Spectral reflectance properties of carbonaceous chondrites: 2. CM chondrites

We have examined the spectral reflectance properties and available modal mineralogies of 39 CM carbonaceous chondrites to determine their range of spectral variability and to diagnose their spectral features. We have also reviewed the published literature on CM mineralogy and subclassification, surveyed the published spectral literature and added new measurements of CM chondrites and relevant end members and mineral mixtures, and measured 11 parameters and searched pair-wise for correlations between all quantities. CM spectra are characterized by overall slopes that can range from modestly blue-sloped to red-sloped, with brighter spectra being generally more red-sloped. Spectral slopes, as measured by the 2.4:0.56 μm and 2.4 μm:visible region peak reflectance ratios, range from 0.90 to 2.32, and 0.81 to 2.24, respectively, with values <1 indicating blue-sloped spectra. Matrix-enriched CM spectra can be even more blue-sloped than bulk samples, with ratios as low as 0.85. There is no apparent correlation between spectral slope and grain size for CM chondrite spectra - both fine-grained powders and chips can exhibit blue-sloped spectra. Maximum reflectance across the 0.3-2.5 μm interval ranges from 2.9% to 20.0%, and from 2.8% to 14.0% at 0.56 μm. Matrix-enriched CM spectra can be darker than bulk samples, with maximum reflectance as low as 2.1%. CM spectra exhibit nearly ubiquitous absorption bands near 0.7, 0.9, and 1.1 μm, with depths up to 12%, and, less commonly, absorption bands in other wavelength regions (e.g., 0.4-0.5, 0.65, 2.2 μm). The depths of the 0.7, 0.9, and 1.1 μm absorption features vary largely in tandem, suggesting a single cause, specifically serpentine-group phyllosilicates. The generally high Fe content, high phyllosilicate abundance relative to mafic silicates, and dual Fe valence state in CM phyllosilicates, all suggest that the phyllosilicates will exhibit strong absorption bands in the 0.7 μm region (due to Fe³⁺-Fe²⁺ charge transfers), and the 0.9-1.2 μm region (due to Fe²⁺ crystal field transitions), and generally dominate over mafic silicates. CM petrologic subtypes exhibit a positive correlation between degree of aqueous alteration and depth of the 0.7 μm absorption band. This is consistent with the decrease in fine-grained opaques that accompanies aqueous alteration. There is no consistent relationship between degree of aqueous alteration and evidence for a 0.65 μm region saponite-group phyllosilicate absorption band. Spectra of different subsamples of a single CM can show large variations in absolute reflectance and overall slope. This is probably due to petrologic variations that likely exist within a single CM chondrite, as duplicate spectra for a single subsample show much less spectral variability. When the full suite of available CM spectra is considered, few clear spectral-compositional trends emerge. This indicates that multiple compositional and physical factors affect absolute reflectance, absorption band depths, and absorption band wavelength positions. Asteroids with reflectance spectra that exhibit absorption features consistent with CM spectra (i.e., absorption bands near 0.7 and 0.9 μm) include members from multiple taxonomic groups. This suggests that on CM parent bodies, aqueous alteration resulted in the consistent production of serpentine-group phyllosilicates, however resulting absolute reflectances and spectral shapes seen in CM reflectance spectra are highly variable, accounting for the presence of phyllosilicate features in reflectance spectra of asteroids across diverse taxonomic groups.     

Alkali‐halogen metasomatism of the CM carbonaceous chondrites

Meteorite Hills (MET) 01075 is unique among the CM carbonaceous chondrites in containing the feldspathoid mineral sodalite, and hence it may provide valuable evidence for a nebular or parent body process that has not been previously recorded by this meteorite group. MET 01075 is composed of aqueously altered chondrules and calcium‐ and aluminum‐rich inclusions (CAIs) in a matrix that is predominantly made of serpentine‐ and tochilinite‐rich particles. The chondrules have been impact flattened and define a foliation petrofabric. Sodalite occurs in a 0.6 mm size CAI that also contains spinel, perovskite, and diopside together with Fe‐rich phyllosilicate and calcite. By analogy with feldspathoid‐bearing CAIs in the CV and CO carbonaceous chondrites, the sodalite is interpreted to have formed by replacement of melilite or anorthite during alkali‐halogen metasomatism in a parent body environment. While it is possible that the CAI was metasomatized in a precursor parent body, then excavated and incorporated into the MET 01075 parent body, in situ metasomatism is the favored model. The brief episode of relatively high temperature water–rock interaction was driven by radiogenic or impact heating, and most of the evidence for metasomatism was erased by subsequent lower temperature aqueous alteration. MET 01075 is very unusual in sampling a CM parent body region that underwent early alkali‐halogen metasomatism and has retained one of its products.     

Oxygen isotope characteristics of chondrules from the Yamato‐82094 ungrouped carbonaceous chondrite: Further evidence for common O‐isotope environments sampled among carbonaceous chondrites

High‐precision secondary ion mass spectrometry (SIMS) was employed to investigate oxygen three isotopes of phenocrysts in 35 chondrules from the Yamato (Y) 82094 ungrouped 3.2 carbonaceous chondrite. Twenty‐one of 21 chondrules have multiple homogeneous pyroxene data (?¹⁷O 3SD analytical uncertainty: 0.7‰); 17 of 17 chondrules have multiple homogeneous pyroxene and plagioclase data. Twenty‐one of 25 chondrules have one or more olivine data matching coexisting pyroxene data. Such homogeneous phenocrysts (1) are interpreted to have crystallized from the final chondrule melt, defining host O‐isotope ratios; and (2) suggest efficient O‐isotope exchange between ambient gas and chondrule melt during formation. Host values plot within 0.7‰ of the primitive chondrule mineral (PCM) line. Seventeen chondrules have relict olivine and/or spinel, with some δ¹⁷O and δ¹⁸O values approaching ?40‰, similar to CAI or AOA‐like precursors. Regarding host chondrule data, 22 of 34 have Mg#s of 98.8–99.5 and ?¹⁷O of ?3.9‰ to ?6.1‰, consistent with most Acfer 094, CO, CR, and CV chondrite chondrules, and suggesting a common reduced O‐isotope reservoir devoid of ¹⁶O‐poor H₂O. Six Y‐82094 chondrules have ?¹⁷O near ?2.5‰, with Mg#s of 64–97, consistent with lower Mg# chondrules from Acfer 094, CO, CR, and CV chondrites; their signatures suggest precursors consisting of those forming Mg# ~99, ?¹⁷O: ?5‰ ± 1‰ chondrules plus ¹⁶O‐poor H₂O, at high dust enrichments. Three type II chondrules plot slightly above the PCM line, near the terrestrial fractionation line (?¹⁷O: ~+0.1‰). Their O‐isotopes and olivine chemistry are like LL3 type II chondrules, suggesting they sampled ordinary chondrite‐like chondrule precursors. Finally, three Mg# >99 chondrules have ?¹⁷O of ?6.7‰ to ?8.1‰, potentially due to ¹⁶O‐rich refractory precursor components. The predominance of Mg# ~99, ?¹⁷O: ?5‰ ± 1‰ chondrules and a high chondrule‐to‐matrix ratio suggests bulk Y‐82094 characteristics are closely related to anhydrous dust sampled by most carbonaceous chondrite chondrules.     

The nanoscale mineralogy of Fe,Ni sulfides in pristine and metamorphosed CM and CM/CI‐like chondrites: Tapping a petrogenetic record

We have sampled sulfide grains from one pristine CM2 chondrite (Yamato [Y‐] 791198), one thermally metamorphosed CM2 chondrite (Y‐793321), and two anomalous, metamorphosed CM/CI‐like chondrites (Y‐86720 and Belgica [B‐] 7904) by the focused ion beam (FIB) technique and studied them by analytical transmission electron microscopy (TEM). Our study aims at exploring the potential of sulfide assemblages and microstructures to decipher processes and conditions of chondrite petrogenesis. Complex exsolution textures of pyrrhotite (crystallographic NC‐type with N ≈ 6), troilite, and pentlandite occur in grains of Y‐791198 and Y‐793321. Additionally, polycrystalline 4C‐pyrrhotite‐pentlandite‐magnetite aggregates occur in Y‐791198, pointing to diverse conditions of gas–solid interactions in the solar nebula. Coarser exsolution textures of Y‐793321 grains indicate higher long‐term average temperatures in the <100 °C range compared to Y‐791198 and other CM chondrites. Sulfide mineralogy of Y‐86720 and B‐7904 is dominated by aggregates of pure troilite and metal, indicating metamorphic equilibration at sulfur fugacities (fS₂) of the iron‐troilite buffer. Absence of magnetite in equilibrium with sulfide and metal in Y‐86720 indicates higher peak temperatures compared with B‐7904, in which coexistence of troilite, metal, and magnetite constrains metamorphic temperature to less than 570 °C. NC‐pyrrhotite occurs in both meteorites as nm‐wide rims on troilite grains and, together with frequent anhydrite, indicates a retrograde metamorphic stage at higher fS₂ slightly above the fayalite‐magnetite‐quartz‐pyrrhotite buffer. Fine‐grained troilite‐olivine intergrowths in both meteorites suggest the pre‐metamorphic presence of tochilinite‐serpentine interlayer phases, pointing to mineralogical CM affinity. Pseudomorphs after euhedral pyrrhotite crystals in Y‐86720 in turn suggest CI affinity as do previously published O isotopic data of both meteorites.     

Extraterrestrial amino acids and L‐enantiomeric excesses in the CM2 carbonaceous chondrites Aguas Zarcas and Murchison

The abundances, distributions, enantiomeric ratios, and carbon isotopic compositions of amino acids in two fragments of the Aguas Zarcas CM2 type carbonaceous chondrite fall and a fragment of the CM2 Murchison meteorite were determined via liquid chromatography time‐of‐flight mass spectrometry and gas chromatography isotope ratio mass spectrometry. A suite of two‐ to six‐carbon aliphatic primary amino acids was identified in the Aguas Zarcas and Murchison meteorites with abundances ranging from ~0.1 to 158 nmol/g. The high relative abundances of α‐amino acids found in these meteorites are consistent with a Strecker‐cyanohydrin synthesis on these meteorite parent bodies. Amino acid enantiomeric and carbon isotopic measurements in both fragments of the Aguas Zarcas meteorites indicate that both samples experienced some terrestrial protein amino acid contamination after their fall to Earth. In contrast, similar measurements of alanine in Murchison revealed that this common protein amino acid was both racemic (D ≈ L) and heavily enriched in ¹³C, indicating no measurable terrestrial alanine contamination of this meteorite. Carbon isotope measurements of two rare non‐proteinogenic amino acids in the Aguas Zarcas and Murchison meteorites, α‐aminoisobutyric acid and D‐ and L‐isovaline, also fall well outside the typical terrestrial range, confirming they are extraterrestrial in origin. The detections of non‐terrestrial L‐isovaline excesses of ~10–15% in both the Aguas Zarcas and Murchison meteorites, and non‐terrestrial L‐glutamic acid excesses in Murchison of ~16–40% are consistent with preferential enrichment of circularly polarized light generated L‐amino acid excesses of conglomerate enantiopure crystals during parent body aqueous alteration and provide evidence of an early solar system formation bias toward L‐amino acids prior to the origin of life.     

Sulfur isotopic composition of Fe‐Ni sulfide grains in CI and CM carbonaceous chondrites

Abstract– In situ secondary ion mass spectrometry analyses of ³²S, ³³S, and ³⁴S in iron‐nickel sulfide grains in two CI1 chondrites and six CM chondrites were performed. The results show a wider range of both enrichment and depletion in δ³⁴S relative to troilite from the Canyon Diablo meteorite (CDT) than has been observed in previous studies. All data points lie within error of a single mass dependent fractionation line. Sulfides from CI1 chondrites show δ³⁴S_CDT from ?0.7 to 6.8‰, while sulfide grains in the CM1 chondrite are generally depleted in heavy sulfur relative to CDT (δ³⁴S from ?2.9 to 1.8‰). CM2 chondrites contain sulfide grains that show enrichment and depletion in ³⁴S (δ³⁴S_CDT from ?7.0 to 6.8‰). Sulfates forming from sulfide grains during aqueous alteration on the chondrite parent body are suggested to concentrate light sulfur, leaving the remaining sulfide grains enriched in the heavy isotopes of sulfur. The average degree of enrichment in ³⁴S in CM chondrite sulfides is broadly consistent with previously suggested alteration sequences.     

Magnesium isotopic fractionation in chondrules from the Murchison and Murray CM2 carbonaceous chondrites

We present high‐precision measurements of the Mg isotopic compositions of a suite of types I and II chondrules separated from the Murchison and Murray CM2 carbonaceous chondrites. These chondrules are olivine‐ and pyroxene‐rich and have low ²⁷Al/²⁴Mg ratios (0.012–0.316). The Mg isotopic compositions of Murray chondrules are on average lighter (δ²⁶Mg ranging from ?0.95‰ to ?0.15‰ relative to the DSM‐3 standard) than those of Murchison (δ²⁶Mg ranging from ?1.27‰ to +0.77‰). Taken together, the CM2 chondrules exhibit a narrower range of Mg isotopic compositions than those from CV and CB chondrites studied previously. The least‐altered CM2 chondrules are on average lighter (average δ²⁶Mg = ?0.39 ± 0.30‰, 2SE) than the moderately to heavily altered CM2 chondrules (average δ²⁶Mg = ?0.11 ± 0.21‰, 2SE). The compositions of CM2 chondrules are consistent with isotopic fractionation toward heavy Mg being associated with the formation of secondary silicate phases on the CM2 parent body, but were also probably affected by volatilization and recondensation processes involved in their original formation. The low‐Al CM2 chondrules analyzed here do not exhibit any mass‐independent variations in ²⁶Mg from the decay of ²⁶Al, with the exception of two chondrules that show only small variations just outside of the analytical error. In the case of the chondrule with the highest Al/Mg ratio (a type IAB chondrule from Murchison), the lack of resolvable ²⁶Mg excess suggests that it either formed >1 Ma after calcium‐aluminum‐rich inclusions, or that its Al‐Mg isotope systematics were reset by secondary alteration processes on the CM2 chondrite parent body after the decay of ²⁶Al.     

Type 1 aqueous alteration in CM carbonaceous chondrites: Implications for the evolution of water‐rich asteroids

The CM carbonaceous chondrite meteorites experienced aqueous alteration in the early solar system. They range from mildly altered type 2 to almost completely hydrated type 1 chondrites, and offer a record of geochemical conditions on water‐rich asteroids. We show that CM1 chondrites contain abundant (84–91 vol%) phyllosilicate, plus olivine (4–8 vol%), magnetite (2–3 vol%), Fe‐sulfide (<5 vol%), and calcite (<2 vol%). The CM1/2 chondrites contain phyllosilicate (71–88 vol%), olivine (4–20 vol%), enstatite (2–6 vol%), magnetite (2–3 vol%), Fe‐sulfides (1–2 vol%), and calcite (~1 vol%). As aqueous alteration progressed, the abundance of Mg‐serpentine and magnetite in the CM chondrites increased. In contrast, calcite abundances in the CM1/2 and CM1 chondrites are often depleted relative to the CM2s. The modal data support the model, whereby metal and Fe‐rich matrix were the first components to be altered on the CM parent body(ies), before further hydration attacked the coarser Mg‐rich silicates found in chondrules and fragments. Based on the absence of tochilinite, we suggest that CM1 chondrites experienced increased alteration due to elevated temperatures (>120 °C), although higher water/rock ratios may also have played a role. The modal data provide constraints for interpreting the composition of asteroids and the mineralogy of samples returned from these bodies. We predict that “CM1‐like” asteroids, as has been proposed for Bennu—target for the OSIRIS‐REx mission—will have a high abundance of Mg‐rich phyllosilicates and Fe‐oxides, but be depleted in calcite.     

Thermal metamorphism of CI and CM carbonaceous chondrites: An internal heating model

Abstract— Infrared diffuse reflectance spectra were measured for several thermally metamorphosed carbonaceous chondrites with CI-CM affinities which were recently found from Antarctica. Compared with other CI or CM carbonaceous chondrites, these Antarctic carbonaceous chondrites show weaker absorption bands near 3 μm due to hydrous minerals, and weaker absorption bands near 6.9 μm due to carbonates, interpreted as thermal metamorphic features. These absorption bands also disappear in the spectra of samples of the Murchison (CM) carbonaceous chondrite heated above 500 °C, implying that the metamorphic temperatures of the Antarctic carbonaceous chondrites considered here were higher than about 500 °C. Model calculations were performed to study thermal metamorphism of carbonaceous chondrites in a parent body internally heated by the decay of the extinct nuclide ²⁶Al. The maximum temperature of the interior of a body more than 20 km in radius is 500–700 °C for the bulk Al contents of CI and CM carbonaceous chondrites, assuming a ratio of ²⁶Al/²⁷Al = 5 × 10^?6 which has been previously proposed for an ordinary-chondrite parent body. The metamorphic temperatures experienced by the Antarctic carbonaceous chondrites considered here may be attainable by an internally heated body with an ²⁶Al/²⁷Al ratio similar to that inferred for an ordinary-chondrite parent body.     

Origin of the metamorphosed clasts in the CV3 carbonaceous chondrite breccias of Graves Nunataks 06101, Vigarano,Roberts Massif 04143, and Yamato‐86009

We observed metamorphosed clasts in the CV3 chondrite breccias Graves Nunataks 06101, Vigarano, Roberts Massif 04143, and Yamato‐86009. These clasts are coarse‐grained polymineralic rocks composed of Ca‐bearing ferroan olivine (Fa_24–40, up to 0.6 wt% CaO), diopside (Fs_7–12Wo_44–50), plagioclase (An_52–75), Cr‐spinel (Cr/[Cr + Al] = 0.4, Fe/[Fe + Mg] = 0.7), sulfide and rare grains of Fe‐Ni metal, phosphate, and Ca‐poor pyroxene (Fs₂₄Wo₄). Most clasts have triple junctions between silicate grains. The rare earth element (REE) abundances are high in diopside (REE ~3.80–13.83 × CI) and plagioclase (Eu ~12.31–14.67 × CI) but are low in olivine (REE ~0.01–1.44 × CI) and spinel (REE ~0.25–0.49 × CI). These REE abundances are different from those of metamorphosed chondrites, primitive achondrites, and achondrites, suggesting that the clasts are not fragments of these meteorites. Similar mineralogical characteristics of the clasts with those in the Mokoia and Yamato‐86009 breccias (Jogo et al. 2012 ) suggest that the clasts observed in this study would also form inside the CV3 chondrite parent body. Thermal modeling suggests that in order to reach the metamorphosed temperatures of the clasts of >800 °C, the clast parent body should have accreted by ~2.5–2.6 Ma after CAIs formation. The consistency of the accretion age of the clast parent body and the CV3 chondrule formation age suggests that the clasts and CV3 chondrites could be originated from the same parent body with a peak temperature of 800–1100 °C. If the body has a peak temperature of >1100 °C, the accretion age of the body becomes older than the CV3 chondrule formation age and multiple CV3 parent bodies are likely.     

Altered primary iron sulfides in CM2 and CR2 carbonaceous chondrites: Insights into parent body processes

The presence of primary iron sulfides that appear to be aqueously altered in CM and CR carbonaceous chondrites provides the potential to study the effects and, by extension, the conditions of aqueous alteration. In this work, we have used SEM, TEM, and EPMA techniques to characterize primary sulfides that show evidence of secondary alteration. The alteration styles consist of primary pyrrhotite altering to secondary pentlandite (CMs only), magnetite (CMs and CRs), and phyllosilicates (CMs only) in grains that initially formed by crystallization from immiscible sulfide melts in chondrules (pyrrhotite‐pentlandite intergrowth [PPI] grains). Textural, microstructural, and compositional data from altered sulfides in a suite of CM and CR chondrites have been used to constrain the conditions of alteration of these grains and determine their alteration mechanisms. This work shows that the PPI grains exhibit two styles of alteration—one to form porous pyrrhotite‐pentlandite (3P) grains by dissolution of precursor PPI grain pyrrhotite and subsequent secondary pentlandite precipitation (CMs only), and the other to form the altered PPI grains by pseudomorphic replacement of primary pyrrhotite by magnetite (CMs and CRs) or phyllosilicates (CMs only). The range of alteration textures and products is the result of differences in conditions of alteration due to the role of microchemical environments and/or brecciation. Our observations show that primary sulfides are sensitive indicators of aqueous alteration processes in CM and CR chondrites.     

Extraterrestrial organic compounds and cyanide in the CM2 carbonaceous chondrites Aguas Zarcas and Murchison

Evaluating the water‐soluble organic composition of carbonaceous chondrites is key to understanding the inventory of organic matter present at the origins of the solar system and the subsequent processes that took place inside asteroid parent bodies. Here, we present a side‐by‐side analysis and comparison of the abundance and molecular distribution of aliphatic amines, aldehydes, ketones, mono‐ and dicarboxylic acids, and free and acid‐releasable cyanide species in the CM2 chondrites Aguas Zarcas and Murchison. The Aguas Zarcas meteorite is a recent fall that occurred in central Costa Rica and constitutes the largest recovered mass of a CM‐type meteorite after Murchison. The overall content of organic species we investigated was systematically higher in Murchison than in Aguas Zarcas. Similar to previous meteoritic organic studies, carboxylic acids were one to two orders of magnitude more abundant than other soluble organic compound classes investigated in both meteorite samples. We did not identify free cyanide in Aguas Zarcas and Murchison; however, cyanide species analyzed after acid digestion of the water‐extracted meteorite mineral matrix were detected and quantified at slightly higher abundances in Aguas Zarcas compared to Murchison. Although there were differences in the total abundances of specific compound classes, these two carbonaceous chondrites showed similar isomeric distributions of aliphatic amines and carboxylic acids, with common traits such as a complete suite of structural isomers that decreases in concentration with increasing molecular weight. These observations agree with their petrologic CM type‐2 classification, suggesting that these meteorites experienced similar organic formation processes and/or conditions during parent body aqueous alteration.     

Amino acids in Antarctic CM1 meteorites and their relationship to other carbonaceous chondrites

Abstract— CM2 carbonaceous chondrites are the most primitive material present in the solar system, and some of their subtypes, the CM and CI chondrites, contain up to 2 wt% of organic carbon. The CM2 carbonaceous chondrites contain a wide variety of complex amino acids, while the CI1 meteorites Orgueil and Ivuna display a much simpler composition, with only glycine and β‐alanine present in significant abundances. CM1 carbonaceous chondrites show a higher degree of aqueous alteration than CM2 types and therefore provide an important link between the CM2 and CI1 carbonaceous chondrites. Relative amino acid concentrations have been shown to be indicative for parent body processes with respect to the formation of this class of compounds. In order to understand the relationship of the amino acid composition between these three types of meteorites, we have analyzed for the first time three Antarctic CM1 chondrites, Meteorite Hills (MET) 01070, Allan Hills (ALH) 88045, and LaPaz Icefield (LAP) 02277, using gas chromatography‐mass spectrometry (GC‐MS) and high performance liquid chromatography‐fluorescence detection (HPLC‐FD). The concentrations of the eight most abundant amino acids in these meteorites were compared to those of the CM2s Murchison, Murray, Mighei, Lewis Cliff (LEW) 90500, ALH 83100, as well as the CI1s Orgueil and Ivuna. The total amino acid concentration in CM1 carbonaceous chondrites was found to be much lower than the average of the CM2s. Relative amino acid abundances were compared in order to identify synthetic relationships between the amino acid compositions in these meteorite classes. Our data support the hypothesis that amino acids in CM‐ and CI‐type meteorites were synthesized under different physical and chemical conditions and may best be explained with differences in the abundances of precursor compounds in the source regions of their parent bodies in combination with the decomposition of amino acids during extended aqueous alteration.     

Heavily metamorphosed clasts from the CV chondrite breccias Mokoia and Yamato‐86009

Abstract– Metamorphosed clasts in the CV carbonaceous chondrite breccias Mokoia and Yamato‐86009 (Y‐86009) are coarse‐grained, granular, polymineralic rocks composed of Ca‐bearing (up to 0.6 wt% CaO) ferroan olivine (Fa_34–39), ferroan Al‐diopside (Fs_9–13Wo_47–50, approximately 2–7 wt% Al₂O₃), plagioclase (An_37–84Ab_63–17), Cr‐spinel (Cr/(Cr + Al) = 0.19–0.45, Fe/(Fe + Mg) = 0.60–0.79), nepheline, pyrrhotite, pentlandite, Ca‐phosphate, and rare grains of Ni‐rich taenite; low‐Ca pyroxene is absent. Most clasts have triple junctions between silicate grains, indicative of prolonged thermal annealing. Based on the olivine‐spinel and pyroxene thermometry, the estimated metamorphic temperature recorded by the clasts is approximately 1100 K. Few clasts experienced thermal metamorphism to a lower degree and preserved chondrule‐like textures. The Mokoia and Y‐86009 clasts are mineralogically unique and different from metamorphosed chondrites of known groups (H, L, LL, R, EH, EL, CO, CK) and primitive achondrites (acapulcoites, brachinites, lodranites). On a three‐isotope oxygen diagram, compositions of olivine in the clasts plot along carbonaceous chondrite anhydrous mineral line and the Allende mass‐fractionation line, and overlap with those of the CV chondrule olivines; the Δ¹⁷O values of the clasts range from about ?4.3‰ to ?3.0‰. We suggest that the clasts represent fragments of the CV‐like material that experienced metasomatic alteration, high‐temperature metamorphism, and possibly melting in the interior of the CV parent asteroid. The lack of low‐Ca pyroxene in the clasts could be due to its replacement by ferroan olivine during iron‐alkali metasomatic alteration or by high‐Ca ferroan pyroxene during melting under oxidizing conditions.     

Iron‐rich aureoles in the CM carbonaceous chondrites Murray,Murchison, and Allan Hills 81002: Evidence for in situ aqueous alteration

Abstract— Iron‐rich aureoles in CM carbonaceous chondrites are previously unidentified domains of aqueously altered matrix material, whose FeO content may exceed that of the surrounding matrix by up to more than 15 wt%. We describe the petrography and mineralogy of these objects in the CM chondrites Murray, Murchison, and Allan Hills (ALH) 81002. The size of Fe‐rich aureoles ranges from a few hundred microns to several millimeters in diameter and appears to be a function of the degree of alteration of the host chondrite. The origin of Fe‐rich aureoles is related to the alteration of large metal grains that has resulted in the formation of characteristic PCP‐rich reaction products that are frequently observed at the centers of the aureoles. This suggests that Fe‐rich aureoles in CM chondrites are the result of the mobilization of Fe from altering metal grains into the matrix. The fact that Fe‐rich aureoles enclose numerous chondritic components such as chondrules, calcium‐aluminum‐rich inclusions (CAIs), and mineral fragments, as well as their radial symmetric appearance, are strong evidence that they formed in situ and that significant directional fluid flow was not involved in the alteration process. This and additional constraints, such as the distribution of S and other elements, as well as the inferred alteration conditions, are consistent with in situ parent‐body alteration. The observations are, however, entirely incompatible with preaccretionary alteration models in which the individual CM chondrite components have experienced diverse alteration histories. The presence of numerous intact aureoles in the brecciated CM chondrites Murray and Murchison further suggests that the alteration occurred largely after brecciation affected these meteorites. Therefore, the progressive aqueous alteration of CM chondrites may not be necessarily coupled to brecciation as has been previously proposed.     

Primary iron sulfides in CM and CR carbonaceous chondrites: Insights into nebular processes

We have carried out a systematic study involving SEM, EPMA, and TEM analyses to determine the textures and compositions of sulfides and sulfide–metal assemblages in a suite of minimally to weakly altered CM and CR carbonaceous chondrites. We have attempted to constrain the distribution and origin of primary sulfides that formed in the solar nebula, rather than by secondary asteroidal alteration processes. Our study focused primarily on sulfide assemblages associated with chondrules, but also examined some occurrences of sulfides within the matrices of these meteorites. Although sulfides are a minor phase in carbonaceous chondrites, we have determined that primary sulfide grains are actually a major proportion of the sulfide grains in weakly altered CM chondrites and have survived aqueous alteration relatively unscathed. In minimally altered CR chondrites, we have determined that essentially all of the sulfides are of primary origin, confirming the observations of Schrader et al. ( 2015 ). The pyrrhotite–pentlandite intergrowth (PPI) grains formed from crystallization of monosulfide solid solution (mss) melts, while sulfide-rimmed metal (SRM) grains formed from sulfidization of Fe,Ni metal. Micron-sized metal inclusions in some PPI grains may have formed by co-crystallization of metal and sulfide from a sulfide melt that experienced S volatilization during the chondrule formation event, or alternatively, may be a remnant of sulfidization of Fe,Ni metal that also occurred during chondrule formation. Sulfur fugacity for SRM grains ranged from −18 to −10 (log units) largely in agreement with predicted solar nebular values. Our observations show that understanding the formation mechanisms of primary sulfide grains provides clues to solar nebular conditions, such as the sulfur fugacity during chondrule formation.     

Geochemistry of the ungrouped carbonaceous chondrite Tagish Lake,the anomalous CM chondrite Bells,and comparison with CI and CM chondrites

Abstract— I have determined the composition via instrumental neutron activation analysis of a bulk pristine sample of the Tagish Lake carbonaceous chondrite fall, along with bulk samples of the CI chondrite Orgueil and of several CM chondrites. Tagish Lake has a mean of refractory lithophile element/Cr ratios like those of CM chondrites, and distinctly higher than the CI chondrite mean. Tagish Lake exhibits abundances of the moderately volatile lithophile elements Na and K that are slightly higher than those of mean CM chondrites. Refractory through moderately volatile siderophile element abundances in Tagish Lake are like those of CM chondrites. Tagish Lake is distinct from CM chondrites in abundances of the most volatile elements. Mean CI‐normalized Se/Co, Zn/Co and Cs/Co for Tagish Lake are 0.68 ± 0.01, 0.71 ± 0.07 and 0.76 ± 0.02, while for all available CM chondrite determinations, these ratios lie between 0.31 and 0.61, between 0.32 and 0.58, and between 0.39 and 0.74, respectively. Considering petrography, and oxygen isotopic and elemental compositions, Tagish Lake is an ungrouped member of the carbonaceous chondrite clan. The overall abundance pattern is similar to those of CM chondrites, indicating that Tagish Lake and CMs experienced very similar nebular fractionations. Bells is a CM chondrite with unusual petrologic characteristics. Bells has a mean CI‐normalized refractory lithophile element/Cr ratio of 0.96, lower than for any other CM chondrite, but shows CI‐normalized moderately volatile lithophile element/Cr ratios within the ranges of other CM chondrites, except for Na which is low. Iridium, Co, Ni and Fe abundances are like those of CM chondrites, but the moderately volatile siderophile elements, Au, As and Sb, have abundances below the ranges for CM chondrites. Abundances of the moderately volatile elements Se and Zn of Bells are within the CM ranges. Bells is best classified as an anomalous CM chondrite.     

Petrology and bulk chemistry of Yamato‐82094, a new type of carbonaceous chondrite

Carbonaceous chondrites are classified into several groups. However, some are ungrouped. We studied one such ungrouped chondrite, Y‐82094, previously classified as a CO. In this chondrite, chondrules occupy 78 vol%, and the matrix is distinctly poor in abundance (11 vol%), compared with CO and other C chondrites. The average chondrule size is 0.33 mm, different from that in C chondrites. Although these features are similar to those in ordinary chondrites, Y‐82094 contains 3 vol% Ca‐Al‐rich inclusions and 5% amoeboid olivine aggregates (AOAs). Also, the bulk composition resembles that of CO chondrites, except for the volatile elements, which are highly depleted. The oxygen isotopic composition of Y‐82094 is within the range of CO and CV chondrites. Therefore, Y‐82094 is an ungrouped C chondrite, not similar to any other C chondrite previously reported. Thin FeO‐rich rims on AOA olivine and the mode of occurrence of Ni‐rich metal in the chondrules indicate that Y‐82094 is petrologic type 3.2. The extremely low abundance of type II chondrules and high abundance of Fe‐Ni metal in the chondrules suggest reducing condition during chondrule formation. The depletion of volatile elements indicates that the components formed under high‐temperature conditions, and accreted to the parent body of Y‐82094. Our study suggests a wider range of formation conditions than currently recorded by the major C chondrite groups. Additionally, Y‐82094 may represent a new, previously unsampled, asteroidal body.     

P‐O‐rich sulfide phase in CM chondrites: Constraints on its origin on the CM parent body

CM chondrites are a group of primitive meteorites that have recorded the alteration history of the early solar system. We report the occurrence, chemistry, and oxygen isotopic compositions of P‐O‐rich sulfide phase in two CM chondrites (Grove Mountains [GRV] 021536 and Murchison). This P‐O‐rich sulfide is a polycrystalline aggregate of nanometer‐size grains. It occurs as isolated particles or aggregates in both CM chondrites. These grains, in the matrix and in type‐I chondrules from Murchison, were partially altered into tochilinite; however, grains enclosed by Ca‐carbonate are much less altered. This P‐O‐rich sulfide in Murchison is closely associated with magnetite, FeNi phosphide, brezinaite (Cr₃S₄), and eskolaite (Cr₂O₃). In addition to sulfur as the major component, this sulfide contains ~6.3 wt% O, ~5.4 wt% P, and minor amounts of hydrogen. Analyses of oxygen isotopes by SIMS resulted in an average δ¹⁸O value of ?22.5 ‰ and an average Δ¹⁷O value of 0.2 ± 9.2 ‰ (2σ). Limited variations in both chemical compositions and electron‐diffraction patterns imply that the P‐O‐rich sulfide may be a single phase rather than a polyphase mixture. Several features indicate that this P‐O‐rich sulfide phase formed at low temperature on the parent body, most likely through the alteration of FeNi metal (a) close association with other low‐temperature alteration products, (b) the presence of hydrogen, (c) high Δ¹⁷O values and the presence in altered mesostasis of type‐I chondrules and absence in type‐II chondrules. The textural relations of the P‐O‐rich sulfide and other low‐temperature minerals reveal at least three episodic‐alteration events on the parent body of CM chondrites (1) formation of P‐O‐rich sulfide during sulfur‐rich aqueous alteration of P‐rich FeNi metal, (2) formation of Ca‐carbonate during local carbonation, and (3) alteration of P‐O‐rich sulfide and formation of tochilinite during a period of late‐stage intensive aqueous alteration.     

Nanophase iron carbides in fine‐grained rims in CM2 carbonaceous chondrites: Formation of organic material by Fischer–Tropsch catalysis in the solar nebula

Transmission electron microscope studies of fine‐grained rims in three CM2 carbonaceous chondrites, Y‐791198, Murchison, and ALH 81002, have revealed the presence of widespread nanoparticles with a distinctive core–shell structure, invariably associated with carbonaceous material. These nanoparticles vary in size from ~20 nm up to 50 nm in diameter and consist of a core of Fe,Ni carbide surrounded by a continuous layer of polycrystalline magnetite. These magnetite shells are 5–7 nm in thickness irrespective of the diameter of the core Fe,Ni carbide grains. A narrow layer of amorphous carbon a few nanometers in thickness is present separating the carbide core from the magnetite shell in all the nanoparticles observed. The Fe,Ni carbide phases that constitute the core are consistent with both haxonite and cohenite, based on electron diffraction data, energy dispersive X‐ray analysis, and electron energy loss spectroscopy. Z‐contrast scanning transmission electron microscopy shows that these core–shell magnetite‐carbide nanoparticles can occur as individual isolated grains, but more commonly occur in clusters of multiple particles. In addition, energy‐filtered transmission electron microscopy (EFTEM) images show that in all cases, the nanoparticles are embedded within regions of carbonaceous material or are coated with carbonaceous material. The observed nanostructures of the carbides and their association with carbonaceous material can be interpreted as being indicative of Fischer–Tropsch‐type (FTT) reactions catalyzed by nanophase Fe,Ni metal grains that were carburized during the catalysis reaction. The most likely environment for these FTT reactions appears to be the solar nebula consistent with the high thermal stability of haxonite and cohenite, compared with other carbides and the evidence of localized catalytic graphitization of the carbonaceous material. However, the possibility that such reactions occurred within the CM parent body cannot be excluded, although this scenario seems unlikely, because the kinetics of the reaction would be extremely slow at the temperatures inferred for CM asteroidal parent bodies. In addition, carbides are unlikely to be stable under the oxidizing conditions of alteration experienced by CM chondrites. Instead, it is most probable that the magnetite rims on all the carbide particles are the product of parent body oxidation of Fe,Ni carbides, but this oxidation was incomplete, because of the buildup of an impermeable layer of amorphous carbon at the interface between the magnetite and the carbide phase that arrested the reaction before it went to completion. These observations suggest that although FTT catalysis reactions may not have been the major mechanism of organic material formation within the solar nebula, they nevertheless contributed to the inventory of complex insoluble organic matter that is present in carbonaceous chondrites.