Éditeur(s) : HAL CCSD Taylor & Francis: SSH Journals
Résumé : International audience
We investigated the oxygen-conserving potential of the human diving response by comparing trained breath-hold divers (BHDs) to non-divers (NDs) during simulated dynamic breath-holding (BH). Changes in haemodynamics [heart rate (HR), stroke volume (SV), cardiac output (CO)] and peripheral muscle oxygenation [oxyhaemoglobin ([HbO2]), deoxyhaemoglobin ([HHb]), total haemoglobin ([tHb]), tissue saturation index (TSI)] and peripheral oxygen saturation (SpO2) were continuously recorded during simulated dynamic BH. BHDs showed a breaking point in HR kinetics at mid-BH immediately preceding a more pronounced drop in HR (−0.86 bpm.%−1) while HR kinetics in NDs steadily decreased throughout BH (−0.47 bpm.%−1). By contrast, SV remained unchanged during BH in both groups (all P > 0.05). Near-infrared spectroscopy (NIRS) results (mean ± SD) expressed as percentage changes from the initial values showed a lower [HHb] increase for BHDs than for NDs at the cessation of BH (+24.0 ± 10.1 vs. +39.2 ± 9.6%, respectively; P < 0.05). As a result, BHDs showed a [tHb] drop that NDs did not at the end of BH (−7.3 ± 3.2 vs. −3.0 ± 4.7%, respectively; P < 0.05). The most striking finding of the present study was that BHDs presented an increase in oxygen-conserving efficiency due to substantial shifts in both cardiac and peripheral haemodynamics during simulated BH. In addition, the kinetic-based approach we used provides further credence to the concept of an “oxygen-conserving breaking point” in the human diving response.
ISSN: 0264-0414

hal-01325466
https://hal-univ-perp.archives-ouvertes.fr/hal-01325466
DOI : 10.1080/02640414.2016.1183809

Éditeur(s) : HAL CCSD IOS Press
Résumé : International audience
The hematocrit-to-viscosity ratio (HVR) has been widely used has an estimate of red blood cell (RBC) oxygen transport effectiveness into the microvasculature or as an oxygen delivery index. However, no study investigated the possibility of HVR to truly reflect RBC oxygen transport effectiveness or to be an oxygen delivery index. We measured blood viscosity at high shear rate (225 s-1), hematocrit, HVR, as well as the microvascular oxyhemoglobin saturation (TOI; tissue oxygen index) by spatial resolved near-infrared spectroscopy (NIRS) at cerebral and muscle levels in three population known to have various degrees of hemorheological abnormalities: healthy subjects (AA), patients with sickle cell SC disease (SC) characterized by moderate anemia and patients with sickle cell anemia (SS) marked by severe anemia. At both the cerebral and muscle level, HVR was positively correlated with TOI (r = 0.28; p = 0.03 and r = 0.38; p = 0.003, at the cerebral and muscle level, respectively). These findings suggest that HVR probably play a key role in blood flow and hemodynamic regulation in the microvasculature, hence modulating the amount of oxygen available for tissues. Nevertheless, the strengths of the associations are weak (R2 < 0.50), suggesting that other determinants modulate microvascular blood flow and oxygenation, such as vascular geometry and vasomotor reserve.
ISSN: 1386-0291

inserm-01081701
http://www.hal.inserm.fr/inserm-01081701
http://www.hal.inserm.fr/inserm-01081701/document
http://www.hal.inserm.fr/inserm-01081701/file/2013%2C%20Waltz%20-%20Is%20there%20a%20relationship%20between%20the%20hematocrit-to-viscosity%20ratio%20and%20microvascular%20oxygenation%20in%20brain%20and%20muscle.pdf
PUBMED : 23719422

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : International audience
Polarized emittance measurements were acquired for synthetic forsterite, the pure magnesium end member of the olivines group, on the whole infrared spectral range and up to the melting point by using CO2 laser heating. The experimental data, fitted with a semi-quantum dielectric function model, allowed the retrieval of the temperature dependence of the absorption coefficient of forsterite both in the opaque and semi-transparent regions. The analysis of the phonon parameters indicates that the lattice dynamics evolve drastically with increasing temperature. The normal modes involving motions of the magnesium cations located in site 1 are the more impacted, and some of them vanish around 1,200 K. The results confirm that the enhancement of the lattice anharmonicity and the increasing mobility of the magnesium cations are closely linked and are at the origin of the anomalies observed in the evolution of the thermophysical properties. This complete set of spectroscopic data may be a step toward a more precise evaluation of the impact of thermal radiation heat transfer inside systems involving forsterite and quantification of their heat budget.
ISSN: 0342-1791

hal-00817079
https://hal.archives-ouvertes.fr/hal-00817079
DOI : 10.1007/s00269-013-0570-z

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

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

Éditeur(s) : HAL CCSD 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
Low Density Polyethylene (LDPE) films were treated by direct fluorination at different conditions, i.e. static and dynamic ones. Modification of the treated films chemical composition was studied by spectroscopic methods (solid state NMR, XPS and infrared spectroscopy). Surface morphology was investigated by SEM and AFM. Also surface energy measurements and electron paramagnetic resonance (EPR) were carried out. Direct fluorination resulted in printability, barrier properties towards O2 and tribological properties enhancement. On the contrary, the barrier properties towards water, initially good, were not improved but maintained.
ISSN: 0257-8972

hal-01324133
https://hal.archives-ouvertes.fr/hal-01324133
DOI : 10.1016/j.surfcoat.2016.03.021

Éditeur(s) : HAL CCSD Springer/Terra Scientific Publishing Company
Résumé : International audience
Titanian clinohumite is an accessory phase found in peridotites, and it can be a key repository of volatile and other trace elements in sub-arc mantle. To characterize spectroscopic variations due to volatile elements in the phase, we have investigated the infrared spectroscopic characteristics of a suite of naturally occurring Ti clinohumite minerals with varying F and Ti concentrations. Samples were ultramafic rocks from Cerro del Almirez, Spain and Cima di Gagnone, Switzerland. The infrared spectra corresponding to OH vibrations showed systematic variation in regard to the abundance of F in Ti clinohumite. In particular, the intensity ratios of infrared absorption spectra at 3,565 and 3,390 cm-1 correlated linearly with the abundance of F independently of the crystal orientation. Raman spectra did not corroborate the Fourier transform infrared (FTIR) results. This intensity ratio provides an alternative analytical criterion for the characterization of Ti clinohumite.
ISSN: 1343-8832

hal-01133685
https://hal.archives-ouvertes.fr/hal-01133685
DOI : 10.1186/1880-5981-66-60

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The kinetics of hydrogenation of dry iron-bearing olivine single crystals was determined by performing hydration experiments under hydrothermal conditions at high pressure. The experiments were performed in a multi-anvil press at 3 GPa, for a temperature range between 900 and 1200 °C and for various durations. The oxygen fugacity was buffered along Ni-NiO joint. Polarized Fourier transform infrared spectroscopy and recent empirical calibration were used to quantify the hydroxyl distributions in the samples along crystallographic axes after the experiments. The chemical diffusion coefficients are similar (barely slower) than in olivine hydrated at lower pressure (0.2 and 0.3 GPa) for the same diffusion mechanism. Under the given experimental conditions, the anisotropy of diffusion is the same as for proton-vacancy mechanism, with diffusion along the [0 0 1] axis faster than along the [1 0 0]. However, the anisotropy at 3 GPa is weaker compared to measurements at lower pressures and the analysis of concentration profiles using 3D models shows that an isotropic solution could also be relevant. Fits of the diffusion data to an Arrhenius law yield activation energies for the slightly faster [0 0 1] axis of the crystallographic axes around 198 ± 5 kJ mol−1, a value only slightly lower than the results from previous experimental studies for natural iron-bearing olivine hydrogenated at lower confining pressure. At 3 GPa, hydrogenation can be well approximated by a single mechanism controlled by coupled diffusion of protons and octahedral vacancies (di- and tri-valent ions). The diffusion rates are fast enough to alter hydrogen concentration within olivine in xenoliths ascending from the mantle or experiencing hydrogen-rich metasomatism events, but too slow to permit complete homogenization of hydrogen in olivine-rich rocks at kilometer scale in less than one My.
ISSN: 0031-9201

hal-01412663
https://hal.archives-ouvertes.fr/hal-01412663
DOI : 10.1016/j.pepi.2016.08.005

Éditeur(s) : HAL CCSD IOS Press
Résumé : International audience
The hematocrit-to-viscosity ratio (HVR) has been widely used has an estimate of red blood cell (RBC) oxygen transport effectiveness into the microvasculature or as an oxygen delivery index. However, no study investigated the possibility of HVR to truly reflect RBC oxygen transport effectiveness or to be an oxygen delivery index. We measured blood viscosity at high shear rate (225 s −1), hematocrit, HVR, as well as the microvascular oxyhemoglobin saturation (TOI; tissue oxygen index) by spatial resolved near-infrared spectroscopy (NIRS) at cerebral and muscle levels in three population known to have various degrees of hemorheological abnormalities: healthy subjects (AA), patients with sickle cell SC disease (SC) characterized by moderate anemia and patients with sickle cell anemia (SS) marked by severe anemia. At both the cerebral and muscle level, HVR was positively correlated with TOI (r = 0.28; p = 0.03 and r = 0.38; p = 0.003, at the cerebral and muscle level, respectively). These findings suggest that HVR probably play a key role in blood flow and hemodynamic regulation in the microvasculature, hence modulating the amount of oxygen available for tissues. Nevertheless, the strengths of the associations are weak (R 2 < 0.50), suggesting that other determinants modulate microvascular blood flow and oxygenation, such as vascular geometry and vasomotor reserve.
ISSN: 1386-0291

hal-01163460
https://hal.univ-antilles.fr/hal-01163460
DOI : 10.3233/CH-131742

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The present study investigated cerebral and muscle hemoglobin oxygen saturation (tissue oxygen index, TOI) in children with sickle cell anemia (SS), sickle cell hemoglobin C disease (SC) and healthy children (AA). TOI was measured by near-infrared spectroscopy (NIRS) and spectral analysis of the TOI variability was used to assess flowmotion and vasomotion. Arterial oxyhemoglobin saturation (SpO2), hemorheological and hematological parameters were also measured in SS and SC children. Both TOI were lower in SS compared to both AA and SC children, with SC exhibiting lower values than AA children. Cerebral vasomotion expressed in absolute values was enhanced in SS compared to AA and SC children. Muscle vasomotion did not differ between the three groups. Hematocrit, SpO2 and red blood cell deformability were positively associated with cerebral TOI in SS children. We demonstrated that 1) cerebral and muscle TOI were markedly decreased in SS children while the decrease of TOI was milder in SC children, 2) cerebral TOI level was associated with several biological markers in SS children only and 3) cerebral vasomotion was enhanced in SS, possibly to counterbalance the effects of chronic cerebral hypoxia.
ISSN: 1079-9796

hal-01668321
https://hal.univ-antilles.fr/hal-01668321
DOI : 10.1016/j.bcmd.2017.03.015

Éditeur(s) : HAL CCSD Elsevier
Résumé :  
Microbial-based indicators, such as C and N contents or microbial functions involved in C and N cycles, are currently used to describe the status of soils in disturbed areas. Microbial functions are more accurate indicators but their measurement for studies at the ecosystem level remains problematical because of the huge spatial variability of these processes and, consequently, of the large number of soil samples which must be analyzed. Our goal was to test the capacity of near-infrared reflectance spectroscopy (NIRS) to predict respiration and denitrification but also carbon and nitrogen contents of soils submitted to various procedures of restoration. To achieve this objective, we took advantage of an experiment conducted on a reforestation system established after open-cast gold mining in French Guiana. In this experimental station, plantations of various ages and various soil textures were at our disposal. Our results showed that both plantations and soil texture had a strong impact on the recovery of soil functioning: carbon and nitrogen contents, respiration and denitrification increased with age of plantation and clay content. Calibrations were performed between spectral data and microbial-based indicators using partial least squares regression (PLS). The results showed that C and N contents were accurately predicted. Microbial functions were less precisely predicted with results more accurate on clayey soils than on sandy soils. In clayey soils, perturbed or restored soils and the year of plantation were discriminated very efficiently through principal component analyses of spectral signatures (over 80% of variance explained on the first two axes). Near-infrared spectroscopy may thus be extended to the prediction of functional soil parameters, but the capacity of this method must be strengthened by expending the databases with other soils in other contexts. The possibility of using NIRS provides many opportunities for understanding both the temporal dynamics and the spatial variability of the recovery of key microbial functions during soil restoration.
ISSN: 0929-1393

hal-01032188
https://hal.archives-ouvertes.fr/hal-01032188
DOI : 10.1016/j.apsoil.2007.07.001

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) : Wiley-blackwell
Résumé : Aims Exopolysaccharides (EPS) are industrially valuable molecules with numerous useful properties. This study describes the techniques used for the identification of a novel Vibrio bacterium and preliminary characterization of its EPS. Methods and Results Bioprospection in marine intertidal areas of New Caledonia followed by screening for EPS producing brought to selection of the isolate NC470. Phylogenetic analysis (biochemical tests, gene sequencing and DNADNA relatedness) permitted to identify NC470 as a new member of the Vibrio genus. The EPS was produced in batch fermentation, purified using the ultrafiltration process and analysed by colorimetry, Fourier Transform Infrared spectroscopy, gas chromatography, Nuclear Magnetic Resonance and HPLC-size exclusion chromatography. This EPS exhibits a high N-acetyl-hexosamines and uronic acid content with a low amount of neutral sugar. The molecular mass was 672x103Da. These data are relevant for possible technological exploitation. Conclusions We propose the name Vibrio neocaledonicus sp. nov for this isolate NC470, producing an EPS with an unusual sugar composition. Comparison with other known polymers permitted to select applications for this polymer. Significance and Impact of the Study This study contributes to evaluate the marine biodiversity of New Caledonia. It also highlights the biotechnological potential of New Caledonia marine bacteria.
Journal Of Applied Microbiology (1364-5072) (Wiley-blackwell), 2013-06 , Vol. 114 , N. 6 , P. 1702-1712

Droits : 2013 The Society for Applied Microbiology
http://archimer.ifremer.fr/doc/00144/25501/24036.pdf
DOI:10.1111/jam.12184
http://archimer.ifremer.fr/doc/00144/25501/

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The present study investigated cerebral and muscle hemoglobin oxygen saturation (tissue oxygen index, TOI) in children with sickle cell anemia (SS), sickle cell hemoglobin C disease (SC) and healthy children (AA). TOI was measured by near-infrared spectroscopy (NIRS) and spectral analysis of the TOI variability was used to assess flowmotion and vasomotion. Arterial oxyhemoglobin saturation (SpO2), hemorheological and hematological parameters were also measured in SS and SC children. Both TOI were lower in SS compared to both AA and SC children, with SC exhibiting lower values than AA children. Cerebral vasomotion expressed in absolute values was enhanced in SS compared to AA and SC children. Muscle vasomotion did not differ between the three groups. Hematocrit, SpO2 and red blood cell deformability were positively associated with cerebral TOI in SS children. We demonstrated that 1) cerebral and muscle TOI were markedly decreased in SS children while the decrease of TOI was milder in SC children, 2) cerebral TOI level was associated with several biological markers in SS children only and 3) cerebral vasomotion was enhanced in SS, possibly to counterbalance the effects of chronic cerebral hypoxia.
ISSN: 1079-9796

inserm-01519106
http://www.hal.inserm.fr/inserm-01519106
http://www.hal.inserm.fr/inserm-01519106/document
http://www.hal.inserm.fr/inserm-01519106/file/2017%2C%20Charlot%20-%20Cerebral%20and%20muscle%20microvascular%20oxygenation%20in%20children%20with%20sickle%20celle%20disease.pdf
DOI : 10.1016/j.bcmd.2017.03.015

Éditeur(s) : HAL CCSD Elsevier
Résumé : Understanding the pattern in spatial distribution of soil microbial processes is critical to understand the environmental factors that regulate them as well as to scale up these processes to ecosystem. Soil samples from a I ha tropical rainforest plot (Paracou, French Guiana) were analyzed according a nested sampling approach using different separation distances ranging from 0.4 to 40 m. The variability of substrate induced respiration (SIR) and of denitrification enzyme activity (DEA) was characterized in relation to various soil properties (total C and N contents, NIRS related index of soil organic matter quality, SOMQ and index of tree influence potential, IP). The variability of SIR and DEA was higher than that of environmental properties. The patterns of accumulated variance as a function of distance varied among the soil properties. The variability of SIR and DEA mainly occurred at small (1 m) scale (and at the 10-40 m-scales for SIR), probably reflecting the quality of litter input that results of the influence of local assemblage of different tree species, though changes in the soil N and C contents. Indeed, total soil C and N contents explained the microbial properties at every scale. Coefficients of codispersion showed that neither SOMQ nor IP did correlate with SIR and DEA, and confirmed that total C and N contents explained microbial properties in a scale dependent and complex manner. Such spatial dependency underlines the importance of soil heterogeneity in this tropical forest with implications for sampling strategies when studying the microbial processes and their response to disturbances. (C) 2012 Elsevier B.V. All rights reserved.
ISSN: 0016-7061

hal-01032409
https://hal.archives-ouvertes.fr/hal-01032409
DOI : 10.1016/j.geoderma.2012.12.009

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 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 Institute of Electrical and Electronics Engineers (IEEE)
Résumé : International audience
Non-alcoholic fatty liver disease (NAFLD) is defined as an excessive accumulation of fat in the liver in the absence of excessive drinking of alcohol. Initially considered as benign and self-limited, NAFLD may progress to the malignant stage of non-alcoholic steatohepatitis (NASH) characterized by degenerate hepatocellular ballooning and lobular inflammation. NASH can lead to hepatic fibrosis and ultimately to cirrhosis and hepatocellular carcinoma. Unfortunately, the transition from NAFLD to NASH is difficult to detect so far. In this paper, we propose to evaluate the characterization of NASH using mid infrared fiber evanescent wave spectroscopy on blood serum. We used an heuristic variable selection method and a generalized linear model to classify NAFLD and NASH spectra. The obtained results proved that this technique is a promising non-invasive and simple diagnosis tool for NASH.
ISSN: 1557-170X

inserm-01476033
http://www.hal.inserm.fr/inserm-01476033
http://www.hal.inserm.fr/inserm-01476033/document
http://www.hal.inserm.fr/inserm-01476033/file/EMBC_2016_CameraReady.pdf
DOI : 10.1109/EMBC.2016.7591507

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
Wadsleyites with various iron contents were synthesized at ~12-14 GPa and 1400 °C under oxidizing and hydrous conditions in coexistence with enstatite. The samples were studied using micro-X-ray absorption near edge structure (XANES) and micro-Mössbauer spectroscopy to determine the ferric iron contents in polyphasic samples and secondary ion mass spectrometry (SIMS) to determine the water concentrations. XANES and Mössbauer analyses show that ferric iron content increases with increasing total iron content, and reaches a maximum of ~30% Fe3+/Fetotal. Two XANES results were cross-checked by Mössbauer analysis and both methods are in reasonable agreement. The use of Fourier transform infrared spectroscopy reveals a new protonation scheme in wadsleyite, with a significant proportion of protons associated with the high-frequency band at 3611 cm−1 and a new band located at 3500 cm−1. The intensity of these two bands is higher for Fe3+-rich wadsleyite. SIMS analyses show that water contents in wadsleyite vary from 4500 to 9400 ppm H2O by weight. Pyroxene water contents range from 790 to 1600 ppm wt H2O. The concentration of water in both phases decreases with increasing iron content. The partition coefficient of water between wadsleyite and pyroxene varies between 5 and 9 and increases with increasing Fe-number of wadsleyite [i.e., XFe/(XFe + XMg) × 100 ratio]. The divalent cation concentrations (i.e., Mg2+ + Fe2+), the Si as well as the H content in wadsleyite decrease with increasing Fe3+ content, indicating an incorporation mechanism via substitution into the metal (Me = Mg2+ and Fe2+) and Si sites with a ratio of 5/3 for (Fe3++H+):Me and of 5/1 for (Fe3++H+):Si, similarly as in the dry system. Thus, coupled substitution of Fe3+ and H+ does not affect the incorporation mechanism of Fe3+, but does affect the location of H+, which is partly incorporated at tetrahedral edges forming [FeSi′-(OH)o*]X neutral defects substituting for Si. In this model 25% of the ferric iron occupies the tetrahedral sites.
ISSN: 0003-004X

hal-00758071
https://hal.archives-ouvertes.fr/hal-00758071
DOI : 10.2138/am.2012.3869

Éditeur(s) : HAL CCSD Elsevier
Résumé : We have studied the phase transformation of forsterite to wadsleyite under shear stress at the Earth's transition zone pressure and temperature conditions. Two-step experiments were performed using a multi-anvil press. First, we hot pressed iron-free forsterite at 6 or 11 GPa and 1100 degrees C. Then we deformed a slab of this starting material using a direct simple shear assembly at 16 GPa and 1400 degrees C for 1, 15, 35, 40, or 60 min. Both the starting material and the deformed samples were characterized using optical and scanning electron microscopy including measurements of crystal preferred orientations (CPO) by electron back scattered diffraction (EBSD), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FTIR). The phase transformation occurs very rapidly, in less than 1 min, and metastable forsterite relics are not observed after deformation. The grain size of wadsleyite is slightly smaller than the forsterite starting material. The water contents obtained from FTIR analyses in forsterite and wadsleyite are 65-124 wt ppm H2O and 114-736 wt ppm H2O, respectively, which are well below water solubility at similar conditions in the presence of free water. Wadsleyite aggregates display weak CPO patterns with [1 0 0] axes concentrated at low angle to the shear direction, [0 1 0] axes perpendicular to the shear plane and nearly random [0 0 1] axes. Only a few dislocations were observed in wadsleyite with TEM. This observation is consistent with the assumption that most dislocations formed during the initial high-stress stages of these stress-relaxation experiments, were consumed in the phase transformation, probably enhancing the transformation rate. CPO patterns vary as a function of the water content: with increasing water content the density of [1 0 0] axes parallel to the shear direction decreases, and the density of [0 0 1] axes increases. Viscoplastic self-consistent modeling of CPO evolution using previously reported glide systems for wadsleyite, i.e., [1 0 0]{0 k 1} and 1/2 (1 1 1){1 0 1}, cannot reproduce the measured CPO, unless the [0 0 1](0 1 0) system, for which dislocations have not been observed by TEM, is also activated. In addition, wadsleyite grain growth suggests the participation of diffusion-assisted processes in deformation. Calculated anisotropies for P and S-waves using measured CPO are always below 1%. This very low anisotropy is due to both the low finite strain achieved in the experiments, which leads to weak wadsleyite CPO, and to the diluting effect of added majorite. The present experiments emphasize the importance of stress, grain size evolution and water content in the forsterite to wadsleyite phase transformation and subsequent deformation in the transition zone.
ISSN: 0031-9201

hal-00617430
https://hal.archives-ouvertes.fr/hal-00617430
DOI : 10.1016/j.pepi.2010.11.001