Lithium isotope composition of ordinary and carbonaceous chondrites, and differentiated planetary bodies: Bulk solar system and solar reservoirs

In order to better constrain the Li isotope composition of the bulk solar system and Li isotope fractionation during accretion and parent body processes, Li isotope compositions and concentrations were determined on a number of meteorite falls and finds. This is the first comprehensive study that systematically investigates a representative set of samples from carbonaceous chondrites (CI, CM2, CO3, CV3, CK4 and one ungrouped member), enstatite chondrites (EH, EL), ordinary chondrites (H, L, LL), and achondrites (one eucrite, diogenites, one pallasite, and a silicate inclusion from a IAB iron).

Carbonaceous chondrites have an average isotope composition of δ⁷Li = + 3.2‰ ± 1.9 (2σ) which agrees with the average composition of relatively pristine olivines (representative for the bulk composition) from the Earth primitive upper mantle (PUM). This is lighter than the average δ⁷Li of the basaltic differentiates of the Earth, Moon and Mars and the achondrites. It is an important observation, however, that the lighter end of the isotopic range of the differentiates always coincides with the averages of the mantle olivines and the carbonaceous chondrites. From this we conclude that the bulk of the inner solar system consists mostly of material from carbonaceous chondrites and that the variation seen in the differentiates is due to planetary body processes. Ordinary chondrites are significantly lighter than carbonaceous chondrites. No significant differences in δ⁷Li exist between enstatite chondrites (n = 3) and carbonaceous or ordinary chondrites. The difference between carbonaceous and ordinary chondrites and the variability within the chondrites could indicate the existence of distinct Li isotope reservoirs in the early solar nebula.     

The type three ordinary chondrities: A review

The ordinary chondrites are the largest group of meteorites, and the type 3 ordinary chondrites are those which experienced only very mild parent metamorphism; their study provides a unique means of studying the first solid material to from in the early solar system which is either free from the effects of mild metamorphism, or in which the effects of mild metamorphism can be distinguished from primary, nebular effects. In this paper we list all known type 3 ordinary chondrites and references to their study, their compositional data and data relating to the metamorphic history. We review current theories on their formation and the effects of metamorphism, with emphasis on quantitative considerations. Studies on the thermoluminescence properties of these meteorites, which have provided many new insights into their metamorphic history, are reviewed. Some of the least metamorphosed meteorites show evidence for aqueous alteration, which provides a link between the type 3 ordinary chondrites and objects containing water in various forms the carbonaceous chondrites, comets and planets with wet mantles.     

New kind of type 3 chondrite with a graphite-magnetite matrix

We have discovered four clasts in three ordinary-chondrite regolith breccias which are a new kind of type 3 chondrite. Like ordinary and carbonaceous type 3 chondrites, they have distinct chondrules, some of which contain glass, highly heterogeneous olivines and pyroxenes, and predominantly monoclinic low-Ca pyroxenes. But instead of the usual fine-grained, Fe-rich silicate matrix, the clasts have a matrix composed largely of aggregates of micron- and submicron-sized graphite and magnetite. The bulk compositions of the clasts as well as the types of chondrules (largely porphyritic) are typical of type 3 ordinary chondrites, although chondrules in the clasts are somewhat smaller (0.1–0.5 mm). A close relationship with ordinary chondrites is also indicated by the presence of similar graphite-magnetite aggregates in seven type 3 ordinary chondrites. This new kind of chondrite is probably the source of the abundant graphite-magnetite inclusions in ordinary-chondrite regolith breccias, and may be more common than indicated by the absence of whole meteorites made of chondrules and graphite-magnetite.     

A classification of meteorites based on oxygen isotopes

On the basis of¹⁸O/¹⁶O and¹⁷O/¹⁶O ratios, meteorites and planets can be grouped into at least six categories, as follows: (1) the terrestrial group, consisting of the earth, moon, differentiated meteorites and enstatite chondrites; (2) types L and LL ordinary chondrites; (3) type H ordinary chondrites; (4) anhydrous minerals of C2, C3, C4 carbonaceous chondrites; (5) hydrous matrix minerals of C2 carbonaceous chondrites; (6) the ureilites. Objects of one category cannot be derived by fractionation or differentiation from the source materials of any other category.     

Chondrite thermal histories: Clues from electron microscopy of orthopyroxene

Optically “striated” orthopyroxenes in two ordinary chondrites, Allegan (H5) and Quenggouk (H4), are compared with shock-affected orthopyroxenes in Saint-Sévérin (LL6) and Ambapur Nagla (H5) by high-voltage transmission electron microscopy. The striated orthopyroxenes have very many, thin, evenly distributed lamellae of clinopyroxene. They are undeformed and also lack evidence of partial inversion from clinopyroxene to orthopyroxene. Striated orthopyroxene does not seem to be a reliable indicator of prograde metamorphism. Instead, it is interpreted as inverted protopyroxene, produced during the cooling of chondrules at slower rates than the rapid quenching of Type 3 chondrules. The conclusions are consistent with retrograde models for the evolution of H-group chondrites, in which the higher Petrologic Types are attributed to retarded cooling due to accretionary processes leading to the growth of the parent body. The thermal histories of ordinary chondrites could be greatly clarified by further experimental work on inversions in bronzitic pyroxenes.     

Allan Hills 77081—an unusual stony meteorite

Allan Hills (ALHA) 77081 is achondritic in texture while the mineral composition and the chemistry are chondritic with the exception of a few elements. An assignment to one specific group of ordinary chondrites is therefore difficult. In many respects this meteorite is similar to the unusual stone meteorite Acapulco. The REE pattern of ALHA 77081 is essentially flat and the distribution ratios of siderophile elements between metal and silicates are high compared to ordinary chondrites.Gas retention ages are 3.5±0.5 AE for U, Th-He and 4.50±0.15 AE for K-Ar. In spite of the high degree of recrystallisation the meteorite contains trapped noble gases in amounts comparable to type 4 chondrites.Cosmic ray tracks and spallogenic noble gases indicate a small preatmospheric radius of about 2–3 cm. Spallogenic nuclides produced by solar cosmic rays or stopped solar flare ions may be present.     

Moderately volatile siderophiles in ordinary chondrites

The contents of the moderately volatile elements Ga, Ge, Cu and Sb in ordinary chondrites give us some clues with regard to the metal-silicate fractionation process. Their concentration in coexisting magnetic and non-magnetic portions of members of each ordinary chondrite group will be discussed. Germanium and Sb are mostly siderophilic, but Ga is strongly lithophilic in unequilibrated chondrites; its partition coefficient between magnetic and non-magnetic portions is positively correlated with petrologic type in L and LL chondrites, but not in H4–6 chondrites. From 25 to 50% of the total Cu is found in the non-magnetic fraction of chondrites, but there is no correlation between Cu content and petrologic type. The abundances of Ga, Cu and Sb (relative to Si) are constant in ordinary chondrites, independent of the amount of metal present, indicating that these elements were not in solid solution in the metal phase of chondrites when the metal-silicate fractionation process occurred. Germanium, which is the most volatile among the four elements analyzed, is more abundant in H than in L and LL chondrites, indicating that it was fractionated by this process. Nebular oxidation processes can be responsible for the behavior of Ga if this element was in oxidized form when loss of metal occurred, but cannot explain the results for Cu and Sb which are predicted to condense as metals and accrete mostly in metallic form. It is possible that Cu and Sb, upon condensation, did not form solid solutions with metallic Ni-Fe until after the separation of metal from silicates took place.     

Nitrogen abundances and isotopic compositions in stony meteorites

Nitrogen contents range from a few parts per million in ordinary chondrites and achondrites to several hundred parts per million in enstatite chondrites and carbonaceous chondrites. Four major isotopic groups are recognized: (1) C1 and C2 carbonaceous chondrites have δ¹⁵N of+30to+50%.; (2) enstatite chondrites have δ¹⁵N of?30to?40‰; (3) C3 chondrites have low δ¹⁵N with large internal variations; (4) ordinary chondrites have δ¹⁵N of?10to+20‰. The major variations are primary, representing isotopic abundances established at the time of condensation and accretion. Secondary processes, such as spallation reactions, solar wind implantation and metamorphic loss may cause small but observable isotopic variations in particular cases. The large isotopic difference between enstatite chondrites and carbonaceous chondrites cannot be accounted for by equilibrium condensation from a homogeneous nebular gas, and requires either unusually large kinetic effects, or a temporal or spatial variation of isotopic composition of the nebula. Nitrogen isotopic heterogeneity in the nebula due to nuclear processes has not been firmly established, but may be required to account for the large variations found within the Allende and Leoville meteorites. The unique carbonaceous chondrite, Renazzo, has δ¹⁵N of+170%., which is well beyond the range of all other data, and also requires a special source. It is not yet possible, from the meteoritic data, to establish the mode of accretion of nitrogen onto the primitive Earth.     

Nickel isotope heterogeneity in the early Solar System

We report small but significant variations in the ⁵⁸Ni/⁶¹Ni-normalised ⁶⁰Ni/⁶¹Ni and ⁶²Ni/⁶¹Ni ratios (expressed as ε⁶⁰Ni and ε⁶²Ni) of bulk iron and chondritic meteorites. Carbonaceous chondrites have variable, positive ε⁶²Ni (0.05 to 0.25), whereas ordinary chondrites have negative ε⁶²Ni (− 0.04 to − 0.09). The Ni isotope compositions of iron meteorites overlap with those of chondrites, and define an array with negative slope in the ε⁶⁰Ni versus ε⁶²Ni diagram. The Ni isotope compositions of the volatile-depleted Group IVB irons are similar to those of the refractory CO, CV carbonaceous chondrites, whereas the other common magmatic iron groups have Ni isotope compositions similar to ordinary chondrites. Only enstatite chondrites have identical Ni isotope compositions to Earth and so appear to represent the most appropriate terrestrial building material. Differences in ε⁶²Ni reflect distinct nucleosynthetic components in precursor solids that have been variably mixed, but some of the ε⁶⁰Ni variability could reflect a radiogenic component from the decay of ⁶⁰Fe. Comparison of the ε⁶⁰Ni of iron and chondritic meteorites with the same ε⁶²Ni allows us to place upper limits on the ⁶⁰Fe/⁵⁶Fe of planetesimals during core segregation. We estimate that carbonaceous chondrites had initial ⁶⁰Fe/⁵⁶Fe < 1 × 10^− 7. Our data place less good constraints on initial ⁶⁰Fe/⁵⁶Fe ratios of ordinary chondrites but our results are not incompatible with values as high as 3 × 10^− 7 as determined by in-situ measurements. We suggest that the Ni isotope variations and apparently heterogeneous initial ⁶⁰Fe/⁵⁶Fe results from physical sorting within the protosolar nebula of different phases (silicate, metal and sulphide) that carry different isotopic signatures.     

Genetic relations between iron and stony meteorites

The main group pallasites and the mesosiderites fall within the oxygen isotope group previously determined for the calcium-rich achondrites (eucrites, howardites and diogenites), consistent with derivation from a common source material, and perhaps a common parent body. The group IIE iron meteorites were derived from the same source material as H-group ordinary chondrites. The chondrite-like silicate inclusions in group IAB iron meteorites are not related to the ordinary chondrites, but may be related to the enstatite chondrites. Several meteorites previously considered “anomalous” fall into these groups: Pontlyfni and Winona with the IAB irons, and Netschaëvo possibly with the H chondrites and IIE irons. The unusual pallasites Eagle Station and Itzawisis have remarkable oxygen isotopic compositions, and have more of the ¹⁶O-rich component than any other meteorite. Bencubbin and Weatherford are also unusual in their isotopic compositions, and may bear some relationship to the C2 carbonaceous chondrites. Lodran and Enon are isotopically similar to one another and are close to the achondrite-mesosiderite-pallasite group.     

Iron-silicate fractionation within ordinary chondrite groups

A comparison of recent bulk chemical analyses of fresh, well-classified ordinary chondrites reveals that the unequilibrated H-3 and LL-3 chondrites tend to be iron-poor relative to equilibrated H- and LL-group chondrites (types 4–6). A more complex relationship in the L-group suggests that it consists of two chemical subgroups, in each of which iron is deficient in the lower petrologic types. The available data suggest that the chondrite parent bodies accreted inhomogeneously.     

Boron cosmochemistry

Boron, sulfur, silicon, and sodium abundances have been measured in 50 pieces from 28 chondritic meteorites. Thirty-one of these samples were carefully selected and prepared to avoid composition changes from contamination or alteration in the terrestrial environment. Boron and sodium abundances define two domains within C2M carbonaceous chondrites: one contains8.5 B10⁶ Si and0.044 NaSi and the other25 B10⁶ Si and0.021 Na10⁶ Si. It is proposed that these differences are the result of element redistribution within C2M chondrites in response to low-temperature hydrous processes. Petrologic type 5 and 6 chondrites are also composed of two types of material, one has3.5 B10⁶ Si and the other11 B10⁶ Si. The mass weighted average of the boron concentration in high-petrologic-type ordinary chondrites is indistinguishable from the measured abundances in petrologic type 3 and 4 ordinary chondrites. We suggest that the compositional differences within petrologic types 5 and 6 are the result of high-temperature modifications of materials that had boron abundances like those now observed in the low petrologic types.We assumed that the redistribution of these elements was closed on the scale of the mass of the available meteorites, and determined the abundances in unaltered material by calculating the mass weighted average of the measured abundances in all the samples of one chondrite type. We used these averages to calculate boron depletion factors in chondrite types. The factors areC2 = 0.62, C3 = 0.31, andordinary chondrites= 0.34. These are similar to the sulfur depletion factors in the same types of meteorites. The agreement suggests that boron, like sulfur, had a nebular condensation temperature at the lower end of the range of moderately volatile elements. Within the context of this interpretation, the solar abundance of boron is21 B10⁶ Si—the concentration in the interior piece of the C-1 carbonaceous chondrite Orgueil.     

The unique cosmic-ray history of the Malakal chondrite

Cosmogenic radionuclides, including²²Na,²⁶Al and⁵⁴Mn, were measured in a sample of the recently-fallen Malakal hypersthene chondrite. The high²⁶Al activity, 79 ± 2 dpm/kg, greatly exceeds the levels expected from elemental production rates, shielding considerations, or comparisons with other ordinary chondrites, and can only be explained by exposure to a uniquely high cosmic-ray flux. Calculations including noble gas,³H, and⁵³Mn data from other laboratories require a two-stage irradiation. Malakal's most probable history is: exposure in excess of 4 m.y. to an effective cosmic-ray flux approximately three times that experienced by other chondrites, an orbit change (very possibly caused by a collision), and a final period of about 2 m.y. during which it was exposed to a “normal” cosmic-ray flux.     

Tungsten in ordinary chondrites

In ordinary chondrites tungsten displays both lithophile and siderophile characteristics. Its concentration in the metal phase is positively correlated with petrologic type, and with the distribution coefficientK_D =W in metal/W in silicates plus troilite. The oxidation-reduction reactions involved are temperature-dependent and the recrystallization temperature recorded on the basis of the partition of W between coexisting metal and silicate plus troilite fractions are950° ± 100°C for equilibrated chondrites (types 5 and 6), and800° ± 50°C for type 4, while Shaw (L7) records the highest recrystallization temperature (>1200°C).The different metallic content of the three groups of ordinary chondrites has been attributed to a metal-silicate fractionation process. Such a process appears to have fractionated W and Ir, but not W and Fe as these elements were partly oxidized when the fractionation process took place.     

ALH85085: a unique volatile-poor carbonaceous chondrite with possible implications for nebular fractionation processes

Allan Hills 85085 is a unique chondrite with affinities to the Al Rais-Renazzo clan of carbonaceous chondrites. Its constituents are less than 50 μm in mean size. Chondrules and microchondrules of all textures are present; nonporphyritic chondrules are unusually abundant. The mean compositions of porphyritic, nonporphyritic and barred olivine chondrules resemble those in ordinary chondrites except that they are depleted in volatile elements. Ca-, Al-rich inclusions are abundant and largely free of nebular alteration; they comprise types similar to those in CM and CO chondrites, as well as unique types. Calcium dialuminate occurs in several inclusions. Metal, silicate and sulfide compositions are close to those in CM-CO chondrites and Al Rais and Renazzo. C1-chondrite clasts and metal-rich “reduced” clasts are present, but opaque matrix is absent. Siderophile abundances in ALH85085 are extremely high (e.g., Fe/Si= 1.7 × solar), and volatiles are depleted (e.g., Na/Si= 0.25 × solar, S/Si= 0.03 × solar). Nonvolatile lithophile abundances are similar to those in Al Rais, Renazzo, and CM and CO chondrites.ALH85085 agglomerated when temperatures in the nebula were near 1000 K, in the same region where Renazzo, Al Rais and the CI chondrites formed. Agglomeration of high-temperature material may thus be a mechanism by which the fractionation of refractory lithophiles occurred in the nebula. Chondrule formation must have occurred at high temperatures when clumps of precursors were small. After agglomeration, ALH85085 was annealed and lightly shocked. C1 and other clasts were subsequently incorporated during late-stage brecciation.     

The abundance of barium in stony meteorites

The concentration of Ba in 7 carbonaceous chondrites, 18 ordinary chondrites, 3 achondrites and 1 stony-iron meteorite has been determined by the stable isotope dilution technique using solid source mass spectrometry. Analysis of the C1 chondrite Orgueil indicates a small adjustment of the “cosmic” abundance of Ba to 4.2 on the Si=10⁶ abundance scale. The present work provides a more complete coverage of a number of meteorite classes than has so far been available for the abundance of Ba in stony meteorites.     

Origin of iron-rich olivine in the matrices of type 3 ordinary chondrites: an experimental study

In order to understand the origin of iron-rich olivine in the matrices of type 3 ordinary chondrites, the reaction of metallic iron and enstatite, with and without forsterite and SiO₂, has been experimentally reproduced at temperatures between 1150° and 800°C and P_O2 between 10⁻¹¹ and 10⁻¹⁶ atm (between the IQF and MW buffers). The olivine produced ranges from Fo₅₈ to Fo₃₄ and this composition does not change significantly with temperature and time of the runs. The magnesian olivine which forms does become more magnesian with increasing forsterite/enstatite ratio of the starting materials. Iron-rich olivine (Fo< 35) cannot be formed by the reaction of enstatite and metallic iron, with or without forsterite as starting materials but it can be formed in the presence of free silica. The composition of olivine becomes more iron-rich with increasing silica/enstatite ratio. The compositional range of olivine formed from each mixture is 25–30 mole% Fo regardless of the temperature, composition, mineral assemblage, and run duration.From these experimental results, two possibilities suggested for the origin of the iron-rich olivine in the matrices of type 3 ordinary chondrites: (1) free silica must have been present if the iron-rich olivine was formed by solid-state reactions under oxidizing condition in the solar nebula; (2) reaction of silicon-rich gas with metallic iron took place under oxidizing condition in the solar nebula. Though it is difficult to define which alternative was dominant, the formation of free silica or silicon-rich gas may be a result of fractional condensation. This is possible if there is a reaction relation between forsterite and gas to produce enstatite. The suggested fractional condensation is supported by the fact that the compositions of the fine-grained matrices of type 3 ordinary chondrites are more silica-rich than the bulk compositions of the chondrites. Though it is not known whether such conditions were established all over the nebula or locally in the nebula, both fractionation and more oxidizing conditions than the average solar nebula are required for the formation of matrix olivine.     

Some clues to the history of the H-group chondrites

SEM, optical and chemical observations have been performed on 12 H3-6 chondrites, 9 of them being also studied by other groups. Morphological features of chondrules and crystals (growth steps) are shown; the significance of the finely crystallised troilite in Menow and Ambapur Nagla is discussed in the light of the discovery that the NiFe blebs associated with it are Ni-rich (50–60% Ni). Sulphur should have been mobilized without shock evidence possibly as a result of solar heating. Pre-chondritic relict material is recognized by anomalous or variable mineral compositions, and in some cases, by the presence of overgrowths on relict cores. After short notes on individual chondrites, a tentative history of H chondrites is proposed. The chondrule-forming episode is considered as a remelting of pre-existing material. The accretion would immediately follow this event for type 6 (around 1000°C), and would occur at progressively lower temperature for types 5 and 4. Type 3 would represent material coming from an extended source region, an hypothesis consistent with the broader range composition of the particles and with their cooling before accretion to much lower temperatures (below 350°C).     

Petrogenesis of complex veins in the Chantonnay (L6f) chondrite

Two cross-cutting veins in the Chantonnay (L6f) chondrite illustrate different patterns of fractionation of total chondritic shock melts. The earlier vein, which is dark-colored and bears abundant host rock xenoliths, is strongly reduced and sodium-poor relative to the bulk meteorite. It resembles and may be cogenetic with melt pockets in Chantonnay. The later vein, which is lighter-colored and somewhat vesicular, lacks evidence of either Na loss or reduction but shows modest internal differentiation. Its metal and total iron contents (26.5 wt.%) are higher than normal for L-group chondrites.The trend of chemical fractionation recorded in the earlier Chantonnay vein resembles that reported for chondrules in ordinary chondrites, suggesting that chemical variations among chondrules in part reflect variations among their parental shock melts.     

Primitive ultrafine matrix in ordinary chondrites

Ultrafine matrix material has been concentrated by sieving and filtering disaggregated samples of six ordinary chondrites of different classes. This component(s), “Holy Smoke” (HS), is enriched in both volatile, e.g. Na, K, Zn, Sb, and Pb, as well as refractory elements, e.g. W and REE; however, the element ratios vary greatly among the different chondrites. SEM studies show that HS contains fragile crystals, differing in composition, and apparently in gross disequilibrium not only among themselves but also with the major mineral phases and consequently thermodynamic equilibration did not occur. Thus HS must have originated from impacting bodies and/or was inherent in the “primitive” regolith. Subsequent impact brecciation and reheating appears to have altered, to varying degrees, the original composition of this ultrafine matrix material. Recent “cosmic dust” studies may indicate that HS still exists in the solar system. Survival of such delicate material must be considered in all theories for the origin of chondrites.