Presolar spinel grains from the Murray and Murchison carbonaceous chondrites

With a new type of ion microprobe, the NanoSIMS, we determined the oxygen isotopic compositions of small (<1μm) oxide grains in chemical separates from two CM2 carbonaceous meteorites, Murray and Murchison. Among 628 grains from Murray separate CF (mean diameter 0.15 μm) we discovered 15 presolar spinel and 3 presolar corundum grains, among 753 grains from Murray separate CG (mean diameter 0.45 μm) 9 presolar spinel grains, and among 473 grains from Murchison separate KIE (mean diameter 0.5 μm) 2 presolar spinel and 4 presolar corundum grains. The abundance of presolar spinel is highest (2.4%) in the smallest size fraction. The total abundance in the whole meteorite is at least 1 ppm, which makes spinel the third-most abundant presolar grain species after nanodiamonds (if indeed a significant fraction of them are presolar) and silicon carbide. The O-isotopic distribution of the spinel grains is very similar to that of presolar corundum, the only statistically significant difference being that there is a larger fraction of corundum grains with large ¹⁷O excesses (¹⁷O/¹⁶O > 1.5 × 10⁻³), which indicates parent stars with masses between 1.8 and 4.5 M_⊙.     

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

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

Fine,nickel-poor Fe-Ni grains in the olivine of unequilibrated ordinary chondrites

Fine (?2 μm), Ni-poor (? 10 mg/g) Fe-Ni grains are common inclusions in the olivine in porphyritic chondrules in unequilibrated ordinary chondrites. The olivine grains appear to be relicts that survived chondrule formation without melting. The most common occurrence of this “dusty” metal is in the core of olivine grains having clear Fe-poor rims and surrounded either by small euhedral clear olivine grains zoned with FeO increasing toward the border of the grains or by large elongated Fe-poor orthopyroxenes oriented parallel to the chondrule surface and enclosing small round olivine grains. Various amounts of Ca, Al-rich glass are always present. The dusty metal is occasionally found in the rims of olivine grains either isolated in the matrix or included in chondrules. A rare occurrence is as bands in highly deformed olivines.This dusty metal appears to be the product of in situ reduction of FeO from the host olivine. Among the possible reductants H₂ or carbonaceous matter (CH₂)_n seem the most likely. Hydrogen may have been implanted by solar-wind or solar-flare irradiation, but this requires that dissipation of nebular gas occurred before the end of the chondrule formation process. Carbonaceous matter may have been implanted by shock. Less likely reductants are nebular CO or C dissolved in the olivine lattice. The large relict olivine grains may be nebular condensates or, more likely, fragments broken off earlier generations of chondrules.     

Amoeboid olivine aggregates and related objects in carbonaceous chondrites: records of nebular and asteroid processes

Amoeboid olivine aggregates (AOAs) are the most common type of refractory inclusions in CM, CR, CH, CV, CO, and ungrouped carbonaceous chondrites Acfer 094 and Adelaide; only one AOA was found in the CB_b chondrite Hammadah al Hamra 237 and none were observed in the CB_a chondrites Bencubbin, Gujba, and Weatherford. In primitive (unaltered and unmetamorphosed) carbonaceous chondrites, AOAs consist of forsterite (Fa_<2), Fe, Ni-metal (5-12 wt% Ni), and Ca, Al-rich inclusions (CAIs) composed of Al-diopside, spinel, anorthite, and very rare melilite. Melilite is typically replaced by a fine-grained mixture of spinel, Al-diopside, and ±anorthite; spinel is replaced by anorthite. About 10% of AOAs contain low-Ca pyroxene replacing forsterite. Forsterite and spinel are always ¹⁶O-rich (δ^17,18O∼−40‰ to −50‰), whereas melilite, anorthite, and diopside could be either similarly ¹⁶O-rich or ¹⁶O-depleted to varying degrees; the latter is common in AOAs from altered and metamorphosed carbonaceous chondrites such as some CVs and COs. Low-Ca pyroxene is either ¹⁶O-rich (δ^17,18O∼−40‰) or ¹⁶O-poor (δ^17,18O∼0‰). Most AOAs in CV chondrites have unfractionated (∼2-10×CI) rare-earth element patterns. AOAs have similar textures, mineralogy and oxygen isotopic compositions to those of forsterite-rich accretionary rims surrounding different types of CAIs (compact and fluffy Type A, Type B, and fine-grained, spinel-rich) in CV and CR chondrites. AOAs in primitive carbonaceous chondrites show no evidence for alteration and thermal metamorphism. Secondary minerals in AOAs from CR, CM, and CO, and CV chondrites are similar to those in chondrules, CAIs, and matrices of their host meteorites and include phyllosilicates, magnetite, carbonates, nepheline, sodalite, grossular, wollastonite, hedenbergite, andradite, and ferrous olivine.Our observations and a thermodynamic analysis suggest that AOAs and forsterite-rich accretionary rims formed in ¹⁶O-rich gaseous reservoirs, probably in the CAI-forming region(s), as aggregates of solar nebular condensates originally composed of forsterite, Fe, Ni-metal, and CAIs. Some of the CAIs were melted prior to aggregation into AOAs and experienced formation of Wark-Lovering rims. Before and possibly after the aggregation, melilite and spinel in CAIs reacted with SiO and Mg of the solar nebula gas enriched in ¹⁶O to form Al-diopside and anorthite. Forsterite in some AOAs reacted with ¹⁶O-enriched SiO gas to form low-Ca pyroxene. Some other AOAs were either reheated in ¹⁶O-poor gaseous reservoirs or coated by ¹⁶O-depleted pyroxene-rich dust and melted to varying degrees, possibly during chondrule formation. The most extensively melted AOAs experienced oxygen isotope exchange with ¹⁶O-poor nebular gas and may have been transformed into magnesian (Type I) chondrules. Secondary mineralization and at least some of the oxygen isotope exchange in AOAs from altered and metamorphosed chondrites must have resulted from alteration in the presence of aqueous solutions after aggregation and lithification of the chondrite parent asteroids.     

Chemical and petrographic constraints on the origin of chondrules and inclusions in carbonaceous chondrites

Bulk chemical compositions of the various petrographie types of chondrules and inclusions in Type 3 carbonaceous chondrites (excluding those affected by metamorphism) have been determined by microprobe defocused beam analysis. Inclusion compositions follow approximately the theoretical compositional trajectory for equilibrium condensation. Analyses of chondrules occurring in the same meteorites have higher silica contents and show only slight overlap with inclusion compositions. Dust fusion is apparently an inadequate mechanism for producing the wide chemical variations observed among chondrules. Impact melting models require sampling of complex target rocks which are unknown as components of meteorites; this mechanism also demands efficient mechanical processing of chondrules before accretion. A genetic relationship between chondrules and inclusions in carbonaceous chondrites is suggested by the compositional continuum between these objects. A condensation sequence which dips into the liquid stability field at lower temperatures is advocated for the production of both inclusions and chondrules. Textural relationships between intergrown chondrules and inclusions support such a sequence. This model suggests that the assembled components (inclusions and chondrules) of carbonaceous chondrites are related by a common process.     

Boron concentrations in carbonaceous chondrites

We have analyzed B in carbonaceous chondrites in order to clarify a factor of 100 difference between the solar system B abundance derived from the solar photosphere and that inferred from previous meteorite data. Consistent results were obtained from two instrumental methods for B analysis: (a) counting of the high energy betas from ¹²B produced by the ¹¹B(d,p) reaction, and (b) measurement of particle track densities from ¹⁰B(n,α)⁷Li in a plastic track detector affixed to a homogenized meteorite sample. Contamination is a major problem in B analyses, but extensive testing showed that our results were not seriously affected. Our B concentrations are typically 1–2 ppm and are a factor of 2–6 lower than previous carbonaceous chondrite measurements. Our data for the Cl chondrites Ivuna and Orgueil would indicate a solar system B/Si atomic abundance ratio of 58 × 10^?6, but this is still a factor of 2–10 higher than the photospheric estimates. It may be that B is depleted in the sun by thermonuclear processes; however, the similarity of photospheric and meteoritic Be abundances is a problem for this point of view. Alternatively, B may be enhanced in carbonaceous chondrites, but this would make B a cosmochemically unique element. A mm-sized (Fe,Mn,Mg)CO₃ crystal from Orgueil shows no B enrichment. We find ¹⁰B ≤ 10¹⁶ atoms/g in two Allende fine-grained inclusions suggesting that B is not a refractory element under solar nebula conditions. This ¹⁰B limit, when taken as a limit on ¹⁰Be when the inclusion formed, puts constraints on the possibility of a solar system synthesis of ²⁶Al. For a proton spectrum of E^?a, a must be ≥ 3 if a solar gas is irradiated or a ≥1.5 if dust of solar composition is irradiated.     

The insoluble organic matter in carbonaceous chondrites: Chemical structure,isotopic composition and origin

Carbonaceous chondrites are characterized by their enrichment in organic matter, mainly represented by insoluble organic matter (IOM), which consists of small aromatic units linked by short-branched aliphatic chains. Furthermore, IOM contains organic radicals heterogeneously distributed along with diradicaloids. These chemical features discriminate IOM from terrestrial counterparts. Isotopic compositions, especially the D/H isotopic ratio, are also distinct. IOM is highly enriched in D (D/H > 350 × 10⁻⁶), and the D/H isotopic ratio is heterogeneous. The isotopic composition is the result of interstellar-like processes that could have taken place during the first ages of the protosolar nebula. Chemical structure and isotopic composition clearly show that IOM is synthesized by an abiotic process and is subsequently affected by aqueous alteration or high-temperature metamorphism on the parent body.     

Oxygen isotope studies of carbonaceous chondrites

The carbonaceous chondrites display the widest range of oxygen isotopic composition of any meteorite group, as a consequence of the interaction of primordial isotopic reservoirs in the solar nebula. These isotopic variations can be used to identify the reservoirs and to determine conditions and loci of their interactions. We present a comprehensive set of whole-rock analyses of CV, CO, CK, CM, CR, CH, and CI chondrites, as well as selected components of some of these meteorites. A simple model is developed which describes the isotopic behavior during parent-body aqueous alteration processes. The process of thermal dehydration also produces a recognizable effect in the oxygen isotopic composition.     

Amino acids of the Nogoya and Mokoia carbonaceous chondrites

Amino acids were found in acid hydrolyzed, hot water extracts of the Nogoya (C2) and Mokoia (C3V) chondrites. About 40 n moles/g of amino acids were found in the Nogoya extract while Mokoia contained less than 1 n mole/g. The amino acid composition of Nogoya differs from that of other C2 chondrites studied earlier. The results from Mokoia are similar to previous data obtained from the C3V chondrite Allende.     

The origin and history of ordinary chondrites: A study by iron isotope measurements of metal grains from ordinary chondrites

Chondrules and chondrites provide unique insights into early solar system origin and history, and iron plays a critical role in defining the properties of these objects. In order to understand the processes that formed chondrules and chondrites, and introduced isotopic fractionation of iron isotopes, we measured stable iron isotope ratios ⁵⁶Fe/⁵⁴Fe and ⁵⁷Fe/⁵⁴Fe in metal grains separated from 18 ordinary chondrites, of classes H, L and LL, ranging from petrographic types 3-6 using multi-collector inductively coupled plasma mass spectrometry. The δ⁵⁶Fe values range from −0.06 ± 0.01 to +0.30 ± 0.04‰ and δ⁵⁷Fe values are −0.09 ± 0.02 to +0.55 ± 0.05‰ (relative to IRMM-014 iron isotope standard). Where comparisons are possible, these data are in good agreement with published data. We found no systematic difference between falls and finds, suggesting that terrestrial weathering effects are not important in controlling the isotopic fractionations in our samples. We did find a trend in the ⁵⁶Fe/⁵⁴Fe and ⁵⁷Fe/⁵⁴Fe isotopic ratios along the series H, L and LL, with LL being isotopically heavier than H chondrites by ∼0.3‰ suggesting that redox processes are fractionating the isotopes. The ⁵⁶Fe/⁵⁴Fe and ⁵⁷Fe/⁵⁴Fe ratios also increase with increasing petrologic type, which again could reflect redox changes during metamorphism and also a temperature dependant fractionation as meteorites cooled. Metal separated from chondrites is isotopically heavier by ∼0.31‰ in δ⁵⁶Fe than chondrules from the same class, while bulk and matrix samples plot between chondrules and metal. Thus, as with so many chondrite properties, the bulk values appear to reflect the proportion of chondrules (more precisely the proportion of certain types of chondrule) to metal, whereas chondrule properties are largely determined by the redox conditions during chondrule formation. The chondrite assemblages we now observe were, therefore, formed as a closed system.     

Abundance of 17 trace elements in carbonaceous chondrites

Seventeen trace elements (Ag, Au, Bi, Br, Cd, Cs, Ge, In, Ir, Rb, Re, Sb, Se, Te, Tl, U and Zn) were measured by neutron activation analysis in 8 C1 samples (1 Alais, 3 Ivuna, 4 Orgueil) and in 3 C2 samples (one each of Mighei, Murchison, Murray). The results show far less scatter than earlier literature data. The standard deviation of a single measurement from the mean of 8 C1 samples lies between 2 and 14 per cent, except for the following 4 elements: Au ±18 per cent, Ag ±22 per cent, Rb ±19 per cent and Br ±33 per cent. The first two probably reflect contamination and sample heterogeneity, the last two, analytical error. Apparently C1 chondrites have a far more uniform composition than some authors have claimed.The new data suggest significant revisions in cosmic abundance for the following elements (old values in parentheses): Zn 1250 (1500), Cd 1.51 (2.12), Ir 0.72 (0.43) atoms/10⁶ Si atoms. The Br value is also lower, 6.8 vs 20.6, but may be affected by analytical error.Relative to C1 chondrites, the C2 chondrites Mighei, Murchison and Murray are depleted in volatile elements by a factor of 0.508 ± 0.038, much more constant than indicated by oldor data. Ordinary chondrites also show a more uniform depletion relative to the new C1 data. The mean depletion factor of Sb, F, Cu, Ga, Ge, Sn, S, Se, Te and Ag is 0.227 ± 0.027 in H-chondrites. This constancy further strengthens the case for the two-component model of chondrite formation.     

Chemical and petrographic correlations among carbonaceous chondrites

Detailed study of the petrographic and chemical properties of carbonaceous chondrites shows that the four distinct petrographic subtypes may be related to one of two distinct chemical subdivisions. These subdivisions are recognized primarily by the relative abundances of the nonvolatile elements Si, Ca, Al, Ti, Cu and Fe. C1, C2 and C3(O) chondrites form one subdivision. Vigarano subtype chondrites form the other subdivision and include chondrites previously referred to as C2, C3 and C4. Normalized to silicon, the abundances of Ca, Al and Ti are relatively enriched in Vigarano subtype chondrites, whereas Fe and Cu are relatively more abundant in C1, C2 and C3(O) chondrites. Volatile elements tend to correlate with petrographic subtypes rather than with chemical subdivisions. The available data suggest that nonvolatile element chemical fractionation of carbonaceous chondrites into the two chemical subdivisions occurred before chondrule formation and that present textural and mineralogic properties and volatile element abundances can be attributed to variations in chondrule-producing and accretion processes.     

Alkylation of polycyclic aromatic hydrocarbons in carbonaceous chondrites

Using microprobe laser-desorption, laser-ionization mass spectrometry (μL²MS), we measured the distributions of alkylated and unalkylated polycyclic aromatic hydrocarbons (PAHs) in the free organic material of 20 carbonaceous chondrites. These meteorites represent a variety of meteorite classes and alteration histories, including CI, CK, CM, CO, CR, CV, and Tagish Lake. This work provides information on free organic compounds that is complementary to studies of the structure and composition of meteoritic macromolecular content.For the nine CM2 meteorites analyzed, we observe that higher relative abundances of alkylated PAHs correlate with more intense aqueous activity. We attribute this correlation to the differences in solubility and volatility between unalkylated and alkylated PAHs. Naphthalene and its alkylation series are more susceptible to the effects of aqueous exposure than the less-soluble PAH phenanthrene and its alkylated derivatives. These observations are consistent with the possibility of chromatographic separations on the meteorite parent bodies. We identify six CM2 meteorites with similar PAH distributions that may represent the original, unaltered organic composition of the parent body.Increased metamorphic intensity reduces the abundance of all PAHs. The thermally metamorphosed CK chondrites had no detectable levels of typical meteoritic PAHs. This observation might be explained either by a loss of PAHs caused by volatilization or by a significantly different organic content of the CK parent body.     

Evolution of the iron-silicate and carbon material of carbonaceous chondrites

The observed consistence of the composition of chondrules and the matrix in chondrites is explained by their origin as a result of chondrule-matrix splitting of the material of primitive (not layered) planets. According to the composition of chondrites, two main stages in the evolution of chondritic planets (silicate-metallic and olivine) are distinguished. Chondritic planets of the silicate-metallic stage were analogs of chondritic planets, whose layering resulted in the formation of the terrestrial planets. The iron-silicate evolution of chondritic matter is correlated with the evolution of carbon material in the following sequence: diamond ± moissanite → hydrocarbons → primitive organic compounds.     

The distribution of trace elements in carbonaceous chondrites

12 carbonaceous chondrites, amongst them representatives of nearly all known petrologic types were analyzed for twenty trace elements by spark source mass spectrography combined with the isotope dilution method. Data on different element groups (refractory, moderately volatile and volatile) show that the distribution of the trace elements in the carbonaceous chondrites, with the exception of Renazzo, can be well explained by Anders' two-component model. This is also valid for the highly metamorphosed CV5 chondrite Karoonda.Furthermore, it is observed that the $\text{Zr}\text{Hf}$-ratios in the carbonaceous chondrites increase with increasing petrologic type which is interpreted as the result of mixing two components with different $\text{Zr}\text{Hf}$-ratios     

Investigating the variations in carbon and nitrogen isotopes in carbonaceous chondrites

The carbonaceous chondrites contain significant amounts of carbon- and nitrogen-bearing components, the most abundant of which is organic matter. Stepped combustion data of whole rock and HF/HCl residues of carbonaceous chondrites reveal that the organic material can be subdivided operationally into three components: (1) free organic matter (FOM), which is readily extractable from whole-rock meteorites and is enriched in ¹³C and ¹⁵N; (2) labile organic matter (LOM), which has a macromolecular structure but is liberated by hydrous pyrolysis; LOM is the parent structure for some FOM and is also enriched in ¹³C and ¹⁵N; and (3) refractory organic matter (ROM), which is also macromolecular but is virtually unaffected by hydrous pyrolysis and is relatively depleted in ¹³C and ¹⁵N. The macromolecular entities (LOM and ROM) are by far the most abundant organic components present, and as such, the relative abundances of the ¹³C- and ¹⁵N-enriched LOM and the ¹³C- and ¹⁵N-depleted ROM will have a major influence on the overall isotopic composition of the whole-rock meteorite. Laboratory experiments designed to simulate the effects of parent body aqueous alteration indicate that this form of processing removes LOM from the macromolecular material, allowing ROM to exert a stronger influence on the overall isotopic compositions. Hence, aqueous alteration of macromolecular materials on the meteorite parent body may have a significant control on the stable isotopic compositions of whole-rock carbonaceous chondrites. The enstatite chondrites are also carbon rich but have been subjected to high levels of thermal metamorphism on their parent body. Stepped combustion data of HF/HCl residues of enstatite chondrites indicate, that if they and carbonaceous chondrites inherited a common organic progenitor, metamorphism under reducing conditions appears to incorporate and preserve some of the ¹³C enrichments in LOM during graphitisation. However, when metamorphism is at its most extreme, the ¹⁵N enrichments in LOM are lost.     

The compositional classification of chondrites: III. Ungrouped carbonaceous chondrites

Seven carbonaceous chondrites (Allan Hills A77307, Adelaide, Al Rais, Coolidge, Grosnaja, Karoonda and Renazzo) with uncertain classifications were analyzed by instrumental and radiochemical neutron activation analysis for 29 elements: Na, Mg, Al, K, Ca, Sc, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, Ge, As, Se, Br, Ru, Cd, Sb, La, Sm, Eu, Yb, Lu, Os, Ir and Au. Five of these chondrites (A77307, Adelaide, Al Rais, Karoonda and Renazzo) are unique ‘grouplets’, not closely related to other groups or to each other. Only Coolidge (CV4) and Grosnaja (CV3-an) are members of previously established groups. A77307 and Adelaide have refractory lithophile abundances similar to those in the CM-CO clan; A77307 probably is a member of that clan, but Adelaide, which shows CV-like petrographic characteristics, cannot as yet be assigned to a clan. Al Rais and Renazzo have similar refractory lithophile abundances (essentially at CI levels) and probably belong to the same clan, i.e., formed in the same region of the nebula. There are insufficient data to determine whether they formed at the same general region as the CI chondrites, but separates having O-isotope compositions near the terrestrial fractionation line indicate that this is plausible. Karoonda has refractory lithophile abundances ~ 1.21 × CI and appears to belong to a new clan distinct from CM-CO (1.11 × CI) and CV (1.34×).