Elemental composition of individual chondrules from carbonaceous chondrites,including Allende

Major and trace element analyses of over 180 individual chondrules from 12 carbonaceous chondrites are reported, including individual analyses of 60 chondrules from Pueblito de Allende. Siderophile elements in most chondrules are depleted, compared to the whole chondrite. Correlations of Al-Ir and Ir-Sc among chondrules high in Ca and Al were observed. A Cu-Mn correlation was also found for chondrules from some meteorites. No correlation was observed between Au and other siderophile elements (Fe, Ni, Co and Ir). It is suggested that these elemental associations were present in the material from which the chondrules formed. Compositionally, chondrules appear to be a multicomponent mixture of remelted dust. One component displaying an Al-Ir correlation is identified as Allende-type white aggregates. The other components are a material chemically similar to the present matrix and sulfides-plus-metal material. Abundances of the REE (rare earth elements) were measured in ‘ordinary’ Allende chondrules and were 50% higher than REE abundances in Mokoia chondrules; REE abundances in Ca-Al rich chondrules were similar to REE abundances in Ca-rich white aggregates.     

Relationships among intrinsic properties of ordinary chondrites: Oxidation state, bulk chemistry, oxygen-isotopic composition, petrologic type, and chondrule size

The properties of ordinary chondrites (OC) reflect both nebular and asteroidal processes. OC are modeled here as having acquired nebular water, probably contained within phyllosilicates, during agglomeration. This component had high Δ¹⁷O and acted like an oxidizing agent during thermal metamorphism. The nebular origin of this component is consistent with negative correlations in H, L, and LL chondrites between oxidation state (represented by olivine Fa) and bulk concentration ratios of elements involved in the metal-silicate fractionation (e.g., Ni/Si, Ir/Si, Ir/Mn, Ir/Cr, Ir/Mg, Ni/Mg, As/Mg, Ga/Mg). LL chondrites acquired the greatest abundance of phyllosilicates with high Δ¹⁷O among OC (and thus became the most oxidized group and the one with the heaviest O isotopes); H chondrites acquired the lowest abundance, becoming the most reduced OC group with the lightest O isotopes.Chondrule precursors may have grown larger and more ferroan with time in each OC agglomeration zone. Nebular turbulence may have controlled the sizes of chondrule precursors. H-chondrite chondrules (which are the smallest among OC) formed from the smallest precursors. In each OC region, low-FeO chondrules formed before high-FeO chondrules during repeated episodes of chondrule formation.During thermal metamorphism, phyllosilicates were dehydrated; the liberated water oxidized metallic Fe-Ni. This caused correlated changes with petrologic type including decreases in the modal abundance of metal, increases in olivine Fa and low-Ca pyroxene Fs, increases in the olivine/pyroxene ratio, and increases in the kamacite Co and Ni contents. As water (with its heavy O isotopes) was lost during metamorphism, inverse correlations between bulk δ¹⁸O and bulk δ¹⁷O with petrologic type were produced.The H5 chondrites that were ejected from their parent body ∼7.5 Ma ago during a major impact event probably had been within a few kilometers of each other since they accreted ∼4.5 Ga ago. There are significant differences in the olivine compositional distributions among these rocks; these reflect stochastic nebular sampling of the oxidant (i.e., phyllosilicates with high Δ¹⁷O) on a 0.1-1 km scale during agglomeration.     

Metamorphism of the H-group chondrites: implications from compositional and textural trends in chondrules

Major and minor element bulk compositions of 373 individual chondrules from 18 H3 to H6 chondrites were determined in polished thin sections by broad-beam electron probe analysis. Bulk chondrule FeO and Al₂O₃ increase and TiO₂ and Cr₂O₃ decrease with increasing petrologic type; normative fayalite, albite and plagioclase increase through the petrologic sequence. Chondrule diameters correlate with phenocryst sizes in porphyritic chondrules of type 3 chondrites, but this correlation is diminished in the higher petrologic types. Furthermore, for a given chondrule diameter, phenocryst sizes are larger in the higher petrologic types. We attribute most compositional trends in chondrules through the petrologic sequence to diffusion and equilibration among chondrules and between chondrules and matrix in response to increasing degrees of thermal metamorphism. Increased phenocryst sizes in the higher petrologic types are probably the result of grain growth during metamorphism.We suggest that H-group chondrites formed by accretion of high-temperature (chondrules) and low-temperature (matrix) materials. Parent materials of each of the petrologic types resembled type 3 chondrites, but had slight compositional differences (e.g. volatiles, rare gases, total iron) inherited during accretion. These differences were predominantly functions of decreasing temperature in the nebula as accretion progressed. Internal reheating of the parent materials to different temperatures and (probably) for different times, as a function of depth in the parent body, caused compositional equilibration, grain coarsening, and reduction of FeO to Fe° by carbon.     

Experimental study of evaporation and isotopic mass fractionation of potassium in silicate melts

The behavior of Na and K during evaporation from chondrule composition melts was studied using a vacuum furnace. Though Na is the less volatile of the two as an element, it is lost more rapidly than K from silicate melts. Mass fractionation of K isotopes was measured by ion microprobe and Rayleigh fractionation is observed for vacuum evaporation (10⁻⁵ atm). With higher pressures of air, the K loss rate decreases but with increasing hydrogen pressure, K is lost more rapidly. δ⁴¹K decreases with higher pressures, because of back reaction between melt and K in the gas. With long heating duration, the release of light K condensed within the furnace leads to interaction with the K-depleted melt and a further reduction of δ⁴¹K. Natural chondrules differ in some ways from our experimental residues. Some (especially type IIA) have superchondritic Na and K, despite their assumed formation in nebular hydrogen, which enhances volatile loss, and chondrules do not show K isotopic fractionation. Type I chondrules in Semarkona (LL3.0) either plot on our evaporation trend, or are depleted in K but slightly enriched in Na, relative to K. In Bishunpur (LL3.1), type I chondrules are mostly K-depleted but moderately to strongly enriched in Na. In petrologic type 3.2 to 3.4 chondrites they are enriched in both K and Na, like type II chondrules. The alkali contents suggest type I chondrules experienced evaporation and subsequent metasomatism. Their normal δ⁴¹K values suggest closed-system evaporation of a chondritic precursor in a gas with relatively high K pressures due to vaporization of dust accompanying chondrule precursor aggregates. Type II chondrules are volatile-rich, as well as unfractionated in K isotopes. They probably formed in a gas with higher pK than in the case of type I chondrules, due to heating of a more dust-rich parcel of gas.     

Formation processes of compound chondrules in CV3 carbonaceous chondrites: Constraints from oxygen isotope ratios and major element concentrations

We found thirty compound chondrules in two CV3 carbonaceous chondrites. The abundance in each meteorite relative to single chondrules is 29/1846 (1.6%) in Allende and 1/230 (0.4%) in Axtell. We examined petrologic features, major element concentrations and oxygen isotopic compositions. Textural, compositional and isotopic evidence suggests that multiple, different mechanisms are responsible for the formation of compound chondrules.Seven compound chondrules are composed of two conjoined porphyritic chondrules with a blurred boundary. At the boundary region of this type of compounds, a poikilitic texture is commonly observed. This suggests that the two chondrules were melted when they came to be in contact. On the other hand, seventeen compound chondrules consist of two conjoined chondrules with a discrete boundary. The preservation of spherical boundary planes of an earlier-formed chondrule of this type implies that it already solidified before fusing with a later-formed chondrule that was still melted. Six samples out of 17 compound chondrules of this type are composed of two BO chondrules. The BO-BO compound chondrules have a unique textural feature in common: the directions of the barred olivines are mostly parallel between two chondrules. This cannot be explained by a simple collision process and forces another mechanism to be taken into consideration.The remaining six compound chondrules differ from the others; they consist of an earlier-formed chondrule enclosed by a later-formed chondrule. A large FeO enrichment was observed in the later-formed chondrules and the enrichment was much greater than that in the later-formed chondrules of other types of compounds. This is consistent with the relict chondrule model, which envisages that the later-formed chondrule was made by a flash melting of a porous FeO-rich dust clump on an earlier-formed chondrule. The textural evidence of this type of compound shows that the earlier-formed chondrule has melted again to varying degrees at the second heating event. This implies that FeO concentrations in bulk chondrules increases during the second heating event if an earlier-formed chondrule was totally melted together with the FeO-rich dust aggregates.Silicate minerals such as olivine and low-Ca pyroxene in compound chondrules have oxygen isotope compositions similar to those in single chondrules from CV3 chondrites. The oxygen isotope composition of each part of the compound chondrule is basically similar to their chondrule pair, but silicates in some chondrules show varying degrees of ¹⁶O-enrichment down to −15‰ in δ¹⁸O, while those in their partners have ¹⁶O-poor invariable compositions near 0 ‰ in δ¹⁸O. This implies that the two chondrules in individual compounds formed in the same environments before they became conjoined and the heterogeneous oxygen isotope compositions in some chondrules resulted from incomplete exchange of oxygen atoms between ¹⁶O-rich chondrule melts and ¹⁶O-poor nebular gas.     

Chemistry, petrology and bulk oxygen isotope compositions of chondrules from the Mokoia CV3 carbonaceous chondrite

We report bulk chemical compositions and physical properties for a suite of 94 objects, mostly chondrules, separated from the Mokoia CV3_ox carbonaceous chondrite. We also describe mineralogical and petrologic information for a selected subset of the same suite of chondrules. The data are used to examine the range of chondrule bulk compositions, and to investigate the relationships between chondrule mineralogy, texture and bulk compositions, as well as oxygen isotopic properties that we reported previously. Most of the chondrules show minimal metamorphism, corresponding to petrologic subtype <3.2. In general, elemental fractionations observed in chondrule bulk compositions are reflected in the compositions of constituent minerals. For chondrules, mean bulk compositions and compositional ranges are very similar for large (>2 mg) and small (<2 mg) size fractions. Two of the objects studied are described as matrix-rich clasts. These have similar bulk compositions to the chondrule mean, and are potential chondrule precursors. One of these clasts has a similar bulk oxygen isotopic composition to Mokoia chondrules, but the other has an anomalously high value of Δ¹⁷O (+3.60‰).Chondrules are diverse in bulk chemical composition, with factor of 10 variations in most major element abundances that cannot be attributed to secondary processes. The chondrules examined show evidence for extensive secondary oxidation, and possible sulfidization, as expected for an oxidized CV chondrite, but minimal aqueous alteration. Some of the bulk chondrule compositional variation might be the result of chemical (e.g. volatilization or condensation) or physical (e.g. metal loss) processes during chondrule formation. However, we suggest that it is mainly the result of significant variations in the assembly of particles that constituted chondrule precursors. Precursor material likely included a refractory component, possibly inherited from disaggregated CAIs, an FeO-poor ferromagnesian component such as olivine or pyroxene, an oxidized ferromagnesian component, and a metal component. Bulk oxygen isotope ratios of chondrules can be explained if refractory and ferromagnesian precursor materials initially shared similar oxygen isotopic compositions of δ¹⁷O, δ¹⁸O around −50‰, and then significant exchange occurred between the chondrule and surrounding ¹⁶O-poor gas during melting.     

Refractory precursor components of Semarkona chondrules and the fractionation of refractory elements among chondrites

Chondrules from the Semarkona (LL3.0) chondrite show refractory and common lithophile fractionation trends similar to those observed among the chondrite groups. It appears that chondrules are mixtures of a small number of pre-existing solid components, and we infer that chondrule precursor materials were related to the nebular components involved in the lithophile element fractionations recognized in ordinary chondrites. Compositional trends among the chondrules can be used to deduce the compositions of these components.We use instrumental neutron activation analysis to measure many (~20) of the lithophile elements in 30 chondrules. The amounts of oxidized iron were calculated from other compositional parameters; concentrations of Si were estimated using mass-balance considerations. The data were corrected for the diluting effects of non-lithophile constituents. Plots of lithophile elements versus a reference refractory element such as Al show that there were two major chondrule silicate precursor components: a refractory, olivine-rich, FeO-free one, and a non-refractory, SiO₂-, FeO-rich one.The refractory component probably forms from olivine-enriched condensates formed above the condensation temperature of enstatite. The non-refractory component must have formed from fine-grained materials that were able to equilibrate down to lower nebular temperatures. Chondrite matrix may have had an origin similar to that of the non-refractory material, and constitutes a third lithophile-bearing component that took part in chondrite fractionation processes. The low abundance of refractories and Mg in ordinary and enstatite chondrites was produced by the loss of materials having a higher refractory-element/Mg ratio than that in the refractory component of chondrules.     

Spinel group minerals in LL3.00-6 chondrites: Indicators of nebular and parent body processes

We carried out a systematic study of spinel group minerals in LL3.00-3.9 and LL4-6 chondrites. With increasing petrologic type, the size and abundance of spinel increase. The compositions of spinel group minerals in type 3 chondrites depend on the occurrence; Mg-Al-rich spinel occurs mainly in chondrules. Some chromite occurs in chondrules and matrix, and nearly pure chromite is exclusively encountered in the matrix. The occurrence of nearly pure chromite and the wide compositional variations distinguish spinel group minerals in types 3.00-3.3 from those in the other types. Spinel group minerals in types 3.5-3.9 show a narrower range of compositions, and those in types 4-6 are homogeneous. The changes in composition and abundance of spinel in type 3 chondrites are most likely due to thermal metamorphism. Therefore, the chemistry of spinel group minerals could be used as a sensitive indicator of metamorphic conditions, not only for type 3-6, but also 3.00-3.9. They can be applied to identify the most primitive (least metamorphosed) chondrites. The bulk compositions of spinel-bearing chondrules and the textural setting of the spinel indicate that most spinel group minerals crystallized directly from chondrule melts. However, some spinel grains, especially those enclosed in olivine phenocrysts, can not be explained by in situ crystallization in the chondrule. We interpret these spinel grains to be relic phases that survived chondrule melting. This is supported by the oxygen isotopic composition of a spinel grain, which has significantly lighter oxygen than the coexisting olivine. The oxygen isotopic composition of this spinel is similar to those of Al-rich chondrules. Our discovery of relic spinel in chondrules is an indication of the complexities in the early solar nebular processes that ranged from formation of refractory inclusion, through Al-rich chondrule, to ferromagnesian chondrules, and attests to the recycling of earlier formed materials into the precursors of later formed materials. The characteristic features of spinel group minerals are not only sensitive to thermal metamorphism, but also shed light on chondrule formation processes.     

Metal in CR chondrites

In section many low-FeO CR chondrules are surrounded by rings of metal; this metal-cladding seems to have formed during chondrule melting events as films of metal that wetted the surface. Electron microprobe studies show that in each ring the metal is very uniform in composition, consistent with efficient mixing during formation of the metal film. In contrast the mean Ni contents of 13 different rings vary by up to a factor of 2. There is no FeS associated with ring metal. Ring metal Co is positively correlated with Ni but the Co/Ni ratio seems to decrease with increasing Ni. We observed a weak negative correlation between ring metal Ni and the fayalite content of the host olivine. Coarse interior metal has higher Ni contents than that in the surrounding rings. At any specific chondrule location, smaller grains tend to have lower Ni contents than larger grains. These trends in Ni seem to reflect two processes: (1) The mean Ni content of metal (and easily reduced sulfides or oxides) in chondrule precursor materials seems to have decreased with the passage of time; on average, the metal in earlier-formed chondrules had higher Ni contents than the metal in later-formed chondrules. (2) Some oxidized Fe was reduced during chondrule formation leading to lower Ni contents in small grains compared to large grains; prior to reduction the Fe was in FeS or in FeO in accessible (fine-grained) sites. We suggest that the compositional evolution of nebular solids was responsible for the interchondrule variations whereas reduction of minor amounts of FeS or FeO was responsible for the size-related small variations in Ni content. We suggest that, during chondrule formation events, CR chondrules experienced relatively long thermal pulses that were responsible for the thorough loss of FeS and the common granoblastic texture observed in low-FeO chondrules. The preservation of the structures of internal rings shows, however, that even though high temperatures occurred in the secondary chondrule, temperatures in the centers of large (>20 μm) metal and silicate grains in the primary chondrule did not get high enough to cause appreciable melting.     

普通球粒陨石的物理和岩石学性质及其分类参数

不同球粒陨石群的物理和岩石学性质,包括球粒的平均大小、球粒结构类型、复合球粒、带火成边球粒及含硫化物的比例、化学组成及矿物学特征等可用以划分球粒陨石的化学-岩石类型和小行星类型,这些性质提供了不同球粒陨石群有用的分类参数及其形成环境的信息.由于不同球粒陨石群的△17O与日心距离存在有相关关系,因此,依据不同球粒陨石群形...     

The origin and history of the metal and sulfide components of chondrules

Fourteen siderophile and other non-lithophile elements determined in 31 Semarkona (LL3.0) chondrules by neutron activation analysis are severely fractionated relative to lithophile elements. Their chondrule/whole-rock abundance ratios vary by factors of up to 1000; the mean ratio is ~0.2. Non-refractory siderophile abundance patterns in Ni-rich chondrules are smooth functions of volatility and in Ni-poor chondrules patterns are more irregular. Refractory siderophile elements are often fractionated from Ni; they covary, confirming the presence of a refractory metal component. The chalcophile element Se correlates with Br and siderophile elements. Zinc is uniformly low and uncorrelated with other elements.Most metal and sulfide in chondrules was probably present in the solar nebula before chondrule formation; most siderophile and chalcophile elements were in these materials. Some Fe was also in silicates, as were minor amounts of Ni, Co, Au, Ge and possibly Se. The amount of metal formed by reduction during chondrule melting was minor. The common metal component in chondrules is similar to, and may be the same as the common component involved in the metal/silicate fractionation of the ordinary chondrite groups.Chondrules are depleted in metal chiefly because they sampled metal-poor precursor assemblages. Metal segregation during the molten period and subsequent loss was a minor process that may be responsible for most surface craters on chondrules.     

Evaporation and recondensation of sodium in Semarkona Type II chondrules

We have investigated the Na distributions in Semarkona Type II chondrules by electron microprobe, analyzing olivine and melt inclusions in it, mesostasis and bulk chondrule, to see whether they indicate interactions with an ambient gas during chondrule formation. Sodium concentrations of bulk chondrule liquids, melt inclusions and mesostases can be explained to a first approximation by fractional crystallization of olivine ± pyroxene. The most primitive olivine cores in each chondrule are mostly between Fa₈ and Fa₁₃, with 0.0022–0.0069 ± 0.0013 wt.% Na₂O. Type IIA chondrule olivines have consistently higher Na contents than olivines in Type IIAB chondrules. We used the dependence of olivine–liquid Na partitioning on FeO in olivine as a measure of equilibration. Extreme olivine rim compositions are ～Fa₃₅ and 0.03 wt.% Na₂O and are close to being in equilibrium with the mesostasis glass. Olivine cores compared with the bulk chondrule compositions, particularly in IIA chondrules, show very high apparent D_Na, indicating disequilibrium and suggesting that chondrule initial melts were more Na-rich than present chondrule bulk compositions. The apparent D_Na values correlate with the Na concentrations of the olivine, but not with concentrations in the bulk melt. We use equilibrium D_Na to find the Na content of the true parent liquid and estimate that Type IIA chondrules lost more than half their Na and recondensation was incomplete, whereas Type IIAB chondrules recovered most of theirs in their mesostases.Glass inclusions in olivine have lower Na than expected from fractionation of bulk composition liquids, and mesostases have higher Na than expected in calculated daughter liquids formed by fractional crystallization alone. These observations also require open system behavior of chondrules, specifically evaporation of Na before formation of melt inclusions followed by recondensation of Na in mesostases. Within this record of evaporation followed by recondensation, there is no indication of a stage with zero Na in the chondrules, which is predicted by models for shock wave cooling at canonical nebular pressures, suggesting high P_T.The high Na concentrations in olivine and mesostases indicate very high P_Na while chondrules were molten. This may be explained by local, very high particle densities where Type II chondrules formed. The high P_T, P_Na and number densities of chondrules implied suggest formation in debris clouds after protoplanetary collisions as an alternative to formation after passage of shock waves through large particle-rich clumps in the disk. Encounters of partially molten chondrules should have been frequent in these dense swarms. However, in many ordinary chondrites like Semarkona, “cluster chondrites”, compound chondrules are not abundant but instead chondrules aggregated into clusters. Chondrule melting, cooling and clustering in dense swarms contributed to rapid accretion, possibly after collision, by fallback on the grandparent body and by reaccretion as a new body downrange.     

Matrix material in type 3 chondrites—occurrence,heterogeneity and relationship with chondrules

Matrix material in type 3 chondrites forms rims on chondrules, metal-sulfide aggregates, Ca,Al-rich inclusions and chondritic clasts; it also forms lumps up to a millimeter in size, which may contain coarser silicates. Chondrules of all types were found with internal matrix lumps that appear to have entered the chondrules before the latter had crystallized. Mean concentrations of Mg, Na, Al and Ca in matrix occurrences show up to fivefold variations in a single chondrite. Variations between mean matrix compositions of individual type 3 ordinary chondrites are almost as large and partly reflect systematic differences between H, L and LL matrices. Such variations are probably a result of nebular separation of feldspathic material and ferromagnesian silicates.Compositions of chondrules and their matrix rims are normally unrelated, although rim compositions are correlated with those of matrix lumps inside chondrules. A single chondrule was found with a composition nearly identical to that of its internal matrix lump, suggesting that some chondrules may have formed from matrix material. Matrix lumps are as heterogeneous as chondrules, but mean chondrule and matrix compositions differ, even allowing for possible loss of metallic Fe,Ni during chondrule formation. Since bulk compositions of matrix lumps and rims have probably not changed significantly since their formation except for Fe-Mg exchange, our matrix samples cannot represent typical chondrule precursor materials.     

The formation of chondrules by open-system melting of nebular condensates

Experiments were conducted under canonical nebular conditions to see whether the chemical compositions of the various chondrule types can be derived from a single CI-like starting material by open-system melting and evaporation. Experimental charges, produced at 1580 °C and P_H2 of 1.31×10⁻⁵ atm over 1 to 18 hours, consisted of only two phases, porphyritic olivine crystals in glass. Sulfur, metallic-iron and alkalis were completely evaporated in the first minutes of the experiments and subsequently the main evaporating liquid oxides were FeO and SiO₂. Olivines from short runs (2-4 hours) have compositions of Fo₈₃-Fo₈₉, as in Type IIA chondrules, while longer experimental runs (12-18 hours) produce ∼Fo₉₉ olivine, similar to Type IA chondrules. The concentration of CaO in both olivine (up to 0.6 wt.%) and glass, and their Mg#, increased with increasing heating duration. Natural chondrules also show increasing CaO with decreasing S, alkalis, FeO and SiO₂. The similarities in bulk chemistry, mineralogy and textures between Type IIA and IA chondrules and the experimental charges demonstrate that these chondrules could have formed by the evaporation of CI precursors. The formation of silica-rich chondrules (IIB and IB) by evaporation requires a more pyroxene-rich precursor.Based on the FeO evaporation rates measured here, Type IIA and IA chondrules, were heated for at least ∼0.5 and ∼3.5 h, respectively, if formed at 1580 °C and P_H2 of 1.31×10⁻⁵ atm. Type II chondrules may have experienced higher cooling-rates and less evaporation than Type I.The experimental charges experienced free evaporation and exhibited heavy isotopic enrichments in silicon, as well as zero concentrations of S, Na and K, which are not observed in natural chondrules. However, experiments on potassium-rich melts at the same pressure but in closed capsules showed less evaporation of K, and less K isotopic mass fractionation, than expected as a function of decreasing cooling rate. Thus the environment in which chondrules formed is as important as the kinetic processes they experienced. If chondrule formation occurred under conditions in which evaporated gases remained in the vicinity of the residual melts, the extent of evaporation would be reduced and back reaction between the gas and the melt could contribute to the suppression of isotopic mass fractionation. Hence chondrule formation could have involved evaporative loss without Rayleigh fractionation. Volatile-rich Type II and volatile-poor Type I chondrules may have formed in domains with high and low chondrule concentrations, and high partial pressures of lithophile elements, respectively.     

Sulfur isotope composition of putative primary troilite in chondrules from Bishunpur and Semarkona

The sulfur isotopic compositions of putative primary troilite grains within 15 ferromagnesian chondrules (10 FeO-poor and 5 FeO-rich chondrules) in the least metamorphosed ordinary chondrites, Bishunpur and Semarkona, have been measured by ion microprobe. Some troilite grains are located inside metal spherules within chondrules. Since such an occurrence is unlikely to be formed by secondary sulfidization processes in the solar nebula or on parent bodies, those troilites are most likely primary, having survived chondrule-forming high-temperature events. If they are primary, they may be the residues of evaporation at high temperatures during chondrule formation and may have recorded mass-dependent isotopic fractionations. However, the supposed primary troilites measured in this study do not show any significant sulfur isotopic fractionations (<1 ‰/amu) relative to large troilite grains in matrix. Among other chondrule troilites that we measured, only one (BI-CH22) apparently has a small excess of heavy isotopes (2.7 ± 1.4 ‰/amu) consistent with isotopic fractionation during evaporation. All other grains have isotopic fractionations of <1 ‰/amu. Because sulfur is so volatile that evaporation during chondrule formation is probably inevitable, non-Rayleigh evaporation most likely explains the lack of isotopic fractionation in putative primary troilite inside chondrules. Evaporation through the surrounding silicate melt would have suppressed the isotopic fractionation after silicate dust grains melted. At lower temperatures below extensive melting of silicates, a heating rate of >10⁴-10⁶ K/h would be required to avoid a large degree of sulfur isotopic fractionation in the chondrule precursors. This heating rate may provide a new constraint on the chondrule formation processes.     

Distribution of moderately volatile trace elements in fine-grained chondrule rims in the unequilibrated CO3 chondrite, ALH A77307

The concentrations of Ni, Cu, Zn, Ga, Ge, and Se in five, fine-grained chondrule rims in the highly unequilibrated CO3 chondrite ALH A77307 (3.0) have been determined for the first time by synchrotron X-ray fluorescence (SXRF) microprobe at Brookhaven National Laboratory. These elements are especially useful for tracing the role of condensation and evaporation processes which occurred at moderate temperatures in the solar nebula. Understanding the distribution of moderately volatile elements between matrix and chondrules is extremely important for evaluating the different models for the volatile depletions in chondritic meteorites. The data show that the trace element chemistry of rims on different chondrules is remarkably similar, consistent with data obtained for the major and minor elements by electron microprobe. These results support the idea that rims are not genetically related to individual chondrules, but all sampled the same reservoir of homogeneously mixed dust. Of the trace elements analyzed, Zn and Ga show depletions relative to CI chondrite values, but in comparison with bulk CO chondrites all the elements are enriched by approximately 1.5 to 3.5 x CO. The abundance patterns for moderately volatile elements in ALH A77307 chondrule rims closely mimic those observed in the bulk chondrite, indicating that matrix is the major reservoir for these elements. The close matching of the patterns for the volatile depleted bulk chondrite and enriched matrix is especially striking for Na, which is anomalously depleted in ALH A77307 in comparison with average CO chondrite abundances. The depletion in Na is probably attributable to the effects of leaching in Antarctica. With the exception of Na, the volatile elements show a relatively smooth decrease in abundance as a function of condensation temperature, indicating that their behavior is largely controlled by their volatility.     

The conditions of chondrule formation, Part I: Closed system

Mixing was an important process in the early solar nebula and is often used as an argument to explain the compositional scatter among chondrules—mm-sized, once molten silicate spherules in chondritic meteorites. If it is hypothesized that chondrules only acted as closed systems and the scatter in chondrule bulk chemical compositions is only the result of mixing heterogeneous precursor grains—the basic components of chondrules—, it is in turn possible to determine the sizes of the precursor grains using statistical calculations. In order to reproduce the observed compositional scatter in chondrules not more than ∼10 precursor grains should contribute to a single chondrule, each with a diameter of several 100 μm. This finding has important implications for the conditions of chondrule formation and replaces the so far widely accepted model that chondrules formed from fine-grained “dust-balls”. Chondrules rather formed from coarse-grained precursor aggregates with variable amounts of μm-fine matrix material. As a consequence, only chondrite matrix or interstellar material winnows as precursor material. Large grains of variable composition serving as precursor grains must have been formed prior to chondrule formation. Chondrules probably have not been their immediate precursors, as only 1-2 chondrule recycling steps would have homogenized bulk chondrule compositions. Chondrule recycling can therefore only have occurred to a limited extent. Chondrule formation needed at least three steps: (1) production of large and heterogeneous chondrule precursor grains, (2) agglomeration of large precursor grains and fine-grained precursors into aggregates, (3) formation of chondrules during transient heating events. Al-rich chondrules can in this context be explained by the admixture of CAIs to either chondrule precursors or a population of existing chondrules.     

Petrogenesis of Al-rich chondrules: Evidence from bulk compositions and phase equilibria

We measured major, minor, and trace-element compositions for eleven Al-rich chondrules from unequilibrated ordinary chondrites to investigate the relationships between Al-rich chondrules, ferromagnesian chondrules, Ca-, Al-rich inclusions (CAIs), and amoeboid olivine aggregates (AOAs). Phase equilibrium considerations show that, for the most part, mineral assemblages in Al-rich chondrules are those expected from melts of the observed compositions. The diversity of mineral assemblages and Al-rich chondrule types arises mainly from the fact that the array of compositions spans both the spinel-saturated anorthite-forsterite reaction curve and a thermal divide defined by where the anorthite-forsterite join crosses the reaction curve. The reaction curve accounts for the two principal varieties of Al-rich chondrule, plagioclase-phyric and olivine-phyric, with or without aluminous spinel. The thermal divide influences the subsequent evolution of each variety. A third variety of Al-rich chondrule contains abundant sodium-rich glass; trace-element fractionation patterns suggest that these glassy Al-rich chondrules could have been derived from the other two by extensive alteration of plagioclase to nepheline followed by remelting. The bulk compositions of Al-rich chondrules (except sodium-rich ones) are intermediate in a volatility sense between ferromagnesian chondrules and type C CAIs. The combined trend of bulk compositions for CAIs, Al-rich chondrules, and ferromagnesian chondrules mirrors, but does not exactly match, the trend predicted from equilibrium condensation at P_T ∼ 10^-3 atm; the observed trend does not match the trend found for evaporation from a liquid of chondritic composition. We thus infer that the bulk compositions of the precursors to CAIs, Al-rich chondrules, were ferromagnesian chondrules were controlled primarily by vapor-solid reactions (condensation or sublimation) in the solar nebula. Some Al-rich chondrules are consistent with an origin by melting of a compound CAI-ferromagnesian chondrule hybrid; others cannot be so explained. Any hybrid model is restricted by the constraint that the CAI precursor consisted dominantly of pyroxene + plagioclase + spinel; melilite cannot have been a significant component. Amoeboid olivine aggregates also have the inferred mineralogical characteristics of Al-rich chondrule precursors—they are mixtures of olivine with plagioclase-spinel-pyroxene-rich CAIs—but the few measured bulk compositions are more olivine-rich than those of Al-rich chondrules.     

Heating experiments relevant to the depletion of Na,K and Mn in the Earth and other planetary bodies

We have studied the evaporation of Na, K and Mn from Al-Na-K- and Mn-rich silicates at various conditions. Total alkali oxide contents ranged from 5 to 20%. The evaporation rate of Na increases with temperature and decreasing oxygen fugacity and decreases with duration of heating. The loss of K is in all cases less pronounced than for Na. Heating in an evacuated vacuum furnace is more effective in removing Na and K from melt droplets than in furnaces with one atm gas flow of air or gas mixtures controlling the oxygen fugacity. The strong pumping required to keep the vacuum removes Na and K atoms very effectively. In all experiments, the rate of evaporation is determined by quasi-equilibrium between a thin layer of Na and K rich gas above the molten silicates. The results of the experiments are in agreement with several other studies.In experiments with more than one sample in the furnace, equilibration of Na- and K-rich samples with Na- and K-poor samples occurred rapidly, mediated by the ambient gas phase.The results of experiments with Mn in starting compositions showed much stronger losses of Na than Mn under a variety of conditions.Thus the nearly chondritic Mn/Na ratios in the Earth cannot be the result of evaporation of Na and Mn in Earth-making materials, as the Mn/Na ratios in evaporation residues would be much higher than chondritic ratios. Such evaporation processes may have occurred in the parent material of Moon, Vesta and Mars.The data suggest, in agreement with earlier hypotheses, that the high and variable contents of Na and K in chondrules require a gas phase high in Na and K equilibrating with chondrule melts. The volume of nebular gas parental to a certain type of chondrites was heated and Na and K were lost from the chondrule precursors to the gas phase. Subsequently the nebular parcel was compressed leading to higher partial pressures of Na and K. Flash heating then produced chondrule melts which incorporated some of the gaseous Na and K and then cooled rapidly. The large range of Na and K contents in chondrule melts reflects very local enrichments of Na and K in the gas phase. Despite these variations bulk chondritic meteorites have well defined bulk Na and K contents, implying a closed system during formation of chondrules and matrix.     

Physical properties of chondrules in different chondrite groups: Implications for multiple melting events in dusty environments

Chondrite groups (CV, CK, CR) with large average chondrule sizes have low proportions of RP plus C chondrules, high proportions of enveloping compound chondrules, high proportions of chondrules with (thick) igneous rims, and relatively low proportions of type-I chondrules containing sulfide. In contrast, chondrite groups (CM, CO, OC, R, EH, EL) with smaller average chondrule sizes have the opposite properties. Equilibrated CK chondrites have plagioclase with relatively low Na; equilibrated OC, R, EH and EL chondrites have more sodic plagioclase. Enveloping compound chondrules and chondrules with igneous rims formed during a remelting event after the primary chondrule was incorporated into a dustball. Repeated episodes of remelting after chondrules were surrounded by dust would tend to produce large chondrules. RP and C chondrules formed by complete melting of their precursor assemblages; remelting of RP and C chondrules surrounded by dust would tend to produce porphyritic chondrules as small dust particles mixed with the melt, providing nuclei for crystallizing phenocrysts. This process would tend to diminish the numbers of RP and C chondrules. Correlations among these chondrule physical properties suggest that chondrite groups with large chondrules were typically surrounded by thick dust-rich mantles that formed in locally dusty nebular environments. Chondrules that were surrounded by thick dust mantles tended to cool more slowly because heat could not quickly radiate away. Slow cooling led to enhanced migration of sulfide to chondrule surfaces and more extensive sulfide evaporation. These chondrules also lost Na; the plagioclase that formed from equilibrated CK chondrites was thus depleted in Na.