Aqueous alteration of kamacite in CM chondrites

Abstract– The study of aqueous alteration of kamacite in CM chondrites provides insight on the conditions, products, and relative timing of aqueous alteration. We studied unaltered, partially altered, and fully altered kamacite grains from Murray, Murchison, Cold Bokkeveld, and Nogoya using optical microscopy, electron microprobe analysis, scanning electron microscopy, and Raman spectroscopy. From textual evidence and chemical analysis, we established three separate microchemical environments. 1) In a microchemical environment with a high S activity, kamacite alters to form tochilinite, P‐bearing sulfides, eskolaite, and schreibersite. Mass balance calculations show that 81% of the Fe in kamacite is removed from the alteration region, making it available for the formation of other minerals or Fe‐rich aureoles. The release of Fe can alter the mesostasis of type‐I chondrules forming cronstedtite. 2) In a microchemical environment with a high Si activity and a low S activity, kamacite alters to form cronstedtite with small accessory sulfide inclusions. 3) A microchemical environment with limited S and Si activity results in kamacite alteration forming magnetite. The resulting magnetite retains associated Ni that can distinguish it from precipitated magnetite. In addition, the accessory phases of pentlandite and apatite can be formed if S or Ca are present. Finally, we note that small tochilinite grains in the matrix lack typical Ni, P, and Co levels, suggesting that they did not form from kamacite but possibly by sulfidization of magnetite.     

Northwest Africa 11024—A heated and dehydrated unique carbonaceous (CM) chondrite

Based on the high abundance of fine‐grained material and its dark appearance, NWA 11024 was recognized as a CM chondrite, which is also confirmed by oxygen isotope measurements. But contrary to known CM chondrites, the typical phases indicating aqueous alteration (e.g., phyllosilicates, carbonates) are missing. Using multiple analytical techniques, this study reveals the differences and similarities to known CM chondrites and will discuss the possibility that NWA 11024 is the first type 3 CM chondrite. During the investigation, two texturally apparent tochilinite–cronstedtite intergrowths were identified within two thin sections. However, the former phyllosilicates were recrystallized to Fe‐rich olivine during a heating event without changing the textural appearance. A peak temperature of 400–600 °C is estimated, which is not high enough to destroy or recrystallize calcite grains. Thus, calcites were never constituents of the mineral paragenesis. Another remarkable feature of NWA 11024 is the occurrence of unknown clot‐like inclusions (UCLIs) within fine‐grained rims, which are unique in this clarity. Their density and S concentration are significantly higher than of the surrounding fine‐grained rim and UCLIs can be seen as primary objects that were not formed by secondary alteration processes inside the rims. Similarities to chondritic and cometary interplanetary dust particles suggest an ice‐rich first‐generation planetesimal for their origin. In the earliest evolution, NWA 11024 experienced the lowest degree of aqueous alteration of all known CM chondrites and subsequently, a heating event dehydrated the sample. We suggest to classify the meteorite NWA 11024 as the first type 3 CM chondrite similar to the classification of CV3 chondrites (like Allende) that could also have lost their matrix phyllosilicates by thermal dehydration.     

Deciphering the conditions of tochilinite and cronstedtite formation in CM chondrites from low temperature hydrothermal experiments

Tochilinite/cronstedtite intergrowths are commonly observed as alteration products in CM chondrite matrices, but the conditions under which they formed are still largely underconstrained due to their scarcity in terrestrial environments. Here, we report low temperature (80 °C) anoxic hydrothermal experiments using starting assemblages similar to the constituents of the matrices of the most pristine CM chondrite and S‐rich and S‐free fluids. Cronstedtite crystals formed only in S‐free experiments under circumneutral conditions with the highest Fe/Si ratios. Fe‐rich tochilinite with chemical and structural characteristics similar to chondritic tochilinite was observed in S‐bearing experiments. We observed a positive correlation between the Mg content in the hydroxide layer of synthetic tochilinite and temperature, suggesting that the composition of tochilinite is a proxy for the alteration temperature in CM chondrites. Using this relation, we estimate the mean precipitation temperatures of tochilinite to be 120–160 °C for CM chondrites. Given the different temperature ranges of tochilinite and cronstedtite in our experiments, we propose that Fe‐rich tochilinite crystals resulted from the alteration of metal beads under S‐bearing alkaline conditions at T = 120–160 °C followed by cronstedtite crystals formed by the reaction of matrix amorphous silicates, metal beads, and water at a low temperature (50–120 °C).     

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

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

Polyhedral serpentine grains in CM chondrites

Abstract— We used high‐resolution transmission electron microscopy (HRTEM), electron tomography, electron energy‐loss spectroscopy (EELS), and energy‐dispersive spectroscopy (EDS) to investigate the structure and composition of polyhedral serpentine grains that occur in the matrices and fine‐grained rims of the Murchison, Mighei, and Cold Bokkeveld CM chondrites. The structure of these grains is similar to terrestrial polygonal serpentine, but the data show that some have spherical or subspherical, rather than cylindrical morphologies. We therefore propose that the term polyhedral rather than polygonal be used to describe this material. EDS shows that the polyhedral grains are rich in Mg with up to 8 atom% Fe. EELS indicates that 70% of the Fe occurs as Fe³⁺. Alteration of cronstedtite on the meteorite parent body under relatively oxidizing conditions is one probable pathway by which the polyhedral material formed. The polyhedral grains are the end‐member serpentine in a mineralogic alteration sequence for the CM chondrites.     

The presolar grain inventory of fine‐grained chondrule rims in the Mighei‐type (CM) chondrites

We investigated the inventory of presolar silicate, oxide, and silicon carbide (SiC) grains of fine‐grained chondrule rims in six Mighei‐type (CM) carbonaceous chondrites (Banten, Jbilet Winselwan, Maribo, Murchison, Murray and Yamato 791198), and the CM‐related carbonaceous chondrite Sutter's Mill. Sixteen O‐anomalous grains (nine silicates, six oxides) were detected, corresponding to a combined matrix‐normalized abundance of ~18 ppm, together with 21 presolar SiC grains (~42 ppm). Twelve of the O‐rich grains are enriched in ¹⁷O, and could originate from low‐mass asymptotic giant branch stars. One grain is enriched in ¹⁷O and significantly depleted in ¹⁸O, indicative of additional cool bottom processing or hot bottom burning in its stellar parent, and three grains are of likely core‐collapse supernova origin showing enhanced ¹⁸O/¹⁶O ratios relative to the solar system ratio. We find a presolar silicate/oxide ratio of 1.5, significantly lower than the ratios typically observed for chondritic meteorites. This may indicate a higher degree of aqueous alteration in the studied meteorites, or hint at a heterogeneous distribution of presolar silicates and oxides in the solar nebula. Nevertheless, the low O‐anomalous grain abundance is consistent with aqueous alteration occurring in the protosolar nebula and/or on the respective parent bodies. Six O‐rich presolar grains were studied by Auger Electron Spectroscopy, revealing two Fe‐rich silicates, one forsterite‐like Mg‐rich silicate, two Al‐oxides with spinel‐like compositions, and one Fe‐(Mg‐)oxide. Scanning electron and transmission electron microscopic investigation of a relatively large silicate grain (490 nm × 735 nm) revealed that it was crystalline åkermanite (Ca₂Mg[Si₂O₇]) or a an åkermanite‐diopside (MgCaSi₂O₆) intergrowth.     

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

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

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

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

Indigenous aliphatic amines in the aqueously altered Orgueil meteorite

The CI1 Orgueil meteorite is a highly aqueously altered carbonaceous chondrite. It has been extensively studied, and despite its extensive degree of aqueous alteration and some documented instances of contamination, several indigenous organic compounds including amino acids, carboxylic acids, and nucleobases have been detected in its carbon‐rich matrix. We recently developed a novel gas chromatographic method for the enantiomeric and compound‐specific isotopic analyses of meteoritic aliphatic monoamines in extracts and have now applied this method to investigate the monoamine content in Orgueil. We detected 12 amines in Orgueil, with concentrations ranging from 1.1 to 332 nmol g^?1 of meteorite and compared this amine content in Orgueil with that of the CM2 Murchison meteorite, which experienced less parent‐body aqueous alteration. Methylamine is four times more abundant in Orgueil than in Murchison. As with other species, the amine content in Orgueil extracts shows less structural diversity than that in Murchison extracts. We measured the compound‐specific stable carbon isotopic ratios (δ¹³C) for 5 of the 12 monoamines detected in Orgueil and found a range of δ¹³C values from –20 to +59‰. These δ¹³C values fall into the range of other meteoritic organic compounds, although they are ¹³C‐depleted relative to their counterparts extracted from the Murchison meteorite. In addition, we measured the enantiomeric composition for the chiral monoamines (R)‐ and (S)‐sec‐butylamine in Orgueil, and found it was racemic within experimental error, in contrast with the l ‐enantiomeric excess found for its amino acid structural analog isovaline. The racemic nature of sec‐butylamine in Orgueil was comparable to that previously observed in Murchison, and to other CM2 and CR2 carbonaceous chondrites measured in this work (ALH 83100 [CM1/2], LON 94101 [CM2], LEW 90500 [CM2], LAP 02342 [CR2], and GRA 95229 [CR2]). These results allow us to place some constraints on the effects of aqueous alteration observed over the monoamine concentrations in Orgueil and Murchison, and to evaluate the primordial synthetic relationships between meteoritic monoamines and amino acids.     

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.     

A microchondrule‐bearing micrometeorite and comparison with microchondrules in CM chondrites

We report the discovery of a partially altered microchondrule within a fine‐grained micrometeorite. This object is circular, <10 μm in diameter, and has a cryptocrystalline texture, internal zonation, and a thin S‐bearing rim. These features imply a period of post‐accretion parent body aqueous alteration, in which the former glassy igneous texture was subject to hydration and phyllosilicate formation as well as leaching of fluid‐mobile elements. We compare this microchondrule to three microchondrules found in two CM chondrites: Elephant Moraine (EET) 96029 and Murchison. In all instances, their formation appears closely linked to the late stages of chondrule formation, chondrule recycling, and fine‐grained rim accretion. Likewise, they share cryptocrystalline textures and evidence of mild aqueous alteration and thus similar histories. We also investigate the host micrometeorite's petrology, which includes an unusually Cr‐rich mineralogy, containing both Mn‐chromite spinel and low‐Fe‐Cr‐rich (LICE) anhydrous silicates. Because these two refractory phases cannot form together in a single geochemical reservoir under equilibrium condensation, this micrometeorite's accretionary history requires a complex timeline with formation via nonequilibrium batch crystallization or accumulation of materials from large radial distances. In contrast, the bulk composition of this micrometeorite and its internal textures are consistent with a hydrated carbonaceous chondrite source. This micrometeorite is interpreted as a fragment of fine‐grained rim material that once surrounded a larger parent chondrule and was derived from a primitive carbonaceous parent body; either a CM chondrite or Jupiter family comet.     

Fe‐Ni metal in primitive chondrites: Indicators of classification and metamorphic conditions for ordinary and CO chondrites

Abstract— We report the results of our petrological and mineralogical study of Fe‐Ni metal in type 3 ordinary and CO chondrites, and the ungrouped carbonaceous chondrite Acfer 094. Fe‐Ni metal in ordinary and CO chondrites occurs in chondrule interiors, on chondrule surfaces, and as isolated grains in the matrix. Isolated Ni‐rich metal in chondrites of petrologic type lower than type 3.10 is enriched in Co relative to the kamacite in chondrules. However, Ni‐rich metal in type 3.15–3.9 chondrites always contains less Co than does kamacite. Fe‐Ni metal grains in chondrules in Semarkona typically show plessitic intergrowths consisting of submicrometer kamacite and Ni‐rich regions. Metal in other type 3 chondrites is composed of fine‐ to coarse‐grained aggregates of kamacite and Ni‐rich metal, resulting from metamorphism in the parent body. We found that the number density of Ni‐rich grains in metal (number of Ni‐rich grains per unit area of metal) in chondrules systematically decreases with increasing petrologic type. Thus, Fe‐Ni metal is a highly sensitive recorder of metamorphism in ordinary and carbonaceous chondrites, and can be used to distinguish petrologic type and identify the least thermally metamorphosed chondrites. Among the known ordinary and CO chondrites, Semarkona is the most primitive. The range of metamorphic temperatures were similar for type 3 ordinary and CO chondrites, despite them having different parent bodies. Most Fe‐Ni metal in Acfer 094 is martensite, and it preserves primary features. The degree of metamorphism is lower in Acfer 094, a true type 3.00 chondrite, than in Semarkona, which should be reclassified as type 3.01.     

The effects of secondary processing in the unique carbonaceous chondrite Miller Range 07687

Our detailed mineralogical, elemental, and isotopic study of the Miller Range (MIL) 07687 meteorite showed that, although this meteorite has affinities to CO chondrites, it also exhibits sufficient differences to warrant classification as an ungrouped carbonaceous chondrite. The most notable feature of MIL 07687 is the presence of two distinct matrix lithologies that result from highly localized aqueous alteration. One of these lithologies is Fe‐rich and exhibits evidence for interaction with water, including the presence of fibrous (dendritic) ferrihydrite. The other lithology, which is Fe‐poor, appears to represent relatively unaltered protolith material. MIL 07687 has presolar grain abundances consistent with those observed in other modestly altered carbonaceous chondrites: the overall abundance of O‐rich presolar grains is 137 ± 3 ppm and the overall abundance of SiC grains is 71 ± 11 ppm. However, there is a large difference in the observed O‐rich and SiC grain number densities between altered and unaltered areas, reflecting partial destruction of presolar grains (both O‐ and C‐rich grains) due to the aqueous alteration experienced by MIL 07687 under highly oxidizing conditions. Detailed coordinated NanoSIMS‐TEM analysis of a large hotspot composed of an isotopically normal core surrounded by a rim composed of ¹⁷O‐rich grains is consistent with either original condensation of the core and surrounding grains in the same parent AGB star, or with grain accretion in the ISM or solar nebula.     

Presolar silicate and oxide abundances and compositions in the ungrouped carbonaceous chondrite Adelaide and the K chondrite Kakangari: The effects of secondary processing

Abstract– Although it has been suggested that the ungrouped carbonaceous chondrite Adelaide and the K chondrite Kakangari could be considered highly primitive, our study of their presolar grain abundances shows that both have experienced more secondary processing than other primitive chondrites with high presolar grain abundances. Presolar grains are rare in Kakangari and are present in reduced abundances in Adelaide (approximately 70 ppm for O‐anomalous grains). Thermal annealing has led to widespread crystallization of their fine‐grained matrices, and accounts for the partial to complete destruction of presolar grains. In addition, presolar silicates in Adelaide show elevated Fe abundances and Fe‐rich rims indicative of infiltration of Fe into the grains from the surrounding matrix. This process probably also took place during annealing, most likely in the solar nebula, in a region with an enhanced dust‐to‐gas ratio. The most primitive meteorites, with the highest presolar grain abundances, appear to be those whose matrices contain abundant amorphous material that has escaped any significant thermal or aqueous alteration.     

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.     

The Paris CM chondrite: Secondary minerals and asteroidal processing

We report a petrographic and mineralogical survey of Paris, a new CM chondrite considered to be the least‐altered CM identified so far (Hewins et al. 2014 ). Compared to other CMs, Paris exhibits (1) a higher concentration of Fe‐Ni metal beads, with nickel contents in the range 4.1–8.1 wt%; (2) the systematic presence of thin lamellae and tiny blebs of pentlandite in pyrrhotite grains; and (3) ubiquitous tochilinite/cronstedtite associations with higher FeO/SiO₂ and S/SiO₂ ratios. In addition, Paris shows the highest concentration of trapped ³⁶Ar reported so far for a CM chondrite (Hewins et al. 2014 ). In combination with the findings of previous studies, our data confirm the reliability of (1) the alteration sequence based on the chemical composition of tochilinite/cronstedtite associations to quantify the fluid alteration processes and (2) the use of Cr content variability in type II ferroan chondrule olivine as a proxy of thermal metamorphism. In contrast, the scales based on (1) the Fe³⁺ content of serpentine in the matrix to estimate the degree of aqueous alteration and (2) the chemical composition of Fe‐Ni metal beads for quantifying the intensity of the thermal metamorphism are not supported by the characteristics of Paris. It also appears that the amount of trapped ³⁶Ar is a sensitive indicator of the secondary alteration modifications experienced by chondrites, for both aqueous alteration and thermal metamorphism. Considering Paris, our data suggest that this chondrite should be classified as type 2.7 as it suffered limited but significant fluid alteration and only mild thermal metamorphism. These results point out that two separated scales should be used to quantify the degree of the respective role of aqueous alteration and thermal metamorphism in establishing the characteristics of CM chondrites.     

The role of Bells in the continuous accretion between the CM and CR chondrite reservoirs

CM meteorites are dominant members of carbonaceous chondrites (CCs), which evidently accreted in a region separated from the terrestrial planets. These chondrites are key in determining the accretion regions of solar system materials, since in Mg and Cr isotope space, they intersect between what are identified as inner and outer solar system reservoirs. In this model, the outer reservoir is represented by metal‐rich carbonaceous chondrites (MRCCs), including CR chondrites. An important question remains whether the barrier between MRCCs and CCs was a temporal or spatial one. CM chondrites and chondrules are used here to identify the nature of the barrier as well as the timescale of chondrite parent body accretion. We find based on high precision Mg and Cr isotope data of seven CM chondrites and 12 chondrules, that accretion in the CM chondrite reservoir was continuous lasting <3 Myr and showing late accretion of MRCC‐like material reflected by the anomalous CM chondrite Bells. We further argue that although MRCCs likely accreted later than CM chondrites, CR chondrules must have initially formed from a reservoir spatially separated from CM chondrules. Finally, we hypothesize on the nature of the spatial barrier separating these reservoirs.     

Multiple precursors of secondary mineralogical assemblages in CM chondrites

We report a petrographic and mineralogical survey of tochilinite/cronstedtite intergrowths (TCIs) in Paris, a new CM chondrite considered to be the least altered CM identified to date. Our results indicate that type‐I TCIs consist of compact tochilinite/cronstedtite rims surrounding Fe‐Ni metal beads, thus confirming kamacite as the precursor of type‐I TCIs. In contrast, type‐II TCIs are characterized by complex compositional zoning composed of three different Fe‐bearing secondary minerals: from the outside inwards, tochilinite, cronstedtite, and amakinite. Type‐II TCIs present well‐developed faces that allow a detailed morphological analysis to be performed in order to identify the precursors. The results demonstrate that type‐II TCIs formed by pseudomorphism of the anhydrous silicates, olivine, and pyroxene. Hence, there is no apparent genetic relationship between type‐I and type‐II TCIs. In addition, the complex chemical zoning observed within type‐II TCIs suggests that the alteration conditions evolved dramatically over time. At least three stages of alteration can be proposed, characterized by alteration fluids with varying compositions (1) Fe‐ and S‐rich fluids; (2) S‐poor and Fe‐ and Si‐rich fluids; and (3) S‐ and Si‐poor, Fe‐rich fluids. The presence of unaltered silicates in close association with euhedral type‐II TCIs suggests the existence of microenvironments during the first alteration stages of CM chondrites. In addition, the absence of Mg‐bearing secondary minerals in Paris TCIs suggests that the Mg content increases during the course of alteration.     

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.     

Fe‐Ni metal and sulfide minerals in CM chondrites: An indicator for thermal history

Abstract– CM chondrites were subjected to aqueous alteration and, in some cases, to secondary metamorphic heating. The effects of these processes vary widely, and have mainly been documented in silicate phases. Herein, we report the characteristic features of Fe‐Ni metal and sulfide phases in 13 CM and 2 CM‐related chondrites to explore the thermal history of these chondrites. The texture and compositional distribution of the metal in CM are different from those in unequilibrated ordinary and CO chondrites, but most have similarities to those in highly primitive chondrites, such as CH, CR, and Acfer 094. We classified the CM samples into three categories based on metal composition and sulfide texture. Fe‐Ni metal in category A is kamacite to martensite. Category B is characterized by pyrrhotite grains always containing blebs or lamellae of pentlandite. Opaque mineral assemblages of category C are typically kamacite, Ni‐Co‐rich metal, and pyrrhotite. These categories are closely related to the degree of secondary heating and are not related to degree of the aqueous alteration. The characteristic features of the opaque minerals can be explained by secondary heating processes after aqueous alteration. Category A CM chondrites are unheated, whereas those in category B experienced small degrees of secondary heating. CMs in category C were subjected to the most severe secondary heating process. Thus, opaque minerals can provide constraints on the thermal history for CM chondrites.