Early solar system processes recorded in the matrices of two highly pristine CR3 carbonaceous chondrites, MET 00426 and QUE 99177

The mineralogy and bulk compositions of the matrices of the CR chondrites MET 00426 and QUE 99177 have been studied using a combination of SEM, EPMA, and TEM techniques. The matrices of these two chondrites are texturally, chemically, and mineralogically similar and are characterized by significant FeO-enrichments with respect to other CR chondrite matrices, nearly flat refractory lithophile patterns, variable volatile element patterns, and a simple mineral assemblage dominated by amorphous silicate material and Fe,Ni sulfides. Fine-grained, crystalline silicate phases such as olivine and pyroxene appear to be extremely rare in the matrices of both meteorites. Instead, the mineralogy of matrices and fine-grained rims of both meteorites consists of abundant amorphous FeO-rich silicate material, containing nanoparticles of Fe,Ni sulfides (troilite, pyrrhotite, and pentlandite). Secondary alteration minerals that are characteristic of other CR chondrites (e.g., Renazzo and Al Rais), such as phyllosilicates, magnetite, and calcite are also rare. The texture and mineralogy of the matrices of MET 00426 and QUE 99177 share many features with matrices in the primitive carbonaceous chondrites ALH A77307 (CO3.0) and Acfer 094 (unique). These observations show that MET 00426 and QUE 99177 are very low petrologic type 3 chondrites that have escaped the effects of aqueous alteration, unlike other CR chondrites, which are typically classified as petrologic type 2. We suggest that these meteorites represent additional samples of highly primitive, but extremely rare carbonaceous chondrites of petrologic type 3.00, according to the classification scheme of Grossman and Brearley (2005). The highly pristine nature of MET 00426 and QUE 99177 provides important additional insights into the origins of fine-grained materials in carbonaceous chondrites. Based on our new observations, we infer that the amorphous silicate material and nanosulfide particles that dominate the matrices of these meteorites formed in the solar nebula by rapid condensation of material following high-temperature events, such as those that formed chondrules.     

Oxygen isotope compositions of chondrules in CR chondrites

We report in situ ion microprobe analyses of oxygen isotopic compositions of olivine, low-Ca pyroxene, high-Ca pyroxene, anorthitic plagioclase, glassy mesostasis, and spinel in five aluminum-rich chondrules and nine ferromagnesian chondrules from the CR carbonaceous chondrites EET92042, GRA95229, and MAC87320. Ferromagnesian chondrules are isotopically homogeneous within ±2‰ in Δ¹⁷O; the interchondrule variations in Δ¹⁷O range from 0 to −5‰. Small oxygen isotopic heterogeneities found in two ferromagnesian chondrules are due to the presence of relict olivine grains. In contrast, two out of five aluminum-rich chondrules are isotopically heterogeneous with Δ¹⁷O values ranging from −6 to −15‰ and from −2 to −11‰, respectively. This isotopic heterogeneity is due to the presence of ¹⁶O-enriched spinel and anorthite (Δ¹⁷O = −10 to −15‰), which are relict phases of Ca,Al-rich inclusions (CAIs) incorporated into chondrule precursors and incompletely melted during chondrule formation. These observations and the high abundance of relict CAIs in the aluminum-rich chondrules suggest a close genetic relationship between these objects: aluminum-rich chondrules formed by melting of spinel-anorthite-pyroxene CAIs mixed with ferromagnesian precursors compositionally similar to magnesium-rich (Type I) chondrules. The aluminum-rich chondrules without relict CAIs have oxygen isotopic compositions (Δ¹⁷O = −2 to −8‰) similar to those of ferromagnesian chondrules. In contrast to the aluminum-rich chondrules from ordinary chondrites, those from CRs plot on a three-oxygen isotope diagram along the carbonaceous chondrite anhydrous mineral line and form a continuum with amoeboid olivine aggregates and CAIs from CRs. We conclude that oxygen isotope compositions of chondrules resulted from two processes: homogenization of isotopically heterogeneous materials during chondrule melting and oxygen isotopic exchange between chondrule melt and ¹⁶O-poor nebular gas.     

Oxygen isotopic constraints on the origin of magnesian chondrules and on the gaseous reservoirs in the early Solar System

We report in situ ion microprobe analyses of the oxygen isotopic composition of the major silicate phases (olivine, low-Ca pyroxene, silica, and mesostasis) of 37 magnesian porphyritic (type I) chondrules from CV (Vigarano USNM 477-2, Vigarano UH5, Mokoia, and Efremovka) and CR (EET 92042, EET 92147, EET 87770, El Djouf 001, MAC 87320, and GRA 95229) carbonaceous chondrites. In spite of significant variations of the modal proportions of major mineral phases in CR and CV chondrules, the same isotopic characteristics are observed: (i) olivines are isotopically homogeneous at the ‰ level within a chondrule although they may vary significantly from one chondrule to another, (ii) low-Ca pyroxenes are also isotopically homogeneous but systematically ¹⁶O-depleted relative to olivines of the same chondrule, and (iii) all chondrule minerals analyzed show ¹⁶O-enrichments relative to the terrestrial mass fractionation line, enrichments that decrease from olivine (±spinel) to low-Ca pyroxene and to silica and mesostasis. The observation that, in most of the type I chondrules studied, the coexisting olivine and pyroxene crystals and glassy mesostasis have different oxygen isotopic compositions implies that the olivine and pyroxene grains are not co-magmatic and that the glassy mesostasis is not the parent liquid of the olivine. The δ¹⁸O and δ¹⁷O values of pyroxene and olivine appear to be strongly correlated for all the studied CR and CV chondrules according to:

     

Compositional evolution of the protoplanetary disk: Oxygen isotopes of type-II chondrules from CR2 chondrites

Chondrules are the dominant component of chondritic meteorites and attest to high-temperature transient heating events within the protoplanetary disk. They provide valuable constraint on the disk environments in which they formed and potentially the evolution of primitive planetary materials in the disk. The oxygen isotopic composition of CR2 chondrite type-II chondrules was investigated. Our data show significant variation in the isotopic compositions of the chondrules with no petrographic or geochemical means to identify what chondrule will plot where on a three-isotope diagram. Although we cannot rule out that these chondrules may have come from another chondrite-forming region, we argue in context of type-I chondrules from CR2 chondrites that CR2 type-II chondrules record changes in solid and gas composition during formation due to the vaporization of icy bodies in localized regions of the inner disk.     

Mineralogy and texture of Fe-Ni sulfides in CI1 chondrites: Clues to the extent of aqueous alteration on the CI1 parent body

To better understand the role of aqueous alteration on the CI1 parent body, we have analyzed the texture, composition and mineral associations of iron nickel sulfides in four of the five known CI1 chondrites.The most commonly-occurring sulfide present in the CI1 chondrites is the iron-deficient Fe,Ni sulfide pyrrhotite ([Fe,Ni]_1−xS), that has a composition close to that of stoichiometric troilite (FeS). Three of the CI1s (Alais, Ivuna and Tonk) also contain pentlandite ([Fe,Ni]₉S₈), although pentlandite is a rare phase in Ivuna. Cubanite (CuFe₂S₃) was found in both Alais and Ivuna in this study, although it has also been reported in Orgueil (MacDougall and Kerridge, 1977). The pyrrhotite grains in all four chondrites form hexagonal, rectangular or irregular shapes, and show no evidence of Ni or Co zoning. The pyrrhotite grains in Orgueil and Ivuna are, in general, smaller, and show more “corrosions,” or “embayments,” than those in Alais or Tonk.We suggest that the precursor sulfide present in the CI1 chondrites was troilite which, during brecciation and oxidation on the parent body at a temperature of 100°C or less, converted the troilite to magnetite and pyrrhotite with pentlandite inclusions. Subsequently, continued alteration on the parent body removed pentlandite—partially from Alais, Tonk and Ivuna, completely from Orgueil—leaving behind pyrrhotite with spaces (“corrosions”) where the pentlandite had been. Ni derived from the pentlandite was incorporated into ferrihydrite, onto the surface of which the Ni,Na sulfate Ni-bloedite formed.Based on the size and abundant “corrosions” within pyrrhotite grains, combined with observations from other authors, we conclude that Orgueil and Ivuna have undergone a greater degree of alteration than Alais and Tonk. Further work is needed to assess the conditions under which pentlandite would be dissolved preferentially to pyrrhotite, as the study of terrestrial literature indicates that the latter mineral is preferentially removed.     

The formation and alteration of the Renazzo-like carbonaceous chondrites I: Implications of bulk-oxygen isotopic composition

To better understand the role of aqueous alteration on the CR chondrite parent asteroid, a whole-rock oxygen isotopic study of 20 meteorites classified as Renazzo-like carbonaceous chondrites (CR) was conducted. The CR chondrites analyzed for their oxygen isotopes were Dhofar 1432, Elephant Moraine (EET) 87770, EET 92042, EET 96259, Gao-Guenie (b), Graves Nunataks (GRA) 95229, GRA 06100, Grosvenor Mountains (GRO) 95577, GRO 03116, LaPaz Ice Field (LAP) 02342, LAP 04720, Meteorite Hills (MET) 00426, North West Africa (NWA) 801, Pecora Escarpment (PCA) 91082, Queen Alexandra Range (QUE) 94603, QUE 99177, and Yamato-793495 (Y-793495). Three of the meteorites, Asuka-881595 (A-881595), GRA 98025, and MET 01017, were found not to be CR chondrites. The remaining samples concur petrographically and with the well-established oxygen-isotope mixing line for the CR chondrites. Their position along this mixing line is controlled both by the primary oxygen-isotopic composition of their individual components and their relative degree of aqueous alteration. Combined with literature data and that of this study, we recommend the slope for the CR-mixing line to be 0.70 ± 0.04 (2σ), with a δ¹⁷O-intercept of −2.23 ± 0.14 (2σ).Thin sections of Al Rais, Shi?r 033, Renazzo, and all but 3 samples analyzed for oxygen isotopes were studied petrographically. The abundance of individual components is heterogeneous among the CR chondrites, but FeO-poor chondrules and matrix are the most abundant constituents and therefore, dominate the whole-rock isotopic composition. The potential accreted ice abundance, physico-chemical conditions of aqueous alteration (e.g. temperature and composition of the fluid) and its duration control the degree of alteration of individual CR chondrites. Combined with literature data, we suggest that LAP 02342 was exposed to lower temperature fluid during alteration than GRA 95229. With only two falls, terrestrial alteration of the CR chondrites complicates the interpretation of their whole rock isotopic composition, particularly in the most aqueously altered samples, and those with relatively higher matrix abundances. We report that QUE 99177 is the isotopically lightest whole rock CR chondrite known (δ¹⁸O = −2.29‰, δ¹⁷O = −4.08‰), possibly due to isotopically light unaltered matrix; which shows that the anhydrous component of the CR chondrites is isotopically lighter than previously thought. Although it experienced aqueous alteration, QUE 99177 provides the best approximation of the pristine CR-chondrite parent body’s oxygen-isotopic composition, before aqueous alteration took place. Using this value as a new upper limit on the anhydrous component of the CR chondrites, water/rock ratios were recalculated and found to be higher than previously thought; ratios now range from 0.281 to 1.157. We also find that, according to their oxygen isotopes, a large number of CR chondrites appear to be minimally aqueously altered; although sample heterogeneity complicates this interpretation.     

Microscale oxygen isotopic exchange and magnetite formation in the Ningqiang anomalous carbonaceous chondrite

We report in situ measurements of O-isotopic compositions of magnetite, olivine and pyroxene in chondrules of the Ningqiang anomalous carbonaceous chondrite. The petrographic setting of Ningqiang magnetite is similar to those in oxidized-CV chondrites such as Allende, where magnetite is found together with Ni-rich metal and sulfide in opaque assemblages in chondrules. Both magnetite and silicate oxygen data fall close to the carbonaceous-chondrite-anhydrous-mineral line with relatively large ranges in δ¹⁸O in magnetite (−4.9 to +4.2‰) and in silicates (−15.2 to −4.5‰). Magnetite and silicates are not in O-isotopic equilibrium: the weighted average Δ¹⁷O (=δ¹⁷O − 0.52 × δ¹⁸O) values of magnetite are 1.7 to 3.6‰ higher than those of the silicates in the same chondrules. The petrological characteristics and O-isotopic disequilibrium between magnetite and silicates suggest the formation of Ningqiang magnetite by the oxidation of preexisting metal grains by an aqueous fluid during parent body alteration. The weighted average Δ¹⁷O of −3.3 ± 0.3‰ is the lowest magnetite value measured in unequilibrated chondrites and there is a positive correlation between Δ¹⁷O values of magnetite and silicates in each chondrule. These observations indicate that, during aqueous alteration in the Ningqiang parent asteroid, the water/rock ratio was relatively low and O-isotopic exchange between the fluid and chondrule silicates occurred on the scale of individual chondrules.     

Formation and destruction of magnetite in CO3 chondrites and other chondrite groups

Primitive CO3.00–3.1 chondrites contain ∼2-8 vol.% magnetite, minor troilite and accessory carbide and chromite; some CO3.1 chondrites have fayalite-rich veins, chondrule rims and euhedral matrix grains. All CO3.00–3.1 chondrites contain little metallic Fe-Ni (0.4–1.2 vol.%). CO3.2–3.7 chondrites contain 1–5 vol.% metallic Fe-Ni, minor troilite, accessory chromite and 0-0.6 vol.% magnetite. Magnetite is formed in primitive CO3 chondrites from metallic Fe by parent-body aqueous alteration, resulting in decreased metallic Fe-Ni and an increase in the proportion of high-Ni metal grains. The paucity or absence of magnetite in CO chondrites of subtype ≥3.2 suggests that magnetite is destroyed during thermal metamorphism; thermochemical calculations from the literature suggest that magnetite is reduced by H₂ and reacts with SiO₂ to form fayalite and secondary kamacite. Analogous processes of magnetite formation and destruction occur in other chondrite groups: (1) Primitive type-3 OC have opaque assemblages containing magnetite, carbide, Ni-rich metal and Ni-rich sulfide, but OC of subtype >3.4 contain little or no magnetite. (2) Primitive R3 chondrites and clasts (subtype ≲3.5) contain up to 6 vol.% magnetite, but most R chondrites contain no magnetite. The principal exception is magnetite with 9–20 wt.% Cr₂O₃ in a few R4-6 chondrites. Magnetite grains with high Cr₂O₃ behave like chromite and are more stable under reducing conditions. (3) CK chondrites average ∼4 vol.% magnetite with substantial Cr₂O₃ (up to ∼15 wt.%); these magnetite grains also are stable against reduction during metamorphism. (4) The modal abundance of magnetite decreases with metamorphic grade in CV3 chondrites. (5) Chromite occurs instead of magnetite in those rare samples classified CR6, CR7 and CV7.     

Mineralogy, aqueous alteration, and primitive textural characteristics of fine-grained rims in the Y-791198 CM2 carbonaceous chondrite: TEM observations and comparison to ALHA81002

Transmission electron microscopy (TEM) was used to study the microtextural and mineralogical characteristics of fine-grained rims in the unbrecciated CM2 chondrites, Y-791198 and ALHA81002, in an effort to provide constraints on the origins of the rims themselves. Our TEM observations show that the rims in Y-791198 are composed of two distinct types of region, sulfide-poor and sulfide-rich, that are intermixed in a complex manner at the micron to submicron level. The sulfide-poor regions are largely composed of amorphous silicate material or nanocrystalline serpentine, but rare fibrous and coarse-grained serpentine grains have also been identified. No fine-grained cronstedtite or tochilinite were observed, although coarse-grained lumps of tochilinite are present in the rims. In contrast, the sulfide-rich regions are characterized by the presence of a myriad, nanometer-sized Fe, Ni sulfide grains (pentlandite with some Ni-rich pyrrhotite) embedded within an amorphous silicate similar in composition to that of the sulfide-poor regions. The sulfide-rich regions also contain rare phases such as olivine, and Fe, Ni metal grains with grain sizes that are always >100 nm in size. Z-contrast scanning transmission electron microscopy (STEM) reveals that the fine-grained rims consist of a mosaic of irregularly-shaped sulfide-poor and sulfide-rich-regions with sizes of about 0.2-0.5 μm, that have been compacted together during parent body lithification. Despite aqueous alteration, the distinct mineralogical characteristics of these different regions are preserved on a fine-scale and probably represent primitive heterogeneity in the dust from which these rims formed.Serpentine is much better developed and more widespread in the fine-grained rims of ALHA81002 than Y-791198. Complex mats of serpentine fibers are commonly found and cronstedtite and tochilinite are plentiful. Anhydrous minerals such as olivine are rare and have usually been replaced by serpentine. Like Y-791198, all the fine-grained rims studied in ALHA81002 show the same mineral assemblages and textural characteristics throughout and between rims. The homogeneity of the mineralogy, textural relationships and degree of hydration in the rims of these two chondrites is more consistent with parent-body alteration than with pre-accretionary alteration.     

Zambales ophiolite,Philippines

The Acoje massif is part of a mafic-ultramafic complex, the Zambales ophiolite, and is a fragment of Mesozoic oceanic crust. This paper documents the occurrence and phase relations of sulfides and associated phases in the critical zone of the Acoje massif. The Acoje critical zone (ACZ) forms the basal cumulate sequence of the massif and consists of a variably serpentinized lower ultramafic zone and a relatively less altered upper mafic zone. Two distinct sulfide associations have been identified: (1) a troilite (±pyrrhotite)-dominated group hosted by the mafic zone and (2) a pentlandite-dominated group hosted by the ultramafic zone. Troilite-dominated assemblages represent the original mineralogy of magmatically precipitated sulfides in the entire cumulate sequence. The pentlandite-dominated group appears to have evolved from the primary magmatic sulfides during low-temperature re-equilibration. The paragenetic evolution from the magmatic assemblage to the low-temperature assemblage appears to have proceeded as follows: (1) S-rich hexagonal pyrrhotite+pentlandite+chalcopyrite (or cubanite)+magnetite, (2) S-poor hexagonal pyrrhotite+pentlandite+intermediate solid solution (iss) phase (and/or cubanite)+magnetite, (3) troilite (or mackinawite)+pentlandite+iss+magnetite, (4) troilite (or mackinawite)+pentlandite+iss+native Cu+magnetite, (5) pentlandite+native Cu+magnetite, and (6) pentlandite+native Cu+Fe-Ni alloy+magnetite. This evolutionary trend, in conjunction with the observed textural, chemical, and sulfur-isotopic relations, indicates that the native metal and alloy phases in the ACZ were produced by low-temperature reduction of the primary magmatic sulfides. Correlations between sulfide assemblages and coexisting silicate-hydrosilicate-oxide assemblages further indicate that this alteration occurred during retrograde serpentinization of the Acoje massif. Two end-member models that could explain the inferred low-temperature mineralogic evolution of the ACZ sulfides are described: (1) an isothermal reduction model and (2) a non-isothermal equilibration model. Both isothermal and non-isothermal effects apparently were involved in the development of variably reduced sulfide-oxide-metal assemblages from the initial magmatic sulfides.     

The unequilibrated enstatite chondrites

The enstatite chondrites formed under highly reducing (and/or sulfidizing) conditions as indicated by their mineral assemblages and compositions, which are sharply different from those of other chondrite groups. Enstatite is the major silicate mineral. Kamacite is Si-bearing and the enstatite chondrites contain a wide variety of monosulfide minerals that are not present in other chondrite groups. The unequilibrated enstatite chondrites are comprised of two groups (EH3 and EL3) and one anomalous member (LEW 87223), which can be distinguished by differences in their mineral assemblages and compositions. EH3 chondrites have >1.8 wt.% Si in their kamacite and contain the monosulfide niningerite (MgS), whereas EL3 chondrites have less than 1.4 wt.% Si in their kamacite and contain the monosulfide alabandite (MnS). The distinct mineralogies, compositions and textures of E3 chondrites make comparisons with ordinary chondrites (OCs) and carbonaceous chondrites (CCs) difficult, however, a range of recrystallization features in the E3s are observed, and some may be as primitive as type 3.1 OCs and CCs. Others, especially the EL3 chondrites, may have been considerably modified by impact processes and their primary textures disturbed. The chondrules in E3 chondrites, although texturally similar to type I pyroxene-rich chondrules, are sharply different from chondrules in other chondrite groups in containing Si-bearing metal, Ca- and Mg–Mn-rich sulfides and silica. This indicates formation in a reduced nebular environment separate from chondrules in other chondrites and possibly different precursor materials. Additionally the oxygen isotope compositions of E3 chondrules indicate formation from a unique oxygen reservoir. Although the abundance, size distribution, and secondary alteration minerals are not always identical, CAIs in E3 chondrites generally have textures, mineral assemblages and compositions similar to those in other groups. These observations indicates that CAIs in O, C and E chondrites all formed in the reservoir under similar conditions, and were redistributed to the different chondrite accretion zones, where the secondary alteration took place. Thus, chondrule formation was a local process for each particular chondrite group, but all CAIs may have formed in the similar nebular environment. Lack of evidence of water (hydrous minerals), and oxygen isotope compositions similar to Earth and Moon suggest formation of the E chondrites in the inner solar system and make them prime candidates as building blocks for the inner planets.     

Sulfur isotope composition of putative primary troilite in chondrules from Bishunpur and Semarkona

The sulfur isotopic compositions of putative primary troilite grains within 15 ferromagnesian chondrules (10 FeO-poor and 5 FeO-rich chondrules) in the least metamorphosed ordinary chondrites, Bishunpur and Semarkona, have been measured by ion microprobe. Some troilite grains are located inside metal spherules within chondrules. Since such an occurrence is unlikely to be formed by secondary sulfidization processes in the solar nebula or on parent bodies, those troilites are most likely primary, having survived chondrule-forming high-temperature events. If they are primary, they may be the residues of evaporation at high temperatures during chondrule formation and may have recorded mass-dependent isotopic fractionations. However, the supposed primary troilites measured in this study do not show any significant sulfur isotopic fractionations (<1 ‰/amu) relative to large troilite grains in matrix. Among other chondrule troilites that we measured, only one (BI-CH22) apparently has a small excess of heavy isotopes (2.7 ± 1.4 ‰/amu) consistent with isotopic fractionation during evaporation. All other grains have isotopic fractionations of <1 ‰/amu. Because sulfur is so volatile that evaporation during chondrule formation is probably inevitable, non-Rayleigh evaporation most likely explains the lack of isotopic fractionation in putative primary troilite inside chondrules. Evaporation through the surrounding silicate melt would have suppressed the isotopic fractionation after silicate dust grains melted. At lower temperatures below extensive melting of silicates, a heating rate of >10⁴-10⁶ K/h would be required to avoid a large degree of sulfur isotopic fractionation in the chondrule precursors. This heating rate may provide a new constraint on the chondrule formation processes.     

Non-spherical lobate chondrules in CO3.0 Y-81020: General implications for the formation of low-FeO porphyritic chondrules in CO chondrites

Non-spherical chondrules (arbitrarily defined as having aspect ratios ≥1.20) in CO3.0 chondrites comprise multi-lobate, distended, and highly irregular objects with rounded margins; they constitute ∼70% of the type-I (low-FeO) porphyritic chondrules in Y-81020, ∼75% of such chondrules in ALHA77307, and ∼60% of those in Colony. Although the proportion of non-spherical type-I chondrules in LL3.0 Semarkona is comparable (∼60%), multi-lobate OC porphyritic chondrules (with lobe heights equivalent to a significant fraction of the mean chondrule diameter) are rare. If the non-spherical type-I chondrules in CO chondrites had formed from totally molten droplets, calculations indicate that they would have collapsed into spheres within ∼10⁻³ s, too little time for their 20-μm-size olivine phenocrysts to have grown from the melt. These olivine grains must therefore be relicts from an earlier chondrule generation; the final heating episode experienced by the non-spherical chondrules involved only minor amounts of melting and crystallization. The immediate precursors of the individual non-spherical chondrules may have been irregularly shaped chondrule fragments whose fracture surfaces were rounded during melting. Because non-spherical chondrules and “circular” chondrules form a continuum in shape and have similar grain sizes, mineral and mesostasis compositions, and modal abundances of non-opaque phases, they must have formed by related processes. We conclude that a large majority of low-FeO chondrules in CO3 chondrites experienced a late, low-degree melting event. Previous studies have shown that essentially all type-II (high-FeO) porphyritic chondrules in Y-81020 formed by repeated episodes of low-degree melting. It thus appears that the type-I and type-II porphyritic chondrules in Y-81020 (and, presumably, all CO3 chondrites) experienced analogous formation histories. Because these two types constitute ∼95% of all CO chondrules, it is clear that chondrule recycling was the rule in the CO chondrule-formation region and that most melting events produced only low degrees of melting. The rarity of significantly non-spherical, multi-lobate chondrules in Semarkona may reflect more-intense heating of chondrule precursors in the ordinary-chondrite region of the solar nebula.     

Microchondrule-bearing clast in the Piancaldoli LL3 meteorite: a new kind of type 3 chondrite and its relevance to the history of chondrules

In the Piancaldoli LL3 chondrite, we found a mm-sized clast containing ~100 chondrules 0.2–64 μm in apparent diameter (much smaller than any previously reported) that are all of the same textural type (radial pyroxene; FS_1–17). This clast, like other type 3 chondrites, has a fine-grained Ferich opaque silicate matrix, sharply defined chondrules, abundant low-Ca clinopyroxene and minor troilite and Si- and Cr-bearing metallic Fe,Ni. However, the very high modal matrix abundance (63 ± 8 vol. %), unique characteristics of the chondrules, and absence of microscopically-observable olivine indicate that the clast is a new kind of type 3 chondrite. Most chondrules have FeO-rich edges, and chondrule size is inversely correlated with chondrule-core FeO concentration (the first reported correlation of chondrule size and composition). Chondrules acquired Fe by diffusion from Fe-rich matrix material during mild metamorphism, possibly before final consolidation of the rock. Microchondrules (those chondrules ? 100 μm in diameter) are also abundant in another new kind of type 3 chondrite clast in the Rio Negro L chondrite regolith breccia. In other type 3 chondrite groups, microchondrule abundance appears to be anticorrelated with mean chondrule size, viz. 0.02–0.04 vol. % in H and CO chondrites and ?0.006 vol. % in L, LL, and CV chondrites.Microchondrules probably formed by the same process that formed normal-sized droplet chondrules: melting of pre-existing dustballs. Because most compound chondrules in the clast and other type 3 chondrites formed by collisions between chondrules of the same textural type, we suggest that dust grains were mineralogically sorted in the nebula before aggregating into dustballs. The sizes of compound chondrules and chondrule craters, which resulted from collisions of similarly-sized chondrules while they were plastic, indicate that size-sorting (of dustballs) occurred before chondrule formation, probably by aerodynamic processes in the nebula. We predict that other kinds of type 3 chondrites exist which contain chondrule abundances, size-ranges and proportions of textural types different from known chondrite groups.     

Evidence for aqueous activity on comet 81P/Wild 2 from sulfide mineral assemblages in Stardust samples and CI chondrites

The discovery of nickel-, copper-, and zinc-bearing iron sulfides from comet 81P/Wild 2 (Wild 2) represents the strongest evidence, in the Stardust collection, of grains that formed in an aqueous environment. We investigated three microtomed TEM sections which contain crystalline sulfide assemblages from Wild 2 and twelve thin sections of the hydrothermally altered CI chondrite Orgueil. Detailed structural and compositional characterizations of the sulfide grains from both collections reveal striking similarities. The Stardust samples include a cubanite (CuFe₂S₃) grain, a pyrrhotite [(Fe,Ni)_1−xS]/pentlandite [(Fe,Ni)₉S₈] assemblage, and a pyrrhotite/sphalerite [(Fe,Zn)S] assemblage. Similarly, the CI-chondrite sulfides include individual cubanite and pyrrhotite grains, cubanite/pyrrhotite assemblages, pyrrhotite/pentlandite assemblages, as well as possible sphalerite inclusions within pyrrhotite grains. The cubanite is the low temperature orthorhombic form, which constrains temperature to a maximum of 210 °C. The Stardust and Orgueil pyrrhotites are the 4C monoclinic polytype, which is not stable above ∼250 °C. The combinations of cubanite and pyrrhotite, as well as pyrrhotite and pentlandite signify even lower temperatures. The crystal structures, compositions, and petrographic relationships of these sulfides constrain formation and alteration conditions. Taken together, these constraints attest to low-temperature hydrothermal processing.Our analyses of these minerals provide constraints on large scale issues such as: heat sources in the comet-forming region; aqueous activity on cometary bodies; and the extent and mechanisms of radial mixing of material in the early nebula. The sulfides in the Wild 2 collection are most likely the products of low-temperature aqueous alteration. They provide evidence of radial mixing of material (e.g. cubanite, troilite) from the inner solar system to the comet-forming region and possible secondary aqueous processing on the cometary body.     

Accretion, dispersal, and reaccumulation of the Bishunpur (LL3.1) brecciated chondrite: Evidence from troilite-silicate-metal inclusions and chondrule rims

A set of troilite-silicate-metal (TSM) inclusions and chondrule rims in the Bishunpur (LL3.1) chondrite provide information regarding impact brecciation of small bodies in the early solar system. The TSM inclusions and chondrule rims consist of numerous angular to subrounded silicate grains that are individually enclosed by fine networks of troilite. FeNi metal also occurs in the troilite matrix. The silicates include olivine (Fo_55-98), low-Ca pyroxene (En_78-98), and high-Ca pyroxene (En_48-68Wo_11-32). Al- and Si-rich glass coexists with the silicates. Relatively coarse silicate grains are apparently fragments of chondrules typical of petrologic type-3 chondrites. Troilite fills all available cracks and pores in the silicate grains. Some of the TSM inclusions and rims are themselves surrounded by fine-grained silicate-rich rims (FGR).The TSM inclusions and rims texturally resemble the troilite-rich regions in the Smyer H-chondrite breccia. They probably formed by shock-induced mobilization of troilite during an impact event on a primitive asteroidal body. Because silicates in the TSM inclusions and rims have highly unequilibrated compositions, their precursor was presumably type-3 chondritic material like Bishunpur itself. The TSM inclusions and the chondrules with the TSM rims were fragmented and dispersed after the impact-induced compaction, then reaccreted onto the Bishunpur parent body. FGR probably formed around the TSM inclusions and rims, as well as around some chondrules, during the reaccumulation process. Components of most type-2 and 3 chondrites probably experienced similar processing, i.e., dispersal of unconsolidated materials and subsequent reaccumulation.     

Physical properties of chondrules in different chondrite groups: Implications for multiple melting events in dusty environments

Chondrite groups (CV, CK, CR) with large average chondrule sizes have low proportions of RP plus C chondrules, high proportions of enveloping compound chondrules, high proportions of chondrules with (thick) igneous rims, and relatively low proportions of type-I chondrules containing sulfide. In contrast, chondrite groups (CM, CO, OC, R, EH, EL) with smaller average chondrule sizes have the opposite properties. Equilibrated CK chondrites have plagioclase with relatively low Na; equilibrated OC, R, EH and EL chondrites have more sodic plagioclase. Enveloping compound chondrules and chondrules with igneous rims formed during a remelting event after the primary chondrule was incorporated into a dustball. Repeated episodes of remelting after chondrules were surrounded by dust would tend to produce large chondrules. RP and C chondrules formed by complete melting of their precursor assemblages; remelting of RP and C chondrules surrounded by dust would tend to produce porphyritic chondrules as small dust particles mixed with the melt, providing nuclei for crystallizing phenocrysts. This process would tend to diminish the numbers of RP and C chondrules. Correlations among these chondrule physical properties suggest that chondrite groups with large chondrules were typically surrounded by thick dust-rich mantles that formed in locally dusty nebular environments. Chondrules that were surrounded by thick dust mantles tended to cool more slowly because heat could not quickly radiate away. Slow cooling led to enhanced migration of sulfide to chondrule surfaces and more extensive sulfide evaporation. These chondrules also lost Na; the plagioclase that formed from equilibrated CK chondrites was thus depleted in Na.     

Compositions of three low-FeO ordinary chondrites: Indications of a common origin with the H chondrites

Burnwell, EET 96031, and LAP 04575 are ordinary chondrites (OC) that possess lower than typical olivine Fa content than has been established for the H chondrites (<∼17 mol%). Mean low-Ca pyroxene Fs contents are typically lower than mean Fa content, with generally ?16 mol% Fs. We have investigated these three low-FeO chondrites by measuring their trace element abundances, oxygen isotopic compositions, and examining their three-dimensional (3D) petrography with synchrotron X-ray microtomography. We compare our results with those established for more common OC. The low FeO chondrites studied here have bulk trace element abundances that are identical to the H chondrites. From bulk oxygen isotopic analysis, we show that Burnwell, EET 96010, and LAP 04757 sampled oxygen reservoirs identical to the H chondrites. Burnwell, EET 96031, and LAP 04575 possess common 3D opaque mineral structures that could be distinct from the H chondrites, as evidenced by X-ray microtomographic analysis, but our comparison suite of H chondrites is small and unrepresentative. Overall, our data suggest a common origin for the low-FeO chondrites Burnwell, EET 96010, and LAP 04757 and the H chondrites. These three samples are simply extreme members of a redox process where a limiting nebular oxidizing agent, probably ice, reacted with material containing slightly higher amounts of metal than typically seen in the H chondrites.     

Metal in CR chondrites

In section many low-FeO CR chondrules are surrounded by rings of metal; this metal-cladding seems to have formed during chondrule melting events as films of metal that wetted the surface. Electron microprobe studies show that in each ring the metal is very uniform in composition, consistent with efficient mixing during formation of the metal film. In contrast the mean Ni contents of 13 different rings vary by up to a factor of 2. There is no FeS associated with ring metal. Ring metal Co is positively correlated with Ni but the Co/Ni ratio seems to decrease with increasing Ni. We observed a weak negative correlation between ring metal Ni and the fayalite content of the host olivine. Coarse interior metal has higher Ni contents than that in the surrounding rings. At any specific chondrule location, smaller grains tend to have lower Ni contents than larger grains. These trends in Ni seem to reflect two processes: (1) The mean Ni content of metal (and easily reduced sulfides or oxides) in chondrule precursor materials seems to have decreased with the passage of time; on average, the metal in earlier-formed chondrules had higher Ni contents than the metal in later-formed chondrules. (2) Some oxidized Fe was reduced during chondrule formation leading to lower Ni contents in small grains compared to large grains; prior to reduction the Fe was in FeS or in FeO in accessible (fine-grained) sites. We suggest that the compositional evolution of nebular solids was responsible for the interchondrule variations whereas reduction of minor amounts of FeS or FeO was responsible for the size-related small variations in Ni content. We suggest that, during chondrule formation events, CR chondrules experienced relatively long thermal pulses that were responsible for the thorough loss of FeS and the common granoblastic texture observed in low-FeO chondrules. The preservation of the structures of internal rings shows, however, that even though high temperatures occurred in the secondary chondrule, temperatures in the centers of large (>20 μm) metal and silicate grains in the primary chondrule did not get high enough to cause appreciable melting.     

Oxygen, silicon, and Mn-Cr isotopes of fayalite in the Kaba oxidized CV3 chondrite: Constraints for its formation history

The iron-rich olivine end-member, fayalite, occurs in the matrix, chondrules, Ca-Al-rich inclusions (CAIs), silicate aggregates, and dark inclusions in the Kaba and Mokoia oxidized CV3 chondrites. In most occurrences, fayalite is associated with magnetite and troilite. To help constrain the origin of the fayalite (Fa_98-100), we measured oxygen and silicon isotopic compositions and Mn-Cr systematics in fayalite from two petrographic settings of the Kaba meteorite. One setting consists of big fayalite laths embedded in the matrix and radiating from a core of fine-grained magnetite and sulfide, while the other setting consists of small fayalite-magnetite-sulfide assemblages within or at the surface of Type I barred or porphyritic olivine chondrules. Oxygen in the big fayalite laths and small chondrule fayalites falls on the terrestrial fractionation line, and is distinct from that in chondrule forsterites, which are enriched in ¹⁶O (Δ¹⁷O = ∼−4‰). Oxygen in the big fayalite laths may be isotopically heavier than that in chondrule fayalites. Silicon isotopes suggest that forsterite is ∼1‰/amu heavier than adjacent fayalite within Kaba chondrules. However, we were unable to confirm large silicon isotopic differences among fayalites reported previously. The Mn-Cr data for big Kaba fayalites give an initial ⁵³Mn/⁵⁵Mn ratio of (2.07 ± 0.17) × 10⁻⁶, consistent with literature results on Mokoia chondrule fayalites. The combined data suggest that fayalites in both petrographic settings formed at about the same time, ∼9.7 Ma after the formation of CAIs. Our data indicate that those fayalite-magnetite-troilite assemblages replacing metal inside and around chondrules formed by aqueous alteration on the meteorite parent body. The formation site and mechanism for the big fayalite laths is less clear, but the petrographic setting indicates that they did not form in situ. None of the models that have been suggested for formation of these fayalites is entirely satisfactory.