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Raman spectroscopy of Ryugu particles and their extracted residues: Fluorescence background characteristics and similarities to CI chondrites

We present here an investigation of Ryugu particles recovered by the Hayabusa2 space mission and their extracted carbonaceous acid residues using Raman spectroscopy. Raman parameters of Ryugu intact grains and their acid residues are characterized by broad D (defect induced) and G (graphite) band widths, indicating the presence of polyaromatic carbonaceous matter with low thermal maturity. Raman spectra of Ryugu particles and CI (type 1) chondrites exhibit stronger laser-induced fluorescence backgrounds compared to Type 2 and Type 3 carbonaceous chondrites. The high fluorescence signatures and wide bandwidths of the D and G bands of Ryugu intact grains are similar to the Raman spectra observed in CI chondrites, reflecting the low structural order of their aromatic carbonaceous matter, and strengthening the link between Ryugu particles and CI chondrites. The high fluorescence background intensity of the Ryugu particles is due to multiple causes, but it is likely that the relative abundance of geometry-bearing macromolecular organic matter in total organic carbon contents makes a large contribution to the fluorescence intensities. Locally observed high fluorescence in the acid-extracted residues of Ryugu is due to nitrogen-bearing outlier phase. The high fluorescence signature is one consequence of the low degree of thermal maturity of the organic matter and supports evidence that the Ryugu particles have escaped significant parent body thermal metamorphism.

Ryugu particles↗

I-Xe Dating of Aqueous Alteration in the CI Chondrite Orgueil: I. Magnetite and Ferromagnetic Separates

The I-Xe system was studied in a ferromagnetic sample separated from the Orgueil CI carbonaceous chondrite with a hand-held magnet and in two magnetite samples, one chemically separated before and the other one after neutron irradiation. This work was done in order to investigate the effects of chemical separation by LiCl and NaOH on the I-Xe system in magnetite. Our test demonstrated that the chemical separation of magnetite before irradiation using either LiCl or NaOH, or both, does not contaminate the sample with iodine and thus cannot lead to erroneous I-Xe ages due to introduction of uncor-related128*Xe. The I-Xe ages of two Orgueil magnetite samples are mutually consistent within experimental uncertainties and, when normalized to an absolute time scale with the reevaluated Shallowater aubrite standard, place the onset of aqueous alteration on the CI parent body at 4564.3 ± 0.3 Ma, 2.9 ± 0.3 Ma after formation of the CV Ca-AI-rich inclusions (CAIs). The I-Xe age ofthe ferromagnetic Orgueil separate is 3.4 Ma younger, corresponding to a closure of the I-Xe system at 4560.9 ± 0.2 Ma. These and previously published I-Xe data for Orgueil (Hohenberg et al., 2000) indicate that aqueous alteration on the CI parent body lasted for at least 5 Ma. Although the two magnetite samples gave indistinguishable I-Xe ages, their temperature release profiles differed. One of the two Orgueil magnetites released less radiogenic Xe than the other, 80% of it corresponding to the low-temperature peak of the release profile, compared to only 6% in case of the second Orgueil magnetite sample. This could be due to the difference in iodine trapping efficiencies for magnetite grains of different morphologies. Alternatively, the magnetite grains with the lower radiogenic Xe concentrations may have formed at a later stage of alteration when iodine in an aqueous solution was depleted.

I-Xe systematics↗

Oxygen isotope evidence from Ryugu samples for early water delivery to Earth by CI chondrites

The delivery of water to the inner Solar System, including Earth, is still a debated topic. A preferential role for hydrated asteroids in this process is supported by isotopic measurements. Carbonaceous chondrite (CC) meteorites represent our main source of information about these volatile-rich asteroids. However, the destruction of weaker materials during atmospheric entry creates a bias in our CC data. The return of surface materials from the C-type asteroid 162173 Ryugu by the Hayabusa2 spacecraft provides a unique opportunity to study high-porosity, low-density, primitive materials, unrepresented in the meteorite record. We measured the bulk oxygen isotope composition from four Ryugu particles and show that they most closely resemble the rare CI (CC Ivuna-type) chondrites, but with some differences that we attribute to the terrestrial contamination of the CI meteorites. We suggest that CI-related material is widespread among carbonaceous asteroids and a more important source of Earth’s water and other volatiles than its limited presence in our meteoritic collection indicates.

58 GEOSCIENCES↗

Application of an alkylammonium method for characterization of phyllosilicates in CI chondrites

Many meteorites and interplanetary dust particles (IDP's) with primitive compositions contain significant amounts of phyllosilicates, which are generally interpreted as evidence of protoplanetary aqueous alteration at an early period in the solar system. These meteorites are chondrites of the carbonaceous and ordinary varieties. Characterization of phyllosilicates in these materials is important because of the important physico-chemical information they hold, e.g., from well characterized phyllosilicates, thermodynamic stability relations and hence the conditions of formation of phyllosilicates in the parent body of the meteorite can be predicted. Although we are at a rudimentary level of understanding of the minerals resulting from the aqueous alteration in the early solar nebula, we know that the most common phyllosilicates present in chondritic extraterrestrial materials are serpentines, smectites, chlorites, and micas. The characterization of fine grained minerals in meteorites and IDP's rely heavily on electron beam instruments, especially transmission electron microscopy (TEM). Typically, phyllosilicates are identified by a combination of high resolution imaging of basal spacings, electron diffraction analysis, and chemical analysis. Smectites can be difficult to differentiate from micas because the smectites loose their interlayer water and the interlayers collapse to the same basal spacing as mica in the high vacuum of the TEM. In high-resolution TEM (HRTEM) images, smectite basal spacings vary from 1 nm up to 1.5 nm, while micas show 1 or 2 nm basal spacings. Not only is it difficult to differentiate smectites from micas, but there is no way of identifying different classes of smectites in meteorites and IDP's. To differentiate smectites from micas and also to recognize the charge differences among smectites, an alkylammonium method can be employed because the basal spacings of alkylammonium saturated smectites expand as a function of alkylamine chain length and the layer-charge density of the 2:1 expanding phyllosilicate, and the final product is significantly more stable under electron beam examination. Such a method was tested on standard clays and several meteorite samples using four alkylammonium salts.

Golden, D. C.↗

Bright Stuff on Ceres = Sulfates and Carbonates on CI Chondrites

Recent reports of the DAWN spacecraft's observations of the surface of Ceres indicate that there are bright areas, which can be explained by large amounts of the Mg sulfate hexahydrate (MgSO4•6(H2O)), although the identification appears tenuous. There are preliminary indications that water is being evolved from these bright areas, and some have inferred that these might be sites of contemporary hydro-volcanism. A heat source for such modern activity is not obvious, given the small size of Ceres, lack of any tidal forces from nearby giant planets, probable age and presumed bulk composition. We contend that observations of chondritic materials in the lab shed light on the nature of the bright spots on Ceres

Zolensky, Michael↗

CI chondrite-like clasts in the Nilpena polymict ureilite - Implications for aqueous alteration processes in CI chondrites

Petrographic studies of Nilpena polymict ureilite have revealed the presence of small quantities of carbonaceous chondrite matrix clasts. Detailed electron microprobe and TEM studies show that the chemistry and fine-scale mineralogy of one of these clasts is consistent with CI carbonaceous chondrite matrix. Compared to Orgeuil, the phyllosilicate, sulfide, and oxide mineralogy suggests that the Nilpena clasts may represent a less altered type of CI matrix. It is suggested that increased oxidation and aqueous alteration of Nilpena-type materials could result in the formation of the type of mineral assemblage observed in Orgueil. Increased alteration produces progressive more Mg-rich phyllosilicates and more Fe(3+)-rich iron oxides, such as ferrihydrite. As a function of increased alteration, Ca is also progressively leached from the matrix material to form carbonate veins. The depletion of Ca in CI chondrite matrices suggests the Ivuna and Alais may be intermediate in their degree of alteration to Nilpena and Orgueil.

Brearley, Adrian J.↗

Fractionation of moderately volatile elements in ordinary chondrites

The CI chondrites are the most volatile-rich meteorites. Relative to the CI chondrites, the ordinary chondrites have lower abundances of refractory and volatile elements. Four types of fractionations are summarized in a table. Ordinary-chondrite/CI abundance ratios for moderately volatile elements in H- and L-group chondrites are presented in a graph. Possible explanations for the observed relations are considered, giving attention to several processes which could result in the separation of nebular solids and gases.

Wasson, J. T.↗

The Effects of Thermal Metamorphism on the Amino Acid Content of the CI-Like Chondrite Y-86029

Carbonaceous chondrites con-tain a diverse suite of amino acids that varies in abundance and structural diversity depending on the degree of aqueous alteration and thermal histo-ry that the parent body experienced [1 - 3]. We recently determined the amino acid contents of several fragments of the Sutter's Mill CM2 chon-drite [4]. In contrast with most other CM2 chon-drites, the Sutter's Mill meteorites showed minimal evidence for the presence of indigenous amino acids. A notable difference between the Sutter's Mill meteorites and other CM2 chondrites are that the Sutter's Mill stones were heated to tempera-tures of 150 - 400 C [4], whereas most other CM2 chondrites do not show evidence for thermal met-amorphism [5]. Because empirical studies have shown that amino acids rapidly degrade in aqueous solutions above 150 C and the presence of miner-als accelerates this degradation [6], a plausible explanation for the lack of amino acids observed in the Sutter's Mill meteorites is that they were destroyed during metamorphic alteration. Fewer CI chondrites have been analyzed for amino acids because only a small number of these meteorites have been recovered. Nevertheless, indigenous amino acids have been reported in the CI chondrites Ivuna and Orgueil [7]. Here we report on the amino acid analysis of the CI-like chondrite, Yamato 86029 (Y-86029; sample size of 110 mg). Just as the Sutter's Mill meteorites were thermally metamporphosed CM2 chondrites, Y-86029 has experienced thermal metamorphism at higher temperatures than Orgueil and Ivuna (normal CI chondrites) experienced, possibly up to 600 C [8].

Burton, A. S.↗

Nuclear track and compositional studies of olivines in CI and CM chondrites

The CI and CM chondrites, with bulk chemical compositions closely resembling solar values, are important for the study of early solar system processes. Noble gas and particle track studies have revealed that a majority of the CI and CM chondrites contain precompaction solar wind and solar flare irradiation records. A quantitative understanding of these records is important because it would allow constraints to be placed on the environment in which the irradiation occurred, and, therefore, on the mode of evolution of the CI and CM chondrites. The present investigation is concerned primarily with fossil track evidence, taking into account selected specimens of several CI and CM chondrites. In addition, the results are presented of extensive studies of the angular distributions of tracks in irradiated grains from four CM chondrites. The results provide information on the exposure geometry of the grains.

Goswami, J. N.↗

Constraints on the surface materials of Ryugu from spectral and water analysis of experimentally-heated CI carbonaceous chondrite

We performed heating experiments of the Orgueil CI chondrite in vacuum conditions at fO2 around I/W to evaluate systematic changes in mineralogy, water contents, and visible to infrared spectral features. Our goal is to interpret the spectra of Ryugu, the target C asteroid of the Hayabusa2 mission, because Ryugu shows spectral features similar to partially dehydrated carbonaceous chondrites. However heated carbonaceous chondrites can be easily contaminated by terrestrial water, which makes it almost impossible for laboratory data to be compared with spectra of asteroids directly. Therefore, our heated samples were analyzed without exposure to the air after experimental heating to minimize the effects of terrestrial water. The depth of the 2.7-µm absorption band and the water content of the heated Orgueil form a positive correlation trend which follows the results of experimental heating of CM and Tagish Lake meteorites using our experimental procedures. It is found that 500-°C heated Orgueil sample shows the best spectral match with Ryugu in terms of the low reflectance (~2%) at visible wavelengths and a weak absorption (~10%) at around 2.72 µm owing to survival of Mg-rich phyllosilicates. We suggest that Ryugu might have experienced heating and dehydration at a temperature around 500 °C, after aqueous alteration, and presently contains a small quantity of hydrated minerals equivalent to 1-2 wt.% of water at the surface.

K. Amano↗

Metamorphosed CM and CI Carbonaceous Chondrites Could Be from the Breakup of the Same Earth-crossing Asteroid

Far from being the relatively unprocessed materials they were once believed to be, we now know that a significant number of carbonaceous chondrites were thermally metamorphosed on their parent asteroid(s). Numerous studies indicate that 7 "CM" and 2 "CI" chondrites have been naturally heated, variously, at from 400 to over 700 C on their parent asteroid(s). Petrographic textures reveal that this thermal metamorphism occurred after the dominant aqueous alteration phase, although some meteorites show evidence of a heating event between two aqueous alteration episodes, i.e. pro- and retrograde aqueous alteration. Aside from the issues of the identification of the transient heat source, timing of metamorphism, and the relation of these materials (if any) to conventional CM and CI chondrites, there is also a mystery related to their recovery. All of these meteorites have been recovered from the Antarctic; none are falls or finds from anyplace else. Indeed, the majority have been collected by the Japanese NIPR field parties in the Yamato Mountains. In fact, one estimate is that these meteorites account for approx. 64 wt% of the CM carbonaceous chondrites at the NIPR. The reasons for this are unclear and might be due in part to simple sampling bias. However we suggest that this recovery difference is related to the particular age of the Yamato Mountains meteorite recovery surfaces, and differences in meteoroid fluxes between the Yamato meteorites and recent falls and substantially older Antarctic meteorites. Additional information is included in the original extended abstract.

Zolensky, Michael↗

Bulk Major and Trace Elemental Composition of an Aggregate Sample From Asteroid Bennu

On September 24, 2023, NASA’s OSIRIS-REx mission returned a capsule to Earth carrying material from asteroid Bennu. This event was the first time a U.S. mission delivered pristine samples from an asteroid and is the largest asteroid sample return to date. As these samples represent some of the oldest, most primitive, and pristine materials available to us, and which originate from a known and well-studied asteroid, they allow us a rare opportunity to gain a better understanding of the formation and evolution of our solar system. Key to understanding the material returned from asteroid Bennu is establishing its bulk chemical composition. Previous studies have shown that each chondrite group has a distinct elemental composition. For the carbonaceous chondrites specifically, each group exhibits a distinct pattern of moderately and highly volatile elemental depletions, relative to CI chondrites. CI chondrites are considered the most primitive chondrite group and broadly represent the solar photosphere composition. The two most striking features of these depletion patterns is that the moderately volatile element depletions increase with decreasing 50% condensation temperature and then plateau out at abundances that roughly correlate with matrix abundance. Due to these distinctive patterns, bulk elemental composition has become an important classification tool for establishing the different chondrite groups and the connections between them. As such, determining the bulk chemical composition of the Bennu aggregates will help to test two mission hypothesis: “Bennu’s bulk elemental composition reflects that of its main parent asteroid and is similar to the composition of the Sun, with depletions in moderately to highly volatile elements” and “Bennu’s dominant lithologies are comparable in bulk mineralogy, petrology, and composition to the most aqueously altered carbonaceous chondrites” . Furthermore as the carbonaceous and non-carbonaceous chondrites are thought to have likely formed in the inner and outer protoplanetary disk, respectively (e.g., [8]), determining the bulk chemical compositions of the Bennu aggregates will also help test the major mission hypothesis that “Bennu's parent body formed beyond the snow line by accretion of material in the pro-toplanetary disk” . Regarding chondrite formation, observed elemental patterns have been successfully used to model how the mixing of volatile-rich and volatile-poor chondritic components can produce the observed carbonaceous chondrites groups. They have also been significant in investigating how volatilization processes influenced chondrite formation. As such, establishing bulk chemical compositions of the pristine Bennu samples is vital for understanding the asteroid, and solar system formation. To begin this processes, we analyzed the bulk major and trace elemental compositions of Bennu aggregates.

P Koefoed↗

3-μm Reflectance Spectroscopy of Carbonaceous Chondrites Under Asteroid-Like Conditions

We measured 3-μm reflectance spectra of 21 meteorites that represent all carbonaceous chondrite types available in terrestrial meteorite collections. The measurements were conducted at the Laboratory for Spectroscopy under Planetary Environmental Conditions (LabSPEC) at the Johns Hopkins University Applied Physics Laboratory (JHU APL) under asteroid-like conditions (vacuum at room temperature after slight overnight heating at T < 400 K). This is the most comprehensive 3-μm dataset of carbonaceous chondrites ever acquired in environments similar to the ones experienced by asteroids. The 3-μm reflectance spectra are extremely important for direct comparisons with and appropriate interpretations of reflectance data from ground-based telescopic and spacecraft observations of asteroids. We found good agreement between 3-μm spectral characteristics of carbonaceous chondrites and carbonaceous chondrite classifications. The 3-μm band is diverse, indicative of varying composition, thus suggesting that these carbonaceous chondrites experienced distinct parent body aqueous alteration and metamorphism environments. The spectra of CI chondrites, from which significant amount of water adsorbed under ambient conditions was removed, are consistent with Mg-serpentine and clay minerals. The high abundances of organics in CI chondrites is also associated with the mineralogy of these chondrites, oxyhydroxides- and complex clay minerals-rich. CM chondrites, which are cronstedtite-rich, have shallower 3-μm band than CI chondrites, suggesting they experienced less aqueous alteration. CR chondrites showed moderate aqueous alteration relative to CI and CM chondrites. CV chondrites, except for Efremovka, have a very shallow 3-μm band, consistent with their lower phyllosilicate proportions. CO chondrites, like most CVs, have a very shallow 3-μm spectra that suggest they experienced minor aqueous alteration. The 3-μm band in CH/CBb is deep and broad centered ~ 3.11 μm, possibly due the high abundance of FeNi metal and presence of heavily hydrated clasts in these chondrites. The 3-μm spectra of Essebi (C2-ung) and EET 83226 are more consistent with CM chondrites’ spectra. The 3-μm spectra of Tagish lake (C2-ung), on the other hand, are consistent with CI chondrites. None of these spectral details could have been resolved without removing the adsorbed water before acquiring spectra.

Driss Takir↗

The Oxygen Isotopic Composition of Samples Returned From Asteroid Ryugu With Implications for the Nature of the Parent Planetesimal

We present oxygen isotopic analyses of fragments of the near-Earth C b -type asteroid Ryugu returned by the Hayabusa2 spacecraft that reinforce the close correspondence between Ryugu and CI chondrites. Small differences between Ryugu samples and CI chondrites in ∆' 17 O can be explained at least in part by contamination of the latter by terrestrial water. The discovery that a randomly sampled C-complex asteroid is composed of CI-chondrite-like rock, combined with thermal models for formation prior to significant decay of the short-lived radioisotope 26 Al, suggests that if lithified at the time of alteration, the parent body was small (<<50 km radius). If the parent planetesimal was large (>50 km in radius), it was likely composed of high-permeability, poorly lithified sediment rather than consolidated rock.

Asteroids↗

Coordinates Analyses of Hydrated Interplanetary Dust Particles: Samples of Primitive Solar System Bodies

Interplanetary dust particles (IDPs) collected in the stratosphere fall into two major groups: an anhydrous group termed the "chondritic-porous (CP) IDPs and a hydrated group, the "chondritic-smooth (CS) IDPs, although rare IDPs with mineralogies intermediate between these two groups are known [1]. The CP-IDPs are widely believed to be derived from cometary sources [e.g. 2]. The hydrated CS-IDPs show mineralogical similarities to heavily aqueously altered carbonaceous chondrites (e.g. CI chondrites), but only a few have been directly linked to carbonaceous meteorite parent bodies [e.g. 3, 4]. Most CS-IDPs show distinct chemical [5] and oxygen isotopic composition differences [6-8] from primitive carbonaceous chondrites. Here, we report on our coordinated analyses of a suite of carbon-rich CS-IDPs focusing on their bulk compositions, mineralogy, mineral chemistry, and isotopic compositions.

Keller, L. P.↗

Results of the Preliminary Analyses of Asteroid Ryugu Regolith Samples Returned by the Hayabusa2 Mission

The Hayabusa2 spacecraft returned 5.5g of regolith material from asteroid 162173 Ryugu in December 2021. The samples were maintained in near-vacuum conditions up to and even during many analyses, a factor that was critical for comparisons of Ryugu lithologies to meteorites because of ubiquitous terrestrial alteration of the latter. Observations of asteroid Ryugu by the Hayabusa2 spacecraft found that it is spinning, top-shaped rubble pile, formed from re-accretion of a (probably) small subset of fragments from a disrupted parent asteroid. Samples retrieved from Ryugu by the spacecraft during two brief touchdowns were expected to contain a record of this history, including the formation and early evolution of the parent body, its subsequent impact destruction and partial re-accretion, and later space weathering. The composition of Ryugu was expected to be similar to that of naturally-heated Ivuna-type carbonaceous chondrite meteorites (CI chondrites), based on ground- and spacecraft-based spectroscopy. Six preliminary examination teams investigated the formation history of Ryugu through laboratory analysis of the returned samples over the past 18 months. Specifically, we sought to determine (1) when and where in the Solar System the parent asteroid of Ryugu formed; (2) the original mineralogy, bulk elemental abundances, and chemical compositions of the accreted materials; (3) how these materials evolved through chemical and physical processing of the parent asteroid; and (4) how the parent asteroid was disrupted during impact and reaccumulated into Ryugu. This brief report mainly summarizes results from the mineralogy and petrology subteams, although results of the composition and isotope subteams are also mentioned. To address these issues, we analyzed numerous Ryugu particles up to ~8 mm in size.

Michael Zolensky↗