Electronic environments of ferrous iron in rhyolitic and basaltic glasses at high pressure

The physical properties of silicate melts within Earth's mantle affect the chemical and thermal evolution of its interior. Chemistry and coordination environments affect such properties. We have measured the hyperfine parameters of iron-bearing rhyolitic and basaltic glasses up to ~120 GPa and ~100 GPa, respectively, in a neon pressure medium using time domain synchrotron Mössbauer spectroscopy. The spectra for rhyolitic and basaltic glasses are well explained by three high-spin Fe^(2+)-like sites with distinct quadrupole splittings. Absence of detectable ferric iron was confirmed with optical absorption spectroscopy. The sites with relatively high and intermediate quadrupole splittings are likely a result of fivefold and sixfold coordination environments of ferrous iron that transition to higher coordination with increasing pressure. The ferrous site with a relatively low quadrupole splitting and isomer shift at low pressures may be related to a fourfold or a second fivefold ferrous iron site, which transitions to higher coordination in basaltic glass, but likely remains in low coordination in rhyolitic glass. These results indicate that iron experiences changes in its coordination environment with increasing pressure without undergoing a high-spin to low-spin transition. We compare our results to the hyperfine parameters of silicate glasses of different compositions. With the assumption that coordination environments in silicate glasses may serve as a good indicator for those in a melt, this study suggests that ferrous iron in chemically complex silicate melts likely exists in a high-spin state throughout most of Earth's mantle

Isotope tracers of core formation

The study of siderophile element isotope compositions in planetary mantles offers a new methodology to constrain the temperatures of core formation, provided there is an appropriate calibration of the temperature dependence and possibly pressure-dependence of isotope fractionation between metal and silicate and of the metal-silicate partitioning for these elements. In this review, we examine recent studies that have shown that Si, Fe, Mo, Cr, Cu, Ni, N and C could potentially be used to constrain the temperature of metal-silicate equilibration using single stage or continuous models of core formation, yielding contrasted results. Such an approach requires assumptions about the building blocks of the Earth and it is generally considered that the composition of some chondrites is representative of bulk Earth. This is obviously more complex for volatile elements such as Cu, N or C, as the isotope composition of the building blocks of the Earth could have been affected by thermal processing. On the basis of a chondritic bulk composition, one can estimate a temperature of core formation assuming a model for this process. If the metal-silicate equilibration is incomplete, as is likely the case for giant impacts, then the composition of the mantle of the impactor and the fraction of metal that equilibrates needs to be assessed carefully. It has been shown recently that the degree of equilibration will be a function of the metal silicate partition coefficient and will be hence very different for Si, Cr, or Mo, an aspect that has not been considered in previous studies and may help explain differences in interpretation. In this context, the expected temperatures of equilibration are quite variable and are a function of the impactor's conditions of metal-silicate segregation. Another complication arises when considering continuous models of core formation: the most siderophile elements will be sensitive to the last episodes of core formation, while the budget of less siderophile elements will reflect its integrated accretion history (e.g. Cr or Si). A model including Si, Cr and Mo isotope data that takes into account these aspects has been constructed and shown to be consistent with scenarii that were derived from siderophile element data

Electronic environments of ferrous iron in rhyolitic and basaltic glasses at high pressure

The physical properties of silicate melts within Earth's mantle affect the chemical and thermal evolution of its interior. Chemistry and coordination environments affect such properties. We have measured the hyperfine parameters of iron-bearing rhyolitic and basaltic glasses up to ~120 GPa and ~100 GPa, respectively, in a neon pressure medium using time domain synchrotron Mössbauer spectroscopy. The spectra for rhyolitic and basaltic glasses are well explained by three high-spin Fe^(2+)-like sites with distinct quadrupole splittings. Absence of detectable ferric iron was confirmed with optical absorption spectroscopy. The sites with relatively high and intermediate quadrupole splittings are likely a result of fivefold and sixfold coordination environments of ferrous iron that transition to higher coordination with increasing pressure. The ferrous site with a relatively low quadrupole splitting and isomer shift at low pressures may be related to a fourfold or a second fivefold ferrous iron site, which transitions to higher coordination in basaltic glass, but likely remains in low coordination in rhyolitic glass. These results indicate that iron experiences changes in its coordination environment with increasing pressure without undergoing a high-spin to low-spin transition. We compare our results to the hyperfine parameters of silicate glasses of different compositions. With the assumption that coordination environments in silicate glasses may serve as a good indicator for those in a melt, this study suggests that ferrous iron in chemically complex silicate melts likely exists in a high-spin state throughout most of Earth's mantle

Nickel isotope fractionation during metal-silicate differentiation of planetesimals: Experimental petrology and ab initio calculations

Metal-silicate fractionation of nickel isotopes has been experimentally quantified at 1623 K, with oxygen fugacities varying from 10−8.2 to 10−9.9 atm and for run durations from 0.5 to 1 h. Both kinetic and equilibrium fractionations have been studied. A wire loop set-up was used in which the metal reservoir is a pure nickel wire holding a silicate melt droplet of anorthite-diopside eutectic composition. During the course of the experiment, diffusion of nickel from the wire to the silicate occurred. The timescale to reach chemical equilibrium was fO2 dependent and decreased from 17 to 1 hour, as conditions became more reducing. The isotopic composition of each reservoir was determined by Multicollector-Inductively Coupled Plasma-Mass Spectrometry (MC-ICPMS) after Ni purification. The isotopic composition was found to be constant in the metallic wire, which therefore behaved as an infinite reservoir. On the contrary, strong kinetic fractionation was observed in the silicate melt (δNi down to −0.98‰.amu−1 relative to the standard). Isotopic equilibrium was typically reached after 24 hours. For equilibrated samples at 1623 K, no metal-silicate fractionation was observed within uncertainty (2SD), with ΔNiMetal-Silicate = 0.02 ± 0.04‰.amu−1. Theoretical calculations of metal-silicate isotope fractionation at equilibrium were also performed on different metal-silicate systems. These calculations confirm (1) the absence of fractionation at high temperature and (2) a weak temperature dependence for Ni isotopic fractionation for the metal-olivine and metal-pyroxene pairs with the metal being slightly lighter isotopically. Our experimental data were finally compared with natural samples. Some mesosiderites (stony-iron meteorites) show a ΔNiMetal-Silicate close to experimental values at equilibrium, whereas others exhibit positive metal-silicate fractionation that could reflect kinetic processes. Conversely, pallasites display a strong negative metal-silicate fractionation. This most likely results from kinetic processes with Ni diffusion from the silicate to the metal phase due to a change of Ni partition coefficient during cooling. In this respect we note that in these pallasites, iron isotopes show metal-silicate fractionation that is opposite direction to Ni, supporting the idea of kinetic isotope fractionation, associated with Fe-Ni interdiffusion

Nucléation et croissance cristalline dans les silicates liquides

Texte intégral accessible uniquement aux membres de l'Université de LorraineMicroscopic mechanisms controling crystal nucieation and growth at temperatures below the solidus 1 but above Tg have been studied on glasses in the system CaO-AlzO3-SiOz. Experimental charges have been characterized over a wide range of length scaIes (SEM, TEM, Microprobe, DRX, raman spectroscopy). Minerais are enriched in Ca and have Si/Al approaching that of the parent liquid. A gradual change of Al/Si is observed with temperature. These results are explained by the relative mobilities of the different cations, of which Ca is several orders of magnitude faster than that of Si and Al.. The link between crystal growth and viscosity has been tested and explained by the common microscopic origine of these processes which is the breaking and formation of Si-O bonds. This link is broken when Al/Si of crystals and liquids are different, because the coupled diffusion of Al and Ca becomes the limiting factor of the crystal growth.Les mécanismes microscopiques contrôlant la nucléation et la croissance cristalline à des températures inférieures au solidus, mais au-dessus de Tg ont été étudiés sur des verres du système CaO-AlzO3- SiOz. Les charges expérimentales ont été caractérisées à différentes échelles (MEB, MET, microsonde, DRX, spectroscopie Raman). Les minéraux sont enrichis en Ca et possèdent un Al/Si proche de celui i du liquide parent. Un changement, progressif de ce rapport est observé avec la température. Ces résultats sont expliqués par les mobilités relatives des différents cations, celle de Ca étant supérieure de plusieurs ordres de grandeurs à celles de Si et Al. Le lien entre vitesse de croissance et viscosité a été testé et expliqué par l'origine microscopique commune des deux processus.: la rupture et les échanges de liaisons Si-O. Ce lien est rompu lorsque Si/Al du cristal et du liquide sont différents, la diffusion couplée de Al et Ca devenant le facteur limitant de la croissance minérale

A SIGNIFICANT AMOUNT OF CRYSTALLINE SILICA IN RETURNED COMETARY SAMPLES: BRIDGING THE GAP BETWEEN ASTROPHYSICAL AND METEORITICAL OBSERVATIONS

International audienceCrystalline silica (SiO2) is recurrently identified at the percent level in the infrared spectra of protoplanetary disks. By contrast, reports of crystalline silica in primitive meteorites are very unusual. This dichotomy illustrates the typical gap existing between astrophysical observations and meteoritical records of the first solids formed around young stars. The cometary samples returned by the Stardust mission in 2006 offer an opportunity to have a closer look at a silicate dust that experienced a very limited reprocessing since the accretion of the dust. Here, we provide the first extended study of silica materials in a large range of Stardust samples. We show that cristobalite is the dominant form. It was detected in 5 out of 25 samples. Crystalline silica is thus a common minor phase in Stardust samples. Furthermore, olivine is generally associated with this cristobalite, which put constraints on possible formation mechanisms. A low-temperature subsolidus solid–solid transformation of an amorphous precursor is most likely. This crystallization route favors the formation of olivine (at the expense of pyroxenes), and crystalline silica is the natural byproduct of this transformation. Conversely, direct condensation and partial melting are not expected to produce the observed mineral assemblages. Silica is preserved in cometary materials because they were less affected by thermal and aqueous alterations than their chondritic counterparts. The common occurrence of crystalline silica therefore makes the cometary material an important bridge between the IR-based mineralogy of distant protoplanetary disks and the mineralogy of the early solar system

Nucléation et croissance cristalline dans les silicates liquides

Les mécanismes microscopiques contrôlant la nucléation et la croissance cristalline à des températures inférieures au solidus, mais au-dessus de Tg ont été étudiés sur des verres du système CaO-AlzO3- SiOz. Les charges expérimentales ont été caractérisées à différentes échelles (MEB, MEr, microsonde, DRX, spectroscopie Raman). Les minéraux sont enrichis en Ca et possèdent un Al/Si proche de celui i du liquide parent. Un changement, progressif de ce rapport est observé avec la température. Ces résultats sont expliqués par les mobilités relatives des différents cations, celle de Ca étant supérieure de plusieurs ordres de grandeurs à celles de Si et Al. Le lien entre vitesse de croissance et viscosité a été testé et expliqué par l'origine microscopique commune des deux processus.: la rupture et les échanges de liaisons Si-O. Ce lien est rompu lorsque Si/Al du cristal et du liquide sont différents, la diffusion couplée de Al et Cà devenant le facteur limitant de la croissance minérale.Microscopic mechanisms controling crystal nucieation and growth at temperatures below the solidus 1 but above Tg have been studied on glasses in the system CaO-AlzO3-SiOz. Experimental charges have been characterized over a wide range of length scaIes (SEM, TEM, Microprobe, DRX, raman spectroscopy). Minerais are enriched in Ca and have Si/Al approaching that of the parent liquid. A gradual change of Al/Si is observed with temperature. These results are explained by the relative mobilities of the different cations, of which Ca is several orders of magnitude faster than that of Si and Al.. The link between crystal growth and viscosity has been tested and explained by the common microscopic origine of these processes which is the breaking and formation of Si-O bonds. This link is broken when Al/Si of crystals and liquids are different, because the coupled diffusion of Al and Ca becomes the limiting factor of the crystal growth.NANCY/VANDOEUVRE-INPL (545472102) / SudocSudocFranceF

Synthèse et cristallisation de silicates amorphes poreux dans le ternaire MgO-CaO-SiO2 (application à la transition amorphe-cristal des disques d'accrétion)

La poussière interstellaire peut être considérée comme le précurseur des minéraux qui ont peuplé les disques protoplanétaires. En effet, les étoiles commencent leur histoire par l effondrement d un nuage interstellaire composé de gaz et de silicates amorphes riches en magnésium. Dans les premiers temps de la formation stellaire, celui-ci est réarrangé sous forme d un disque en orbite autour l étoile et dans lequel la poussière subit d intenses transformations. Une conséquence majeure est l apparition d une transition amorphe-cristal de la poussière. Le disque est alors caractérisé par une zonation minéralogique constituée par une variation d abondance de deux phases majeures, la forstérite et l enstatite. Deux mécanismes peuvent rendre compte de leur formation à partir des silicates amorphes qui alimentent le disque : l évaporation-condensation et la cristallisation solide-solide. Les présents travaux étudient ce dernier mécanisme comme alternatif au premier pour donner des éléments d interprétation à la zonation minéralogique observée. Dans un premier temps, une méthode de synthèse sol-gel est mise au point afin de produire des silicates amorphes magnésiens et magnéso-calciques analogues aux silicates interstellaires. Dans un second temps, leur cristallisation est étudiée par diffraction des rayons X et microscopie électronique à transmission. Cette cristallisation se fait de manière séquencée et est marquée par une forte germination, conférant une petite taille de grain aux silicates. Les phases les plus riches en alcalino-terreux se forment les premières. Ce comportement se révèle un mécanisme pertinent pour expliquer la zonation minéralogique des disques et certains minéraux contenus dans les objets tels que les poussières interplanétaires, les comètes et les météorites.In the framework of mineral evolution, interstellar dust could be claimed as the oldest ancestor of all minerals which spread on Earth and, further, in all comic objects traveling through the solar system, like comets, meteorites and interplanetary dust particles. History of stars begin with the collapse of an interstellar cloud made of gas and dust. Dust is mainly composed of Mg-rich amorphous silicates. In first stages of star formation, the diffuse mixture of gas and dust is dragged out by stellar winds and radiations to form a accretion disk in orbital motion around the new burning body. Then, processing of dust occurs. One consequence is an impressive amorphous-crystal transition known as the crystalline revolution . A mineral zoning appears along the disk with the formation of two major Mg-rich crystalline silicates, forsterite and enstatite. Two mechanisms can account for the formation of these two phases from the in-falling amorphous dust : evaporation-condensation and solid crystallization. The present work focuses on the solid state crystallization process in order to give support for the interpretation of the mineralogical zoning. First, a sol-gel synthesis is worked out to produce amorphous and porous magnesium and calcium rich silicates as analogs of interstellar dust. Second, their crystallization behavior is studied by x-ray diffraction and by transmission electron microscopy. Main results are an enhanced nucleation and a sequenced crystallization with systematic Mg- or Ca- enriched crystalline phases formed at first. Using a material science frame, the results are discussed in the context of the mineralogical zoning in disks and the occurrence of crystalline silicates in extraterrestrial objects such as interplanetary dust particles, comets and meteorites.LILLE1-Bib. Electronique (590099901) / SudocSudocFranceF

Glass formation in silicates: Insights from composition

International audienceThe composition dependence of glass formation is examined in a variety of silicate systems that include alkali and alkaline earth alumino-, titano-, ferro- and ferrisilicates. Empirically, there is a clear correlation between wide extent of glass formation, possible crystallization from the melt of numerous compounds, and moderate liquidus temperatures. Vitrification with usual cooling rates is in contrast impossible when binary and ternary compounds are scarce and liquidus temperatures are high. These correlations imply that vitrification is favored by moderately negative enthalpies of mixing in the melt but made difficult by high configurational heat capacities. The close connection between glass formation and viscosity is reviewed in the light of these melt properties. That bulk viscosity is in general not directly relevant to the kinetics of crystal nucleation in particular indicates that vitrification theories cannot be considered as by-products of crystallization theories