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.     

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

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

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

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

Evaporation of nebular fines during chondrule formation

Studies of matrix in primitive chondrites provide our only detailed information about the fine fraction (diameter <2 μm) of solids in the solar nebula. A minor fraction of the fines, the presolar grains, offers information about the kinds of materials present in the molecular cloud that spawned the Solar System. Although some researchers have argued that chondritic matrix is relatively unaltered presolar matter, meteoritic chondrules bear witness to multiple high-temperature events each of which would have evaporated those fines that were inside the high-temperature fluid. Because heat is mainly transferred into the interior of chondrules by conduction, the surface temperatures of chondrules were probably at or above 2000 K. In contrast, the evaporation of mafic silicates in a canonical solar nebula occurs at around 1300 K and FeO-rich, amorphous, fine matrix evaporates at still lower temperatures, perhaps near 1200 K. Thus, during chondrule formation, the temperature of the placental bath was probably >700 K higher than the evaporation temperatures of nebular fines. The scale of chondrule forming events is not known. The currently popular shock models have typical scales of about ¹⁰⁵ km. The scale of nebular lightning is less well defined, but is certainly much smaller, perhaps in the range 1 to 1000 m. In both cases the temperature pulses were long enough to evaporate submicrometer nebular fines. This interpretation disagrees with common views that meteoritic matrix is largely presolar in character and CI-chondrite-like in composition. It is inevitable that presolar grains (both those recognized by their anomalous isotopic compositions and those having solar-like compositions) that were within the hot fluid would also have evaporated. Chondrule formation appears to have continued down to the temperatures at which planetesimals formed, possibly around 250 K. At temperatures >600 K, the main form of C is gaseous CO. Although the conversion of CO to CH₄ at lower temperatures is kinetically inhibited, radiation associated with chondrule formation would have accelerated the conversion. There is now evidence that an appreciable fraction of the nanodiamonds previously held to be presolar were actually formed in the solar nebula. Industrial condensation of diamonds from mixtures of CH₄ and H₂ implies that high nebular CH₄/CO ratios favored nanodiamond formation. A large fraction of chondritic insoluble organic matter may have formed in related processes. At low nebular temperatures appreciable water should have been incorporated into the smoke that condensed following dust (and some chondrule) evaporation. If chondrule formation continued down to temperatures as low as 250 K this process could account for the water concentration observed in primitive chondrites such as LL3.0 and CO3.0 chondrites. Higher H₂O contents in CM and CI chondrites may reflect asteroidal redistribution. In some chondrite groups (e.g., CR) the Mg/Si ratio of matrix material is appreciably (30%) lower than that of chondrules but the bulk Mg/Si ratio is roughly similar to the CI or solar ratio. This has been interpreted as a kind of closed-system behavior sometimes called “complementarity.” This leads to the conclusion that nebular fines were efficiently agglomerated. Its importance, however is obscured by the observation that bulk Mg/Si ratios in ordinary and enstatite chondrites are much lower than those in carbonaceous chondrites, and thus that complementarity did not hold throughout the solar nebula.     

Aqueous alteration of carbonaceous chondrites: Evidence for preaccretionary alteration—A review

Abstract— In most groups of carbonaceous chondrites, minerals occur that are formed due to aqueous alteration in the nebula and/or within meteorite parent bodies. For determining the evolution of materials in the early solar system, it is of significant importance to clearly identify evidence for either nebular or planetary aqueous alteration. Therefore, results from the study of chondrites have fundamental implications for ideas concerning nebular dynamics, gas-solid interactions in the nebula, and accretionary processes. Considering the topic of this review, it is important to define nebular and parent body processes. The solar nebula activity should include condensation processes of high- and low-temperature components as well as processes of chemical fractionation and grain-size sorting, mixing of solids and gas, and interactions between early formed solids with the remaining gas; but it should exclude processes that occurred in small uncompacted protoplanetary objects that may have been totally destroyed again before accretion of the final meteorite parent bodies. Therefore, the term “preaccretionary” instead of “nebula” is used in this paper to include all these processes that may have occurred in small precursor planetesimals. Currently, there is no doubt that parent body aqueous alteration is a fundamental process in the evolution of several groups of carbonaceous chondrites. However, due to textural and mineralogical observations and chemical analyses, strong arguments have been found also indicating preaccretionary aqueous alteration of distinct components in carbonaceous chondrites. In this paper, evidence for preaccretionary aqueous alteration in carbonaceous chondrites and their components taken from previous studies is discussed in detail. The strongest evidence for preaccretionary alteration comes from studies of CM chondrites. The survival of highly unequilibrated mineral assemblages in accretionary rims, and sharp contacts between chondrule glass and surrounding phyllosilicates, are only two important arguments for preaccretionary alteration features among many others discussed in the paper. Similar observations were also made in CR, CH and related chondrites. Due to the small abundance of water-bearing phases in CO and CV chondrites, the origin of phyllosilicates in these groups is less clear. A preaccretionary origin of hydrous phases in Ca-Al-rich inclusions (CAIs) has also been suggested by several scientists. In CI chondrites, no strong indications for such processes have been found, mainly due to heavy brecciation and severe parent body alteration.     

Opaque assemblages in CR2 Graves Nunataks (GRA) 06100 as indicators of shock‐driven hydrothermal alteration in the CR chondrite parent body

We have studied the petrologic characteristics of sulfide‐metal lodes, polymineralic Fe‐Ni nodules, and opaque assemblages in the CR2 chondrite Graves Nunataks (GRA) 06100, one of the most altered CR chondrites. Unlike low petrologic type CR chondrites, alteration of metal appears to have played a central role in the formation of secondary minerals in GRA 06100. Differences in the mineralogy and chemical compositions of materials in GRA 06100 suggest that it experienced higher temperatures than other CR2 chondrites. Mineralogic features indicative of high temperature include: (1) exsolution of Ni‐poor and Ni‐rich metal from nebular kamacite; (2) formation of sulfides, oxides, and phosphates; (3) changes in the Co/Ni ratios; and (4) carbidization of Fe‐Ni metal. The conspicuous absence of pentlandite may indicate that peak temperatures exceeded 600 °C. Opaques appear to have been affected by the action of aqueous fluids that resulted in the formation of abundant oxides, Fe‐rich carbonates, including endmember ankerite, and the sulfide‐silicate‐phosphate scorzalite. We suggest that these materials formed via impact‐driven metamorphism. Mineralogic features indicative of impact metamorphism include (1) the presence of sulfide‐metal lodes; (2) the abundance of polymineralic opaque assemblages with mosaic‐like textures; and (3) the presence of suessite. Initial shock metamorphism probably resulted in replacement of nebular Fe‐Ni metal in chondrules and in matrix by Ni‐rich, Co‐rich Fe metal, Al‐Ti‐Cr‐rich alloys, and Fe sulfides, while subsequent hydrothermal alteration produced accessory oxides, phosphates, and Fe carbonates. An extensive network of sulfide‐metal veins permitted effective exchange of siderophile elements from pre‐existing metal nodules with adjacent chondrules and matrix, resulting in unusually high Fe contents in these objects.     

Fractionated sulfur isotopes in sulfides of the Kaidun meteorite

Abstract— The Kaidun meteorite contains carbonaceous chondrite (CM1) clasts that have been highly altered by reactions with hydrothermal fluids. Pyrrhotite in these clasts occurs as unusual needles wrapped by sheaths of phyllosilicate, and pentlandite forms veins that crosscut aggregates of phyllosilicate and garnet but not pyrrhotite. The isotopic compositions of S (δ³⁴S_CDT) in individual sulfide grains, measured by ion micro-probe, are fractionated compared to troilite in ordinary chondrites. The S in Kaidun sulfides is isotopically light (as much as ?4.2% for pyrrhotite and ?5.7%0 for pentlandite), unlike sulfides in other carbonaceous chondrites, which are enriched in ³⁴S. The unusual S-isotopic composition of these texturally unique sulfides supports the hypothesis that Kaidun CM1 clasts were pervasively altered under extreme thermal conditions, possibly by fluids that had lost isotopically heavy SO₂.     

Sulfide–oxide assemblages in Acfer 094—Clues to nebular metal–gas interactions

The ungrouped carbonaceous chondrite Acfer 094 is among the least altered samples of the early solar system. We have studied concentric sulfide–oxide aggregates from this meteorite by transmission electron microscopy (TEM) and nanoscale secondary ion mass spectrometry (NanoSIMS). The main minerals present are magnetite, pentlandite, and pyrrhotite/troilite. The outer parts of the aggregates include μm-sized olivine and pyroxenes with variable Mg/Fe ratios. One aggregate contains taenite (56.7 wt% Ni) within its central part that is surrounded by pentlandite and magnetite. We conclude that both phases have formed by oxidation and sulfidization of metal and, based on the metal and sulfide Fe/Ni ratio, a (sulfide)-formation temperature of 400–550 °C can be constrained. This temperature is higher than any temperature that could be expected to have occurred on the Acfer 094 parent body, and also textural evidence indicates that the aggregates formed before parent-body accretion. We therefore conclude that the formation of the sulfide–oxide aggregates occurred most likely in the solar nebular at highly variable H₂O and H₂S fugacities. Oxygen-isotopic compositions of magnetite within these assemblages show that they are indistinguishable from the meteorite's matrix (δ¹⁷O_SMOW ≈ 4 ± 8‰, δ¹⁸O_SMOW ≈ 10 ± 6‰, and ∆¹⁷O_SMOW ≈ −1 ± 5‰). An enrichment of ^17,18O relative to chondrules of Acfer 094 suggests a link between the formation of the sulfide–oxide aggregates and the preaccretionary processing of matrix grains in a volatile-enriched nebular environment.     

Origin of the differences in refractory-lithophile-element abundances among chondrite groups

Chondrite groups can be distinguished on the basis of their abundances of refractory lithophile elements (RLE). These abundances are, in part, functions of the mass fraction of Ca-Al-rich inclusions (CAIs) within the chondrites. Carbonaceous chondrites contain the most CAIs and the highest RLE abundances; they also contain modally abundant fine-grained matrix material that consists largely of modified nebular dust. The amount of dust varied throughout the solar nebula: enstatite and ordinary chondrites formed in low-dust regions in the inner part of the nebula, R chondrites formed in higher-dust zones at somewhat greater heliocentric distances, and carbonaceous chondrites formed in even dustier regions farther from the Sun. The amount of ambient dust peaked in the region where CV and CK chondrites accreted; these chondrites have abundant matrix, the highest modal abundances of CAIs, and the highest bulk RLE contents. Substantial amounts of nebular dust occurred in highly porous multi-millimeter-to-centimeter-size dustballs that were on the order of 100 times more massive than CAIs. Radial drift processes in the nebula affected these dustballs to approximately the same extent as the CAIs; both types of objects were aerodynamically concentrated in the same nebular regions. These regions maintained approximately the same relative amounts of dust through the periods of chondrule formation and chondrite accretion.     

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.     

Chondrules: Precursors and interactions with the nebular gas

Abstract– Chondrule compositions suggest either ferroan precursors and evaporation, or magnesian precursors and condensation. Type I chondrule precursors include granoblastic olivine aggregates (planetary or nebular) and fine‐grained (dustball) precursors. In carbonaceous chondrites, type I chondrule precursors were S‐free, while type II chondrules have higher Fe/Mn than in ordinary chondrites. Many type II chondrules contain diverse forsteritic relicts, consistent with polymict dustball precursors. The relationship between finer and coarser grained type I chondrules in ordinary chondrites suggests more evaporation from more highly melted chondrules. Fe metal in type I, and Na and S in type II chondrules indicate high partial pressures in ambient gas, as they are rapidly evaporated at canonical conditions. The occurrence of metal, sulfide, or low‐Ca pyroxene on chondrule rims suggests (re)condensation. In Semarkona type II chondrules, Na‐rich olivine cores, Na‐poor melt inclusions, and Na‐rich mesostases suggest evaporation followed by recondensation. Type II chondrules have correlated FeO and MnO, consistent with condensation onto forsteritic precursors, but with different ratios in carbonaceous chondrites and ordinary chondrites, indicating different redox history. The high partial pressures of lithophile elements require large dense clouds, either clumps in the protoplanetary disk, impact plumes, or bow shocks around protoplanets. In ordinary chondrites, clusters of type I and type II chondrules indicate high number densities and their similar oxygen isotopic compositions suggest recycling together. In carbonaceous chondrites, the much less abundant type II chondrules were probably added late to batches of type I chondrules from different O isotopic reservoirs.     

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

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

The formation and alteration of the Renazzo‐like carbonaceous chondrites III: Toward understanding the genesis of ferromagnesian chondrules

To better understand the formation conditions of ferromagnesian chondrules from the Renazzo‐like carbonaceous (CR) chondrites, a systematic study of 210 chondrules from 15 CR chondrites was conducted. The texture and composition of silicate and opaque minerals from each observed FeO‐rich (type II) chondrule, and a representative number of FeO‐poor (type I) chondrules, were studied to build a substantial and self‐consistent data set. The average abundances and standard deviations of Cr₂O₃ in FeO‐rich olivine phenocrysts are consistent with previous work that the CR chondrites are among the least thermally altered samples from the early solar system. Type II chondrules from the CR chondrites formed under highly variable conditions (e.g., precursor composition, redox conditions, cooling rate), with each chondrule recording a distinct igneous history. The opaque minerals within type II chondrules are consistent with formation during chondrule melting and cooling, starting as S‐ and Ni‐rich liquids at 988–1350 °C, then cooling to form monosulfide solid solution (mss) that crystallized around olivine/pyroxene phenocrysts. During cooling, Fe,Ni‐metal crystallized from the S‐ and Ni‐rich liquid, and upon further cooling mss decomposed into pentlandite and pyrrhotite, with pentlandite exsolving from mss at 400–600 °C. The composition, texture, and inferred formation temperature of pentlandite within chondrules studied here is inconsistent with formation via aqueous alteration. However, some opaque minerals (Fe,Ni‐metal versus magnetite and panethite) present in type II chondrules are a proxy for the degree of whole‐rock aqueous alteration. The texture and composition of sulfide‐bearing opaque minerals in Graves Nunataks 06100 and Grosvenor Mountains 03116 suggest that they are the most thermally altered CR chondrites.     

The distribution of aluminum-26 in the early Solar System—A reappraisal

Abstract— A compilation of over 1500 Mg-isotopic analyses of Al-rich material from primitive solar system matter (meteorites) shows clearly that ²⁶Al existed live in the early Solar System. Excesses of ²⁶Mg observed in refractory inclusions are not the result of mixing of “fossil” interstellar ²⁶Mg with normal solar system Mg. Some material was present that contained little or no ²⁶Al, but it was a minor component of solar system matter in the region where CV3 and CO3 carbonaceous chondrites accreted and probably was a minor component in the accretion regions of CM chondrites as well. Data for other chondrite groups are too scanty to make similar statements. The implied long individual nebular histories of CAIs and the apparent gap of one or more million years between the start of CAI formation and the start of chondrule formation require the action of some nebular mechanism that prevented the CAIs from drifting into the Sun. Deciding whether ²⁶Al was or was not the agent of heating that caused melting in the achondrite parent bodies hinges less on its widespread abundance in the nebula than it does on the timing of planetesimal accretion relative to the formation of the CAIs.     

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.     

Noble gases in chondrules and associated metal‐sulfide‐rich samples: Clues on chondrule formation and the behavior of noble gas carrier phases

Abstract— Chondrules are generally believed to have lost most or all of their trapped noble gases during their formation. We tested this assumption by measuring He, Ne, and Ar in chondrules of the carbonaceous chondrites Allende (CV3), Leoville (CV3), Renazzo (CR2), and the ordinary chondrites Semarkona (LL3.0), Bishunpur (LL3.1), and Krymka (LL3.1). Additionally, metalsulfide‐rich chondrule coatings were measured that probably formed from chondrule metal. Low primordial ²⁰Ne concentrations are present in some chondrules, while even most of them contain small amounts of primordial ³⁶Ar. Our preferred interpretation is that‐in contrast to CAIs‐the heating of the chondrule precursor during chondrule formation was not intense enough to expel primordial noble gases quantitatively. Those chondrules containing both primordial ²⁰Ne and ³⁶Ar show low presolar‐diamond‐like ³⁶Ar/²⁰Ne ratios. In contrast, the metal‐sulfide‐rich coatings generally show higher gas concentrations and Q‐like ³⁶Ar/²⁰Ne ratios. We propose that during metalsilicate fractionation in the course of chondrule formation, the Ar‐carrying phase Q became enriched in the metal‐sulfide‐rich chondrule coatings. In the silicate chondrule interior, only the most stable Ne‐carrying presolar diamonds survived the melting event leading to the low observed ³⁶Ar/²⁰Ne ratios. The chondrules studied here do not show evidence for substantial amounts of fractionated solar‐type noble gases from a strong solar wind irradiation of the chondrule precursor material as postulated by others for the chondrules of an enstatite chondrite.     

Mineralogical and chemical modification of components in CV3 chondrites: Nebular or asteroidal processing?

Abstract— Calcium- and aluminum-rich inclusions (CAIs), chondrules, dark inclusions and matrices in certain CV3 carbonaceous chondrites appear to have been modified by different degrees of late-stage alteration processes that caused significant variations in mineralogy and chemistry. Some chondrules and CAIs are rimmed with fayalitic olivine. Metal in all components may be oxidized and sulphidized to magnetite, Ni-rich metal and sulfides. Silicates in all components are aqueously altered to different degrees to phyllosilicates. Primary minerals in some CAIs experienced Fe-alkali-halogen metasomatism forming nepheline, sodalite, wollastonite, hedenbergite and other secondary minerals. In CV3 chondrites with metasomatized CAIs, nepheline, sodalite, etc. are also present in chondrule mesostases and in matrices. McSween's (1977b) reduced subgroup of CV3 chondrites generally shows minimal alteration of all components and may represent the unaltered precursors for the oxidized CV3 chondrites, which generally show major alteration. Most studies have been focused on specific components in CV3 chondrites and have not considered possible relationships between alteration processes. We infer from the correlated occurrences of the alteration features that they were closely related in time and space and review nebular and asteroidal models for their origins. We prefer an asteroidal model.     

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.     

Cosmogenic and trapped noble gases in individual chondrules: Clues to chondrule formation

Abstract— We studied the elemental and isotopic abundances of noble gases (He, Ne, Ar in most cases, and Kr, Xe also in some cases) in individual chondrules separated from six ordinary, two enstatite, and two carbonaceous chondrites. Most chondrules show detectable amounts of trapped ²⁰Ne and ³⁶Ar, and the ratio (³⁶Ar/²⁰Ne)_t (from ordinary and carbonaceous chondrites) suggests that HL and Q are the two major trapped components. A different trend between (³⁶Ar/²⁰Ne)_t and trapped ³⁶Ar is observed for chondrules in enstatite chondrites indicating a different environment and/or mechanism for their formation compared to chondrules in ordinary and carbonaceous chondrites. We found that a chondrule from Dhajala chondrite (DH‐11) shows the presence of solar‐type noble gases, as suggested by the (³⁶Ar/²⁰Ne)_t ratio, Ne‐isotopic composition, and excess of ⁴He. Cosmic‐ray exposure (CRE) ages of most chondrules are similar to their host chondrites. A few chondrules show higher CRE age compared to their host, suggesting that some chondrules and/or precursors of chondrules have received cosmic ray irradiation before accreting to their parent body. Among these chondrules, DH‐11 (with solar trapped gases) and a chondrule from Murray chondrite (MRY‐1) also have lower values of (²¹Ne/²²Ne)_c, indicative of SCR contribution. However, such evidences are sporadic and indicate that chondrule formation event may have erased such excess irradiation records by solar wind and SCR in most chondrules. These results support the nebular environment for chondrule formation.     

A comparative study of opaque phases in Qingzhen (EH3) and MacAlpine Hills 88136 (EL3): Representatives of EH and EL parent bodies

Abstract— Opaque minerals in the Qingzhen (EH3) and MacAlpine Hills (MAC) 88136 (EL3) enstatite chondrites were studied and compared with other EH and EL chondrites. All opaque minerals usually occur in multi‐sulfide‐metal clasts and nodules in the matrix between chondrules (El Goresy et al., 1988). The higher abundance of opaque minerals, the occurrence of niningerite and various alkali‐sulfides (e.g., caswellsilverite, phases A and B, djerfisherite) are diagnostic criteria for EH chondrites, while alabandite is characteristic for EL chondrites. In addition, EH chondrites are characterized by enrichments of Si in both kamacite and perryite, and alkali elements in sphalerite and chalcopyrite. The Mn contents of daubreelite and sphalerite are lower in EH than in EL chondrites. These are consistent with lower oxygen fugacity and higher H₂S fugacity of EH than EL chondrites. In contrast, the discovery of sphalerite and Zn‐rich daubreelite in MAC 88136 indicates that their absence in EL6 chondrites is probably related to thermal metamorphism in the parent body. Schreibersite microspherules are commonly enclosed in most sulfides in Qingzhen, but are absent in MAC 88136. They were once molten, and probably predated all sulfide host phases. The petrographic setting and chemical compositions of the sulfide hosts of the schreibersite microspherules in EH3 chondrites are consistent with formation by condensation. The earliest sulfide condensates oldhamite and niningerite occupy the interiors of the clasts and nodules, whereas the rims consist of troilite and djerfisherite. In addition, in Qingzhen, some other troilite, djerfisherite and sphalerite assemblages coexist with perryite. They were produced by sulfurization of metallic Fe‐Ni in the nebula. In MAC 88136, sulfurization of Si‐bearing Fe‐Ni metal is less pronounced, and it produced troilite, schreibersite and less abundant perryite. Two kinds of normal zoning and a reverse zoning trends of niningerite, and both normal and reverse zoning of sphalerite were found in clasts and nodules in Qingzhen. The coexistence of normal and reverse zoning profiles in niningerite grains in the same meteorite strongly suggests that they formed before accretion in the parent body, because an asteroidal metamorphic or an impact event in the parent body would have erased these contrasting profiles and destroyed the textural settings. In contrast, alabandite in MAC 88136 shows only normal zoning, with the FeS content decreasing to 9.3 mol% toward troilite, indicating very slow cooling at low temperature.