Mineralogy,petrography, and oxygen isotopic compositions of ultrarefractory inclusions from carbonaceous chondrites

We report on the mineralogy, petrography, and in situ oxygen isotopic composition of twenty-five ultrarefractory calcium-aluminum-rich inclusions (UR CAIs) in CM2, CR2, CH3.0, CV3.1–3.6, CO3.0–3.6, MAC 88107 (CO3.1-like), and Acfer 094 (C3.0 ungrouped) carbonaceous chondrites. The UR CAIs studied are typically small, < 100 μm in size, and contain, sometimes dominated by, Zr-, Sc-, and Y-rich minerals, including allendeite (Sc₄Zr₃O₁₂), and an unnamed ((Ti,Mg,Sc,Al)₃O₅) mineral, davisite (CaScAlSiO₆), eringaite (Ca₃(Sc,Y,Ti)₂Si₃O₁₂), kangite ((Sc,Ti,Al,Zr,Mg,Ca,□)₂O₃), lakargiite (CaZrO₃), warkite (Ca₂Sc₆Al₆O₂₀), panguite ((Ti,Al,Sc,Mg,Zr,Ca)_1.8O₃), Y-rich perovskite ((Ca,Y)TiO₃), tazheranite ((Zr,Ti,Ca)O_2−x), thortveitite (Sc₂Si₂O₇), zirconolite (orthorhombic CaZrTi₂O₇), and zirkelite (cubic CaZrTi₂O₇). These minerals are often associated with 50–200 nm-sized nuggets of platinum group elements. The UR CAIs occur as: (i) individual irregularly-shaped, nodular-like inclusions; (ii) constituents of unmelted refractory inclusions – amoeboid olivine aggregates (AOAs) and Fluffy Type A CAIs; (iii) relict inclusions in coarse-grained igneous CAIs (forsterite-bearing Type Bs and compact Type As); and (iv) relict inclusions in chondrules. Most UR CAIs, except for relict inclusions, are surrounded by single or multilayered Wark-Lovering rims composed of Sc-rich clinopyroxene, ±eringaite, Al-diopside, and ±forsterite. Most of UR CAIs in carbonaceous chondrites of petrologic types 2–3.0 are uniformly ¹⁶O-rich (Δ¹⁷O ∼ −23‰), except for one CH UR CAI, which is uniformly ¹⁶O-depleted (Δ ¹⁷O ∼ −5‰). Two UR CAIs in Murchison have heterogeneous Δ¹⁷O. These include: an intergrowth of corundum (∼ ‒24‰) and (Ti,Mg,Sc,Al)₃O₅ (∼ 0‰), and a thortveitite-bearing CAI (∼ −20 to ∼ ‒5‰); the latter apparently experienced incomplete melting during chondrule formation. In contrast, most UR CAIs in metamorphosed chondrites are isotopically heterogeneous (Δ¹⁷O ranges from ∼ −23‰ to ∼ −2‰), with Zr- and Sc-rich oxides and silicates, melilite and perovskite being ¹⁶O-depleted to various degrees relative to uniformly ¹⁶O-rich (Δ¹⁷O ∼ −23‰) hibonite, spinel, Al-diopside, and forsterite. We conclude that UR CAIs formed by evaporation/condensation, aggregation and, in some cases, melting processes in a ¹⁶O-rich gas of approximately solar composition in the CAI-forming region(s), most likely near the protoSun, and were subsequently dispersed throughout the protoplanetary disk. One of the CH UR CAIs formed in an ¹⁶O-depleted gaseous reservoir providing an evidence for large variations in Δ¹⁷O of the nebular gas in the CH CAIs-forming region. Subsequently some UR CAIs experienced oxygen isotopic exchange during melting in ¹⁶O-depleted regions of the disk, most likely during the epoch of chondrule formation. In addition, UR CAIs in metamorphosed CO and CV chondrites, and, possibly, the corundum-(Ti,Mg,Sc,Al)₃O₅ intergrowth in Murchison experienced O-isotope exchange with aqueous fluids on the CO, CV, and CM chondrite parent asteroids. Thus, both nebular and planetary exchange with ¹⁶O-depleted reservoirs occurred.     

Carbonates in CM2 chondrites: constraints on alteration conditions from oxygen isotopic compositions and petrographic observations

High-precision measurements of the oxygen isotopic compositions of carbonates (calcite and dolomite) from five CM2 chondrites are presented and put into context of the previously determined mineralogic alteration index (MAI), which places these meteorites into an alteration sequence. The carbonate oxygen isotopic compositions range from +20.0 to +35.7‰ for δ¹⁸O, +8.0 to +17.7‰ for δ¹⁷O, and −0.7 to −2.7‰ for Δ¹⁷O. Carbonate Δ¹⁷O values are inversely correlated with MAI and track the evolution of fluid composition from higher to lower Δ¹⁷O values with increasing alteration on the CM parent body. Similar Δ¹⁷O values for calcite and dolomite fractions from the same splits of the same meteorites indicate that calcite and dolomite in each split precipitated from a single fluid reservoir. However, reversed calcite dolomite fractionations (δ¹⁸O_dol − δ¹⁸O_cc) indicate that the fluid was subject to processes, such as freeze-thaw or evaporation, that fractionated isotopes in a mass-dependent way. Consideration of the carbonate isotopic data in the context of previously proposed models for aqueous alteration of carbonaceous chondrites has provided important insights into both the evolving alteration conditions and the utility of the models themselves. The data as a whole indicate that the isotopic evolution of the fluid was similar to that predicted by the closed-system, two-reservoir models, but that a slightly larger matrix-water fractionation factor may apply. In the context of this model, more altered samples largely reflect greater reaction progress and thus probably indicate more extended times of fluid exposure. Petrographic observations of carbonates reveal a trend of variable carbonate morphology correlated with alteration that is also consistent with changes in the duration of fluid-rock interaction. The data can also be reconciled with fluid-flow models in a restricted region of the parent body, which is consistent with assertions that the different types of carbonaceous chondrites derive from different regions of their parent bodies. In this case, the model results for a 9-km-radius body, and our data place the location of the CM chondrite formation in a 100-m-thick zone 1 km from the surface. The size of this zone could be increased if the model parameters were adjusted.     

Primordial compositions of refractory inclusions

Bulk chemical and O-, Mg- and Si-isotopic compositions were measured for each of 17 Types A and B refractory inclusions from CV3 chondrites. After bulk chemical compositions were corrected for non-representative sampling in the laboratory, the Mg- and Si-isotopic compositions of each inclusion were used to calculate its original chemical composition assuming that the heavy-isotope enrichments of these elements are due to Rayleigh fractionation that accompanied their evaporation from CMAS liquids. The resulting pre-evaporation chemical compositions are consistent with those predicted by equilibrium thermodynamic calculations for high-temperature nebular condensates, but only if different inclusions condensed from nebular regions that ranged in total pressure from 10⁻⁶ to 10⁻¹ bar, regardless of whether they formed in a system of solar composition or in one enriched in dust of ordinary chondrite composition relative to gas by a factor of 10 compared to solar composition. This is similar to the range of total pressures predicted by dynamic models of the solar nebula for regions whose temperatures are in the range of silicate condensation temperatures. Alternatively, if departure from equilibrium condensation and/or non-representative sampling of condensates in the nebula occurred, the inferred range of total pressure could be smaller. Simple kinetic modeling of evaporation successfully reproduces observed chemical compositions of most inclusions from their inferred pre-evaporation compositions, suggesting that closed-system isotopic exchange processes did not have a significant effect on their isotopic compositions. Comparison of pre-evaporation compositions with observed ones indicates that 80% of the enrichment in refractory CaO + Al₂O₃ relative to more volatile MgO + SiO₂ is due to initial condensation and 20% due to subsequent evaporation for both Types A and B inclusions.     

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.     

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.     

不同类型球粒陨石钙同位素组成特征及对比研究

准确限定球粒陨石的Ca同位素组成对于研究太阳星云物质演化和行星形成都具有重要意义。选取7块典型的球粒陨石,包括3块CV3型陨石(Leoville、Allende和Vigarano)、1块CM2型陨石(Murchison)、1块CO3.2型陨石(Kainsaz)、1块EH4型陨石(Indarch)以及1块H4型陨石(LaPaz Icefield 03601),进行了Ca同位素组成的研究。其中, Kainsaz、Leoville和LaPaz Icefield 03601共3块陨石的Ca同位素组成是首次报道。结果显示:(1)在增大样品量以规避"样品量效应"的情况下,我们对CV群球粒陨石Ca同位素组成进行更加精确的制约,δ^44/40Ca的平均值为0.45‰±0.04‰(n=3, 2SE);(2)碳质球粒陨石的Ca同位素组成相对于硅酸盐地球偏轻,从CV群(0.45‰±0.04‰, 2SE)、CM群(0.73‰±0.04‰, 2SE)到CO群(0.78‰±0.03‰, 2SE)逐渐变重,可能与不同化学群陨石中富钙铝难熔包体(CAIs)丰度的变化有关;(3)顽火辉石球粒陨石和普...     

Origin of compact type A refractory inclusions from CV3 carbonaceous chondrites

Compact type A (CTA) inclusions are one of the major types of coarse-grained refractory inclusions found in carbonaceous chondrites. They have not been studied in a systematic fashion, leading to some uncertainties and unproven assumptions about their origin. To address this situation, we studied a total of eight CTAs from Allende, Efremovka and Axtell by scanning electron-microscopic and electron and ion-microprobe techniques. These inclusions are very melilite-rich, ranging from ∼60 vol% to nearly monomineralic. Also present are Mg–Al spinel (5–20%), perovskite (trace–∼3%) and, in some samples, Ti-rich (∼17 wt% TiO₂^tot) fassaite (trace–∼20%), and rhönite (≤1%). Melilite compositions are mostly between Åk₁₅ and Åk₄₀. Chondrite-normalized REE abundance patterns for melilite (flat at ∼10 × CI with positive Eu anomalies) and fassaite (slight HREE enrichment relative to LREE and negative Eu anomalies) are like those for their counterparts in once-molten type B inclusions. The patterns for rhönite have positive slopes from La through Lu and abundances <10 × CI for La and 35–60 × CI for Lu. Features of CTAs that suggest that they were once molten include: rounded inclusion shapes; positively correlated Sc and V abundances in fassaite; radially oriented melilite laths at inclusion rims; and the distribution of trace elements among the phases. Fractional crystallization models show that, with one exception, the REE contents of perovskite and fassaite arose by crystallization of these phases from late, residual liquids that would have resulted from prior crystallization of the observed proportions of melilite and spinel from liquids having the bulk compositions of the inclusions. One Allende CTA (TS32), however, has several features (irregular shape, reversely zoned melilite, fassaite REE contents) that are not readily explained by crystallization from a melt. This inclusion may have undergone little melting and may be dominated by relict grains.     

Chemical evolution of metal in refractory inclusions in CV3 chondrites

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to measure distributions of the siderophile elements V, Fe, Co, Ni, Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, and Au in Fremdlinge with a spatial resolution of 15 to 25 μm. A sulfide vein in a refractory inclusion in Allende (CV3-oxidized) is enriched in Rh, Ru, and Os with no detectable Pd, Re, Ir, or Pt, indicating that Rh, Ru, and Os were redistributed by sulfidation of the inclusion, causing fractionation of Re/Os and other siderophile element ratios in Allende CAIs. Fremdlinge in compact Type-A inclusions from Efremovka (CV3-reduced) exhibit subsolidus exsolution into kamacite and taenite and minimal secondary formation of V-magnetite and schreibersite. Siderophile element partitioning between taenite and kamacite is similar to that observed previously in iron meteorites, while preferential incorporation of the light PGEs (Ru, Rh, Pd) relative to Re, Os, Ir, and Pt by schreibersite was observed. Fremdling EM2 (CAI Ef2) has an outer rim of P-free metal that preserves the PGE signature of schreibersite, indicating that EM2 originally had a phosphide rim and lost P to the surrounding inclusion during secondary processing. Most Fremdlinge have chondrite-normalized refractory PGE patterns that are unfractionated, with PGE abundances derived from a small range of condensation temperatures, ∼1480 to 1468 K at P_tot = 10⁻³ bar. Some Fremdlinge from the same CAI exhibit sloping PGE abundance patterns and Re/Os ratios up to 2 × CI that likely represent mixing of grains that condensed at various temperatures.     

Petrology and oxygen isotope compositions of chondrules in E3 chondrites

Chondrules in E3 chondrites differ from those in other chondrite groups. Many contain near-pure endmember enstatite (Fs_<1). Some contain Si-bearing FeNi metal, Cr-bearing troilite, and, in some cases Mg, Mn- and Ca-sulfides. Olivine and more FeO-rich pyroxene grains are present but much less common than in ordinary or carbonaceous chondrite chondrules. In some cases, the FeO-rich grains contain dusty inclusions of metal. The oxygen three-isotope ratios (δ¹⁸O, δ¹⁷O) of olivine and pyroxene in chondrules from E3 chondrites, which are measured using a multi-collection SIMS, show a wide range of values. Most enstatite data plots on the terrestrial fractionation (TF) line near whole rock values and some plot near the ordinary chondrite region on the 3-isotope diagram. Pyroxene with higher FeO contents (∼2-10 wt.% FeO) generally plots on the TF line similar to enstatite, suggesting it formed locally in the EC (enstatite chondrite) region and that oxidation/reduction conditions varied within the E3 chondrite chondrule-forming region. Olivine shows a wide range of correlated δ¹⁸O and δ¹⁷O values and data from two olivine-bearing chondrules form a slope ∼1 mixing line, which is approximately parallel to but distinct from the CCAM (carbonaceous chondrite anhydrous mixing) line. We refer to this as the ECM (enstatite chondrite mixing) line but it also may coincide with a line defined by chondrules from Acfer 094 referred to as the PCM (Primitive Chondrite Mineral) line (Ushikubo et al., 2011). The range of O isotope compositions and mixing behavior in E3 chondrules is similar to that in O and C chondrite groups, indicating similar chondrule-forming processes, solid-gas mixing and possibly similar ¹⁶O-rich precursors solids. However, E3 chondrules formed in a distinct oxygen reservoir.Internal oxygen isotope heterogeneity was found among minerals from some of the chondrules in E3 chondrites suggesting incomplete melting of the chondrules, survival of minerals from previous generations of chondrules, and chondrule recycling. Olivine, possibly a relict grain, in one chondrule has an R chondrite-like oxygen isotope composition and may indicate limited mixing of materials from other reservoirs. Calcium-aluminum-rich inclusions (CAIs) in E3 chondrites have petrologic characteristics and oxygen isotope ratios similar to those in other chondrite groups. However, chondrules from E3 chondrites differ markedly from those in other chondrite groups. From this we conclude that chondrule formation was a local event but CAIs may have all formed in one distinct place and time and were later redistributed to the various chondrule-forming and parent body accretion regions. This also implies that transport mechanisms were less active at the time of and following chondrule formation.     

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

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

Carbon,hydrogen and nitrogen in carbonaceous chondrites: Abundances and isotopic compositions in bulk samples

Whole-rock samples of 25 carbonaceous chondrites were analysed for contents of C, H and N and δ¹³C, δD and δ¹⁵N. Inhomogeneous distribution of these isotopes within individual meteorites is pronounced in several cases. Few systematic intermeteorite trends were observed; N data are suggestive of isotopic inhomogeneity in the early solar system. Several chondrites revealed unusual compositions which would repay further, more detailed study. The data are also useful for classification of carbonaceous chondrites; N abundance and isotopic compositions can differentiate existing taxonomic groups with close to 100% reliability; Al Rais and Renazzo clearly constitute a discrete “grouplet”; and there are hints that both CI and CM groups may each be divisible into two subgroups.     

Dark inclusions in CO3 chondrites: new indicators of parent-body processes

A petrographic and scanning electron microscopic study of the four CO3 chondrites Kainsaz, Ornans, Lancé, and Warrenton reveals for the first time that dark inclusions (DIs) occur in all the meteorites. DIs are mostly smaller in size than those reported from CV3 chondrites. They show evidence suggesting that they were formed by aqueous alteration and subsequent dehydration of a chondritic precursor and so probably have a formation history similar to that of DIs in CV3 chondrites. DIs in the CO3 chondrites consist mostly of fine-grained, Fe-rich olivine and can be divided into two types on the basis of texture. Type I DIs contain rounded, porous aggregates of fine grains in a fine-grained matrix and have textures suggesting that they are fragments of chondrule pseudomorphs. Veins filled with Fe-rich olivine are common in type I DIs, providing evidence that they experienced aqueous alteration on the parent body. Type II DIs lack rounded porous aggregates and have a matrix-like, featureless texture. Bulk chemical compositions of DIs and mineralogical characteristics of olivine grains in DIs suggest that these two types of DIs have a close genetic relationship.The DIs are probably clasts that have undergone aqueous alteration and subsequent dehydration at a location different from the present location in the meteorites. The major element compositions, the mineralogy of metallic phases, and the widely dispersed nature of the DIs suggest that their precursor was CO chondrite material. The CO parent body has been commonly regarded to have been dry, homogeneous, and unprocessed. However, the DIs suggest that the CO parent body was a heterogeneous conglomerate consisting of water-bearing regions and water-free regions and that during asteroidal heating, the water-bearing regions were aqueously altered and subsequently dehydrated. Brecciation may also have been active in the parent body.The DIs and the matrices are similarly affected by thermal metamorphism in their own host CO3 chondrites (petrologic subtypes 3.1 to 3.6), but the degree of the secondary processing (aqueous alteration and subsequent dehydration) of the DIs has no apparent correlation with the petrologic grades of the host chondrites. These observations suggest that the DIs had been incorporated into the host chondrites before the thermal metamorphism took place and that the secondary processes that affected the DIs largely occurred before the thermal metamorphism.     

Chemical compositions of refractory inclusions in the Murchison C2 chondrite

Samples from ten refractory inclusions in Murchison, some of which are splits of inclusions whose mineralogical and petrographic characteristics are known, have been analysed for thirty-six elements by neutron activation. Six inclusions have group II or group III patterns or variants of such patterns. Two inclusions, BB-5 and MUCH-1, have large negative Yb anomalies unaccompanied by correspondingly large negative Eu anomalies. It is possible that the latter condensed originally with group III patterns and preferentially took up Eu in later exchange processes under reducing conditions. One inclusion, SH-2, has heavy REE enrichment factors that increase with the refractoriness of the REE, indicating the presence of an extremely high-temperature, or ultrarefractory, REE condensate, but it also has a heavy REE/light REE ratio that indicates mixing of that component with a lower-temperature REE condensate. The frequency of highly fractionated REE patterns and absence of group I patterns suggest that refractory inclusions in Murchison stopped equilibrating with the nebular gas at higher temperatures than most Allende coarse-grained inclusions. The lower Ir/Os and Ru/Re ratios of some Murchison inclusions compared to those of Allende coarse-grained inclusions indicate that condensate alloys that contributed noble metals to the former also stopped equilibrating with the nebular gas at higher temperatures than those that contributed noble metals to the latter. Murchison inclusions tend to be lower in non-refractory elements than Allende coarse-grained inclusions, suggesting that, on average, the former underwent less severe secondary alteration than the latter.     

Kainsaz(CO3)陨石中两个富Al球粒的氧同位素组成特征与形成演化

富Al球粒是原始球粒陨石中一种矿物岩石学特征介于富钙铝包体(CAIs)和镁铁质硅酸盐球粒之间的特殊集合体,所以常常认为富Al球粒在认识CAIs和镁铁质硅酸盐球粒形成演化过程中的相互联系具有特殊意义。然而,对富Al球粒的初始物质组成以及形成演化过程一直存在较多争议,而氧同位素组成研究能够对球粒演化和早期星云环境等提供重要的信息。在本文中我们报导了来自Kainsaz(1937年降落于俄罗斯,CO3型)碳质球粒陨石中的2个富Al球粒(编号K1-CH1和K2-CH2)的矿物岩石学和氧同位素组成特征。K1-CH1的矿物组成主要为橄榄石、低钙辉石和富钙长石,K2-CH2为橄榄石和富钙长石。2个球粒中的矿物均具有贫~(16)O同位素组成特征。K1-CH1中矿物的△~(17)O组成基本上位于2个区间:-11.1‰～-8.7‰和-3.9‰～0.4‰;而K2-CH2的△~(17)O介于-6.6‰～-0.6‰之间,且具有从中部至边部升高的趋势。矿物岩石学和氧同位素特征表明,这2个富Al球粒的初始物质组成为富CAIs和镁铁质硅酸盐。在球粒熔融结晶过程中,与贫~(16)O同位素组成(△~(17)O:-8.7‰～-7.8‰)的星云发生了氧同位素交换。球粒形成后,发生迁移进入陨石母体,在相对更贫~(16)O同位素组成(△~(17)O:-0.6‰～0.4‰)的母体中(流体参与)发生变质作用,并再次发生了氧同位素交换。     

Origin of low-Ca pyroxene in amoeboid olivine aggregates: Evidence from oxygen isotopic compositions

Amoeboid olivine aggregates (AOAs) in primitive carbonaceous chondrites consist of forsterite (Fa_<2), Fe,Ni-metal, spinel, Al-diopside, anorthite, and rare gehlenitic melilite (Åk_<15). ∼10% of AOAs contain low-Ca pyroxene (Fs_1-3Wo_1-5) that is in corrosion relationship with forsterite and is found in three major textural occurrences: (i) thin (<15 μm) discontinuous layers around forsterite grains or along forsterite grain boundaries in AOA peripheries; (ii) 5-10-μm-thick haloes and subhedral grains around Fe,Ni-metal nodules in AOA peripheries, and (iii) shells of variable thickness (up to 70 μm), commonly with abundant tiny (3-5 μm) inclusions of Fe,Ni-metal grains, around AOAs. AOAs with the low-Ca pyroxene shells are compact and contain euhedral grains of Al-diopside surrounded by anorthite, suggesting small (10%-20%) degree of melting. AOAs with other textural occurrences of low-Ca pyroxene are rather porous. Forsterite grains in AOAs with low-Ca pyroxene have generally ¹⁶O-rich isotopic compositions (Δ¹⁷O < −20‰). Low-Ca pyroxenes of the textural occurrences (i) and (ii) are ¹⁶O-enriched (Δ¹⁷O < −20‰), whereas those of (iii) are ¹⁶O-depleted (Δ¹⁷O = −6‰ to −4‰). One of the extensively melted (>50%) objects is texturally and mineralogically intermediate between AOAs and Al-rich chondrules. It consists of euhedral forsterite grains, pigeonite, augite, anorthitic mesostasis, abundant anhedral spinel grains, and minor Fe,Ni-metal; it is surrounded by a coarse-grained igneous rim largely composed of low-Ca pyroxene with abundant Fe,Ni-metal-sulfide nodules. The mineralogical observations suggest that only spinel grains in this igneous object were not melted. The spinel is ¹⁶O-rich (Δ¹⁷O ∼ −22‰), whereas the neighboring plagioclase mesostasis is ¹⁶O-depleted (Δ¹⁷O ∼ −11‰).We conclude that AOAs are aggregates of solar nebular condensates (forsterite, Fe,Ni-metal, and CAIs composed of Al-diopside, anorthite, spinel, and ±melilite) formed in an ¹⁶O-rich gaseous reservoir, probably CAI-forming region(s). Solid or incipiently melted forsterite in some AOAs reacted with gaseous SiO in the same nebular region to form low-Ca pyroxene. Some other AOAs appear to have accreted ¹⁶O-poor pyroxene-normative dust and experienced varying degrees of melting, most likely in chondrule-forming region(s). The most extensively melted AOAs experienced oxygen isotope exchange with ¹⁶O-poor nebular gas and may have been transformed into chondrules. The original ¹⁶O-rich signature of the precursor materials of such chondrules is preserved only in incompletely melted grains.     

南极碳质球粒陨石中两个富尖晶石球粒状难熔包体的岩石学和矿物化学特征

富尖晶石球粒状CAI(富Ca-Al难熔包体)是球粒陨石中一种特殊类型的CAI,在南极格罗夫山碳质球粒陨石GRV020025和GRV021579中共发现两个富尖晶石球粒状CAI———GRV020025-3RI8和GRV021579-3RI5。GRV020025-3RI8具有占统治地位的尖晶石,在球粒的最外边存在严重蚀变的不规则边,钙钛矿主要分布在靠近边的位置。与GRV020025-3RI8比较,GRV021579-3RI5的尖晶石中的钙钛矿消失,深绿辉石出现,薄薄的蚀变层位于尖晶石核和富钙辉石边之间。两个富尖晶石球粒状CAI的尖晶石均具有低含量FeO和ZnO的特征,而且GRV021579-3RI5具有较GRV020025-3RI8更高的TiO2含量。岩石学和矿物化学特征表明,GRV020025-3RI8和GRV021579-3RI5都经历过熔融结晶过程,它们的蚀变均发生在非氧化的含水或无水的环境中。     

不纯碳酸盐碳氧同位素组成的在线分析

利用 GV IsoPrime(R)Ⅱ型稳定同位素质谱仪测量不纯碳酸盐样品的碳氧同位素组成,这些样品是用国家碳酸盐碳氧同位素一级标准物质 GBW04406与去除了碳酸盐的沉积物混合配制而成的, CaCO3含量在 2%～ 90%之间.结果显示 ,δ 13C内部精度为 0.002‰～ 0.005‰ (1σ ),δ 18O内部精度为 0.003‰～ 0.009‰ (1σ ),与测量所得的纯 CaCO3国际国内标准物质结果的内部精度范围一致,且外部精度达到仪器的指标要求,同时 ,不同 CaCO3含量样品的δ 13C和δ 18O的测量值 (测量平均值:δ 13C =-10.932‰± 0.021‰,δ 18O=-12.483‰± 0.054‰; 1σ )也在误差允许范围之内与 GBW04406推荐值 (δ 13C=-10.85‰± 0.05‰, δ 18O =-12.40‰± 0.15‰ ; 1σ )一致.可见碳酸盐的含量并不影响其碳氧同位素组成的分析结果,所以在线分析不纯碳酸盐的碳氧同位素组成是可行的,在线分析不纯碳酸盐样品的碳氧同位素组成之前应先对样品中碳酸盐含量进行大致估计,根据碳酸盐含量高低来确定样品用量以达到最佳分析效果.     

Mercury abundances and isotopic compositions in the Murchison (CM) and Allende (CV) carbonaceous chondrites

The abundance and isotopic composition of Hg was determined in bulk samples of both the Murchison (CM) and Allende (CV) carbonaceous chondrites using single- and multi-collector inductively coupled plasma mass spectrometry (ICP-MS). The bulk abundances of Hg are 294 ± 15 ng/g in Murchison and 30.0 ± 1.5 ng/g in Allende. These values are within the range of previous measurements of bulk Hg abundances by neutron activation analysis (NAA). Prior studies suggested that both meteorites contain isotopically anomalous Hg, with δ^196/202Hg values for the anomalous, thermal-release components from bulk samples ranging from −260 ‰ to +440 ‰ in Murchison and from −620 ‰ to +540 ‰ in Allende Jovanovic and Reed 1976a, Jovanovic and Reed 1976b, Kumar and Goel 1992. Our multi-collector ICP-MS measurements suggest that the relative abundances of all seven stable Hg isotopes in both meteorites are identical to terrestrial values within 0.2 to 0.5 ‰.On-line thermal-release experiments were performed by coupling a programmable oven with the single-collector ICP-MS. Powdered aliquots of each meteorite were linearly heated from room temperature to 900°C over twenty-five minutes under an Ar atmosphere to measure the isotopic composition of Hg released from the meteorites as a function of temperature. In separate experiments, the release profiles of S and Se were determined simultaneously with Hg to constrain the Hg distribution within the meteorites and to evaluate the possibility of Se interferences in previous NAA studies. The Hg-release patterns differ between Allende and Murchison. The Hg-release profile for Allende contains two distinct peaks, at 225° and 343°C, whereas the profile for Murchison has only one peak, at 344°C. No isotopically anomalous Hg was detected in the thermal-release experiments at a precision level of 5 to 30 ‰, depending on the isotope ratio. In both meteorites the Hg peak at ∼340°C correlates with a peak in the S-release profile. This correlation suggests that Hg is associated with S-bearing phases and, thus, that HgS is a major Hg-bearing phase in both meteorites. The Hg peak at 225°C for Allende is similar to release patterns of physically adsorbed Hg on silicate and metal grains. Prior studies suggested that the isotopic anomalies reported from NAA resulted from interference between ²⁰³Hg and ⁷⁵Se. However, the amount of Se released from both meteorites, relative to Hg, is insufficient to produce all of the observed anomalies.     

Fe-Ni and Mn-Cr isotopic systems in sulfides from unequilibrated enstatite chondrites

In situ measurements of ⁶⁰Fe-⁶⁰Ni and ⁵³Mn-⁵³Cr isotopic systems with an ion microprobe have been carried out for sulfide assemblages from unequilibrated enstatite chondrites (UECs). Evidence for the initial presence of ⁶⁰Fe has been observed in nine sulfide inclusions from three UECs: ALHA77295, MAC88136, and Qingzhen. The inferred initial (⁶⁰Fe/⁵⁶Fe) [(⁶⁰Fe/⁵⁶Fe)₀] ratios show a large variation range, from ∼2 × 10⁻⁷ to ∼2 × 10⁻⁶. The sulfide inclusions with high Fe/Ni ratios yield (⁶⁰Fe/⁵⁶Fe)₀ ratios of ∼(2-7) × 10⁻⁷, similar to most of the (⁶⁰Fe/⁵⁶Fe)₀ values of troilite and pyroxene observed in unequilibrated ordinary chondrites (UOCs). Inclusions with high inferred (⁶⁰Fe/⁵⁶Fe)₀ ratios (∼1-2 × 10⁻⁶) have low Fe/Ni ratios and the magnitude of the ⁶⁰Ni excesses is similar in two MAC88136 assemblages in spite of a difference of a factor of two in their Fe/Ni ratios. The inferred high (⁶⁰Fe/⁵⁶Fe)₀ ratios were probably the result of Fe-Ni re-distribution in the sulfides during later alteration processes.The ⁵³Mn-⁵³Cr system was measured in five of the sulfide assemblages that were examined for their ⁶⁰Fe-⁶⁰Ni systematics. The ⁵³Mn-⁵³Cr isochrons yielded variable initial (⁵³Mn/⁵⁵Mn) [(⁵³Mn/⁵⁵Mn)₀] ratios from ∼(2-7) × 10⁻⁷. There is no obvious correlation between the (⁶⁰Fe/⁵⁶Fe)₀ and (⁵³Mn/⁵⁵Mn)₀ ratios. The variable ⁵³Mn-⁵³Cr isochrons probably also indicate later disturbance to the isotopic systems in these sulfides. Even though no chronological information can be extracted from the ⁶⁰Fe-⁶⁰Ni and ⁵³Mn-⁵³Cr systems in these UEC sulfides, our results indicate that ⁶⁰Fe was present in the enstatite chondrite formation region of the early Solar System.     

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.