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.     

LIME silicates in amoeboid olivine aggregates in carbonaceous chondrites: Indicator of nebular and asteroidal processes

MnO/FeO ratios in olivine from amoeboid olivine aggregates (AOAs) reflect conditions of nebular condensation and can be used in concert with matrix textures to compare metamorphic conditions in carbonaceous chondrites. LIME (low‐iron, Mn‐enriched) olivine was identified in AOAs from Y‐81020 (CO3.05), Kaba (CV~3.1), and in Y‐86009 (CV3), Y‐86751 (CV3), NWA 1152 (CR/CV3), but was not identified in AOAs from Efremovka (CV3.1–3.4) or Allende (CV>3.6). According to thermodynamic models of nebular condensation, LIME olivine is stable at lower temperatures than Mn‐poor olivine and at low oxygen fugacities (dust enrichment <10× solar). Although this set of samples does not represent a single metamorphic sequence, the higher subtypes tend to have AOA olivine with lower Mn/Fe, suggesting that Mn/Fe decreases during parent body metamorphism. Y‐81020 has the lowest subtype and most forsteritic AOA olivine (Fo_>95) in our study, whereas Efremovka AOAs are slightly Fe‐rich (Fo_>92). AOA olivines from Kaba are mostly forsteritic, but rare Fe‐rich olivine precipitated from an aqueous fluid. A combination of precipitation of Fe‐rich olivine and diffusion of Fe into primary olivine grains resulted in iron‐rich compositions (Fo_97–59) in Allende AOAs. Variations from fine‐grained, nonporous matrix toward higher porosity and coarser lath‐like matrix olivine can be divided into six stages represented by (1) Y‐81020, Efremovka, NWA 1152; (2) Y‐86751 lithology B; (3) Y‐86009; (4) Kaba; (5) Y‐86751 lithology A; (6) Allende. These stages are inferred to represent general degree of metamorphism, although the specific roles of thermally driven grain growth and diffusion versus aqueous dissolution and precipitation remain uncertain.     

The fate of primary iron sulfides in the CM1 carbonaceous chondrites: Effects of advanced aqueous alteration on primary components

We have carried out a SEM-EPMA-TEM study to determine the textures and compositions of relict primary iron sulfides and their alteration products in a suite of moderately to heavily altered CM1 carbonaceous chondrites. We observed four textural groups of altered primary iron sulfides: (1) pentlandite+phyllosilicate (2P) grains, characterized by pentlandite with submicron lenses of phyllosilicates; (2) pyrrhotite+pentlandite+magnetite (PPM) grains, characterized by pyrrhotite–pentlandite exsolution textures with magnetite veining and secondary pentlandite; (3) pentlandite+serpentine (PS) grains, characterized by relict pentlandite exsolution, serpentine, and secondary pentlandite; and (4) pyrrhotite+pentlandite+magnetite+serpentine (PPMS) grains, characterized by features of both the PPM and PS grains. We have determined that all four groups were initially primary iron sulfides, which formed from crystallization of immiscible sulfide melts within silicate chondrules in the solar nebula. The fact that such different alteration products could result from the same precursor sulfides within even the same meteorite sample further underscores the complexity of the aqueous alteration environment for the CM chondrites. The different alteration reactions for each textural group place constraints on the mechanisms and conditions of alteration with evidence for acidic environments, oxidizing environments, and changing fluid compositions (Ni-bearing and Si-Mg-bearing).     

The iron record of asteroidal processes in carbonaceous chondrites

The valence of iron has been used in terrestrial studies to trace the hydrolysis of primary silicate rocks. Here, we use a similar approach to characterize the secondary processes, namely thermal metamorphism and aqueous alteration, that have affected carbonaceous chondrites. X‐ray absorption near‐edge structure spectroscopy at the Fe‐K‐edge was performed on a series of 36 CM, 9 CR, 10 CV, and 2 CI chondrites. While previous studies have focused on the relative distribution of Fe⁰ with respect to oxidized iron (Fe_ox = Fe²⁺ + Fe³⁺) or the iron distribution in some specific phases (e.g., Urey–Craig diagram; Urey and Craig 1953), our measurements enable us to assess the fractions of iron in each of its three oxidation states: Fe⁰, Fe²⁺, and Fe³⁺. Among the four carbonaceous chondrites groups studied, a correlation between the iron oxidation index (IOI = [2(Fe²⁺) + 3(Fe³⁺)]/[Fe_TOT]) and the hydrogen content is observed. However, within the CM group, for which a progressive alteration sequence has been defined, a conversion of Fe³⁺ to Fe²⁺ is observed with increasing degree of aqueous alteration. This reduction of iron can be explained by an evolution in the mineralogy of the secondary phases. In the case of the few CM chondrites that experienced some thermal metamorphism, in addition to aqueous alteration, a redox memory of the aqueous alteration is present: a significant fraction of Fe³⁺ is present, together with Fe²⁺ and sometimes Fe⁰. From our data set, the CR chondrites show a wider range of IOI from 1.5 to 2.5. In all considered CR chondrites, the three oxidation states of iron coexist. Even in the least‐altered CR chondrites, the fraction of Fe³⁺ can be high (30% for MET 00426). This observation confirms that oxidized iron has been integrated during formation of fine‐grained amorphous material in the matrix (Le Guillou and Brearley 2014; Le Guillou et al. 2015; Hopp and Vollmer 2018). Last, the IOI of CV chondrites does not reflect the reduced/oxidized classification based on metal and magnetite proportions, but is strongly correlated with petrographic types. The valence of iron in CV chondrites therefore appears to be most closely related to thermal history, rather than aqueous alteration, even if these processes can occur together (Krot et al. 2004; Brearley and Krot 2013).     

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.     

Spectral reflectance properties of carbonaceous chondrites: 3. CR chondrites

Powdered samples of a suite of 14 CR and CR-like chondrites, ranging from petrologic grade 1 to 3, were spectrally characterized over the 0.3–2.5 μm interval as part of a larger study of carbonaceous chondrite reflectance spectra. Spectral analysis was complicated by absorption bands due to Fe oxyhydroxides near 0.9 μm, resulting from terrestrial weathering. This absorption feature masks expected absorption bands due to constituent silicates in this region. In spite of this interference, most of the CR spectra exhibit absorption bands attributable to silicates, in particular an absorption feature due to Fe²⁺-bearing phyllosilicates near 1.1 μm. Mafic silicate absorption bands are weak to nonexistent due to a number of factors, including low Fe content, low degree of silicate crystallinity in some cases, and presence of fine-grained, finely dispersed opaques. With increasing aqueous alteration, phyllosilicate: mafic silicate ratios increase, resulting in more resolvable phyllosilicate absorption bands in the 1.1 μm region. In the most phyllosilicate-rich CR chondrite, GRO 95577 (CR1), an additional possible phyllosilicate absorption band is seen at 2.38 μm. In contrast to CM spectra, CR spectra generally do not exhibit an absorption band in the 0.65–0.7 μm region, which is attributable to Fe³⁺–Fe²⁺ charge transfers, suggesting that CR phyllosilicates are not as Fe³⁺-rich as CM phyllosilicates. CR2 and CR3 spectra are uniformly red-sloped, likely due to the presence of abundant Fe–Ni metal. Absolute reflectance seems to decrease with increasing degree of aqueous alteration, perhaps due to the formation of fine-grained opaques from pre-existing metal. Overall, CR spectra are characterized by widely varying reflectance (4–21% maximum reflectance), weak silicate absorption bands in the 0.9–1.3 μm region, overall red slopes, and the lack of an Fe³⁺–Fe²⁺ charge transfer absorption band in the 0.65–0.7 μm region.     

Silica‐rich igneous rims around magnesian chondrules in CR carbonaceous chondrites: Evidence for condensation origin from fractionated nebular gas

Abstract— The outer portions of many type I chondrules (Fa and Fs <5 mol%) in CR chondrites (except Renazzo and Al Rais) consist of silica‐rich igneous rims (SIRs). The host chondrules are often layered and have a porphyritic core surrounded by a coarse‐grained igneous rim rich in low‐Ca pyroxene. The SIRs are sulfide‐free and consist of igneously‐zoned low‐Ca and high‐Ca pyroxenes, glassy mesostasis, Fe, Ni‐metal nodules, and a nearly pure SiO₂ phase. The high‐Ca pyroxenes in these rims are enriched in Cr (up to 3.5 wt% Cr₂O₃) and Mn (up to 4.4 wt% MnO) and depleted in Al and Ti relative to those in the host chondrules, and contain detectable Na (up to 0.2 wt% Na₂O). Mesostases show systematic compositional variations: Si, Na, K, and Mn contents increase, whereas Ca, Mg, Al, and Cr contents decrease from chondrule core, through pyroxene‐rich igneous rim (PIR), and to SIR; FeO content remains nearly constant. Glass melt inclusions in olivine phenocrysts in the chondrule cores have high Ca and Al, and low Si, with Na, K, and Mn contents that are below electron microprobe detection limits. Fe, Ni‐metal grains in SIRs are depleted in Ni and Co relative to those in the host chondrules. The presence of sulfide‐free, SIRs around sulfide‐free type I chondrules in CR chondrites may indicate that these chondrules formed at high (>800 K) ambient nebular temperatures and escaped remelting at lower ambient temperatures. We suggest that these rims formed either by gas‐solid condensation of silica‐normative materials onto chondrule surfaces and subsequent incomplete melting, or by direct SiO_(gas) condensation into chondrule melts. In either case, the condensation occurred from a fractionated, nebular gas enriched in Si, Na, K, Mn, and Cr relative to Mg. The fractionation of these lithophile elements could be due to isolation (in the chondrules) of the higher temperature condensates from reaction with the nebular gas or to evaporation‐recondensation of these elements during chondrule formation. These mechanisms and the observed increase in pyroxene/olivine ratio toward the peripheries of most type I chondrules in CR, CV, and ordinary chondrites may explain the origin of olivine‐rich and pyroxene‐rich chondrules in general.     

Nature and degree of aqueous alteration in CM and CI carbonaceous chondrites

We investigated the petrologic, geochemical, and spectral parameters that relate to the type and degree of aqueous alteration in nine CM chondrites and one CI (Ivuna) carbonaceous chondrite. Our underlying hypothesis is that the position and shape of the 3 μm band is diagnostic of phyllosilicate mineralogy. We measured reflectance spectra of the chondrites under dry conditions (elevated temperatures) and vacuum (10^?8 to 10^?7 torr) to minimize adsorbed water and mimic the space environment, for subsequent comparison with reflectance spectra of asteroids. We have identified three spectral CM groups in addition to Ivuna. “Group 1,” the least altered group as determined from various alteration indices, is characterized by 3 μm band centers at longer wavelengths, and is consistent with cronstedtite (Fe‐serpentine). “Group 3,” the most altered group, is characterized by 3 μm band centers at shorter wavelengths and is consistent with antigorite (serpentine). “Group 2” is an intermediate group between group 1 and 3. Ivuna exhibits a unique spectrum that is distinct from the CM meteorites and is consistent with lizardite and chrysotile (serpentine). The petrologic and geochemical parameters, which were determined using electron microprobe analyses and microscopic observations, are found to be consistent with the three spectral groups. These results indicate that the distinct parent body aqueous alteration environments experienced by these carbonaceous chondrites can be distinguished using reflectance spectroscopy. High‐quality ground‐based telescopic observations of Main Belt asteroids can be expected to reveal not just whether an asteroid is hydrated, but also details of the alteration state.     

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.     

Constraints on the anhydrous precursor mineralogy of fine-grained materials in CM carbonaceous chondrites

Abstract— Mass balance calculations were performed to constrain the precursor mineralogy of fine-grained, aqueously altered materials in CM carbonaceous chondrites. The bulk composition of unaltered fine-grained CM materials was estimated and then used to calculate phase proportions for several different initial assemblages. All starting assemblages contain relic, unaltered Fe-poor phases observed in CM chondrites, plus iron sulfides. The original sources of Fe are uncertain, because most primary Fe-rich phases were aqueously altered. Four endmember assemblages are considered by adding Fe metal, Fa₅₀, Fa₁₀₀, or FeO-rich amorphous materials to the Fe-poor phases. These represent the Fe-bearing phases in CM and/or other chondritic classes. Results indicate that the precursor CM assemblage may have contained a maximum of either ～10 vol% Fe metal, 57 vol% Fa₅₀, ～28 vol% Fa₁₀₀, or 37.0 vol% FeO-rich amorphous materials. Additional calculations were performed in which Fe metal was added to the various FeO-bearing assemblages. These reveal a strong positive correlation between the forsterite/(forsterite + enstatite) ratio and the amount of FeO-bearing phases that coexist with metal. If forsterite was more abundant than low-Ca pyroxene in the accreted CM materials, then these materials must have also contained significant amounts of FeO-rich phases (e.g., at least 36 vol% Fa₅₀, 10 vol% Fa₁₀₀, or 17 vol% FeO-bearing glasses). Calculated mineral proportions suggest that intact calcium-aluminum-rich inclusions (CAIs) represent only about one-half of the original CAI budget, which is consistent with previous hypotheses that the initial CAI contents of CM and CO chondrites were similar. Some similarities exist between the primary CM assemblages calculated here and the mineralogies of other chondrite classes, but the initial CM materials do not appear to be represented in our meteorite inventory.     

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.     

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.     

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.     

Refractory inclusions in carbonaceous chondrites: Records of early solar system processes

Chondrites consist of three major components: refractory inclusions (Ca,Al‐rich inclusions [CAIs] and amoeboid olivine aggregates), chondrules, and matrix. Here, I summarize recent results on the mineralogy, petrology, oxygen, and aluminum‐magnesium isotope systematics of the chondritic components (mainly CAIs in carbonaceous chondrites) and their significance for understanding processes in the protoplanetary disk (PPD) and on chondrite parent asteroids. CAIs are the oldest solids originated in the solar system: their U‐corrected Pb‐Pb absolute age of 4567.3 ± 0.16 Ma is considered to represent time 0 of its evolution. CAIs formed by evaporation, condensation, and aggregation in a gas of approximately solar composition in a hot (ambient temperature >1300 K) disk region exposed to irradiation by solar energetic particles, probably near the protoSun; subsequently, some CAIs were melted in and outside their formation region during transient heating events of still unknown nature. In unmetamorphosed, type 2–3.0 chondrites, CAIs show large variations in the initial ²⁶Al/²⁷Al ratios, from <5 × 10^–6 to ~5.25 × 10^–5. These variations and the inferred low initial abundance of ⁶⁰Fe in the PPD suggest late injection of ²⁶Al by a wind from a nearby Wolf–Rayet star into the protosolar molecular cloud core prior to or during its collapse. Although there are multiple generations of CAIs characterized by distinct mineralogies, textures, and isotopic (O, Mg, Ca, Ti, Mo, etc.) compositions, the ²⁶Al heterogeneity in the CAI‐forming region(s) precludes determining the duration of CAIs formation using ²⁶Al‐²⁶Mg systematics. The existence of multiple generations of CAIs and the observed differences in CAI abundances in carbonaceous and noncarbonaceous chondrites may indicate that CAIs were episodically formed and ejected by a disk wind from near the Sun to the outer solar system and then spiraled inward due to gas drag. In type 2–3.0 chondrites, most CAIs surrounded by Wark–Lovering rims have uniform Δ¹⁷O (= δ¹⁷O?0.52 × δ¹⁸O) of ~ ?24‰; however, there is a large range of Δ¹⁷O (from ~?40 to ~ ?5‰) among them, suggesting the coexistence of ¹⁶O‐rich (low Δ¹⁷O) and ¹⁶O‐poor (high Δ¹⁷O) gaseous reservoirs at the earliest stages of the PPD evolution. The observed variations in Δ¹⁷O of CAIs may be explained if three major O‐bearing species in the solar system (CO, H₂O, and silicate dust) had different O‐isotope compositions, with H₂O and possibly silicate dust being ¹⁶O‐depleted relative to both the Genesis solar wind Δ¹⁷O of ?28.4 ± 3.6‰ and even more ¹⁶O‐enriched CO. Oxygen isotopic compositions of CO and H₂O could have resulted from CO self‐shielding in the protosolar molecular cloud (PMC) and the outer PPD. The nature of ¹⁶O‐depleted dust at the earliest stages of PPD evolution remains unclear: it could have either been inherited from the PMC or the initially ¹⁶O‐rich (solar‐like) MC dust experienced O‐isotope exchange during thermal processing in the PPD. To understand the chemical and isotopic composition of the protosolar MC material and the degree of its thermal processing in PPD, samples of the primordial silicates and ices, which may have survived in the outer solar system, are required. In metamorphosed CO3 and CV3 chondrites, most CAIs exhibit O‐isotope heterogeneity that often appears to be mineralogically controlled: anorthite, melilite, grossite, krotite, perovskite, and Zr‐ and Sc‐rich oxides and silicates are ¹⁶O‐depleted relative to corundum, hibonite, spinel, Al,Ti‐diopside, forsterite, and enstatite. In texturally fine‐grained CAIs with grain sizes of ~10–20 μm, this O‐isotope heterogeneity is most likely due to O‐isotope exchange with ¹⁶O‐poor (Δ¹⁷O ~0‰) aqueous fluids on the CO and CV chondrite parent asteroids. In CO3.1 and CV3.1 chondrites, this process did not affect Al‐Mg isotope systematics of CAIs. In some coarse‐grained igneous CV CAIs, O‐isotope heterogeneity of anorthite, melilite, and igneously zoned Al,Ti‐diopside appears to be consistent with their crystallization from melts of isotopically evolving O‐isotope compositions. These CAIs could have recorded O‐isotope exchange during incomplete melting in nebular gaseous reservoir(s) with different O‐isotope compositions and during aqueous fluid–rock interaction on the CV asteroid.     

On the origin of rim textures surrounding anhydrous silicate grains in CM carbonaceous chondrites

Abstract— Fine‐grained, optically opaque rims coat individual olivine and pyroxene grains in CM matrices and chondrules. Bulk chemical analyses and observations of these rims indicate the presence of phyllosilicates and disseminated opaques. Because phyllosilicates could not have survived the chondrule formation process, chondrule silicate rims must have formed entirely by late‐state aqueous reactions. As such, these textures provide a useful benchmark for isolating alteration features from more complex CM matrix materials. Both chondrule silicate and matrix silicate rims exhibit morphological features commonly associated with advancing stages of replacement reactions in terrestrial serpentinites. Contacts between many matrix silicate rims and the adjacent matrix materials suggest that these rims formed entirely by aqueous reactions in a parent‐body setting. This contrasts with previous assertions that rim textures can only form by the accretion of nebular dust but does not imply an origin for the rims surrounding other types of CM core components, such as chondrules.     

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.     

Fine-grained chondrule rims in Mighei-like carbonaceous chondrites: Evidence for a nebular origin and modification by impacts and recurrent solar radiation heating

The Mighei-like carbonaceous (CM) chondrites, the most abundant carbonaceous chondrite group by number, further our understanding of processes that occurred in their formation region in the protoplanetary disk and in their parent body/bodies and provide analogs for understanding samples returned from carbonaceous asteroids. Chondrules in the CMs are commonly encircled by fine-grained rims (FGRs) whose origins are debated. We present the abundances, sizes, and petrographic observations of FGRs in six CMs that experienced varying intensities of parent body processing, including aqueous and thermal alteration. The samples studied here, in approximate order of increasing thermal alteration experienced, are Allan Hills 83100, Murchison, Meteorite Hills 01072, Elephant Moraine 96029, Yamato-793321, and Pecora Escarpment 91008. Based on observations of these CM chondrites, we recommend a new average apparent (2-D) chondrule diameter of 170 μm, which is smaller than previous estimates and overlaps with that of the Ornans-like carbonaceous (CO) chondrites. Thus, we suggest that chondrule diameters are not diagnostic for distinguishing between CM and CO chondrites. We also argue that chondrule foliation noted in ALH 83100, MET 01072, and Murchison resulted from multiple low-intensity impacts; that FGRs in CMs formed in the protoplanetary disk and were subsequently altered by both aqueous and thermal secondary alteration processes in their parent asteroid; and that the heat experienced by some CM chondrites may have originated from solar radiation of their source body/bodies during close solar passage as evidenced by the presence of evolved desiccation cracks in FGRs that formed by recurrent wetting and desiccation cycles.     

The effects of parent body processes on amino acids in carbonaceous chondrites

Abstract– To investigate the effect of parent body processes on the abundance, distribution, and enantiomeric composition of amino acids in carbonaceous chondrites, the water extracts from nine different powdered CI, CM, and CR carbonaceous chondrites were analyzed for amino acids by ultra performance liquid chromatography‐fluorescence detection and time‐of‐flight mass spectrometry (UPLC‐FD/ToF‐MS). Four aqueously altered type 1 carbonaceous chondrites including Orgueil (CI1), Meteorite Hills (MET) 01070 (CM1), Scott Glacier (SCO) 06043 (CM1), and Grosvenor Mountains (GRO) 95577 (CR1) were analyzed using this technique for the first time. Analyses of these meteorites revealed low levels of two‐ to five‐carbon acyclic amino alkanoic acids with concentrations ranging from approximately 1 to 2,700 parts‐per‐billion (ppb). The type 1 carbonaceous chondrites have a distinct distribution of the five‐carbon (C₅) amino acids with much higher relative abundances of the γ‐ and δ‐amino acids compared to the type 2 and type 3 carbonaceous chondrites, which are dominated by α‐amino acids. Much higher amino acid abundances were found in the CM2 chondrites Murchison, Lonewolf Nunataks (LON) 94102, and Lewis Cliffs (LEW) 90500, the CR2 Elephant Moraine (EET) 92042, and the CR3 Queen Alexandra Range (QUE) 99177. For example, α‐aminoisobutyric acid (α‐AIB) and isovaline were approximately 100 to 1000 times more abundant in the type 2 and 3 chondrites compared to the more aqueously altered type 1 chondrites. Most of the chiral amino acids identified in these meteorites were racemic, indicating an extraterrestrial abiotic origin. However, nonracemic isovaline was observed in the aqueously altered carbonaceous chondrites Murchison, Orgueil, SCO 06043, and GRO 95577 with l ‐isovaline excesses ranging from approximately 11 to 19%, whereas the most pristine, unaltered carbonaceous chondrites analyzed in this study had no detectable l ‐isovaline excesses. These results are consistent with the theory that aqueous alteration played an important role in amplification of small initial left handed isovaline excesses on the parent bodies.     

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.     

Dhofar 225 and Dhofar 735: Relationship to CM2 chondrites and metamorphosed carbonaceous chondrites,Belgica‐7904 and Yamato‐86720

Abstract– Dhofar (Dho) 225 and Dho 735 are carbonaceous chondrites found in a hot desert and having affinities to Belgica‐like Antarctic chondrites (Belgica [B‐] 7904 and Yamato [Y‐] 86720). Texturally they resemble CM2 chondrites, but differ in mineralogy, bulk chemistry and oxygen isotopic compositions. The texture and main mineralogy of Dho 225 and Dho 735 are similar to the CM2 chondrites, but unlike CM2 chondrites they do not contain any (P, Cr)‐sulfides, nor tochilinite 6Fe_0.9S*5(Fe,Mg)(OH)₂. H₂O‐contents of Dho 225 and Dho 735 (1.76 and 1.06 wt%) are lower than those of CM2 chondrites (2–18 wt%), but similar to those in the metamorphosed carbonaceous chondrites of the Belgica‐like group. Bulk compositions of Dho 225 and Dho 735, as well as their matrices, have low Fe and S and low Fe/Si ratios relative to CM2 chondrites. X‐ray powder diffraction patterns of the Dho 225 and Dho 735 matrices showed similarities to laboratory‐heated Murchison CM2 chondrite and the transformation of serpentine to olivine. Dho 225 and 735’s oxygen isotopic compositions are in the high ¹⁸O range on the oxygen diagram, close to the Belgica‐like meteorites. This differs from the oxygen isotopic compositions of typical CM2 chondrites. Experimental results showed that the oxygen isotopic compositions of Dho 225 and Dhofar 725, could not be derived from those of typical CM2 chondrites via dehydration caused by thermal metamorphism. Dho 225 and Dho 735 may represent a group of chondrites whose primary material was different from typical CM2 chondrites and the Belgica‐like meteorites, but they formed in an oxygen reservoir similar to that of the Belgica‐like meteorites.