Amorphous Silicate Grains Research Articles

Gas-phase Condensation of Carbonated Silicate Grains

Reports on the detection of carbonates in planetary nebulae (PNe) and protostars have suggested the existence of a mechanism that produces these compounds in stellar winds and outflows. A subsequent laboratory study has reported a possible mechanism by presenting the non-thermodynamic-equilibrium (TE), gas-phase condensation of amorphous silicate grains with amorphous calcium carbonate inclusions. The authors concluded that water vapor was necessary for the formation of the carbonates. We present a laboratory study with pulsed laser ablation of a MgSi target in O2 and CO2 gases and report, in the absence of water vapor, the non-TE, gas-phase condensation of amorphous carbonated magnesium silicate dust. It consists of amorphous silicate grains with the formula MgSiO3, which comprise carbonate groups homogeneously dispersed in their structure. The IR spectra of the grains show the characteristic bands of amorphous silicates and two bands at ∼6.3 and ∼7.0 μm, which we assign to the carbonate groups. The silicate bands are not significantly affected at an estimated Si:C ratio of 9:1–9:2. Such grains could form in winds and outflows of evolved stars and PNe if C atoms are present during silicate condensation. Additionally, we find that Lyα radiation dissociates the carbonate groups at the surface of the carbonated silicate grains and we estimate the corresponding photodissociation cross section of (0.04 ± 0.02) ×10−16 cm2. Therefore, photodissociation would limit the formation of carbonate groups on grains in winds and outflows of stars emitting vacuum ultraviolet photons, and the carbonates observed in protostars have not formed by gas-phase condensation.

An experimental simulation of oxygen isotope exchange reaction between amorphous silicate dust and carbon monoxide gas in the early Solar System

The reaction mechanism and kinetics of oxygen isotope exchange between tens of nanometer-sized amorphous silicate grains with forsterite composition (amorphous forsterite) and low-pressure carbon monoxide (CO) gas (PCO) of 0.05–1 Pa at 643–883 K were examined to investigate oxygen isotopic evolution in the protosolar disk that led to the mass-independent oxygen isotopic variation of planetary materials. Both CO gas supply- and diffusion-controlled isotope exchange reactions were observed. At 753–883 K and PCO of 0.05–1 Pa, the supply of CO gas controls the isotope exchange reaction, and its rate is 2–3 orders of magnitude smaller than that of the H2O supply-controlled isotope exchange reaction. The diffusion-controlled isotope exchange occurred at 643–703 K and PCO of 0.3 Pa, and the reaction rate of D (m2/s) = (3.1 ± 2.3) × 10−23 exp[−41.7 ± 9.6 (kJ mol−1) R−1 (1/T − 1/1200)] was obtained.We found that the oxygen isotope exchange rates of amorphous forsterite with CO and H2O gases are larger than those of gaseous isotope exchange between CO and H2O gases at a wide range of temperatures, wherein amorphous forsterite crystallization does not precede the isotope exchange reaction of amorphous forsterite with these gases. The most sluggish isotope exchange rate between H2O and CO in the gas phase suggests that amorphous forsterite would play a role in accelerating gaseous isotopic equilibrium through the isotope exchange of amorphous forsterite with both CO and H2O. We found that the oxygen isotopic equilibrium between 0.1 μm-sized amorphous forsterite, CO, and H2O would be accomplished through the isotope exchange of amorphous forsterite at temperatures as low as ∼600–700 K in the dynamically accreting protosolar disk, which is significantly lower than expected for the case of gaseous isotope exchange (>∼800 K).

JWST/MIRI Spectroscopy of the Disk of the Young Eruptive Star EX Lup in Quiescence

EX Lup is a low-mass pre-main-sequence star that occasionally shows accretion-related outbursts. Here, we present JWST/MIRI medium-resolution spectroscopy obtained for EX Lup 14 yr after its powerful outburst. EX Lup is now in quiescence and displays a Class II spectrum. We detect a forest of emission lines from molecules previously identified in infrared spectra of classical T Tauri disks: H2O, OH, H2, HCN, C2H2, and CO2. The detection of organic molecules demonstrates that they are back after disappearing during the large outburst. Spectral lines from water and OH are for the first time deblended and will provide a much-improved characterization of their distribution and density in the inner disk. The spectrum also shows broad emission bands from warm, submicron-size amorphous silicate grains at 10 and 18 μm. During the outburst, in 2008, crystalline forsterite grains were annealed in the inner disk within 1 au, but their spectral signatures in the 10 μm silicate band later disappeared. With JWST we rediscovered these crystals via their 19.0, 20.0, and 23.5 μm emission, the strength of which implies that the particles are at ∼3 au from the star. This suggests that crystalline grains formed in 2008 were transported outwards and now approach the water snowline, where they may be incorporated into planetesimals. Containing several key tracers of planetesimal and planet formation, EX Lup is an ideal laboratory to study the effects of variable luminosity on the planet-forming material and may provide an explanation for the observed high crystalline fraction in solar system comets.

Condensation of cometary silicate dust using an induction thermal plasma system

Glass with embedded metal and sulfides (GEMS), the major components of chondritic-porous interplanetary dust particles (CP-IDPs), is one of the most primitive materials in the Solar System and may be analogous to the amorphous silicate dust observed in various astronomical environments. Mineralogical characteristics of GEMS should reflect their formation process and condition. In this study, synthetic experiments in the sulfur-bearing system of Fe–Mg–Si–O–S were performed with a systematic change in redox conditions using thermal plasma systems to reproduce the mineralogy and textures of GEMS. The resulting condensates were composed of amorphous silicates with Fe-bearing nano-inclusions. The Fe content and texture in the amorphous silicates as well as the mineral phases of the nanoparticles correlate with redox conditions. Fe dissolved in the amorphous silicate as FeO in oxidizing conditions formed Fe-metal nanoparticles in intermediate redox conditions, and gupeiite (Fe3 Si) nanoparticles in reducing conditions. In intermediate to reducing redox conditions, Fe-poor amorphous silicate formed a biphasic texture with Mg- and Si-rich regions, indicating liquid immiscibility during the melt phase. Most Fe-metal particles were surrounded by FeS and formed on the surface of amorphous silicate grains. Condensates produced in intermediate to slightly reducing redox conditions resemble GEMS in that they have similar mineral assemblages and chemical compositions to amorphous silicate, except that the Fe-metal grains are absent from the interior of the amorphous silicate grains. This textural difference can be explained by the sulfidation at high temperatures in this study, in contrast to sulfidation occurring at low temperatures in the presence of H2 in natural GEMS formation. Based on the two-liquid structures observed in the experimental products and in GEMS, also recognized in infrared spectra, we propose that GEMS condensed as silicate melt under limited redox conditions followed by incorporation of multiple metal grains into the silicate melt or by aggregation of coreshell structured grains before sulfidation of the metallic iron. Condensates produced in oxidizing conditions are similar to GEMS-like material in the matrices of primitive carbonaceous chondrite meteorites, indicating the possibility that they form by direct condensation from nebula gas in relatively oxidizing conditions compared to GEMS.

Formation of Complex Organic and Prebiotic Molecules in H2O:NH3:CO2 Ices at Temperatures Relevant to Hot Cores, Protostellar Envelopes, and Planet-Forming Disks.

Photochemistry in H2O:NH3:CO2 cosmic ice analogues was studied at temperatures of 75, 120, and 150 K, relevant to hot cores and warmer regions in protostellar envelopes and planet-forming disks. A combination of two triggers of surface chemistry in cosmic ice analogues, heat and UV irradiation, compared to using either just heat or UV irradiation, leads to a larger variety and an increased production of complex organic molecules, including potential precursors of prebiotic molecules. In addition to complex organic molecules detected in previous studies of H2O:NH3:CO2 ices, ammonium carbamate, carbamic acid, ammonium formate and formamide, we detected acetaldehyde, urea, and, tentatively, glycine, the simplest amino acid. Water ice hampers reactions at low temperature (75 K) but allows the parent molecules, CO2 and NH3, to stay in the solid state and react at higher temperatures (120 and 150 K, above their desorption temperatures). The experiments were performed on the surface of KBr substrates and amorphous silicate grains, analogs of cosmic silicate dust. The production of complex molecules on the silicate surface is decreased compared to KBr. This result suggests that the larger surface area and/or surface properties of the silicate grains play a role in controlling the chemistry, preventing it taking place to the same extent as on the flat KBr substrate. This is further evidence of the fact that cosmic dust grains play an important role in the chemistry taking place on their surface.

Condensation of cometary silicate dust using an induction thermal plasma system

Glass with embedded metal and sulfides (GEMS) is a major component of chondritic porous interplanetary dust particles. Although GEMS is one of the most primitive components in the Solar System, its formation process and conditions have not been constrained. We performed condensation experiments of gases in the system of Mg–Si–O (MgSiO3 composition) and of the S-free CI chondritic composition (Si–Mg–Fe–Na–Al–Ca–Ni–O system) in induction thermal plasma equipment. Amorphous Mg-silicate particles condensed in the experiments of the Mg–Si–O system, and their grain size distribution depended on the experimental conditions (mainly partial pressure of SiO). In the CI chondritic composition experiments, irregularly shaped amorphous silicate particles of less than a few hundred nanometers embedded with multiple Fe–Ni nanoparticles of ≤20 nm were successfully synthesized. These characteristics are very similar to those of GEMS, except for the presence of FeSi instead of sulfide grains. We propose that the condensation of amorphous silicate grains smaller than a few tens of nanometers and with metallic cores, followed by coagulation, could be the precursor material that forms GEMS prior to sulfidation.

Condensation of Glass with Multimetal Nanoparticles: Implications for the Formation Process of GEMS Grains

Abstract Interplanetary dust particles contain grains of glass with embedded metals and sulfides (GEMS; i.e., amorphous silicate grains with diameters of a few hundred nanometers containing Fe nanoinclusions and Fe sulfide particles), which are considered to be among the building blocks of the solar system. To explore that GEMS grains formed during the condensation process, condensation experiments were carried out in Si–Mg–Fe–Al–Ca–Ni–O and Mg–Si–Fe–Ca–Al–Na–O systems using an induction thermal plasma furnace. In all experimental runs, spherical grains (mostly composed of amorphous silicate) with diameter <100 nm formed. The analysis of the amorphous silicates, which were classified as Mg rich or Si rich, indicated that the condensates formed via melting. Fe led to the formation of fine magnetite grains in most of the oxidative experiments, to 10 nm metal grains (i.e., kamacite and taenite) under intermediate redox conditions, and to 30–100 nm Fe silicide grains (i.e., gupeiite, xifengite, and fersilicite) in most of the reductive experiments. Under intermediate redox conditions, some amorphous silicate particles showed multiple Fe inclusions with textures very similar to those of GEMS grains except for FeS, indicating that GEMS could form via melt condensation of high-temperature gases. Considering the nucleation and growth of solids from high-temperature gas during cooling, we infer that GEMS grains form either in the local environment of a protosolar disk (and be related to chondrule formations) or around evolved stars related to Type II-P supernovae and asymptotic giant branch–type stars.

Evidence of Surface Catalytic Effect on Cosmic Dust Grain Analogs: The Ammonia and Carbon Dioxide Surface Reaction

Abstract Surface chemistry on cosmic dust grains plays an important role in the formation of molecules at low temperatures in the interstellar and circumstellar environments. For the first time, we experimentally put in evidence the catalytic role of dust surfaces using the thermal reaction CO2 + 2NH3 → NH2COO−, which is also a proxy of radical–radical reactions. Nanometer-sized amorphous silicate and carbon grains produced in our laboratory were used as grain analogs. Surface catalysis on grains accelerates the kinetics of the reaction studied at a temperature of 80 K by a factor of up to 3 compared to the reaction occurring in the molecular solid. The evidence of the catalytic effect of grain surfaces opens a door for experiments and calculations on the formation of interstellar and circumstellar molecules on dust. Ammonium carbamate on the surface of grains or released intact into protostellar or protoplanetary disk phases can give start to a network of prebiotic reactions. Therefore, there should be a great interest to search for ammonium carbamate and its daughter molecule, carbamic acid, in interstellar clouds, protostellar envelopes, and protoplanetary disks.

Mid-infrared Spectroscopic Observations of Comet 17P/Holmes Immediately After Its Great Outburst in 2007 October

Abstract Dust grains of crystalline silicate, which are rarely present in interstellar space, were found in cometary nuclei. These crystalline silicates are thought to have formed by annealing of amorphous silicate grains or direct condensation of gaseous materials near the Sun in the solar nebula (SN), and incorporated into cometary nuclei in the cold comet-forming region after radial transportation of grains in the SN. Abundances of the crystalline silicate dust grains were therefore expected to be smaller farther from the Sun. We aim to better understand the formation mechanism of minerals incorporated into comet 17P/Holmes based on its mineral abundances. To derive the mineral composition of comet 17P/Holmes, we applied a thermal emission model for cometary dust grains to mid-infrared spectra of comet 17P/Holmes taken with the Cooled Mid-Infrared Camera and Spectrograph mounted on the Subaru Telescope a few days later the great outburst in 2007 October. The resulting mass fraction of crystalline silicate, f cry, and an olivine-to-pyroxene abundance ratio, f OP, are f cry = 0.31 ± 0.03 and f OP = 1.20+0.16/−0.12, respectively. Based on a simple consideration of the mixing of dust grains originating in both the interstellar medium and SN, the minerals of 17P/Holmes formed by nonequilibrium condensation. This result is consistent with theoretical and experimental predictions for vaporization and condensation of olivine in the SN.

Propylene Oxide Formation on a Silica Surface with Peroxo Defects: Implications in Astrochemistry.

The formation of the chiral molecule propylene oxide (CH3CHCH2O) recently detected in the interstellar medium (ISM) is proposed to take place on an amorphous silicate grain surface where peroxo defects are present. A computational analysis conducted at the DFT and MP2-F12 levels of theory on a neat amorphous silica model supports such a hypothesis resulting in (a) strong thermodynamic driving forces and low activation energies allowing the synthesis of CH3CHCH2O at low temperatures, (b) chemical defects on silica surfaces promoting heterogeneous catalysis of the increasing molecular complexity found in interstellar and circumstellar medium, and (c) chemical defects that have implications on understanding how processing phases modify the nature of the reactive groups on a silica surface affecting the surface catalytic activity.

Temperature Programmed Desorption of Water Ice from the Surface of Amorphous Carbon and Silicate Grains as Related to Planet-forming Disks

Abstract Understanding the history and evolution of small bodies, such as dust grains and comets, in planet-forming disks is very important to reveal the architectural laws responsible for the creation of planetary systems. These small bodies in cold regions of the disks are typically considered to be mixtures of dust particles with molecular ices, where ices cover the surface of a dust core or are actually physically mixed with dust. While the first case, ice-on-dust, has been intensively studied in the laboratory in recent decades, the second case, ice-mixed-with-dust, presents uncharted territory. This work is the first laboratory study of the temperature-programmed desorption of water ice mixed with amorphous carbon and silicate grains. We show that the kinetics of desorption of H2O ice depends strongly on the dust/ice mass ratio, probably due to the desorption of water molecules from a large surface of fractal clusters composed of carbon or silicate grains. In addition, it is shown that water ice molecules are differently bound to silicate grains in contrast to carbon. The results provide a link between the structure and morphology of small cosmic bodies and the kinetics of desorption of water ice included in them.

Circumstellar dust, IR spectroscopy, and mineralogy

AbstractWe review the mineralogy of circumstellar dust grains around AGB stars as investigated through infrared spectroscopic studies. The expanding envelopes of AGB stars are chemically fresh because of the strong binding force of CO molecules. O-rich dust grains (silicates and oxides) form in O-rich envelopes and C-rich dust grains (amorphous carbon and SiC) form in C-rich envelopes. Amorphous silicate grains can be crystallized by annealing processes in various environments of AGB stars. We also discuss dust mineralogy for objects that have undergone chemical transition processes.

Outbursts of young Sun-like stars may change how terrestrial planets form

AbstractWhile the Sun is nowadays a quiet and well-balanced star, in its first few million years it might have been often out of temper, like those young low-mass stars which episodically undergo unpredictable outbursts. The prototype of one of the two classes of young erupting stars, EX Lupi, had its historically largest outburst in 2008. It brightened by a factor of 30 for six months, due to elevated accretion from the circumstellar disk on to the star. Our group observed the system during the outburst, and discovered the crystallisation of amorphous silicate grains in the inner disk by the heat of the outburst. Our mid-infrared monitoring of the freshly produced crystals revealed that their emission in the inner disk quickly dropped already within a year after the outburst. Here we report on new observations of the 10 µm silicate feature, obtained with the MIDI and VISIR instruments at Paranal Observatory, which demonstrate that within five years practically all forsterite disappeared from the inner disk. We attempt to model this process by an expanding wind that transports the crystals from the terrestrial zone to outer disk regions where comets are supposed to form. Since the eruptions of EX Lup are recurrent, we speculate that the early Sun also experienced similar brightenings, and the forming planetary system might have incorporated some of the mineralogical and chemical yields provided by the outbursts. EX Lup, as a proxy for the proto-Sun, may be a telltale object to understand the origin of molecules and minerals we routinely encounter on Earth.

Mid-infrared interferometric variability of DG Tauri: Implications for the inner-disk structure

Context. DG Tau is a low-mass pre-main sequence star, whose strongly accreting protoplanetary disk exhibits a so-far enigmatic behavior: its mid-infrared thermal emission is strongly time-variable, even turning the 10 $\mu$m silicate feature from emission to absorption temporarily. Aims. We look for the reason for the spectral variability at high spatial resolution and at multiple epochs. Methods. We study the temporal variability of the mid-infrared interferometric signal, observed with the VLTI/MIDI instrument at six epochs between 2011 and 2014. We fit a geometric disk model to the observed interferometric signal to obtain spatial information about the disk. We also model the mid-infrared spectra by template fitting to characterize the profile and time dependence of the silicate emission. We use physically motivated radiative transfer modeling to interpret the mid-infrared interferometric spectra. Results. The inner disk (r<1-3 au) spectra exhibit a 10 $\mu$m absorption feature related to amorphous silicate grains. The outer disk (r>1-3 au) spectra show a crystalline silicate feature in emission, similar to the spectra of comet Hale-Bopp. The striking difference between the inner and outer disk spectral feature is highly unusual among T Tauri stars. The mid-infrared variability is dominated by the outer disk. The strength of the silicate feature changed by more than a factor of two. Between 2011 and 2014 the half-light radius of the mid-infrared-emitting region decreased from 1.15 to 0.7 au. Conclusions. For the origin of the absorption we discuss four possible explanations: a cold obscuring envelope, an accretion heated inner disk, a temperature inversion on the disk surface and a misaligned inner geometry. The silicate emission in the outer disk can be explained by dusty material high above the disk plane, whose mass can change with time, possibly due to turbulence in the disk.

Physical Properties of the Very Young PN Hen3-1357 (Stingray Nebula) Based on Multiwavelength Observations

Abstract We carried out a detailed analysis of the interesting and important very young planetary nebula (PN) Hen3-1357 (Stingray Nebula) based on a unique data set of optical to far-IR spectra and photometric images. We calculated the abundances of nine elements using collisionally excited lines (CELs) and recombination lines (RLs). The RL C/O ratio indicates that this PN is O-rich, which is also supported by the detection of the broad 9/18 μm bands from amorphous silicate grains. The observed elemental abundances can be explained by asymptotic giant branch (AGB) nucleosynthesis models for initially 1–1.5 M ⊙ stars with Z = 0.008. The Ne overabundance might be due to the enhancement of 22Ne isotope in the He-rich intershell. Using the spectrum of the central star synthesized by Tlusty as the ionization/heating source of the PN, we constructed the self-consistent photoionization model with Cloudy to the observed quantities and derived the gas and dust masses, dust-to-gas mass ratio, and core mass of the central star. About 80% of the total dust mass is from warm–cold dust component beyond ionization front. Comparison with other Galactic PNe indicates that Hen3-1357 is an ordinary amorphous silicate-rich and O-rich gas PN. Among other studied PNe, IC4846 shows many similarities in properties of the PN to Hen3-1357, although their post-AGB evolution is quite different from each other. Further monitoring of observations and comparisons with other PNe such as IC4846 are necessary to understand the evolution of Hen3-1357.

SILICATE COMPOSITION OF THE INTERSTELLAR MEDIUM

ABSTRACT The composition of silicate dust in the diffuse interstellar medium and in protoplanetary disks around young stars informs our understanding of the processing and evolution of the dust grains leading up to planet formation. An analysis of the well-known 9.7 μm feature indicates that small amorphous silicate grains represent a significant fraction of interstellar dust and are also major components of protoplanetary disks. However, this feature is typically modeled assuming amorphous silicate dust of olivine and pyroxene stoichiometries. Here, we analyze interstellar dust with models of silicate dust that include non-stoichiometric amorphous silicate grains. Modeling the optical depth along lines of sight toward the extinguished objects Cyg OB2 No. 12 and ζ Ophiuchi, we find evidence for interstellar amorphous silicate dust with stoichiometry intermediate between olivine and pyroxene, which we simply refer to as “polivene.” Finally, we compare these results to models of silicate emission from the Trapezium and protoplanetary disks in Taurus.

Mantle formation, coagulation, and the origin of cloud/core shine

Context. The observed cloudshine and coreshine (C-shine) have been explained in terms of grain growth leading to enhanced scatter- ing from clouds in the J, H and K photometric bands and the Spitzer IRAC 3.6 and 4.5 {\mu}m bands. Aims. Using our global dust modelling approach THEMIS (The Heterogeneous dust Evolution Model at the IaS) we explore the effects of dust evolution in dense clouds, through aliphatic-rich carbonaceous mantle formation and grain-grain coagulation. Methods. We model the effects of wide band gap a-C:H mantle formation and the low-level aggregation of diffuse interstellar medium dust in the moderately-extinguished outer regions of molecular clouds. Results. The formation of wide band gap a-C:H mantles on amorphous silicate and amorphous carbon (a-C) grains leads to a decrease in their absorption cross-sections but no change in their scattering cross-sections at near-IR wavelengths, resulting in higher albedos. Conclusions. The evolution of dust, with increasing density and extinction in the diffuse to dense molecular cloud transition, through mantle formation and grain aggregation, appears to be a likely explanation for the observed C-shine.

GEMS-like material in the matrix of the Paris meteorite and the early stages of alteration of CM chondrites

The Paris meteorite is a weakly altered CM chondrite that has been discovered recently (Hewins et al., 2014). Its matrix offers the opportunity to search for well-preserved pristine pre-accretional material, as well as to study the earliest stages of aqueous alteration in the CM parent body. The study of the matrix of Paris has been conducted by analytical transmission electron microscopy on focused ion beam sections extracted from matrix areas showing different degrees of aqueous alteration.The least altered matrix sample consists of amorphous silicate grains, a few hundreds of nm in size, separated from one another by an abundant porosity. The amorphous silicates enclose numerous Fe-sulfide nanograins and their average composition is close to the chondritic composition. They share many similarities with GEMS (glass with embedded metal and sulfides) grains present in chondritic-porous interplanetary dust particles and with primitive type 3.0 carbonaceous chondrites. This first discovery of GEMS-like texture in a CM chondrite suggests that GEMS grains could have been the building blocks of the CM matrices.In more aqueously altered samples, pronounced microstructural heterogeneities were detected at the micrometer scale. The matrix consists mostly of a mixture of amorphous material and Fe-rich, spongy to fine-fibrous, poorly crystalline phyllosilicates. The porosity fraction is significantly reduced and the mixed amorphous-fibrous material frequently forms a continuous groundmass. The close association between these two material types suggests a replacement mechanism due to aqueous alteration. Chemical compositions correlate strongly with the microstructure. The amorphous material has a composition close to the chondritic value while the fine-fibrous phyllosilicate material is Fe-enriched. This Fe enrichment is found to be continuous from weakly to more heavily altered areas, in which the fibrous morphology is coarser and better crystalline. Cronstedtite with intercalated tochilinite is also found, but in pore spaces. This chemical evolution, concomitant with the maturation of the phyllosilicates, demonstrates that the early aqueous fluids that interacted with silicates in the matrix were enriched in Fe. This composition is probably the consequence of the preferential dissolution of metal and iron sulfides during the first stages of alteration. The enrichment of phyllosilicates in Mg seen in more altered CM chondrites is not observed in Paris.

Widespread oxidized and hydrated amorphous silicates in CR chondrites matrices: Implications for alteration conditions and H2 degassing of asteroids

The CR chondrites carry one of the most pristine records of the solar nebula materials that accreted to form planetesimals. They have experienced very variable degrees of aqueous alteration, ranging from incipient alteration in their matrices to the complete hydration of all of their components. In order to constrain their chemical alteration pathways and the conditions of alteration, we have investigated the mineralogy and Fe oxidation state of silicates in the matrices of 8 CR chondrites, from type 3 to type 1. Fe-L edge X-ray Absorption Near Edge Structure (XANES) was performed on matrix FIB sections using synchrotron-based scanning transmission X-ray microscopy (STXM). The Fe3+/∑Fe ratio of submicron silicate particles was obtained and coordinated with TEM observations.In all the least altered CR chondrites (QUE 99177, EET 87770, EET 92042, LAP 02342, GRA 95229 and Renazzo), we find that the matrices consist of abundant submicron Fe-rich hydrated amorphous silicate grains, mixed with nanometer-sized phyllosilicates. The Fe3+/∑Fe ratios of both amorphous and nanocrystalline regions are very high with values ranging from 68 to 78%. In the most altered samples (Al Rais and GRO 95577), fine-grained phyllosilicates also have a high Fe3+/∑Fe ratio (around 70%), whereas the coarse, micrometer-sized phyllosilicates are less oxidized (down to 55%) and have a lower iron content.These observations suggest the following sequence: submicron Fe2+-amorphous silicate particles were the building blocks of CR matrices; after accretion they were quickly hydrated and oxidized, leading to a metastable, amorphous gel-like phase. Nucleation and growth of crystalline phyllosilicates was kinetically-limited in most type 3 and 2 CRs, but increased as alteration became more extensive in Al Rais and GRO 95577. The decreasing Fe3+/∑Fe ratio is interpreted as a result of the transfer of Fe3+ from silicates to oxides during growth, while aqueous alteration progressed (higher temperature, longer duration, change of fluid composition). In a fully closed system, equilibrium thermodynamics suggest that the water to rock ratios, typically assumed to be low (<1) for chondrites, should primarily control the iron valency of the silicates and predict a lower Fe3+/∑Fe ratio. Such a high Fe3+/∑Fe value could be accounted for, however, if the system was partially open, at least with respect to H2 (and other gases as well). Rapid degassing of the fluid would have favored more oxidizing fluid conditions. Recently proposed scenarios involving some degree of water D/H increase through Rayleigh isotopic fractionation are supported by these results.

THE COMPOSITION OF INTERSTELLAR GRAINS TOWARD ζ OPHIUCHI: CONSTRAINING THE ELEMENTAL BUDGET NEAR THE DIFFUSE-DENSE CLOUD TRANSITION

We investigate the composition of interstellar grains along the line of sight toward Zeta Ophiuchi, a well-studied environment near the diffuse-dense cloud transition. A spectral decomposition analysis of the solid-state absorbers is performed using archival spectroscopic observations from the Spitzer Space Telescope and Infrared Space Observatory. We find strong evidence for the presence of sub-micron-sized amorphous silicate grains, principally comprised of olivine-like composition, with no convincing evidence of H2O ice mantles. However, tentative evidence for thick H2O ice mantles on large (a ~ 2.8 microns) grains is presented. Solid-state abundances of elemental Mg, Si, Fe, and O are inferred from our analysis and compared to standard reference abundances. We find that nearly all of elemental Mg and Si along the line of sight are present in amorphous silicate grains, while a substantial fraction of elemental Fe resides in compounds other than silicates. Moreover, we find that the total abundance of elemental O is largely inconsistent with the adopted reference abundances, indicating that as much as ~156 ppm of interstellar O is missing along the line of sight. After taking into account additional limits on the abundance of elemental O in other O-bearing solids, we conclude that any missing reservoir of elemental O must reside on large grains that are nearly opaque to infrared radiation.