Kinetic isotope effect during reduction of iron from a silicate melt

Iron isotopic compositions measured in chondrules from various chondrites vary between δ⁵⁷Fe/⁵⁴Fe = +0.9‰ and −2.0‰, a larger range than for igneous rocks. Whether these compositions were inherited from chondrule precursors, resulted from the chondrule-forming process itself or were produced by later parent body alteration is as yet unclear. Since iron metal is a common phase in some chondrules, it is important to explore a possible link between the metal formation process and the observed iron isotope mass fractionation. In this experimental study we have heated a fayalite-rich composition under reducing conditions for heating times ranging from 2 min to 6 h. We performed chemical and iron isotope analyses of the product phases, iron metal and silicate glass. We demonstrated a lack of evaporation of Fe from the silicate melt in similar isothermal experiments performed under non-reducing conditions. Therefore, the measured isotopic mass fractionation in the glass, ranging between −0.32‰ and +3.0‰, is attributed to the reduction process. It is explained by the faster transport of lighter iron isotopes to the surface where reduction occurs, and is analogous to kinetic isotope fractionation observed in diffusion couples [Richter, F.M., Davis, A.M., Depaolo, D.J., Watson, E.B., 2003. Isotope fractionation by chemical diffusion between molten basalt and rhyolite. Geochim. Cosmochim. Acta67, 3905-3923]. The metal phase contains 90-99.8% of the Fe in the system and lacks significant isotopic mass fractionation, with values remaining similar to that of the starting material throughout. The maximum iron isotope mass fractionation in the glass was achieved within 1 h and was followed by an isotopic exchange and re-equilibration with the metal phase (incomplete at ∼6 h). This study demonstrates that reduction of silicates at high temperatures can trigger iron isotopic fractionation comparable in its bulk range to that observed in chondrules. Furthermore, if metal in Type I chondrules was formed by reduction of Fe silicate, our observed isotopic fractionations constrain chondrule formation times to approximately 60 min, consistent with previous work.     

Oxygen, silicon, and Mn-Cr isotopes of fayalite in the Kaba oxidized CV3 chondrite: Constraints for its formation history

The iron-rich olivine end-member, fayalite, occurs in the matrix, chondrules, Ca-Al-rich inclusions (CAIs), silicate aggregates, and dark inclusions in the Kaba and Mokoia oxidized CV3 chondrites. In most occurrences, fayalite is associated with magnetite and troilite. To help constrain the origin of the fayalite (Fa_98-100), we measured oxygen and silicon isotopic compositions and Mn-Cr systematics in fayalite from two petrographic settings of the Kaba meteorite. One setting consists of big fayalite laths embedded in the matrix and radiating from a core of fine-grained magnetite and sulfide, while the other setting consists of small fayalite-magnetite-sulfide assemblages within or at the surface of Type I barred or porphyritic olivine chondrules. Oxygen in the big fayalite laths and small chondrule fayalites falls on the terrestrial fractionation line, and is distinct from that in chondrule forsterites, which are enriched in ¹⁶O (Δ¹⁷O = ∼−4‰). Oxygen in the big fayalite laths may be isotopically heavier than that in chondrule fayalites. Silicon isotopes suggest that forsterite is ∼1‰/amu heavier than adjacent fayalite within Kaba chondrules. However, we were unable to confirm large silicon isotopic differences among fayalites reported previously. The Mn-Cr data for big Kaba fayalites give an initial ⁵³Mn/⁵⁵Mn ratio of (2.07 ± 0.17) × 10⁻⁶, consistent with literature results on Mokoia chondrule fayalites. The combined data suggest that fayalites in both petrographic settings formed at about the same time, ∼9.7 Ma after the formation of CAIs. Our data indicate that those fayalite-magnetite-troilite assemblages replacing metal inside and around chondrules formed by aqueous alteration on the meteorite parent body. The formation site and mechanism for the big fayalite laths is less clear, but the petrographic setting indicates that they did not form in situ. None of the models that have been suggested for formation of these fayalites is entirely satisfactory.     

Oxygen isotope heterogeneity in chondrules from the Mokoia CV3 carbonaceous chondrite

We report a study of the oxygen isotope ratios of chondrules and their constituent mineral grains from the Mokoia, oxidized CV3 chondrite. Bulk oxygen isotope ratios of 23 individual chondrules were determined by laser ablation fluorination, and oxygen isotope ratios of individual grains, mostly olivine, were obtained in situ on polished mounts using secondary ion mass spectrometry (SIMS). Our results can be compared with data obtained previously for the oxidized CV3 chondrite, Allende. Bulk oxygen isotope ratios of Mokoia chondrules form an array on an oxygen three-isotope plot that is subparallel to, and slightly displaced from, the CCAM (carbonaceous chondrite anhydrous minerals) line. The best-fit line for all CV3 chondrite chondrules has a slope of 0.99, and is displaced significantly (by δ¹⁷O ∼ −2.5‰) from the Young and Russell slope-one line for unaltered calcium-aluminum-rich inclusion (CAI) minerals. Oxygen isotope ratios of many bulk CAIs also lie on the CV-chondrule line, which is the most relevant oxygen isotope array for most CV chondrite components. Bulk oxygen isotope ratios of most chondrules in Mokoia have δ¹⁸O values around 0‰, and olivine grains in these chondrules have similar oxygen isotope ratios to their bulk values. In general, it appears that chondrule mesostases have higher δ¹⁸O values than olivines in the same chondrules. Our bulk chondrule data spread to lower δ¹⁸O values than any ferromagnesian chondrules that have been measured previously. Two chondrules with the lowest bulk δ¹⁸O values (−7.5‰ and −11.7‰) contain olivine grains that display an extremely wide range of oxygen isotope ratios, down to δ¹⁷O, δ¹⁸O around -50‰ in one chondrule. In these chondrules, there are no apparent relict grains, and essentially no relationships between olivine compositions, which are homogeneous, and oxygen isotopic compositions of individual grains. Heterogeneity of oxygen isotope ratios within these chondrules may be the result of incorporation of relict grains from objects such as amoeboid olivine aggregates, followed by solid-state chemical diffusion without concomitant oxygen equilibration. Alternatively, oxygen isotope exchange between an ¹⁶O-rich precursor and an ¹⁶O-poor gas may have taken place during chondrule formation, and these chondrules may represent partially equilibrated systems in which isotopic heterogeneities became frozen into the crystallizing olivine grains. If this is the case, we can infer that the earliest nebular solids from which chondrules formed had δ¹⁷O and δ¹⁸O values around -50‰, similar to those observed in refractory inclusions.     

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.     

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.     

Oxygen isotope compositions of chondrules in CR chondrites

We report in situ ion microprobe analyses of oxygen isotopic compositions of olivine, low-Ca pyroxene, high-Ca pyroxene, anorthitic plagioclase, glassy mesostasis, and spinel in five aluminum-rich chondrules and nine ferromagnesian chondrules from the CR carbonaceous chondrites EET92042, GRA95229, and MAC87320. Ferromagnesian chondrules are isotopically homogeneous within ±2‰ in Δ¹⁷O; the interchondrule variations in Δ¹⁷O range from 0 to −5‰. Small oxygen isotopic heterogeneities found in two ferromagnesian chondrules are due to the presence of relict olivine grains. In contrast, two out of five aluminum-rich chondrules are isotopically heterogeneous with Δ¹⁷O values ranging from −6 to −15‰ and from −2 to −11‰, respectively. This isotopic heterogeneity is due to the presence of ¹⁶O-enriched spinel and anorthite (Δ¹⁷O = −10 to −15‰), which are relict phases of Ca,Al-rich inclusions (CAIs) incorporated into chondrule precursors and incompletely melted during chondrule formation. These observations and the high abundance of relict CAIs in the aluminum-rich chondrules suggest a close genetic relationship between these objects: aluminum-rich chondrules formed by melting of spinel-anorthite-pyroxene CAIs mixed with ferromagnesian precursors compositionally similar to magnesium-rich (Type I) chondrules. The aluminum-rich chondrules without relict CAIs have oxygen isotopic compositions (Δ¹⁷O = −2 to −8‰) similar to those of ferromagnesian chondrules. In contrast to the aluminum-rich chondrules from ordinary chondrites, those from CRs plot on a three-oxygen isotope diagram along the carbonaceous chondrite anhydrous mineral line and form a continuum with amoeboid olivine aggregates and CAIs from CRs. We conclude that oxygen isotope compositions of chondrules resulted from two processes: homogenization of isotopically heterogeneous materials during chondrule melting and oxygen isotopic exchange between chondrule melt and ¹⁶O-poor nebular gas.     

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.     

Oxygen isotope systematics of chondrules in the Allende CV3 chondrite: High precision ion microprobe studies

The oxygen three-isotope systematics of 36 chondrules from the Allende CV3 chondrite are reported using high precision secondary ion mass spectrometer (CAMECA IMS-1280). Twenty-six chondrules have shown internally homogenous Δ¹⁷O values among olivine, pyroxene, and spinel within a single chondrule. The average Δ¹⁷O values of 19 FeO-poor chondrules (13 porphyritic chondrules, 2 barred olivine chondrules, and 4 chondrule fragments) show a peak at −5.3 ± 0.6‰ (2SD). Another 5 porphyritic chondrules including both FeO-poor and FeO-rich ones show average Δ¹⁷O values between −3‰ and −2‰, and 2 other FeO-poor barred olivine chondrules show average Δ¹⁷O values of −3.6‰ and 0‰. These results are similar to those for Acfer 094 chondrules, showing bimodal Δ¹⁷O values at −5‰ and −2‰. Nine porphyritic chondrules contain olivine grains with heterogeneous Δ¹⁷O values as low as −18‰, indicating that they are relict olivine grains and some of them were derived from precursors related to refractory inclusions. However, most relict olivine grains show oxygen isotope ratios that overlap with those in homogeneous chondrules. The Δ¹⁷O values of four barred olivine chondrules range from −5‰ to 0‰, indicating that not all BO chondrules plot near the terrestrial fractionation line as suggested by previous bulk chondrule analyses. Based on these data, we suggest the presence of multiple oxygen isotope reservoirs in local dust-rich protoplanetary disk, from which the CV3 parent asteroid formed.A compilation of 225 olivine and low-Ca pyroxene isotopic data from 36 chondrules analyzed in the present study lie between carbonaceous chondrite anhydrous mineral (CCAM) and Young and Russell lines. These data define a correlation line of δ¹⁷O = (0.982 ± 0.019) × δ¹⁸O − (2.91 ± 0.10), which is similar to those defined by chondrules in CV3 chondrites and Acfer 094 in previous studies. Plagioclase analyses in two chondrules plot slightly below the CCAM line with Δ¹⁷O values of −2.6‰, which might be the result of oxygen isotope exchange between chondrule mesostasis and aqueous fluid in the CV parent body.     

Chemical equilibrium and kinetic constraints for chondrule and CAI formation conditions

While many uncertainties remain, a kinetic evaporation-condensation model is used to show that type A chondrules, and compact Type A and B calcium-aluminum-rich inclusions (CAIs) could have formed from CI-like precursors under conditions that are consistent with predictions for 2-3 AU in a canonical solar nebula. Type B and Al-rich chondrules, and Type C CAIs, on the other hand, may have formed from fractionated precursors. Based primarily on chondrule and CAI isotopic compositions, previous studies have reached different conclusions because they did not take into account the effects of gas-melt exchange.Assuming CI-like precursor compositions, equilibrium silicate melts with elemental compositions like those of type A chondrules could have formed over a wide range of conditions (T, P_tot, solid/gas/solar). Metal is not predicted to be stable when T ≥ 1600°C. When T < 1600°C, the abundances and compositions of metal in chondrules appear to be less successfully reproduced than the silicates, e.g., at a given temperature more metal is predicted in type II chondrules than is generally observed, and under some conditions type IIs are predicted to be more metal-rich than type Is. These differences could be overcome if type Is formed from precursors that were more reduced than CI, and if type IIs formed after significant metal-silicate fractionation.The formation conditions of molten CAIs are much more restricted than for chondrules, perhaps in part explaining their lower abundances. The Mg, Si and O isotopic mass fractionations in non-FUN CAIs can be reproduced if they formed between ∼1400 to 1500°C in regions where CAI-like equilibrium melts were stable, but they did not quite reach equilibrium with the gas. CAI formation times at P_tot = 10⁻⁴-10⁻³ bars are consistent with estimates of Type B CAI cooling times, but pressures much below this require formation times that are too long. The isotopic mass fractionations in FUN CAIs can be explained if they formed at or below the ranges of solid/gas/solar ratios where CAI-like equilibrium compositions are stable. Under these conditions, FUN inclusions undergo less gas-melt exchange than non-FUN CAIs. The FUN CAI formation temperatures are consistent with formation at 1400 to 1500°C, but may have been higher.Two general explanations for the distribution of O mass independent fractionations (MIF) in chondrules/CAIs have been explored: creation of the MIF before chondrule/CAI formation, and creation of the MIF during chondrule/CAI formation. If the MIF was established before chondrule/CAI formation, the most promising explanation is that H₂O (presumably as ice) and silicate dust with MIFs of opposite sign are fractionated together from the remaining gas. On heating, the H₂O now in the gas exchanges with the melt.If the MIF was generated during chondrule/CAI formation, it must be generated in the H₂O, because it exchanges most rapidly with the melt, and mass balance requires creation of MIF of opposite sign in CO. Self-shielding from UV radiation is one possibility, but the effect may be quenched at high temperatures. Non-RRKM intramolecular kinetic isotope effects are another possibility, but a continuous source of radiation may be needed to prevent gas phase reactions from approaching equilibrium.     

Oxygen isotopic constraints on the origin of magnesian chondrules and on the gaseous reservoirs in the early Solar System

We report in situ ion microprobe analyses of the oxygen isotopic composition of the major silicate phases (olivine, low-Ca pyroxene, silica, and mesostasis) of 37 magnesian porphyritic (type I) chondrules from CV (Vigarano USNM 477-2, Vigarano UH5, Mokoia, and Efremovka) and CR (EET 92042, EET 92147, EET 87770, El Djouf 001, MAC 87320, and GRA 95229) carbonaceous chondrites. In spite of significant variations of the modal proportions of major mineral phases in CR and CV chondrules, the same isotopic characteristics are observed: (i) olivines are isotopically homogeneous at the ‰ level within a chondrule although they may vary significantly from one chondrule to another, (ii) low-Ca pyroxenes are also isotopically homogeneous but systematically ¹⁶O-depleted relative to olivines of the same chondrule, and (iii) all chondrule minerals analyzed show ¹⁶O-enrichments relative to the terrestrial mass fractionation line, enrichments that decrease from olivine (±spinel) to low-Ca pyroxene and to silica and mesostasis. The observation that, in most of the type I chondrules studied, the coexisting olivine and pyroxene crystals and glassy mesostasis have different oxygen isotopic compositions implies that the olivine and pyroxene grains are not co-magmatic and that the glassy mesostasis is not the parent liquid of the olivine. The δ¹⁸O and δ¹⁷O values of pyroxene and olivine appear to be strongly correlated for all the studied CR and CV chondrules according to:

     

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.     

High precision SIMS oxygen three isotope study of chondrules in LL3 chondrites: Role of ambient gas during chondrule formation

We report high precision SIMS oxygen three isotope analyses of 36 chondrules from some of the least equilibrated LL3 chondrites, and find systematic variations in oxygen isotope ratios with chondrule types. FeO-poor (type I) chondrules generally plot along a mass dependent fractionation line (Δ¹⁷O ∼ 0.7‰), with δ¹⁸O values lower in olivine-rich (IA) than pyroxene-rich (IB) chondrules. Data from FeO-rich (type II) chondrules show a limited range of δ¹⁸O and δ¹⁷O values at δ¹⁸O = 4.5‰, δ¹⁷O = 2.9‰, and Δ¹⁷O = 0.5‰, which is slightly ¹⁶O-enriched relative to bulk LL chondrites (Δ¹⁷O ∼ 1.3‰). Data from four chondrules show ¹⁶O-rich oxygen isotope ratios that plot near the CCAM (Carbonaceous Chondrite Anhydrous Mineral) line. Glass analyses in selected chondrules are systematically higher than co-existing minerals in both δ¹⁸O and Δ¹⁷O values, whereas high-Ca pyroxene data in the same chondrule are similar to those in olivine and pyroxene phenocrysts.Our results suggest that the LL chondrite chondrule-forming region contained two kinds of solid precursors, (1) ¹⁶O-poor precursors with Δ¹⁷O > 1.6‰ and (2) ¹⁶O-rich solid precursors derived from the same oxygen isotope reservoir as carbonaceous chondrites. Oxygen isotopes exhibited open system behavior during chondrule formation, and the interaction between the solid and ambient gas might occur as described in the following model. Significant evaporation and recondensation of solid precursors caused a large mass-dependent fractionation due to either kinetic or equilibrium isotope exchange between gas and solid to form type IA chondrules with higher bulk Mg/Si ratios. Type II chondrules formed under elevated dust/gas ratios and with water ice in the precursors, in which the ambient H₂O gas homogenized chondrule melts by isotope exchange. Low temperature oxygen isotope exchange may have occurred between chondrule glasses and aqueous fluids with high Δ¹⁷O (∼5‰) in LL the parent body. According to our model, oxygen isotope ratios of chondrules were strongly influenced by the local solid precursors in the proto-planetary disk and the ambient gas during chondrule melting events.     

Microscale oxygen isotopic exchange and magnetite formation in the Ningqiang anomalous carbonaceous chondrite

We report in situ measurements of O-isotopic compositions of magnetite, olivine and pyroxene in chondrules of the Ningqiang anomalous carbonaceous chondrite. The petrographic setting of Ningqiang magnetite is similar to those in oxidized-CV chondrites such as Allende, where magnetite is found together with Ni-rich metal and sulfide in opaque assemblages in chondrules. Both magnetite and silicate oxygen data fall close to the carbonaceous-chondrite-anhydrous-mineral line with relatively large ranges in δ¹⁸O in magnetite (−4.9 to +4.2‰) and in silicates (−15.2 to −4.5‰). Magnetite and silicates are not in O-isotopic equilibrium: the weighted average Δ¹⁷O (=δ¹⁷O − 0.52 × δ¹⁸O) values of magnetite are 1.7 to 3.6‰ higher than those of the silicates in the same chondrules. The petrological characteristics and O-isotopic disequilibrium between magnetite and silicates suggest the formation of Ningqiang magnetite by the oxidation of preexisting metal grains by an aqueous fluid during parent body alteration. The weighted average Δ¹⁷O of −3.3 ± 0.3‰ is the lowest magnetite value measured in unequilibrated chondrites and there is a positive correlation between Δ¹⁷O values of magnetite and silicates in each chondrule. These observations indicate that, during aqueous alteration in the Ningqiang parent asteroid, the water/rock ratio was relatively low and O-isotopic exchange between the fluid and chondrule silicates occurred on the scale of individual chondrules.     

Mass independently fractionated sulfur components in chondrites

We report high precision sulfur isotopic data obtained by sequential extraction from various physically separated phases (bulk, matrix, and chondrules) from chondrites. A significant excess of ³³S (up to Δ³³S of 0.112‰ for Dhajala Chondrule) has been observed and is most likely carried by chondrule rims, though chondrule interiors cannot be ruled out as a carrier. Stellar nucleosynthesis and spallation are ruled out as a cause for this anomaly. Photochemical irradiation of sulfur gaseous species in the early solar nebula has, most likely, produced this anomaly. Observations of mass independent sulfur of photochemical origin suggest that chondrules and their rims must have formed in an optically thin nebular region. This also suggests that the chondrules were formed near the protoSun when it was active in ultraviolet light emission.     

An experimental study of the formation of metallic iron in chondrules

The abundance of metallic iron is highly variable in different kinds of chondrites. The precise mechanism by which metal fractionation occurred and its place in time relative to chondrule formation are unknown. As metallic iron is abundant in most Type I (FeO-poor) chondrules, determining under what conditions metal could form in chondrules is of great interest. Assuming chondrules were formed from low temperature nebular condensate, we heated an anhydrous CI-like material at 1580°C in conditions similar to those of the canonical nebula (P_H2 = 1.3 × 10⁻⁵ atm). We reproduced many of the characteristics of Type IA and IIA chondrules but none of them contained any iron metal. In these experiments FeO was abundant in charges that were heated for as long as 6 h. At a lower temperature, 1350°C, dendritic/cellular metal crystallized from Fe-FeS melts during the evaporation of S. However, the silicate portion consisted of many relict grains and vesicles, not typical of chondrules.Evaporation experiments conducted at P_H2 = 1 atm and 1565°C produced charges containing metallic iron both as melt droplets and inclusions in olivine, similar to those found in chondrules. Formation of iron in these experiments was primarily the result of desulfurization of FeS. With long heating times Fe° was lost by evaporation. Apart from some reduction of FeO by kerogen to make metal inclusions within olivine grains, reduction of FeO to make Fe° in these charges was not observed.This study shows that under canonical nebular conditions FeS and iron-metal are extremely volatile so that metal-rich Type I chondrules could not form by melting “CI.” Under these conditions FeO is lost predominantly by hydrogen stripping and, due to the relative low abundance of hydrogen at low pressures, remains in the melt for as long as 6 h. Conversely, at higher total pressures (1-atm H₂) iron metal (produced mainly by the desulfurization of troilite) is less volatile and remains in the melt for longer times (at least 6 h). In addition, due to elevated pressures of hydrogen, FeO is stripped away much faster. These results suggest that chondrule formation occurred in environments with elevated pressures relative to the canonical nebula for iron metal to be present.     

Mass-independent fractionation of oxygen isotopes in the mesostasis of a chondrule from the Semarkona LL3.0 ordinary chondrite

A large chondrule from Semarkona, the most primitive ordinary chondrite known, has been discovered to contain a record of mass transport during its formation. In most respects, it is a normal Type I, group A1, low-FeO chondrule that was produced by reduction and mass-loss during the unidentified flash-heating event that produced the chondrules, the most abundant structural component in primitive meteorites. We have previously measured elemental abundances and abundance profiles in this chondrule. We here report oxygen isotope ratio abundances and ratio abundance profiles. We have found that the mesostasis is zoned in oxygen isotope ratio, with the center of the chondrule containing isotopically heavier oxygen than the outer regions, the outer regions being volatile rich from the diffusion of volatiles into the chondrule during cooling. The δ¹⁷O values range from −2.0‰ to 9.9‰, while δ¹⁸O range from −1.9‰ to 9.6‰. More importantly, a plot of δ¹⁷O against δ¹⁸O has a slope of 1.1 ± 0.2 (1σ) and 0.88 ± 0.10 (1σ) when measured by two independent methods. Co-variation of δ¹⁷O with δ¹⁸O that does not follow mass-dependent fractionation has often been seen in primitive solar system materials and is usually ascribed to the mixing of different oxygen reservoirs. We argue that petrographic and compositional data indicate that this chondrule was completely melted at the time of its formation so that relic grains could not have survived. Furthermore, there is petrographic and compositional evidence that there was no aqueous alteration of this chondrule subsequent to its formation. Although it is possible to formulate a series of exchanges between the chondrule and external ¹⁶O-rich and ¹⁶O-poor reservoirs that may explain the detailed oxygen isotope systematics of this chondrule, such a sequence of events looks very contrived. We therefore hypothesize that reduction, devolatilization, and crystallization of the chondrule melt may have produced ¹⁶O-rich olivines and ¹⁶O-poor mesostasis plotting on a slope-one line as part of the chondrule-forming process in an analogous fashion to known chemical mass-independent isotopic fractionation mechanisms. During cooling, volatiles and oxygen near the terrestrial line in oxygen isotope composition produced the outer zone of volatile rich and ¹⁶O-rich mesostasis. The chondrule therefore not only retains a record of considerable mass transport accompanying formation, but also may indicate that the isotopes of oxygen underwent mass-independent fractionation during the process.     

Mg isotope heterogeneity in the Allende meteorite measured by UV laser ablation-MC-ICPMS and comparisons with O isotopes

First results from a new UV laser ablation MC-ICPMS method for measuring Mg isotope ratios in situ in meteoritical materials show that there are mass-dependent variations in δ²⁵Mg and δ²⁶Mg up to 1.5 ‰ per amu in chondrules and 0.3‰ per amu in a CAI from the Allende meteorite. In both cases the mass-dependent fractionation is associated with alteration. Comparisons with laser ablation O isotope data indicate that incorporation of pre-existing grains of forsterite with distinct Mg and O isotopic compositions and post-formation alteration both contributed to the variability in Mg isotope ratios in the chondrules, resulting in a correlation between high δ²⁵Mg and low Δ¹⁷O. The laser ablation analyses of the CAI show that high-precision determinations of both δ²⁵Mg and δ²⁶Mg can be used to discriminate features of the ²⁶Al-²⁶Mg isotope system that are relevant to chronology from those that result from element mobility.     

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.     

Highly N-enriched chondritic clasts in the CB/CH-like meteorite Isheyevo

The metal-rich carbonaceous chondrites (CB and CH) have the highest whole-rock ¹⁵N-enrichments (δ¹⁵N up to 1500‰) among planetary materials. They are also characterized by the absence of interchondrule fine-grained matrix. The only fine-grained material is present as lithic clasts, which experienced extensive aqueous alteration in contrast to the surrounding high-temperature components (chondrules, refractory inclusions, metal grains). Hence, the clasts are foreign objects that were incorporated at a late stage into the final parent body of Isheyevo. Their origin is poorly constrained. Based on mineralogy, petrography, and thermal processing of the aromatic carbonaceous component, different types of clasts have been previously identified in the CB/CH-like chondrite Isheyevo. Here, we focus on the rare lithic clasts characterized by the presence of anhydrous silicates (chondrules, chondrule fragments, and CAIs). Their mineralogy and oxygen isotopic compositions reveal them to be micro-chondrules, fragments of chondrules, and refractory inclusions related to those in the Isheyevo host, suggesting accretion in the same region. In contrast to previously studied IDPs or primitive chondritic matrices, the fine-grained material in the clasts we studied is highly and rather uniformly enriched in heavy nitrogen, with bulk δ¹⁵N values ranging between 1000‰ and 1300‰. It is also characterized by the presence of numerous ¹⁵N hotspots (δ¹⁵N ranging from 1400‰ to 4000‰). No bulk (δD <-240‰) or localized deuterium enrichments were observed. These clasts have the highest bulk enrichment in heavy nitrogen measured to date in a fine-grained material. They represent a unique material, of asteroidal or cometary origin, in our collection of cosmomaterials. We show that they were ¹⁵N-enriched before their incorporation in the final parent body of Isheyevo. They experienced an extensive aqueous alteration that most likely played a role in redistributing ¹⁵N over the whole fine-grained material and may have significantly modified its initial hydrogen isotopic composition. Based on a review of isotopic fractionation models, we conclude that the nitrogen isotopic fractionation process, its timing, and its location are still poorly constrained. The ¹⁵N-rich clasts may represent the surviving original carrier of the ¹⁵N anomaly in Isheyevo whole-rock.     

Isotopic compositions of oxygen, iron, chromium, and nickel in cosmic spherules: Toward a better comprehension of atmospheric entry heating effects

Large, correlated, mass-dependent enrichments in the heavier isotopes of O, Cr, Fe, and Ni are observed in type-I (metal/metal oxide) cosmic spherules collected from the deep sea. Limited intraparticle variability of oxygen isotope abundances, typically <5‰ in δ¹⁸O, indicates good mixing of the melts and supports the application of the Rayleigh equation for the calculation of fractional evaporative losses during atmospheric entry. Fractional losses for oxygen evaporation from wüstite, assuming a starting isotopic composition equal to that of air (δ¹⁸O = 23.5‰; δ¹⁷O = 11.8‰), are in the range 55%-77%, and are systematically smaller than evaporative losses calculated for Fe (69%-85%), Cr (81%-95%), and especially Ni (45%-99%). However, as δ¹⁸O values increase, fractional losses for oxygen approach those of Fe, Cr, and Ni indicating a shift in the evaporating species from metallic to oxidized forms as the spherules are progressively oxidized during entry heating. The observed unequal fractional losses of O and Fe can be reconciled by allowing for a kinetic isotope mass-dependent fractionation of atmospheric oxygen during the oxidation process and/or that some metallic Fe may have undergone Rayleigh evaporation before oxidation began.In situ measurements of oxygen isotopic abundances were also performed in 14 type-S (silicate) cosmic spherules, 13 from the Antarctic ice and one from the deep sea. Additional bulk Fe and Cr isotopic abundances were determined for two type-S deep-sea spherules. The isotopic fractionation of Cr isotopes suggest appreciable evaporative loss of Cr, perhaps as a sulfide. The oxygen isotopic compositions for the type-S spherules range from δ¹⁸O = −2‰ to + 27‰. The intraspherule isotopic variations are typically small, ∼5% relative, except for the less-heated porphyritic spherules which have preserved large isotopic heterogeneities in at least one case. A plot of δ¹⁷O vs. δ¹⁸O values for these spherules defines a broad parallelogram bounded at higher values of δ¹⁷O by the terrestrial fractionation line, and at lower values of δ¹⁷O by a line parallel to it and anchored near the isotopic composition of δ¹⁸O = −2.5‰ and δ¹⁷O = −5‰. Lack of independent evidence for substantial evaporative losses suggests that much of this variation reflects the starting isotopic composition of the precursor materials, which likely resembled CO, CM, or CI chondrites. However, the enrichments in heavy isotopes indicate that some mixing with atmospheric oxygen was probably involved during atmospheric entry for some of the spherules. Isotopic fractionation due to evaporation of incoming grain is not required to explain most of the oxygen isotopic data for type-S spherules. However spherules with barred olivine textures that are thought to have experienced a more intense heating than the porphyritic ones might have undergone some distillation. Two cosmic spherules, one classified as a radial pyroxene type and the other showing a glassy texture, show unfractionated oxygen isotopic abundances. They are probably chondrule fragments that survived atmospheric entry unmelted.Possible reasons type-I spherules show larger degrees of isotopic fractionation than type-S spherules include: a) the short duration of the heating pulse associated with the high volatile content of the type-S spherule precursors compared to type-I spherules; b) higher evaporation temperatures for at least a refractory portion of the silicates compared to that of iron metal or oxide; c) lower duration of heating of type-S spherules compared to type-I spherules as a consequence of their lower densities.