Alexander N. Krot

The Absolute Chronology and Thermal Processing of Solids in the Solar Protoplanetary Disk

Dating the First Solids The solar systems first solids: calcium-aluminum–rich inclusions and chondrules are found in meteorites and provide a direct record of the dynamics of the solar protoplanetary disk that led to the formation of the solar system. Previous results indicate that chondrules formed 1 to 2 million years after the inclusions—an age difference that has been used in constructing models of chondrule formation. Based on uranium- and lead-isotope measurements of a collection of these primitive materials, Connelly et al. (p. 651) show that chondrules in fact started to form at the same time as the inclusions, 4.567 billion years ago, and that their formation took about 3 million years. Isotopic dating implies that, contrary to previous results, two types of primitive solar system solids formed coevally. Transient heating events that formed calcium-aluminum–rich inclusions (CAIs) and chondrules are fundamental processes in the evolution of the solar protoplanetary disk, but their chronology is not understood. Using U-corrected Pb-Pb dating, we determined absolute ages of individual CAIs and chondrules from primitive meteorites. CAIs define a brief formation interval corresponding to an age of 4567.30 ± 0.16 million years (My), whereas chondrule ages range from 4567.32 ± 0.42 to 4564.71 ± 0.30 My. These data refute the long-held view of an age gap between CAIs and chondrules and, instead, indicate that chondrule formation started contemporaneously with CAIs and lasted ~3 My. This time scale is similar to disk lifetimes inferred from astronomical observations, suggesting that the formation of CAIs and chondrules reflects a process intrinsically linked to the secular evolution of accretionary disks.

Origin of zoned metal grains in the QUE94411 chondrite

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to measure distributions of the siderophile elements P, V. Cr, Fe, Co, Ni, Mo, Ru, Rh, Pd, W, Re, Os, Ir, and Pt in metal grains in the metal-rich chondrite QUE94411 with a spatial resolution of similar to 30 mum. The platinum group elements (PGEs), except Pd, exhibit radial zoning in these grains that mimics that previously observed in Ni and Co; the concentrations of these elements decreases from the cores to the rims of the grains. The PGE distributions support a condensation origin for the enhanced refractory element abundances in the zoned grains; the lack of zoning in Pd refutes an origin by a redox-controlled process, and none of the PGE-Ni relationships support an origin by fractional crystallization from a metallic melt. Several models of grain formation were explored, including equilibrium fractional condensation, which failed to yield the correct radial zoning. The zoning may be the product of a nonequilibrium fractional condensation process, in which the refractory siderophiles remained supersaturated in the cooling solar nebula, or of diffusion between refractory-enhanced Fe-Ni cores and other Fe-Ni metal that may have been deposited later from the solar nebula. Copyright (C) 2001 Elsevier Science Ltd.

Oxygen Isotopic Composition of the Sun and Mean Oxygen Isotopic Composition of the Protosolar Silicate Dust: Evidence from Refractory Inclusions

Preliminary analysis of the oxygen isotopic composition of the solar wind recorded by the Genesis spacecraft suggests that the Sun is 16O-rich compared to most chondrules, fine-grained chondrite matrices, and bulk compositions of chondrites, achondrites, and terrestrial planets (Δ17O = –26.5‰ ± 5.6‰ and –33‰ ± 8‰ (2σ) versus Δ17O ~ ±5‰). The inferred 16O-rich composition of the Sun is similar or slightly lighter than the 16O-rich compositions of amoeboid olivine aggregates and typical calcium-aluminum-rich inclusions (CAIs) from primitive (unmetamorphosed) chondrites (Δ17O = –24‰ ± 2‰), which are believed to have condensed from and been melted in a gas of approximately solar composition (dust/gas ratio ~ 0.01 by weight) within the first 0.1 Myr of the solar system formation. Based on solar system abundances, 26% of the solar system oxygen must be initially contained in dust and 74% in gas. Because solar oxygen is dominated by the gas component, these observations suggest that oxygen isotopic composition of the solar nebula gas was initially 16O-rich. Due to significant thermal processing of the protosolar molecular cloud silicate dust (primordial dust) in the solar nebula and its possible isotope exchange with the isotopically evolved solar nebula gas, the mean oxygen isotopic composition of the primordial dust is not known. In CO self-shielding models, it is assumed that primordial dust and solar nebula gas had initially identical, 16O-rich compositions, similar to that of the Sun (Δ17O ~ –25‰ or –35‰), and solids subsequently evolved toward the terrestrial value (Δ17O = 0). However, there is no clear evidence that the oxygen isotopic compositions of the solar system solids evolved in the direction of increasing Δ17O with time and no 16O-rich primordial dust have yet been discovered. Here we argue that the assumption of the CO self-shielding models that primordial dust and solar nebula gas had initially identical 16O-rich compositions is incorrect. We show that igneous CAIs with highly fractionated oxygen isotopic compositions, fractionation and unidentified nuclear effects (FUN), and fractionation (F) CAIs, have Δ17O ranging from –0.5‰ to –24.8‰. Within an individual FUN or F CAI, oxygen isotopic compositions of spinel, forsterite, and pyroxene define a mass-dependent fractionation trend with a constant Δ17O value. The degree of mass-dependent fractionation of these minerals correlates with the sequence of their crystallization from the host CAI melt. These observations and evaporation experiments on CAI-like melts indicate that FUN and F CAIs formed by melting of solid precursors with diverse Δ17O values in vacuum (total pressure 50☉) ejecta. The 16O-depleted compositions of chondrules, fine-grained matrices, chondrites, and achondrites compared to the Suns value reflect their formation in the protoplanetary disk regions with enhanced dust/gas ratio (up to 105× solar).

Early Solar Nebula Condensates with Canonical, Not Supracanonical, Initial 26Al/27Al Ratios

The short-lived radionuclide 26 Al existed throughout the solar nebula 4.57 Ga ago, and the initial abundance ratio ( 26 Al/ 27 Al)0, as inferred from magnesium isotopic compositions of calcium–aluminum-rich inclusions (CAIs) in chondritic meteorites, has become a benchmark for understanding early solar system chronology. Internal mineral isochrons in most CAIs measured by secondary ion mass spectrometry (SIMS) give ( 26 Al/ 27 Al)0 ∼ (4–5) × 10 −5 , called “canonical.” Some recent high-precision analyses of (1) bulk CAIs measured by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS), (2) individual CAI minerals and their mixtures measured by laserablation MC-ICPMS, and (3) internal isochrons measured by multicollector (MC)-SIMS indicated a somewhat higher “supracanonical” ( 26 Al/ 27 Al)0 ranging from (5.85 ± 0.05) × 10 −5 to >7 × 10 −5 . These measurements were done on coarse-grained Type B and Type A CAIs that probably formed by recrystallization and/or melting of fine-grained condensate precursors. Thus the supracanonical ratios might record an earlier event, the actual nebular condensation of the CAI precursors. We tested this idea by performing in situ high-precision magnesium isotope measurements of individual minerals in a fine-grained CAI whose structures and volatility-fractionated trace element abundances mark it as a primary solar nebula condensate. Such CAIs are ideal candidates for the fine-grained precursors to the coarse-grained CAIs, and thus should best preserve a supracanonical ratio. Yet, our measured internal isochron yields ( 26 Al/ 27 Al)0 = (5.27 ± 0.17) × 10 −5 . Thus our data do not support the existence of supracanonical ( 26 Al/ 27 Al)0 = (5.85–7) × 10 −5 . There may not have been a significant time interval between condensation of the CAI precursors and their subsequent melting into coarse-grained CAIs.

182Hf–182W age dating of a 26Al-poor inclusion and implications for the origin of short-lived radioisotopes in the early Solar System

Refractory inclusions [calcium–aluminum-rich inclusions, (CAIs)] represent the oldest Solar System solids and provide information regarding the formation of the Sun and its protoplanetary disk. CAIs contain evidence of now extinct short-lived radioisotopes (e.g., 26Al, 41Ca, and 182Hf) synthesized in one or multiple stars and added to the protosolar molecular cloud before or during its collapse. Understanding how and when short-lived radioisotopes were added to the Solar System is necessary to assess their validity as chronometers and constrain the birthplace of the Sun. Whereas most CAIs formed with the canonical abundance of 26Al corresponding to 26Al/27Al of ∼5 × 10−5, rare CAIs with fractionation and unidentified nuclear isotope effects (FUN CAIs) record nucleosynthetic isotopic heterogeneity and 26Al/27Al of <5 × 10−6, possibly reflecting their formation before canonical CAIs. Thus, FUN CAIs may provide a unique window into the earliest Solar System, including the origin of short-lived radioisotopes. However, their chronology is unknown. Using the 182Hf–182W chronometer, we show that a FUN CAI recording a condensation origin from a solar gas formed coevally with canonical CAIs, but with 26Al/27Al of ∼3 × 10−6. The decoupling between 182Hf and 26Al requires distinct stellar origins: steady-state galactic stellar nucleosynthesis for 182Hf and late-stage contamination of the protosolar molecular cloud by a massive star(s) for 26Al. Admixing of stellar-derived 26Al to the protoplanetary disk occurred during the epoch of CAI formation and, therefore, the 26Al–26Mg systematics of CAIs cannot be used to define their formation interval. In contrast, our results support 182Hf homogeneity and chronological significance of the 182Hf–182W clock.

The ZONMET thermodynamic and kinetic model of metal condensation

The ZONMET model of metal condensation is a FORTRAN computer code that calculates condensation with partial isolation-type equilibrium partitioning of the 19 most abundant elements among 203 gaseous and 488 condensed phases and growth in the nebula of a zoned metal grain by condensation from the nebular gas accompanied by diffusional redistribution of Ni, Co, and Cr. Of five input parameters of the ZONMET model (chemical composition of the system expressed as the dust/gas (D/G) ratio, nebular pressure (Ptot), isolation degree (), cooling rate (CR), and seed size), only two—the D/G ratio and the CR of the nebular source region of a zoned Fe,Ni grain—are important in determining the grain radius and Ni, Co, and Cr zoning profiles. We found no evidence for the supercooling during condensation of Fe,Ni metal that is predicted by the homogeneous nucleation theory. The model allows estimates to be made of physicochemical parameters in the CH chondrite nebular source regions. Modeling growth and simultaneous diffusional redistribution of Ni, Co, and Cr in the zoned metal grains of CH chondrites reveals that the condensation zoning profiles were substantially modified by diffusion while the grains were growing in the nebula. This means that previous estimates of the physicochemical conditions in the nebular source regions of CH and CB chondrites, based on measured zoning profiles of Ni, Co, Cr, and platinum group elements in Fe,Ni metal grains, need to be corrected. The two zoned metal grains in the PAT 91456 and NWA 470 CH chondrites studied so far require nebular source regions with different chemical compositions (D/G 1 and D/G 4, respectively) and thermal histories characterized by variable cooling rates ( CR 0.011 0.0022 T K/h and CR 0.05 0.0035 T K/h, respectively). It appears that the metal grains of the CH chondrites were formed in multiple nebular source regions or in different events within the same source region as the CB chondrite metal grains were formed. Copyright

Isotopic evidence for primordial molecular cloud material in metal-rich carbonaceous chondrites

Significance Comets are pristine, volatile-rich objects formed beyond the orbits of the gas giants and, thus, thought to preserve a record of the primordial molecular cloud material parental to our Solar System. We use magnesium and chromium isotopes to show that a class of pristine chondrites, the metal-rich carbonaceous chondrites, has a signature distinct from most inner Solar System planets and asteroids. This signature is consistent with that predicted for unprocessed primordial molecular cloud material, suggesting that—similar to comets—metal-rich carbonaceous chondrites are samples of asteroids that accreted in the outer Solar System. Therefore, these objects may provide a direct window into the formation history of the outer Solar System. The short-lived 26Al radionuclide is thought to have been admixed into the initially 26Al-poor protosolar molecular cloud before or contemporaneously with its collapse. Bulk inner Solar System reservoirs record positively correlated variability in mass-independent 54Cr and 26Mg*, the decay product of 26Al. This correlation is interpreted as reflecting progressive thermal processing of in-falling 26Al-rich molecular cloud material in the inner Solar System. The thermally unprocessed molecular cloud matter reflecting the nucleosynthetic makeup of the molecular cloud before the last addition of stellar-derived 26Al has not been identified yet but may be preserved in planetesimals that accreted in the outer Solar System. We show that metal-rich carbonaceous chondrites and their components have a unique isotopic signature extending from an inner Solar System composition toward a 26Mg*-depleted and 54Cr-enriched component. This composition is consistent with that expected for thermally unprocessed primordial molecular cloud material before its pollution by stellar-derived 26Al. The 26Mg* and 54Cr compositions of bulk metal-rich chondrites require significant amounts (25–50%) of primordial molecular cloud matter in their precursor material. Given that such high fractions of primordial molecular cloud material are expected to survive only in the outer Solar System, we infer that, similarly to cometary bodies, metal-rich carbonaceous chondrites are samples of planetesimals that accreted beyond the orbits of the gas giants. The lack of evidence for this material in other chondrite groups requires isolation from the outer Solar System, possibly by the opening of disk gaps from the early formation of gas giants.

Extreme 16O Enrichment in Calcium-Aluminum-Rich Inclusions from the Isheyevo (CH/CB) Chondrite

Calcium-aluminum-rich inclusions (CAIs) from the metal-rich (CH/CB-like) carbonaceous chondrite Isheyevo are mineralogically pristine and show no evidence for postcrystallization alteration. Many of them are composed of very refractory minerals, such as hibonite (CaAl12O19), grossite (CaAl4O7), aluminum-rich pyroxene, and perovskite (CaTiO3). Twenty-eight out of 35 studied CAIs from Isheyevo have oxygen isotopic compositions similar to those of CAIs from the CM and CR carbonaceous chondrites (?17O ~ ?20?). Five igneous CAIs are 16O-depleted to a level observed in Isheyevo chondrules (?17O ?10?), suggesting remelting and isotope exchange in an 16O-poor gaseous reservoir. Two CAIs, WA9 and B1, show the highest enrichment in 16O (?17O ~ ?68?, ?18O ~ ?66?, ?17O ~ ?34?) ever observed among refractory inclusions. In the context of the self-shielding model for the evolution of oxygen isotopes in the solar accretion disk, these CAIs may have recorded the initial oxygen isotopic composition of the solar system, and hence of the Sun.

EVIDENCE FOR MULTIPLE SOURCES OF 10 Be IN THE EARLY SOLAR SYSTEM

Beryllium-10 is a short-lived radionuclide (t1/2 = 1.4 Myr) uniquely synthesized by spallation reactions and inferred to have been present when the solar system’s oldest solids (calcium–aluminum-rich inclusions, CAIs) formed. Yet, the astrophysical site of 10 Be nucleosynthesis is uncertain. We report Li–Be–B isotope measurements of CAIs from CV chondrites, including CAIs that formed with the canonical 26 Al/ 27 Al ratio of ∼5 × 10 −5 (canonical CAIs) and CAIs with Fractionation and Unidentified Nuclear isotope effects (FUN-CAIs) characterized by 26 Al/ 27 Al ratios much lower than the canonical value. Our measurements demonstrate the presence of four distinct fossil 10 Be/ 9 Be isochrons, lower in the FUN-CAIs than in the canonical CAIs, and variable within these classes. Given that FUN-CAI precursors escaped evaporation–recondensation prior to evaporative melting, we suggest that the 10 Be/ 9 Be ratio recorded by FUN-CAIs represents a baseline level present in presolar material inherited from the protosolar molecular cloud, generated via enhanced trapping of galactic cosmic rays. The higher and possibly variable apparent 10 Be/ 9 Be ratios of canonical CAIs reflect additional spallogenesis, either in the gaseous CAI-forming reservoir, or in the inclusions themselves: this indicates at least two nucleosynthetic sources of 10 Be in the early solar system. The most promising locale for 10 Be synthesis is close to the proto-Sun during its early mass-accreting stages, as these are thought to coincide with periods of intense particle irradiation occurring on timescales significantly shorter than the formation interval of canonical CAIs.

MAGNESIUM ISOTOPE EVIDENCE FOR SINGLE STAGE FORMATION OF CB CHONDRULES BY COLLIDING PLANETESIMALS

We report C, Si, and S isotope measurements on 34 presolar silicon carbide grains of Type AB, characterized by 12C/13C < 10. Nitrogen, Mg–Al-, and Ca–Ti-isotopic compositions were measured on a subset of these grains. Three grains show large 32S excesses, a signature that has been previously observed for grains from supernovae (SNe). Enrichments in 32S may be due to contributions from the Si/S zone and the result of S molecule chemistry in still unmixed SN ejecta or due to incorporation of radioactive 32Si from C-rich explosive He shell ejecta. However, a SN origin remains unlikely for the three AB grains considered here, because of missing evidence for 44Ti, relatively low 26Al/27Al ratios (a few times 10−3), and radiogenic 32S along with low 12C/13C ratios. Instead, we show that born-again asymptotic giant branch (AGB) stars that have undergone a very-late thermal pulse (VLTP), known to have low 12C/13C ratios and enhanced abundances of the light s-process elements, can produce 32Si, which makes such stars attractive sources for AB grains with 32S excesses. This lends support to the proposal that at least some AB grains originate from born-again AGB stars, although uncertainties in the born-again AGB star models and possible variations of initial S-isotopic compositions in the parent stars of AB grains make it difficult to draw a definitive conclusion.Chondrules are igneous spherical objects preserved in chondritic meteorites and believed to have formed during transient heating events in the solar protoplanetary disk. Chondrules present in the metal-rich CB chondrites show unusual chemical and petrologic features not observed in other chondrite groups, implying a markedly distinct formation mechanism. Here, we report high-precision Mg-isotope data for 10 skeletal olivine chondrules from the Hammadah al Hamra 237 (HH237) chondrite to probe the formation history of CB chondrules. The 27 Al/ 24 Mg ratios of individual chondrules are positively correlated to their stable Mg-isotope composition (μ 25 Mg), indicating that the correlated variability was imparted by a volatility-controlled process (evaporation/condensation). The mass-independent 26 Mg composition (μ 26 Mg*) of chondrules is consistent with single stage formation from an initially homogeneous magnesium reservoir if the observed μ 25 Mg variability was generated by non-ideal Rayleigh- type evaporative fractionation characterized by a β value of 0.5142, in agreement with experimental work. The magnitude of the mass-dependent fractionation (∼300 ppm) is significantly lower than that suggested by the increase in 27 Al/ 24 Mg values, indicating substantial suppression of isotopic fractionation during evaporative loss of Mg, possibly due to evaporation at high Mg partial pressure. Thus, the Mg-isotope data of skeletal chondrules from HH237 are consistent with their origin as melts produced in the impact-generated plume of colliding planetesimals. The inferred μ 26 Mg* value of −3.87 ± 0.93 ppm for the CB parent body is significantly lower than the bulk solar system value of 4.5 ± 1.1 ppm inferred from CI chondrites, suggesting that CB chondrites accreted material comprising an early formed 26 Al-free component.