Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The Cerro del Almirez massif (Nevado–Filábride Complex, Betic Cordillera, SE Spain) is composed of antigorite (Atg-) serpentinite and chlorite (Chl-) harzburgite separated by a thin reaction front formed in a palaeo-subduction setting. These ultramafic rocks preserve unique prograde structures related to the pre- and peak high-pressure event (1.6–1.9 GPa and 680–710 °C). The oldest subduction-related structures are preserved in Atg-serpentinites: a penetrative S1 foliation and associated L1 stretching lineation that formed in a non-coaxial regime with a top-to-the-W sense of shear. This planar–linear fabric is crosscut by olivine ± Ti-clinohumite veins, formed during the prograde breakdown of brucite and pre-metamorphic clinopyroxene, which form a system of veins decimetres long. They record embrittlement processes due to the release of 6 vol.% of H2O associated with brucite dehydration. The growth of prograde olivine and/or tremolite porphyroblasts is syn- to post-kinematic in relation to the S1 foliation. Further reactions at higher temperature related to the complete breakdown of the Atg (i.e. Atg-out) are post-kinematic to S1. Prograde Chl-harzburgite is crosscut by sets of conjugate zones associated with grain-size reduction of olivine grains. These grain-size reduction zones are interpreted as brittle structures generated by hydrofracturing due to overpressure fluids in a compressional setting at low-differential stresses.Structures related to the exhumation process are mainly preserved in the metasedimentary host rock, where an S2/L2 planar–linear fabric developed within a shear zone dominated by a non-coaxial regime with a top-to-the-W sense of movement in a transpressional regime. Peak metamorphic conditions deduced for the schists are similar in pressure (1.3–1.9 GPa) but lower in temperature (560–590 °C) compared to the ultramafic rocks in contact with them, suggesting a major shear zone at the base of the ultramafic massif during D2 deformation in a right-handed transpressional regime.
ISSN: 0040-1951

hal-01172303
https://hal.archives-ouvertes.fr/hal-01172303
DOI : 10.1016/j.tecto.2014.12.022

Éditeur(s) : HAL CCSD Springer Verlag (Germany) Springer Verlag
Résumé : International audience
La Cabaña peridotite is part of a dismembered ophiolite complex located within the metamorphic basement of the Coastal Cordillera of south-central Chile, and is the only location in Chile were Cr-spinels have been described so far. The La Cabaña peridotite is part of the Western Series unit, which comprises meta-sedimentary rocks, metabasites, and serpentinized ultramafic rocks. This unit has been affected by greenschist-facies metamorphism with reported peak PT conditions of 7.0–9.3 kbar and 380°–420 °C. Within La Cabaña peridotite Cr-spinels are present in two localities: Lavanderos and Centinela Bajo. In Lavanderos, Cr-spinel occurs in small chromitite pods and as accessory/disseminated grains with a porous or spongy texture in serpentinite, whereas in Centinela Bajo Cr-spinel is present as accessory zoned grains in partly serpentinized dunites, and in chromitite blocks. All Cr-spinels display variable degrees of alteration to Fe2+-rich chromite with a variation trend of major elements from chromite to Fe2+-rich chromite similar to those observed in other locations, i.e., an increase in Fe2O3 and FeO, a decrease in Al2O3 and MgO. Cr2O3 content increases from chromite to Fe2+-rich chromite in chromitite pods from Lavanderos and chromitite blocks from Centinela Bajo, but decreases in ferrian chromite zones in accessory grains from Centinela Bajo. The minor element (Ti, V, Zn, Ni) content is mostly low and does not exceed 0.4 wt.%, with the exception of MnO (<0.9 wt.%), which shows a correspondence with increasing degree of alteration. Cr# (Cr/Cr + Al) versus Mg# (Mg/Mg + Fe2+) and Fe3+/Fe3++Fe2+ versus Mg# plots are used to illustrate the Cr-spinel alteration process. Overall, the Cr-spinels from Lavanderos (chromitite pods and disseminated grains) exhibit Cr# values ranging from 0.6 to 1.0, Mg# (Mg/Mg + Fe2+) below 0.5, and (Fe3+/Fe3++Fe2+) <0.4. Cr-spinels from chromitites in Centinela Bajo have Cr# and Mg# values that range from 0.65 to 1.0, and 0.7-0.3, respectively, and (Fe3+/Fe3++Fe2+) < 0.4. Accessory Cr-spinels from Centinela Bajo have Cr# and Mg# values that range from 0.55 to 1.0, and 0.6- < 0.1, respectively. The (Fe3+/Fe3++Fe2+) ratio is less than 0.4 in chromite cores and Fe2+-rich chromite, and >0.5 in ferrian chromite and Cr-magnetite. Interpretation of the data obtained and Cr-spinel textures indicate that the alteration of Cr-spinel is a progressive process that involves in its initial stages the reaction of chromite with olivine under water-saturated conditions to produce clinochlore and Fe2+-rich chromite. During this stage the chromite can also incorporate Ni, Mn, and/or Zn from the serpentinization fluids. As alteration progresses, Fe2+-rich chromite loses mass resulting in the development of a spongy texture. In a later stage and under more oxidizing conditions Fe3+ is incorporated in chromite/Fe2+-rich chromite shifting its composition to an Fe3+-rich chromite (i.e., ferrian chromite). Depending on the fluid/rock and Cr-spinel/silicate ratios, Cr-magnetite can also form over Fe2+-rich chromite and/or ferrian chromite as a secondary overgrowth. The compositional changes observed in Cr-spinels from La Cabaña reflect the initial stages of alteration under serpentinization conditions. Results from this study show that the alteration of Cr-spinels is dependent on temperature. The degree and extent of alteration (formation of Fe2+-rich and/or ferrian chromite) are controlled by the redox nature of the fluids, the Cr-spinel/silicate and the fluid/rock ratios.
ISSN: 0930-0708

hal-01172266
https://hal.archives-ouvertes.fr/hal-01172266
DOI : 10.1007/s00710-014-0335-5

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Serpentinites form by hydration of mantle peridotite and constitute the largest potential reservoir of fluid-mobile elements entering subduction zones. Isotope ratios of one such element, boron, distinguish fluid contributions from crustal versus serpentinite sources. Despite 85% of boron hosted within abyssal peridotite being lost at the onset of subduction at the lizardite-to-antigorite transition, a sufficient cargo of boron to account for the composition of island arc magma is retained (c. 7 μg g− 1, with a δ11B of + 22‰) until the down-going slab reaches the antigorite-out isograd. At this point a 11B-rich fluid, capable of providing the distinctive δ11B signature of island arc basalts, is released. Beyond the uniquely preserved antigorite-out isograd in serpentinites from Cerro del Almirez, Betic Cordillera, Spain, the prograde lithologies (antigorite–chlorite–orthopyroxene–olivine serpentinite, granofels-texture chlorite-harzburgite and spinifex-texture chlorite-harzburgite) have very different boron isotope signatures (δ11B = − 3 to + 6‰), but with no significant difference in boron concentration compared to the antigorite-serpentinite on the low P–T side of the isograd. 11B-rich fluid, which at least partly equilibrated with pelagic sediments, is implicated in the composition of these prograde lithologies, which dehydrated under open-system conditions. Serpentinite-hosted boron lost during the early stages of dehydration is readily incorporated into forearc peridotite. This, in turn, may be dragged to sub-arc depths as a result of subduction erosion and incorporated in a mélange comprising forearc serpentinite, altered oceanic crust and pelagic sediment. At the antigorite-out isograd it dehydrates, thus potentially providing an additional source of 11B-rich fluids.
ISSN: 0009-2541

hal-01172276
https://hal.archives-ouvertes.fr/hal-01172276
DOI : 10.1016/j.chemgeo.2014.03.015

Éditeur(s) : HAL CCSD Springer Verlag (Germany) Springer Verlag
Résumé : International audience
Separated olivine grains from a deeply subducted serpentinized wehrlite (Changawuzi in the western Tianshan ultrahigh-pressure belt, China) were analysed with unpolarized transmission FTIR and the Ti contents were determined using LA-ICP-MS. The major bands in the olivine spectra display striking similarities to Ti-clinohumite and are interpreted as OH in lamellae. The quantification of the water content in lamellae requires calibration of the IR-absorption for such bands. We have obtained a new absorption coefficient for Ti-clinohumite of 0.125+/−0.017 ppm cm2 based on polarized FTIR measurements on three orthogonal sections through a large single crystal of Ti-clinohumite from Val Malenco, which has a known water content of 1.53 wt%. The resulting water content in olivine using this calibration factor ranges from 440 to 2,600 ppm and correlates positively with the Ti content that ranges from 130 to 1,400 ppm. For the quantification of the water content in Ti-chondrodite and Ti-clinohumite that are associated with olivine, we developed a new method using attenuated total reflectance FTIR spectroscopy. Ti-chondrodite and Ti-clinohumite display similar IR bands at ~3,562, 3,525 and ~3,583–3,586 cm−1. As in olivine, the water content and Ti content correlate in both Ti-clinohumite and Ti-chondrodite, indicating an intergrowth of these minerals, which has been confirmed by TEM analyses. Our results confirm previous suggestions that there is a strong correlation between the Ti content of ultramafic rocks and their capacity to transport water to the deeper mantle in subduction zones beyond conditions where hydrous phases are stable.
ISSN: 0010-7999

hal-01172237
https://hal.archives-ouvertes.fr/hal-01172237
DOI : 10.1007/s00410-014-0992-8

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We report gabbroic dikes in the plagioclase tectonite domains of the Ojén and Ronda massifs (Betic Cordillera, southern Spain), which record crystallization at low-pressure syn-, or slightly postkinematic to the late ductile history of the Betic Peridotite in the westernmost Mediterranean. We present mineral major and trace element compositional data of discordant gabbroic dikes in the Ojén massif and gabbroic patches in the Ronda massif, complemented by the whole rock and electron backscattered diffraction (EBSD) data of the Ojén occurrence. In the Ojén massif, gabbro occurs as 1–3 centimeter wide discordant dikes that crosscut the plagioclase tectonite foliation at high angle. These dikes are composed of cm-scale igneous plagioclase and clinopyroxene crystals that show shape preferred orientations subparallel to the lineation of the host peridotite and oblique to the trend of the dike. Intrusion of Ojén gabbro dikes is coherent with the stress field that formed the high temperature, ductile plagioclase tectonite foliation and then attests for a mantle igneous event prior to the intracrustal emplacement of the massif. In the Ronda massif, gabbroic rocks crystallized in subcentimeter wide anastomozing veins, or as interstitial patches in the host dunite. They are mostly composed of plagioclase and clinopyroxene. Plagioclase composition is bytownitic in the Ojén, and andesinic in the Ronda massif. Clinopyroxene in both places shows identical, light Rare-Earth Element (LREE) depleted trace element patterns. The calculated trace element composition of melts in exchange equilibrium with the studied igneous clinopyroxenes reflects LREE-enriched character coupled with negative Eu anomaly, and indicates that gabbro-forming melts in Ronda and Ojén share a common melt source with an island arc tholeiitic affinity. Geothermobarometric data and liquidus mineralogy indicate that gabbro crystallization occurred at shallow depths (0.2–0.5 GPa) in a 7–16 km thick lithospheric section. These data suggest that gabbro-forming melts in the Betic Peridotite record a mantle igneous event at very shallow depths and provide evidence for the hyperextension of the continental lithosphere compatible with extreme backarc basin extension induced by the slab rollback of the Cenozoic subduction system in the westernmost Mediterranean.
ISSN: 0040-1951

hal-01172246
https://hal.archives-ouvertes.fr/hal-01172246
DOI : 10.1016/j.tecto.2015.03.011

Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : International audience
We report structural evidence of ductile strain localization in mantle pyroxenite from the spinel to plagioclase websterite transition in the Ronda Peridotite (southern Spain). Mapping shows that, in this domain, small-scale shear zones occurring at the base of the lithospheric section are systematically located within thin pyroxenite layers, suggesting that the pyroxenite was locally weaker than the host peridotite. Strain localization is associated with a sudden decrease of grain size and increasing volume fractions of plagioclase and amphibole as a result of a spinel to plagioclase phase transformation reaction during decompression. This reaction also fostered hydrogen extraction ('dehydroxylation') from clinopyroxene producing effective fluid saturation that catalyzed the synkinematic net-transfer reaction. This reaction produced fine-grained olivine and plagioclase, allowing the onset of grain-size sensitive creep and further strain localization in these pyroxenite bands. The strain localization in the pyroxenites is thus explained by their more fertile composition, which allowed earlier onset of the phase transition reactions. Geothermobarometry undertaken on compositionally zoned constituent minerals suggests that this positive feedback between reactions and deformation is associated with cooling from at least 1000°C to 700°C and decompression from 1*0 to 0*5 GPa.
ISSN: 0022-3530

hal-00941293
https://hal.archives-ouvertes.fr/hal-00941293
DOI : 10.1093/petrology/egt039

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We combined microstructural observations and high-resolution crystallographic preferred orientation (CPO) mapping to unravel the active deformation mechanisms in garnet clinopyroxenites, garnet-spinel websterites, and spinel websterites from the Beni Bousera peridotite massif. All pyroxenites display microstructures recording plastic deformation by dislocation creep. Pyroxene CPOs are consistent with dominant slip on [001]{110} in clinopyroxene and on [001](100) or [001](010) in orthopyroxene. Garnet clinopyroxenites have however high recrystallized fractions and finer grain sizes than spinel websterites. Recrystallization mechanisms also differ: subgrain rotation dominates in garnet clinopyroxenites, whereas in spinel websterites nucleation and growth also contribute. Elongated shapes and strong intracrystalline misorientations suggest plastic deformation of garnet, but CPOs are weak. Clinopyroxene porphyroclasts in spinel websterites show deformation twins underlined by orthopyroxene exsolutions. Thermodynamic calculations indicate that garnet clinopyroxenites deformed at 2.0 GPa and 950-1000 °C and spinel pyroxenites at 1.8 GPa and 1100-1150 °C. The lower temperatures may explain the faster work rates implied by the finer grained microstructures in garnet clinopyroxenites. Greater stresses may have also reduced the competence contrast between garnet and pyroxene in the garnet pyroxenites and, at the outcrop scale, lowered the competence contrast between pyroxenites and peridotites, favoring mechanical dispersion of pyroxenites in the cooler lithospheric mantle.
ISSN: 0191-8141

hal-00750322
https://hal.archives-ouvertes.fr/hal-00750322
DOI : 10.1016/j.jsg.2012.02.019

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
Low-level water measurements of geological materials are fundamental in understanding the volatile inventories of the Earth from the mantle to crustal reservoirs. Here we describe the development of microanalytical techniques using the new SHRIMP SI ion microprobe to measure the abundances of OH− (as a proxy for water) in volcanic glass and nominally anhydrous minerals (NAMs). Samples were first analysed at the Carnegie Institute of Washington (CIW) on their Cameca ims-6f with calibrations based on previous FTIR and manometry analyses. SHRIMP SI is a large geometry ion microprobe and is currently mainly used for O and S isotope analyses. The analytical protocol used here incorporates multiple collection of 16O− and 16O1H− allowing rapid measurements. A single calibration line incorporating all glasses and NAMs for the SHRIMP SI allows calibration of 16O1H−/16O− to H2O over a wide range in concentration (50 to 15 000 ppm H2O). This calibration line has around a 10% uncertainty, which appears to be limited only by sample heterogeneity. The current background for SHRIMP analysis is between 20–40 ppm but this is expected to improve with improved pumping on the source chamber. A current limitation to water analysis of NAM samples, by any technique, is having a range of standard materials to enable OH− calibration to absolute H2O concentrations. Data are presented for 7 NAM samples (2 olivines, 2 orthopyroxenes and 3 clinopyroxenes) that appear to be promising as potential standards for international laboratory H2O measurements. These NAM samples have been analysed and characterised here by SHRIMP SI, FTIR, EMP and the Cameca ims-6f ion microprobe at CIW. Four of these samples have previously been measured by manometry to determine absolute H2O concentrations.
ISSN: 0267-9477

hal-01243514
https://hal.archives-ouvertes.fr/hal-01243514
DOI : 10.1039/c5ja00047e

Éditeur(s) : HAL CCSD American Geophysical Union (AGU)
Résumé : Mantle xenoliths in Pliocene alkali basalts of the eastern Betics (SE Iberia, Spain) are spinel ± plagioclase lherzolite, with minor harzburgite and wehrlite, displaying porphyroclastic or equigranular textures. Equigranular peridotites have olivine crystal preferred orientation (CPO) patterns similar to those of porphyroclastic xenoliths but slightly more dispersed. Olivine CPO shows [100]-fiber patterns characterized by strong alignment of [100]-axes subparallel to the stretching lineation and a girdle distribution of [010]-axes normal to it. This pattern is consistent with simple shear or transtensional deformation accommodated by dislocation creep. One xenolith provides evidence for synkinematic reactive percolation of subduction-related Si-rich melts/fluids that resulted in oriented crystallization of orthopyroxene. Despite a seemingly undeformed microstructure, the CPO in orthopyroxenite veins in composite xenoliths is identical to those of pyroxenes in the host peridotite, suggesting late-kinematic crystallization. Based on these observations, we propose that the annealing producing the equigranular microstructures was triggered by melt percolation in the shallow subcontinental lithospheric mantle coeval to the late Neogene formation of veins in composite xenoliths. Calculated seismic properties are characterized by fast propagation of P waves and polarization of fast S waves parallel to olivine [100]-axis (stretching lineation). These data are compatible with present-day seismic anisotropy observations in SE Iberia if the foliations in the lithospheric mantle are steeply dipping and lineations are subhorizontal with ENE strike, implying dominantly horizontal mantle flow in the ENE-WSW direction within vertical planes, that is, subparallel to the paleo-Iberian margin. The measured anisotropy could thus reflect a lithospheric fabric due to strike-slip deformation in the late Miocene in the context of WSW tearing of the subducted south Iberian margin lithosphere.
ISSN: 0278-7407

Droits : info:eu-repo/semantics/OpenAccess
hal-01685809
https://hal.archives-ouvertes.fr/hal-01685809
https://hal.archives-ouvertes.fr/hal-01685809/document
https://hal.archives-ouvertes.fr/hal-01685809/file/Hidas_et_al-2016-Tectonics.pdf
DOI : 10.1002/2016TC004165

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Synthetic hydroxylated titanium-bearing and undoped MgO-buffered forsterite crystals were heated at atmospheric pressure in air at temperatures from 800 to 1200 °C to determine hydrogen diffusion as a function of the type of point-defect mechanism by which the hydroxyl is incorporated. OH-stretching bands, measured by infrared spectroscopy, were assigned to the four substitution mechanisms: Ti-clinohumite point defects, silicon and magnesium vacancies, and point defects associated with trivalent cations. In the experiments at 800 to 1000 °C, hydrous defects related to trivalent cations and Mg-vacancies disappear first in the Ti-doped forsterite, followed by the hydrous defects related to Ti and a fraction of the hydrated Si-vacancies. Measured bulk diffusion coefficients for hydrogen exchange related to the latter process are one order of magnitude slower than previously reported and with higher activation energy (View the MathML source296±14 kJmol−1). After the elimination of the defects related to Ti, the hydroxyl concentration related to Si-vacancies remained constant for the duration of the experiments. This observation is in agreement with the very slow diffusivity of hydrogen in Si-vacancies measured in the undoped MgO-buffered dehydroxylation experiments at higher temperatures (from 1000 to 1200 °C), which were ∼3 orders of magnitude slower than previously reported at 1000 °C, and with an activation energy of View the MathML source461±11 kJmol−1. Hydrogen diffusion in forsterite is far more complex than previously assumed. This complexity can be used to gain more information on the timescales of the processes causing olivine to lose its structural “water”, but quantitative modeling will require not only the knowledge of the intrinsic diffusivities of the different hydrous defects but also their relative proportions and the possible reactions between them.
ISSN: 0012-821X

hal-01172253
https://hal.archives-ouvertes.fr/hal-01172253
DOI : 10.1016/j.epsl.2014.01.055

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We have inferred the deformation mechanisms of antigorite by high-resolution EBSD mapping of samples from Cerro del Almirez ultramafic massif (Betic Cordillera, SE Spain). Textural relations and phase diagram calculations constrain the foliation development conditions to the subduction prograde path at up to 600-630 °C and 1.6-1.9 GPa. Deformation was followed by static annealing of antigorite at ca. 680 °C. The Crystal Preferred Orientation (CPO) of antigorite is characterised by a strong alignment of (001) poles normal to the foliation plane and a weaker, but clear, parallelism between [100] axes and the macroscopic lineation defined by the elongation of magnetite aggregates. Analysis of misorientations across subgrains shows predominance of [010] rotation axis, consistent with activation of the [100](001) slip system. However, tilt subgrain boundaries subparallel to (100), probably formed by edge dislocations of this system, are subsidiary. Most subgrain boundaries are subparallel to (001) planes. They are interpreted as (001) twins wherein continuing viscoplastic deformation resulted in a slight increase of the misorientation between the twins. Modelling of the evolution of the antigorite CPO using a lower bound approach and considering different deformation regimes and sets of basal and non-basal slip systems has shown that intensities of [100] and [010] maxima reflect the relative strength of the antigorite [100](001) and [010](001) systems. Activation of other basal or non-basal slip systems does not change significantly the CPO patterns, but results in less concentrated CPO. 3D transpression models better reproduce the CPO of natural antigorite serpentinites. We propose that the widespread occurrence of strong CPO in high-pressure antigorite serpentinite is consistent with deformation by dislocation creep with dominant glide on [hk0](001), together with the activation of twinning, implying that a power law rheology would better account for the mechanical behaviour of antigorite serpentinite deep in the subduction channel and mantle wedge.
ISSN: 0012-821X

hal-00795511
https://hal.archives-ouvertes.fr/hal-00795511
DOI : 10.1016/j.epsl.2012.06.049

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This study reports petrostructural observations in the pargasite and phlogopite-bearing Finero peridotite massif (Italian Western Alps), which suggest that the pervasive foliation in this massif was formed by deformation concomitant with percolation of hydrous Si-rich melts: (1) diffuse contacts, but systematic parallelism between the pyroxenitic layers and the foliation of the peridotite (2) strong shape and crystal preferred orientations (SPO and CPO), but subhedral or interstitial shapes and weak intracrystalline deformation of the hydrous phases, (3) CPO, but interstitial shapes of the pyroxenes, (4) very coarse olivine grain sizes, which are correlated to the olivine abundance, and (5) elongated shapes, but weak intracrystalline deformation, and extremely weak and highly variable CPO of olivine. The pervasive deformation of the Finero peridotite occurred therefore under conditions that allowed coexistence of H2O–CO2-bearing melts, pargasite, and spinel, that is, temperatures of 980–1080 °C and pressures <2 GPa. The petrostructural observations suggest that the presence of hydrous melts results in accommodation of large amounts of deformation by stress-controlled dissolution–precipitation and advective transport of matter by the melts and in fast grain boundary migration in olivine. By consequence, it produces significant rheological weakening. Water contents in olivine are <4 ppm wt., implying limited contribution of hydration of olivine to weakening. In addition, the analysis of protomylonites composing the external domains of the shear zones that overprint the pervasive foliation indicates that the transition to melt-free conditions results in enhanced contribution of dislocation creep to the deformation. The associated increase of the peridotites' strength leads to onset of strain localization. The latter is not correlated to the local abundance in pargasite or phlogopite, implying that crystallization of amphiboles or phlogopite, even at concentrations of 25 vol.%, does not produce rheological weakening in the upper mantle.
ISSN: 0012-821X

hal-01667879
https://hal.archives-ouvertes.fr/hal-01667879
DOI : 10.1016/j.epsl.2017.08.015

Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : International audience
The diffusion of titanium along with Ni, Co and Mn in pure synthetic forsterite has been studied as a function of temperature, oxygen fugacity, crystallographic orientation and chemical potentials in the four-component system MgO–SiO2–TiO2–TiO1·5. In over 100 different experimental conditions, no Ti diffusion profiles with the classical shape of the error function were observed. Instead, the profiles vary between ‘stepped’ at high fO2 (probably owing to diffusion on octahedral sites and trapping in tetrahedral sites), to hockey-stick shapes at low fO2 owing to concentration-dependent diffusion. The profile shapes vary systematically between these end-members according to oxygen fugacity. These profile shapes are also reproduced in experiments using natural San Carlos olivine. The change in profile shape is interpreted to be a function of valence-state change from Ti4+ to Ti3+, shown by a sigmoidal log fO2–diffusivity relationship. To distinguish between Ti4+ and Ti3+ in forsterite, a diffusion profile was also investigated using ‘hydroxylation spectroscopy’ whereby a crystal from a diffusion experiment was hydroxylated by annealing in an H2O-rich fluid at moderate pressure and temperature. The point defects associated with the added structural OH were then determined by infrared spectroscopy, providing evidence for the presence of Ti4+ and Ti3+ at intermediate oxygen fugacity. The transition from Ti4+ to Ti3+ occurs at considerably higher fO2 in these diffusion experiments than in equilibrium experiments in similar systems. Titanium diffusion, qualified using a mobility parameter (M), is fastest along the c-axis, at high activity of silica, low oxygen fugacity and high temperature. The rate of Ti diffusion is broadly similar to those of Mn, Ni and Co, and closer to published rates of Mg self-diffusion in olivine than Si self-diffusion. The observed Ti3+ and Ti4+ diffusion occurs on the M-sites. From statistical examination of the large Mn, Ni and Co diffusivity dataset, we determine that there is a 102/3 dependence of diffusion on aSiO2; the cations diffuse more rapidly at high aSiO2. In addition, diffusivity has a 10–1/8 dependence on fO2, suggested to be the result of increased concentration of loosely bound Ti3+–vacancy pairs, which enhance the mobility of other cations. This behaviour is likely to be present in natural systems where trivalent (e.g. Fe3+, Al3+, Cr3+) and divalent cations diffuse together. Consideration should be given to diffusive interference by highly charged, fast-moving cations when extracting time scales from frozen diffusion profiles.
ISSN: 0022-3530

hal-01531344
https://hal.archives-ouvertes.fr/hal-01531344
DOI : 10.1093/petrology/egw067

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 Oxford University Press (OUP)
Résumé : International audience
The southwestern Tianshan (China) metamorphic belt records high-pressure (HP) to ultrahigh-pressure (UHP) conditions corresponding to a cold oceanic subduction-zone setting. Serpentinites enclosing retrogressed eclogite and rodingite occur as lenses within metapelites in the UHP unit, which also hosts coesite-bearing eclogites. Based on the petrology and petrography of these serpentinites, five events are recognized: (1) formation of a wehrlite–harzburgite–dunite association in the mantle; (2) retrograde metamorphism and partial hydration during exhumation of the mantle rocks close to the seafloor; (3) oceanic metamorphism leading to the first serpentinization and rodingitization; (4) UHP metamorphism during subduction; (5) retrograde metamorphism during exhumation together with a second serpentinization. The peak metamorphic mineral assemblage of the serpentinized wehrlite comprises Ti-chondrodite + olivine + antigorite + chlorite + magnetite + brucite. A computed pseudosection for this serpentinized wehrlite shows that the Al content in antigorite is mostly sensititive to temperature but can also be used to constrain pressure. The average XAl = 0·204 ± 0·026 of antigorite (XAl = Al (a.p.f.u.)/8, where Al is in atoms per formula unit for a structural formula M48T34O85(OH)62, and M and T are octahedral and tetrahedral sites, respectively) included in Ti-chondrodite and average XAl = 0·203 ± 0·019 of antigorite in the matrix result in a well-constrained peak metamorphic temperature of 510–530°C. Peak pressures are less precisely constrained at 37 ± 7 kbar. The Tianshan serpentinites thus record UHP metamorphic conditions and represent the deepest subducted serpentinites discovered so far. The retrograde evolution occurs within the stability field of brucite + antigorite + olivine + chlorite and formation of Ti-clinohumite at the expense of Ti-chondrodite has been observed, suggesting isothermal decompression. The resulting P–T path is in excellent agreement with the metamorphic evolution of country rocks, indicating that the UHP unit in Tianshan was subducted and exhumed as a coherent block. To refine the metamorphic path of the ultramafic rocks, we have investigated the stability fields of Ti-chondrodite and Ti-clinohumite using piston-cylinder experiments. A total of 11 experiments were conducted at 25–55 kbar and 600–750°C in a F-free natural system. Combined with previous experiments and information from natural rocks we constructed a petrogenetic grid for the stability of Ti-chondrodite and Ti-clinohumite in F-free peridotite compositions. The formation of Ti-chondrodite in serpentinites requires a minimum pressure of about 26 kbar, whereas in Ti-rich systems it can form at considerably lower pressures. A key finding is that at UHP conditions, F-free Ti-chondrodite or Ti-clinohumite breaks down in the presence of orthopyroxene between 700 and 750°C, at temperatures that are significantly lower than those of the terminal breakdown reactions of these humite minerals. These breakdown reactions are an additional source of fluid during prograde subduction of serpentinites.
ISSN: 0022-3530

hal-01243507
https://hal.archives-ouvertes.fr/hal-01243507
DOI : 10.1093/petrology/egv042

Éditeur(s) : HAL CCSD Springer Verlag (Germany) Springer Verlag
Résumé : International audience
The Cerro del Almirez massif (Spain) represents a unique fragment of serpentinized oceanic lithosphere that has been first equilibrated in the antigorite stability field (Atg-serpentinites) and then dehydrated into chlorite–olivine–orthopyroxene (Chl-harzburgites) at eclogite facies conditions during subduction. The massif preserves a dehydration front between Atg-serpentinites and Chl-harzburgites. It constitutes a suitable place to study redox changes in serpentinites and the nature of the released fluids during their dehydration. Relative to abyssal serpentinites, Atg-serpentinites display a low Fe3+/FeTotal(BR) (=0.55) and magnetite modal content (=2.8–4.3 wt%). Micro-X-ray absorption near-edge structure (μ-XANES) spectroscopy measurements of serpentines at the Fe–K edge show that antigorite has a lower Fe3+/FeTotal ratio (=0.48) than oceanic lizardite/chrysotile assemblages. The onset of Atg-serpentinites dehydration is marked by the crystallization of a Fe3+-rich antigorite (Fe3+/FeTotal = 0.6–0.75) in equilibrium with secondary olivine and by a decrease in magnetite amount (=1.6–2.2 wt%). This suggests a preferential partitioning of Fe3+ into serpentine rather than into olivine. The Atg-breakdown is marked by a decrease in Fe3+/FeTotal(BR) (=0.34–0.41), the crystallization of Fe2+-rich phases and the quasi-disappearance of magnetite (=0.6–1.4 wt.%). The observation of Fe3+-rich hematite and ilmenite intergrowths suggests that the O2 released by the crystallization of Fe2+-rich phases could promote hematite crystallization and a subsequent increase in fo2 inside the portion of the subducted mantle. Serpentinite dehydration could thus produce highly oxidized fluids in subduction zones and contribute to the oxidization of the sub-arc mantle wedge.
ISSN: 0010-7999

hal-01172310
https://hal.archives-ouvertes.fr/hal-01172310
DOI : 10.1007/s00410-015-1130-y

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We report microstructural evidence for fluid-assisted ductile strain localization in a ≤ 50 m-wide mylonitic–ultramylonitic shear zone in the Ronda Peridotite massif, Southern Spain. Strain localization occurred at relatively low pressure (< 0.8 GPa) and moderate temperature (750–1000 °C). Initial deformation by dislocation creep resulted in formation of mylonites. Focusing of aqueous fluids in the shear zone favored the activation of dissolution–precipitation creep, resulting in further strain localization. This process is recorded by two generations of ultramylonitic bands composed of fine-grained, well-mixed olivine–orthopyroxene aggregates. Microstructural observations in the ultramylonites suggest alternating dissolution and precipitation of olivine and orthopyroxene, which may be explained by local changes in silica molality of the percolating fluid (disequilibrium and mass transfer at scales > mm). In the mylonites, olivine shows a crystal preferred orientation (CPO) coherent with dominant (001)[100] glide, probably due to the presence of interstitial fluids during deformation. In the ultramylonites, olivine CPO is weak to very weak, consistently with a decreasing contribution of dislocation creep to deformation. In contrast, fine-grained orthopyroxene in both mylonites and ultramylonites displays a clear CPO characterized by a [001] maximum normal to the foliation, which is not consistent with dislocation glide in any known slip system for orthopyroxene. We interpret this CPO as formed by oriented crystallization during dissolution–precipitation. In the present study, dissolution–precipitation creep predominates only in small-scale ultramylonite bands due to limited fluid availability and localized dynamic permeability. However, this process may be important in intermediate temperature domains of subduction zones, where it may lead to a feedback between strain localization and fluid transport.
ISSN: 0024-4937

hal-01395122
https://hal.archives-ouvertes.fr/hal-01395122
DOI : 10.1016/j.lithos.2016.07.038

Éditeur(s) : HAL CCSD Springer Verlag (Germany) Springer Verlag
Résumé : Dehydration reactions result in minerals’ replacement and a transient fluid-filled porosity. These reactions involve interface-coupled dissolution–precipitation and might therefore lead to fixed crystallographic orientation relations between reactant (protolith) and product phases (i.e. topotaxy). We investigate these two phenomena in the dehydration of a foliated antigorite (atg) serpentinite by comparing the crystallographic preferred orientation (CPO) developed by olivine (ol), orthopyroxene (opx) and chlorite (chl) during high-pressure antigorite and chlorite dehydration in piston-cylinder experiments and in natural samples recording the dehydration of antigorite (Cerro del Almirez, Betic Cordillera, Spain). Experiments were performed under undrained conditions resulting in fluid-filled porosity and in strong CPO of the prograde minerals, controlled by the pre-existing antigorite CPO in the reactant foliated serpentinite. The orientation of a ol,opx and c∗chl is parallel to c∗atg from the protolith. The Cerro del Almirez samples show similar, locally well-developed topotactic relations between orthopyroxene, chlorite and antigorite, but the product CPOs are weaker and more complex at the thin section scale. In contrast to the experiments, olivine from natural samples shows a weak correlation between b ol and the former c∗atg. We relate the strengthening of local topotactic relations and the weakening of the inherited CPO at a larger scale in natural samples to compaction and associated fluid migration. Microstructural features that might be related to compaction in the natural samples include: (1) smooth bending of the former foliation, (2) gradual crystallographic misorientation (up to 16°) of prismatic orthopyroxene due to buckling by dislocation creep, (3) inversion of enstatite to low clinoenstatite (P21/c) along lamellae and (4) brittle fracturing of prismatic orthopyroxene enclosed by plastically deformed chlorite. The coexistence of orthopyroxene buckling and clinoenstatite lamellae enables estimating the local strain rates and shear stresses generated during compaction. An lower bound for the strain rates in the order of 10−12 to 10−13 s−1 and shear stresses of 60–70 MPa are estimated based on creep data. Lower shear stresses (20–40 MPa) are retrieved using a theoretical approach. These data point to slow compaction (and fluid extraction) in nature if the system is not perturbed by external forces, with rates only marginally higher than the viscoplastic deformation of the solid matrix.
ISSN: 0010-7999

hal-01174158
https://hal.archives-ouvertes.fr/hal-01174158
DOI : 10.1007/s00410-015-1129-4