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 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 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 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
A subject of continuing debate is how the Earth's lithospheric portion of the upper mantle has remained the thickest (> 200 km) and oldest (> 3 Gy) beneath cratons and is yet surrounded by a vigorously convecting asthenosphere. It is generally admitted that water is a key parameter in the strength and longevity of cratonic roots, because olivine, the main phase of the lithospheric mantle, becomes stronger if its water content decreases. Expanding upon the work presented in Novella et al. (2015) and Taylor et al. (2016), we report new water contents for additional olivine inclusions in diamonds together with the trace-element composition for all olivine inclusions, as well as for mantle xenoliths from various kimberlite pipes located on the Siberian craton. The olivine diamond inclusions from this study have systematically low-water contents (< 50 ppmw H2O), moderate to high forsterite (e.g., Fo91–94) contents and low Ni, Co, and Zn ppm contents (e.g., < 2848, < 108, and < 47 ppm, respectively). In contrast, olivines from Siberian craton mantle xenoliths have a wide range of water contents (6–323 ppmw H2O) and extend to lower-Fo (91–92), Ni, Co, and Zn-rich compositions, compared to the diamond inclusions. Depleted incompatible trace-element concentrations in olivine (0.1–0.001 × Primitive Mantle) advance our hypothesis for the protogenetic origins for the majority of Siberian diamond inclusions. These observations are consistent with the peridotite xenoliths as representing a part of the cratonic lithosphere that has experienced melt re-fertilization, which has also transported water. The olivine diamond inclusions, on the other hand, preserve “micro-samples” of an initial, dry cratonic lithosphere, mostly resulting from melting events. These inclusions are likely sourced from the initial cratonic mantle lithosphere, which thereby, resisted delamination over time, due to its buoyancy and strength, imparted from melt and water depletion, respectively. And thus, our data provides a major argument that the kimberlite-hosted mantle xenoliths may be more metasomatized than common rocks at the base of the Siberian and other cratonic roots away from kimberlite fields.
ISSN: 0024-4937

hal-01467731
https://hal.archives-ouvertes.fr/hal-01467731
DOI : 10.1016/j.lithos.2016.07.023

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We carried out detailed petrographic, major and trace element geochemical, microstructural and FTIR analyses on eight characteristic ultramafic xenoliths from Nyos and Barombi Mbo Lakes in the continental sector of the Cameroon Volcanic Line (CVL). The studied xenoliths are spinel lherzolites showing lithologies similar to the other xenoliths reported previously along the CVL. They have protogranular and porphyroclastic textures. One of the Barombi xenolith contains amphibole, which had not been previously reported in this locality. Amphibole is common in the Nyos xenoliths suite. Peridotite xenoliths from both localities show some chemical heterogeneity, but Barombi xenoliths generally are less depleted in basaltic elements with respect to Nyos xenoliths. Trace element compositions of Nyos spinel lherzolites show a moderately depleted initial (premetasomatic) composition and variable enrichment in REE. Evidence for both modal and cryptic metasomatism is present in Nyos xenoliths. Rare earth element patterns of clinopyroxene suggest that interaction between mafic melts and the upper mantle occurred beneath the Nyos locality. Barombi Mbo xenoliths, on the other hand, record a small degree of partial melting. The Barombi Mbo xenoliths have weak, dominantly orthorhombic olivine crystal preferred orientations, whereas Nyos ones have strong axial-[010] patterns, which may have formed in response to transpression. Nominally anhydrous mantle minerals (NAMs) of the Barombi Mbo xenoliths show generally higher bulk concentrations of ‘water’ (70–127 ppm) than Nyos xenoliths (32–81 ppm). The Barombi Mbo xenoliths could originate from a juvenile segment of the lithospheric mantle, which had been originally part of the asthenosphere. It became a part of the lithosphere in response to thermal relaxation following the extension, forming a weakly deformed lower lithospheric mantle region along the CVL. The Nyos xenoliths, however, represent a shallow lithospheric mantle bearing imprints of several depletion and enrichment events probably prior or following the extension (at ∼30 Ma).
ISSN: 0899-5362

hal-01236039
https://hal.archives-ouvertes.fr/hal-01236039
DOI : 10.1016/j.jafrearsci.2015.07.006

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