Éditeur(s) : HAL CCSD E Schweizerbart Science Publishers
Résumé : Mafic microgranular enclaves produced by co-mingling between minette and syenite magmas are found in the Piquiri Syenite, southern Brazil. These enclaves were crystallized under upper mantle conditions. K-clinopyroxene and pyrope are among the early-crystallized phases, suggesting an initial pressure around 5GPa. The mineralogy of minettes comprises phenocrysts of magnesium biotite and diopside, occasionally apatite, in a groundmass formed by these minerals plus alkali feldspar. Two types of apatites are observed: (i) euhedral grains, as inclusions or groundmass constituents, and (ii) aciculate crystals formed during undercooling of mafic magma. Substitutional schemes suggested for these apatites are Si ⇆ P in the tetrahedral site, and Sr and LREE replacing Ca. La, Ce, Nd, and Sr concentrations reveal that these elements are extremely enriched in apatite. Partition coefficients between early-crystallized apatites and estimated melt compositions are DLa (11.8 - 30.6), DCe (16.1-33), DNd (12-31) and DSr (5.1-8.2). Apatite concentrates the LREE up to 200 times compared to clinopyroxene, even higher values were determined for ap/mica partitioning. The ap/cpx and ap/mica partition coefficients for undercooled minerals are close to the values determined for the near-liquidus phases, which indicates constant behavior of LREE and Sr between apatite-clinopyroxene-mica parageneses and minette liquids. Furthermore, these partitioning data preclude any chemical diffusion of these elements between minette and syenite magmas during co-mingling.
ISSN: 0935-1221

hal-00407602
https://hal.archives-ouvertes.fr/hal-00407602
DOI : 10.1127/0935-1221/2007/0019-0039

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
Accessory phases are important hosts of trace elements; allanite may contain >90% of the REE in a bulk rock. The mobility and redistribution of several trace elements, notably HREE, Th, U, and Y is thus controlled by reactions involving allanite and other REE phases, as well as several rock-forming minerals. As these elements are commonly concentrated in mature elastic sediments, a suite of impure quartzite was studied. Two eclogite facies samples from the Monometamorphic Cover Complex of the Sesia Zone (Western Italian Alps) are presented in some detail, as they reveal a remarkably rich spectrum of reaction relationships that involve REE phases.;Two allanite-forming reactions were inferred from textures and phase compositions;(1) monazite + Ca-silicate(?) + fluid -> allanite + apatite + thorite;;(2) monazite + thorite + Ca-silicate(?) + fluid -> Th-rich allanite + auerlite +/- apatite.;Petrographic observations and thermodynamic models suggest that allanite entered the HP assemblage at similar to 530 degrees C and 17-18 kbar during prograde metamorphism.;In one sample, allanite is rimmed by epidote rich in Y and HREE that grew at the expense of xenotime. Two net transfer reactions were derived;(3) xenotime + allanite + fluid -> Y-rich epidote + apatite + thorite;;(4) xenotime + allanite + fluid -> Y-rich epidote + aeschynite + thorite + (phosphate?).;Textural relationships and trace element analyses of coexisting allanite/monazite and xenotime/Y-rich epidote reveal systematic partitioning of the REE. Partition coefficients for the HREE are compatible with equilibrium fractionation, whereas those for the LREE show patterns that seem to be inherited from the precursor phases, in this case zircon with variable LREE composition.
ISSN: 0003-004X

hal-00745674
https://hal.archives-ouvertes.fr/hal-00745674
DOI : 10.2138/am.2012.3832

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The indoor gas-phase concentrations of semi-volatile organic compounds (SVOCs) can be predicted from their respective concentrations in airborne particles by applying the particle/gas partitioning equilibrium. The temperature used for partitioning is often set to 25 °C. However, indoor temperatures frequently differ from this reference value. This assumption may result in errors in the predicted equilibrium gas-phase SVOC concentrations. To improve the prediction model, the temperature dependence of the particle/gas partition coefficient must be addressed. In this paper, a theoretical relationship between the particle/gas partition coefficient and temperature was developed based on the SVOC absorptive mechanism. The SVOC particle/gas partition coefficients predicted by employing the derived theoretical relationship agree well with the experimental data retrieved from the literature (R > 0.93). The influence of temperature on the equilibrium gas-phase SVOC concentration was quantified by a dimensionless analysis of the derived relationship between the SVOC particle/gas partition coefficient and temperature. The predicted equilibrium gas-phase SVOC concentration decreased by between 31% and 53% when the temperature was lowered by 6 °C, while it increased by up to 750% when the indoor temperature increased from 15 °C to 30 °C.
ISSN: 0048-9697

hal-01313749
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01313749
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01313749/document
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01313749/file/Temperature%20dependence%20of%20the%20particle%20gas%20partition%20coefficient_accepted.pdf
DOI : 10.1016/j.scitotenv.2016.04.106

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : International audience
The composition of S-rich apatite, of volatile-rich glass inclusions in apatite, and of interstitial glasses in alkaline xenoliths from the 1949 basanite eruption in La Palma has been investigated to constrain the partitioning of volatiles between apatite and alkali-rich melts. The xenoliths are interpreted as cumulates from alkaline La Palma magmas. Apatite contains up to 0.89 wt% SO3 (3560 ppm S), 0.31 wt% Cl, and 0.66 wt% Ce2O3. Sulfur is incorporated in apatite via several independent exchange reactions involving (P5+, Ca2+) vs. (S6+, Si4+, Na+, and Ce3+). The concentration of halogens in phonolitic to trachytic glasses ranges from 0.15 to 0.44 wt% for Cl and from < 0.07 to 0.65 wt% for F. The sulfur concentration in the glasses ranges from 0.06 to 0.23 wt% SO3 (sulfate-saturated systems). The chlorine partition coefficients (D (Cl) (apatite/glass) ) range from 0.4 to 1.3 (average D (Cl) (apatite/glass) = 0.8), in good agreement with the results of experimental data in mafic and rhyolitic system with low Cl concentrations. With increasing F in glass inclusions D (F) (apatite/glass) decreases from 35 to 3. However, most of our data display a high partition coefficient (similar to 30) close to D (F) (apatite/glass) determined experimentally in felsic rock. D (S) (apatite/glass) decreases from 9.1 to 2.9 with increasing SO3 in glass inclusions. The combination of natural and experimental data reveals that the S partition coefficient tends toward a value of 2 for high S content in the glass (> 0.2 wt% SO3). D (S) (apatite/glass) is only slightly dependent on the melt composition and can be expressed as: SO3 apatite (wt%) = 0.157 * ln SO3 glass (wt%) + 0.9834. The phonolitic compositions of glass inclusions in amphibole and hauyne are very similar to evolved melts erupted on La Palma. The lower sulfur content and the higher Cl content in the phonolitic melt compared to basaltic magmas erupted in La Palma suggest that during magma evolution the crystallization of hauyne and pyrrhotite probably buffered the sulfur content of the melt, whereas the evolution of Cl concentration reflects an incompatible behavior. Trachytic compositions similar to those of the (water-rich) glass inclusions analyzed in apatite and clinopyroxene are not found as erupted products. These compositions are interpreted to be formed by the reaction between water-rich phonolitic melt and peridotite wall-rock.
ISSN: 0010-7999

hal-00644803
https://hal.archives-ouvertes.fr/hal-00644803
DOI : 10.1007/s00410-011-0606-7

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

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

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Particle/gas and dust/gas partition coefficients (Kp and Kd) are two key parameters that address the partitioning of semi-volatile organic compounds (SVOCs) between gas-phase, airborne particles, and settled dust in indoor environment. A number of empirical equations to calculate the values of Kp and Kd have been reported in the literature. Therefore, the difficulty lies in the selection of a specific empirical equation in a given situation. In this study, we retrieved from the literature 38 empirical equations for calculating Kp and Kd values from the SVOC saturation vapor pressure and octanol/air partition coefficient. These values were calculated for 72 SVOCs: 9 phthalates, 9 polybrominated diphenyl ethers (PBDEs), 11 polychlorinated biphenyls (PCBs), 22 biocides, 14 polycyclic aromatic hydrocarbons (PAHs), 3 alkylphenols, 2 synthetic musks, tributylphosphate, and bisphenol A. The mean and median values of log10 Kp or log10 Kd for most SVOCs were of the same order of magnitude. The distribution of log10 Kp values was fitted to either a normal distribution (for 27 SVOCs) or a log-normal distribution (for 45 SVOCs). This work provides a reference distribution of the log10 Kp for 72 SVOCs, and its use may reduce the bias associated with the selection of a specific value or equation
ISSN: 0045-6535

hal-01295671
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01295671
DOI : 10.1016/j.chemosphere.2016.03.007
PUBMED : 27016817

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The oxygen fugacity and therefore the iron redox state of a melt is known to have a strong influence on the liquid line of descent of magmas and thus on the composition of the coexisting melts and crystals. We present a new method to estimate this critical parameter from electron probe microanalyses of two of the most common minerals of basaltic series, plagioclase and clinopyroxene. This method is not based on stoichiometric calculations, but on the different partitioning behaviour of Fe3+ and Fe2+ between both minerals and a melt phase: plagioclase can incorporate more Fe3+ than Fe2+, while clinopyroxene can incorporate more Fe2+ than Fe3+. For example, the effect of oxidizing a partly molten basaltic system (Fe3+ is stabilized with respect to Fe2+) results in an increase of FeOtotal in plagioclase, but a decrease in the associated clinopyroxene. We propose an equation, based on published partition coefficients, that allows estimating the redox state of a melt from these considerations. An application to a set of experimental and natural data attests the validity of the proposed model. The associated error can be calculated and is on average <1 log unit of the prevailing oxygen fugacity.;In order to reduce the number of different variables influencing the Fe2+/Fe3+ mineral/melt equilibrium, our model is restricted to basaltic series with SiO2<60% that have crystallized at intermediate to low pressure (<0.5 GPa) and under relatively oxidizing conditions (Delta FMQ>0; where FMQ is the fayalite-magnetite-quartz oxygen buffer equilibrium), but it may be parameterized for other conditions. A spreadsheet is provided to assist the use of equations, and to perform the error propagation analysis.
ISSN: 0377-0273

hal-00475550
https://hal.archives-ouvertes.fr/hal-00475550
DOI : 10.1016/j.jvolgeores.2009.11.023

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Melting experiments were performed on a silica-rich peridotite composition at 10-17 GPa to determine majoritic garnet-melt partition coefficients (D) for major and trace elements. Our results show that D for many elements, including Na, Sc, Y and rare earth elements (REE), varies significantly with increasing pressure or proportion of majorite component. Lu and Sc become incompatible at 17 GPa, with D decreasing from 1.5 at 10 GPa to 0.9 at 17 GPa. As predicted from lattice strain, log D for isovalent cations entering the large site of majoritic garnet exhibits a near-parabolic dependence on ionic radius. Our data are used to refine a previously published predictive model for garnet-melt partitioning of trivalent cations, which suffered from a lack of calibration in the 10-20 GPa range. Our results suggest that Archean Al-depleted komatiites from Barberton (South Africa) may have been generated by partial melting of dry peridotite at depths between 200 and 400 km. We also speculate that transition zone diamonds from Kankan (Guinea), which contain inclusions of majoritic garnet, may have formed from the partial reduction of CO2-rich magmas that subsequently transported them to the surface. This hypothesis would provide an explanation for the REE patterns of majoritic garnet trapped within these diamonds, including Eu anomalies. Finally, we show that segregation of majoritic garnet-bearing cumulates during crystallisation of a deep Martian magma ocean could lead to a variety of Lu/Hf and Sm/Nd ratios depending on pressure, leading to a range of ε143Nd and ε176Hf isotope signatures for potential mantle sources of Martian rocks.
ISSN: 0024-4937

hal-00767567
https://hal.archives-ouvertes.fr/hal-00767567
DOI : 10.1016/j.lithos.2012.06.013

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 Elsevier
Résumé : International audience
Mid-ocean ridge basalts (MORBs) are the most abundant magmas produced on Earth. They are widely studied to infer mantle compositions and melting processes. However, MORB liquids are also the complex end-product of a variety of intra-crustal processes such as partial or fractional crystallization, melt–rock interaction, and contamination. Deciphering the relative contribution of these different processes is of first-order importance. Contamination at ocean crustal levels is likely, and may occur at magma chamber margins where fresh magmas can interact with previously hydrothermally altered rocks. Characterizing the composition of this crustal contaminant component is critical if we are to understand the relative importance of each component in the resulting MORB liquid.Here we present the results of experiments designed to reproduce the processes occurring at oceanic magma chamber roofs, where crustal contamination should be most extensive, by melting a representative sample of the sheeted dike complex. Anatectic melts thus produced are likely to represent the principal crustal contaminant in MORB. These melts were characterized for major and trace elements, showing B, Zr, Hf, and U enrichment, and Sr, Ti, and V depletion relative to original MORB liquids. In comparison to the starting material, relative element fractionations are observed in the anatectic melts, with enrichments of: U relative to Ba, Nb, and Th; LREE and MREE relative to Sr; and Zr–Hf relative to LREE. Bulk partition coefficients for element partitioning during magma chamber roof anatexis are derived and proposed as valuable tools for tracking MORB contamination.Comparison with natural samples from the East Pacific Rise and the Oman ophiolite shows that anatectic melts can crystallize in situ to form oceanic plagiogranite intrusions, and that residual assemblages associated with the hydrous partial melting stage are represented by hornfelsic dikes and enclaves (also named granoblastic basalts). We now recognize these as commonplace at the root of the sheeted dike complex both at present-day and fossil oceanic spreading centers.
ISSN: 0024-4937

hal-01115500
https://hal.archives-ouvertes.fr/hal-01115500
DOI : 10.1016/j.lithos.2014.05.018