Al-Mg systematics of chondrules in a primitive CO chondrite

We have conducted systematic investigations of formation age, chemical compositions, and mineralogical characteristics of ferromagnesian chondrules in Yamato-81020 (CO3.05), one of the most primitive carbonaceous chondrites, to get better understanding of the origin of chemical groups of chondrites. The ²⁶Al-²⁶Mg isotopic system were measured in fourteen FeO-poor (Type I), six FeO-rich (Type II) and two aluminum-rich (Al-rich) chondrules using a secondary ion mass spectrometer. Excesses of ²⁶Mg in plagioclase (1.0-13.5‰) are resolved with sufficient precision (mostly 0.4-6.6‰ at 2σ level) in all the chondrules studied except one. Chemical zoning of Mg and Na in plagioclase were investigated in detail in order to evaluate the applicability of ²⁶Al-²⁶Mg chronometer. We conclude that the Al-Mg isotope system of the chondrules in Y-81020 have not been disturbed by parent-body metamorphism and can be used as chronometer assuming homogeneous distribution of ²⁶Al. Assuming an initial ²⁶Al/²⁷Al ratio of 5 × 10⁻⁵ in the early solar system, ²⁶Al-²⁶Mg ages were found to be 1.7-2.5 Ma after CAI formation for Type I, 2.0-3.0 Ma for Type II and 1.9 and 2.6 Ma for Al-rich chondrules.The formation ages of ferromagnesian chondrules in Y-81020 are in good agreement with those of L and LL (type 3.0-3.1) chondrites in the literature, which indicates that common chondrules in the CO chondrite were formed contemporaneously with those in L and LL chondrites. The concurrent formation of chondrules of CO and L/LL chondrites suggests that the chemical differences between CO and L/LL chondrites might be caused by spatial separation of chondrule formation environments in the protoplanetary disk.     

Chemistry, petrology and bulk oxygen isotope compositions of chondrules from the Mokoia CV3 carbonaceous chondrite

We report bulk chemical compositions and physical properties for a suite of 94 objects, mostly chondrules, separated from the Mokoia CV3_ox carbonaceous chondrite. We also describe mineralogical and petrologic information for a selected subset of the same suite of chondrules. The data are used to examine the range of chondrule bulk compositions, and to investigate the relationships between chondrule mineralogy, texture and bulk compositions, as well as oxygen isotopic properties that we reported previously. Most of the chondrules show minimal metamorphism, corresponding to petrologic subtype <3.2. In general, elemental fractionations observed in chondrule bulk compositions are reflected in the compositions of constituent minerals. For chondrules, mean bulk compositions and compositional ranges are very similar for large (>2 mg) and small (<2 mg) size fractions. Two of the objects studied are described as matrix-rich clasts. These have similar bulk compositions to the chondrule mean, and are potential chondrule precursors. One of these clasts has a similar bulk oxygen isotopic composition to Mokoia chondrules, but the other has an anomalously high value of Δ¹⁷O (+3.60‰).Chondrules are diverse in bulk chemical composition, with factor of 10 variations in most major element abundances that cannot be attributed to secondary processes. The chondrules examined show evidence for extensive secondary oxidation, and possible sulfidization, as expected for an oxidized CV chondrite, but minimal aqueous alteration. Some of the bulk chondrule compositional variation might be the result of chemical (e.g. volatilization or condensation) or physical (e.g. metal loss) processes during chondrule formation. However, we suggest that it is mainly the result of significant variations in the assembly of particles that constituted chondrule precursors. Precursor material likely included a refractory component, possibly inherited from disaggregated CAIs, an FeO-poor ferromagnesian component such as olivine or pyroxene, an oxidized ferromagnesian component, and a metal component. Bulk oxygen isotope ratios of chondrules can be explained if refractory and ferromagnesian precursor materials initially shared similar oxygen isotopic compositions of δ¹⁷O, δ¹⁸O around −50‰, and then significant exchange occurred between the chondrule and surrounding ¹⁶O-poor gas during melting.     

Petrogenesis of Al-rich chondrules: Evidence from bulk compositions and phase equilibria

We measured major, minor, and trace-element compositions for eleven Al-rich chondrules from unequilibrated ordinary chondrites to investigate the relationships between Al-rich chondrules, ferromagnesian chondrules, Ca-, Al-rich inclusions (CAIs), and amoeboid olivine aggregates (AOAs). Phase equilibrium considerations show that, for the most part, mineral assemblages in Al-rich chondrules are those expected from melts of the observed compositions. The diversity of mineral assemblages and Al-rich chondrule types arises mainly from the fact that the array of compositions spans both the spinel-saturated anorthite-forsterite reaction curve and a thermal divide defined by where the anorthite-forsterite join crosses the reaction curve. The reaction curve accounts for the two principal varieties of Al-rich chondrule, plagioclase-phyric and olivine-phyric, with or without aluminous spinel. The thermal divide influences the subsequent evolution of each variety. A third variety of Al-rich chondrule contains abundant sodium-rich glass; trace-element fractionation patterns suggest that these glassy Al-rich chondrules could have been derived from the other two by extensive alteration of plagioclase to nepheline followed by remelting. The bulk compositions of Al-rich chondrules (except sodium-rich ones) are intermediate in a volatility sense between ferromagnesian chondrules and type C CAIs. The combined trend of bulk compositions for CAIs, Al-rich chondrules, and ferromagnesian chondrules mirrors, but does not exactly match, the trend predicted from equilibrium condensation at P_T ∼ 10^-3 atm; the observed trend does not match the trend found for evaporation from a liquid of chondritic composition. We thus infer that the bulk compositions of the precursors to CAIs, Al-rich chondrules, were ferromagnesian chondrules were controlled primarily by vapor-solid reactions (condensation or sublimation) in the solar nebula. Some Al-rich chondrules are consistent with an origin by melting of a compound CAI-ferromagnesian chondrule hybrid; others cannot be so explained. Any hybrid model is restricted by the constraint that the CAI precursor consisted dominantly of pyroxene + plagioclase + spinel; melilite cannot have been a significant component. Amoeboid olivine aggregates also have the inferred mineralogical characteristics of Al-rich chondrule precursors—they are mixtures of olivine with plagioclase-spinel-pyroxene-rich CAIs—but the few measured bulk compositions are more olivine-rich than those of Al-rich 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.     

Condensation of major elements during chondrule formation and its implication to the origin of chondrules

Two glassy refractory Al-rich chondrules in Semarkona (LL3.0), the most primitive unequilibrated ordinary chondrite, provide direct evidence for condensation of Si and Mg on melt droplets during cooling. The chondrules are completely rounded, rich in Ca and Al, and poor in Fe and alkalis. They have extraordinarily abundant glass (70-80 vol%) with a subordinate amount of forsterite as the only crystalline phase that occurs mostly rimming the chondrule edge. The groundmass glass is concentrically zoned in terms of Si with an outward increase, which is overlapped with local heterogeneity of Mg and Al induced by crystallization of forsterite. The outward increase of Si, mostly compensated by Al, cannot be formed solely by crystallization of forsterite from a homogeneous melt in a closed system. Combined with skeletal or dendritic morphology and sector zoning of forsterite, it is suggested that Si condensed onto totally molten droplets (“initial melts”) accompanied by nucleation and rapid growth of forsterite with lowering temperature. The “initial melts”, the compositions of which were estimated from the Ca contents of the first crystallized forsterite, are very similar to Type C CAI but are notably poorer in Mg and Si than the bulk chondrules, indicating condensation of Mg in addition to Si with an atomic ratio of Mg:Si ∼ 3:2. The condensation after the nucleation of forsterite took place below ∼1300 °C under cooling at ∼70 °C/h and amounted to 30 wt% of the current chondrule. This study suggests a model that a short-time and local shock heating event induced melting of Type C CAI and concomitant evaporation of dusts, ferromagnesian chondrules of earlier generation, and their fragments to generate Mg and Si-rich gas, which condensed onto the melt droplets upon cooling accompanying condensation of Type I chondrules.     

Al in plagioclase-rich chondrules in carbonaceous chondrites: Evidence for an extended duration of chondrule formation

The ²⁶Al-²⁶Mg isotope systematics in 33 petrographically and mineralogically characterized plagioclase-rich chondrules (PRCs) from 13 carbonaceous chondrites (CCs) - one ungrouped (Acfer 094), six CR, five CV, and one CO - reveal large variations in the initial ²⁶Al/²⁷Al ratio, (²⁶Al/²⁷Al)₀. Well-resolved ²⁶Mg excesses (δ²⁶Mg) from the in situ decay of the short-lived nuclide ²⁶Al (t_1/2 ∼ 0.72 Ma) were found in nine chondrules, two from Acfer 094, five from the CV chondrites, Allende and Efremovka, and one each from the paired CR chondrites, EET 92147 and EET 92042, with (²⁶Al/²⁷Al)₀ values ranging from ∼3 × 10⁻⁶ to ∼1.5 × 10⁻⁵. Data for seven additional chondrules from three CV and two CR chondrites show evidence suggestive of the presence of ²⁶Al but do not yield well defined values for (²⁶Al/²⁷Al)₀, while the remaining chondrules do not contain excess radiogenic ²⁶Mg and yield corresponding upper limits of (11-2) × 10⁻⁶ for (²⁶Al/²⁷Al)₀. The observed range of (²⁶Al/²⁷Al)₀ in PRCs from CCs is similar to the range seen in chondrules from unequilibrated ordinary chondrites (UOCs) of low metamorphic grade (3.0-3.4). However, unlike the UOC chondrules, there is no clear trend between the (²⁶Al/²⁷Al)₀ values in PRCs from CCs and the degree of thermal metamorphism experienced by the host meteorites. High and low values of (²⁶Al/²⁷Al)₀ are found equally in PRCs from both CCs lacking evidence for thermal metamorphism (e.g., CRs) and CCs where such evidence is abundant (e.g., CVs). The lower (²⁶Al/²⁷Al)₀ values in PRCs from CCs, relative to most CAIs, are consistent with a model in which ²⁶Al was distributed uniformly in the nebula when chondrule formation began, approximately a million years after the formation of the majority of CAIs. The observed range of (²⁶Al/²⁷Al)₀ values in PRCs from CCs is most plausibly explained in terms of an extended duration of ∼2-3 Ma for the formation of CC chondrules. This interval is in sharp contrast to most CAIs from CCs, whose formation appears to be restricted to a narrow time interval of less than 10⁵ years. The active solar nebula appears to have persisted for a period approaching 4 Ma, encompassing the formation of both CAIs and chondrules present in CCs, and raising important issues related to the storage, assimilation and mixing of chondrules and CAIs in the early solar system.     

Oxygen isotopic compositions of chondrules: Implications for evolution of oxygen isotopic reservoirs in the inner solar nebula

We review the oxygen isotopic compositions of minerals in chondrules and compound objects composed of a chondrule and a refractory inclusion, and bulk oxygen isotopic compositions of chondrules in unequilibrated ordinary, carbonaceous, enstatite, and Kakangari-like chondrites, focusing on data acquired using secondary ion mass-spectrometry and laser fluorination coupled with mass-spectrometry over the last decade. Most ferromagnesian chondrules from primitive (unmetamorphosed) chondrites are isotopically uniform (within 3–4‰ in Δ¹⁷O) and depleted in ¹⁶O (Δ¹⁷O>−7‰) relative to amoeboid olivine aggregates (AOAs) and most calcium–aluminum-rich inclusions (CAIs) (Δ¹⁷O<−20‰), suggesting that these classes of objects formed in isotopically distinct gaseous reservoirs, ¹⁶O-poor and ¹⁶O-rich, respectively. Chondrules uniformly enriched in ¹⁶O (Δ¹⁷O<−15‰) are exceptionally rare and have been reported only in CH chondrites. Oxygen isotopic heterogeneity in chondrules is mainly due to the presence of relict grains. These appear to consist of chondrules of earlier generations and rare refractory inclusions; with rare exceptions, the relict grains are ¹⁶O-enriched relative to chondrule phenocrysts and mesostasis. Within a chondrite group, the magnesium-rich (Type I) chondrules tend to be ¹⁶O-enriched relative to the ferrous (Type II) chondrules. Aluminum-rich chondrules in ordinary, enstatite, CR, and CV chondrites are generally ¹⁶O-enriched relative to ferromagnesian chondrules. No systematic differences in oxygen isotopic compositions have been found among these chondrule types in CB chondrites. Aluminum-rich chondrules in carbonaceous chondrites often contain relict refractory inclusions. Aluminum-rich chondrules with relict CAIs have heterogeneous oxygen isotopic compositions (Δ¹⁷O ranges from −20‰ to 0‰). Aluminum-rich chondrules without relict CAIs are isotopically uniform and have oxygen isotopic compositions similar to, or approaching, those of ferromagnesian chondrules. Phenocrysts and mesostases of the CAI-bearing chondrules show no clear evidence for ¹⁶O-enrichment compared to the CAI-free chondrules. Spinel, hibonite, and forsterite of the relict refractory inclusions largely retained their original oxygen isotopic compositions. In contrast, plagioclase and melilite of the relict CAIs experienced melting and ¹⁶O-depletion to various degrees, probably due to isotopic exchange with an ¹⁶O-poor nebular gas. Several igneous CAIs experienced isotopic exchange with an ¹⁶O-poor nebular gas during late-stage remelting in the chondrule-forming region. On a three-isotope diagram, bulk oxygen isotopic compositions of most chondrules in ordinary, enstatite, and carbonaceous chondrites plot above, along, and below the terrestrial fractionation line, respectively. Bulk oxygen isotopic compositions of chondrules in altered and/or metamorphosed chondrites show evidence for mass-dependent fractionation, reflecting either interaction with a gaseous/fluid reservoir on parent asteroids or open-system thermal metamorphism. Bulk oxygen isotopic compositions of chondrules and oxygen isotopic compositions of individual minerals in chondrules and refractory inclusions from primitive chondrites plot along a common line of slope of 1, suggesting that only two major reservoirs (gas and solids) are needed to explain the observed variations. However, there is no requirement that each had a permanently fixed isotopic composition. The absolute (²⁰⁷Pb–²⁰⁶Pb) and relative (²⁷Al–²⁶Mg) chronologies of CAIs and chondrules and the differences in oxygen isotopic compositions of most chondrules (¹⁶O-poor) and most refractory inclusions (¹⁶O-rich) can be interpreted in terms of isotopic self-shielding during UV photolysis of CO in the initially ¹⁶O-rich (Δ¹⁷O−25‰) parent molecular cloud or protoplanetary disk. According to these models, the UV photolysis preferentially dissociates C¹⁷O and C¹⁸O in the parent molecular cloud and in the peripheral zones of the protoplanetary disk. If this process occurs in the stability field of water ice, the released atomic ¹⁷O and ¹⁸O are incorporated into water ice, while the residual CO gas becomes enriched in ¹⁶O. During the earliest stages of evolution of the protoplanetary disk, the inner solar nebula had a solar H₂O/CO ratio and was ¹⁶O-rich. During this time, AOAs and the ¹⁶O-rich CAIs and chondrules formed. Subsequently, the inner solar nebula became H₂O- and ¹⁶O-depleted, because ice-rich dust particles, which were depleted in ¹⁶O, agglomerated outside the snowline (5 AU), drifted rapidly towards the Sun and evaporated. During this time, which may have lasted for 3 Myr, most chondrules and the ¹⁶O-depleted igneous CAIs formed. We infer that most chondrules formed from isotopically heterogeneous, but ¹⁶O-depleted precursors, and experienced isotopic exchange with an ¹⁶O-poor nebular gas during melting. Although the relative roles of the chondrule precursor materials and gas–melt isotopic exchange in establishing oxygen isotopic compositions of chondrules have not been quantified yet, mineralogical, chemical, and isotopic evidence indicate that Type I chondrules may have formed in chemical and isotopic equilibrium with nebular gas of variable isotopic composition. Whether these variations were spatial or temporal are not known yet.     

Chemical and oxygen isotopic compositions of accretionary rim and matrix olivine in CV chondrites: Constraints on the evolution of nebular dust

A correlation of petrography, mineral chemistry and in situ oxygen isotopic compositions of fine-grained olivine from the matrix and of fine- and coarse-grained olivine from accretionary rims around Ca-Al-rich inclusions (CAIs) and chondrules in CV chondrites is used here to constrain the processes that occurred in the solar nebula and on the CV parent asteroid. The accretionary rims around Leoville, Vigarano, and Allende CAIs exhibit a layered structure: the inner layer consists of coarse-grained, forsteritic and ¹⁶O-rich olivine (Fa_1-40 and Δ¹⁷O = −24‰ to −5‰; the higher values are always found in the outer part of the layer and only in the most porous meteorites), whereas the middle and the outer layers contain finer-grained olivines that are more fayalitic and ¹⁶O-depleted (Fa_15-50 and Δ¹⁷O = −18‰ to +1‰). The CV matrices and accretionary rims around chondrules have olivine grains of textures, chemical and isotopic compositions similar to those in the outer layers of accretionary rims around CAIs. There is a correlation between local sample porosity and olivine chemical and isotopic compositions: the more compact regions (the inner accretionary rim layer) have the most MgO- and ¹⁶O-rich compositions, whereas the more porous regions (outer rim layers around CAIs, accretionary rims around chondrules, and matrices) have the most MgO- and ¹⁶O-poor compositions. In addition, there is a negative correlation of olivine grain size with fayalite contents and Δ¹⁷O values. However, not all fine-grained olivines are FeO-rich and ¹⁶O-poor; some small (<1 μm in Leoville and 5-10 μm in Vigarano and Allende) ferrous (Fa_>20) olivine grains in the outer layers of the CAI accretionary rims and in the matrix show significant enrichments in ¹⁶O (Δ¹⁷O = −20‰ to −10‰). We infer that the inner layer of the accretionary rims around CAIs and, at least, some olivine grains in the finer portions of accretionary rims and CV matrices formed in an ¹⁶O-rich gaseous reservoir, probably in the CAI-forming region. Grains in the outer layers of the CAI accretionary rims and in the rims around chondrules as well as matrix may have also originated as ¹⁶O-rich olivine. However, these olivines must have exchanged O isotopes to variable extents in the presence of an ¹⁶O-poor reservoir, possibly the nebular gas in the chondrule-forming region(s) and/or fluids in the parent body. The observed trend in isotopic compositions may arise from mixtures of ¹⁶O-rich forsterites with grain overgrowths or newly formed grains of ¹⁶O-poor fayalitic olivines formed during parent body metamorphism. However, the observed correlations of chemical and isotopic compositions of olivine with grain size and local porosity of the host meteorite suggest that olivine accreted as a single population of ¹⁶O-rich forsterite and subsequently exchanged Fe-Mg and O isotopes in situ in the presence of aqueous solutions (i.e., fluid-assisted thermal metamorphism).     

Origin and chronology of chondritic components: A review

Mineralogical observations, chemical and oxygen-isotope compositions, absolute ²⁰⁷Pb-²⁰⁶Pb ages and short-lived isotope systematics (⁷Be-⁷Li, ¹⁰Be-¹⁰B, ²⁶Al-²⁶Mg, ³⁶Cl-³⁶S, ⁴¹Ca-⁴¹K, ⁵³Mn-⁵³Cr, ⁶⁰Fe-⁶⁰Ni, ¹⁸²Hf-¹⁸²W) of refractory inclusions [Ca,Al-rich inclusions (CAIs) and amoeboid olivine aggregates (AOAs)], chondrules and matrices from primitive (unmetamorphosed) chondrites are reviewed in an attempt to test (i) the x-wind model vs. the shock-wave model of the origin of chondritic components and (ii) irradiation vs. stellar origin of short-lived radionuclides. The data reviewed are consistent with an external, stellar origin for most short-lived radionuclides (⁷Be, ¹⁰Be, and ³⁶Cl are important exceptions) and a shock-wave model for chondrule formation, and provide a sound basis for early Solar System chronology. They are inconsistent with the x-wind model for the origin of chondritic components and a local, irradiation origin of ²⁶Al, ⁴¹Ca, and ⁵³Mn. ¹⁰Be is heterogeneously distributed among CAIs, indicating its formation by local irradiation and precluding its use for the early solar system chronology. ⁴¹Ca-⁴¹K, and ⁶⁰Fe-⁶⁰Ni systematics are important for understanding the astrophysical setting of Solar System formation and origin of short-lived radionuclides, but so far have limited implications for the chronology of chondritic components. The chronological significance of oxygen-isotope compositions of chondritic components is limited. The following general picture of formation of chondritic components is inferred. CAIs and AOAs were the first solids formed in the solar nebula ∼4567-4568 Myr ago, possibly within a period of <0.1 Myr, when the Sun was an infalling (class 0) and evolved (class I) protostar. They formed during multiple transient heating events in nebular region(s) with high ambient temperature (at or above condensation temperature of forsterite), either throughout the inner protoplanetary disk (1-4 AU) or in a localized region near the proto-Sun (<0.1 AU), and were subsequently dispersed throughout the disk. Most CAIs and AOAs formed in the presence of an ¹⁶O-rich (Δ¹⁷O ∼ −24 ± 2‰) nebular gas. The ²⁶Al-poor [(²⁶Al/²⁷Al)₀ < 1 × 10⁻⁵], ¹⁶O-rich (Δ¹⁷O ∼ −24 ± 2‰) CAIs - FUN (fractionation and unidentified nuclear effects) CAIs in CV chondrites, platy hibonite crystals (PLACs) in CM chondrites, pyroxene-hibonite spherules in CM and CO chondrites, and the majority of grossite- and hibonite-rich CAIs in CH chondrites—may have formed prior to injection and/or homogenization of ²⁶Al in the early Solar System. A small number of igneous CAIs in ordinary, enstatite and carbonaceous chondrites, and virtually all CAIs in CB chondrites are ¹⁶O-depleted (Δ¹⁷O > −10‰) and have (²⁶Al/²⁷Al)₀ similar to those in chondrules (<1 × 10⁻⁵). These CAIs probably experienced melting during chondrule formation. Chondrules and most of the fine-grained matrix materials in primitive chondrites formed 1-4 Myr after CAIs, when the Sun was a classical (class II) and weak-lined T Tauri star (class III). These chondritic components formed during multiple transient heating events in regions with low ambient temperature (<1000 K) throughout the inner protoplanetary disk in the presence of ¹⁶O-poor (Δ¹⁷O > −5‰) nebular gas. The majority of chondrules within a chondrite group may have formed over a much shorter period of time (<0.5-1 Myr). Mineralogical and isotopic observations indicate that CAIs were present in the regions where chondrules formed and accreted (1-4 AU), indicating that CAIs were present in the disk as free-floating objects for at least 4 Myr. Many CAIs, however, were largely unaffected by chondrule melting, suggesting that chondrule-forming events experienced by a nebular region could have been small in scale and limited in number. Chondrules and metal grains in CB chondrites formed during a single-stage, highly-energetic event ∼4563 Myr ago, possibly from a gas-melt plume produced by collision between planetary embryos.     

Implications of the carbonaceous chondrite Mn-Cr isochron for the formation of early refractory planetesimals and chondrules

An excellent ⁵³Mn-⁵³Cr isochron for bulk CI, CM, CO, CV, CB, and ungrouped C3 chondrites seems to suggest that each carbonaceous chondrite group acquired its Mn/Cr ratio 4568 ± 1 Myr ago. This age is indistinguishable from the age of Ca-Al-rich inclusions (CAIs), which is considered to be the start of the solar system (t₀). However, carbonaceous chondrites were not assembled until at least 1.5-5 Myr after t₀, to judge by the ²⁰⁷Pb-²⁰⁶Pb and ²⁶Al-²⁶Mg ages of the chondrules within them, and by the fact that they were not melted by heat from the decay of ²⁶Al. Presumably, therefore, these meteorites inherited their bulk Mn-Cr isochron from precursor materials which experienced Mn-Cr fractionation at t₀. As a possible physical mechanism for how the isochron was established initially, and later inherited by the carbonaceous chondrites, we propose the rapid formation at t₀ of planetesimals that were variably depleted in moderately volatile elements, and hence had variably low Mn/Cr. The planetesimals and the undepleted (high Mn/Cr) primitive dust from which they were made shared the same initial ε⁵³Cr, and therefore evolved on an isochron. We suggest that later impact-disruption of the planetesimals produced dusty debris, which became mixed, in various proportions, with unprocessed (high Mn/Cr) dust before accreting to the carbonaceous chondrite parent bodies. With mixing in a closed system, the isochron was unchanged. We infer that some debris-rich material was converted to chondrules prior to accretion. The chondrules could have been formed by flash melting of the mixed dust, or could instead have been made directly by the impact splashing of molten planetesimals, or by condensation from impact-generated vapor plumes.     

Formation conditions of aluminum-rich chondrules

We have studied the formation conditions of Al-rich chondrules by doing isothermal and dynamic crystallization experiments at one atmosphere on four different chondrule analogue compositions within the pure CaO-MgO-Al₂O₃-SiO₂ system. For the dynamic crystallization experiments, we cooled from both liquidus and subliquidus peak temperatures (T_max), at cooling rates from 5-1000 °C/h. The starting compositions include two with anorthite and two with forsterite as the dominant liquidus phases, all at or near spinel-saturation. One of each pair evolves towards diopside crystallization, and the others cordierite or enstatite crystallization, giving a total of four completely different crystallization sequences analogous to the four basic varieties of Al-rich chondrule recently proposed. Bulk composition is the main controlling factor, both in terms of mineralogy and texture. The textures of the anorthite-rich compositions are more sensitive to T_max than they are to cooling rate, whereas the textures of the forsterite-rich compositions are more sensitive to cooling rate. Comparisons of natural Al-rich chondrules having similar compositions to our synthetic analogues indicate that the natural objects reflect a range of peak heating temperatures, ∼1400-1500 °C, and cooling rates of 10-500 °C/h for porphyritic chondrules and possibly higher (1000 °C/h) for barred chondrules. These conditions are consistent with the conditions inferred for ferromagnesian chondrules but differ from those inferred for some calcium-aluminum-rich inclusions.     

Oxygen isotope heterogeneity in chondrules from the Mokoia CV3 carbonaceous chondrite

We report a study of the oxygen isotope ratios of chondrules and their constituent mineral grains from the Mokoia, oxidized CV3 chondrite. Bulk oxygen isotope ratios of 23 individual chondrules were determined by laser ablation fluorination, and oxygen isotope ratios of individual grains, mostly olivine, were obtained in situ on polished mounts using secondary ion mass spectrometry (SIMS). Our results can be compared with data obtained previously for the oxidized CV3 chondrite, Allende. Bulk oxygen isotope ratios of Mokoia chondrules form an array on an oxygen three-isotope plot that is subparallel to, and slightly displaced from, the CCAM (carbonaceous chondrite anhydrous minerals) line. The best-fit line for all CV3 chondrite chondrules has a slope of 0.99, and is displaced significantly (by δ¹⁷O ∼ −2.5‰) from the Young and Russell slope-one line for unaltered calcium-aluminum-rich inclusion (CAI) minerals. Oxygen isotope ratios of many bulk CAIs also lie on the CV-chondrule line, which is the most relevant oxygen isotope array for most CV chondrite components. Bulk oxygen isotope ratios of most chondrules in Mokoia have δ¹⁸O values around 0‰, and olivine grains in these chondrules have similar oxygen isotope ratios to their bulk values. In general, it appears that chondrule mesostases have higher δ¹⁸O values than olivines in the same chondrules. Our bulk chondrule data spread to lower δ¹⁸O values than any ferromagnesian chondrules that have been measured previously. Two chondrules with the lowest bulk δ¹⁸O values (−7.5‰ and −11.7‰) contain olivine grains that display an extremely wide range of oxygen isotope ratios, down to δ¹⁷O, δ¹⁸O around -50‰ in one chondrule. In these chondrules, there are no apparent relict grains, and essentially no relationships between olivine compositions, which are homogeneous, and oxygen isotopic compositions of individual grains. Heterogeneity of oxygen isotope ratios within these chondrules may be the result of incorporation of relict grains from objects such as amoeboid olivine aggregates, followed by solid-state chemical diffusion without concomitant oxygen equilibration. Alternatively, oxygen isotope exchange between an ¹⁶O-rich precursor and an ¹⁶O-poor gas may have taken place during chondrule formation, and these chondrules may represent partially equilibrated systems in which isotopic heterogeneities became frozen into the crystallizing olivine grains. If this is the case, we can infer that the earliest nebular solids from which chondrules formed had δ¹⁷O and δ¹⁸O values around -50‰, similar to those observed in refractory inclusions.     

On early Solar System chronology: Implications of an heterogeneous spatial distribution of Al and Mn

Early Solar System chronology is usually built with the assumption that the distribution of short-lived radionuclides was homogeneous through the solar accretion disk. At present, there is no unambiguous evidence for a homogeneous distribution of short-lived radionuclides in the solar accretion disk, while some data point to a heterogeneous distribution of short-lived radionuclides. In this paper, we explore a possible chronology based on a heterogeneous distribution of ²⁶Al and ⁵³Mn in the accretion disk. Our basic assumption is that the different abundances of extinct short-lived radionuclides in calcium-aluminium-rich inclusions (CAIs) and chondrules are due to spatial rather than temporal differences. We develop a simple model where CAIs and chondrules form contemporaneously, in different spatial locations, and are characterised by distinct initial ²⁶Al and ⁵³Mn abundances. In this model, all evolved bodies are supposed to be originally chondritic, i.e., to be made of a mixture of CAIs, chondrules, and matrix. This mixture determines the initial content in ²⁶Al and ⁵³Mn of a chondritic parent-body as a function of its CAI and chondrule abundance fraction. This approach enables us to calculate coherent ²⁶Al and ⁵³Mn ages from the agglomeration of the parent-body precursors (CAIs and chondrules) until the isotopic closure of ²⁶Al and ⁵³Mn, thereafter called ²⁶Al-⁵³Mn age. We calculate such ²⁶Al-⁵³Mn ages for a diversity of evolved objects, with the constraint that they should be found for realistic chondritic parent-body precursors, i.e., objects having similar or identical petrograpy to the existing chondrite groups. The so defined age of the d’Orbigny angrite is 4.3 ± 1.1 Myr, for the Asuka-881394 eucrite 2.8 ± 1.0 Myr, for the H4 chondrite Sainte Marguerite ∼3 Myr, and for H4 Forest Vale ∼5 Myr. The calculated ²⁶Al-⁵³Mn ages give timescales for the evolution of the respective parent-bodies/meteorites that can be investigated in the light of further petrographic studies. We anchor the calculated relative chronology to an absolute chronology using absolute Pb-Pb ages and relative Hf-W ages of the objects under scrutiny. The precursors of Sainte Marguerite and Forest Vale agglomerated at the same time (∼4565.8 ± 1.2 Ma ago). The precursors of eucrites (Asuka-881394) agglomerated 4564.8 ± 1.2 Ma ago. The precursors of angrites agglomerated late (4561.5 ± 1.8 Ma ago). Our model provides a fully compatible Al-Mg/Mn-Cr/Pb-Pb chronology, and is shown to be robust to reasonable changes in the input parameters. The calculated initial ²⁶Al/²⁷Al ratios are high enough to have ²⁶Al as a possible heat source for differentiation.     

Al-Mg systematics in D’Orbigny and Sahara 99555 angrites: Implications for high-resolution chronology using extinct chronometers

We report on an investigation of the ²⁶Al-²⁶Mg isotope systematics in the D’Orbigny and Sahara 99555 angrites. High precision Mg isotope compositions and Al/Mg ratios were measured in mineral separates and whole rock samples from D’Orbigny and Sahara 99555 using multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS). Plagioclase separates from both angrites have resolvable excesses in ²⁶Mg (Δ²⁶Mg) that correlate with their respective Al/Mg ratios. ²⁶Al-²⁶Mg systematics in the mineral separates and whole rocks define precise isochrons that correspond to ²⁶Al/²⁷Al ratios of (5.06 ± 0.92) × 10⁻⁷ and (5.13 ± 1.90) × 10⁻⁷ and initial Δ²⁶Mg values of −0.006 ± 0.040‰ and −0.016 ± 0.047‰ for D’Orbigny and Sahara 99555, respectively. The slopes and initial Δ²⁶Mg values are identical for these two meteorites within errors and the data for both angrites considered together define an isochron corresponding to a ²⁶Al/²⁷Al ratio of (5.10 ± 0.55) × 10⁻⁷ and initial Δ²⁶Mg value of −0.012 ± 0.019. Relative to the Efremovka E60 CAI, the ²⁶Al/²⁷Al values reported here for these angrites imply ²⁶Al-²⁶Mg ages of 4562.42 ± 0.29 Ma and 4562.43 ± 0.53 Ma for D’Orbigny and Sahara 99555, respectively. These ²⁶Al-²⁶Mg ages are concordant with model ages determined using other extinct radionuclide chronometers (e.g., ⁵³Mn-⁵³Cr and ¹⁸²Hf-¹⁸²W), but are ∼2 Myr younger than the absolute ²⁰⁷Pb-²⁰⁶Pb ages that have been reported recently for these angrites. The reason for this discrepancy is not presently known, but may imply disturbance of one or more of the isotope systems under consideration or a possible bias in the ²⁰⁷Pb-²⁰⁶Pb ages of the angrites resulting from natural or analytical causes.     

Oxygen isotopic compositions of chondrules from the metal-rich chondrites Isheyevo (CH/CBb), MAC 02675 (CBb) and QUE 94627 (CBb)

It has been recently suggested that (1) CH chondrites and the CB_b/CH-like chondrite Isheyevo contain two populations of chondrules formed by different processes: (i) magnesian non-porphyritic (cryptocrystalline and barred) chondrules, which are similar to those in the CB chondrites and formed in an impact-generated plume of melt and gas resulted from large-scale asteroidal collision, and (ii) porphyritic chondrules formed by melting of solid precursors in the solar nebula. (2) Porphyritic chondrules in Isheyevo and CH chondrites are different from porphyritic chondrules in other carbonaceous chondrites ( [Krot et al., 2005], [Krot et al., 2008a] and [Krot et al., 2008b]). In order to test these hypotheses, we measured in situ oxygen isotopic compositions of porphyritic (magnesian, Type I and ferroan, Type II) and non-porphyritic (magnesian and ferroan cryptocrystalline) chondrules from Isheyevo and CB_b chondrites MAC 02675 and QUE 94627, paired with QUE 94611, using a Cameca ims-1280 ion microprobe.On a three-isotope oxygen diagram (δ¹⁷O vs. δ¹⁸O), compositions of chondrules measured follow approximately slope-1 line. Data for 19 magnesian cryptocrystalline chondrules from Isheyevo, 24 magnesian cryptocrystalline chondrules and 6 magnesian cryptocrystalline silicate inclusions inside chemically-zoned Fe,Ni-metal condensates from CB_b chondrites have nearly identical compositions: Δ¹⁷O = −2.2 ± 0.9‰, −2.3 ± 0.6‰ and −2.2 ± 1.0‰ (2σ), respectively. These observations and isotopically light magnesium compositions of cryptocrystalline magnesian chondrules in CB_b chondrites (Gounelle et al., 2007) are consistent with their single-stage origin, possibly as gas-melt condensates in an impact-generated plume. In contrast, Δ¹⁷O values for 11 Type I and 9 Type II chondrules from Isheyevo range from −5‰ to +4‰ and from −17‰ to +3‰, respectively. In contrast to typical chondrules from carbonaceous chondrites, seven out of 11 Type I chondrules from Isheyevo plot above the terrestrial fractionation line. We conclude that (i) porphyritic chondrules in Isheyevo belong to a unique population of objects, suggesting formation either in a different nebular region or at a different time than chondrules from other carbonaceous chondrites; (ii) Isheyevo, CB and CH chondrites are genetically related meteorites: they contain non-porphyritic chondrules produced during the same highly-energetic event, probably large-scale asteroidal collision; (iii) the differences in mineralogy, petrography, chemical and whole-rock oxygen isotopic compositions between CH and CB chondrites are due to various proportions of the nebular and the impact-produced materials.     

The oxygen-isotope composition of chondrules and isolated forsterite and olivine grains from the Tagish Lake carbonaceous chondrite

The oxygen-isotope compositions (obtained by laser fluorination) of hand-picked separates of isolated forsterite, isolated olivine and chondrules from the Tagish Lake carbonaceous chondrite describe a line (δ¹⁷O = 0.95 * δ¹⁸O − 3.24; R² = 0.99) similar to the trend known for chondrules from other carbonaceous chondrites. The isolated forsterite grains (Fo_99.6-99.8; δ¹⁸O = −7.2‰ to −5.5‰; δ¹⁷O = −9.6‰ to −8.2‰) are more ¹⁶O-rich than the isolated olivine grains (Fo_39.6-86.8; δ¹⁸O = 3.1‰ to 5.1‰; δ¹⁷O = −0.3‰ to 2.2‰), and have chemical and isotopic characteristics typical of refractory forsterite. Chondrules contain olivine (Fo_97.2-99.8) with oxygen-isotope compositions (δ¹⁸O = −5.2‰ to 5.9‰; δ¹⁷O = −8.1‰ to 1.2‰) that overlap those of isolated forsterite and isolated olivine. An inverse relationship exists between the Δ¹⁷O values and Fo contents of Tagish Lake isolated forsterite and chondrules; the chondrules likely underwent greater exchange with ¹⁶O-poor nebular gases than the forsterite. The oxygen-isotope compositions of the isolated olivine grains describe a trend with a steeper slope (1.1 ± 0.1, R² = 0.94) than the carbonaceous chondrite anhydrous mineral line (CCAM_slope = 0.95). The isolated olivine may have crystallized from an evolving melt that exchanged with ¹⁶O-poor gases of somewhat different composition than those which affected the chondrules and isolated forsterite. The primordial components of the Tagish Lake meteorite formed under conditions similar to other carbonaceous chondrite meteorite groups, especially CMs. Its alteration history has its closest affinities to CI carbonaceous chondrites.     

Elemental composition of individual chondrules from ordinary chondrites

Sequential non-destructive neutron activation analysis was used to determine the bulk abundance of Fe, Al, Na, Mn, Or, Sc, Co and Ir in approximately 300 individual chondrules from 16 chondrites representing the H (3–5), L4 and LL(3–6) compositional and petrologic classes. For some of the chondrules, Si, Ni, Ca and V were also determined. The histograms indicate that the most probable abundances for lithophilic elements, except Cr, are enriched in the chondrules, while the siderophilic elements are depleted in the chondrules compared to the whole chondrite. Some of the abundance populations, such as Al and Fe, appear to be multimodal. Systematic variations in the composition of the chondrules with increasing petrologic type were observed; most consistent are an increasing Na-Al and Cr-Al correlation, a decreasing Na-Mn correlation, increasing Na abundance and decreasing Na and Mn dispersions among chondrules. The systematic compositional variations with increasing petrologic type are consistent with an increasing approach to equilibrium between chondrules and matrix.Observed elemental correlations are generally consistent with mineralogical controls expected on the basis of geochemical affinities suggested by the mineral assemblages present in the chondrules. However, a prevalent Al-Ir correlation was observed, and is most pronounced for a group of chondrules belonging to a population high in Al. A Sc-Ir correlation was observed. Also, an anti-correlation between chondrule masses and Al (and Ir for some chondrules) content of the chondrules was observed. These correlations are attributed to a fractionation during condensation or chondrule formation and cannot be attributed to classical geochemical similarities i.e. these correlations result from a cosmochemical fractionation. From the compositional evidence, it is suggested that there may be two mechanisms for chondrule production. Some high Al chondrules which exhibit the Al-Ir correlation are believed to be remelted primitive high-temperature aggregates. The elemental composition of the chondrules from the lower Al abundance population is consistent with a preferential remelting of pre-existing silicates.     

Robust 24 ± 6 ka Ar/Ar age of a low-potassium tholeiitic basalt in the Lassen region of NE California

⁴⁰Ar/³⁹Ar ages on the Hat Creek Basalt (HCB) and stratigraphically related lava flows show that latest Pleistocene tholeiitic basalt with very low K₂O can be dated reliably. The HCB underlies ∼ 15 ka glacial gravel and overlies four andesite and basaltic andesite lava flows that yield ⁴⁰Ar/³⁹Ar ages of 38 ± 7 ka (Cinder Butte; 1.65% K₂O), 46 ± 7 ka (Sugarloaf Peak; 1.85% K₂O), 67 ± 4 ka (Little Potato Butte; 1.42% K₂O) and 77 ± 11 ka (Potato Butte; 1.62% K₂O). Given these firm age brackets, we then dated the HCB directly. One sample (0.19% K₂O) clearly failed the criteria for plateau-age interpretation, but the inverse isochron age of 26 ± 6 ka is seductively appealing. A second sample (0.17% K₂O) yielded concordant plateau, integrated (total fusion), and inverse isochron ages of 26 ± 18, 30 ± 20 and 24 ± 6 ka, all within the time bracket determined by stratigraphic relations; the inverse isochron age of 24 ± 6 ka is preferred. As with all isotopically determined ages, confidence in the results is significantly enhanced when additional constraints imposed by other isotopic ages within a stratigraphic context are taken into account.     

Partitioning of Na between olivine and melt: An experimental study with application to the formation of meteoritic Na2O-rich chondrule glass and refractory forsterite grains

We report experimentally determined 1 atm olivine/melt D_Na partitioning data for low f_O2, a variety of melt compositions and a temperature range of 1325-1522 °C. We demonstrated that high-current electron microprobe analyses (EPMA, I = 500 nA, 600 s on the peak) allow quantitative determination of Na₂O in olivine down to ∼10 μg/g. The mean olivine/melt D_Na from 12 experimental runs is 0.0031 ± 0.0007 (1σ). This is the recommended value for low pressures and a wide range of natural compositions.This result is applied to the problem of the origin of alkalis in chondrules and the formation of chondritic refractory forsterite grains. The data on Semarkona (LL3.0) chondrules show that Na₂O is primordial and was present during olivine crystallization. For refractory forsterite grains from Murchison (CM2), we demonstrate that high CaO contents are not a result of equilibration with Na₂O-rich melts, but require high activities of CaO during their formation.     

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.