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.     

Trace elements in primitive meteorites—VII Antarctic unequilibrated ordinary chondrites

We report RNAA results for Co, Au, Sb, Ga, Rb, Cs, Se, Ag, Te, Zn, In, Bi, Tl and Cd (in increasing order of metamorphic mobility) in 22 Antarctic unequilibrated ordinary chondrites (UOC). This brings to 38 the number of UOC for which data for highly volatile elements are known. For elements of lesser mobility (Co to Se, omitting Cs) overall variability in UOC are low, relative standard deviations (one sigma) being no more than a factor of two. For Ag, Te and Zn, relative standard deviations are 2-4×, while for Cs and the four most volatile elements, the variabilities are 8-110×. Elemental abundances do not vary with chemical type (H, L and LL) nor with UOC subtype (3.0-3.9). Contents of all elements reach levels up to, even exceeding, cosmic and all but Cd and the two alkalis, seem unaffected by post-accretionary processes. Contents of highly volatile elements are consistent with the idea that source regions producing contemporary falls and older Antarctic UOC differed in thermal histories. The presence or absence of carbide magnetite assemblages (CMA) generally accords with high or low Cd contents, respectively. This relationship accords with the prior suggestion that CMA formed by alteration of Fe-Ni metal by C-O-H-containing fluids at temperatures <700 K, generated by thermal metamorphism in parent body interiors. The absence of CMA in most UOC (and OC), may indicate that they were subsequently destroyed as metamorphic intensity increased. The high, often supercosmic, Rb and Cs levels in UOC may result from their high solubility in liquid water signalling their redistribution by C-O-H-containing fluid while in the liquid water field. Because of its uniquely high mobility, Cd could have been enriched by the C-O-H fluids and should have been lost from parent regions during later, higher temperature anhydrous metamorphism at temperatures in the 500-600 °C range.     

The matrices of unequilibrated ordinary chondrites: Implications for the origin and history of chondrites

The matrices of sixteen unequilibrated ordinary chondrites (all witnessed falls) were studied microscopically in transmitted and reflected light and analyzed by electron microprobe. Selected specimens were also studied by scanning electron microscopy. These studies indicate that the fine-grained, opaque, silicate matrix of type 3 unequilibrated chondrites is compositionally, mineralogically and texturally distinct from the chondrules and chondrule fragments and may be the low temperature condensate proposed by Larimer and Anders (1967, 1970). Examination of the matrices of unequilibrated chondrites also shows that each meteorite has been metamorphosed, with the alteration ranging in intensity from quite mild, where the matrix has been only slightly altered, to a more severe metamorphism that has completely recrystallized the opaque matrix. Most of the metamorphic changes in the matrix occurred without significant effects on the compositions or textures of the chondrules. The metamorphic alteration probably resulted from a combination of processes including thermal metamorphism and the passage of shock waves. The present appearance of each unequilibrated chondrite is a result of the particular temperature and pressure conditions under which it and its components formed, plus the subsequent metamorphic alteration it experienced.     

Abundance patterns of thirteen trace elements in primitive carbonaceous and unequilibrated ordinary chondrites

A neutron activation analysis technique was used to determine Au, Re, Co, Mo, As, Sb, Ga, Se, Te, Hg, Zn, Bi and Tl in 11 carbonaceous chondrites, 12 unequilibrated ordinary chondrites (UOC), and 4 equilibrated ordinary chondrites. The first 6 elements are ‘undepleted’, the next 3 ‘normally-depleted’ and the last 4 ‘strongly-depleted’. Except for Hg, ‘depleted-element’ abundances in carbonaceous chondrites lead to mean relative ratios of C1:C2:C3 = 1.00:0.53:0.29, i.e. those predicted by a two-component (mixing of high-temperature and low-temperature fractions) model. The last 4 nominally ‘undepleted’ elements are somewhat depleted in ordinary chondrites, As and Sb showing partial depletion in C3 and the latter in C2 chondrites as well. This requires a modification of the two-component model to indicate that deposition of elements during condensation of high temperature material was not an all-or-nothing process.Apart from Bi and Tl, the elements studied have similar abundances in unequilibrated and equilibrated ordinary chondrites and only the former are unquestionably correlated with the degree of disequilibrium in silicate minerals. Only some ‘strongly-depleted’ elements exhibit at least one of the following—proportional depletion in UOC, progressive depletion in petrographic grades 3–6 ordinary chondrites and enrichment in the gas-containing dark portion of gas-rich, light-dark meteorites—indicating that such depletion does not ensure that an element will exhibit these trends. Partly or completely siderophile As, Au, Co, Ga, Mo, Re and Sb vary with chemical type in the same manner in both unequilibrated and equilibrated ordinary chondrites and doubtless reflect a process involving fractionation of metallic iron.     

Compositions and textures of relic forsterite in carbonaceous and unequilibrated ordinary chondrites

Several percent of the olivine in the C2, C3 and unequilibrated ordinary chondrites (UOC) can be distinguished by blue cathodoluminescence (CL) and an unusual composition for forsterite. This olivine has the following textural features:

• 1.(1) forms cores in single olivine grains;
• 2.(2) shows subhedral to euhedral boundaries against rim olivine;
• 3.(3) rarely contains inclusions;
• 4.(4) has embayments containing olivine like that of the rim;
• 5.(5) occurs within chondrules especially in UOC meteorites.

The blue olivine is always Fe-poor (0.25 < FeO < 1.0%) and shows the following average and maximum values (%): Al₂O₃ (0.25, 0.5), TiO₂ (0.05, 0.09), CaO (0.5, 0.8), Cr₂O₃ (0.15, 0.5), and MnO (0.02, 0.15); vanadium is present. Within a single olivine and within all blue olivines Al, Ca and Ti are strongly positively correlated as are Mn, Fe, and Cr in olivine surrounding the blue. The blue cores are not zoned but each element shows a marked change at the boundary of the blue with Al showing the most rapid change. These are interpreted as diffusion profiles between rim and core olivine.Textures suggest initial free growth probably from a gas and later addition of olivine by liquid crystallization to form single crystals or chondrules. The unusual olivine composition indicates high temperature growth from a refractory-rich reservoir with Al entering olivine in tetrahedral coordination. Vapor growth is suggested as the process allowing the high minor element levels. The occurrence of blue olivine in all primitive meteorites indicates that it is relic material which was widespread prior to chondrule and hence meteorite formation. Similarities in composition exist between this relic olivine and olivine of cosmic dust and Deep Sea Particles pointing to this olivine being a common component in all primitive extraterrestrial material.     

Inter-element relationships between trace elements in primitive carbonaceous and unequilibrated ordinary chondrites

The results of a search for significant (95 % confidence level) inter-element relationships among 13 trace elements in carbonaceous chondrites and 26 elements and the disequilibrium parameter for silicate phases in unequilibrated ordinary chondrites (UOC) indicate pronounced differences in the formation processes of these two sorts of primitive chondrites. Twenty-six pairs of elements are correlated in carbonaceous chondrites and these correlations lend support to a model involving mixing in different ratios of material differing in thermal history.Comparison of the 26 elements in UOC shows that 39 pairs of elements are significantly related and only very volatile elements are correlated with the disequilibrium parameter. Each of the inter-element relationships can be specifically ascribed to a metal-silicate fractionation in the solar nebula or to a thermal fractionation. These relationships are about equally consistent with the metamorphism, two-component condensation and simultaneous accretion-condensation models for the origin, of the ordinary chondrites, each requiring adoption of specific ad hoc assumptions for complete consistency.     

On the nature and origin of isolated olivine grains in carbonaceous chondrites

Many carbonaceous chondrites contain discrete olivine fragments that have been considered to be primitive material, i.e. direct condensates from the solar nebula or pre-solar system material. Olivine occurring in chondrules and as isolated grains in C3(0) chondrites has been characterized chemically and petrographically. Type I chondrules contain homogeneous forsterite grains that exhibit a negative correlation between FeO and CaO. Type II chondrules contain zoned fayalite olivines in which FeO is positively correlated with CaO and MnO. The isolated olivines in C3(0) chondrites form two compositional populations identical to olivines in the two types of porphyritic olivine chondrules in the same meteorites. Isolated olivines contain trapped melt inclusions similar in composition to glassy mesostasis between olivines in chondrules. Such glasses can be produced by fractional crystallization of olivine and minor spinel in the parent chondrule melts if plagioclase does not nucleate. The isolated olivine grains are apparently clastic fragments of chondrules. Some similarities between olivines in C3(0), C2, and Cl chondrites may suggest that olivine grains in all these meteorites crystallized from chondrule melts.     

A study of chondrule rims and chondrule irradiation records in unequilibrated ordinary chondrites

In order to investigate the possibility that chondrules may have had an independent existence in space, we have searched for unusual nuclear track densities in chondrules and studied the compositions of chondrule rims on chondrules from thirteen unequilibrated ordinary chondrites. Our search for unusual radiation features has been negative. Observed track densities can be explained in terms of cosmic ray exposure ages of the respective meteorites. Fine-grained rims that surround chondrules in unequilibrated ordinary chondrites are heterogeneous in composition consisting of varying proportions of iron sulfide and a poorly characterized silicate phase. The latter phase or phases are roughly chondritic in composition. Fine-grained rims of the kind seen in primitive type 3 ordinary chondrites are absent in higher petrographie grades; more crystalline, coarse-grained and lacy sulfide rims, however, are observed. Our observations can be explained by chondrules having had an independent existence in space during which they acquired rims either by condensation on their surfaces or by accretion of fine particles. However, accumulation of rims while chondrules resided on a meteorite parent body cannot be ruled out at this time. In any case, we do not propose that the chondrules themselves formed by condensation. Absence of a track record of space exposure of chondrules could be due to shielding by matter in space if, for example, chondrules were present in space in clouds made of dust, gas and/or chondrules.     

The metal phase in unequilibrated ordinary chondrites and its implications for calculated accretion temperatures

The abundance, composition and grain size of the metal available to volatile siderophile elements strongly affect the condensation of these elements. These parameters are redefined on the basis of published chemical analyses and new mechanical analyses of the unequilibrated ordinary chondrites. The results suggest that previous workers have seriously overestimated the amount of metal present and available during condensation, and seriously underestimated the heat of solution of Bi in chondritic metal. Correction of these parameters results in nominal accretion temperatures for Bi which are substantially (95–110°K) lower than those calculated earlier, and which are discordant with the temperatures inferred for chalcophile trace elements.     

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.     

Crystallization of chondrules in ordinary chondrites

The process of crystallization and the origin of chondrules are discussed, in terms of the phase relations of the minerals in chondrules in six ordinary chondrites of the Yamato-74 meteorites, especially the Yamato-74191 (L3).Chondrules are classified into six types. The bulk compositions of chondrules projected onto the MgO-FeO-SiO₂ system show that the compositions of chondrules vary widely. Investigations by means of the MgO-Al₂O₃-SiO₂ system indicate that porphyritic chondrules can be regarded as products of supercooling crystallization. The growth rates of crystals in porphyritic chondrules were fairly small. The difference between types of chondrules is interpreted in terms of the compositions of chondrules and the nucleation temperatures of the supercooled droplets.All these observations and estimations must be taken into account for discussing the origin of chondrules. The impact and dust fusion theories do not appear to be plausible. Molten droplets due to these mechanisms will be glassy spherules, or crystallize at equilibrium. Only a liquid condensation theory can well explain the characteristic features and the process of the crystallization of chondrules.     

Trace elements in primitive meteorites—VI. Abundance patterns of thirteen trace elements and interelement relationships in unequilibrated ordinary chondrites

Neutron activation analysis was used to determine As, Au, Bi, Cd, Co, Cu, Ga, In, Sb, Se, Te, Tl and Zn in 13 different unequilibrated ordinary chondrites (UOC), i.e. those having chemicallyinhomogeneous silicates. This study together with prior data completes our coverage of this group of 23 primitive chondrites. Four elements are quite variable in UOC (Cd—20 x, In—30 x, Bi—300 x and Tl—1300 x), the others varying by 2–8 x. Three highly-depleted elements—Bi, In and Tl—are richer by 5–35 x in unequilibrated chondrites than in their equilibrated congeners. All 3 elements vary directly in characteristic fashion with disequilibrium parameters for olivine and pyroxene in UOC and generally with petrologic type 3 > 4 > 5 > 6. The data do not provide unambiguous evidence for nebular fractionation of siderophile elements. Examination of statistically-significant interelement relationships among various ordinary chondrite populations involving 34 elements reveals patterns distinct from those of other chondritic groups. These patterns reflect nebular metal-silicate fractionation which preceded or accompanied thermal fractionation. The results point to significant differences in the formation of primitive carbonaceous, enstatite and ordinary chondrites.     

Metal and associated phases in Bishunpur,a highly unequilibrated ordinary chondrite

It appears that the highly unequilibrated Bishunpur ordinary chondrite preserves phase relations acquired during solar nebular processes to a relatively high degree; metamorphic temperatures may not have exceeded 300–350°C. The major categories of metal are: 3 kinds of metal in the metal matrix, three kinds in chondrule interiors and 2 kinds in chondrule rims. The fine-grained matrix metal is highly variable in composition: the kamacite Co content (7.8 ± 2.0 mg/g) is within the L-group range (6.7–8.2 mg/g) but extends well above and below; its Ni content (38 ± 5 mg/g) is considerably lower than in more equilibrated chondrites and taenite is Ni-rich ( > 450 mg/g) and unzoned. These compositions imply equilibration at very low temperatures of about 300–350°C. It seems unlikely that volume diffusion could account for the observed relatively unzoned phases; a better model involves mass transport by grain boundary diffusion and grain growth at the indicated temperatures. We find no evidence that the matrix was ever at higher temperatures. Large (50–650 μm) polycrystalline metal aggregates consisting of individually zoned crystals are also found in the matrix; they probably represent clusters formed in the solar nebula. A few large (50–250 μm) round monocrystalline grains are also present in the matrix.Metal-bearing chondrules tend to be highly reduced; they contain low-Ni metal that occasionally contains Si and/or Cr. Silicates in these chondrules tend to have low $\text{FeO}\text{(FeO + MgO)}$ ratios. The Si-rich metal grains are never in contact with silicates and are always surrounded by troilite with a poorly characterized Ca, Cr-sulfide at the metal-troilite interface; they appear to be high temperature nebular condensates that avoided oxidation even during the chondrule forming process. Silicon contents drop below our detection limit when the sulfide coating is absent. Much more common in chondrule interiors are Si-free spheroidal metal grains not associated with sulfides. These have Ni and Co contents very similar to the Si-bearing grains, and appear to be oxidized variants of the same material. The third class of chondrule metal is fine ( ~1 μm) dusty grains inside individual olivine grains. These seem to reflect high temperature in situ reduction of FeO from the olivine.The composition of kamacite is different in sulfide-rich and sulfide-poor chondrule rims and in both cases it is dissimilar to the compositions in the chondrule interiors and matrix; this indicates that chondrule rims could not have resulted from reactions with the matrix, but are primary features acquired prior to accretton.     

The formation of clear taenite in ordinary chondrites

The metallic phases in six bronzite and six hypersthene chondrites were studied metallographically and by electron microprobe. All of the chondrites studied contain zoned taenite. In bronzite chondrites, only about 5 per cent of the zoned taenite abuts on kamacite (the rest being apparently isolated from it) whereas in hypersthene chondrites an average of over 20 per cent abuts on kamacite. The compositions of the centers of zoned taenite can be used to obtain cooling rates by Wood's method. Including Wood's results, 14 out of 18 ordinary chondrites have cooling rates between 1 and 10°C/m.y.     

An Fe isotope study of ordinary chondrites

The Fe isotope composition of ordinary chondrites and their constituent chondrules, metal and sulphide grains have been systematically investigated. Bulk chondrites fall within a restricted isotopic range of <0.2‰ δ⁵⁶Fe, and chondrules define a larger range of >1‰ (−0.84‰ to 0.21‰ relative to the IRMM-14 Fe standard). Fe isotope compositions do not vary systematically with the very large differences in total Fe concentration, or oxidation state, of the H, L, and LL chondrite classes. Similarly, the Fe isotope compositions of chondrules do not appear to be determined by the H, L or LL classification of their host chondrite. This may support an origin of the three ordinary chondrite groups from variable accretion of identical Fe-bearing precursors.A close relationship between isotopic composition and redistribution of Fe during metamorphism on ordinary chondrite parent bodies was identified; the largest variations in chondrule compositions were found in chondrites of the lowest petrologic types. The clear link between element redistribution and isotopic composition has implications for many other non-traditional isotope systems (e.g. Mg, Si, Ca, Cr). Isotopic compositions of chondrules may also be determined by their melting history; porphyritic chondrules exhibit a wide range in isotope compositions whereas barred olivine and radial pyroxene chondrules are generally isotopically heavier than the ordinary chondrite mean. Very large chondrules preserve the greatest heterogeneity of Fe isotopes.The mean Fe isotope composition of bulk ordinary chondrites was found to be −0.06‰ (±0.12‰ 2 SD); this is isotopically lighter than the terrestrial mean composition and all other published non-chondritic meteorite suites e.g. lunar and Martian samples, eucrites, pallasites, and irons. Ordinary chondrites, though the most common meteorites found on Earth today, were not the sole building blocks of the terrestrial planets.     

Elemental composition of individual chondrules from ordinary chondrites

Sequential non-destructive neutron activation analysis was used to determine the bulk abundance of Fe, Al, Na, Mn, Or, Sc, Co and Ir in approximately 300 individual chondrules from 16 chondrites representing the H (3–5), L4 and LL(3–6) compositional and petrologic classes. For some of the chondrules, Si, Ni, Ca and V were also determined. The histograms indicate that the most probable abundances for lithophilic elements, except Cr, are enriched in the chondrules, while the siderophilic elements are depleted in the chondrules compared to the whole chondrite. Some of the abundance populations, such as Al and Fe, appear to be multimodal. Systematic variations in the composition of the chondrules with increasing petrologic type were observed; most consistent are an increasing Na-Al and Cr-Al correlation, a decreasing Na-Mn correlation, increasing Na abundance and decreasing Na and Mn dispersions among chondrules. The systematic compositional variations with increasing petrologic type are consistent with an increasing approach to equilibrium between chondrules and matrix.Observed elemental correlations are generally consistent with mineralogical controls expected on the basis of geochemical affinities suggested by the mineral assemblages present in the chondrules. However, a prevalent Al-Ir correlation was observed, and is most pronounced for a group of chondrules belonging to a population high in Al. A Sc-Ir correlation was observed. Also, an anti-correlation between chondrule masses and Al (and Ir for some chondrules) content of the chondrules was observed. These correlations are attributed to a fractionation during condensation or chondrule formation and cannot be attributed to classical geochemical similarities i.e. these correlations result from a cosmochemical fractionation. From the compositional evidence, it is suggested that there may be two mechanisms for chondrule production. Some high Al chondrules which exhibit the Al-Ir correlation are believed to be remelted primitive high-temperature aggregates. The elemental composition of the chondrules from the lower Al abundance population is consistent with a preferential remelting of pre-existing silicates.