mantle xenoliths from the Kaapvaal craton, and two sets of xenoliths from different localities along the East African Rift (North Tanzanian Divergence and SE Ethiopia).The coarse-granular microstructures and the well-defined CPOs in Kaapvaal peridotites suggest a deformation followed by a long quiescence time. Orthorhombic olivine CPOs predominates, but axial-[100] and axial-[010] are also measured. Cratonic peridotites record multiple metasomatic episodes, leading to a significant compositional heterogeneity, which cannot be imaged by seismic studies. Olivine hydrogen contents are variable, but tend to increase until 150 km depth, reaching up to 50 ppm wt. H2O. The deeper samples are almost dry. Piston-cylinder experiments on hydrogen diffusion between a volatile-rich kimberlitic melt and forsterite suggest that the presence of CO2 in the system could significantly decrease water fugacity and thus forsterite hydration. These experimental results indicate that the hydrogen contents measured in olivine were acquired during a metasomatic event rather than during xenolith extraction by kimberlites. However, this metasomatism was not followed by remobilization of the cratonic root.In the North Tanzanian Divergence, localities within the rift axis and the volcanic transverse belt (Lashaine and Olmani) show significant differences in microstructures and olivine CPO patterns. In Lashaine, coarse-granular microstructures and orthorhombic to axial-[100] CPO patterns in olivine can be explained by transpressional deformation during the formation of the Mozambique belt, or by the occurrence of a remnant of a cratonic domain embedded within the Mozambique belt. Within the rift axis, porphyroclastic to mylonitic microstructures suggest a recent rift-related deformation accompanied by syn-kinematic melt-rock reactions, and followed by variable annealing. The strong heterogeneity in microstructures and olivine CPO suggests that this deformation was acquired during multiple tectonic events probably linked to episodic magma percolation, separated by quiescence episodes. The axial-[100] patterns in olivine and the oblique fast directions reported by SKS studies are coherent with transtensional deformation within the lithospheric mantle beneath the rift.The peridotites from SE Ethiopia are less recrystallized than the rift-axis Tanzanian peridotites, displaying coarse-porphyroclastic microstructures. Microstructures and orthorhombic CPOs in olivine suggest syn- to post-metasomatic deformation. S-waves polarization anisotropies calculated for these samples cannot explain alone the delay times reported by SKS studies in this part of the East-African Rift.
Les travaux réalisés durant cette thèse apportent de nouvelles contraintes sur les relations entre déformation, hydratation et percolation de fluides et/ou de magmas dans le manteau subcontinental sous un craton et sous un rift, et leurs implications sur son comportement rhéologique. Il repose sur l'analyse des microstructures, des OPRs et des teneurs en hydrogène de xénolites mantelliques du craton du Kaapvaal, et sur deux séries de xénolites provenant de différentes localités le long du rift Est-Africain (Divergence Nord Tanzanienne et SE de l'Ethiopie). Les microstructures granulaires à gros grains et les OPRs bien définies des péridotites du craton du Kaapvaal sont cohérentes avec un épisode de déformation suivi d'une longue période de quiescence. Les OPRs de l'olivine sont majoritairement à symétrie orthorhombique, mais des symétries axiale-[100] et axiale-[010] sont aussi mesurées. Les péridotites cratoniques enregistrent de multiples épisodes métasomatiques, ayant entraîné une hétérogénéité de compositions à petite échelle ne pouvant être détectée par les études sismiques. Les teneurs en hydrogène mesurées dans l'olivine sont variables, mais ont tendance à augmenter jusqu'à 150 km de profondeur, atteignant alors jusqu'à 50 ppm wt. H2O. En dessous de cette profondeur, les échantillons montrent des teneurs en hydrogène très faibles. Les expériences réalisées en piston-cylindre sur la diffusion de l'hydrogène issue d'un liquide kimberlitique vers de la forstérite suggèrent que la fugacité en eau pourrait fortement être diminuée par la présence de CO2, empêchant l'hydratation de l'olivine durant extraction des xénolites par les kimberlites. Ces résultats expérimentaux suggèrent que les teneurs en hydrogène dans l'olivine des péridotites du craton du Kaapvaal ont été acquises durant un épisode métasomatique en profondeur et non pendant leur extraction par les kimberlites. Ces teneurs n'ont toutefois pas à ce jour entraîné de remobilisation de la racine cratonique. Enfin, le calcul des propriétés sismiques des péridotites cratoniques révèle que les anisotropies générées par les OPRs de ces échantillons sont suffisantes pour expliquer les anisotropies mesurées par les ondes SKS et les ondes de surface.Les xénolites de la Divergence Nord-Tanzanienne, montrent des variations significatives de microstructures et d'OPR de l'olivine entre les péridotites des localités dans l'axe du rift et celles de la chaîne volcanique transverse (Lashaine et Olmani). A Lashaine, les microstructures granulaires à gros grains et les OPRs de type orthorhombique et axial-[010] peuvent être expliquée par une déformation en transpression liée à la formation de la chaîne Mozambique ou par la présence d'une relique d'un domaine cratonique à l'intérieur de la chaîne Mozambique. Dans l'axe du rift, les microstructures porphyroclastiques à mylonitiques suggèrent une déformation plus récente, accompagnée de réactions magma-roche sous des conditions proches du solidus, suivie d'un recuit variable. L'hétérogénéité des microstructures enregistrées par les échantillons du rift suggère de multiples épisodes de déformation localisée, probablement liés à l'injection percolation épisodique de magmas, espacés de périodes d'accalmie. Les OPRs de l'olivine de type axial-[100] et l'orientation des directions de polarisation des ondes SKS suggère que le rift s'est formé en régime de transtension Les péridotites du Sud-Est de l’Éthiopie présentent des microstructures porphyroclastiques à gros grains moins recristallisées qu'en Tanzanie. Les microstructures et les OPRs principalement de type orthorhombique suggèrent une déformation syn- à post-métasomatisme. Les anisotropies de polarisation des ondes S calculées pour ces échantillons sont insuffisantes pour expliquer à elles seules les déphasages des ondes SKS dans cette partie du rift.
https://tel.archives-ouvertes.fr/tel-01684759

Droits : info:eu-repo/semantics/OpenAccess
NNT : 2014MON20139
tel-01684759
https://tel.archives-ouvertes.fr/tel-01684759
https://tel.archives-ouvertes.fr/tel-01684759/document
https://tel.archives-ouvertes.fr/tel-01684759/file/43443_BAPTISTE_2014_archivage_cor.pdf

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
A suite of eclogite xenoliths from the Roberts Victor kimberlite (South Africa) is remarkable for its high abundances of base metal sulfides (BMS; up to 2 modal %). However, while sulfides are nearly ubiquitous in Type I eclogites (garnet > 0.07% Na2O), Type II eclogites (garnet < 0.07% Na2O) systematically lack sulfides. Two different sulfide assemblages are recognised within the Type I xenolith suite. Both populations are polyphase Cu-Ni-Fe sulfides, one characterised by the pyrrhotite (Po) + pentlandite (Pn) + chalcopyrite (Cp) assemblage and the other by the smythite/violarite (Smy/Vi) + (Ni)pyrite (Py) + Cp assemblage. The latter is the most abundant assemblage and reflects the supergene alteration of the "primary" Po + Pn + Cp assemblage. This process overprints the original composition of the sulfides by remobilising elements such as S, Fe, Ni, Se and Te. In the Type I eclogites, BMS occur as inclusions within silicates (garnet and clinopyroxene) and as interstitial grains. No chemical differences were observed between enclosed and interstitial sulfides. However, their relative abundances are correlated, indicating a similar origin. The Po + Pn + Cp assemblage is identical to eclogitic sulfides previously described in some Roberts Victor diamonds. Silicate-enclosed sulfides could appear to be early phases, but they are restricted to the outer parts of the silicate grains, suggesting a late incorporation during partial recrystallisation of silicate phases, induced by fluid-rock percolation-reaction during a metasomatic event. Positive whole-rock correlations between Se and (La/Sm)N⁎ and between Cu and ΣLREEN⁎ indicate a direct link between sulfide content and the enrichment of Mg + incompatible elements in the Type I eclogites, further supporting a metasomatic origin of the sulfide component. Similarly, a negative correlation between ΣLREEN⁎ and Cucpx implies that the metasomatic agent was at least partially composed of S-rich fluid (e.g. H2S, SO2) that reacted with the rock and leached Cu out of the silicates. The coupling between sulfides and LREE in the Type I eclogites, as well as the absence of sulfides and metasomatic features (e.g. unequilibrated grain boundaries, melt pockets, fluid inclusions, phlogopite) in the Type II eclogites, demonstrate that Type II eclogites did not undergo such a metasomatic event and therefore may represent the less-modified protoliths of Type I eclogites.
ISSN: 0009-2541

hal-00903856
https://hal.archives-ouvertes.fr/hal-00903856
DOI : 10.1016/j.chemgeo.2013.06.015

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The platinum-group element (PGE) systematics of continental mantle peridotites show large variability, reflecting petrogenetic processing of the upper mantle during partial melting and melt/fluid percolation inside the lithosphere. By removing Pd-Cu-Ni rich sulfides, partial melting events that have stabilized the sub-continental mantle lithosphere fractionated PPGEs (Palladium-group PGE; Pt, Pd) relative to IPGEs (Iridium-group PGE; Os, Ir, Ru, Rh). Residual base-metal sulfides (BMS) survive as enclosed IPGE-enriched Monosulfide Solid Solutions (Mss), which otherwise decompose into Ru-Os-Ir-rich refractory platinum-group minerals (PGMs) once the partial melts become S-undersaturated. The small-scale heterogeneous distribution of these microphases may cause extreme nugget effects, as seen in the huge variations in absolute PGE concentrations documented in cratonic peridotites. Magmas fluxing through the lithospheric mantle may change the initial PGE budgets inherited from the melting events, resulting in the great diversity of PGE systematics seen in peridotites from the sub-continental lithosphere. For instance, melt-rock reactions at increasing melt/rock ratios operate as open-system melting processes removing residual BMS/PGMs. Highly percolated peridotites are characterized by extreme PGE depletion, coupled with PGE patterns and Os-isotope compositions that gradually evolve toward that of the percolating melt. Reactions at decreasing melt-rock ratios (usually referred to as "mantle metasomatism") precipitate PPGE-enriched BMS that yield suprachondritic Pd/Ir and occasionally affect Pt/Ir and Rh/Ir ratios as well. Moreover, volatile-rich, small volume melts fractionate Os relative to Ir and S relative to Se, thereby producing rocks with supra-chondritic Os/Ir and S/Se coupled with supra-chondritic Pd/Ir and Pt/Ir. Major magmatic inputs at the lithosphere-asthenosphere boundary may rejuvenate the PGE systematics of the depleted mantle. Integrated studies of "refertilized" peridotites with worldwide provenance provide evidence for mixing between old PGM-rich harzburgitic protoliths and newly-precipitated BMS. Long-lived PGMs carry the Os-isotope compositions of ancient melt‐depletion events into seemingly undepleted fertile lherzolites. Another diagnostic feature of major refertilization processes is the increasing modal abundance of Pt-Pd-Te-Bi or Pt-As-S microphases. Due to regional-scale refertilization processes, sizeable (> 100 km) domains of the upper lithospheric mantle are now significantly enriched in Pd, Au, Cu, Se, and other incompatible chalcophile elements that are of considerable importance in PGE-ore forming events.
ISSN: 0024-4937

hal-00828626
https://hal.archives-ouvertes.fr/hal-00828626
DOI : 10.1016/j.lithos.2012.08.017

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Interactions between deformation and melt percolation yield important consequences for the evolution of the mantle lithosphere, controlling its composition and mechanical behavior. In the Lherz massif (Pyrenees, France), the analysis of structural relationships between harzburgites, lherzolites and pyroxenites and of the crystal-preferred orientations (CPO) of olivine and pyroxenes highlights a strong feedback between percolation of basaltic melts and deformation under near-solidus conditions at the lithosphere–asthenosphere boundary. Elongated harzburgite bodies up to tens of meters wide, which are the remnants of an old lithospheric mantle, preserve a constant foliation. This foliation is locally outlined by cm-scale flattened websteritic lenses. At the contact with the enclosing lherzolites, the harzburgite foliation is crosscut by the lherzolites foliation and by cm-wide websterite bands parallel to the contact. Strain intensity in the lherzolites increases with distance to the harzburgites. Based on these observations, we propose that reactive percolation was synchronous to the deformation and propose that variations in instantaneous melt fraction, due to pyroxenes and spinel crystallization during reactive melt transport, guided strain localization. Accordingly, the observed decrease in olivine CPO intensity and change in CPO patterns from harzburgites to distal lherzolites are interpreted as recording changes in the relative contribution of dislocation glide and diffusion processes, which is ruled by a balance between the instantaneous melt fraction and the local strain rate. We also propose that the pervasive websteritic layering in the refertilized lherzolites may result from deformation-assisted melt segregation in a system with decreasing permeability due to refertilization reactions. Finally, we discuss the possible timing and geodynamical context of the refertilization episode.
ISSN: 0012-821X

hal-00411724
https://hal.archives-ouvertes.fr/hal-00411724
DOI : 10.1016/j.epsl.2008.07.053

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We studied the deformation in a partially molten mantle through detailed petrostructural analysis of plagioclase lherzolites from the northwestern part of the central Lanzo massif. These peridotites display a pervasive anastomosed network of millimetre to centimetre-scale plagioclase-rich bands, which grades locally into a planar layering marked by an intercalation of plagioclase-rich and olivine-rich layers up to tens of centimetres wide. Both the anastomosed and the planar layering are subparallel to the deformation fabric, characterized by a foliation defined by the shape-preferred orientation of olivine and by crystal preferred orientation (CPO) of olivine, orthopyroxene, and clinopyroxene. This parallelism, the coexistence of microstructural evidence for melt-rock reactions and for deformation by dislocation creep, and the predominance of axial-[010] olivine CPO patterns, characterized by [010] axes clustered normal to the layering, indicate that deformation and the reactive melt percolation that formed the layering were coeval. Strong heterogeneity in mineral composition in the planar layering domains, with Fe-enrichment in olivine and spinel and highly variable Ti content in spinel in cm-scale plagioclase-rich bands, implies that the latter interacted with higher melt volumes. High Ti contents in pyroxenes and spinel in the anastomosed layering domains point to changes in melt composition, hinting to less effective melt transport. We propose therefore that the planar layering records melt segregation in layers parallel to the shear plane, whereas the anastomosed layering results from melt alignment along grain boundaries subparallel to the shear plane, without segregation. Finite strain in the different layers cannot be quantified, but comparison of the present observations with data from experiments and from other mantle outcrops displaying shear-controlled melt organization suggests that the transition from the anastomosed to the planar layering might record an increase in finite strain, that is, strain localization associated with variations in the instantaneous melt fraction.
ISSN: 0040-1951

hal-01053509
https://hal.archives-ouvertes.fr/hal-01053509
DOI : 10.1016/j.tecto.2014.01.007

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We report chlorine (Cl) and fluorine (F) abundances in minerals, interstitial glasses, and melt inclusions in 12 andesite-hosted, spinel harzburgite xenoliths and crosscutting pyroxenite veins exhumed from the sub-arc lithospheric mantle beneath Avacha volcano in the Kamchatka Arc (NE Russia). The data are used to calculate equilibrium mineral-melt partition coefficients (Dmineral/meltDmineral/melt) for Cl and F relevant to subduction-zone processes and unravel the history of volatile depletion and enrichment mechanisms in an arc setting.Chlorine is ∼100 times more incompatible in pyroxenes (View the MathML sourceDClmineral/melt = 0.005–0.008 [±0.002–0.003]) than F (View the MathML sourceDFmineral/melt = 0.50–0.57 [±0.21–0.24]), which indicates that partial melting of mantle sources leads to strong depletions in Cl relative to F in the residues. The data set in this study suggests a strong control of melt composition on View the MathML sourceDCl,Fpyroxene/melt, in particular H2O contents and Al/(Al + Si), which is in line with recent experiments. Fluorine is compatible in Ca-amphibole in the ‘wet’ sub-arc mantle (View the MathML sourceDFamphibole/melt = 3.5–3.7 [±1.5]) but not Cl (View the MathML sourceDClamphibole/melt = 0.03–0.05 [±0.01–0.03]), indicating that amphibole may fractionate F from Cl in the mantle wedge. The inter-mineral partition coefficients for Cl and F in this study are consistent amongst different harzburgite samples, whether they contain glass or not. In particular, disseminated amphibole hosts much of the Cl and F bulk rock budgets of spinel harzburgites (View the MathML sourceDClamphibole/pyroxene up to 14 and View the MathML sourceDFamphibole/pyroxene up to 40). Chlorine and fluorine are variably enriched (up to 1500 ppm Cl and 750 ppm F) in the parental arc picrite and boninite melts of primitive pyroxenite veins (and related melt inclusions) crosscutting spinel harzburgites.Based on the data in this study, the main inferences on the behaviour of Cl and F during melting and metasomatic processes in the sub-arc mantle are as follow:(i) Melting models show that most depleted mantle protoliths of intra-oceanic arc sources can have extremely low Cl/F (0.002–0.007) before being overprinted by subduction-derived components.(ii) Chlorine has a higher percolation distance in the mantle than F. Even for small fluid or melt volumes, Cl and F signatures of partial melting are overprinted by those of pervasive percolation, which increases Cl/F in percolating agents and bulk peridotites during chromatographic interaction and/or amphibole-forming metasomatic reactions. These processes ultimately control the bulk Cl and F compositions of the residual mantle lithosphere beneath arcs, and likely in other tectonic settings.(iii) Fluxed melting models suggest that Cl enrichment in arc picrite and boninite melts in this study, and in many arc melt inclusions reported in the literature, could be related to the infiltration of high Cl/F fluids derived from subducted serpentinite or altered crust in mantle wedge sources. However, these high Cl/F signatures should be re-evaluated with new models in light of the possible overprint of pervasive percolation effects in the mantle. The breakdown of amphibole (and/or mica) in the deep metasomatised mantle at higher pressure and temperature conditions than in the slab may explain, at least in part, the positive correlations between F abundances and Cl/F in primitive arc melt inclusions and slab depth.
ISSN: 0016-7037

hal-01553610
https://hal.archives-ouvertes.fr/hal-01553610
DOI : 10.1016/j.gca.2016.10.035