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.     

Accretion of the ordinary chondrites

The narrow size distributions of silicate and metal particles in 19 unequilibrated ordinary chondrites and other textural properties of these meteorites strongly suggest that chondritic material was sorted before or during its accumulation in parent bodies. Gravitational sorting during accretion is possible, but the conditions which it requires are implausible. Aerodynamic sorting - exclusion of small and/or low-density particles from a planetesimal moving through a mixture of gas and dust - can account for the textures of ordinary chondrites. It may also explain observed variations of siderophile element contents among and within the three groups of ordinary chondrites.     

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.     

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.     

Matrix textures in unequilibrated ordinary chondrites

High-voltage electron microscope observations are reported for specimens of the meteorites Hedjaz, Parnallee, Chainpur and Weston. Clastic matrix in Weston and Chainpur is distinguished from non-clastic material found in the other two specimens and in dark rims around chondrules in Chainpur. The variety of grain-size distributions and porosities found in this type of matrix is interpreted in terms of grain growth during the aggregation of the meteorite, and incipient solid-state recrystallization of aggregates (metamorphism). The formation of fine-grained non-clastic aggregates with low porosity was not accompanied by sufficient diffusion within the aggregates to equilibrate the mineral assemblages.     

The metamorphic history of LL-group ordinary chondrites

A study of feldspar grain size and microprobe analysis of coexisting orthopyroxene, olivine, diopside, and metal in twenty equilibrated LL-group chondrites and clasts defines the conditions of metamorphism, indicates the relative position of samples within the parent body, and suggests an accretionary-metamorphic history.

Variation of mineral chemistry indicates a range of equilibrium temperature and parallels textural variation, providing two continuous relative temperature scales, based on mean feldspar grain size and the calcium content of orthopyroxene coexisting with diopside. Maximum equilibrium temperatures range from less than 600° up to 950°C. The total Tschermak's component in orthopyroxene indicates that maximum pressure was less than 1 kbar, and a pressure gradient correlates directly with temperature. A reduction sequence, evident from systematic variation of iron in ferromagnesian silicates and metal, correlates inversely with temperature.

The maximum permissible sampling depth for the formation of surface breccias (2/10 r) also limits pressure to less than 1 kbar. The LL parent body had a minimum radius of 200 km, determined using the permissible sampling depth and published cooling rates.

The data are broadly consistent with simple reheating of colder material within a completely accreted body. This model may have problems with volatile depletion, a required lack of impact sampling during metamorphism, and the timing of the event. The data are more consistent with accretion of colder material on a hot but cooling surface. Both models apparently require a recycling process during accretion to account for the reduction sequence.     

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.     

Organic thermometry for chondritic parent bodies

A unique spectroscopic feature has been identified in a study of twenty-five different samples of meteoritic insoluble organic matter (IOM) spanning multiple chemical classes, groups, and petrologic types, using carbon X-ray Absorption Near Edge Structure (XANES) spectroscopy. The intensity of this feature, a 1s − σ exciton, appears to provide a precise measure of parent body metamorphism. The intensity of this exciton is also shown to correlate well with a large negative paramagnetic shift observed through solid state ¹³C NMR. Experiments reveal that upon heating primitive IOM is transformed into material that is indistinguishable from that in thermally processed chondrites, including the development of the 1s − σ exciton. A thermo-kinetic expression is derived from the experimental data that allows the intensity of the 1s − σ exciton to be used to estimated the effective temperature integrated over time. A good correlation is observed between the intensity of the 1s − σ exciton and previously published microRaman spectral data. These data provide a self-consistent organic derived temperature scale for the purpose of calibrating Raman based thermometric expressions.     

Hydrothermal convection in carbonaceous chondrite parent bodies

Numerical simulations of the thermal evolution of carbonaceous chondrite parent bodies indicate a period of several million years during which convective motion of water could occur. The present study considers variations of permeability, radiogenic heating, and body radius. The model accounts for the radial variation of gravity within the body, melting of ice, freezing of liquid water, and variable water properties and incorporates a realistic equation of state for water. Some regions of a parent body experience no pore water flow while other regions experience hundreds of pore volumes of liquid water flow. The spatial heterogeneity in pore water flow reflects the convective pattern in the body. Hydrothermal alteration of minerals inside the parent body will accordingly vary greatly with location in the body, and one parent body could be the source of chemically diverse 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.     

In situ SIMS oxygen isotope analyses: Evidence for the formation of aluminum-rich chondrules from ordinary chondrites

Aluminum-rich chondrules(ARCs),which share mineralogic and chemical properties with both Ca,Al-rich inclusions(CAIs)and ferromagnesian chondrules,play an important role in revealing their temporal and petrogenetic relationships.In this work,seven ARCs were found in three ordinary chondrites GRV 022410(H4),GRV 052722(H3.7)and Julesburg(L3.6).They contain bulk Al2O3~17%-33%and exhibit igneous textures composed of olivine,high-and low-Ca pyroxene,plagioclase,spinel and glass.In situ SIMS analyses show that ARCs have oxygen isotopic compositions(δ18O=–6.1‰–7.1‰;δ17O=–4.5‰–5.1‰)close to ferromagnesian chondrules but far more depleted in 16O than CAIs(δ18O=-40‰;δ17O=-40‰).Most ARCs plot close to the terrestrial mass fractionation(TF)line,and a few between the TF and carbonaceous chondrite anhydrous mixing(CCAM)lines.Plagioclase,nepheline and glass suffered O-isotopic exchanges during the metamorphism processes in the parent body.Spinel,olivine and pyroxene represent the primary O-isotopic compositions of ARCs,and define a fitted line with a slope of~0.7±0.1.Compared with the results of previous studies,shallower slope as well as more depleted16O compositions further demonstrates that ARCs in ordinary chondrites are not a simple mixing product of ferromagnesian chondrules and CAIs.Instead,they probably experienced higher-degree oxygen isotope exchange with a 16O-poor nebular gas reservoir during multiple melting episodes.     

Enstatite chondrites and enstatite achondrites (aubrites) were not derived from the same parent body

Enstatite achondrites (aubrites) were not derived from known enstatite chondrites by melting and fractionation on one and the same parent body, for these and other reasons: (1) There is no satisfactory mechanism for fractionating metal plus troilite in enstatite chondrites to form these phases in different proportions and with different Ti contents in aubrites. (2) Many enstatite chondrites and aubrites are regolith or fragmental breccias, but clasts of one within the other have not been found. (3) Cosmic ray exposure ages of the two groups are difficult to explain if they are from the same parent body, but are easy to explain if they are from different parent bodies.Siderophile element abundances in metal from the Mt. Egerton meteorite, which consists of enstatite and metallic Fe,Ni, preclude it from being a complementary differentiate of the aubrites. Rather, it appears that Mt. Egerton was formed from the same source material as enstatite chondrites, but the components were mixed in different proportions.     

Hf–W evidence for rapid differentiation of iron meteorite parent bodies

New, high-precision W isotope data on iron meteorites are presented that provide important constraints on the timing of silicate–metal segregation in planetesimals. Magmatic iron meteorites all have ε¹⁸²W within error or less radiogenic than initial ε¹⁸²W estimated by studies of chondritic meteorites. At face value this implies that iron meteorites are as old and older than refractory calcium–aluminium rich inclusions (CAI), which are widely thought to be the oldest solar system objects. Moreover, different meteorites from the same magmatic groups, believed to be derived from the same planetissimal core, display a range of ε¹⁸²W. We suggest that the paradoxical ε¹⁸²W values more negative than initial Solar System Initial (SSI) are most readily explained as a result of secondary, spallation reactions with cosmic rays during transit between parent body and the earth. This is supported by the most negative ε¹⁸²W being found in meteorites with the oldest exposure ages and the magnitude of the effect is shown to be consistent with known nuclear reactions. On the other hand, it is also striking that none of the magmatic iron group meteorites have ε¹⁸²W analyses, outside error, more radiogenic than the estimated solar system initial ratio. This suggests that core formation in parent bodies of magmatic iron meteorites occurred ≤ 1.5 Myr after the formation age of CAI [Y. Amelin, A.N. Krot, I.D. Hutcheon, and A.A. Ulyanov, Lead isotopic ages of chondrules and calcium-aluminum inclusions, Science 297, 1678–1683, 2002]. This extremely early metal–silicate differentiation is coeval with the first chondrules [M. Bizzarro, J.A. Baker, and H. Haack, Mg isotope evidence for contemporaneous formation of chondrules and refractory inclusions, Nature 431, 275–278, 2004, A.N. Krot, Y. Amelin, P. Cassen, and A. Meibom, Young chondrules in CB chondrites from a giant impact in the early Solar System, Nature 436, 989–992, 2005]. Formation of later chondrules, and hence the parent bodies of some chondritic meteorites, must therefore have occurred in the presence of planetesimals large enough to possess iron cores. We conclude that early planetary accretion and differentiation was sufficiently fast for ²⁶Al-decay to be an important heat source. Non-magmatic iron meteorites, however, display more radiogenic and varied W isotope signatures. This is in keeping with them being generated later, by impact melting during which the metal (partially) re-equilibrated with the then more radiogenic silicate fraction.     

Oxygen isotopic heterogeneities,their petrological correlations,and implications for melt origins of chondrules in unequilibrated ordinary chondrites

Ten whole chondrules separated from the Dhajala (H3, 4), Hallingeberg (L3), and Semarkona (LL3) chondrites were individually analyzed for bulk element composition by instrumental neutron activation with half of each chondrule subsequently sacrificed for oxygen isotopic analysis and half retained for petrographic and electron microprobe analysis. On a three-isotope plot (δ¹⁷O vs. δ¹⁸O), the chondrules neither cluster near their respective chondrite hosts nor in the vicinities of previously recognized chondrite group averages. Instead, they define a trend resolvable into mixing and fractionation components but dominated by mixing in a manner similar to that previously observed for clasts from the LL3 chondrite ALHA76004. Covariations of chondrule isotopic mixing and fractionation parameters with petrological parameters were sought by two-variable linear least-squares regression analyses. However, the only two isotopic/petrological correlations significant at the 95% confidence level were δ¹⁷O vs. total bulk Fe (r = ?0.68) and mixing parameter,m¹⁸, vs. bulk weight ratio (CaO + Al₂O₃)/MgO (r = +0.67). Other correlations of apparent statistical significance were found by treating the chondrules as separate porphyritic (3 porphyritic olivine-pyroxene, 1 porphyritic olivine, 1 barred olivine) and non-porphyritic (4 radial pyroxene, 1 granular pyroxene/cryptocrystalline) textural subgroups. The reliability of the trends, based on so few samples, is not clear but the results at least indicate that possible existence of distinct isotopic/petrological subgroups of chondrules should be further investigated. Absence of certain isotopic/petrological trends expected as condensation effects argues against direct nebular condensation as the dominant process of chondrule formation. Instead, a model involving melting of heterogeneous solids, followed by various degrees of liquid/gas exchange, is favored. In any case, chondrule oxygen isotopic evolution was dominated by two-component mixing; fractional vaporization was, at most, a second-order effect. In addition to chondrules, parent bodies of unequilibrated ordinary chondrites must have also incorporated a¹⁶O-rich component which might have been fine-grained “matrix”.     

Reply to Edward Anders: A discussion of alternative models for explaining the distribution of moderately volatile elements in ordinary chondrites

The high observed abundances of Na and Cu in chondrules indicate that the amount of loss during chondrule formation was minor and possibly negligible, consistent with the view that loss was controlled by diffusion kinetics rather than equilibrium volatility, and that the surface of the chondrule quickly cooled to temperatures at which diffusional transport was negligible. Ordinary chondrite/CI abundance ratios appear to be randomly distributed in the range 0.9-0.1. Very few values are observed in the 0.36–0.70 range, but this is not statistically significant, nor is it predicted by the two-component (chondrule-matrix) model.If CI chondrite abundances are representative of mean solar-system material, the very low chondrule content in CM chondrites (<5% of high-temperature materials) indicates that the observed volatile distribution resulted from incomplete accretion of volatile carriers (perhaps a fine aerosol). At the ordinary chondrite formation location the fraction of an element sited in unaccreted carriers increased with decreasing condensation temperature. At the CM location a similar trend is observed for elements less volatile than S, but the unaccreted fraction of more volatile elements was nearly constant.     

Deuterium in carbonaceous chondrites

Hydrogen isotopic compositions in seven carbonaceous chondrites lie in the range ?70 to +771‰ relative to SMOW. These values decrease, to a range from ?145 to +219‰, after low-temperature oxidation in an oxygen plasma. Deuterium enrichment is therefore concentrated in the organic matter, the hydrous silicates probably lying close to the terrestrial range for such material. Calculated values for δD of the organic fraction are +450 ‰ for Orgueil and Ivuna and up to +1600‰ for Renazzo. These enrichments, at least for Orgueil and Ivuna, suggest equilibration with protosolar hydrogen at very low temperatures. Assuming a value of 2.5 × 10^?5 for the protosolar D/H ratio, nominal equilibration temperatures of 230°K for silicates and 180°K for organic matter may be derived.     

Sm-Nd isotopic evolution of chondrites

The¹⁴³Nd/¹⁴⁴Nd and¹⁴⁷Sm/¹⁴⁴Nd ratios have been measured in five chondrites and the Juvinas achondrite. The range in¹⁴³Nd/¹⁴⁴Nd for the analyzed meteorite samples is 5.3 ε-units (0.511673–0.511944) normalized to¹⁵⁰Nd/¹⁴²Nd= 0.2096. This is correlated with the variation of 4.2% in¹⁴⁷Sm/¹⁴⁴Nd (0.1920–0.2000). Much of this spread is due to small-scale heterogeneities in the chondrites and does not appear to reflect the large-scale volumetric averages. It is shown that none of the samples deviate more than 0.5 ε-units from a 4.6-AE reference isochron and define an initial¹⁴³Nd/¹⁴⁴Nd ratio at 4.6 AE of0.505828 ± 9. Insofar as there is a range of values of¹⁴⁷Sm/¹⁴⁴Nd there is no unique way of picking solar or average chondritic values. From these data we have selected a new set of self-consistent present-day reference values for CHUR (“chondritic uniform reservoir”) of (¹⁴³Nd/¹⁴⁴Nd)_CHUR⁰ = 0.511836and(¹⁴⁷Sm/¹⁴⁴Nd)_CHUR⁰ = 0.1967. The new¹⁴⁷Sm/¹⁴⁴Nd value is 1.6% higher than the previous value assigned to CHUR using the Juvinas data of Lugmair. This will cause a small but significant change in the CHUR evolution curve. Some terrestrial samples of Archean age show clear deviations from the new CHUR curve. If the CHUR curve is representative of undifferentiated mantle then it demonstrates that depleted sources were also tapped early in the Archean. Such a depleted layer may represent the early evolution of the source of present-day mid-ocean ridge basalts. There exists a variety of discrepancies with most earlier meteorite data which includes determination of all Nd isotopes and Sm/Nd ratios. These discrepancies require clarification in order to permit reliable interlaboratory comparisons. The new CHUR curve implies substantial changes in model ages for lunar rocks and thus also in the interpretation of early lunar chronology.     

Natural remanent magnetization of carbonaceous chondrites

We have observed natural remanent magnetizations (NRM), ranging from 10⁻³ to 10⁻⁵ Gauss cm³/g, at least two orders of magnitude greater than 10⁻⁷, the noise level of our spinner magnetometer, in the carbonaceous chondrites, Orgueil, Cold Bokkeveld, Nogoya and Mighei. Preliminary alternating field demagnetization of two samples of Orgueil showed a moderate sized stable component of 10⁻⁴ Gauss cm³/g. Microscopic study reveals that a grey spinel oxide, Ni-Fe and an Fe sulphide are the principal opaque minerals in both Cold Bokkeveld and Orgueil; the oxide phase predominates in both, while the Ni-Fe is more visible in the former. Coercive force determinations in Orgueil and Cold Bokkeveld indicate single domain particles as the NRM carrier. These meteorites are suitable for the determination of the magnetic field intensity in the primary solar nebula.     

Fine-grained aggregates in L3 chondrites

The textures and chemical compositions of the constituent minerals of the fine-grained aggregates (FGA's) of L3 chondrites were studied by the backscattered electron image technique, electron probe microanalysis, and transmission electron microscopy. Plagioclase and glass in the interstices between fine grains of olivine and pyroxene indicate that the FGA's once partly melted. Compositional zoning and decomposition texture of pyroxenes are similar to those observed in chondrules, indicating a common cooling history of the FGA's and chondrules. Therefore, the mechanism that caused melting of the FGA's is considered to be the same as for chondrules. Bulk compositions of the FGA's are within the range of those of chondrules, so some chondrules probably were produced by complete melting of the same precursor materials as those of the FGA's. The precursor materials must have included fine olivine and other grains that probably are condensates.     

Consequences of explosive eruptions on small Solar System bodies: the case of the missing basalts on the aubrite parent body

Aubrite meteorites are composed of constituents which are almost certainly of igneous origin. If they were generated by the melting and fractionation of enstatite chondrite-like parental material, as seems very likely, then plagioclase-rich, basaltic complements to the aubrites should have formed. However, such materials are not known as individual meteorites, and the compositions of two plagioclase-silica clasts and one albite-silica-(diopside-anorthite) clast (probably an impact melt) in the Norton County aubrite breccia suggest that they are not the putative enstatite-plagioclase basalts. We propose a new mechanism that explains the absence of these materials, showing that the expansion of even very small amounts of volatiles present in a melt approaching the surface of a small, low-gravity body will be enough to disrupt the melt into a spray of droplets moving faster than the local escape velocity. This explosive volcanic process of melt removal requires larger melt volatile contents on larger bodies, and data on the solubility of volatiles in basaltic melts suggest that the process was limited to bodies smaller than about 100 km in radius.