Altered CM Chondrites Research Articles

Cyanide Abundance and Soluble Organic Composition in Highly Aqueously Altered CM Chondrites

Cyanide Abundance and Soluble Organic Composition in Highly Aqueously Altered CM Chondrites

Hydrogen isotopic evidence for nebular pre-hydration and the limited role of parent-body processes in CM chondrites

The conditions and environments in which hydrated phases in unequilibrated meteorites formed remain debated. Among carbonaceous chondrites, Mighei-type chondrites (CMs) display a large range in the degree of aqueous alteration, and thus record different stages of hydration and alteration. Here, we report the bulk H, C, and N contents, H and C isotopic compositions, and thermogravimetric signatures of the most- and least-altered CMs known so far, Kolang and Asuka 12236, respectively. We also report in-situ SIMS measurements of the hydrogen isotopic compositions of water in both chondrites. Compared to other CMs, Asuka 12236 has the lowest bulk water content (3.3 wt.% H2O) and the most D-rich water and bulk isotopic compositions (δD = 180‰ and 280‰, respectively). Combined with literature data, our results show that phyllosilicate-bearing CMs altered to varying degrees accreted water-ice grains with similar isotopic compositions. These results demonstrate that the hydrogen isotopic variations in CM chondrites (i) are not controlled by secondary alteration processes and (ii) were mostly shaped by interactions between the protoplanetary disk and the molecular cloud that episodically fed the disk over several million years. The minimally altered CM chondrites Paris and Asuka 12236 display peculiar, D-rich, hydrogen isotopic compositions that imply the presence of another H-bearing component in addition to insoluble organic matter and phyllosilicates. This component is most likely the hydrated amorphous silicates that are ubiquitous in these chondrites. CM bulk H and O isotopic compositions are linearly correlated, implying that (i) amorphous silicates in CM matrices were already hydrated by disk processes before the onset of CM parent-body alteration, and (ii) the quest for a hypothetically water-free CM3 is illusory.

A Review of Research on Grove Mountains CM-Type Chondrites

CM chondrite is the most important carbonaceous chondrite containing abundant Ca, Al-rich inclusions (CAIs) and other interesting objects, which probably experienced early condensation processes in the Solar Nebula environment and later alteration in parent body surroundings. Thus, it is a vital raw material to explore in the formation and evolution of the early Solar System. Grove Mountains (GRV) CM chondrites have been collected from Antarctica by Chinese Antarctic Research Expedition (CARE) for nearly 20 years. In this paper, we review the study of GRV CM chondrites. In total, there are eight CM chondrites named Grove Mountains officially approved by the Meteoritical Society. Petrology and mineral, matrix, CAIs, metal and sulfide in GRV CM chondrites are carefully reviewed. All the meteorites have similar characteristics with a dominant component of matrix. Phyllosilicate minerals generally developed in the matrix. The different altered mineral assemblages, contents and chemical compositions show that these chondrites underwent varying degrees of aqueous alteration, of which GRV 020005 is the most heavily altered CM chondrite. GRV 020025 is the second heaviest of the CM samples with the most extensive studies among these chondrites. It contains abundant CAIs and amoeboid olivine aggregates (AOAs). The modal content is about 1.0 vol% for CAIs. The findings of some new types of CAIs (such as hibonite-rich and spinel-pyroxene inclusions with forsterite-rich accretionary rims), AOAs and a complex, fine-grained P-bearing sulfide phase enrich the study of GRV 020025.

Tracing the earliest stages of hydrothermal alteration on the CM chondrite parent body

AbstractThe CM carbonaceous chondrites are an important resource in our efforts to understand the role of volatiles in the formation of planetary systems. We report the bulk mineralogy, water abundance, and infrared (IR) reflectance spectra of the CM chondrites LaPaz Icefield (LAP) 04514, LAP 04796, LAP 04565, and LAP 02333. They contain abundant Fe‐ and Mg‐rich serpentines (~70–80 vol%), and based on their phyllosilicate fractions, we classify LAP 04514, LAP 04796, and LAP 04565 as petrologic subtype 1.6 and LAP 02333 as 1.4. This is consistent with estimated water abundances of 9.9 (±1.1) wt% for LAP 04796, 10.4 (±0.1) wt% for LAP 04565, and 11.5 (±0.5) wt% for LAP 02333. However, LAP 04514 contains less water (8.8 ± 0.3 wt%), has a shallower 3 µm band depth, and lacks tochilinite having experienced posthydration temperatures of ~300–400 °C. We conclude that LAP 04514, LAP 04796, and LAP 04565 are among the least altered CM chondrites, which retain primitive features from the initial building blocks of the CM parent body. Finally, we use the IR spectral features of LAP 04514, LAP 04796, and LAP 04565 to identify C‐complex asteroid surfaces that record mild levels of hydration.

Mineralogy of fine-grained matrix, fine-grained rim, chondrule rim, and altered mesostasis of a chondrule in Asuka 12169, one of the least altered CM chondrites

Mineralogy of fine-grained matrix (FGM), fine-grained rim (FGR), chondrule rim, and altered mesostasis of a chondrule from the Asuka (A) 12169 CM3.0 chondrite was investigated by field emission scanning electron microscopy (FE-SEM), synchrotron radiation-based X-ray nano-tomography (SR-XCT), and transmission electron microscopy (TEM). SR-XCT and TEM observations revealed that both FGM and FGR contain abundant amorphous silicate embedding nano-inclusions (most are Fe–Ni sulfide). Although the amorphous silicate is more or less hydrated based on the analysis of the X-ray linear attenuation coefficients in SR-XCT, there are no areas filled by abundant phyllosilicate even in three dimensions. However, FGM and FGR contain ~2-10 μm-sized aggregates composed of tochilinite, nano-inclusions of possible magnetite, and poorly crystalline serpentine without sharp boundaries with the surroundings. It is unlikely that the heterogeneity resulted from brecciation and mixing of materials that experienced different degrees of aqueous alteration, but more likely from a very early stage of aqueous alteration that proceeded heterogeneously depending on locally different chemistry. Chondrule mesostasis near the surface of a chondrule was altered to saponite with tochilinite-rich aggregates. These observations indicate that the degree aqueous alteration of A 12169 is very low and that it is comparable with that of Acfer 094, ALH 77307, and the least altered areas of Paris.

A primordial 15N-depleted organic component detected within the carbonaceous chondrite Maribo

We report on the detection of primordial organic matter within the carbonaceous chondrite Maribo that is distinct from the majority of organics found in extraterrestrial samples. We have applied high-spatial resolution techniques to obtain C-N isotopic compositions, chemical, and structural information of this material. The organic matter is depleted in 15N relative to the terrestrial value at around δ15N ~ -200‰, close to compositions in the local interstellar medium. Morphological investigations by electron microscopy revealed that the material consists of µm- to sub-µm-sized diffuse particles dispersed within the meteorite matrix. Electron energy loss and synchrotron X-ray absorption near-edge structure spectroscopies show that the carbon functional chemistry is dominated by aromatic and C=O bonding environments similar to primordial organics from other carbonaceous chondrites. The nitrogen functional chemistry is characterized by C-N double and triple bonding environments distinct from what is usually found in 15N-enriched organics from aqueously altered carbonaceous chondrites. Our investigations demonstrate that Maribo represents one of the least altered CM chondrite breccias found to date and contains primordial organic matter, probably originating in the interstellar medium.

Calcite and dolomite formation in the CM parent body: Insight from in situ C and O isotope analyses

Abstract To constrain the conditions of aqueous alteration in early planetesimals, we carried out in situ C and O isotope analyses of calcite and dolomite and O isotope analyses of magnetite from the highly altered CM chondrites ALH 83100, ALH 84034, and MET 01070. Petrographic and isotopic analyses of these samples support previous findings of multiple generations of carbonate growth. We observe wide ranges in the C and O isotope compositions of carbonates of up to 80‰ and 30‰, respectively, that span the full range of previously reported bulk carbonate values for CM chondrites. Variations in the Δ17O values indicate that fluid evolution varied for each chondrite. ALH 83100 dolomite-magnetite δ18O fractionation of 23‰ ± 7‰ (2SD) corresponds to dolomite formation temperature of 125 °C ± 60 °C. δ13C vs δ18O values fall into two groups, one consisting of primary calcite and the other consisting of dolomite and secondary calcite. The positive correlation between δ13C and δ18O for primary calcite is consistent with the precipitation of calcite in equilibrium with a gas mixture of CO (or CH4) and CO2. The isotopic composition of calcite in CM1s and CM2s overlap significantly; however, many CM1 calcite grains are more depleted in δ18O compared to CM2s. Altogether, the data indicate that the fluid composition during calcite formation was initially the same for both CM1s and CM2s. CM1s experienced more episodes of carbonate dissolution and reprecipitation where some fraction of the carbonate grains survive each episode resulting in a highly disequilibrium assemblage of carbonates on the thin-section scale.

The Amino Acid Distribution in Laboratory Analogs of Extraterrestrial Organic Matter: A Comparison to CM Chondrites

Abstract Laboratory experiments that simulate the photo- and thermo-chemistry of extraterrestrial ices always lead to the formation of semi-refractory organic residues. These residues can be considered as laboratory analogs for the primitive organic matter incorporated into comets and asteroids. Many specific organic molecules have been detected in them. Here we focus on amino acids because of their possible relevance to further prebiotic chemistry on Earth as well as in other solar system bodies. We compare the amino acid content and distribution measured in organic residues produced in our photochemical experiments to those observed in various CM chondrites presenting an increasing degree of aqueous alteration, a process that is thought to impact amino acid chemistry. We find that the amino acid profile of our residues shows similarities with that of the least aqueously altered CM chondrites. In particular, the β-alanine to glycine ratio is comparable to the one measured in the Paris meteorite, a minimally altered CM chondrite, and matches the trend followed by other CM chondrites with different degrees of aqueous alteration. Additionally, the relative abundances of α-, β-, and γ-amino acids in one of our residues are similar to those of the least altered CM chondrites. These results support the idea of a general formation process for amino acids from photo- and thermo-processing of icy grains as an important source for the inventory of amino acids in the early solar system.

Redox-influenced trace element compositional differences among variably aqueously altered CM chondrites

It is generally agreed that the CM chondrites are remarkably compositionally uniform. To date, this observation has largely been based on major and selected trace element bulk elemental abundances. Here, we examine the trace element compositional uniformity of the CM chondrites in detail. We quantified the abundances of 43 trace elements in 21 CM chondrites displaying variable degrees of petrographically identified aqueous alteration. With these data, we used graphic and standard statistical methods for examining evidence for compositional differences with respect to degree of aqueous alteration. The results show that suites of variably aqueously altered CM chondrites have readily apparent and statistically significant trace element compositional differences. Higher degrees of aqueous alteration are associated with depleted bulk trace elemental abundances; however, when the variable mineralogy and hydration (H2O or OH) are taken into account, the compositional differences between variably aqueously altered suites of CM chondrites largely disappear. Nevertheless, some trace elements still show statistically significant differences between suites of CM chondrites that experienced extensive and milder degrees of aqueous alteration. These elements are observed to be redox sensitive species (e.g. Mn, Zn, Mo, Re, U), whose mobilities between aqueous solutions and solids are mediated by complex ions whose solubilities are sensitive to a complicated combination of either the presence of Mn or Fe (oxy)hydroxide surfaces, specific redox environments, solution pH, presence of organic matter, and phyllosilicate surface binding. The studies suggest that the apparent compositional differences of these elements reflect an evolving redox environment during the history of the CM chondrites. It is unclear if the compositional differences between variably aqueously altered CM chondrites are the result of anisochemical (open system) aqueous alteration for some redox condition sensitive trace elements on the CM parent body or bodies or if the differences are the result of the meteorites’ terrestrial residence.

Isotope record of mineralogical changes in a spectrum of aqueously altered CM chondrites

The recent fall of the relatively unaltered CM chondrite Maribo provides a unique opportunity to study the early stages of aqueous alteration on the CM chondrite parent body. We show using transmission electron microscopy of a matrix FIB-section from Maribo that this meteorite mainly appears to consist of tochilinite-cronstedtite intergrowths (TCIs), but also contains regions of amorphous or nanocrystalline silicates, anhydrous silicates and FeNi metal aggregates with thin iron oxide rims, suggesting that it experienced aqueous alteration to a relatively small degree. A comparison of Maribo with increasingly altered CM chondrites such as Jbilet Winselwan and Bells shows that during progressive aqueous alteration (1) the TCIs are replaced by coarser sulfides and increasingly Mg-rich serpentine, and (2) the abundance of 15N-rich hotspots increases, whereas the magnitude of their 15N enrichment decreases. We observe that the overall N isotope variability related to aqueous alteration is an order of magnitude lower than the variability observed between different chondrite groups. We suggest these high order differences are the result of heterogeneous accretion of insoluble or soluble organic carriers of 15N to the different chondrite parent bodies. D/H ratios of matrices from Maribo, Jbilet Winselwan and Bells increase with progressive aqueous alteration, a trend that is opposite to expectations of mixing between D-poor water and D-rich organic matter. We argue that this behaviour cannot be related to Fe oxidation or serpentinization reactions and subsequent loss of D-poor H2 gas. We offer an alternative hypothesis and suggest that CM chondrites experienced two-stage aqueous alteration. During the first stage occurring at relatively low temperature, mixing of increasing amounts of D-poor water with D-rich organic matter results in a decrease of D/H ratio with increasing degree of alteration. During the second stage of alteration occurring at relatively high temperature (T < 300 °C), decomposition of TCIs in CMs of petrologic type <2.7 releases gaseous D-poor water that results in increase of the D/H ratio of the CM matrices. Finally, we report on changes in the organic structure of Maribo, Jbilet Winselwan and Bells using Carbon-K and Nitrogen-K edge electron energy loss spectroscopy. The organic matter initially has higher aromatic/aliphatic ratios (e.g., Maribo) and lower abundances of ketone and carboxyl functional groups, which we suggest are the result of chemical degradation of double bonded carbon from oxidation during hydrothermal alteration. Consequently, we propose that the organic matter of the CM chondrite Paris, for which lower aromatic/aliphatic ratios have been observed, may have been different from Maribo, perhaps reflecting the early accretion of Paris relative to Maribo.

What is controlling the reflectance spectra (0.35–150 µm) of hydrated (and dehydrated) carbonaceous chondrites?

In order to determine the controls on the reflectance spectra of hydrated carbonaceous chondrites, reflectance spectra were measured for a series of samples with well-determined mineralogy, water-content, and thermal history. This includes 5 CR chondrites, 11 CM chondrites, and 7 thermally metamorphosed CM chondrites. These samples were characterized over the 0.35–150 µm range by reflectance spectroscopy in order to cover the full spectral range accessible from ground based observation, and that will be determined in the near-future by the Hayabusa-2 and Osiris-REx missions. While spectra show absorption features shortward of 35 µm, no strong absorption bands were identified in this suite of samples longward of 35 µm. This work shows that the 0.7-µm band observed in hydrated carbonaceous chondrites is correlated with the total water content as well as with the band depth at 2.7 µm, confirming the suggestion that they are related to Mg-rich, Fe-bearing phyllosilicates. A feature at 2.3 µm, diagnostic of such phyllosilicates was found for all samples with a detectable 0.7-µm band, also indicative of Mg-rich phyllosilicates.A strong variability is found in the shape of the 3-µm band among CM chondrites, and between CM, CR and thermally metamorphosed CM chondrites. Heavily altered CM chondrites show a single strong band around 2.72 µm while more thermally metamorphosed CM samples show an absorption band at higher wavelength. The CR chondrite GRO 95577 has a 3-µm feature very similar to those of extensively altered CM chondrites while other CR chondrite rather shows goethite-like signatures (possibly due to terrestrial weathering of metals). Thermally metamorphosed CM chondrites all have 3-µm features, which are not purely due to terrestrial adsorbed water. The band shape ranges from heavily altered CM-like to goethite-like.The overall reflectance was found to be significantly higher for CR chondrites than for CM chondrites. This is also true for the hydrated CR chondrite GRO 95577 whose reflectance spectrum is almost identical to spectra obtained for CM chondrites except that it is brighter by about 40% in the visible. Another possibility to distinguish hydrated CM from hydrated CR chondrites is to use the combination of band depths at 0.7 and 2.3 µm.When comparing the spectra obtained with Cg and Cgh spectral end member, it is found that the band depth determined for hydrated chondrites (0.7 and 2.3 µm) are always higher than calculated for these spectral endmembers. If one considers only asteroids with unambiguous hydration detection, band depth at 0.7 µm is of similar value to those measured for hydrated carbonaceous chondrites.

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

AbstractWe 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. (). 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.

Paris vs. Murchison: Impact of hydrothermal alteration on organic matter in CM chondrites

Unravelling the origin of organic compounds that were accreted into asteroids requires better constraining the impact of asteroidal hydrothermal alteration on their isotopic signatures, molecular structures, and spatial distribution. Here, we conducted a multi-scale/multi-technique comparative study of the organic matter (OM) from two CM chondrites (that originate from the same parent body or from identical parent bodies that accreted the same mixture of precursors) and underwent a different degree of hydrothermal alteration: Paris (a weakly altered CM chondrite – CM 2.8) and Murchison (a more altered one – CM 2.5). The Paris insoluble organic matter (IOM) shows a higher aliphatic/aromatic carbon ratio, a higher radical abundance and a lower oxygen content than the Murchison IOM. Analysis of the OM in situ shows that two texturally distinct populations of organic compounds are present within the Paris matrix: sub-micrometric individual OM particles and diffuse OM finely distributed within phyllosilicates and amorphous silicates. These results indicate that hydrothermal alteration on the CM parent body induced aromatization and oxidation of the IOM, as well as a decrease in radical and nitrogen contents. Some of these observations were also reported by studies of variably altered fragment of Tagish Lake (C2), although the hydrothermal alteration of the OM in Tagish Lake was apparently much more severe. Finally, comparison with data available in the literature suggests that the parent bodies of other chondrite petrologic groups could have accreted a mixture of organic precursors different from that accreted by the parent body of CMs.

Fluid evolution in CM carbonaceous chondrites tracked through the oxygen isotopic compositions of carbonates

The oxygen isotopic compositions of calcite grains in four CM carbonaceous chondrites have been determined by NanoSIMS, and results reveal that aqueous solutions evolved in a similar manner between parent body regions with different intensities of aqueous alteration. Two types of calcite were identified in Murchison, Mighei, Cold Bokkeveld and LaPaz Icefield 031166 by differences in their petrographic properties and oxygen isotope values. Type 1 calcite occurs as small equant grains that formed by filling of pore spaces in meteorite matrices during the earliest stages of alteration. On average, the type 1 grains have a δ18O of ∼32–36‰ (VSMOW), and Δ17O of between ∼2‰ and −1‰. Most grains of type 2 calcite precipitated after type 1. They contain micropores and inclusions, and have replaced ferromagnesian silicate minerals. Type 2 calcite has an average δ18O of ∼21–24‰ (VSMOW) and a Δ17O of between ∼−1‰ and −3‰. Such consistent isotopic differences between the two calcite types show that they formed in discrete episodes and from solutions whose δ18O and δ17O values had changed by reaction with parent body silicates, as predicted by the closed-system model for aqueous alteration. Temperatures are likely to have increased over the timespan of calcite precipitation, possibly owing to exothermic serpentinisation. The most highly altered CM chondrites commonly contain dolomite in addition to calcite. Dolomite grains in two previously studied CM chondrites have a narrow range in δ18O (∼25–29‰ VSMOW), with Δ17O ∼−1‰ to −3‰. These grains are likely to have precipitated between types 1 and 2 calcite, and in response to a transient heating event and/or a brief increase in fluid magnesium/calcium ratios. In spite of this evidence for localised excursions in temperature and/or solution chemistry, the carbonate oxygen isotope record shows that fluid evolution was comparable between many parent body regions. The CM carbonaceous chondrites studied here therefore sample either several parent bodies with a very similar initial composition and evolution or, more probably, a single C-type asteroid.

GEMS-like material in the matrix of the Paris meteorite and the early stages of alteration of CM chondrites

The Paris meteorite is a weakly altered CM chondrite that has been discovered recently (Hewins et al., 2014). Its matrix offers the opportunity to search for well-preserved pristine pre-accretional material, as well as to study the earliest stages of aqueous alteration in the CM parent body. The study of the matrix of Paris has been conducted by analytical transmission electron microscopy on focused ion beam sections extracted from matrix areas showing different degrees of aqueous alteration.The least altered matrix sample consists of amorphous silicate grains, a few hundreds of nm in size, separated from one another by an abundant porosity. The amorphous silicates enclose numerous Fe-sulfide nanograins and their average composition is close to the chondritic composition. They share many similarities with GEMS (glass with embedded metal and sulfides) grains present in chondritic-porous interplanetary dust particles and with primitive type 3.0 carbonaceous chondrites. This first discovery of GEMS-like texture in a CM chondrite suggests that GEMS grains could have been the building blocks of the CM matrices.In more aqueously altered samples, pronounced microstructural heterogeneities were detected at the micrometer scale. The matrix consists mostly of a mixture of amorphous material and Fe-rich, spongy to fine-fibrous, poorly crystalline phyllosilicates. The porosity fraction is significantly reduced and the mixed amorphous-fibrous material frequently forms a continuous groundmass. The close association between these two material types suggests a replacement mechanism due to aqueous alteration. Chemical compositions correlate strongly with the microstructure. The amorphous material has a composition close to the chondritic value while the fine-fibrous phyllosilicate material is Fe-enriched. This Fe enrichment is found to be continuous from weakly to more heavily altered areas, in which the fibrous morphology is coarser and better crystalline. Cronstedtite with intercalated tochilinite is also found, but in pore spaces. This chemical evolution, concomitant with the maturation of the phyllosilicates, demonstrates that the early aqueous fluids that interacted with silicates in the matrix were enriched in Fe. This composition is probably the consequence of the preferential dissolution of metal and iron sulfides during the first stages of alteration. The enrichment of phyllosilicates in Mg seen in more altered CM chondrites is not observed in Paris.

An American on Paris: Extent of aqueous alteration of a CM chondrite and the petrography of its refractory and amoeboid olivine inclusions

AbstractParis is the least aqueously altered CM chondrite identified to date, classified as subtype 2.7; however, literature data indicate that some regions of this apparently brecciated meteorite may be subtype 2.9. The suite of CAIs in Paris includes 19% spinel–pyroxene inclusions, 19% spinel inclusions, 8% spinel–pyroxene–olivine inclusions, 43% pyroxene inclusions, 8% pyroxene–olivine inclusions, and 3% hibonite‐bearing inclusions. Both simple and complex inclusions are present; some have nodular, banded, or distended structures. No melilite was identified in any of the inclusions in the present suite, but other recent studies have found a few rare occurrences of melilite in Paris CAIs. Because melilite is highly susceptible to aqueous alteration, it is likely that it was mostly destroyed during early‐stage parent‐body alteration. Two of the CAIs in this study are part of compound CAI–chondrule objects. Their presence suggests that there were transient heating events (probably associated with chondrule formation) in the nebula after chondrules and CAIs were admixed. Also present in Paris are a few amoeboid olivine inclusions (AOI) consisting of relatively coarse forsterite rims surrounding fine‐grained, porous zones containing diopside and anorthite. The interior regions of the AOIs may represent fine‐grained rimless CAIs that were incorporated into highly porous forsterite‐rich dustballs. These assemblages were heated by an energy pulse that collapsed and coarsened their rims, but failed to melt their interiors.

The amino acid and hydrocarbon contents of the Paris meteorite: Insights into the most primitive CM chondrite

AbstractThe Paris meteorite is one of the most primitive carbonaceous chondrites. It is reported to be the least aqueously altered CM chondrite, and to have experienced only weak thermal metamorphism. We have analyzed for the first time the amino acid and hydrocarbon contents of this pristine meteorite by gas chromatography–mass spectrometry (GC–MS). When plotting the relative amino acids abundances of several CM chondrites according to the increasing hydrothermal scale (petrologic subtypes), from the CM2.7/2.8 Paris to the CM2.0 MET 01070, Paris has the lowest relative abundance of β‐alanine/glycine (0.15), which fits with the relative abundances of β‐alanine/glycine increasing with increasing aqueous alteration for CM chondrites. These results confirm the influence of aqueous alteration on the amino acid abundances and distribution. The amino acid analysis shows that the isovaline detected in this meteorite is racemic (d/l = 0.99 ± 0.08; l‐enantiomer excess = 0.35 ± 0.5%; corrected d/l = 1.03; corrected l‐enantiomer excess = −1.4 ± 2.6%). The identified hydrocarbons show that Paris has n‐alkanes ranging from C16 to C25 and 3‐ to 5‐ring nonalkylated polycyclic aromatic hydrocarbons (PAHs). The lack of alkylated PAHs in Paris seems to be also related to this low degree of aqueous alteration on its parent body. The extraterrestrial hydrocarbon content, suggested by the absence of any biomarker, may well have a presolar origin. The chemistry of the Paris meteorite may thus be closely related to the early stages of the solar nebula with a contribution from interstellar (molecular cloud) precursors.

Comprehensive study of carbon and oxygen isotopic compositions, trace element abundances, and cathodoluminescence intensities of calcite in the Murchison CM chondrite

We have performed in situ analyses of C and O isotopic compositions, trace element concentrations, and cathodoluminescence (CL) intensities on calcite in Murchison, a weakly altered CM chondrite. We found that the trace element (Mg, Mn, and Fe) concentrations are heterogeneous within single calcite grains. Grain to grain heterogeneity is even more pronounced. The analyzed calcite grains can be separated into two distinct types with respect to their C isotopic ratios, trace element concentrations, and CL characteristics: Calcite grains with higher δ13CPDB values (∼75‰) have low trace element concentrations and uniformly dark CL, while grains with lower δ13C values (∼35‰) have higher trace element concentrations and CL zoning. In contrast to the C isotopic ratios, O isotopic ratios are similar for both types of calcites (δ18OSMOW ∼ 34‰).The O isotopic ratios, trace element concentrations, and CL characteristics provide no evidence for C-isotope evolution in fluids from a single C reservoir by Rayleigh-type isotope fractionation (i.e., removal of C-bearing gaseous species). Also, it seems difficult to explain the O and C isotopic compositions of the two types of calcites by their formation at different temperatures from a single fluid. Instead, the δ13C variation suggests the presence of at least two C reservoirs with different isotopic ratios in the aqueous fluids from which the calcites precipitated. The C reservoirs with lower δ13C values are likely to be organic matter. The same holds for the C reservoirs with higher δ13C values which might have significant contributions from the 13C-enriched grains identified in meteoritic insoluble organic matter. Thermodynamic calculations show that calcite with lower Fe concentrations formed under more reduced conditions than calcite with higher Fe concentrations. If this is the case, the 13C-rich organic grains may have been destroyed and dissolved in the fluids under more reduced conditions than other organic components. The fact that the two types of calcites were found in different domains in the same thin section suggests that microenvironments with diverse physicochemical conditions such as redox states were present at scales of 100’sμm.

The secondary history of Sutter's Mill CM carbonaceous chondrite based on water abundance and the structure of its organic matter from two clasts

AbstractSutter's Mill is a regolith breccia composed of both heavily altered clasts and more reduced xenoliths. Here, we present a detailed investigation of fragments of SM18 and SM51. We have characterized the water content and the mineralogy by infrared (IR) and thermogravimetric analysis (TGA) and the structure of the organic compounds by Raman spectroscopy, to characterize the secondary history of the clasts, including aqueous alteration and thermal metamorphism. The three methods used in this study suggest that SM18 was significantly heated. The amount of water contained in phyllosilicates derived by TGA is estimated to be approximately 3.2 wt%. This value is quite low compared with other CM chondrites that typically range from 6 to 12 wt%. The infrared transmission spectra of SM18 show that the mineralogy of the sample is dominated by a mixture of phyllosilicate and olivine. SM18 shows an intense peak at 11.2 μm indicative of olivine (Fig. 1). If we compare SM18 with other CM and metamorphosed CM chondrites, it shows one of the most intense olivine signatures, and therefore a lower proportion of phyllosilicate minerals. The Raman results tend to support a short‐duration heating hypothesis. In the ID/IG versus FWHM‐D diagram, SM18 appears to be unusual compared to most CM samples, and close to the metamorphosed CM chondrites Pecora Escarpment (PCA) 91008 and PCA 02012. In the case of SM51, infrared spectroscopy reveals that olivine is less abundant than in SM18 and the 10 μm silicate feature is more similar to that of moderately altered CM chondrites (like Murchison or Queen Alexandra Range [QUE] 97990). Raman spectroscopy does not clearly point to a heating event for SM51 in the ID/IG versus FWHM‐D diagram. However, TGA analysis suggests that SM51 was slightly dehydrated as the amount of water contained in phyllosilicates is approximately 3.7 wt%, which is higher than SM18, but still lower than phyllosilicate water contents in weakly altered CM chondrites. Altogether, these results confirm that fragments with different secondary histories are present within the Sutter's Mill fall. The dehydration that is clearly observed for SM18 is attributed to a short‐duration heating based on the similarity of its Raman spectra to that of PCA 91008. Because of the brecciated nature of Sutter's Mill and the presence of adjacent clasts with different thermal histories, impacts that can efficiently fragment and heat porous materials are the preferred heat source.

The Paris meteorite, the least altered CM chondrite so far

The Paris chondrite provides an excellent opportunity to study CM chondrules and refractory inclusions in a more pristine state than currently possible from other CMs, and to investigate the earliest stages of aqueous alteration captured within a single CM bulk composition. It was found in the effects of a former colonial mining engineer and may have been an observed fall. The texture, mineralogy, petrography, magnetic properties and chemical and isotopic compositions are consistent with classification as a CM2 chondrite. There are ∼45vol.% high-temperature components mainly Type I chondrules (with olivine mostly Fa0–2, mean Fa0.9) with granular textures because of low mesostasis abundances. Type II chondrules contain olivine Fa7 to Fa76. These are dominantly of Type IIA, but there are IIAB and IIB chondrules, II(A)B chondrules with minor highly ferroan olivine, and IIA(C) with augite as the only pyroxene. The refractory inclusions in Paris are amoeboid olivine aggregates (AOAs) and fine-grained spinel-rich Ca–Al-rich inclusions (CAIs). The CAI phases formed in the sequence hibonite, perovskite, grossite, spinel, gehlenite, anorthite, diopside/fassaite and forsterite. The most refractory phases are embedded in spinel, which also occurs as massive nodules. Refractory metal nuggets are found in many CAI and refractory platinum group element abundances (PGE) decrease following the observed condensation sequences of their host phases. Mn–Cr isotope measurements of mineral separates from Paris define a regression line with a slope of 53Mn/55Mn=(5.76±0.76)×106. If we interpret Cr isotopic systematics as dating Paris components, particularly the chondrules, the age is 4566.44±0.66Myr, which is close to the age of CAI and puts new constraints on the early evolution of the solar system. Eleven individual Paris samples define an O isotope mixing line that passes through CM2 and CO3 falls and indicates that Paris is a very fresh sample, with variation explained by local differences in the extent of alteration. The anhydrous precursor to the CM2s was CO3-like, but the two groups differed in that the CMs accreted a higherproportion of water. Paris has little matrix (∼47%, plus 8% fine grained rims) and is less altered than other CM chondrites. Chondrule silicates (except mesostasis), CAI phases, submicron forsterite and amorphous silicate in the matrix are all well preserved in the freshest domains, and there is abundant metal preserved (metal alteration stage 1 of Palmer and Lauretta (2011)). Metal and sulfide compositions and textures correspond to the least heated or equilibrated CM chondrites, Category A of Kimura et al. (2011). The composition of tochilinite–cronstedtite intergrowths gives a PCP index of ∼2.9. Cronstedtite is more abundant in the more altered zones whereas in normal highly altered CM chondrites, with petrologic subtype 2.6–2.0 based on the S/SiO2 and ∑FeO/SiO2 ratios in PCP or tochilinite–cronstedtite intergrowths (Rubin et al., 2007), cronstedtite is destroyed by alteration. The matrix in fresh zones has CI chondritic volatile element abundances, but interactions between matrix and chondrules occurred during alteration, modifying the volatile element abundances in the altered zones. Paris has higher trapped Ne contents, more primitive organic compounds, and more primitive organic material than other CMs. There are gradational contacts between domains of different degree of alteration, on the scale of ∼1cm, but also highly altered clasts, suggesting mainly a water-limited style of alteration, with no significant metamorphic reheating.