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Structure and Bonding of Carbon in Clays from CI Carbonaceous Chondrites

Carbonaceous chondrites (CC) contain a diverse suite of C-rich materials. Acid dissolution of these meteorites leaves a C-rich residue with chemical and structural affinities to kerogen. This material has primarily been analyzed in bulk, and much information has been provided regarding functional groups and elemental and isotopic compositions. However, comparatively little work has been done on C in unprocessed meteorites. Studies of CCs suggest a spatial relationship of some C-rich materials with products of aqueous alteration. Recent studies revealed discrete submicronsized, C-rich particles in Tagish Lake and a range of CM2 meteorites. A challenge is to correlate the findings from the bulk acid-residue studies with those of high-spatial resolution-mineralogical and spectroscopic observations of unprocessed meteorites. Hence, the relationship between the C-rich materials in the acid residues and its form and locations in the unprocessed meteorite remains unclear. Here we provide information on the structure and bonding of C associated with clays in CI carbonaceous chondrites. Additional information is included in the original extended abstract.

Garview, Laurence a. J.↗

Trace Element and Isotopic Evidence for Bennu's Primitive Provenance

The delivery of material from asteroid (101955) Bennu by NASA’s OSIRIS-REx mission provides the opportunity to investigate some of the most pristine material from the early Solar System [1]. Our team at Lawrence LivermoreNational Laboratory (LLNL) utilized the equivalent of 5.0 mg from Bennu sampleOREX-803015-100 to quantify the major and trace element contents and investigate major element isotopics (Ca, Ti, Cr, Fe, and Ni). Our 5.0 mg aliquot ofOREX-803015-100 was a subsample of dissolved homogenized material representing 20.66 mg [2]. A separate 5.0 mg aliquot was sent to ETH Zürich and is discussed in a companion abstract [3]. Before any chemical separation on our 5.0 mg aliquot, the equivalent of 0.5 mg was removed and analyzed for elemental abundances at LLNL using a ThermoScientific Element XR. Our data agree exceptionally well with those reported by[2], showing that Bennu is primitive and compositionally similar to CI chondrites, Ryugu [4], and the solar photosphere [5]. The remaining ~4.5 mg underwent purification procedures to chemically isolate and purify Ca, Ti, Cr, Fe, and Ni from one another and the sample matrix. Their isotopic compositions were measured on either the Triton TIMS (Ca) at JohnsonSpace Center in Houston, Neoma MC-ICPMS (Ti, Cr) at LLNL, or the Neptune MC-ICPMS (Fe, Ni) at LLNL. Results from the Ca, Ti, Cr, Fe, and Ni isotopic compositions suggest that Bennu is closely related to CI chondrites—consistent with conclusions from elemental composition [2] and oxygen isotopics [6]reported for Bennu. The major element isotope compositions that we will present demonstrate that Bennu likely formed in a similar region of the SolarSystem as CI chondrites and potentially at a similar time of Solar System evolution.

Greg Brennecka↗

Infrared diffuse reflectance spectra of carbonaceous chondrites: Amount of hydrous minerals

Infrared diffuse reflectance spectra (2.53-25 microns) of some carbonaceous (C) chondrites were measured. The integrated intensity of the absorption bands near 3 microns caused by hydrous minerals were compared with the modal content of hydrous minerals for the meteorites. The CM and CI chondrites show larger values of the intergated intensity than those of the unique C chondrites Y82162, Y86720 and B7904, suggesting that the amount of hydrous minerals in the CM and CI chondrites is larger, which supports the contention that hydrous minerals were dehydrated by thermal metamorphism in the unique chondrites. Orgueil (CI) has the largest value of the integrated intensity among the C chondrites we measured and shows a sharp absorption band at 3685/cm (2.71 microns) that is not seen in the spectra of the CM chondrites. There is an excellent correlation between the observed hydrogen content in C chondrites and the integrated intensity. The CM chondrites show a wide variation in the strength of absorption bands at 1470/cm (6.8 microns), despite the similarity in absorption features near 3 micron for all CM chondites. The 1470/cm band could be due to the presence of some hydrocarbons but may also be a result of terrestrial alteration processes.

Miyamoto, M.↗

Mineralogy and Petrology of Yamato 86029: A New Type of Carbonaceous Chondrite

Y-86029 resembles CI chondrites. Its matrix is very fine-grained. Olivine shows evidence of shock, which has rarely been observed in carbonaceous chondrites. Y-86029 experienced aqueous and thermal alteration during or after accretion in parent body. Additional information is contained in the original extended abstract.

Tonui, E.↗

Antarctic micrometeorites

Micrometeoroids in the size range 50-500 micron dominate the flux onto the Earth. Contrary to theoretical predictions, many of them survive atmospheric entry almost unchanged. Such micrometeorites can be collected from the Antarctic ice sheet where they account for a surprisingly large proportion of the total dust content of the ice. Early studies of this important class of extraterrestrial material have revealed that some Antarctic micrometeorites are similar to CM chondrites in chemical bulk composition and mineral composition, and a few seem to resemble CI chondrites. However, none of the micrometeorites investigated so far match CM or CI chondrites exactly, nor is there a match between average bulk micrometeorite composition and that of any other chondrite class. Also, the micrometeorite mineral chemistry is different from that of carbonaceous chondrites. Several elements are depleted in micrometeorites as compared to carbonaceous chondrites and some are enriched. The question arises whether these differences are pristine or if some of them are of secondary origin. On the basis of our data we will attempt to answer these questions, some of which have been addressed by us before.

Kurat, G.↗

Igneous rock from Severnyi Kolchim (H3) chondrite: Nebular origin

The discovery of lithic fragments with compositions and textures similar to igneous differentiates in unequilibrated ordinary chondrites (UOC's) and carbonaceous chondrites (CC's) has been interpreted as to suggest that planetary bodies existed before chondrites were formed. As a consequence, chondrites (except, perhaps CI chondrites) cannot be considered primitive assemblages of unprocessed nebular matter. We report about our study of an igneous clast from the Severnyi Kolchim (H3) chondrite. The results of the study are incompatible with an igneous origin of the clast but are in favor of a nebular origin similar to that of chondrules.

Nazarov, M. A.↗

The Pasamonte unequilibrated eucrite: Pyroxene REE systematic and major-, minor-, and trace-element zoning

We are evaluating the trace-element concentrations in the pyroxenes of Pasamonte. Pasamonte is a characteristic member of the main group eucrites, and has recently been redescribed as a polymict eucrite. Our Pasamonte sample contained eucritic clasts with textures ranging from subophitic to moderately coarse-grained. This study concentrates on pyroxenes from an unequilibrated, coarse-grained eucrite clast. Major-, minor-, and trace-element analyses were measured for zoned pyroxenes in the eucritic clast of Pasamonte. The major- and minor-element zoning traverses were measured using the JEOL 733 electron probe with an Oxford-Link imaging/analysis system. Complemenatry trace elements were then measured for the core and rim of each of the grains by SIMS. The trace elements analyzed consisted of eight REE, Sr, Y, and Zr. These analyses were performed on a Cameca 4f ion probe. The results of the CI chondrite normalized (average CI trace-element analyses for several grains and the major- and minor-element zoning patterns from a single pyroxene grain are given. The Eu abundance in the cores of the pyroxenes represents the detection limit and therefore the (-Eu) anomaly is a minimum. Major- and minor-element patterns are typical for igneous zoning. Pyroxene cores are Mg enriched, whereas the rims are enriched in Fe and Ca. Also, Ti and Mn are found to increase, while Cr and Al generally decrease in core-to-rim traverses. The cores of the pyroxenes are more depleted in the Rare Earth Elements (REE) than the rims. Using the minor- and trace-element concentrations of bulk Pasamonte and the minor- and trace-element concentrations from the cores of the pyroxenes in Pasamonte measured in this study, we calculated partition coefficients between pyroxene and melt. This calculation assumes that bulk Pasamonte is representative of a melt composition.

Pun, A.↗

Stacking Defects in Synthetic and Meteoritic Hibonites: Implications for High-Temperature Processes in the Solar Nebula

Hibonite (CaAl12O19) is a primary, highly refractory phase occurring in many Ca-Al-rich inclusions (CAIs) from different chondrite groups, except CI chondrites. Hibonite is predicted to be one of the earliest minerals to condense during cooling of the solar nebula at higher temperatures than any other major CAI mineral. Therefore, hibonite has great potential to reveal the processes and conditions of the very early, high-temperature stages of the solar nebular evolution. Previous microstructural studies of hibonite in CAIs and their Wark-Lovering (WL) rims showed the presence of numerous stacking defects in hibonite. These defects are interpreted as the modification of the stacking sequences of spinel and Ca-containing blocks within the ideal hexagonal hibonite structure, as shown by experimental studies of reaction-sintered ceramic CaO-Al2O3 compounds. We performed preliminary experiments in the CaO-Al2O3-MgO system to understand the formation processes and conditions of defect-structured hibonite found in meteorites.

Han, J.↗

On origin of the olivine inclusions from the Kainsaz CO carbonaceous chondrite

Olivine inclusions and chondrules of Kainsaz were formed in a unique process of dust matter melting. The elemental abundances of four fractions of olivine (01) inclusions from Kainsaz were analyzed by INAA. The inclusions of fraction A (160 less than d less than 260 microns) have Fe-Ni grains, the inclusions of fractions B (100 less than d less than 160 microns), C (160 less than d less than 260 microns), and D (260 less than d less than 360 microns) do not. The average elemental enrichment factors relative to CI chondrite for each fraction and chondrules of Kainsaz is shown. The enrichment factors of siderophile Co, Ni, Ir, Au, and non-refractory Na in all fractions are less than 1. The factors of refractory Ca, Sc, La, Sm, and Yb are comparative with the corresponding values of O1 aggregates of Allende CV (average 4.76). For chondrules of Kainsaz these values are lower. Fraction A is enriched in Co, Ir, Au, and relative Ni and CI chondrites: Ir greater than Au greater than Co. The values of (Me/Ni)inc/(Me/Ni)CI are equal to 3.25 for Ir, 2.1 for Au, and 1.2 for Co. The superabundances in Ir and Au relative to Ni witness to formation of Fe-Ni grains of O1 inclusions by agglomeration of grains enriched in refractory metal with grains enriched in non-refractory metal (Au). The enrichments of fraction A in Ca, Sc, La, Sm, and Yb witness about presence of high-temperature phases in O1 inclusions.

Lavrukhina, A. K.↗

Matrix mineralogy of the Orgueil CI carbonaceous chondrite

This paper presents the results of petrographic, SEM, and TEM studies of the matrix minerals in Orgueil. It was found that the matrix consists mainly of Fe-bearing Mg-rich serpentine and saponite, and a poorly crystallized Fe-rich ferrihydrite containing small and varying amounts of S and Ni. The serpentine and saponite, which occur in roughly equal molar proportions, are coherently intergrown and occur mainly in fine phyllosilicates in intimate association with the ferrihydrite. Coarse phylosilicates occur in clusters relatively free of ferrihydrite. The matrix mineralogy of the Orgueil chondrite suggests that Orgueil experienced considerably different alteration conditions than did the CM chondrites.

Tomeoka, Kazushige↗

Understanding the Heating Kinetics of Asteroid Ryugu By Comparison to Naturally and Experimentally Heated Meteorites

The Hayabusa2 mission visited the near-Earth Cb-type asteroid (162173) Ryugu and has returned to Earth surface material of Ryugu. Ryugu is an airless rubble pile asteroid exposed to space weathering [1]. Visible and near infrared remote observations recorded an absorption feature at 2.72 μm indicating the presence of OH– bearing hydrous components. The weak 2.72 μm feature suggested that Ryugu was once organic- and water-rich and subsequently dehydrated by a brief period of surficial heating with resemblance to “thermally metamorphosed carbonaceous chondrites”, “CI-/CM-like”, or “CY” chondrites [2, 3]. However, initial examination of the returned samples did not identify any significant heating of >150 °C [4, 5], and contrastingly, amino acid analysis of Ryugu samples suggested similarities to thermally-altered meteorites on the grounds of the predominant straight-chain n-ω-amino acid abundances [6]. In this study, we aim at addressing the nonconformal interpretations to the thermal history of Ryugu by comparing the organic composition of fresh Ryugu samples to that of chondritic meteorites that have been naturally (long-term radiogenic thermal metamorphism and short-term heating) and experimentally heated.

Q. H. S. Chan↗

Isotopic Composition of Silicon Carbide in the CO3 Chondrite Colony

Presolar grains have been identified in primitive members of all chondrite classes. The isotopic compositions of presolar grains provide probes of galactic evolution and nucleosynthesis in stars, while the abundances and characteristics of presolar grains contain a record of thermal processing in the solar system. Most of the detailed isotopic work has been done on SiC from Murchison and Orgueil, supplemented by a few studies of ordinary and enstatite chondrites. This work investigates SiC in the Colony CO3.O meteorite. SiC is present in Colony at a matrix-normalized abundance of approximately 3.7 ppm, much less than in CI chondrites and the matrixes of CM and primitive ordinary and enstatite chondrites. The abundances of SiC and other presolar grains in Colony seem to correlate with the chemical processing that produced CO3 chondrites. This implies that the known presolar grains experienced the same processing as the bulk CO3 material and assumes that the parent material was the same as that for other chondrites, including CI. That parent material is most plausibly the average material in the sun s parent molecular cloud. One test of this idea is to look for primary differences between SiC in Colony (and other meteorites) and that in CI and CM chondrites. True differences not related to thermal processing would falsify the assumption that all chondrite classes originated from the same reservoir of presolar dust.

Smith, J. B.↗

Formation of chondrules and CAIs by nebular processes

Chondrules are essential components of most chondritic meteorites. Carbonaceous chondrites, with the exception of CI chondrites, contain 30-50% chondrules, ordinary and enstatite chondrites even more. A better understanding of chondrule formation will therefore lead to an improved understanding of the origin of meteorites. Most studies of chondrules are, however, concerned with their texture and mineralogy. As chondrules, by definition, passed through a molten stage, their present texture and mineralogy can only provide information on conditions of crystallization from a melt and the subsequent solid-state cooling history. Information concerning chondrule formation is contained in their chemical and isotopic composition. The two most important observations relevant to the chemistry of the chondrules are their generally low Fe content and the large compositional variability of chondrules from a single meteorite, reflected in major variations of Mg/Si ratios, of Al and other refractory element abundances, total Fe, metal (Fe, Ni), and sulfide. This large compositional variability is surprising considering the uniform and nearly solar composition of bulk chondrites, which, in some cases, consist of more than 90% of chondrules.

Palme, H.↗

Soluble Organic Matter (SOM) analysis of the Hayabusa2 samples: The first results

The Hayabusa2 spacecraft successfully collected the surface and possible sub-surface materials of the asteroid 162173 Ryugu. Ryugu is a C-type asteroid characterized by a low-albedo surface probably consisting of hydrous minerals and carbonaceous materials. [1] The direct optical and spectral analysis of the returned samples indicates that Ryugu material is dominated by hydrous carbonaceous chondrite-like matter (similar to CI chondrites) [2]. Since carbonaceous chondrites have generally yielded various types of organic matter, the collected Ryugu grains are expected to contain diverse types of organic compounds including bio-related molecules. The occurrence of organic compounds in the Ryugu surface will provide clues to the evolution of prebiotic molecules and their preservations associated with aqueous alteration of the primitive asteroid. The initial analysis of soluble organic matter (SOM) of the Hayabusa2-returned samples has been performed by an international team consisting of 32 members. Because the sample amount available for comprehensive SOM analyses is limited, and because the SOM is expected to be present as a complex mixture of various types of organic compounds with very small concentrations of each compound, high-sensitivity and high-resolution analytical techniques have been developed using carbonaceous meteorites [e.g. 3]. Two aggregate samples of the Ryugu grains (A106 and C107) were allocated for the solvent extractions and bulk carbon (C), hydrogen (H), nitrogen (N), sulfur (S) and oxygen (O) measurements. The A106 sample was collected during the 1st sampling in February 2019 and the C107 sample was collected during the 2nd sampling in July 2019 after the Small Carry Impactor (SCI) operation. They consist mainly of particles smaller than 1 mm in diameter, and each sample mass was 38-39 mg. They were firstly investigated spectroscopically in the near infrared wavelength range by the Stone Team prior to the solvent extractions. Other small grains (A0080 and C0057) were also allocated for this study to investigate the spatial distribution of organic compounds on the sample surface. The extraction and analytical measurements implemented by the SOM Team are summarized in Figure 1. Each powder sample was extracted sequentially with non-polar to polar solvents, i.e., hexane, dichloromethane (DCM), methanol (MeOH) and H2O, for non-targeted analysis to reveal the compound composition. Each solvent extract was analyzed by solution state nuclear magnetic resonance (NMR) spectroscopy [4], Fourier transform- ion cyclotron resonance/mass spectrometry (FT-ICR/MS) with ESI and APPI ionization [5] and by high-resolution mass spectroscopy using Orbitrap MS coupled with nano-liquid chromatography (nanoLC/Orbitrap MS) [6], and using two dimensional gas chromatography/mass spectrometry (GC×GC/MS). The extracted residues were passed to the Chemistry Team for further inorganic element analysis. The other powder sample was subjected to the hot water extraction for amino acid analyses including chiral isomer separation, which was performed by three-dimensional (3D) high-performance liquid chromatography (HPLC) with high-sensitivity fluorescence detection (FD) [7] and by HPLC/FD coupled with quadrupole-time of flight/mass spectrometry (QToF/MS) [8]. After the hot water extraction, the residue was split into two halves. One half was further extracted with hydrochloric acid (HCl) to analyze for amino acids in bound-form. The other half was sequentially extracted with DCM/MeOH (1/1) to analyze semi-polar compounds such as polycyclic aromatic hydrocarbons (PAHs) by GC/MS, followed by further extraction with formic acid to analyze polar heterocyclic compounds, and subsequent extraction with HCl to detect bound-form polar compounds. The extracted residues were passed to the IOM Team for the analysis of insoluble organic matter (IOM). Compound-specific stable isotope analyses will be performed using GC/combustion/isotope ratio mass spectrometry (GC/C/IRMS) if the compound concentration is high enough to enable such an isotopic measurement. All extraction procedures were performed on an ISO 6 (Class 100) clean bench inside an ISO 5 (Class 1000) clean room. Baked serpentine powder was also analyzed as a procedural blank. In situ organic compound analysis with the molecular imaging was performed using desorption electrospray ionization (DESI) equipped with Orbitrap MS [9, 10], followed by spatial imaging of organic compounds using ToF/secondary ion mass spectrometry (ToF/SIMS) [11]. The bulk chemical and isotopic compositions of CNS and HO were determined using nano-elemental analysis/isotope ratio mass spectrometry (nanoEA/IRMS) [12] and EA/pyrolysis/IRMS, respectively. We have identified a variety of indigenous organic compounds in the extracts of both A106 and C107 samples. The Ryugu grains host organic molecules under the high-vacuum and cosmic-ray irradiation environment of the asteroid surface. The analysis of extracted molecules is in progress, and the first results will be presented at the symposium.

Hiroshi Naraoka↗

Recondensation of chondritic material in the early solar system: Results of thermodynamic simulation

We have performed a thermodynamic simulation of the recondensation of evaporated meteoritic material. We suggest that evaporation and recondensation occurred in impact events during the intercollision of planetesimals during the early evolution of the solar system. The source materials adopted for our model are the chondrites CI Orgueil and H5 Richardton. These chondrites are representative examples of the two extremes regarding volatile content and oxidation state. We calculated equilibrium mineral compositions of the closed systems of the Orgueil's and Richardton's elemental composition at the P-T conditions characteristic of the explosion cloud formed at a planetesimal collision. The P-T conditions are as follows: 10(exp -4) bar, and 1500 and 2000 K. The results are presented.

Dorofeyeva, V. A.↗

Aqueous alteration in carbonaceous chondrites - Mass balance constraints on matrix mineralogy

Bulk chemical compositions of matrix material were determined in eleven Antarctic CM chondrites and five non-Antarctic CM and CI chondrites, using microprobe defocused-beam technique. The results, along with previously published data, are used to provide mass balance constraints on the relative proportions of intergrown and intermixed phyllosilicate phases in carbonaceous chondrite matrices. In terms of Fe, Si, and Mg, the CM matrix bulk compositions plot within a triangle defined by the compositions of PCP (a mixture of 25 percent tochilinite and 75 percent cronstedtite), Mg-rich serpentine, and Fe-rich serpentine. Results indicate differing amounts of PCP and serpentines in individual CM matrices. The discrepancies found between predicted and measured S and Ni values require additional sulfide phases. CI matrices were found to contain little, if any, PCP; they consist mostly of serpentine and montmorillonite.

Mcsween, Harry Y., Jr.↗

Carbonates in the Kaidun chondrite

Kaidun is a remarkable chondrite breccia fall containing lithic clasts that span a wide range of chondrite groups including C and E chondrites, as well as having clasts with characteristics not yet found in existing chondrite samples. The dominant lithology in Kaidun appears to be CR chondritic, consonant with recent O isotope data. The carbonates in Kaidun are presented as one mineralogical basis for comparing it to the other hydrated chondrites and to better understand its relative alteration history. The four polished thin sections of Kaidun studied contained a variety of lithologies that we classified into four groups -- CR, E, CM-like, and dark inclusions (DIs). DIs contain sulfide and magnetite morphologies that superficially resemble CI chondrites, and some of the previously reported CI lithologies in Kaidun may be what we term DIs. Carbonates were found in all lithologies studied. Carbonates in Kaidun are similar in composition to those in CR chondrites. Some of the DIs in Kaidun, previously characterized as CI, have carbonates similar to those in CR chondrites and are unlike those in CI or CM chondrites. Most carbonates in Kaidun and CR chondrites are calcites, some of which formed at temperatures above 250 C. Dolomite is less common and some may be metastable. Alteration temperatures in the Renazzo CR chondrite were estimated to be approximately 300 C, based on O isotope fractionation between phyllosilicates and magnetite. Temperatures of up to 450 C were proposed for the alteration of a CR-like dark inclusion in Kaidun, based on the presence of hydrothermal pentlandite veins. The alteration temperatures for Kaidun and the other CR chondrites are considerably higher than those suggested for CI or CM parent bodies.

Weisberg, M. K.↗

Siderophile elements and metal-silicate fractionation in the solar nebula

The most important nebular fractionation affecting the siderophile elements is the metal-silicate fractionation process and its relationship to the chondrule formation process is poorly understood. Understanding these processes is important in terms of understanding the expected compositional range for planetary building blocks. In a general way the composition of chondrites can be derived from the composition of the CI chondrites by addition or subtraction of a refractory component similar to CAI's (in some cases with a Mg2SiO4 component) and by addition or subtraction of Fe metal. Thus normalization to Fe produces the least spread in the normalized abundances of most siderophile elements relative to CI abundances. Detailed bulk chemical studies of chondrules have shown that their siderophile elements have refractory-element siderophile-element signatures (for example, Ir/Ni) that are similar to the bulk meteorites, but distinct among the different chondrite groups. This data suggests that the chondrules were not supplied to the chondrule groups from a single homogeneous source, and that each chondrite group's characteristic siderophile-element signature was established before chondrule formation. These authors make a further inference that all siderophile-lithophile-element fractionation occurred before chondrule formation, but recent discoveries and observations suggest this is not true. The discovery of the metal-rich CH meteorites, the recognition of the role of aerodynamic forces in the solar nebula, and the possible role of metal-silicate segregation during the chondrule formation process suggests that metal-silicate fractionation occurred before, during and after chondrule formation.

Newsom, H. E.↗