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Micrometeorites, a possible major source of Earth’s water, are thought to form from explosive dispersal of hydrated chondritic materials during impact events on their parental asteroids. However, this provenance and formation mechanism have yet to be directly confirmed using asteroid returned samples. Here, we report evidence of mild shock metamorphism in the surface particles of asteroid Ryugu based on electron microscopy. All particles are dominated by phyllosilicates but lack dehydration textures, which are indicative of shock-heating temperatures below ~500 °C. Microfault-like textures associated with extensively shock-deformed framboidal magnetites and a high-pressure polymorph of Fe–Cr–sulfide have been identified. These findings indicate that the average peak pressure was ~2 GPa. The vast majority of ejecta formed during impact on Ryugu-like asteroids would be hydrated materials, larger than a millimetre, originating far from the impact point. These characteristics are inconsistent with current micrometeorite production models, and consequently, a new formation mechanism is required., 小惑星リュウグウ粒子の微小断層から読み解く天体衝突. 京都大学プレスリリース. 2023-04-24.

Volatile components are abundant in carbonaceous asteroids and can be important tracers for the evolution of asteroid surfaces interacting with the space environment, but their behavior on airless surfaces is poorly understood. Samples from the C-type carbonaceous asteroid Ryugu show dehydration of phyllosilicate, indicating ongoing surface modifications on the aqueously-altered asteroid. Here we report the analysis of Ryugu samples showing selective liberation of carbon, oxygen, and sulfur from iron-rich oxide, sulfide, and carbonate, which are major products of aqueous alteration. These mineral surfaces are decomposed to metallic iron, iron nitride, and magnesium-iron oxide. The modifications are most likely caused by solar wind implantation and micrometeorite impacts and are distinct indicators of surface space exposure over 103 years. Nitridation of metallic iron may require micrometeorites rich in solid nitrogen compounds, which implies that the amount of nitrogen available for planetary formation in the inner solar system is larger than previously recognized.

Minerals are solid state nuclear track detectors - nuclear recoils in a mineral leave latent damage to the crystal structure. Depending on the mineral and its temperature, the damage features are retained in the material from minutes (in low-melting point materials such as salts at a few hundred degrees C) to timescales much larger than the 4.5 Gyr-age of the Solar System (in refractory materials at room temperature). The damage features from the $O(50)$ MeV fission fragments left by spontaneous fission of $^{238}$U and other heavy unstable isotopes have long been used for fission track dating of geological samples. Laboratory studies have demonstrated the readout of defects caused by nuclear recoils with energies as small as $O(1)$ keV. This whitepaper discusses a wide range of possible applications of minerals as detectors for $E_R \gtrsim O(1)$ keV nuclear recoils: Using natural minerals, one could use the damage features accumulated over $O(10)$ Myr$-O(1)$ Gyr to measure astrophysical neutrino fluxes (from the Sun, supernovae, or cosmic rays interacting with the atmosphere) as well as search for Dark Matter. Using signals accumulated over months to few-years timescales in laboratory-manufactured minerals, one could measure reactor neutrinos or use them as Dark Matter detectors, potentially with directional sensitivity. Research groups in Europe, Asia, and America have started developing microscopy techniques to read out the $O(1) - O(100)$ nm damage features in crystals left by $O(0.1) - O(100)$ keV nuclear recoils. We report on the status and plans of these programs. The research program towards the realization of such detectors is highly interdisciplinary, combining geoscience, material science, applied and fundamental physics with techniques from quantum information and Artificial Intelligence., Comment: 115 pages, many pictures of tracks. Please see the source file for higher resolution versions of some plots. v2: matches the published version

Minerals on airless bodies exhibit characteristic spectral features such as darkening and reddening. Such space weathering is mainly due to hydrogen-ion irradiation by the solar wind and to micrometeorite impacts. Because of the reactivity of hydrogen, the associated H-implantation into O-bearing minerals can lead to the formation of new chemical bonds and may contribute to formation of water. However, laboratory studies still conflict about production efficiency of water and relevant H-bearing molecules such as OH formed by the H-ion irradiation. The production efficiency of the molecules within minerals may be influenced by short-range structural order of the host minerals. It is thus important to clarify how the implanted H interacts with various irradiation defects produced by H-ion bombardment. Here, we investigated H-ion-irradiated alumina (Al2O3), one of the most basic oxides, using scanning/transmission electron microscopy (S/TEM) and electron energy-loss spectroscopy (EELS). The TEM images revealed dense dislocations, nanoscale voids and nanoscale cracks—instead of amorphization—in the region subject to high energy deposition. Our analyses by STEM–EELS hyperspectral imaging (HSI) isolated a few essential spectral components, suggesting that chemical interactions between the implanted H and the host alumina resulted in local generation of OH species rather than amorphization. We also found a spectral feature which may be explained by H2 gas, presumably remaining in the nanovoids, most of which escaped through fractures formed by the coalescence of the high-pressure H2 nanobubbles. Such fractures/crack surfaces can act as additional reactive sites for the formation of the OH species. The present results strongly imply that H+ irradiation can be a source of water in minerals in various astrophysical conditions. The present methodology can be applied to a wide range of extraterrestrial materials, such as regolith grains, interplanetary-dust particles, and/or presolar grains in primitive meteorites.

Amorphous silicates, abundant in primitive carbonaceous chondrites, are among the most primitive materials from the early Solar System. They show evidence of some aqueous alteration in the meteorite parent bodies, but it is not clear how this highly reactive material changed at an early stage after contact with water. Herein, we report in-situ experiments on the aqueous alteration of amorphous silicate nanoparticles (typically 70 nm in diameter); we used two different compositions that are similar to forsterite (MgO/SiO2 = 2.02) and enstatite (MgO/SiO2 = 1.15) in the simple MgO–SiO2 system to understand basic reaction principles at the onset of the aqueous alteration. The experiments were performed in pure water at room temperature using X-ray diffraction (XRD), transmission electron microscopy (TEM), and pH measurements. The in-situ TEM images of the nanoparticles—in particular those with the forsterite composition—gradually became difficult to recognize in water. The pH value of the water also increased with time, suggesting that preferential Mg2+ dissolution occurred from the amorphous silicates right after mixing with water. The in-situ XRD patterns showed that magnesium silicate hydrate (M-S-H), which is a poorly crystalline phase like a phyllosilicate, newly appeared. The M-S-H seems to have been formed via a dissolution–precipitation process. Its formation rate from amorphous silicates was considerably higher than from crystalline silicates, because amorphous silicates are highly metastable and have high solubility in water. M-S-H formation from the forsterite composition, which has a highly unstable amorphous structure, is ten times faster than from the enstatite composition. The M-S-Hs show string-like or tiny fragmental textures in the final dried products that are very similar to those observed in the matrices of some primitive carbonaceous chondrites. M-S-H would have been the initial product formed in the aqueous alteration of amorphous silicates in the meteorites; thus, it is an important tracer of early aqueous activity at low temperatures in the early Solar System. By comparing the in-situ observations with those obtained after drying the experimental samples, we found two types of M-S-Hs: epigenetic M-S-Hs—which have a slightly Si-rich composition—formed during drying, and syngenetic M-S-Hs formed by in-situ alteration. Carbonaceous chondrites may also contain these two types of hydrous silicates, and this should be investigated to understand the conditions for aqueous alteration in the early Solar System in more detail. The present study clearly showed the importance of Mg/Si ratio in the precursor materials, although the actual chondrites are in more complicated multi-component system. Future experiments based on the present results can extend the investigation to the system containing Fe, S, and other components as in carbonaceous chondrites.

Base-metal sulfides (BMSs) are minerals that host platinum-group elements (PGE) in mantle peridotites and significantly control the bulk PGE content. They have been investigated in detail down to the sub-micrometer scale to elucidate PGE behavior in the Earth's interior. Base-metal sulfides are supposedly subjected to supergene and seawater weathering, leading to the redistribution of PGEs at low temperatures. Careful and thorough measurements of BMSs are thus required to elucidate PGE behavior in the Earth's interior. In the present study, a sub-micrometer-sized PGE-bearing sulfide inclusion in a clinopyroxene crystal in a harzburgite xenolith from Tahiti (Society Islands, French Polynesia) was investigated in detail (down to the sub-micrometer scale) using transmission electron microscopy with energy-dispersive X-ray spectroscopy (TEM-EDS). The sulfide inclusion is of carbonatitic metasomatic origin, as it is enveloped by carbonaceous glass, and forms a planar inclusion array with other PGE-bearing sulfide inclusions. The following sulfide phases were identified using TEM-EDS: Fe- and Ni-rich monosulfide solid solutions (MSSs), Fe- and Ni-rich pentlandite, sugakiite, heazlewoodite, chalcopyrite, and Cu-Ir-Pt-Rh-thiospinel (cuproiridsite–malanite–cuprorhodsite). We established the formation process of the metasomatic PGE-bearing sulfide inclusion by considering morphological and mineral characteristics in addition to the chemical composition. A primary MSS first crystallized from metasomatic sulfide melt at ca. 1000 °C, followed by the crystallization of an intermediate solid solution (ISS) below 900 °C. A high-form (high-temperature origin) Fe-rich pentlandite simultaneously crystallized with the primary MSS below ca. 850 °C and recrystallized into a low-form (low-temperature origin) Fe-rich pentlandite below ca. 600 °C. The primary MSS decomposed to Fe- and Ni-rich MSSs, low-form Ni-rich pentlandite, sugakiite, and heazlewoodite. The ISS decomposed to chalcopyrite below ca. 600 °C. Meanwhile, a Cu-Ir-Pt-Rh-thiospinel crystallized directly from the evolved Cu-rich sulfide melt below ca. 760 °C. Thus, Ir, Pt, and Rh preferentially partitioned into the melt phase during the crystallization process of the metasomatic sulfide melt. Metasomatic sulfide melts could be a significant medium for the transport and condensation of Pt together with Ir and Rh during the fractionation process in the Earth's interior. We hypothesize that the compositional variability of PGEs in carbonatites is due to the separation of sulfide melt leading to the loss of PGEs in the carbonatitic melts.

Deformed polycrystalline rocks show various crystallographic textures reflecting their imposed deformation histories. However, the textures of ultrafine grains, which are in the submicrometer to nanometer order, may be overlooked depending on the analytical technique used. Thus, we report the first application of transmission Kikuchi diffraction (TKD), which is capable of high-spatial-resolution crystallographic texture analysis, to a fine-grained ultramylonitic peridotite sample in a scanning electron microscope. We successfully obtained TKD maps with an effective spatial resolution of ~ 80 nm and with highly reliable indexing using a conventional W-filament scanning electron microscope with a standard electron backscattered diffraction (EBSD) system. Olivine grains, which were clearly visualized by TKD, were slightly elongated in a direction subparallel to the macroscopic lineation texture. Their shapes were nonuniform with serrated grain boundaries, strongly indicating that the sample has been deformed dominantly by dislocation activity, even though the grain size is in the order of several micrometers or smaller. The combined TKD–transmission electron microscope (TEM) analysis indicated that a slip-system transition from the [100] slip to the [001] slip might have occurred, although the crystals’ preferred orientation patterns were not completely overwritten. The transition might have been sufficiently affected by water infiltration, high differential stress, or both along the transform fault. Thus, TKD efficiently analyzed the crystallographic textures and characterized the subgrain boundaries of polycrystalline rocks consisting of submicrometer-order grains. Moreover, combining the EBSD, TKD, and TEM methods allowed us to perform multiscale analyses of the crystallographic textures of ultrafine-grained deformed rocks, seamlessly linking the millimeter- to nanometer-order scales.

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.

Platinum-group elements (PGEs) are one of the key tracers to reveal early differentiation processes of the Earth due to their preferential distribution into the metallic core. Meanwhile, informative evidence for early differentiation has been greatly disturbed through metasomatic PGE disturbance, which has been demonstrated through a number of PGE data for natural mantle peridotites as well as base-metal sulfide and platinum group mineral grains therein. The mechanism and process of metasomatic PGE mobilization should be investigated in detail for an appropriate estimation of PGE abundance in the primitive upper mantle. However, this has not yet been achieved, because sub-micrometer-scale ( i.e. scale of less than a micrometer) descriptions for metasomatic effects imprinted in the mantle peridotites have not been sufficiently recorded. Here, we report a sub-micrometer-sized sulfide–glass inclusion array in a Tahitian harzburgite xenolith. The textural and chemical characteristics were disclosed with employing synchrotron X-ray and transmission electron microscope analyses. The results demonstrate that the sulfide and glass contain appreciable amounts of PGE (9.7 at.% Ir, 4.3 at.% Rh and 5.8 at.% Pt) and carbon (21.2 at.% C), respectively. The sulfide–glass inclusion array is hosted in sodium-enriched clinopyroxene (up to 1.8 wt% Na 2 O) that shows vein-like distribution and partly replaces orthopyroxene. Primitive mantle-normalized trace-element patterns of the clinopyroxene show a general increase from heavy rare-earth elements (REEs) to light REEs with negative anomalies in Pb and high-field-strength elements such as Zr, Hf and Ti, which indicate equilibration with Mg-rich carbonatitic melt. These results suggest that Na-bearing Mg-rich carbonatitic melts were involved in the harzburgite formation and that Ir, Rh and Pt were mobilized through carbonatitic metasomatism and eventually distributed in the sulfides.

High-resolution synchrotron powder X-ray diffraction (XRD) experiments were conducted to clarify the transformation of sillimanite to mullite (mullitization) and determine the mullitization temperature (Tc). We were able to distinguish sillimanite and mullite in the XRD patterns, despite their very similar crystallographic parameters, and to detect the appearance of small mullite peaks among sillimanite peaks. Analysis of the Johnson–Mehl–Avrami (JMA) equation for mullitization ratio (ζ) revealed that at temperatures T ≥1240°C the mullitization had the same kinetics. The activation energy E at T ≥1240°C obtained from the Arrhenius plot was 679.8 kJ mol−1. In analysis using a time–temperature–transformation diagram for mullitization, a mullitization curve of ζ = 1% can be described as $$\hbox{ln } t=({{1}\over{n}}) \hbox{ ln }\hbox{ln} \left( {{1}\over{1-\zeta}} \right)- \hbox{ln }{{k}_{0}}+A/[RT{{\left( T-{{T}_{c}} \right)}^{2}}]+{{E}_{A}}/RT$$ where t is time, n is a reaction-mechanism-dependent parameter determined as 0.324 by JMA-analysis, k0 is the frequency factor, EA is the activation energy for atomic diffusion, and $A/{\left( {{T_c} - T} \right)^2}$. represents the activation energy for nucleation. The results of fitting the data to this equation were Tc = 1199°C, A = 3.9 × 106 kJ mol−1 K−2, EA = 605 kJ mol−1, and k0 = 3.65 × 1015. We conclude that the boundary between sillimanite and mullite + SiO2 in the phase diagram is ~1200°C. This article is protected by copyright. All rights reserved.

The stabilization of coesite is a diagnostic indicator of ultrahigh-pressure metamorphism and in many cases it implies that a rock has been subducted to a minimum depth of 80 km. Coesite typically occurs as rare relicts in rigid host minerals, but most commonly transforms into α-quartz pseudomorphs during exhumation. The abundance of coesite-bearing rocks in orogens worldwide is a contentious issue in the petrological community, despite evidence from numerical modeling that suggests that coesite formation should be a common geological process during ultrahigh-pressure metamorphism. This knowledge gap must be addressed to improve the understanding of the geological aspects of subduction-zone geodynamics. Here we report that minuscule coesites (

Mid-infrared spectroscopic observations of oxygen-rich asymptotic giant branch (AGB) stars show the common presence of dust species that have a broad feature at ∼11–12 μm. Chemically synthesized amorphous alumina (Al2O3) is widely accepted as the source of this emission, although it is not obvious that amorphous alumina can condense in circumstellar conditions. We performed condensation experiments of Al–Si–Mg–O and Mg–Al–O gases using induction thermal plasma systems, in which small particles condense from vapors with a steep temperature gradient. The condensates were analyzed using X-ray diffraction and Fourier transform infrared spectroscopy, and observed with a transmission electron microscope. The condensed nanoparticles from the Al and O gases were transition aluminas based on face-centered cubic (fcc) packed oxygen (δ- and λ-alumina, and an unknown phase). The fcc oxygen frameworks were maintained in the condensed alumina containing small amounts of Mg and Si. Condensates from the gases of Al:Mg = 99:1 and 95:5 had δ- and γ-alumina structures. Particles with λ- and γ-alumina structures formed from starting materials of Al:Si = 9:1 and Al:Si:Mg = 8:1:1, respectively. Amorphous silica-rich particles condensed from gases of Al/(Si+Al) μm broad emission of alumina-rich stars is not amorphous alumina, but is transition alumina containing ∼10% Si.