Manganese-chromium isotope systematics of enstatite meteorites

We present results of a study of the ⁵³Mn-⁵³Cr isotope systematics in the enstatite chondrites and achondrites (aubrites). The goal of this study was to explore the capabilities of this isotope system to obtain chronological information on these important classes of meteorites and to investigate the original distribution in the inner solar system of the short-lived radionuclide ⁵³Mn. Our earlier work (Lugmair and Shukolyukov, 1998; Shukolyukov and Lugmair, 2000a) has shown that the asteroid belt bodies are characterized by essentially the same initial ⁵³Mn abundance. However, we have found the presence of a gradient in the abundance of the radiogenic ⁵³Cr between the earth-moon system, Mars, and the asteroid Vesta. If this gradient is considered as a function of the heliocentric distance a linear radial dependence is indicated. This can be explained either by an early, volatility controlled Mn/Cr fractionation in the nebula or by an original radially heterogeneous distribution of ⁵³Mn. The enstatite chondrites are suggested to form in the inner zones of the solar nebula, much closer to the Sun than the ordinary chondrites. Therefore, their investigation may be an important test on the hypothesis on a radial heterogeneity in the initial ⁵³Mn.We have studied the bulk samples of the EH4-chondrites Indarch and Abee and the EL6-chondrite Khairpur. Although these meteorites have essentially the same Mn/Cr ratio as the ordinary chondrites, the relative abundance of the radiogenic ⁵³Cr is three times smaller than in the ordinary chondrites. Because these meteorites are primitive (undifferentiated) and no Mn/Cr fractionation had occurred within their parent bodies, this difference is a strong argument in favor of an initially heterogeneous distribution of ⁵³Mn in the early inner solar system. This finding is also consistent with formation of the enstatite chondrites in the inner zones of the solar nebula. Using the characteristic ⁵³Cr excess of the enstatite chondrites and the observed gradient, their place of origin falls at about 1.4 AU or somewhat closer to the Sun (i.e. >1.0-1.4 AU).We also present chronological results for the enstatite chondrites and achondrites. The ‘absolute’ ⁵³Mn-⁵³Cr ages of the EH4-chondrites are old: ∼4565 Ma. The EL6-chondrite Khairpur is ∼4.5 Ma younger, which is in good agreement with the ¹²⁹I-¹²⁹Xe data from the literature. The age of the aubrite Peña Blanca Spring appears to be similar to those of the enstatite chondrites while that of the aubrite Bishopville is at least ∼10 Ma younger, which is also in agreement with the ¹²⁹I-¹²⁹Xe data. The results from bulk samples of aubrites indicate that the last Mn/Cr fractionation in their parent body occurred ∼ 4563 Ma ago and imply an evolution of the Mn-Cr isotope system in an environment with an higher than chondritic Mn/Cr ratio for several millions of years.     

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.     

Mn-Cr systematics of the early Solar System revisited

We have reinvestigated the Mn-Cr systematics in a number of primitive meteorites, differentiated planetesimals and terrestrial planets in order to address the chronology of the early stages of protoplanetary disk evolution and planetary formation. Our analytical procedure is based on the assumption of terrestrial abundances for ⁵⁰Cr and ⁵²Cr only; recognizing that a data reduction scheme based on Earth-like ⁵⁴Cr/⁵²Cr abundances in all meteorites is not tenable. Here we show that initial ε_⁵³Cr compositions of ⁵⁴Cr-rich and ⁵⁴Cr-poor acid leach fractions in the primitive carbonaceous chondrite Orgueil differ by 0.9ε, reflecting primordial mineral-scale heterogeneity. However, asteroidal processing effectively homogenized any ε_⁵³Cr variations on the planetesimal scale, providing a uniform present-day solar ε_⁵³Cr=0.20±0.10. Thus, our ⁵³Mn-⁵³Cr data argue against the previously suggested ⁵³Mn heliocentric gradient. Instead, we suggest that inner Solar System objects possessed an initially homogeneous ⁵³Mn/⁵⁵Mn composition, which determined by two independent means is estimated at (6.28 ± 0.66) × 10⁻⁶. Our revised Mn-Cr age for Ste. Marguerite (SM) metamorphism of 4562.9 ± 1.0 Ma is identical to the Pb-Pb age of SM phosphates. Using this age, we confirm that mantle differentiation of the eucrite parent body occurred 4564.9 ± 1.1 Ma ago, and revise the time interval between this event and CAI formation to 2.2 ± 1.1 Ma. We also constrain metamorphism in carbonaceous chondrites of type 2 and 3 to have occurred between 1 and 6 Ma after CAI formation. The ⁵³Mn-⁵³Cr correlation among chondrites, planetesimals and terrestrial planets (the eucrite parent body, Mars and Earth) provides evidence for Mn/Cr fractionation within the protoplanetary disk recorded by all precursor materials of the terrestrial planets and primitive asteroids. This fractionation appears to have occurred within 2 Ma of CAI formation.     

Contributors to chromium isotope variation of meteorites

We report the results of a comprehensive, high precision survey of the Cr isotopic compositions of primitive chondrites, along with some differentiated meteorites. To ensure complete dissolution of our samples, they were first fused with lithium borate-tetraborate at 1050-1000 °C. Relative to the NIST Cr standard SRM 3112a, carbonaceous chondrites exhibit excesses in ⁵⁴Cr/⁵²Cr from 0.4 to 1.6ε (1ε = 1 part in 10,000), and ordinary chondrites display a common ⁵⁴Cr/⁵²Cr deficit of ∼0.4ε. Analyses of acid-digestion residues of chondrites show that carbonaceous and ordinary chondrites share a common ⁵⁴Cr-enriched carrier, which is characterized by a large excess in ⁵⁴Cr/⁵²Cr (up to 200ε) associated with a very small deficit in ⁵³Cr/⁵²Cr (<2ε). We did not find ⁵⁴Cr anomalies in either bulk enstatite chondrites or in leachates of their acid-digestion residues. This either requires that the enstatite chondrite parent bodies did not incorporate the ⁵⁴Cr anomaly carrier phase during their accretion, or the phase was destroyed by parent body metamorphism. Chromium in the terrestrial rocks and lunar samples analyzed here show no deviation from the NIST SRM 3112a Cr standard. The eucrite and Martian meteorites studied exhibit small deficits in ⁵⁴Cr/⁵²Cr. The ⁵⁴Cr/⁵²Cr variations among different meteorite classes suggest that there was a spatial and/or temporal heterogeneity in the distribution of a ⁵⁴Cr-rich component in the inner Solar System.We confirm the correlated excesses in ⁵⁴Cr/⁵²Cr and ⁵³Cr/⁵²Cr for bulk carbonaceous chondrites, but the new data yield a steeper slope (∼6.6) than that reported in Shukolyukov and Lugmair (2006). The correlated excesses may affect the use of the Mn-Cr chronometer in carbonaceous chondrites. We could not confirm the bulk carbonaceous chondrite Mn-Cr isochron reported by Shukolyukov and Lugmair (2006) and Moynier et al. (2007), mostly because we find much smaller total variations in ε⁵³Cr (∼0.2). All bulk chondrites have small ε⁵³Cr excesses (up to 0.3) relative to the Earth, most likely reflecting the sub-chondritic Mn/Cr ratio of the Earth. The ε⁵³Cr variations in chondrites do seem to grossly correlate with Mn/Cr and yield an initial Solar System ⁵³Mn/⁵⁵Mn value of 5.4(±2.4) × 10⁻⁶, corresponding to an absolute age of 4566.4 (±2.2) Ma.Nuclear interactions with cosmic rays result in coupled excesses in ε⁵⁴Cr and ε⁵³Cr with a ∼4:1 ratio in phases with high Fe/Cr. These are most dramatically demonstrated in the iron meteorite Carbo, showing excesses in ε⁵⁴Cr of up to 140ε. These new results show that the Mn-Cr chronometer should be used with caution in samples/minerals with high Fe/Cr and long cosmic ray exposure ages.     

Diffusion kinetics of Cr in olivine and 53Mn–53Cr thermochronology of early solar system objects

We have determined the diffusion coefficient of Cr in olivine as function of temperature, oxygen fugacity (fO₂), and crystallographic orientation and used these data to develop a quantitative understanding of the resetting of the short-lived ⁵³Mn–⁵³Cr decay system in olivine during cooling within meteorite parent body. The diffusion of Cr in olivine was found to be anisotropic, and effectively independent of fO₂ between wüstite–iron buffer and two orders of magnitude above this buffer. The diffusion data were used to calculate the spatially averaged mean closure temperature of the ⁵³Mn–⁵³Cr decay system in olivine as function of the initial temperature, cooling rate and grain size, and also the closure age profile of this system in olivine single crystal as function of radial distance and a dimensionless parameter that incorporates the effects of various parameters that affect the closure age. We also present a thermochronolgic formulation that permits retrieval of cooling rates from the extent of resetting of the bulk ⁵³Mn–⁵³Cr closure age of olivine during cooling. This method was applied to determine the cooling rate of the pallasite Omolon, which showed ⁵³Mn–⁵³Cr bulk age of olivine that is 10 Myr younger than the age of the solar system. The calculated cooling rate, which is 20–40 °C/Myr at ∼985–1000 °C, is in good agreement with the metallographic cooling rate at ∼500 °C, when the two results are considered in terms of a cooling model in which the reciprocal temperature increases linearly with time. The inferred cooling rate of Omolon, which seems to be a sample from the core-mantle boundary, yields a burial depth of ∼30 km in a parent body of at least ∼100 km radius.     

The distribution of short-lived radioisotopes in the early solar system and the chronology of asteroid accretion, differentiation, and secondary mineralization

We evaluate initial (²⁶Al/²⁷Al)_I, (⁵³Mn/⁵⁵Mn)_I, and (¹⁸²Hf/¹⁸⁰Hf)_I ratios, together with ²⁰⁷Pb/²⁰⁶Pb ages for igneous differentiated meteorites and chondrules from ordinary chondrites for consistency with radioactive decay of the parent nuclides within a common, closed isotopic system, i.e., the early solar nebula. The relative initial isotopic abundances of ²⁶Al, ⁵³Mn, and ¹⁸²Hf in differentiated meteorites and chondrules are consistent with decay from common solar system initial values, here denoted by I(Al)_SS, I(Mn)_SS, and I(Hf)_SS, respectively. I(Mn)_SS and I(Hf)_SS = 9.1 ± 1.7 × 10⁻⁶ and 1.07 ± 0.08 × 10⁻⁴, respectively, correspond to “canonical” I(Al)_SS = 5.1 × 10⁻⁵. I(Hf)_SS so determined is consistent with I(Hf)_SS = 9.72 ± 0.44 × 10⁻⁵ directly determined from an internal Hf-W isochron for CAI minerals. I(Mn)_SS is within error of the lowest value directly measured for CAIs. We suggest that erratically higher values measured for CAIs in carbonaceous chondrites may reflect proton irradiation of unaccreted CAIs by the early Sun after other asteroids destined for melting by ²⁶Al decay had already accreted. The ⁵³Mn incorporated within such asteroids would have been shielded from further “local” spallogenic contributions from within the solar system. The relative initial isotopic abundances of the short-lived nuclides are less consistent with the ²⁰⁷Pb/²⁰⁶Pb ages of the corresponding materials than with one another. The best consistency of short- and long-lived chronometers is obtained for (¹⁸²Hf/¹⁸⁰Hf)_I and the ²⁰⁷Pb/²⁰⁶Pb ages of angrites. (¹⁸²Hf/¹⁸⁰Hf)_I decreases with decreasing ²⁰⁷Pb/²⁰⁶Pb ages at the rate expected from the 8.90 ± 0.09 Ma half-life of ¹⁸²Hf. The model solar system age thus determined is T_SS,Hf-W = 4568.3 ± 0.7 Ma. (²⁶Al/²⁷Al)_I and (⁵³Mn/⁵⁵Mn)_I are less consistent with ²⁰⁷Pb/²⁰⁶Pb ages of the corresponding meteorites, but yield T_SS,Mn-Cr = 4568.2 ± 0.5 Ma relative to I(Al)_SS = 5.1 × 10⁻⁵ and a ²⁰⁷Pb/²⁰⁶Pb age of 4558.55 ± 0.15 Ma for the LEW86010 angrite. The Mn-Cr method with I(Mn)_SS = 9.1 ± 1.7 × 10⁻⁶ is useful for dating accretion (if identified with chondrule formation), primary igneous events, and secondary mineralization on asteroid parent bodies. All of these events appear to have occurred approximately contemporaneously on different asteroid parent bodies. For I(Mn)_SS = 9.1 ± 1.7 × 10⁻⁶, parent body differentiation is found to extend at least to ∼5 Ma post-T_SS, i.e., until differentiation of the angrite parent body ∼4563.5 Ma ago, or ∼4564.5 Ma ago using the directly measured ²⁰⁷Pb/²⁰⁶Pb ages of the D’Orbigny-clan angrites. The ∼1 Ma difference is characteristic of a remaining inconsistency for the D’Orbigny-clan between the Al-Mg and Mn-Cr chronometers on one hand, and the ²⁰⁷Pb/²⁰⁶Pb chronometer on the other. Differentiation of the IIIAB iron meteorite and ureilite parent bodies probably occurred slightly later than for the angrite parent body, and at nearly the same time as one another as shown by the Mn-Cr ages of IIIAB irons and ureilites, respectively. The latest recorded episodes of secondary mineralization are for carbonates on the CI carbonaceous chondrite parent body and fayalites on the CV carbonaceous chondrite parent body, both extending to ∼10 Ma post-T_SS.     

太阳系形成及演化研究方法

通过对陨石的研究,说明太阳系的形成与演化历史,包括太阳星云的凝聚过程、高温加热熔融事件和低温蚀变过程,陨石母体的热变质作用、熔融分异作用以及冲击变质作用等。对太阳星云的化学组成和同位素组成不均一性、前太阳物质的存在及其意义、太阳系形成和演化的同位素绝对年龄、间隔年龄以及宇宙射线暴露年龄等进行了讨论。结合太阳系形成和演化的研究,特别对电子探针、离子探针、透射电子显微镜以及拉曼光谱等微束分析技术在该领域的应用和相关问题进行了讨论。     

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.     

Differentiation history of the mesosiderite parent body: constraints from trace elements and manganese-chromium isotope systematics in Vaca Muerta silicate clasts

We report here the results of a study of trace element microdistributions and ⁵³Mn-⁵³Cr systematics in several basaltic and orthopyroxenitic clasts from the Vaca Muerta mesosiderite. Ion microprobe analyses of selected trace and minor element abundances in minerals of the silicate clasts indicate that, following igneous crystallization, these clasts underwent extensive metamorphic equilibration that resulted in intra- and inter-grain redistribution of elements. There is also evidence in the elemental microdistributions that these clasts were subsequently affected to varying degrees by alteration resulting from redox reactions involving the indigenous silicates and externally derived reducing agents (such as phosphorus, derived from the mesosiderite metal) at the time of metal-silicate mixing. Furthermore, our results suggest that the varying degrees of alteration by redox reactions recorded in the different clasts were most likely facilitated by different degrees of remelting induced by heating during the metal-silicate mixing event. After taking into account the effects of these postmagmatic secondary processes, comparison of the trace and minor element concentrations and distributions in minerals of basaltic and orthopyroxenitic clasts with those of noncumulate eucrites and diogenites, respectively, suggests that the primary igneous petrogenesis, including parent magma and source compositions, of Vaca Muerta silicates were similar to those of achondritic meteorites of the Howardite-Eucrite-Diogenite (HED) association. Internal ⁵³Mn-⁵³Cr isochrons obtained for two basaltic (pebble 16 and 4679) and two orthopyroxenitic (4659 and 4670) clasts show that chromium isotopes are equilibrated within each clast. Nevertheless, just as for noncumulate eucrites and diogenites, ⁵³Cr excesses in whole-rock samples of the basaltic clasts (∼1.01 ε in pebble 16; ∼1.07 ε in 4679) are significantly higher than in the orthopyroxene-rich clasts (∼0.62 ε in 4659; ∼0.53 ε in 4670). As in the case of the HED parent body, this suggests that Mn/Cr fractionation in the parent body of the Vaca Muerta silicate clasts occurred very early in the history of the solar system, when ⁵³Mn was still extant. However, the slope of the ⁵³Mn-⁵³Cr isochron defined by the whole-rock samples of Vaca Muerta clasts (corresponding to a ⁵³Mn/⁵⁵Mn ratio of 3.3 ± 0.6 × 10⁻⁶) is distinctly lower than that defined by the HED whole-rock samples (corresponding to a ⁵³Mn/⁵⁵Mn ratio of 4.7 ± 0.5 × 10⁻⁶), indicating that the global Mn/Cr fractionation event that established mantle source reservoirs on the parent body of the Vaca Muerta silicate clasts occurred ∼2 Ma after a similar event on the HED parent body.     

Isotopic composition of surface-correlated chromium in Apollo 16 lunar soils

We have analyzed by thermal ionization mass spectrometry (TIMS) the isotopic composition of Cr in five progressive etches of size-sorted plagioclase grains separated from lunar soils 60601 and 62281. Aliquots of the etch solutions were spiked for isotopic dilution (ID) analysis of Cr and Ca. The Ca ID data indicate that the initial etch steps represent dissolution of an average 0.1 to 0.2 μm depth from the grain surfaces, the approximate depth expected for implanted solar wind. The Cr/Ca ratio in the initial etches is several fold higher than that expected for bulk plagioclase composition, but in subsequent etches decreases to approach the bulk value. This indicates a source of Cr extrinsic to the plagioclase grains, surface-correlated and resident in the outermost fraction of a μm, which we provisionally identify as solar wind Cr. The surface-correlated Cr is isotopically anomalous and by conventional TIMS data reduction has approximately 1 permil excess ⁵⁴Cr and half as great excess ⁵³Cr. In successive etches, as the Cr/Ca ratio decreases and approaches the bulk plagioclase value, the magnitude of the apparent anomalies decreases approaching normal composition. If these results do indeed characterize the solar wind, then either the solar wind is enriched in Cr due to spallation in the solar atmosphere, or the Earth and the various parent bodies of the meteorites are isotopically distinct from the Sun and must have formed from slightly different mixes of presolar materials. Alternative interpretations include the possibility that the anomalous Cr is meteoritic rather than solar or that the observed (solar) Cr is normal except for a small admixture of spallation Cr generated on the Moon. We consider these latter possibilities less likely than the solar wind interpretation. However, they cannot be eliminated and remain working hypotheses.     

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.     

The nature,origin and modification of insoluble organic matter in chondrites,the major source of Earth’s C and N

All chondrites accreted ∼3.5 wt.% C in their matrices, the bulk of which was in a macromolecular solvent and acid insoluble organic material (IOM). Similar material to IOM is found in interplanetary dust particles (IDPs) and comets. The IOM accounts for almost all of the C and N in chondrites, and a significant fraction of the H. Chondrites and, to a lesser extent, comets were probably the major sources of volatiles for the Earth and the other terrestrial planets. Hence, IOM was both the major source of Earth’s volatiles and a potential source of complex prebiotic molecules.Large enrichments in D and ¹⁵N, relative to the bulk solar isotopic compositions, suggest that IOM or its precursors formed in very cold, radiation-rich environments. Whether these environments were in the interstellar medium (ISM) or the outer Solar System is unresolved. Nevertheless, the elemental and isotopic compositions and functional group chemistry of IOM provide important clues to the origin(s) of organic matter in protoplanetary disks. IOM is modified relatively easily by thermal and aqueous processes, so that it can also be used to constrain the conditions in the solar nebula prior to chondrite accretion and the conditions in the chondrite parent bodies after accretion.Here we review what is known about the abundances, compositions and physical nature of IOM in the most primitive chondrites. We also discuss how the IOM has been modified by thermal metamorphism and aqueous alteration in the chondrite parent bodies, and how these changes may be used both as petrologic indicators of the intensity of parent body processing and as tools for classification. Finally, we critically assess the various proposed mechanisms for the formation of IOM in the ISM or Solar System.     

Stable isotopes and the noncarbonaceous derivation of ureilites, in common with nearly all differentiated planetary materials

The abundant, diverse ureilite meteorites are peridotitic asteroidal mantle restites that have remarkably high bulk carbon contents (average 3 wt%) and have long been linked to the so-called carbonaceous chondrites (although this term is potentially misleading, because the high petrologic type “carbonaceous” chondrites are, if anything, C-poor compared to ordinary chondrites). Ureilite oxygen isotopic compositions, i.e., diversely negative (CCAM-like) Δ¹⁷O, viewed in isolation, have long been viewed as confirming the carbonaceous-chondritic derivation hypothesis. However, a very different picture emerges through analysis of a compilation of recently published high-precision isotopic data for chromium, titanium and nickel for ureilites and various other planetary materials. Ureilites have lower ε⁶²Ni and far lower ε⁵⁰Ti and ε⁵⁴Cr than any known variety of carbonaceous chondrite. On a plot of ε⁵⁰Ti vs. ε⁵⁴Cr, and similarly Δ¹⁷O vs. ε⁵⁴Cr, ureilite compositions cluster far from and in a direction approximately orthogonal to a trend internal to the carbonaceous chondrites, and the carbonaceous chondrites are separated by a wide margin from all other planetary materials. I conclude that notwithstanding the impressive resemblance to carbonaceous chondrites in terms of diversely negative Δ¹⁷O, the ureilite precursors accreted from preponderantly noncarbonaceous (sensu stricto) materials. Despite total depletion of basaltic matter, the ureilites retain moderate pyroxene/olivine ratios; which is an expected outcome from simple partial melting of moderate-SiO₂/(FeO + MgO) noncarbonaceous chondritic material, but would imply an additional process of major reduction of FeO if the precursor material were carbonaceous-chondritic. The striking bimodality of planetary materials on the ε⁵⁰Ti vs. ε⁵⁴Cr and Δ¹⁷O vs. ε⁵⁴Cr diagrams may be an extreme manifestation of the effects of episodic accretion of early solids in the protoplanetary nebula. However, an alternative, admittedly speculative, explanation is that the bimodality corresponds to a division between materials that originally accreted in the outer solar system (carbonaceous) and materials that accreted in the inner solar system (noncarbonaceous, including the ureilites).     

26Al as a heat source for early melting of planetesimals: Results from isotopic studies of meteorites

Ion microprobe studies of magnesium isotopic composition in igneous components from several chondritic meteorites have been carried out to look for²⁶Mg excess that may be attributed to the presence of the now-extinct radionuclide²⁶Al(τ ∼ 1 Ma) at the time of formation of these objects. A positive evidence for the presence of²⁶Al in the analysed objects will strengthen its case as the primary heat source for the early thermal metamorphism/melting of meteorite parent bodies. Based on calculated temperature profiles inside chondritic objects of different sizes and initial²⁶Al/²⁷Al ratios, we have estimated the initial abundances of²⁶Al needed to provide the heat necessary for the wide range of thermal processing seen in various types of meteorites. The magnesium isotopic data obtained by us do not provide definitive evidence for the presence of²⁶Al at the time of formation of the analysed igneous phases in different chondritic meteorites. Experimental evidence for a planetary scale distribution of²⁶Al in the early solar system to serve as a significant heat source for the thermal metamorphism and melting of meteorite parent bodies (planetesimals) remains elusive.     

Planet formation processes revealed by meteorites

The history of the solar system is locked within the planets, asteroids and other objects that orbit the Sun. While remote observations of these celestial bodies are essential for understanding planetary processes, much of the geological and geochemical information regarding solar system heritage comes directly from the study of rocks and other materials originating from them. The diversity of materials available for study from planetary bodies largely comes from meteorites; fragments of rock that fall through Earth's atmosphere after impact‐extraction from their parent planet or asteroid. These extra‐terrestrial objects are fundamental scientific materials, providing information on past conditions within planets, and on their surfaces, and revealing the timing of key events that affected a planet's evolution. Meteorites can be sub‐divided into four main groups: (1) chondrites, which are unmelted and variably metamorphosed ‘cosmic sediments’ composed of particles that made up the early solar nebula; (2) achondrites, which represent predominantly silicate materials from asteroids and planets that have partially to fully melted, from a broadly chondritic initial composition; (3) iron meteorites, which represent Fe‐Ni samples from the cores of asteroids and planetesimals; and (4) stony‐iron meteorites such as pallasites and mesosiderites, which are mixtures of metal and dominantly basaltic materials. Meteorite studies are rapidly expanding our understanding of how the solar system formed and when and how key events such as planetary accretion and differentiation occurred. Together with a burgeoning collection of classified meteorites, these scientific advances herald an unprecedented period of further scientific challenges and discoveries, an exciting prospect for understanding our origins.     

地外有机化合物

球粒陨石中的有机化合物起源于星际介质,是构成太阳星云的初始组分,并与其他物质一起吸积形成小行星和行星。在小行星内,有机质经历了不同程度的水蚀变和热变质作用。球粒陨石中的有机化合物尽管是非生命成因,但组成极为复杂,主要是类似于干酪根的大分子物质,以及少量可溶性有机物。大部分可溶有机分子也发现于地球生物圈,但前者可具有完全不同的H、C、N等同位素组成,这也是它们来源于地球之外的重要证据。星云中宇宙线和紫外线（UV）的辐射、小行星的热变质和水蚀变,是地外有机质演化的主要过程。球粒陨石中的有机质是地球生命起源的物质基础,是生命起源不可或缺的重要环节。同样重要的是,大量的火星探测表明,火星历史上有过满足生命存在的基本条件,而在火星陨石中还发现了一些生物活动相关的线索。未来很可能首先在火星上发现地外生命存在的证据。     

Silver isotope variations in chondrites: Volatile depletion and the initial Pd abundance of the solar system

The extinct radionuclide ¹⁰⁷Pd decays to ¹⁰⁷Ag (half-life of 6.5 Ma) and is an early solar system chronometer with outstanding potential to study volatile depletion in the early solar system. Here, a comprehensive Ag isotope study of carbonaceous and ordinary chondrites is presented. Carbonaceous chondrites show limited variations (ε¹⁰⁷Ag = −2.1 to +0.8) in Ag isotopic composition that correlate with the Pd/Ag ratios. Assuming a strictly radiogenic origin of these variations, a new initial ¹⁰⁷Pd/¹⁰⁸Pd of 5.9 (±2.2) × 10⁻⁵ for the solar system can be deduced. Comparing the Pd-Ag and Mn-Cr data for carbonaceous chondrites suggests that Mn-Cr and Pd-Ag fractionation took place close to the time of calcium-aluminium-rich inclusion (CAI) and chondrule formation ∼4568 Ma ago. Using the new value for the initial ¹⁰⁷Pd abundance, the revised ages for the iron-rich meteorites Gibeon (IVA, 8.5 +3.2/−4.6 Ma), Grant (IIIAB, 13.0 +3.5/−4.9 Ma) and Canyon Diablo (IA, 19.5 +24.1/−10.4 Ma) are consistent with cooling rates and the closure temperature of the Pd-Ag system. In contrast to carbonaceous chondrites, ordinary chondrites show large stable isotope fractionation of order of 1 permil for ¹⁰⁷Ag/¹⁰⁹Ag. This indicates that different mechanisms of volatile depletion were active in carbonaceous and ordinary chondrites. Nebular processes and accretion, as experienced by carbonaceous chondrites, did not led to significant Ag isotope fractionation, while the significant Ag isotope variations in ordinary chondrites are most likely inflicted by open system parent body metamorphism.     

The isotopic composition of zirconium in terrestrial and extraterrestrial samples: implications for extinct 92Nb

Since Nb and Zr are only little fractionated during magmatic processes, the ⁹²Nb-⁹²Zr relative chronometer has the potential of dating the formation of the planetary bodies through their differentiation. Thus, we have analyzed the isotopic composition of zirconium in lunar, meteoritic and old and recent terrestrial samples.No isotopic variation has been found. However, the ${}^{92}\text{Zr}{}^{90}\text{Zr}$ ratio of 3.8 Ga. old zircons from the Isua acid conglomerate is on the lower limit of the range of the standard measurements. If considered an anomaly, it would correspond to a +1.5 × 10^?492Zr relative deficiency or to a 3.0 × 10^?494Zr relative excess.Our data constrain the ${}^{92}\text{Nb}{}^{93}\text{Nb}$ isotopic ratio at the time of formation of the solar system to be less than 0.007, so that the maximum sensitivity of the ⁹²Nb-⁹²Zr relative chronometer for the formation of planetary bodies is around 10⁷ a. A discussion of some possible nuclear reactions indicates that zirconium isotopic variations in zircons are not easily produced, and that the ⁹²Nb and ⁹⁴Nb natural activities (Apt et al., 1974) cannot be explained by any single one of the processes proposed so far.     

Noble gas components in planetary atmospheres and interiors in relation to solar wind and meteorites

We discuss observed xenon isotopic signatures in solar system reservoirs and possible relationships. The predominant trapped xenon component in ordinary chondrites (OC) is OC-Xe and its isotopic signature differs from Xe in ureilites, in carbonaceous chondrites, in the atmospheres of Earth and Mars, and in the solar wind. Additional minor Xe components were identified in type 3 chondrites and in the metal phase of chondrites. The OC-Xe and ureilite signatures are both consistent with varying mixtures of HL-Xe and slightly mass fractionated solar-type Xe. Xenon in the Martian atmosphere is found to be strongly mass fractionated by 37.7‰ per amu, relative to solar Xe, favoring the heavy isotopes. Xenon in SNC’s from the Martian mantle show admixture of solar-type Xe, which belongs to an elementally strongly fractionated component. The origin of the isotopic signatures of Ne and Xe in the terrestrial atmosphere are discussed in the light of evidence that the Xe isotopic fractionations in the Martian and terrestrial atmospheres are consistent. However, in the terrestrial atmospheric Xe component excesses are observed for¹³²Xe and also for^129,131Xe, relative to fractionated solar Xe. The suggested chemically fractionated fission Xe component (CFF-Xe) seems to closely match the above excesses. We discuss models of origin for planetary volatiles and possible processes driving their evolution to present day compositions.     

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

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