Early core formation in asteroids and late accretion of chondrite parent bodies: Evidence from Hf-W in CAIs, metal-rich chondrites, and iron meteorites

The ¹⁸²Hf-¹⁸²W isotopic systematics of Ca-Al-rich inclusions (CAIs), metal-rich chondrites, and iron meteorites were investigated to constrain the relative timing of accretion of their parent asteroids. A regression of the Hf-W data for two bulk CAIs, various fragments of a single CAI, and carbonaceous chondrites constrains the ¹⁸²Hf/¹⁸⁰Hf and ε_W at the time of CAI formation to (1.07 ± 0.10) × 10⁻⁴ and −3.47 ± 0.20, respectively. All magmatic iron meteorites examined here have initial ε_W values that are similar to or slightly lower than the initial value of CAIs. These low ε_W values may in part reflect ¹⁸²W-burnout caused by the prolonged cosmic ray exposure of iron meteorites, but this effect is estimated to be less than ∼0.3 ε units for an exposure age of 600 Ma. The W isotope data, after correction for cosmic ray induced effects, indicate that core formation in the parent asteroids of the magmatic iron meteorites occurred less than ∼1.5 Myr after formation of CAIs. The nonmagmatic IAB-IIICD irons and the metal-rich CB chondrites have more radiogenic W isotope compositions, indicating formation several Myr after the oldest metal cores had segregated in some asteroids.Chondrule formation ∼2-5 Myr after CAIs, as constrained by published Pb-Pb and Al-Mg ages, postdates core formation in planetesimals, and indicates that chondrites do not represent the precursor material from which asteroids accreted and then differentiated. Chondrites instead derive from asteroids that accreted late, either farther from the Sun than the parent bodies of magmatic iron meteorites or by reaccretion of debris produced during collisional disruption of older asteroids. Alternatively, chondrites may represent material from the outermost layers of differentiated asteroids. The early thermal and chemical evolution of asteroids appears to be controlled by the decay of ²⁶Al, which was sufficiently abundant (initial ²⁶Al/²⁷Al >1.4 × 10⁻⁵) to rapidly melt early-formed planetesimals but could not raise the temperatures in the late-formed chondrite parent asteroids high enough to cause differentiation. The preservation of the primitive appearance of chondrites thus at least partially reflects their late formation rather than their early and primitive origin.     

Hf-W mineral isochron for Ca,Al-rich inclusions: Age of the solar system and the timing of core formation in planetesimals

Application of ¹⁸²Hf-¹⁸²W chronometry to constrain the duration of early solar system processes requires the precise knowledge of the initial Hf and W isotope compositions of the solar system. To determine these values, we investigated the Hf-W isotopic systematics of bulk samples and mineral separates from several Ca,Al-rich inclusions (CAIs) from the CV3 chondrites Allende and NWA 2364. Most of the investigated CAIs have relative proportions of ¹⁸³W, ¹⁸⁴W, and ¹⁸⁶W that are indistinguishable from those of bulk chondrites and the terrestrial standard. In contrast, one of the investigated Allende CAIs has a lower ¹⁸⁴W/¹⁸³W ratio, most likely reflecting an overabundance of r-process relative to s-process isotopes of W. All other bulk CAIs have similar ¹⁸⁰Hf/¹⁸⁴W and ¹⁸²W/¹⁸⁴W ratios that are elevated relative to average carbonaceous chondrites, probably reflecting Hf-W fractionation in the solar nebula within the first ∼3 Myr. The limited spread in ¹⁸⁰Hf/¹⁸⁴W ratios among the bulk CAIs precludes determination of a CAI whole-rock isochron but the fassaites have high ¹⁸⁰Hf/¹⁸⁴W and radiogenic ¹⁸²W/¹⁸⁴W ratios up to ∼14 ε units higher than the bulk rock. This makes it possible to obtain precise internal Hf-W isochrons for CAIs. There is evidence of disturbed Hf-W systematics in one of the CAIs but all other investigated CAIs show no detectable effects of parent body processes such as alteration and thermal metamorphism. Except for two fractions from one Allende CAI, all fractions from the investigated CAIs plot on a single well-defined isochron, which defines the initial ε¹⁸²W = −3.28 ± 0.12 and ¹⁸²Hf/¹⁸⁰Hf = (9.72 ± 0.44) × 10⁻⁵ at the time of CAI formation. The initial ¹⁸²Hf/¹⁸⁰Hf and ²⁶Al/²⁷Al ratios of the angrites D’Orbigny and Sahara 99555 are consistent with the decay from initial abundances of ¹⁸²Hf and ²⁶Al as measured in CAIs, suggesting that these two nuclides were homogeneously distributed throughout the solar system. However, the uncertainties on the initial ¹⁸²Hf/¹⁸⁰Hf and ²⁶Al/²⁷Al ratios are too large to exclude that some ²⁶Al in CAIs was produced locally by particle irradiation close to an early active Sun. The initial ¹⁸²Hf/¹⁸⁰Hf of CAIs corresponds to an absolute age of 4568.3 ± 0.7 Ma, which may be defined as the age of the solar system. This age is 0.5-2 Myr older than the most precise ²⁰⁷Pb-²⁰⁶Pb age of Efremovka CAI 60, which does not seem to date CAI formation. Tungsten model ages for magmatic iron meteorites, calculated relative to the newly and more precisely defined initial ε¹⁸²W of CAIs, indicate that core formation in their parent bodies occurred in less than ∼1 Myr after CAI formation. This confirms earlier conclusions that the accretion of the parent bodies of magmatic iron meteorites predated chondrule formation and that their differentiation was triggered by heating from decay of abundant ²⁶Al. A more precise dating of core formation in iron meteorite parent bodies requires precise quantification of cosmic-ray effects on W isotopes but this has not been established yet.     

Hf-W chronology of the accretion and early evolution of asteroids and terrestrial planets

The ¹⁸²Hf-¹⁸²W systematics of meteoritic and planetary samples provide firm constraints on the chronology of the accretion and earliest evolution of asteroids and terrestrial planets and lead to the following succession and duration of events in the earliest solar system. Formation of Ca,Al-rich inclusions (CAIs) at 4568.3 ± 0.7 Ma was followed by the accretion and differentiation of the parent bodies of some magmatic iron meteorites within less than ∼1 Myr. Chondrules from H chondrites formed 1.7 ± 0.7 Myr after CAIs, about contemporaneously with chondrules from L and LL chondrites as shown by their ²⁶Al-²⁶Mg ages. Some magmatism on the parent bodies of angrites, eucrites, and mesosiderites started as soon as ∼3 Myr after CAI formation and may have continued until ∼10 Myr. A similar timescale is obtained for the high-temperature metamorphic evolution of the H chondrite parent body. Thermal modeling combined with these age constraints reveals that the different thermal histories of meteorite parent bodies primarily reflect their initial abundance of ²⁶Al, which is determined by their accretion age. Impact-related processes were important in the subsequent evolution of asteroids but do not appear to have induced large-scale melting. For instance, Hf-W ages for eucrite metals postdate CAI formation by ∼20 Myr and may reflect impact-triggered thermal metamorphism in the crust of the eucrite parent body. Likewise, the Hf-W systematics of some non-magmatic iron meteorites were modified by impact-related processes but the timing of this event(s) remains poorly constrained.The strong fractionation of lithophile Hf from siderophile W during core formation makes the Hf-W system an ideal chronometer for this major differentiation event. However, for larger planets such as the terrestrial planets the calculated Hf-W ages are particularly sensitive to the occurrence of large impacts, the degree to which impactor cores re-equilibrated with the target mantle during large collisions, and changes in the metal-silicate partition coefficients of W due to changing fO₂ in differentiating planetary bodies. Calculated core formation ages for Mars range from 0 to 20 Myr after CAI formation and currently cannot distinguish between scenarios where Mars formed by runaway growth and where its formation was more protracted. Tungsten model ages for core formation in Earth range from ∼30 Myr to >100 Myr after CAIs and hence do not provide a unique age for the formation of Earth. However, the identical ¹⁸²W/¹⁸⁴W ratios of the lunar and terrestrial mantles provide powerful evidence that the Moon-forming giant impact and the final stage of Earth’s core formation occurred after extinction of ¹⁸²Hf (i.e., more than ∼50 Myr after CAIs), unless the Hf/W ratios of the bulk silicate Moon and Earth are identical to within less than ∼10%. Furthermore, the identical ¹⁸²W/¹⁸⁴W of the lunar and terrestrial mantles is difficult to explain unless either the Moon consists predominantly of terrestrial material or the W in the proto-lunar magma disk isotopically equilibrated with the Earth’s mantle.Hafnium-tungsten chronometry also provides constraints on the duration of magma ocean solidification in terrestrial planets. Variations in the ¹⁸²W/¹⁸⁴W ratios of martian meteorites reflect an early differentiation of the martian mantle during the effective lifetime of ¹⁸²Hf. In contrast, no ¹⁸²W variations exist in the lunar mantle, demonstrating magma ocean solidification later than ∼60 Myr, in agreement with ¹⁴⁷Sm-¹⁴³Nd ages for ferroan anorthosites. The Moon-forming giant impact most likely erased any evidence of a prior differentiation of Earth’s mantle, consistent with a ¹⁴⁶Sm-¹⁴²Nd age of 50-200 Myr for the earliest differentiation of Earth’s mantle. However, the Hf-W chronology of the formation of Earth’s core and the Moon-forming impact is difficult to reconcile with the preservation of ¹⁴⁶Sm-¹⁴²Nd evidence for an early (<30 Myr after CAIs) differentiation of a chondritic Earth’s mantle. Instead, the combined ¹⁸²W-¹⁴²Nd evidence suggests that bulk Earth may have superchondritic Sm/Nd and Hf/W ratios, in which case formation of its core must have terminated more than ∼42 Myr after formation of CAIs, consistent with the Hf-W age for the formation of the Moon.     

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.     

Ca–Al-rich inclusions in carbonaceous chondrites: the oldest solar system objects

This paper presents a review of recent available data on the first solid condensates of the Solar System, which include refractory CAIs (Ca–Al-rich Inclusions) mostly composed of Ca, Al, Mg, and Ti minerals. A theoretical condensation sequence calculated from thermodynamic data confirmed that CAIs formed as fine-grained aggregates in the protoplanetary disk from an ¹⁶О-rich gas of solar composition at temperatures >1300° K and pressures <10^–4 bar. Based on the diversity of CAI types, their mineralogical, bulk chemical, and isotopic compositions, it can be concluded that CAIs experienced melting and evaporation, possibly by shock waves, which may have occurred in the protoplanetary disk within a brief time interval. Some CAIs may have experienced multiple events such as melting, evaporation, and recycling back to the disk by means of a bipolar outflow. The CAIs having an absolute age of 4567.30 ± 0.16 Myr are the oldest objects in the Solar System. The study of CAIs revealed two distinct oxygen isotope reservoirs (¹⁶О-rich and ¹⁶О-poor) and established a chronology of the sequence of processes forming individual CAI components using Mg–Al, Cr–Mn and Pb–Pb isotopic systematics.     

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.     

Extinct Be in Type A calcium-aluminum-rich inclusions from CV chondrites

We have found clear evidence of live ¹⁰Be in five normal Type A Calcium-aluminum-rich inclusions (CAIs), one normal Type B CAI, and one FUN Type A CAI, all from CV3 chondrites. The (¹⁰Be/⁹Be)₀ ratios range from ∼0.36 × 10^-3 to ∼0.77 × 10^-3 and are similar to those found by previous workers. The (¹⁰Be/⁹Be)₀ ratios do not correlate in a temporal fashion with (²⁶Al/²⁷Al)₀, suggesting that ¹⁰Be and ²⁶Al were produced by different mechanisms. An examination of possible sources for the short-lived radionuclides indicates that production of ¹⁰Be was almost certainly by particle irradiation, possibly within the solar system, and was probably accompanied by significant production of ⁴¹Ca and ⁵³Mn. In contrast, all of the ⁶⁰Fe, most of the ²⁶Al, and some of the ⁵³Mn were probably produced in stars and were imported into the solar system within presolar dust grains.     

Oxygen- and magnesium-isotope compositions of calcium-aluminum-rich inclusions from Rumuruti (R) chondrites

We report oxygen- and magnesium-isotope compositions of Ca,Al-rich inclusions (CAIs) from several Rumuruti (R) chondrites measured in situ using a Cameca ims-1280 ion microprobe. On a three-isotope oxygen diagram, δ¹⁷O vs. δ¹⁸O, compositions of individual minerals in most R CAIs analyzed fall along a slope-1 line. Based on the variations of Δ¹⁷O values (Δ¹⁷O = δ¹⁷O − 0.52 × δ¹⁸O) within individual inclusions, the R CAIs are divided into (i) ¹⁶O-rich (Δ¹⁷O ∼ −23-26‰), (ii) uniformly ¹⁶O-depleted (Δ¹⁷O ∼ −2‰), and (iii) isotopically heterogeneous (Δ¹⁷O ranges from −25‰ to +5‰). One of the hibonite-rich CAIs, H030/L, has an intermediate Δ¹⁷O value of −12‰ and a highly fractionated composition (δ¹⁸O ∼ +47‰). We infer that like most CAIs in other chondrite groups, the R CAIs formed in an ¹⁶O-rich gaseous reservoir. The uniformly ¹⁶O-depleted and isotopically heterogeneous CAIs subsequently experienced oxygen-isotope exchange during remelting in an ¹⁶O-depleted nebular gas, possibly during R chondrite chondrule formation, and/or during fluid-assisted thermal metamorphism on the R chondrite parent asteroid.Three hibonite-bearing CAIs and one spinel-plagioclase-rich inclusion were analyzed for magnesium-isotope compositions. The CAI with the highly fractionated oxygen isotopes, H030/L, shows a resolvable excess of ²⁶Mg (²⁶Mg^∗) corresponding to an initial ²⁶Al/²⁷Al ratio of ∼7 × 10⁻⁷. Three other CAIs show no resolvable excess of ²⁶Mg (²⁶Mg^∗). The absence of ²⁶Mg^∗ in the spinel-plagioclase-rich CAI from a metamorphosed R chondrite NWA 753 (R3.9) could have resulted from metamorphic resetting. Two other hibonite-bearing CAIs occur in the R chondrites (NWA 1476 and NWA 2446), which appear to have experienced only minor degrees of thermal metamorphism. These inclusions could have formed from precursors with lower than canonical ²⁶Al/²⁷Al ratio.     

Oxygen- and magnesium-isotope compositions of calcium-aluminum-rich inclusions from CR2 carbonaceous chondrites

We report both oxygen- and magnesium-isotope compositions measured in situ using a Cameca ims-1280 ion microprobe in 20 of 166 CAIs identified in 47 polished sections of 15 CR2 (Renazzo-type) carbonaceous chondrites. Two additional CAIs were measured for oxygen isotopes only. Most CR2 CAIs are mineralogically pristine; only few contain secondary phyllosilicates, sodalite, and carbonates - most likely products of aqueous alteration on the CR2 chondrite parent asteroid. Spinel, hibonite, grossite, anorthite, and melilite in 18 CAIs have ¹⁶O-rich (Δ¹⁷O = −23.3 ± 1.9‰, 2σ error) compositions and show no evidence for postcrystallization isotopic exchange commonly observed in CAIs from metamorphosed CV carbonaceous chondrites. The inferred initial ²⁶Al/²⁷Al ratios, (²⁶Al/²⁷Al)₀, in 15 of 16 ¹⁶O-rich CAIs measured are consistent with the canonical value of (4.5-5) × 10⁻⁵ and a short duration (<0.5 My) of CAI formation. These data do not support the “supra-canonical” values of (²⁶Al/²⁷Al)₀ [(5.85-7) × 10⁻⁵] inferred from whole-rock and mineral isochrons of the CV CAIs. A hibonite-grossite-rich CAI El Djouf 001 MK #5 has uniformly ¹⁶O-rich (Δ¹⁷O = −23.0 ± 1.7‰) composition, but shows a deficit of ²⁶Mg and no evidence for ²⁶Al. Because this inclusion is ¹⁶O-rich, like CAIs with the canonical (²⁶Al/²⁷Al)₀, we infer that it probably formed early, like typical CAIs, but from precursors with slightly nonsolar magnesium and lower-than-canonical ²⁶Al abundance. Another ¹⁶O-enriched (Δ¹⁷O = −20.3 ± 1.2‰) inclusion, a spinel-melilite CAI fragment Gao-Guenie (b) #3, has highly-fractionated oxygen- and magnesium-isotope compositions (∼11 and 23‰/amu, respectively), a deficit of ²⁶Mg, and a relatively low (²⁶Al/²⁷Al)₀ = (2.0 ± 1.7) × 10⁻⁵. This could be the first FUN (Fractionation and Unidentified Nuclear effects) CAI found in CR2 chondrites. Because this inclusion is slightly ¹⁶O-depleted compared to most CR2 CAIs and has lower than the canonical (²⁶Al/²⁷Al)₀, it may have experienced multistage formation from precursors with nonsolar magnesium-isotope composition and recorded evolution of oxygen-isotope composition in the early solar nebula over  My. Eight of the 166 CR2 CAIs identified are associated with chondrule materials, indicating that they experienced late-stage, incomplete melting during chondrule formation. Three of these CAIs show large variations in oxygen-isotope compositions (Δ¹⁷O ranges from −23.5‰ to −1.7‰), suggesting dilution by ¹⁶O-depleted chondrule material and possibly exchange with an ¹⁶O-poor (Δ¹⁷O > −5‰) nebular gas. The low inferred (²⁶Al/²⁷Al)₀ ratios of these CAIs (<0.7 × 10⁻⁵) indicate melting >2 My after crystallization of CAIs with the canonical (²⁶Al/²⁷Al)₀ and suggest evolution of the oxygen-isotope composition of the inner solar nebula on a similar or a shorter timescale. Because CAIs in CR2 and CV chondrites appear to have originated in a similarly ¹⁶O-rich reservoir and only a small number of CR2 and CV CAIs were affected by chondrule melting events in an ¹⁶O-poor gaseous reservoir, the commonly observed oxygen-isotope heterogeneity in CAIs from metamorphosed CV chondrites is most likely due to fluid-solid isotope exchange on the CV asteroidal body rather than gas-melt exchange. This conclusion does not preclude that some CV CAIs experienced oxygen-isotope exchange during remelting, instead it implies that such remelting is unlikely to be the dominant process responsible for oxygen-isotope heterogeneity in CV CAIs. The mineralogy, oxygen and magnesium-isotope compositions of CAIs in CR2 chondrites are different from those in the metal-rich, CH and CB carbonaceous chondrites, providing no justification for grouping CR, CH and CB chondrites into the CR clan.     

Search for extinct Cl: Vigarano CAIs, the Pink Angel from Allende, and a Ningqiang chondrule

We have searched for excesses of ³⁶S derived from the decay of extinct ³⁶Cl in sodalite, a secondary Cl-rich mineral, in Ca-Al-rich inclusions (CAIs) from the Vigarano and Allende CV3 chondrites and in a chondrule from the Ningqiang carbonaceous chondrite. The presence of sodalite in two CAIs from Vigarano and its absence from surrounding CAI fragments suggests sodalite formation after CAI fragmentation. As for sodalite in the Allende Pink Angel CAI, oxygen isotopic compositions have been interpreted as indicative of high temperature interactions, thus suggesting formation prior to accretion to the parent body, probably in a nebular setting. Sodalite in the Ningqiang chondrule is considered to have formed via alkali-Ca exchange, which is believed to have occurred before accretion to the parent body.Sodalites in the Vigarano CAIs and in the Ningqiang chondrule show no clear evidence for the presence of radiogenic ³⁶S. The inferred 2σ upper limits for ³⁶Cl/³⁵Cl at the time of sodalite formation are 1.6 × 10⁻⁶ (Vigarano CAIs) and 3.3 × 10⁻⁶ (Ningqiang chondrule), respectively. In the Pink Angel CAI sodalite exhibits small ³⁶S excesses which weakly correlate with ³⁵Cl/³⁴S ratios. The inferred ³⁶Cl/³⁵Cl ratio of (1.8 ± 2.2) × 10⁻⁶ (2σ error) is lower than that found by Hsu et al. [Hsu, W., Guan, Y., Leshin, L. A., Ushikubo, T. and Wasserburg, G. J. (2006) A late episode of irradiation in the early solar system: Evidence from extinct ³⁶Cl and ²⁶Al in meteorites. Astrophys. J. 640, 525-529], thus indicative of heterogeneous distribution of ³⁶Cl in this CAI. Spallation reactions induced by energetic particles from the young Sun are suggested for the origin of ³⁶Cl, similar to the case of ¹⁰Be. While ¹⁰Be appears to be present in roughly equal abundance in all studied CAIs, our study indicates the level of ³⁶Cl abundances to be variable so that there seems to be no simple relationship between ¹⁰Be and ³⁶Cl. This would be expected if trapped cosmic rays rather than Early Solar System spallation were the dominant source of ¹⁰Be in the Early Solar System, since their contribution to ³⁶Cl would have been tiny.If the variability of ³⁶Cl abundances is caused by temporal differences in the alteration that formed sodalite, sodalite in the Vigarano CAIs and in the Ningqiang chondrule may have formed ?0.5 and ?0.2 Ma after formation of the sodalite in the Ningqiang CAI analyzed by Lin et al. [Lin, Y., Guan, Y., Leshin, L. A., Ouyang, Z. and Wang, D. (2005) Short-lived chlorine-36 in a Ca- and Al-rich inclusion from the Ningqiang carbonaceous chondrite. Proc. Natl. Acad. Sci. USA 102, 1306-1311]. The Pink Angel sodalite that we analyzed may have formed ∼0.3 Ma after formation of the sodalite in the Pink Angel analyzed by Hsu et al. [Hsu, W., Guan, Y., Leshin, L. A., Ushikubo, T. and Wasserburg G. J. (2006) A late episode of irradiation in the early solar system: Evidence from extinct ³⁶Cl and ²⁶Al in meteorites. Astrophys. J. 640, 525-529]. The estimated temporal differences suggest that alteration extended over at least 0.5 Ma. If previous works showing very low initial ³⁶Cl/³⁵Cl in the Allende CAIs and a H3 chondrite CAI are also considered, then alteration processes may have been more than 1.7 Ma.     

Timing of metal–silicate differentiation in the Eagle Station pallasite parent body

The time of the metal–silicate differentiation of the Eagle Station pallasite (ESP) parent body was investigated using the ²⁶Al–²⁶Mg short-lived chronometer (half-life of 0.72 Myr). The Mg isotope ratios were measured in ESP olivines by both MC–SIMS and HR-MC–ICPMS, allowing us to check the consistency between the results given by two different analytical protocols and data reduction processes. Results show that the two datasets are consistent, with a (δ²⁶Mg*)_av. value of –0.003 (± 0.005)‰ (2 s.e., n = 89). Such a value, associated with data from the ¹⁸²Hf–¹⁸²W short-lived systematics (half-life of 8.9 Myr), indicates an ESP parent body metal–silicate differentiation occurring most likely at least at ∼ 2 Ma, but possibly 4 Ma, after CAI formation. From the ²⁷Al/²⁴Mg ratios measured in ESP olivines using MC–SIMS, the duration of the olivine crystallization process was inferred to have lasted over ∼ 275 kyr if the core has differentiated as early as 2 Ma after CAIs, while in the case of a core differentiation occurring 4 Ma after CAIs, the silicate–silicate differentiation should have lasted for another 4 Myr.     

Hf-W isotope systematics of chondrites, eucrites, and martian meteorites: Chronology of core formation and early mantle differentiation in Vesta and Mars

The timescale of accretion and differentiation of asteroids and the terrestrial planets can be constrained using the extinct ¹⁸²Hf-¹⁸²W isotope system. We present new Hf-W data for seven carbonaceous chondrites, five eucrites, and three shergottites. The W isotope data for the carbonaceous chondrites agree with the previously revised ¹⁸²W/¹⁸⁴W of chondrites, and the combined chondrite data yield an improved ?_W value for chondrites of −1.9 ± 0.1 relative to the terrestrial standard. New Hf-W data for the eucrites, in combination with published results, indicate that mantle differentiation in the eucrite parent body (Vesta) occurred at 4563.2 ± 1.4 Ma and suggest that core formation took place 0.9 ± 0.3 Myr before mantle differentiation. Core formation in asteroids within the first ∼5 Myr of the solar system is consistent with the timescales deduced from W isotope data of iron meteorites. New W isotope data for the three basaltic shergottites EETA 79001, DaG 476, and SAU 051, in combination with published ¹⁸²W and ¹⁴²Nd data for Martian meteorites reveal the preservation of three early formed mantle reservoirs in Mars. One reservoir (Shergottite group), represented by Zagami, ALH77005, Shergotty, EETA 79001, and possibly SAU 051, is characterized by chondritic ¹⁴²Nd abundances and elevated ?_W values of ∼0.4. The ¹⁸²W excess of this mantle reservoir results from core formation. Another mantle reservoir (NC group) is sampled by Nakhla, Lafayette, and Chassigny and shows coupled ¹⁴²Nd-¹⁸²W excesses of 0.5-1 and 2-3 ? units, respectively. Formation of this mantle reservoir occurred 10-20 Myr after CAI condensation. Since the end of core formation is constrained to 7-15 Myr, a time difference between early silicate mantle differentiation and core formation is not resolvable for Mars. A third early formed mantle reservoir (DaG group) is represented by DaG 476 (and possibly SAU 051) and shows elevated ¹⁴²Nd/¹⁴⁴Nd ratios of 0.5-0.7 ? units and ?_W values that are indistinguishable from the Shergottite group. The time of separation of this third reservoir can be constrained to 50-150 Myr after the start of the solar system. Preservation of these early formed mantle reservoirs indicates limited convective mixing in the Martian mantle as early as ∼15 Myr after CAI condensation and suggests that since this time no giant impact occurred on Mars that could have led to mantle homogenization. Given that core formation in planetesimals was completed within the first ∼5 Myr of the solar system, it is most likely that Mars and Earth accreted from pre-differentiated planetesimals. The metal cores of Mars and Earth, however, cannot have formed by simply combining cores from these pre-differentiated planetesimals. The ¹⁸²W/¹⁸⁴W ratios of the Martian and terrestrial mantles require late effective removal of radiogenic ¹⁸²W, strongly suggesting the existence of magma oceans on both planets. Large impacts were probably the main heat source that generated magma oceans and led to the formation metallic cores in the terrestrial planets. In contrast, decay of short-lived ²⁶Al and ⁶⁰Fe were important heat sources for melting and core formation in asteroids.     

Chemical equilibrium and kinetic constraints for chondrule and CAI formation conditions

While many uncertainties remain, a kinetic evaporation-condensation model is used to show that type A chondrules, and compact Type A and B calcium-aluminum-rich inclusions (CAIs) could have formed from CI-like precursors under conditions that are consistent with predictions for 2-3 AU in a canonical solar nebula. Type B and Al-rich chondrules, and Type C CAIs, on the other hand, may have formed from fractionated precursors. Based primarily on chondrule and CAI isotopic compositions, previous studies have reached different conclusions because they did not take into account the effects of gas-melt exchange.Assuming CI-like precursor compositions, equilibrium silicate melts with elemental compositions like those of type A chondrules could have formed over a wide range of conditions (T, P_tot, solid/gas/solar). Metal is not predicted to be stable when T ≥ 1600°C. When T < 1600°C, the abundances and compositions of metal in chondrules appear to be less successfully reproduced than the silicates, e.g., at a given temperature more metal is predicted in type II chondrules than is generally observed, and under some conditions type IIs are predicted to be more metal-rich than type Is. These differences could be overcome if type Is formed from precursors that were more reduced than CI, and if type IIs formed after significant metal-silicate fractionation.The formation conditions of molten CAIs are much more restricted than for chondrules, perhaps in part explaining their lower abundances. The Mg, Si and O isotopic mass fractionations in non-FUN CAIs can be reproduced if they formed between ∼1400 to 1500°C in regions where CAI-like equilibrium melts were stable, but they did not quite reach equilibrium with the gas. CAI formation times at P_tot = 10⁻⁴-10⁻³ bars are consistent with estimates of Type B CAI cooling times, but pressures much below this require formation times that are too long. The isotopic mass fractionations in FUN CAIs can be explained if they formed at or below the ranges of solid/gas/solar ratios where CAI-like equilibrium compositions are stable. Under these conditions, FUN inclusions undergo less gas-melt exchange than non-FUN CAIs. The FUN CAI formation temperatures are consistent with formation at 1400 to 1500°C, but may have been higher.Two general explanations for the distribution of O mass independent fractionations (MIF) in chondrules/CAIs have been explored: creation of the MIF before chondrule/CAI formation, and creation of the MIF during chondrule/CAI formation. If the MIF was established before chondrule/CAI formation, the most promising explanation is that H₂O (presumably as ice) and silicate dust with MIFs of opposite sign are fractionated together from the remaining gas. On heating, the H₂O now in the gas exchanges with the melt.If the MIF was generated during chondrule/CAI formation, it must be generated in the H₂O, because it exchanges most rapidly with the melt, and mass balance requires creation of MIF of opposite sign in CO. Self-shielding from UV radiation is one possibility, but the effect may be quenched at high temperatures. Non-RRKM intramolecular kinetic isotope effects are another possibility, but a continuous source of radiation may be needed to prevent gas phase reactions from approaching equilibrium.     

Extremely Na- and Cl-rich chondrule from the CV3 carbonaceous chondrite Allende

We report on a study of Al3509, a large Na- and Cl-rich, radially-zoned object from the oxidized CV carbonaceous chondrite Allende. Al3509 consists of fine-grained ferroan olivine, ferroan Al-diopside, nepheline, sodalite, and andradite, and is crosscut by numerous veins of nepheline, sodalite, and ferroan Al-diopside. Some poorly-characterized phases of fine-grained material are also present; these phases contain no significant H₂O. The minerals listed above are commonly found in Allende CAIs and chondrules and are attributed to late-stage iron-alkali-halogen metasomatic alteration of primary high-temperature minerals. Textural observations indicate that Al3509 is an igneous object. However, no residual crystals that might be relicts of pre-existing CAI or chondrule minerals were identified. To establish the levels of ²⁶Al and ³⁶Cl originally present, ²⁶Al-²⁶Mg and ³⁶Cl-³⁶S isotopic systematics in sodalite were investigated. Al3509 shows no evidence of radiogenic ²⁶Mg^∗, establishing an upper limit of the initial ²⁶Al/²⁷Al ratio of 3 × 10⁻⁶. All sodalite grains measured show large but variable excesses of ³⁶S, which, however, do not correlate with ³⁵Cl/³⁴S ratio. If these excesses are due to decay of ³⁶Cl, local redistribution of radiogenic ³⁶S^∗ after ³⁶Cl had decayed is required. The oxygen-isotope pattern in Al3509 is the same as found in secondary minerals resulting from iron-alkali-halogen metasomatic alteration of Allende CAIs and chondrules and in melilite and anorthite of most CAIs in Allende. The oxygen-isotope data suggest that the secondary minerals precipitated from or equilibrated with a fluid of similar oxygen-isotope composition. These observations suggest that the formation of Al3509 and alteration products in CAIs and chondrules in Allende requires a very similar fluid phase, greatly enriched in volatiles (e.g., Na and Cl) and with Δ¹⁷O ∼ −3‰. We infer that internal heating of planetesimals by ²⁶Al would efficiently transfer volatiles to their outer portions and enhance the formation of volatile-enriched minerals there. We conclude that the site for the production of Na- and Cl-rich fluids responsible for the formation of Al3509 and the alteration of the Allende CAIs and chondrules must have been on a protoplanetary body prior to incorporation into the Allende meteorite. Galactic cosmic rays cannot be the source of the inferred initial ³⁶Cl in Allende. The problem of ³⁶Cl production by solar energetic particle (SEP) bombardment and the possibility that ³⁶Cl and ⁴¹Ca might be the product of neutron capture resulting from SEP bombardment of protoplanetary surfaces are discussed. This hypothesis can be tested comparing inferred “initial” ³⁶Cl with neutron fluencies measured on the same samples and on phases showing ³⁶S^∗ by Sm and Gd isotopic measurements.     

Al-Mg dating of asteroidal magmatism in the young Solar System

We present high-precision Mg isotope data for most classes of basaltic meteorites including eucrites, mesosiderite silicate clasts, angrites and the ungrouped Northwest Africa (NWA) 2976 measured by pseudo-high-resolution multiple-collector inductively coupled plasma mass spectrometry and utilising improved techniques for chemical purification of Mg. With the exception of the angrites Angra dos Reis, Lewis Cliff (LEW) 86010, NWA 1296 and NWA 2999 and the diogenite Bilanga, which have either been shown to have young ages by other dating techniques or have low Al/Mg ratios, all bulk samples of basaltic meteorites have ²⁶Mg excesses (δ²⁶Mg^∗=+0.0135 to +0.0392‰). The ²⁶Mg excesses cannot be explained by analytical artefacts, cosmogenic effects or heterogeneity of initial ²⁶Al/²⁷Al, Al/Mg ratios or Mg isotopes in asteroidal parent bodies as compared to Earth or chondrites. The ²⁶Mg excesses record asteroidal melting and formation of basaltic magmas with super-chondritic Al/Mg and confirm that radioactive decay of short-lived ²⁶Al was the primary heat source that melted planetesimals. Model ²⁶Al-²⁶Mg ages for magmatism on the eucrite/mesosiderite, angrite and NWA 2976 parent bodies are 2.6-3.2, 3.9-4.1 and 3.5 Myr, respectively, after formation of calcium-aluminium-rich inclusions (CAIs). However, the validity of these model ages depends on whether the elevated Al/Mg ratios of basaltic meteorites result from magma ocean evolution on asteroids through fractional crystallisation or directly during partial melting. Mineral isochrons for the angrites Sahara (Sah) 99555 and D’Orbigny, and NWA 2976, yield ages of and , respectively, after CAI formation. Both isochrons have elevated initial δ²⁶Mg^∗ values. Given the brecciated and equilibrated texture of NWA 2976 it is probable that its isochron age and elevated initial δ²⁶Mg^∗(+0.0175±0.0034‰) reflects thermal resetting during an impact event and slow cooling on its parent body. However, in the case of the angrites the marginally elevated initial δ²⁶Mg^∗(+0.0068±0.0058‰) may reflect either δ²⁶Mg^∗ ingrowth in a magma ocean prior to eruption and crystallisation or in an older igneous protolith with super-chondritic Al/Mg prior to impact melting and crystallisation of these angrites, or partial internal re-equilibration of Mg isotopes after crystallisation. ²⁶Al-²⁶Mg model ages and an olivine + pyroxene + whole rock isochron for the angrites Sah 99555 and D’Orbigny are in good agreement with age constraints from ⁵³Mn-⁵³Cr and ¹⁸²Hf-¹⁸²W short-lived chronometers, suggesting that the ²⁶Al-²⁶Mg feldspar-controlled isochron ages for these angrites may be compromised by the partial resetting of feldspar Mg isotope systematics. Even when age constraints from the ²⁶Al-²⁶Mg angrite model ages or the mafic mineral + whole rock isochron are considered, the relative time difference between Sah 99555/D’Orbigny crystallisation and CAI formation cannot be reconciled with Pb-Pb ages for Sah 99555/D’Orbigny and CAIs, which are ca. 1.0 Myr too old (angrites) or too young (CAIs) for reasons that are not clear. This discrepancy might indicate that ²⁶Al was markedly lower (ca. 40%) in the planetesimal- and planet-forming regions of the proto-planetary disc as compared to CAIs, or that CAI Pb-Pb ages may not accurately date CAI formation, which might be better dated by the ¹⁸²Hf-¹⁸²W and ²⁶Al-²⁶Mg chronometers as 4568.3±0.7 (Burkhardt et al., 2008) and (herein), respectively, when mapped onto an absolute timescale using Pb-Pb ages for angrites.     

Isotopic analysis of early solar system objects by an ion microprobe: Parametric studies and initial results

Magnesium, potassium and calcium isotope compositions in terrestrial samples and refractory phases from primitive meteorites are determined using an ion microprobe. A thorough investigation of the different instrument parameters is carried out to ensure that conditions necessary for high mass resolution and high precision isotopic studies are adequately satisfied. The instrument can be tuned to achieve mass resolution (M/ΔM) of up to 10,000 (M≤60); it has a very good dynamic stability (ΔB/B≤10 ppm over durations of ≤40 minutes) and the counting system has an effective dead-time of ≤25 nsec and a dynamic background of ≤0·01 c/s. Reproducibility and precision of isotopic measurements are checked by analyzing magnesium and titanium isotopic compositions in terrestrial standards and isotopically doped silicate glasses. A precision of 2‰ (2σ _m ) was achieved during magnesium isotopic analysis in samples with low Mg content (200 ppm). Results from studies of magnesium and potassium isotopic compositions in several Ca−Al-rich refractory inclusions (CAIs) from the primitive meteorites Efremovka and Grosnaja, representing some of the early solar system objects, are presented. The well-behaved Mg−Al isotopic systematics confirm the pristine nature of the Efremovka CAIs inferred earlier from petrographic and trace element studies. The Grosnaja CAIs that have experienced secondary alterations show disturbed magnesium isotopic systematics. Observation of excess²⁶Mg in several of the analyzed CAIs confirms the presence of the now extinct²⁶Al (t _1/2=7×10⁵ years) in the solar nebula at the time of CAI formation. Our data also suggest a relatively uniform distribution of²⁶Al in the solar nebula. Several Efremovka CAIs with excess²⁶Mg also have excess⁴¹K resulting from the decay of⁴¹Ca (t _1/2≃10⁵ years). This observation constrains the time interval between cessation of nucleosynthetic input to the solar nebula and the formation of some of the first solar system solids (CAIs) to less than a million years.     

Tungsten and hafnium distribution in calcium-aluminum inclusions (CAIs) from Allende and Efremovka

Recent ¹⁸²Hf-¹⁸²W age determinations on Allende Ca-, Al-rich refractory inclusions (CAIs) and on iron meteorites indicate that CAIs have initial ε¹⁸²W (−3.47 ± 0.20, 2σ) identical to that of magmatic iron meteorites after correction of cosmogenic ¹⁸²W burn-out (−3.47 ± 0.35, 2σ). Either the Allende CAIs were isotopically disturbed or the differentiation of magmatic irons (groups IIAB, IID, IIIAB, and IVB) all occurred <1 m.y. after CAI formation. To assess the extent of isotopic disturbance, we have analyzed the elemental distribution of Hf and W in two CAIs, Ef2 from Efremovka (CV3 reduced), and Golfball from Allende (CV3 oxidized). Fassaite is the sole host of Hf (10-25 ppm) and, therefore, of radiogenic W in CAIs, with ¹⁸⁰Hf/¹⁸⁴W > 10³, which is lowered by the ubiquitous presence of metal inclusions to ¹⁸⁰Hf/¹⁸⁴W > 10 in bulk fassaite. Metal alloy (Ni ∼ 50%) is the sole host of W (∼500 ppm) in Ef2, while opaque assemblages (OAs) and secondary veins are the hosts of W in Golfball. A large metal alloy grain from Ef2, EM2, has ¹⁸⁰Hf/¹⁸⁴W < 0.006. Melilite has both Hf and W below detection limits (<0.01 ppm), but the presence of numerous metallic inclusions or OAs makes melilite a carrier for W, with ¹⁸⁰Hf/¹⁸⁴W < 1 in bulk melilite. Secondary processes had little impact on the ¹⁸²Hf-¹⁸²W systematics of Ef2, but a vein cross-cutting fassaite in Golfball has >100 ppm W with no detectable Pt or S. This vein provides evidence for transport of oxidized W in the CAI. Because of the ubiquitous distribution of OAs, interpretations of the ¹⁸²Hf-¹⁸²W isochron reported for Allende CAIs include: (i) all W in the OAs was derived by alteration of CAI metal, or (ii) at least some of the W in OAs may have been equilibrated with radiogenic W during metamorphism of Allende. Since (ii) cannot be ruled out, new ¹⁸²Hf-¹⁸²W determinations on CAIs from reduced CV3 chondrites are needed to firmly establish the initial W isotopic composition of the solar system.     

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 SIMS analysis in Allende CAI: details of the very early thermal history of the solar system

The oxygen isotopic micro-distributions within and among minerals in a coarse-grained Ca, Al-rich inclusion (CAI), 7R-19-1 from the Allende meteorite, were measured by in situ using secondary ion mass spectrometry (SIMS). All values of O isotopic ratios in 7R-19-1 minerals fall along the carbonaceous chondrite anhydrous mineral mixing (CCAM) line on a δ¹⁷O_SMOW vs. δ¹⁸O_SMOW plot. Major refractory minerals (spinel, fassaite and melilite) in 7R-19-1 showed large negative anomalies of Δ¹⁷O in the order, spinel (−21‰) > ¹⁶O-rich melilite (∼−18‰) > fassaite (−15 to +1‰) > ¹⁶O-poor melilite (−8 to +2‰). However, the lower limit values of Δ¹⁷O are similar at about −21‰, a value commonly observed in CAIs. The similarity in the extreme values of the isotope anomaly anomalies suggests that crystallization of all CAIs started from an ¹⁶O enrichment of 21‰ (Δ¹⁷O) relative to terrestrial values. The order of the O isotopic anomalies observed for 7R-19-1, except for ¹⁶O-poor melilite, is parallel to the crystallization sequence determined by experiment from CAI liquid (Stolper, 1982), indicating that the O isotopic exchange in 7R-19-1 occurred between CAI melt and surrounding gas while 7R-19-1 was crystallizing from the ¹⁶O enriched CAI liquid (∼−21‰ in Δ¹⁷O) in the ¹⁶O-poor solar nebula. However, the a single crystallization sequence during the cooling stage cannot explain the existence of ¹⁶O-poor melilite. The presence of ¹⁶O-poor melilite suggests that multiple heating events occurred during CAI formation. The sharp contact between ¹⁶O-rich and ¹⁶O-poor melilite crystals and within ¹⁶O-rich melilite indicates that these multiple heatings occurred quickly. Based on the O isotopic and chemical compositions, fassaite crystals were aggregates of relic crystals formed from CAI melt whichthat have had various O isotopic compositions from the remelting processes. The results of intra-mineral distributions of O isotopes also support multiple heating events during CAI formation.     

Thermal evolution and physics of melt extraction on the ureilite parent body

We develop a physical model of the thermal history of the ureilite parent body (UPB) that numerically tracks the history of its heating, hydration, dehydration, partial melting and smelting as a function of its formation time and the initial values of its composition, formation temperature and water ice content. Petrologic and chemical data from the main group (non-polymict) ureilite meteorites, which sample the interior of the UPB between depths corresponding to pressures in the range 3-10 MPa, are used to constrain the model. We find that to achieve the ∼30% melting inferred for ureilites from all sampled depths, the UPB must have had a radius between ∼80 and ∼130 km and must have accreted about 0.55 Ma after CAI formation. Melting began in the body at ∼1 Ma after CAI, and the time at which 30% melting was reached varied with depth in the asteroid but was always between ∼4.5 and ∼5.8 Ma after CAI. The total rate at which melt was produced in the UPB varied from more than 100 m³ s⁻¹ in the very early stages of melting at ∼1 Ma after CAI to ∼5 m³ s⁻¹ between 2 and 3 Ma after CAI, decreasing to extremely small values as the end of melting was approached beyond ∼5 Ma. Although the initial period of high melt production occupied only a short time around 1 Ma after CAI, it corresponded to ∼half (16%) of total silicate melting, and all strictly basaltic (i.e. plagioclase-saturated) melts must have been produced during this period.A very efficient melt transport network, consisting of a hierarchy of veins and larger pathways (dikes), developed quickly at the start of melting, ensuring rapid (timescales of months) transport of any single parcel of melt to shallow levels, thus ensuring that chemical interaction between melts and the rocks through which they subsequently passed was negligible. Volatile (mainly carbon monoxide) production due to smelting began at the start of silicate melting in the shallowest parts of the UPB and at later times at greater depths. Except at the very start and very end of melting, the volatile content of the melts produced was always high - generally between 15 and 35 mass % - and most of the melt produced was erupted at the surface of the UPB with speeds well in excess of the escape velocity and was lost into space. However, we show that 30% melting at the 3 MPa pressure level was only possible if ∼15% of the total melt produced in the asteroid was retained as a small number (∼5) of very extensive, sill-like intrusions centered at a depth of ∼7 km below the surface, near the base of the ∼8 km thick outer crust of the asteroid that was maintained at temperatures below the basalt solidus by conductive heat loss to the surface. The horizontal extents of these sills occupied about 75% of the surface area of the UPB, and the sills acted as buffers between the steady supply of melt from depth and the intermittent explosive eruption of the melt into space. We infer that samples from these intrusions are preserved as the rare feldspathic (loosely basaltic) clasts in polymict ureilites, and show that the cooling histories of the sills are consistent with these clasts reaching isotopic closure at ∼5 Ma after CAI, as given by ²⁶Al-²⁶Mg, ⁵³Mn-⁵³Cr and Pb-Pb age dates.