Linking cause and effect: Nanoscale vibrational spectroscopy of space weathering from asteroid Ryugu

Airless bodies are subjected to space-weathering effects that modify the first few microns of their surface. Therefore, understanding their impact on the optical properties of asteroids is key to the interpretation of their color variability and infrared reflectance observations. The recent Hayabusa2 sample return mission to asteroid Ryugu offers the first opportunity to study these effects, in the case of the most abundant spectral type among the main-asteroid belt, C-type objects. This study employs vibrational electron energy-loss spectroscopy in the transmission electron microscope to achieve the spatial resolution required to measure the distinct mid-infrared spectral signature of Ryugu's space-weathered surface. The comparison with the spectrum of the pristine underlying matrix reveals the loss of structural -OH and C-rich components in the space-weathered layers, providing direct experimental evidence that exposure to the space environment tends to mask the optical signatures of phyllosilicates and carbonaceous matter. Our findings should contribute to rectifying potential underestimations of water and carbon content of C-type asteroids when studied through remote sensing with new-generation telescopes.The Hayabusa2 project has been developed and led by JAXA in collaboration with Deutsches Zentrum für Luft- und Raumfahrt (DLR) and Centre national d'études spatiales (CNES), and supported by NASA and Australian Space Agency (ASA). We thank all the members of the Hayabusa2 project for their technical and scientific contributions. This work was carried out on the electron microscopy facility of the Advanced Characterization Platform of the Chevreul Institute, University of Lille—CNRS. This project has been funded by ISITE ULNE and the "Métropole Européenne de Lille" through the "TEM-Aster project," the LARCAS ANR (Reference No. SAN-22199). It has also been funded by in part by the National Agency for Research (ANR) under the program of future investment TEMPOS-CHROMATEM (Reference No. ANR-10-EQPX-50). Micro-infrared spectroscopy was performed at the Institut de Planétologie et d'Astrophysique de Grenoble (IPAG). European Union's Horizon 2020 research and innovation program under grant Agreements No. 823717 (ESTEEM3). The Chevreul Institute is thanked for its help in the development of this work through the CHEMACT project supported by the "Ministère de l'Enseignement Supérieur de la Recherche et de l'Innovation," the region "Hauts-de-France" and the "Métropole Européenne de Lille." JSPS KAKENHI grant numbers related to this study are 19H00725, 19K0094, and 21H05424. This research was supported by the H2020 European Research Council (ERC) (SOLARYS ERC-CoG2017-771691). We acknowledge the funding by the Spanish University Ministry and Next Generation EU through a Margarita Salas fellowship.Peer reviewe

Linking Cause and Effect: Nanoscale Vibrational Spectroscopy of Space Weathering from Asteroid Ryugu

Airless bodies are subjected to space-weathering effects that modify the first few microns of their surface. Therefore, understanding their impact on the optical properties of asteroids is key to the interpretation of their color variability and infrared reflectance observations. The recent Hayabusa2 sample return mission to asteroid Ryugu offers the first opportunity to study these effects, in the case of the most abundant spectral type among the main-asteroid belt, C-type objects. This study employs vibrational electron energy-loss spectroscopy in the transmission electron microscope to achieve the spatial resolution required to measure the distinct mid-infrared spectral signature of Ryugu's space-weathered surface. The comparison with the spectrum of the pristine underlying matrix reveals the loss of structural -OH and C-rich components in the space-weathered layers, providing direct experimental evidence that exposure to the space environment tends to mask the optical signatures of phyllosilicates and carbonaceous matter. Our findings should contribute to rectifying potential underestimations of water and carbon content of C-type asteroids when studied through remote sensing with new-generation telescopes

Four‐dimensional‐STEM analysis of the phyllosilicate‐rich matrix of Ryugu samples

Ryugu asteroid grains brought back to the Earth by the Hayabusa2 space mission are pristine samples containing hydrated minerals and organic compounds. Here, we investigate the mineralogy of their phyllosilicate-rich matrix with four-dimensional scanning transmission electron microscopy (4D-STEM). We have identified and mapped the mineral phases at the nanometer scale (serpentine, smectite, pyrrhotite), observed the presence of Ni-bearing pyrrhotite, and identified the serpentine polymorph as lizardite, in agreement with the reported aqueous alteration history of Ryugu. Furthermore, we have mapped the d-spacings of smectite and observed a broad distribution of values, ranging from 1 to 2 nm, with an average d-spacing of 1.24 nm, indicating significant heterogeneity within the sample. Such d-spacing variability could be the result of either the presence of organic matter trapped in the interlayers or the influence of various geochemical conditions at the submicrometer scale, suggestive of a range of organic compounds and/or changes in smectite crystal chemistry

Hydroxy interlayer minerals of soils : structural characterization using X-ray diffraction profile modeling and determination of formation mechanisms by experimental approach

Le processus d'aluminisation dans les sols acides, conduit à la formation de minéraux argileux hydroxy-alumineux (HIMs). La fixation d'aluminium dans l'espace interfoliaire diminue la réactivité des feuillets expansibles (feuillets HI). La caractérisation des HIMs issus d'un Alocrisol a été réalisée par modélisation des diffractogrammes de rayons X (raies 00l) de la fraction <2 µm et de ses sous-fractions (<0.05, 0.05-0.1, 0.1-0.2 et 0.2-2 µm). Cette étude a montré que les HIMs sont des minéraux interstratifiés à deux ou trois types de feuillets (HI, illites et/ou expansibles). La proportion relative de feuillets HI par rapport à celle des feuillets expansibles diminue avec la taille des particules. La persistance de feuillets illitiques a été observée dans la fraction fine (<0.05 µm). Afin de tester l’effet de la taille des particules sur l'aluminisation, des expériences d'auto-aluminisation de vermiculites saturées K ou Ca séparées en trois fractions (0.1-0.2, 1 2 et 10-20 µm) ont été tentées. Toutes montrent l'importance du couple taille-cation interfoliaire sur le contrôle de l'échange et de la dissolution qui sont les processus de premier ordre pour l'aluminisation. C'est dans les expériences mettant en jeu les K vermiculites que la compétition entre ces deux processus conduit à la formation de minéraux interstratifiés aluminisés à trois composantes similaires à ceux identifiés dans les sols. L'effet de la taille des particules se marque par la persistance de feuillets illitiques comme cela avait été observé dans les fractions infra-micrométriques des sols. La compétition entre échange et dissolution sont donc très probablement le moteur des évolutions minérales dans les sols.The aluminization process of clay minerals in acidic soils, leads to the formation of hydroxyl interlayered minerals (HIMs). It decreases the reactivity of the clay fraction by the fixation of aluminium in the interlayer space of expandable layers (HI). The characterization of HIMs from an Alocrisol was investigated through X-Ray Diffraction profile modeling (00l reflections) of the <2 µm size fraction and its sub-fractions (<0.05, 0.05-0.1, 0.1-0.2 and 0.2-2 µm). The results obtained highlight the mixed layer structure of HIMs which is composed of two or three different layers (HI, illites and/or expendables). The relative proportion of HI layers compared to that of expandable ones decreases with the particle size. In addition, the persistence of illite layers has been observed in the <0.05 µm size fraction. Auto aluminization experiments of K-or Ca- vermiculite separated in three-sized fraction (0.1-0.2, 1-2 and 10-20 µm) have been conducted in order to test the influence of the particle size on the aluminization process. These experiments exhibit the key role played both by the interlayer cation and the particle size on the cationic exchange and the crystal dissolution. The competition between of ion-exchange reactions and that of mineral dissolution on the K-vermiculite experiment, leads to the formation of 3 component MLMs (HI, illite and expandable) similar to those found in acidic soils. A similar effect of particle size leading to the persistence of illite layers was observed between the experiment products and the infra-micrometric particles of soils. Consequently, it is highly probable that both cation exchange and dissolution are the main processes governing the mineral evolutions in soils

Minéraux argileux aluminisés des sols : caractérisation structurale par modélisation des diffractogrammes de rayons X et détermination des mécanismes de formation par approche expérimentale.

The aluminization process of clay minerals in acidic soils, leads to the formation of hydroxyl interlayered minerals (HIMs). It decreases the reactivity of the clay fraction by the fixation of aluminium in the interlayer space of expandable layers (HI). The characterization of HIMs from an Alocrisol was investigated through X-Ray Diffraction profile modeling (00l reflections) of the <2 µm size fraction and its sub-fractions (<0.05, 0.05-0.1, 0.1-0.2 and 0.2-2 µm). The results obtained highlight the mixed layer structure of HIMs which is composed of two or three different layers (HI, illites and/or expendables). The relative proportion of HI layers compared to that of expandable ones decreases with the particle size. In addition, the persistence of illite layers has been observed in the <0.05 µm size fraction. Auto aluminization experiments of K-or Ca- vermiculite separated in three-sized fraction (0.1-0.2, 1-2 and 10-20 µm) have been conducted in order to test the influence of the particle size on the aluminization process. These experiments exhibit the key role played both by the interlayer cation and the particle size on the cationic exchange and the crystal dissolution. The competition between of ion-exchange reactions and that of mineral dissolution on the K-vermiculite experiment, leads to the formation of 3 component MLMs (HI, illite and expandable) similar to those found in acidic soils. A similar effect of particle size leading to the persistence of illite layers was observed between the experiment products and the infra-micrometric particles of soils. Consequently, it is highly probable that both cation exchange and dissolution are the main processes governing the mineral evolutions in soils.Le processus d’aluminisation dans les sols acides, conduit à la formation de minéraux argileux hydroxy-alumineux (HIMs). La fixation d’aluminium dans l’espace interfoliaire diminue la réactivité des feuillets expansibles (feuillets HI). La caractérisation des HIMs issus d’un Alocrisol a été réalisée par modélisation des diffractogrammes de rayons X (raies 00l) de la fraction <2 µm et de ses sous-fractions (<0.05, 0.05-0.1, 0.1-0.2 et 0.2-2 µm). Cette étude a montré que les HIMs sont des minéraux interstratifiés à deux ou trois types de feuillets (HI, illites et/ou expansibles). La proportion relative de feuillets HI par rapport à celle des feuillets expansibles diminue avec la taille des particules. La persistance de feuillets illitiques a été observée dans la fraction fine (<0.05 µm). Afin de tester l’effet de la taille des particules sur l’aluminisation, des expériences d’auto-aluminisation de vermiculites saturées K ou Ca séparées en trois fractions (0.1-0.2, 1 2 et 10-20 µm) ont été tentées. Toutes montrent l’importance du couple taille-cation interfoliaire sur le contrôle de l’échange et de la dissolution qui sont les processus de premier ordre pour l’aluminisation. C’est dans les expériences mettant en jeu les K-vermiculites que la compétition entre ces deux processus conduit à la formation de minéraux interstratifiés aluminisés à trois composantes similaires à ceux identifiés dans les sols. L’effet de la taille des particules se marque par la persistance de feuillets illitiques comme cela avait été observé dans les fractions infra-micrométriques des sols. La compétition entre échange et dissolution sont donc très probablement le moteur des évolutions minérales dans les sols

Experimental reproduction of the martian weathering profiles argues for a dense Noachian CO&lt;sub&gt;2&lt;/sub&gt; atmosphere

On Mars, mineral sequences have been detected and they are composed of a top layer of Al-rich clay minerals, then (Al, Fe)-rich clay minerals and a bottom layer composed of (Mg, Fe)-rich clay minerals. By analogy with Earth, such sequences are interpreted as weathering profiles formed by the interaction of acidic solutions in equilibrium with the atmosphere and the parent rock. Thus, understanding of the aqueous solution composition leading to the above mineral description allows deciphering the atmosphere composition. We designed an experimental column system with three levels containing powdered basaltic rock to test the influence of different acidic fluids on the mineralogical formation. Five solutions were used: H2SO4 and HCl at pH 3 in equilibrium with N2 atmosphere, pure water in equilibrium with 0.1 and 1 atmospheric pressure CO2 leading to pH values of 3.9 and 4.4, respectively and a H2SO4 solution at pH 3 in equilibrium with 0.1 atmospheric pressure CO2 leading to a pH value of 2.98. The results obtained show that the content of Al-rich clay minerals and the evolution from Al, (Al, Fe) to (Fe, Mg)-rich clay minerals formed are better reproduced with an originally high pCO2. Hence, we suggest that acidic alteration driven by a dense CO2 atmosphere reproduced better the observed martian weathering profiles. The experiments involving CO2 led to the formation of carbonates. Their identification by near infrared (NIR) detection methods is challenged, because the laboratory NIR spectra acquired on the experimental products show that: (i) the absorption bands related to carbonates are very weak, and (ii) the strongest feature at 3.95 μm is beyond the CRISM NIR range. Such carbonate formation is consistent with the recent carbonate detection at a planetary scale in weathering profiles, which goes toward that the weathering profiles could have been formed under a dense CO2-rich atmosphere as suggested also by climatic models

Hydrothermalisme expérimental en conditions martiennes : La matière organique structure l’assemblage minéral

International audienc

Hydrothermalisme expérimental d’assemblages organo-minéralogiques,

International audienc

Hydrothermalisme expérimental d’assemblages organo-minéralogiques

International audienc