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.     

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.     

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.     

Comparison of the Murchison CM2 and Allende CV3 chondrites

The size distribution, abundance, and physical and chemical characteristics of chondritic inclusions are key features that define the chondrite groups. We present statistics on the size and abundance of the macroscopic components (inclusions) in the Murchison (CM2) and Allende (CV3) chondrites and measure their general chemical trends using established X‐ray mapping techniques. This study provides a fine‐scale assessment of the two meteorites and a semiquantitative evaluation of the relative abundances of elements and their distribution among meteorite components. Murchison contains 72% matrix and 28% inclusions; Allende contains 57% and 43%, respectively. A broad range of inclusion sizes and relative abundances has been reported for these meteorites, which demonstrates the necessity for a more standardized approach to measuring these characteristics. Nonetheless, the characteristic mean sizes of inclusions in Allende are consistently larger than those in Murchison. We draw two significant conclusions (1) these two meteorites sampled distinct populations of chondrules and refractory inclusions, and (2) complementary Mg/Si ratios between chondrules and matrix are observed in both Murchison and Allende. Both support the idea that chondrules and matrix within each chondrite group originated in single reservoirs of precursors with approximately solar Mg/Si ratios, providing a constraint on astrophysical models of the origin of chondrite parent bodies.     

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.     

Aqueous alteration of chondrules from the Murchison CM carbonaceous chondrite: Replacement,pore filling,and the genesis of polyhedral serpentine

Forsterite and clinoenstatite in type IAB chondrules from the Murchison CM carbonaceous chondrite have been partially serpentinized, and the mechanisms of their alteration reveal crystallographic and microstructural controls on the reaction of silicate minerals with parent body aqueous solutions. Grains of forsterite were altered in two stages. Narrow veinlets of Fe‐rich serpentine formed first and by the filling of sheet pores. Most of these pores were oriented parallel to (010) and (001) and had been produced by earlier fracturing and/or congruent dissolution. In the second stage, the subset of veinlets that were oriented parallel to (001) was widened accompanying the replacement of forsterite by Mg‐Fe serpentine. This reaction proceeded most rapidly parallel to [001], and crystallographic controls on the trajectory of retreating vein walls created fine‐scale serrations. Murchison clinoenstatite grains have a skeletal appearance due to the presence of abundant veinlets and patches of phyllosilicate. Two alteration stages can again be recognized, with initial water–mineral interaction producing tochilinite‐rich veinlets by the filling of (001)‐parallel contraction cracks. Pores then formed by congruent dissolution that was guided principally by orthopyroxene lamellae, and they were subsequently filled by submicrometer‐sized crystals of polyhedral serpentine. This finding that Murchison forsterite and clinoenstatite grains have been altered demonstrates that aqueous processing of magnesium silicate minerals started much earlier in CM parent body history than previously believed. Our results also show that the occurrence of polyhedral serpentine can be used to locate former pore spaces within the parent body.     

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.     

Free dicarboxylic and aromatic acids in the carbonaceous chondrites Murchison and Orgueil

Abstract— We have analyzed an important fraction of the free carboxylic acids present in water extracts of the CM2 chondrite Murchison and the CI1 chondrite Orgueil using gas chromatographymass spectrometry (GC‐MS). The free nature of the carboxylic acids analyzed was ensured by employing a single‐step water extraction. Analyses revealed the presence of a structurally diverse suite of both aliphatic and aromatic acids in Murchison, while Orgueil exhibits a simpler distribution of exclusively aromatic acids. Within the Murchison aromatic acids, there are previously unreported phthalic acids, methyl phthalic acids, and hydroxybenzoic acids. In Orgueil, benzoic acid and very small amounts of methylbenzoic acids and methylhydroxybenzoic acids were detected. For the aromatic acids in both Murchison and Orgueil, most structural isomers were identified, suggesting an origin by abiotic processes. Quantitative differences are evident between acids in the two meteorites; carboxylic acids are much more abundant in Murchison than in Orgueil. The data suggest that differing levels of aqueous alteration on the meteorite parent body(ies) has produced dissimilar distributions of carboxylic acids.     

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.     

Magnesium isotopic fractionations in barred olivine chondrules from the Allende meteorite

Abstract— The Mg‐isotopic compositions in five barred olivine (BO) chondrules, one coarse‐grained rim of a BO chondrule, a relic spinel in a BO chondrule, one skeletal olivine chondrule similar to BO chondrules in mineralogy and composition, and two non‐BO chondrules from the Allende meteorite have been measured by thermal ionization mass spectrometry. The Mg isotopes are not fractionated and are within terrestrial standard values (±2.0%o per amu) in seven of the eight analyzed ferromagnesian chondrules. A clump of relic spinel grain and its host BO chondrule R‐11 give well‐resolvable Mg fractionations that show an enrichment of the heavier isotopes, up to +2.5%‰ per amu. The Mg‐isotopic compositions of coarse‐grained rim are identical to those of the host chondrule with BO texture. The results imply that ferromagnesian and refractory precursor components of the Allende chondrule may have been formed from isotopically heterogeneous reservoirs. In the nebula region where Allende chondrules formed, recycling of chondrules and multiple high‐temperature heating did not significantly alter the chemical and isotopic memory of earlier generations. Chemical and isotopic characteristics of refractory precursors of carbonaceous chondrite chondrules and CAIs are more closely related than previously thought. One of the refractory chondrule precursors of CV Allende is enriched in the heavier Mg isotopes and different from those of more common ferromagnesian chondrule precursors. The most probable scenario at the location where chondrule R‐11 formed is as follows. Before chondrule formation, several high‐temperature events occurred and then RPMs, refractory oxides, and silicates condensed from the nebular gas in which Mg isotopes were fractionated. Then, this CAI was transported into the chondrule formation region and mixed with more common, ferromagnesian precursors with normal Mg isotopes, and formed the BO chondrule. Because Mg isotope heterogeneity among silicates and spinel are found in some CAIs (Esat and Taylor, 1984), we cannot rule out the possibility that Mg isotopes of a melted portion of the refractory precursor (i.e., outer portion of CAI) are normal or enriched in the light isotope. Magnesium isotopes in the R‐11 host are also enriched in the heavier isotopes, +2.5%o per amu, which suggests that effects of isotopic heterogeneity among silicates and spinel, if they existed, are not considered to be large. It is possible that CAI precursor silicates partially dissolved during the chondrule forming event, contributing Mg to the melt and producing a uniform Mg‐isotopic signature but enriched in the heavier Mg isotopes, +2.5%‰ per amu. Most Mg isotopes in more common ferromagnesian chondrules represent normal chondritic material. Chemical and Mg‐isotopic signatures formed during nebular fractionations were not destroyed during thermal processes that formed the chondrule, and these were partly preserved in relic phases. Recycling of Allende chondrules and multiple heating at high temperature did not significantly alter the chemical and Mg‐isotopic memory of earlier generations.     

Alteration of calcium- and aluminium-rich inclusions in the Murray (CM2) carbonaceous chondrite

Abstract— Four different types of calcium- and aluminium-rich inclusions (CAIs) have been identified in the CM2 chondrite Murray, three of which contain alteration products. Two types of altered CAIs, spinel inclusions and spinel-pyroxene inclusions, contain primary spinel (± perovskite ± hibonite ± diopside) and secondary Fe-rich serpentine phyllosilicates (± tochilinite ± calcite). Original melilite in these CAIs is inferred to have been altered during aqueous activity in the parent body and Fe-rich serpentines, tochilinite and calcite were formed in its place. The other type of altered CAI is represented by one inclusion, here called MCA-1. This CAI contains primary spinel, perovskite, fassaite and diopside with secondary calcite, paragonite, Mg-Al-Fe phyllosilicates and a Mg-Al-Fe sulphate. Importantly, MCA-1 is similar in both primary and secondary mineralogy to a small number of altered CAIs described from other CM2 meteorites including Essebi, Murchison and a CM2 clast from Plainview. Features that these CAIs have in common include an unusually large size, a CV3-like primary mineralogy and the presence of secondary aluminosilicates and calcite. The Al-rich alteration products in MCA-1 are also reminiscent of secondary minerals in refractory inclusions from CV3 meteorites, which have previously been interpreted to form by interaction of the inclusions with solar nebula gases. In common with the other types of altered CAIs in Murray, MCA-1 is inferred to have experienced its main phase of alteration in a parent body environment. The Mg-Al-Fe phyllosilicates, calcite and the Mg-Al-Fe sulphate formed following aqueous alteration of an Al-rich precursor, possibly Ca dialuminate. This episode of parent body alteration may have overprinted an earlier phase of alteration in a solar nebula environment from which only paragonite remains.     

Organic compounds in the Murchison and Allende carbonaceous chondrites studied by photoionization mass spectrometry

Abstract— Organic compounds in the Murchison (C2M) and Allende (CV3) carbonaceous chondrites were analyzed by photoionization time-of-flight mass spectrometry; thermal (25–850 °C) and stimulated (7 keV Ar⁺) desorption were combined with either nonresonant single-photon ionization using 118 nm light or resonantly enhanced multiphoton ionization (selective for aromatic compounds) using 266 nm light. Samples weighing only 1–10 mg were sufficient for sensitive quantitative analysis of aromatic compounds using thermal desorption. The detection limits for phenanthrene and pyrene using 118 nm light were determined to be 0.8 and 1.4 picomoles, respectively, and the concentrations of these compounds (including their isomers anthracene and fluoranthene) in the Murchison meteorite were determined to be 9 and 12 μg/g, respectively, in good agreement with previously published values. Thermal-desorption (–75–500 °C) field-ionization mass spectra (activated foil-type ionizing source and magnetic sector mass analyzer) of 20–40 mg of the same meteorite material were obtained to verify that the 118 nm photoionization mass spectra were not affected by photofragmentation or photodecomposition and were representative of the organic material extracted by thermal desorption. Photoionization mass spectrometry is a useful technique for studying small quantities (< 1 nanomole) of organic matter in terrestrial and extraterrestrial samples. The present study aims to provide the background and analytical methods necessary for application to new and unsolved cosmochemical problems. Some potential applications are discussed.     

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.     

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.     

Cr isotopes in physically separated components of the Allende CV3 and Murchison CM2 chondrites: Implications for isotopic heterogeneity in the solar nebula and parent body processes

Chromium isotopic data of physically separated components (chondrules, CAIs, variably magnetic size fractions) of the carbonaceous chondrites Allende and Murchison and bulk rock data of Allende, Ivuna, and Orgueil are reported to evaluate the origin of isotopic heterogeneity in these meteorites. Allende components show ε⁵³Cr and ε⁵⁴Cr from ?0.23 ± 0.07 to 0.37 ± 0.05 and from ?0.43 ± 0.08 to 3.7 ± 0.1, respectively. In components of Murchison, ε⁵³Cr and ε⁵⁴Cr vary from ?0.06 ± 0.08 to 0.5 ± 0.1 and from 0.7 ± 0.2 to 1.7 ± 0.1, respectively. The non‐systematic variations of ε⁵³Cr and ⁵⁵Mn/⁵²Cr in the components of Allende and Murchison were likely caused by small‐scale, alteration‐related redistribution of Mn >20 Ma after formation of the solar system. Chondrule fractions show the lowest ⁵⁵Mn/⁵²Cr and ε⁵⁴Cr values of all components, consistent with evaporation of Mn and ε⁵⁴Cr‐rich carrier phases from chondrule precursors. Components other than the chondrules show higher Mn/Cr and ε⁵⁴Cr, suggestive of chemical and isotopic complementarity between chondrules and matrix‐rich fractions. Bulk rock compositions calculated based on weighted compositions of components agree with measured Cr isotope data of bulk rocks, in spite of the Cr isotopic heterogeneity reported by the present and previous studies. This indicates that on a sampling scale comprising several hundred milligrams, these meteorites sampled isotopically and chemically homogeneous nebular reservoirs. The linear correlation of ⁵⁵Mn/⁵²Cr with ε⁵³Cr in bulk rocks likely was caused by variable fractionation of Mn/Cr, subsequent mixing of phases in nebular domains, and radiogenic ingrowth of ⁵³Cr.     

Magnetite-sulfide chondrules and nodules in CK carbonaceous chondrites: Implications for the timing of CK oxidation

Abstract— CK carbonaceous chondrites contain rare (～0.1 vol%) magnetite-sulfide chondrules. These objects range from ～240 to 500 μm in apparent diameter and have ellipsoidal to spheroidal morphologies, granular textures and concentric layering. They are very similar in size, shape, texture, mineralogy and mineral composition to the magnetite-sulfide nodules which occur inside mafic silicate chondrules in CK chondrites. It seems likely that the magnetite-sulfide chondrules constitute the subset of magnetite-sulfide nodules that escaped as immiscible droplets from their molten silicate chondrule hosts during chondrule formation. The intactness of the magnetite-sulfide chondrules and nodules implies that oxidation of CK metal occurred before agglomeration; otherwise, the factor of two increase in molar volume associated with the conversion of metallic Fe-Ni into magnetite would have disrupted the objects and destroyed their concentrically layered textures. Hence, the pervasive silicate darkening of CK chondrites documented previously was caused by the shock mobilization of magnetite and sulfide, not metallic Fe-Ni and sulfide as in shock-darkened ordinary chondrites.     

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.     

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.     

The lack of potassium‐isotopic fractionation in Bishunpur chondrules

Abstract— In a search for evidence of evaporation during chondrule formation, the mesostases of 11 Bishunpur chondrules and melt inclusions in olivine phenocrysts in 7 of them have been analyzed for their alkali element abundances and K‐isotopic compositions. Except for six points, all areas of the chondrules that were analyzed had δ⁴¹K compositions that were normal within error (typically ±3%, 2s?). The six “anomalous” points are probably all artifacts. Experiments have shown that free evaporation of K leads to large ⁴¹K enrichments in the evaporation residues, consistent with Rayleigh fractionation. Under Rayleigh conditions, a 3% enrichment in δ⁴¹K is produced by ～12% loss of K. The range of L‐chondrite‐normalized K/Al ratios (a measure of the K‐elemental fractionation) in the areas analyzed vary by almost three orders of magnitude. If all chondrules started out with L‐chondrite‐like K abundances and the K loss occurred via Rayleigh fractionation, the most K‐depleted chondrules would have had compositions of up to δ⁴¹K ? 200%. Clearly, K fractionation did not occur by evaporation under Rayleigh conditions. Yet experiments and modeling indicate that K should have been lost during chondrule formation under currently accepted formation conditions (peak temperature, cooling rate, etc.). Invoking precursors with variable alkali abundances to produce the range of K/Al fractionation in chondrules does not explain the K‐isotopic data because any K that was present should still have experienced sufficient loss during melting for there to have been a measurable isotopic fractionation. If K loss and isotopic fractionation was inevitable during chondrule formation, the absence of K‐isotopic fractionation in Bishunpur chondrules requires that they exchanged K with an isotopically normal reservoir during or after formation. There is evidence for alkali exchange between chondrules and rim‐matrix in all unequilibrated ordinary chondrites. However, melt inclusions can have alkali abundances that are much lower than the mesostases of the host chondrules, which suggests that they at least remained closed since formation. If it is correct that some or all melt inclusions remained closed since formation, the absence of K‐isotopic fractionation in them requires that the K‐isotopic exchange took place during chondrule formation, which would probably require gas‐chondrule exchange. Potassium evaporated from fine‐grained dust and chondrules during chondrule formation may have produced sufficient K‐vapor pressure for gas‐chondrule isotopic exchange to be complete on the timescales of chondrule formation. Alternatively, our understanding of chondrule formation conditions based on synthesis experiments needs some reevaluation.     

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.