Éditeur(s) : HAL CCSD Springer Verlag
Résumé : International audience
Hydrogen can be stored in the structure of nominally anhydrous minerals as point defects, and these impurities substantially modify many physical properties of Earth's mantle minerals. However, mantle rocks are composed of mineral grains separated by grain boundaries and interphase grains boundaries. Therefore, as a potential hydrogen reservoir, grain boundaries should be given proper attention. Here, I report an experimental investigation into hydrogen diffusion through grain boundaries in polycrystalline aggregates Sintering and diffusion experiments were performed using a gas-medium high-pressure vessel at under pressure of 300 MPa and over a temperature range of 900-1,250 degrees C. The diffusion assembly consisted of a polycrystalline cylinder of aluminous spinel + olivine crystals with a talc cylinder as the main hydrogen source. A Ni capsule was used to buffer the oxygen fugacity at Ni-NiO Experimental durations varied from 5 min to 5 h. The presence of hydrogen in the crystals was measured by Fourier-transform infrared spectroscopy. The calculation of the diffusion coefficients was based on the estimation of the characteristic distance. The absence or presence of hydrogen recorded by the 'hydrogen sensor' olivines embedded in the aggregate allows the estimation of bounds on this characteristic distance. Results presented here suggest that hydrogen effective diffusion coefficients are only one order of magnitude faster (similar to 10(-9) m(2)s(-1) at 1,000 degrees C) than in an olivine single crystal along the [100] axis. Resulting diffusion coefficients for hydrogen in grain boundary are four orders of magnitude faster than in a single crystal, but this diffusivity is not fast enough to affect hydrogen mobility in mantle rocks with grain sizes greater than similar to 1 mm. Thus, very limited chemical homogenization would occur using grain boundaries diffusion in mantle hydrous peridotite for incompatible and volatile element, such as hydrogen.
ISSN: 0010-7999

hal-00564353
https://hal.archives-ouvertes.fr/hal-00564353
DOI : 10.1007/s00410-010-0512-4

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Talc is a hydrous magnesium rich layered silicate that is widely disseminated in the Earth from the seafloor to over 100 km depth, in ultra-high pressure metamorphism of oceanic crust. In this paper we determine the single crystal elastic constants at pressures from 0 to 12 GPa of talc triclinic (C 1¯) and monoclinic (C2/c) polytypes using ab initio methods. We find that talc has an extraordinarily high elastic anisotropy at zero pressure that reduces with increasing pressure. The exceptional anisotropy is complemented by a negative Poisson's ratio for many directions in crystal space. Calculations show that talc is not only one of very few common minerals to exhibit auxetic behaviour, but the magnitude of this effect may be the largest reported so far for a mineral. The compression (Vp) and shear (Vs) wave velocity anisotropy is 80% and 85% for the triclinic polytype. At pressures where talc is known be stable in the Earth (up to 5 GPa) the Vp and Vs anisotropy is reduced to about 40% for both velocities, which is still a very high value. Vp is slow parallel to the c-axis and fast perpendicular to it. This remains unchanged with increasing pressure and is observed in both polytypes. The shear wave splitting (difference between fast and slow S-wave velocities) at low pressure has high values in the plane normal to the c-axis, with a maximum near the alow asterisk-axis in the triclinic and the b-axis in the monoclinic polytype. The c-axis is the direction of minimum splitting. The pattern of shear wave splitting does not change significantly with pressure. The volume fraction of talc varies between 11 and 41% for hydrated mantle rocks, but the lack of data on the crystallographic preferred orientation (CPO) precludes a detailed analysis of the impact of talc on seismic anisotropy in subduction zones. However, it is highly likely that CPO can easily develop in zones of deformation due to the platy habit of talc crystals. For random aggregates of talc, the isotropic Vp, Vs and Vp/Vs ratio have significantly lower values than those of antigorite and may explain low-velocity regions in the mantle wedge. Vp/Vs ratios are more complex in anisotropic media because there are fast and slow S-waves, resulting in Vp/Vs1 and Vp/Vs2 ratios for every propagation direction, making interpretation difficult in deformed polycrystalline talc with a CPO. Talc on the subduction plate boundary can strongly influence guided wave velocity as CPO would develop in this region of intense shearing. The very low coefficient of friction (< 0.1) of talc above 100 °C could also explain silent earthquakes at shallow depths (ca 30 km) along the subduction plate boundaries, frequently responsible for tsunami.
ISSN: 0012-821X

hal-00411481
https://hal.archives-ouvertes.fr/hal-00411481
DOI : 10.1016/j.epsl.2008.07.047

Éditeur(s) : HAL CCSD Springer-Verlag
Résumé : The seismology is the most effective method to explore the Structure of subduction zones to great depth. The distinguishing feature of the mantle in the subduction regions is the presence of hydrated phases, which transport water into the Earth's interior and release it with dramatic local consequences, triggering earthquakes and melting. The seismological detection of these hydrous phases and geo-dynamic interpretation of flow in the hydrous mantle depend on knowledge of the anisotropic elastic properties and the characteristics of the wave propagation in anisotropic media. In this paper we briefly recall the distinguishing features of anisotropic wave propagation and the observable parameters. We suggest the Vp/Vs ratio is a physically sound parameter than can be observed by seismology in anisotropic regions of the Earth, whereas the Poisson's ratio, which is often quoted, is not directly observable and does not correspond to the characteristics of wave propagation in an anisotropic or isotropic medium. We report for the first time the ratios of Vp/Vs1 and Vp/Vs2, where Vs1 is the fastest and Vs2 slowest S-wave velocities of an anisotropic media. We present the current knowledge of the anisotropic seismic properties of hydrous minerals in the upper mantle, transition zone, and lower mantle that are stable along low temperature geotherms associated with subduction, and identify which minerals are likely to influence seismological observations because they have very high volume fractions, or very high anisotropies, or both of these.;In the upper mantle antigorite and talc are exceptionally anisotropic (Vp 71% Vs 68% and Vp 65%, Vs 68%, respectively) and chlorite is also very anisotropic for S-waves (Vp 35%, Vs 76%). Comparatively less anisotropic are hornblende (Vp 27%, Vs 31%), used as proxy for tremolite in subduction zones, and clinohumite (21.8%, Vs 15.9%). Brucite at 4 GPa (Vp 26.5%, Vs 30.9%) and the dense hydrogen magnesium silicate (DHMS) phase A at 9GPa (Vp 9.3%, Vs 17.6%) are the only hydrous minerals stable in the upper mantle that have had their elastic properties measured at in situ mantle pressures. Except for the phase A, all these minerals are more anisotropic than olivine for at least one parameter (Vp, Vs, Vp/Vs1, or Vp/Vs2). In the transition zone the major phases hydrous wadsleyite and ringwoodite C have moderate to weak anisotropies (Vp 16.3%, Vs 16.5%, and Vp 1.9%, Vs 4.4%, respectively). The DHMS Superhydrous B has a moderate anisotropy (Vp 6.9%, Vs 11.6%). At greater depth the DHMS phase D Lit 24 GPa (Vp 10.8%, Vs 18.0%) is the only hydrous phase that can transport hydrogen from the transition zone into the lower mantle. The phase D is more anisotropic for S than P waves like many of the hydrous phases. From these data it is clear that hydrous phases are in general very anisotropic. However, pressure can play a strong role in reducing anisotropy. It is the case for brucite and talc, in which increasing pressure from ambient to 4 GPa reduces the anisotropy by about 50% for both P and S waves. In contrast, the anisotropy of the DHMS phase A does not change significantly with pressure.;Our picture of the seismic anisotropy of hydrated minerals remains incomplete; the elastic properties of many have not been measured even at ambient conditions (e.g., 10 angstrom phase and phase E) or not measured in their true elastic symmetry (e.g., clinochlore). The majority of hydrous minerals have not been measured at high pressure. and none related to hydrated mantle have been measured at elevated temperature. We have shown in the few cases where hydrous minerals have been measured as a function of pressure, that this variable has an important effect oil the velocity distribution and in most cases reduces the degree of anisotropy, hence we Would expect seismic anisotropy to play a key role in the determination of the shallow structure of subduction zones in the upper mantle.
Subduction zone geodynamics

hal-00420893
https://hal.archives-ouvertes.fr/hal-00420893

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
To understand the deep cycle of water, upper mantle water content and distribution between nominally anhydrous minerals (NAMs) and hydrous minerals (e.g., amphibole) must be constrained. We need then to understand H behaviour during mantle melting and metasomatism. Major, minor and trace element compositions including water contents were obtained on ten xenoliths of spinel-bearing peridotites from the Ray Pic locality, in the Southern part of the Massif Central (France). The sample suite investigated here is composed of rather fertile lherzolites (89.4 ≤ Fo ≤ 90.8%; 11.3 ≤ cr# in spinel ≤ 21.1%; 0.942 ≤ [Yb]cpx ≤ 1.90 ppm; cpx: clinopyroxene), which can be best explained by batch melting, with degree of melting between 3 and 10%. These xenoliths contain up to 8% modal amphibole. Three groups are defined as a function of the amphibole modal abundance (above or below 1%) and equilibrium temperature (above or below 1000 °C). Results show no clear positive correlation between modal metasomatism (amphibole) and incompatible element enrichment in cpx. Trace element compositions in cpx show strong enrichments of the most incompatible elements (e.g., (La/Sm)PM as high as 15.7; PM: normalised to primitive mantle values), but strong negative anomalies of the high field strength elements (e.g., (Th/Nb)PM as high as ~ 680). Such trace element fractionations are usually ascribed to the so-called carbonatitic metasomatism involving the percolation of small volume melts which are enriched in volatiles. The hydrogen concentrations in cpx range from 203 to 330 ppm wt. H2O, in orthopyroxene from 66 to 160 ppm wt. H2O and in olivine from 2 to 6 ppm wt. H2O. These values are within the common concentration range of other spinel-bearing peridotites. Amphiboles contain 1.9 ± 0.5 wt.% of H2O.The effect of metasomatism on water abundances in NAMs is not straightforward. Hydrous metasomatism (i.e., leading to the crystallisation of OH-bearing amphibole) has no effect on the water content of the co-existing NAMs. This suggests thus that the occurrence of hydrous minerals, such as amphibole, does not systematically imply that the coexisting NAMs are water-rich (saturated). Further, the percolation of volatile-rich small volume melts, which is fingerprinted by the strong enrichment of the incompatible elements, has also no clear effect on the water content of the NAMs. These data are thus difficult to reconcile with the admitted highly incompatible behaviour of H in upper mantle minerals.
ISSN: 0024-4937

hal-01278062
https://hal.archives-ouvertes.fr/hal-01278062
DOI : 10.1016/j.lithos.2015.08.013

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The minerals constituting the Earth's upper mantle are nominally anhydrous silicates (NAMs). However they do contain hydrogen as a trace element, decorating point defects in their crystalline structure. Experimental petrology and mineralogy have quantified the maximum concentration under several compositional and thermodynamic conditions, but systematic studies on the hydrogen concentration in minerals from mantle-derived rocks have only recently been carried out. Here, we have compiled the distribution of hydrogen in upper mantle peridotite xenoliths, from which several conclusions can be drawn. NAMs from peridotite xenoliths contain a few ppm wt. H2O in their structure. From the current database, the hydrogen concentrations in olivine regularly increase with increasing depth. The amount of hydrogen in NAMs from peridotite xenoliths from subduction contexts is not higher than in other geological context for similar temperature and pressure conditions. The highest hydrogen concentrations is found in peridotitic olivines from cratonic mantle, and are likely due to the depth of origin. The increasing hydrogen concentration in olivine with increasing depth is likely controlled by the increase of H partitioning into olivine at the expense of orthopyroxene as imposed by a decrease in Al content in opx with depth. However, the sparse data could also indicate that the bulk hydrogen concentration slightly increases with depth > 150 km. In this case, it would suggest, locally (Udachnaya for example), a possible increase in water fugacity due to fluid saturation. Even if the most abundant mineral in mantle rocks is olivine, the bulk hydrogen concentration in peridotites is controlled by the amount of hydrogen stored in pyroxenes. However, hydrogen concentration in olivine remains crucial for consequences on physical properties such as rheology and electrical conductivity. Kinetics of hydrogen transport is reviewed and hydrous melt/fluid percolation appears necessary to homogenize the hydrogen distribution at km-scale. Sampling of natural rock specimens is currently biased (e.g., in favor of optically attractive samples) and needs improvement, which will be achieved by increasing sample diversity (all type of grain sizes, lithologies, geological settings) and size of rock samples, as well as advances in analytical techniques. Acquisition of high quality data will be achieved by studying the co-existing minerals in mantle specimens, exploring each sample by linear and mapping measurements, and using appropriate FTIR calibrations for polarized and unpolarized radiation.
ISSN: 0024-4937

hal-01306676
https://hal.archives-ouvertes.fr/hal-01306676
DOI : 10.1016/j.lithos.2015.11.012

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We report concentrations of hydrogen (H) in upper mantle minerals of peridotites (olivine and pyroxenes) transported by alnöitic lavas, which erupted on the southwestern border of the Ontong Java Plateau (Malaita, Solomon Islands, West Pacific). Unpolarized FTIR analyses show that olivine, orthopyroxene, and diopside contain 2–32 ppm, 162–362 ppm and 159–459 ppm wt H2O, respectively. In the studied lherzolites, garnets are anhydrous. The concentration of hydrogen within individual olivine and pyroxene grains is almost homogeneous, indicating no evidence of dehydration or hydration by ionic diffusion. In the lherzolite, the concentration of hydrogen in olivine tends to increase weakly with depth (based on geothermobarometry), consistent with the increase of water solubility with increasing water fugacity as a function of pressure, but concentrations remain well below water-saturation values determined experimentally. The highest concentration of H in olivine (32 ppm wt H2O) is, however, found in refractory spinel harzburgites, which equilibrated at depths of 85 km., while deeper specimens as the high-temperature spinel harzburgites, and some of the garnet lherzolites, contain less hydrogen in olivine. Olivines from pyroxene- or pargasite-rich peridotites have also lower hydrogen concentrations. We interpret the high hydrogen concentrations in olivine from the refractory spinel harzburgites as due to (1) simultaneous hydration and metasomatism of the lithospheric mantle by a water-rich silicate melt/fluid, during which hydrogen follows MREE and where spinel harzburgite have experienced ‘stealth’ metasomatism, and/or (2) to a late ‘fleeting’ hydrogen metasomatism, which would hydrate the rock after this first ‘stealth’ metasomatism event. In the second case, the composition of the ‘fleeting’ percolating fluid (small volume fraction of very evolved fluids, with high volatiles concentration and transient properties) is likely to be linked to the decrease of the plume activity and resulting in the downwelling of the lithosphere asthenosphere boundary. The difference in hydrogen concentration between harzburgites and lherzolites could be linked to variation in trace elements in olivine induced by the first ‘stealth’ metasomatism alone or associated to the late ‘fleeting’ hydrogen metasomatism, triggered by the lack of secondary crystallization of clinopyroxenes in the harzburgite. To conclude, H concentrations in upper mantle minerals may thus be correlated to metasomatic events, with the later yielding variation of the mineral assemblage and trace element composition that constitute the peridotites.
ISSN: 0024-4937

hal-01143385
https://hal.archives-ouvertes.fr/hal-01143385
DOI : 10.1016/j.lithos.2014.11.005

Éditeur(s) : HAL CCSD Elsevier
Résumé : Nominally anhydrous minerals (NAMs) of Earth's mantle can contain hydrogen as atomic impurity in their crystal structures. This hydrogen substantially modifies many physical properties of Earth's mantle rocks. Also, the Earth's deep interior is made of rocks where minerals are separated by nanometer-scale interfaces call grain boundaries and interphase boundaries. These grain boundaries should carefully be considered as a potential hydrogen reservoir as well. I report here an experimental investigation of hydrogen diffusion through grain boundaries in olivine polycrystalline aggregates. Hot-press and diffusion experiments were performed using a gas-medium high-pressure vessel at a confining pressure of 300 MPa, over a temperature range of 1000-1200 degrees C. The diffusion assembly consisted of a dense polycrystalline cylinder of natural olivine from San Carlos (Arizona) mixed with olivine singles crystals of millimeter size. This mixture was couple with a talc cylinder. Ni capsule were used to buffer the oxygen fugacity at Ni-NiO level. Experiment durations varied from 3 min to 4 h. The presence of hydrogen in the sample was quantified using Fourier transform infrared spectroscopy. The calculation of the diffusion coefficients was based on the estimation of the length of polycrystalline solid affected by the diffusion of hydrogen. The absence or presence of hydrogen was recorded by the large olivines behaving here as "hydrogen sensor", which are implanted in the aggregate. The results indicate that effective hydrogen diffusivity which includes grain boundaries effect in olivine aggregate is barely one order of magnitude faster than hydrogen diffusion in an olivine single crystal with a diffusivity similar to 8.5x 10(-10) m(2) s(-1) 1000 degrees C and only twice faster similar to 2.1 x10(-9) m(2) s(-1) 1200 degrees C. Calculations of the diffusion data in relation to the Arrhenius Law, yield an activation energy of similar to 70 +/- 10 kJ mol(-l) . From these effective diffusivities and combined with published diffusion data for olivine single crystals, hydrogen diffusion in grain boundaries is extracted and yield diffusivities almost three order of magnitude faster (similar to 5 x 10(-6) m(2) s(-1) at 1200 degrees C) than in an olivine single crystal at the equivalent high temperature. On geological scales and for coarse-grain rocks, hydrogen diffusivity in grain boundaries is not fast enough to compete with lattice diffusion. The relative large grain size of mantle rocks will ensure a very limited hydrogen transport by effective diffusion, and a good conservation of water-rich zones in the Earth's mantle.
ISSN: 0012-821X

hal-00512821
https://hal.archives-ouvertes.fr/hal-00512821
DOI : 10.1016/j.epsl.2010.04.019

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

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

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The Tso Morari serpentinites in the Ladakh area, northwest Himalaya, originated from the forearc mantle overlying the northward subducting Neo-Tethys lithosphere and the margin of the Indian continent. The serpentinites are characterized by high concentration of fluid-mobile elements (FME: As, Sb, B, Li, and U) compared to ophiolitic or abyssal serpentinites. The Pb isotopic compositions of serpentinites show influence of the subducted Indian continental lithosphere. Trace element concentrations of antigorite determined in situ with Laser Ablation High Resolution Inductively Coupled Mass Spectrometer (LA-HR-ICP-MS) show high contents of FME including Pb, in contrast to the spatially associated iron oxides. Rare earth elements (REE) and compatible elements, such as Sc and Co, remained immobile during the hydration, allowing the identification of the primary minerals (olivine or orthopyroxene) from which serpentine formed. Serpentinized olivine displays higher Sb and As concentrations (up to 1000 x PM) than serpentinized orthopyroxenes that are enriched in Pb, Cs and Li (2 to up to 10 x PM).;We propose that the observed FME distribution in two types of serpentine reflect the differential incorporation of FME during the downward movement of the serpentinite along the subduction plane. At temperature lower than 400 degrees C, at shallow depths, olivine is preferentially serpentinized and incorporates elements that are fluid soluble at low temperatures, such as Sb and As. Above 400 degrees C, orthopyroxene is hydrated and incorporates Pb, Cs, Li and possibly Ba. Boron and U are incorporated in both types of serpentine suggesting that they are released from slabs at temperatures around 300-400 degrees C. The serpentine acts as a sink for water, but also for FME and transports them to deeper and hotter levels in the mantle, down to the isotherm 600-650 degrees C where dehydration occurs.
ISSN: 0009-2541

hal-00475565
https://hal.archives-ouvertes.fr/hal-00475565
DOI : 10.1016/j.chemgeo.2009.10.002

Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : International audience
At Cima di Gagnone, garnet peridotite and chlorite harzburgite lenses within pelitic schists and gneisses correspond to eclogite-facies breakdown products of hydrated peridotites and are suitable for studying dehydration of serpentinized mantle. Thermobarometry and pseudosection modelling yield peak temperatures of 750-850°C and pressures <3 GPa. The minimum temperature recorded by the garnet peridotite corresponds to the maximum conditions experienced by the chlorite harzburgite, suggesting that these rocks recrystallized cofacially at ∼800°C. Alternatively, they might have decoupled during subduction, as achieved in tectonically active plate interface boundaries. The major and rare earth element (REE) variability of the peridotites was mostly acquired during pre-subduction mantle evolution as a result of partial melting and reactive melt flow. The ultramafic suite is also characterized by fluid-mobile element enrichments (B, Pb, As, Sb, Cs, Li, U, Be), which confirm derivation from variably serpentinized protoliths. Similarity in the U, Pb, B, Li and Sr contents of the Gagnone peridotites to present-day oceanic serpentinites suggests that these elements were partly taken up during initial serpentinization by seawater-derived fluids. Positive Be, As and Sb anomalies suggest involvement of fluids equilibrated with crustal (metasedimentary) reservoirs during subsequent subduction metamorphism and peridotite entrainment in (meta)sediments. Fluid-mobile element enrichment characterizes all peak eclogitic minerals, implying that multiple hydration events and element influx pre-dated the eclogite-facies dehydration. Peak anhydrous minerals retain B, Li, As and Sb concentrations exceeding primitive mantle values and may introduce geochemical anomalies into the Earth's mantle. The relatively low contents of large ion lithophile elements and light REE in the Gagnone peridotites with respect to much higher enrichments shown by metasomatized garnet peridotite pods hosted in migmatites (Ulten Zone, Eastern Alps) suggest that the crustal rocks at Gagnone did not experience partial melting. The Gagnone garnet peridotite, despite showing evidence for chlorite dehydration, retains significant amounts of fluid-mobile elements documenting that no partial melting occurred upon chlorite breakdown. We propose that the Gagnone ultramafic rocks represent a prime example of multi-stage peridotite hydration and subsequent dehydration in a plate interface setting.
ISSN: 0022-3530

hal-01054319
https://hal.archives-ouvertes.fr/hal-01054319
DOI : 10.1093/petrology/egt068

Éditeur(s) : HAL CCSD AGU and the Geochemical Society
Résumé : Mid-ocean ridges magmatism is, by and large, considered to be mostly dry. Nevertheless, numerous works in the last decade have shown that a hydrous component is likely to be involved in ocean ridges magmas genesis and/or evolution. The petrology and geochemistry of peculiar coarse grained gabbros sampled in the upper part of the gabbroic sequence from the northern Oman ophiolite (Wadi Rajmi) provide information on the origin and fate of hydrous melts in fast-spreading oceanic settings. Uncommon crystallization sequences for oceanic settings (clinopyroxene crystallizing before plagioclase), extreme mineral compositions (plagioclase An% up to 99, and clinopyroxene Mg # up to 96), and the presence of magmatic amphibole, imply the presence of a high water activity during crystallization. Various petrological and geochemical constraints point to hydration, resulting from the recycling of hydrothermal fluids. This recycling event may have occurred at the top of the axial magma chamber where assimilation of anatectic hydrous melts is recurrent along mid-ocean ridges or close to segments ends where fresh magma intrudes previously hydrothermally altered crust. In ophiolitic settings, hydration and remelting of hydrothermally altered rocks producing hydrous melts may also occur during the obduction process. Although dry magmatism dominates oceanic magmatism, the dynamic behavior of fast-spreading ocean ridge magma chambers has the potential to produce the observed hydrous melts (either in ophiolites or at spreading centers), which are thus part of the general mid-ocean ridges lineage.
ISSN: 1525-2027

hal-00939400
https://hal.archives-ouvertes.fr/hal-00939400
DOI : 10.1002/ggge.20137

Éditeur(s) : HAL CCSD Nature Publishing Group
Résumé : International audience
The variation of elastic- wave velocities as a function of the direction of propagation through the Earth's interior is a widely documented phenomenon called seismic anisotropy. The geometry and amount of seismic anisotropy is generally estimated by measuring shearwave splitting, which consists of determining the polarization direction of the fast shear- wave component and the time delay between the fast and slow, orthogonally polarized, waves. In subduction zones, the teleseismic fast shear- wave component is oriented generally parallel to the strike of the trench(1), although a few exceptions have been reported (Cascadia(2) and restricted areas of South America(3,4)). The interpretation of shear- wave splitting above subduction zones has been controversial and none of the inferred models seems to be sufficiently complete to explain the entire range of anisotropic patterns registered worldwide(1). Here we show that the amount and the geometry of seismic anisotropies measured in the forearc regions of subduction zones strongly depend on the preferred orientation of hydrated faults in the subducting oceanic plate. The anisotropy originates from the crystallographic preferred orientation of highly anisotropic hydrous minerals (serpentine and talc) formed along steeply dipping faults and from the larger- scale vertical layering consisting of dry and hydrated crust - mantle sections whose spacing is several times smaller than teleseismic wavelengths. Fault orientations and estimated delay times are consistent with the observed shear- wave splitting patterns in most subduction zones.
ISSN: 0028-0836

hal-00412016
https://hal.archives-ouvertes.fr/hal-00412016
DOI : 10.1038/nature07376

Éditeur(s) : HAL CCSD Elsevier
Résumé : The dense hydrous magnesium silicate called the D phase is the most likely candidate to recycle hydrogen into the lower mantle in subduction zones. As seismology represents the preferred method to detect this mineral in subduction zones, the single crystal elastic tensor has been calculated using first principle methods. A triple cell (View the MathML source) was used to account for an ordered ideal composition of the D phase to lower mantle pressures. The elastic tensor of the mineral at ambient conditions is predicted to be C11 = 387.7, C33 = 287.7, C44 = 100.4, C12 = 108.0, C13 = 51.1, C14 = − 14.6 in GPa with bulk modulus at zero pressure Ko = 163 GPa and a statistical error of about 4.0 GPa for all constants. The pressure derivatives of the elastic constants have been determined to pressure of 80 GPa. Our tensor correctly predicts the published experimental measurements of linear compressibility along the a- and c-axes, the logarithmic pressure derivative of the c/a axial ratio and bulk modulus at zero pressure. It contradicts the experimentally measured elastic tensor reported by (Liu, L.-G., Okamoto, K., Yang, Y.-J., Chen, C.-C., Lin, C.-C., 2004. Elasticity of single-crystal phase D (a dense hydrous magnesium silicate) by Brillouin spectroscopy. Solid State Commun. 132, 517–520), which fails to reproduce the experimental compressibility data. Using the elastic constants and density predicted to 85 GPa, the seismic anisotropy of P- and S-waves has been calculated as a function of pressure. The single crystal has high P-wave velocities and shear wave splitting in the basal plane below 20 GPa. At high pressures, the maximum P-wave velocities have threefold symmetry normal to a-axes in the basal plane, whereas the maximum shear wave splitting is parallel to a-axes with twofold symmetry. The D phase has high Vp and Vs anisotropy at ambient pressure, 17.6% for Vp and 19.9% for Vs. The Vp anisotropy decreases with increasing pressure to about 30 GPa, while it remains constant at 8% from 30 to 85 GPa. The Vs anisotropy decreases to 17% at 20 GPa and then increases to 22% at 85 GPa. The isotropic velocity ratios of S to P (Rs/p), bulk sound to S (Rphi/s) and density to S (Rρ/s) are calculated as a function of pressure. The Rs/p shows very little variation with pressure with low value of 0.6, whereas both Rphi/s and Rρ/s increase with pressure to peak values of 2.8 and 2.0 respectively at about 60 GPa. The presence of the D phase in subducted horizontal ‘stagnant' plates in the circum Pacific could contribute to a number of seismic observations, such as the observed velocity heterogeneity at depths between 500 and 1000 km and the fast S-waves travelling horizontally with horizontal polarization in this depth range. Further the lower density of the D phase compared with anhydrous minerals could influence buoyancy of the hydrated ‘stagnant' slabs. The transformation of the D phase to perovskite plus ferripericlase during thermal annealing may be responsible for horizontal slab seismogenesis.
ISSN: 0012-821X

hal-00406379
https://hal.archives-ouvertes.fr/hal-00406379
DOI : 10.1016/j.epsl.2007.04.053

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : International audience
The chemical and isotopic compositions of clay minerals such as illite and chlorite are commonly used to quantify diagenetic and low-grade metamorphic conditions, an approach that is also used in the present study of the Monte Perdido thrust fault from the South Pyrenean fold-and-thrust belt. The Monte Perdido thrust fault is a shallow thrust juxtaposing upper Cretaceous-Paleocene platform carbonates and Lower Eocene marls and turbidites from the Jaca basin. The core zone of the fault, about 6 m thick, consists of intensely deformed clay-bearing rocks bounded by major shear surfaces. Illite and chlorite are the main hydrous minerals in the fault zone. Illite is oriented along cleavage planes while chlorite formed along shear veins (<50 μm in thickness). Authigenic chlorite provides essential information about the origin of fluids and their temperature. δ18O and δD values of newly formed chlorite support equilibration with sedimentary interstitial water, directly derived from the local hanging wall and footwall during deformation. Given the absence of large-scale fluid flow, the mineralization observed in the thrust faults records the P-T conditions of thrust activity. Temperatures of chlorite formation of about 240°C are obtained via two independent methods: chlorite compositional thermometers and oxygen isotope fractionation between cogenetic chlorite and quartz. Burial depth conditions of 7 km are determined for the Monte Perdido thrust reactivation, coupling calculated temperature and fluid inclusion isochores. The present study demonstrates that both isotopic and thermodynamic methods applied to clay minerals formed in thrust fault are useful to help constrain diagenetic and low-grade metamorphic conditions.
ISSN: 0010-7999

hal-00757736
https://hal.archives-ouvertes.fr/hal-00757736
DOI : 10.1007/s00410-011-0718-0

Éditeur(s) : HAL CCSD Springer Verlag (Germany) Springer Verlag
Résumé : International audience
The hydrogen content of nominally anhydrous minerals is of great interest, because it can influence many physical and mechanical properties of mantle rocks. Moreover, the hydrogen diffusion profiles can be used to constrain timescales related to magma eruptions. Here, we report models of ionic diffusion for trace elements in anisotropic crystals and apply them to hydrogen diffusing out of mantle-derived olivine. We first compare and discuss the characteristics of 1D and 3D models and show that only 3D anisotropic diffusion models can lead to diffusion profiles exhibiting non-equilibrium plateau at the center of the solid along the slowest axis, as measured in natural samples. In a second part, we discuss the differences between hydration and dehydration of olivine for diffusion that is linked to two different atomic sites involved in hydrogen mobility. Finally, we apply our 3D anisotropic model to previous results on mantle-derived olivine from Pali-aike to better characterize diffusion coefficients and their anisotropy that could be relevant for dehydration of olivine. Our results show that dehydration has to be strongly anisotropic, with a fast [100] axis and a significantly slower [001] axis.
ISSN: 0342-1791

hal-01115253
https://hal.archives-ouvertes.fr/hal-01115253
DOI : 10.1007/s00269-014-0685-x

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): Policy B - Oxford Open Option A Oxford University Press (OUP)
Résumé : International audience
Peridotites exhumed in the footwall of axial detachment faults at slow-spreading ridges are highly serpentinized. Most mid-ocean ridge detachment settings are magmatically active and hydrous fluid circulation in and near the fault has been shown to be influenced by the presence of melt or magmatic lithologies. Our working area along the Southwest Indian Ridge (62–65°E) is nearly amagmatic and represents an end-member to study the hydrous alteration of exhumed peridotites without these magmatic influences. We use an integrated petrological approach combining microstructural, mineralogical and chemical observations to unravel the sequence of serpentinization in 272 dredged samples of variably serpentinized peridotites and to document the circulation of serpentinizing fluids in and near the exhumation faults. We find that serpentine recrystallization and veins overprint the initial serpentinite mesh texture in ∼25% of the samples. Oxygen isotope data suggest that this sequence developed at relatively high temperatures (271–336°C) and under increasing fluid–rock ratios, from near stoichiometry for mesh texture formation to >10 during recrystallization. Increasing fluid supersaturation relative to serpentine favors the replacement of mesh texture lizardite by chrysotile and polygonal or polyhedral serpentine. We attribute local recrystallization into antigorite to moderate Si-metasomatism, possibly following pyroxene serpentinization. We do not observe the more pronounced Si-metasomatism leading to talc replacing serpentine that is reported for the more magmatically active Mid-Atlantic Ridge detachment settings and is attributed to prior leaching of magmatic rocks. Scales of preferential fluid pathways in our samples evolved from pervasive and close-spaced (<500 µm) microfractures during the formation of the initial serpentine mesh texture, to centimeter-thick planar domains of enhanced fluid flux, spaced at ∼10 cm intervals and probably grouped in corridors that may be up to ∼100 m across. Serpentine minerals are enriched in some fluid-mobile elements (Cl, B, U) relative to the peridotite protolith, and several elements (Al, Fe, Si, Cu, As, Sb, REE) are redistributed at the millimeter to decimeter scale. Serpentinizing fluids were seawater-derived, probably mildly alkaline (small to no europium anomalies), reducing and H2-enriched (formation of magnetite). These fluids may have been similar to, though warmer than, those venting at the ultramafic-hosted Lost City hydrothermal fluid (30°N, Mid-Atlantic Ridge).
ISSN: 0022-3530

hal-01174047
https://hal.archives-ouvertes.fr/hal-01174047
DOI : 10.1093/petrology/egv014

Éditeur(s) : HAL CCSD Elsevier
Résumé : The uppermost mantle in back arc regions is the site of complex interactions between partial melting, melt percolation, and fluid migration. To constrain these interactions and evaluate their consequences on geochemical cycles, we carried out an in situ trace element and water study of a suite of spinel peridotite xenoliths from two regions of the Japan back arc system, Ichinomegata (NE Japan) and Oki-Dogo (SW Japan), using LA-ICPMS and FTIR spectrometry, respectively. This study provides the first full dataset of trace element and hydrogen compositions in peridotites including analyses of all their main constitutive silicate minerals: olivine, orthopyroxene and clinopyroxene. The Ichinomegata peridotites sample a LREE-depleted refractory mantle (Mg# olivine = 0.90; Cr# spinel = 0.07–0.23; Yb clinopyroxene = 7.8–13.3 × C1-chondrite, and La/Yb clinopyroxene = 0.003–0.086 × C1-chondrite), characterized by Th-U positive anomalies and constant values of Nb/Ta. The composition of the studied Ichinomegata samples is consistent with that of an oceanic mantle lithosphere affected by cryptic metasomatic interactions with hydrous/aqueous fluids (crypto-hydrous metasomatism). In contrast, the Oki-Dogo peridotites have low Mg# olivine (0.86–0.93) and a broad range of compositions with clinopyroxene showing “spoon-shaped” to flat, and LREE-enriched patterns. They are also characterized by their homogeneous compositions in the most incompatible LILE (e.g., Rb clinopyroxene = 0.01–0.05 × primitive mantle) and HFSE (e.g., Nb clinopyroxene = 0.01–2.16 × primitive mantle). This characteristic is interpreted as resulting from various degrees of melting and extensive melt-rock interactions. FTIR spectroscopy shows that olivine in both Ichinomegata and Oki-Dogo samples has low water contents ranging from 2 to 7 ppm wt. H2O. In contrast, the water contents of pyroxenes from Ichinomegata peridotites (113–271 ppm wt. H2O for orthopyroxene, and 292–347 ppm wt. H2O for clinopyroxene) are significantly higher than in Oki-Dogo peridotites (9–35 ppm wt. H2O for orthopyroxene, and 15–98 ppm wt. H2O for clinopyroxene). This indicates a relationship between melt-rock interaction and water concentrations in pyroxenes. Our study suggests that the water content of the Japan mantle wedge is controlled by the late melt/fluid/rock interactions evidenced by trace element geochemistry: a mechanism triggered by magma-rock interactions may have acted as an efficient dehydrating process in the Oki-Dogo region while the Ichinomegata mantle water content is controlled by slab-derived crypto-hydrous metasomatism.
ISSN: 0016-7037

hal-01553105
https://hal.archives-ouvertes.fr/hal-01553105
DOI : 10.1016/j.gca.2017.03.042

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) : Gauthier-Villars
Résumé : The analysis of humic compounds by elemental analysis, PY-GC-MS and HPLC techniques permitted determination of the origin of organic inputs, essentially terrestrial, and the effects of environmental conditions in the deposits along a north-south transect through the Rhone delta, from the river mouth to the open sea. In the prodelta the sedimentation of fine particles enriches the sediments in organic matter. The humic compound contents were relatively low in sediments, perhaps due to a rapid burying of organic matter which leads to anoxic conditions. In sediments fulvic acids are more abundant than humic acids. Elemental analysis indicated that fulvic acids were enriched in hydrogen and nitrogen as compared to humic acids. Furthermore, H/C and N/C ratios increased in the fulvic and humic acids towards the open sea, related to a more marine character. Pyrolysis analysis showed some differences between the chemical composition of fulvic acids which correspond to low molecular weights enriched in carbohydrates, and that of humic acids, high molecular weight compounds which are enriched in phenols and aromatic hydrocarbons. The pyrolysis-derived phenols were abundant near the river mouth, decreasing towards the open sea as nitrogen-containing-compounds increased. Near the river mouth, the abundance of phenolic aldehydes demonstrated by HPLC emphasized the existence of fresh organic matter. On the other hand, off the mouth, an increase in phenolic acids could indicate a more degraded organic material. The fractionation of humic acids in various classes of molecular weight species using ultrafiltration (Amicon membranes) and their analysis showed that, close to the river mouth, the large proportion of the high molecular weight humic compounds observed was enriched in phenols and carbohydrates, probably inherited from the terrestrial ligno-cellulosic complex. This process seemed to be superimposed on the increase of molecular weights which is usually observed as the environment becomes purely marine. These humic compounds would derived either from organic matter from terrestrial soils swept along by the river flow, after deposition on its bed or, more probably, from high molecular weight compounds which, associated with the mineral phase, flocculated when reaching the fluvio-marine front. Generally, the low molecular weight fractions were enriched in hydrogen and nitrogen. Near the river mouth, nitrogen-containing compounds were concentrated in the low molecular weight classes which correspond to organic molecules regarded as humic precursors. Off the mouth, they were incorporated into the high molecular weight complexes, certainly of marine origin.
Oceanologica Acta (0399-1784) (Gauthier-Villars), 1992 , Vol. 15 , N. 1 , P. 61-74

Droits : info:eu-repo/semantics/openAccess
http://archimer.ifremer.fr/doc/00101/21187/18804.pdf
http://archimer.ifremer.fr/doc/00101/21187/