Si-rich Glass Research Articles

Copper-Bearing Magnetite and Delafossite in Copper Smelter Slags

The cooling paths and kinetics in the system Cu-Fe-O are investigated by the empirical micro- and nanoscale analysis of slags from the flash furnace smelter at Olympic Dam, South Australia. We aim to constrain the exsolution mechanism of delafossite (Cu1+Fe3+O2) from a spinel solid solution (magnetite, Fe3O4) and understand why cuprospinel (CuFe2O4) is never observed, even though, as a species isostructural with magnetite, it might be expected to form. Flash furnace slags produced in the direct-to-blister copper smelter at Olympic Dam contain four Cu-bearing phases: Cu-bearing magnetite, delafossite, metallic copper, and cuprite. Delafossite coexists with magnetite as rims and lamellar exsolutions, as well as bladed aggregates, associated with cuprite within Si-rich glass. The empirical compositions of magnetite and rim delafossite are (Fe2+6.89Cu2+0.86Co0.13Mg0.15Si0.02)8.05 (Fe3+15.52Al0.41Ti0.01Cr0.01)15.95O32, and (Cu1+0.993Co0.002Mg0.002)0.997(Fe3+0.957Al0.027Ti0.005Si0.004)0.993O2, respectively. The measured Cu content of magnetite represents a combination of a solid solution (~6 mol.% cuprospinel endmember) and exsolved delafossite lamellae. Atomic-resolution high-angle annular dark field scanning transmission electron microscope (HAADF STEM) imaging shows epitaxial relationships between delafossite lamellae and host magnetite. Defects promoting the formation of copper nanoparticles towards the lamellae margins suggest rapid kinetics. Dynamic crystallization under locally induced stress in a supercooled system (glass) is recognized from misorientation lamellae in delafossite formed outside magnetite grains. The observations are concordant with crystallization during the cooling of molten slag from 1300 °C to <1080 °C. Melt separation through an immiscibility gap below the solvus in the system Cu-Fe-O is invoked to form the two distinct delafossite associations: (i) melt-1 from which magnetite + delafossite form; and (ii) melt-2 from which delafossite + cuprite form. Such a path also corroborates the published data explaining the lack of cuprospinel as a discrete phase in the slag. Delafossite rims form on magnetite at a peritectic temperature of ~1150 °C via a reaction between the magnetite and copper incorporated in the oxide/Si-rich melt. The confirmation of such a reaction is supported by the observed misfit orientation (~10°) between the rim delafossite and magnetite. HAADF STEM imaging represents a hitherto underutilized tool for understanding pyrometallurgical processes, and offers a direct visualization of phase relationships at the smallest scale that can complement both experimental approaches and theoretical studies based on thermodynamic modelling.

First Terrestrial Occurrence of Kaitianite (Ti3+2Ti4+O5) from the Upper Mantle beneath Mount Carmel, Israel

Our nanomineralogical investigation of melt inclusions in corundum xenoliths from the Mount Carmel area, Israel, has revealed seven IMA-approved new minerals since 2021. We report here the first terrestrial occurrence of kaitianite (Ti3+2Ti4+O5). Kaitianite occurs as exsolution lamellae in tistarite (Ti2O3), in a melt inclusions together with a Ti,Al,Zr-oxide, a MgTi3+2Al4SiO12 phase, spinel, sapphirine, Ti-sulfide, alabandite, and Si-rich glass in a corundum grain (Grain 1125C2). The chemical composition of kaitianite using electron probe microanalysis is (wt%) Ti2O3 58.04, TiO2 37.82, Al2O3 2.87, MgO 0.85, ZrO2 0.10, CaO 0.02, SiO2 0.02, sum 99.73, yielding an empirical formula of (Ti3+1.78Al0.12Ti4+0.05Mg0.05)(Ti4+1.00)O5, with the Ti3+ and Ti4+ partitioned, assuming a stoichiometry of three cations and five oxygen anions pfu. Electron back-scatter diffraction reveals that kaitianite has the monoclinic C2/c γ-Ti3O5-type structure with cell parameters: a = 10.12 Å, b = 5.07 Å, c = 7.18 Å, β = 112°, V = 342 Å3, and Z = 4. Kaitianite is a high-temperature oxide phase, formed in melt pockets under reduced conditions in corundum-aggregate xenoliths derived from the upper mantle beneath Mount Carmel, Israel.

Microstructure evolution and thermal shock properties of PEO coatings on a TiAl alloy

In this paper, plasma electrolytic oxidation (PEO) coatings were produced on Ti-48Al-2Cr-2Nb alloy in a silicate electrolyte. During the PEO process, four coating growth stages were revealed, which were anodic oxidation (I), breakdown of the anodized film (II), micro-arcing growth (III) and formation of glass phase with coating fusing (IV). It was found that the porous aluminium silicate phase preferentially grew at the Ti3Al regions of the substrate in stage II and the amount of Al2TiO5 phase increased rapidly in stage III. In stage IV, a Si-rich glass phase layer grew rapidly leading to a large increase in coating thickness. The thermal shock tests were conducted for both the substrate and PEO-coated samples from 1123 K to room temperature. The thermal shock resistance study showed that the oxide layer kept growing with the thermal shock cycles on the uncoated TiAl substrate. PEO coatings with predominate Al2TiO5 and aluminium silicate phases can withstand 55 thermal shock cycles without changing. The samples with a thin amorphous anodized layer cannot withstand the internal stress generated during thermal shock cycles due to the weak bond between the outmost layer and the substrate. The coating with thick glass outmost layer also peeled off because of the weak thermal shock resistance of the glass phase. The wear test results showed that, after thermal shock cycles, the PEO coating with suitable thickness and roughness has good wear resistance and potential application in wear protection.

Silica-rich melts originating from melt-hydrated peridotite reactions

Interactions between melts and hydrated peridotite may control production of silica-rich melts, fluids and magmas in the upper mantle and may be predominant mechanism for producing felsic crust in shallow ultramafic settings of rocky planets. This research investigated composition of olivine-hosted mineral, melt and multi-phase inclusions in dunite xenoliths from the 1800–1801 Kaupulehu flow of Hualalai Volcano. The host olivine (forsterite Fo 82–89 , mol. %) appears with mineral inclusions of crystalline chromite having compositions similar to those found in alkaline series rocks. Abundant silica-rich glasses (SiO 2 = 63 ± 2.9 wt%, Al 2 O 3 = 21 ± 1.2 wt%; K 2 O = 4.3 ± 0.5 wt%, Na 2 O = 3.6 ± 0.7 wt%, 38 analyses) found in the olivine-hosted melt and multiphase inclusions are interpreted as quenched silicate liquids entrapped due to nephelinite melt percolation in hydrated harzburgite in the presence of free aqueous fluid at pressures of 0.7 to 0.1 GPa and a melt-to-peridotite mass ratio of 0.2 to 0.3. This work also re-interprets the metasomatic origin of global examples of silica-rich glass inclusions in peridotite xenolith minerals according to results from recent experiments on melt-hydrated peridotite interaction processes. As a planetary process, production of silica-rich melts and fluids within series of associated magmas and their crystallized differentiates can occur due to reaction of primitive mafic (e.g., ocean island basalt, OIB) melts with hydrated peridotite (or serpentinite) in the presence of aqueous fluids at pressures below 1 GPa. • Si-rich glasses are produced due to reaction of mafic melts with hydrated peridotite.

Tridymite in a lacustrine mudstone in Gale Crater, Mars: Evidence for an explosive silicic eruption during the Hesperian

The unexpected detection of ∼16 wt.% monoclinic tridymite, a high-temperature silica polymorph, within an otherwise lacustrine mudstone in Gale crater, Mars raises significant questions about its formation and the extent of magmatic evolution on that planet. The rock sample, analyzed by the X-ray diffractometer onboard the Curiosity rover, also contained feldspar, cristobalite, and opaline silica (±Si-glass). Monoclinic tridymite is extremely rare on Earth, and has only been discovered in silicic volcanic environments, high-temperature impact settings, and extraterrestrial rocks. We review the most common formation pathways of natural tridymite and run thermodynamical models to investigate possible formation mechanisms. We consider the broader context of the sample to propose a formation and transport mechanism based on: (1) the mineralogical assemblage of the mudstone and rocks in the vicinity, (2) the composition of the mudstone layer, and (3) the overall geological context. Based on the large amount of tridymite, the high SiO2 and low Al2O3 concentration of the mudstone, and the low temperature context within distal lacustrine mudstone, we propose that an explosive eruption released Si-rich ashes, which were deposited into Gale crater's watershed as a tridymite-rich ashfall along with cristobalite, feldspar, Ti-oxide, and Si-rich glass, when Gale was still a lake (Hesperian). The dissolution of Si-rich glass and mineral sorting during transport would have concentrated tridymite, caused opaline silica precipitation, and relatively lowered the Al2O3 concentration. This scenario implies that explosive volcanism on Mars occurred during the Hesperian and might not be restricted to basaltic eruptions, revealing the complexity of Mars magmatism.

Cesium immobilization in porous silica and [formula omitted]Cs self-heating simulations

The interest to immobilize 137Cs can pursue different aims. When it is separated from spent nuclear fuels, it is possible to reduce the thermal loading of the host glass and increase the waste loading capacity of the matrix. Also, the separated 137Cs can be used to produce radioactive sealed sources useful in industrial and medical applications. If reprocessing is not envisaged after the generation of electrical energy, the spent nuclear fuel is the most important radioactive waste generated in the nuclear fuel cycle. In this case, aqueous solutions obtained from the chemical dissolution of spent nuclear fuels are high-level wastes. Short-lived fission products, such as 90Sr and 137Cs, constitute the main source of heat generation from beta decay, causing self-heating of the glassy matrix. It is well known that vitrification is the main used technology, capable to immobilize these wastes during hundreds of years generating a waste form with proved structural stability, thermal shock resistance, and high chemical durability. In this article we present in an analogous way the immobilization of an specific amount of stable cesium in a porous Si-rich glass matrix through adsorption and sintering. Sintering requires lower temperature than that required in immobilization by melting. The leaching behavior of the waste form obtained was studied from the procedure described by the MCC-1 test method. Considering 137Cs only for simulations, this work also includes the thermal evolution calculation of a simulated silica glass block loaded with 2 wt.% of 137Cs.

Metallic-Pb nanospheres in zircon from the Challenger Au deposit, South Australia: probing metamorphic and ore formation histories

AbstractAncient metamorphic processes are recorded by the formation of metallic-Pb nanospheres in zircon, a product of internal Pb mobilisation and thermally driven concentration. Here, metallic-Pb nanospheres formed within an ore deposit are characterised for the first time using high-angle annular dark field scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy element-distribution mapping. Exceptional examples from the migmatite-hosted Archean–Paleoproterozoic Challenger Au deposit (Central Gawler Craton, South Australia) support widespread metallic-Pb nanosphere formation in zircon from rocks experiencing granulite-facies metamorphism. We also report new trace-element associations found with metallic-Pb nanospheres and a new mode of occurrence, in which Sc ‘haloes’ form adjacent to metallic-Pb nanospheres within the crystalline zircon lattice. This differs to previously characterised examples of metallic-Pb nanospheres associated with amorphous Si-rich glasses and unidentified Al–Ti, or Fe-bearing phases. Multiple modes of metallic-Pb nanosphere occurrences and trace-element associations suggests multiple modes of formation, probably dependant on zircon composition and metamorphic conditions. Identification of metallic-Pb nanospheres in a growing range of geological settings further highlights the mobility of Pb in zircon and the importance of detailed, nanoscale mineral characterisation, in order to constrain accurate geochronological histories for rocks within high-temperature geological environments.

Silicate Liquid Immiscibility as a Result of Fenner-Type Crystal Fractionation of Wangtian’e Tholeiitic Melts, Northeast China

The results of a study of mineral-hosted melt inclusions were used to reconstruct the evolution of tholeiitic melts that produced the rocks of the shield edifice of Wangtian’e volcano, Northeast China, including the P–T parameters of their crystallization. Primary melt inclusions were studied in plagioclase of tholeiitic basalts. They contain “dry” Fe-rich silicate glass or a crystallized fine-grained mineral aggregate, feldspar rim, and globules of various compositions: water-bearing Fe-rich globules, water-bearing Si-rich globules and “dry” Si-rich globules. In the groundmass of tholeiitic basalts, “dry” Si-rich and Fe-rich glasses, as well as hydrated Fe-rich glass with an H2O content of up to 10–15 wt.% were identified. The fractional crystallization path of Wangtian’e tholeiitic melts was calculated by the COMAGMAT-5.2.2 software using glass compositions of homogenized melt inclusions in plagioclase from the basalts. It was shown that the calculated temperatures of the beginning of plagioclase crystallization are in good agreement with temperatures obtained in thermometric experiments with melt inclusions in plagioclase, and correspond to 1180–1200°C. Based on our studies, several stages of the melt differentiation during the formation of Wangtian’e volcanic rocks were identified. The first stage includes the Fenner-type crystal fractionation of the melt due to the appearance of plagioclase on the liquidus at the beginning of magma crystallization. The separation of the ferrobasaltic melt into Si-rich and Fe-rich silicate immiscible liquids (“dry” and hydrated) corresponds to the second stage of differentiation. The occurrence of silicate liquid immiscibility follows from the presence of Fe-rich and Si-rich glasses in the intergranular space of the basalts and in the melt inclusions in plagioclase of these rocks.

In situ synthesis of melt-grown mullite ceramics using directed laser deposition

While mullite is a significant oxide ceramic material, its current preparation process has many limitations such as complicated process, low efficiency, and high cost. In this paper, directed laser deposition (DLD) was used to prepare mullite ceramics directly using α-Al2O3 and SiO2 powder as raw materials. The phase composition, microstructure, and primary defects of prepared samples were investigated by XRD, Raman spectroscopy, and SEM/EDS. Vickers indentation and three-point bending experiments were used to evaluate mechanical properties. The results showed that microstructure was mainly composed of a mullite crystal phase and Si-rich glass phase. It is shown that mullite ceramics were successfully synthesized in situ during the DLD process with the use of Al2O3 and SiO2 powder. Morphology of mullite crystal inside cylindrical sample was particular “tabular cellular,” which transformed into “rod cellular” at the edge. Two mullite crystals were arranged along deposition direction basically, surrounded by the Si-rich glass phase. The defects included pores with various sizes and crack, in which large pores were mainly distributed at the edge of the sample, and small pores were throughout the section. The crack was distributed in the center of the sample and spread to the edge. Mechanical properties test showed flexural strength, microhardness, and fracture toughness were 62.8 ± 30.3 MPa, 12.7 ± 0.34 GPa, and 1.84 ± 0.14 MPa·m1/2, respectively. It is considered that pores and crack were responsible for poor mechanical properties. This research is expected to provide a new option for the rapid preparation of mullite ceramics.

Effect of in situ SiC and MoSi2 phases on the oxidation behavior of HfB2-based composites

Monolithic HfB2 and HfB2-15vol%SiC-15vol%MoSi2 composite samples were oxidized by a conventional electric furnace at 1700 °C for 5 h. Microstructural and phase analysis of the oxidized samples were performed by X-ray diffraction (XRD) analysis and field emission scanning electron microscope (FESEM) equipped with energy-dispersive spectroscopy (EDS). Besides, for analyzing the oxidation mechanism of the samples, thermodynamic calculations were also accomplished by HSC software. The changes in weight and thickness of the oxide scale were measured and the oxide growth rate of the oxidized samples was subsequently calculated. The results showed that HfB2-15vol%SiC-15vol%MoSi2 composite was much more resisted than that monolithic HfB2 due to the formation of a thin Si-rich glass layer on the surface of the composite sample. By acting to fill the porosities between HfO2 grains, Si-based glass phase enhanced the oxidation resistance of HfB2-15vol%SiC-15vol%MoSi2 composite. Conversely, the oxidized monolithic HfB2 had only a thick porous oxide layer (HfO2) which led to considerably lower oxidation resistance. On the other side, three layers containing HfO2 and Si-based glass phases were formed on the oxidized HfB2-15vol%SiC-15vol%MoSi2 composite. Moreover, no porosities and no porous layers were also detected on the oxidized composite sample. Consequently, HfB2-15vol%SiC-15vol%MoSi2 composite had a parabolic behavior owing to its diffusion-controlled oxidation under the isothermal oxidation process.

High-temperature structural change and microtexture formation of sillimanite and its phase relation with mullite

Abstract Synchrotron powder X-ray diffraction (XRD) experiments and transmission electron microscopy (TEM) observations of heat-treated sillimanite at various pressures were conducted to clarify the detailed phase relation between sillimanite and mullite. Under TEM, heat-treated sillimanite frequently showed anti-phase boundary (APB)-like textures with a displacement vector of ½[001]sil. Additional scanning TEM energy-dispersive X-ray spectroscopy analysis of regions with APB-like texture showed that they were clearly enriched in Al and accompanied by very fine, Si-rich glass inclusions, which indicates that the APB-like textures are composed of fine mullite. Moreover, synchrotron XRD patterns of these samples clearly showed double peaks of newly formed mullite and remnant sillimanite, indicating that the compositional transformation from sillimanite to mullite and glass is discontinuous. We separately determined the cell parameters of the sillimanite and mullite from the XRD pattern and found that the b axial length of the sillimanite increased with the treatment temperature, reflecting disordering of tetrahedral Al and Si in the sillimanite. In contrast, the positions of the deconvoluted mullite peaks indicated that the a axial length of mullite decreased as experimental pressure increased, owing to enrichment of the Si component. By projecting the cell parameters onto the a–b axial plane, the detailed changes in the crystallographic state of the sillimanite and mullite could be easily and comprehensively identified. On the basis of our results, we propose a new P-T diagram for the Al2SiO5 system that shows the transformation boundary between sillimanite and mullite + SiO2-rich melt and the contour of the Al/Si order parameter of sillimanite.

The Influence of Glass Composition on Iodine Solubility

AbstractTwo glass series in the ternary systems K2O-B2O3-SiO2 (KBS) and Na2O-B2O3-SiO2 (NBS) were studied in order to identify the main factors influencing the solubility of iodine. We established that iodine incorporation is strongly linked to the bulk chemistry, i.e. the SiO2/(B2O3+SiO2) molar ratio, and to the physical properties of the glasses, and we assessed three different solubility limits. Iodine in Si-rich glasses has a low solubility (≤1 mol% I) regardless of the alkali ion present. On the contrary, in B-rich glasses, the solubility is five times higher than in Si-rich glasses for Na-glasses, and more than six times higher for K-glasses. The strong dependence of iodine solubility on the bulk chemistry is related to the adaptability of the glass network. Furthermore, our data suggest that iodine is stable with different redox states in the glasses here analyzed.

Metallic Pb nanospheres in ultra-high temperature metamorphosed zircon from southern India

A transmission electron microscope (TEM) study of Paleoproterozoic zircon that has experienced ultra-high temperature (UHT) metamorphism at ca. 570 Ma in the Kerala Khondalite Belt (KKB), southern India, documents the occurrence of metallic Pb nanospheres. These results permit comparison with a previous report from UHT zircon in Enderby Land, Antarctica, and allow further constraints to be placed on possible mechanisms for nanosphere formation. As in Enderby Land, the nanospheres in the KKB occur in non-metamict zircon, emphasising that radiogenic Pb redistribution can occur with only partial interconnectivity of radiation damaged zircon. In contrast, the nanospheres reported here are not closely associated with Si-rich glass inclusions, which is inconsistent with a silicate liquid-metal immiscibility model proposed in the earlier study. Formation of these Pb nanospheres effectively halts Pb-loss from zircon, even under extreme conditions, and can adversely affect geochronological interpretations due to decoupling of Pb from U.

A magmatic origin for silica-rich glass inclusions hosted in porphyritic magnesian olivines in chondrules: An experimental study

Rare silica-rich glass inclusions (69<SiO2<82wt.%) are described within magnesian olivines of porphyritic Type IA chondrules. These glass inclusion compositions are clearly out of equilibrium with their host Mg-olivines and their presence within the olivines is generally attributed to an unclear secondary process such as a late interaction with nebular gases. We performed dynamic crystallisation experiments that demonstrate that these Si-rich glass inclusions are actually magmatic in origin and were trapped inside olivines that crystallized slowly from a magma with a CI, i.e. solar, composition. Their silica-rich compositions are the consequence of the small volumes of inclusions, which inhibit the nucleation of secondary crystalline phase (Ca-poor pyroxene) but allow olivine to continue to crystallize metastably on the walls of the inclusions. We suggest that Si-rich glass inclusions could be the only reliable relicts of what were the first magmas of the solar system, exhibiting a CI, i.e. non-fractionated, composition.

Silicic lunar volcanism: Testing the crustal melting model

Lunar silicic rocks were first identified by granitic fragments found in samples brought to Earth by the Apollo missions, followed by the discovery of silicic domes on the lunar surface through remote sensing. Although these silicic lithologies are thought to make up a small portion of the lunar crust, their presence indicates that lunar crustal evolution is more complex than originally thought. Models currently used to describe the formation of silicic lithologies on the Moon include in situ differentiation of a magma, magma differentiation with silicate liquid immiscibility, and partial melting of the crust. This study focuses on testing a crustal melting model through partial melting experiments on compositions representing lithologies spatially associated with the silicic domes. The experiments were guided by the results of modeling melting temperatures and residual melt compositions of possible protoliths for lunar silicic rocks using the thermodynamic modeling software, rhyolite-MELTS. Rhyolite-MELTS simulations predict liquidus temperatures of 950–1040 °C for lunar granites under anhydrous conditions, which guided the temperature range for the experiments. Monzogabbro, alkali gabbronorite, and KREEP basalt were identified as potential protoliths due to their ages, locations on the Moon (i.e., located near observed silicic domes), chemically evolved compositions, and the results from rhyolite-MELTS modeling. Partial melting experiments, using mixtures of reagent grade oxide powders representing bulk rock compositions of these rock types, were carried out at atmospheric pressure over the temperature range of 900–1100 °C. Because all lunar granite samples and remotely sensed domes have an elevated abundance of Th, some of the mixtures were doped with Th to observe its partitioning behavior. Run products show that at temperatures of 1050 and 1100 °C, melts of the three protoliths are not silicic in nature (i.e., they have <63 wt% SiO2). By 1000 °C, melts of both monzogabbro and alkali gabbronorite approach the composition of granite, but are also characterized by immiscible Si-rich and Fe-rich liquids. Furthermore, Th strongly partitions into the Fe-rich, and not the Si-rich glass in all experimental runs. Our work provides important constraints on the mechanism of silicic melt formation on the Moon. The observed high-Th content of lunar granite is difficult to explain by silicate liquid immiscibility, because through this process, Th is not fractionated into the Si-rich phase. Results of our experiments and modeling suggests that silicic lunar rocks could be produced from monzogabbro and alkali gabbronorite protoliths by partial melting at T < 1000 °C. Additionally, we speculate that at higher pressures ( P ≥ 0.005 GPa), the observed immiscibility in the partial melting experiments would be suppressed.

Impact-generated carbonate melts in the Talemzane impact structure (Laghouat, Algeria)

The 1750-m-diameter, bowl-shaped Talemzane impact structure in Algeria is emplaced in Senonian or Eocene flint-bearing limestones. Field studies reveal a thin layer of light-colored polymict breccia with rounded, dark inclusions beneath a limestone megablock zone located at the top of the crater rim. The matrix of the rounded, dark inclusions consists of Si-rich glass and microcrystalline calcite. The latter is characterized by high contents of Si and Al suggesting rapid crystallization of the calcite from a melt. Backscattered electron imagery shows textural evidence for liquid immiscibility between the CaCO3-rich and Si-rich glass of the matrix in the form of intermingling of calcite with Si-rich glass, coalesced blebs within silicate glass, individual calcite blebs within Si-rich glass, carbonate spherical globules in fresh Si-rich-glass, and sharp menisci between silicate and calcite blebs. These features are interpreted as evidence of impact melting of limestone and flint. The low totals of the Si-Al-Mg-rich glasses suggest that they contain significant amounts of volatiles. X-ray diffraction analyses indicate partial alteration of the Si-Mg-Al-rich glass to phyllosilicates.

In situ structural analysis of calcium aluminosilicate glasses under high pressure

In situ micro-Raman spectroscopy was used to investigate the structural evolution of OH−-free calcium aluminosilicate glasses, under high pressure and at room temperature. Evaluation was made of the role of the SiO2 concentration in percalcic join systems, for Al/(Al + Si) in the approximate range from 0.9 to 0.2. Under high pressure, the intensity of the main band related to the bending mode of bridging oxygen ([T-O-T], where T = Si or Al) decreased gradually, suggesting that the bonds were severely altered or even destroyed. In Si-rich glasses, compression induced a transformation of Qn species to Qn−1. In the case of Al-rich glass, the Al in the smallest Qn units evolved from tetrahedral to higher-coordinated Al ([5]Al and [6]Al). Permanent structural changes were observed in samples recovered from the highest pressure of around 15 GPa and, particularly for Si-rich samples, the recovered structure showed an increase of three-membered rings in the Si/Al tetrahedral network.

Mineralogy and noble gas isotopes of micrometeorites collected from Antarctic snow

We have investigated seven micrometeorites (MMs) from Antarctic snow collected in 2003 and 2010 by means of electron microscopy, X-ray diffraction, micro-Raman spectroscopy, transmission electron microscopy (TEM) observation, and noble-gas isotope analysis. Isotopic ratios of He and Ne indicate that the noble gases in these MMs are mostly of solar wind (SW). Based on the release patterns of SW 4He, which should reflect the degree of heating during atmospheric entry, the seven MMs were classified into three types including two least heated, three moderately heated, and two severely heated MMs. The heating degrees are well correlated to their mineralogical features determined by TEM observation. One of the least heated MMs is composed of phyllosilicates, whereas the other consists of anhydrous minerals within which solar flare tracks were observed. The two severely heated MMs show clear evidence of atmospheric heating such as partial melt of the uppermost surface layer in one and abundant patches of dendritic magnetite and Si-rich glass within an olivine grain in the other. It is noteworthy that a moderately heated MM composed of a single crystal of olivine has a 3He/4He ratio of 8.44 × 10−4, which is higher than the SW value of 4.64 × 10−4, but does not show a cosmogenic 21Ne signature such as 20Ne/21Ne/22Ne = 12.83/0.0284/1. The isotopic compositions of He and Ne in this sample cannot be explained by mixing of a galactic cosmic ray (GCR)-produced component and SW gases. The high 3He/4He ratio without cosmogenic 21Ne signature likely indicates the presence of a 3He-enriched component derived from solar energetic particles.

Xenopumice erupted on 15 October 2011 offshore of El Hierro (Canary Islands): a subvolcanic snapshot of magmatic, hydrothermal and pyrometamorphic processes

On 15 October 2011, a submarine eruption offshore of El Hierro Island gave rise to floating volcanic products, known as xenopumices, i.e., pumiceous xenoliths partly mingled and coated with the juvenile basanitic magma. Over the last few years, no consensus in the scientific community in explaining the origin of these products has been reached. In order to better understand the formation of xenopumice, we present a textural, mineralogical, and geochemical study of the possible magmatic, hydrothermal, and pyrometamorphic processes, which usually operate in the plumbing systems of active volcanoes. We carried out a comprehensive SEM investigation and Sr-Nd-Pb isotope analyses on some samples representative of three different xenopumice facies. All the data were compared with previous studies, new data for El Hierro extrusives and a literature dataset of Canary Islands igneous and sedimentary rocks. In the investigated xenopumices, we emphasize the presence of restitic magmatic phases as well as crystallization of minerals (mainly olivine + pyroxene + magnetite aggregates) as pseudomorphs after pre-existing mafic phenocrysts, providing evidence of pyrometamorphism induced by the high-T juvenile basanitic magma. In addition, we identify veins consisting of zircon + REE-oxides + mullite associated with Si-rich glass and hydrothermal quartz, which indicate the fundamental role played by hydrothermal fluid circulation in the xenopumice protolith. The petrological data agree with a pre-syneruptive formation of the xenopumice, when El Hierro basanite magma intruded hydrothermally altered trachyandesite to trachyte rocks and triggered local partial melting. Therefore, the El Hierro xenopumice represents a snapshot of the transient processes at the magma-wall rock interface, which normally occurs in the feeding system of active volcanoes.

Control of Si-rich region inside a sodalime glass by parallel femtosecond laser focusing at multiple spots

Thermal modification and elemental distributions inside a sodalime glass were modified by parallel irradiation with focused 250 and 1 kHz femtosecond laser pulses at multiple spots. We found that the shape of a Si distribution was modified and the position of a Si-rich layer depended on the relative focal positions between 250 and 1 kHz laser pulses. We demonstrated the formation of a ribbon-shaped Si-rich glass of about 8 μm thickness and about 33 μm width by producing a line of a Si-rich layer by translating a glass sample perpendicular to the laser propagation axis. In addition, we simulated transient temperature distribution during laser exposure and discussed the role of 1 kHz laser irradiation in the modulation of elemental distributions.