Carbonate abundances and isotopic compositions in chondrites

We report the bulk C abundances, and C and O isotopic compositions of carbonates in 64 CM chondrites, 14 CR chondrites, 2 CI chondrites, LEW 85332 (C2), Kaba (CV3), and Semarkona (LL3.0). For the unheated CMs, the total ranges of carbonate isotopic compositions are δ¹³C ≈ 25–75‰ and δ¹⁸O ≈ 15–35‰, and bulk carbonate C contents range from 0.03 to 0.60 wt%. There is no simple correlation between carbonate abundance and isotopic composition, or between either of these parameters and the extent of alteration. Unless accretion was very heterogeneous, the uncorrelated variations in extent of alteration and carbonate abundance suggests that there was a period of open system behavior in the CM parent body, probably prior to or at the start of aqueous alteration. Most of the ranges in CM carbonate isotopic compositions can be explained by their formation at different temperatures (0–130 °C) from a single fluid in which the carbonate O isotopes were controlled by equilibrium with water (δ¹⁸O ≈ 5‰) and the C isotopes were controlled by equilibrium with CO and/or CH₄ (δ¹³C ≈ ?33‰ or ?20‰ for CO‐ or CH₄‐dominated systems, respectively). However, carbonate formation would have to have been inefficient, otherwise carbonate compositions would have resembled those of the starting fluid. A quite similar fluid composition (δ¹⁸O ≈ ?5.5‰, and δ¹³C ≈ ?31‰ or ?17‰ for CO‐ or CH₄‐dominated systems, respectively) can explain the carbonate compositions of the CIs, although the formation temperatures would have been lower (~10–40 °C) and the relative abundances of calcite and dolomite may play a more important role in determining bulk carbonate compositions than in the CMs. The CR carbonates exhibit a similar range of O isotopes, but an almost bimodal distribution of C isotopes between more (δ¹³C ≈ 65–80‰) and less altered samples (δ¹³C ≈ 30–40‰). This bimodality can still be explained by precipitation from fluids with the same isotopic composition (δ¹⁸O ≈ ?9.25‰, and δ¹³C ≈ ?21‰ or ?8‰ for CO‐ or CH₄‐dominated systems, respectively) if the less altered CRs had higher mole fractions of CO₂ in their fluids. Semarkona and Kaba carbonates have some of the lightest C isotopic compositions of the meteorites studied here, probably because they formed at higher temperatures and/or from more CO₂‐rich fluids. The fluids responsible for the alteration of chondrites and from which the carbonates formed were almost certainly accreted as ices. By analogy with cometary ices, CO₂ and/or CO would have dominated the trapped volatile species in the ices. The chondrites studied are too oxidized for CO‐dominated fluids to have formed in their parent bodies. If CH₄ was the dominant C species in the fluids during carbonate formation, it would have to have been generated in the parent bodies from CO and/or CO₂ when oxidation of metal by water created high partial pressures of H₂. The fact that the chondrite carbonate C/H₂O mole ratios are of the order predicted for CO/CO₂‐H₂O ices that experienced temperatures of >50–100 K suggests that the chondrites formed at radial distances of <4–15 AU.     

Implications for behavior of volatile elements during impacts—Zinc and copper systematics in sediments from the Ries impact structure and central European tektites

Moldavites are tektites genetically related to the Ries impact structure, located in Central Europe, but the source materials and the processes related to the chemical fractionation of moldavites are not fully constrained. To further understand moldavite genesis, the Cu and Zn abundances and isotope compositions were measured in a suite of tektites from four different substrewn fields (South Bohemia, Moravia, Cheb Basin, Lusatia) and chemically diverse sediments from the surroundings of the Ries impact structure. Moldavites are slightly depleted in Zn (~10–20%) and distinctly depleted in Cu (>90%) relative to supposed sedimentary precursors. Moreover, the moldavites show a wide range in δ⁶⁶Zn values between 1.7 and 3.7‰ (relative to JMC 3‐0749 Lyon) and δ⁶⁵Cu values between 1.6 and 12.5‰ (relative to NIST SRM 976) and are thus enriched in heavy isotopes relative to their possible parent sedimentary sources (δ⁶⁶Zn = ?0.07 to +0.64‰; δ⁶⁵Cu = ?0.4 to +0.7‰). In particular, the Cheb Basin moldavites show some of the highest δ⁶⁵Cu values (up to 12.5‰) ever observed in natural samples. The relative magnitude of isotope fractionation for Cu and Zn seen here is opposite to oxygen‐poor environments such as the Moon where Zn is significantly more isotopically fractionated than Cu. One possibility is that monovalent Cu diffuses faster than divalent Zn in the reduced melt and diffusion will not affect the extent of Zn isotope fractionation. These observations imply that the capability of forming a redox environment may aid in volatilizing some elements, accompanied by isotope fractionation, during the impact process. The greater extent of elemental depletion, coupled with isotope fractionation of more refractory Cu relative to Zn, may also hinge on the presence of carbonyl species of transition metals and electromagnetic charge, which could exist in the impact‐induced high‐velocity jet of vapor and melts.     

Magnesium isotopic fractionation in chondrules from the Murchison and Murray CM2 carbonaceous chondrites

We present high‐precision measurements of the Mg isotopic compositions of a suite of types I and II chondrules separated from the Murchison and Murray CM2 carbonaceous chondrites. These chondrules are olivine‐ and pyroxene‐rich and have low ²⁷Al/²⁴Mg ratios (0.012–0.316). The Mg isotopic compositions of Murray chondrules are on average lighter (δ²⁶Mg ranging from ?0.95‰ to ?0.15‰ relative to the DSM‐3 standard) than those of Murchison (δ²⁶Mg ranging from ?1.27‰ to +0.77‰). Taken together, the CM2 chondrules exhibit a narrower range of Mg isotopic compositions than those from CV and CB chondrites studied previously. The least‐altered CM2 chondrules are on average lighter (average δ²⁶Mg = ?0.39 ± 0.30‰, 2SE) than the moderately to heavily altered CM2 chondrules (average δ²⁶Mg = ?0.11 ± 0.21‰, 2SE). The compositions of CM2 chondrules are consistent with isotopic fractionation toward heavy Mg being associated with the formation of secondary silicate phases on the CM2 parent body, but were also probably affected by volatilization and recondensation processes involved in their original formation. The low‐Al CM2 chondrules analyzed here do not exhibit any mass‐independent variations in ²⁶Mg from the decay of ²⁶Al, with the exception of two chondrules that show only small variations just outside of the analytical error. In the case of the chondrule with the highest Al/Mg ratio (a type IAB chondrule from Murchison), the lack of resolvable ²⁶Mg excess suggests that it either formed >1 Ma after calcium‐aluminum‐rich inclusions, or that its Al‐Mg isotope systematics were reset by secondary alteration processes on the CM2 chondrite parent body after the decay of ²⁶Al.     

Natural variations in the rhenium isotopic composition of meteorites

Rhenium is an important element with which to test hypotheses of isotope variation. Historically, it has been difficult to precisely correct the instrumental mass bias in thermal ionization mass spectrometry. We used W as an internal standard to correct mass bias on the MC‐ICP‐MS, and obtained the first precise δ¹⁸⁷Re values (~±0.02‰, 2SE) for iron meteorites and chondritic metal. Relative to metal from H chondrites, IVB irons are systematically higher in δ¹⁸⁷Re by ~0.14 ‰. δ¹⁸⁷Re for other irons are similar to H chondritic metal, although some individual samples show significant isotope fractionation. Since ¹⁸⁵Re has a high neutron capture cross section, the effect of galactic cosmic‐ray (GCR) irradiation on δ¹⁸⁷Re was examined using correlations with Pt isotopes. The pre‐GCR irradiation δ¹⁸⁷Re for IVB irons is lower, but the difference in δ¹⁸⁷Re between IVB irons and other meteoritic metal remains. Nuclear volume‐dependent fractionation for Re is about the right magnitude near the melting point of iron, but because of the refractory and compatible character of Re, a compelling explanation in terms of mass‐dependent fractionation is elusive. The magnitude of a nucleosynthetic s‐process deficit for Re estimated from Mo and Ru isotopes is essentially unresolvable. Since thermal processing reduced nucleosynthetic effects in Pd, it is conceivable that Re isotopic variations larger than those in Mo and Ru may be present in IVBs since Re is more refractory than Mo and Ru. Thus, the Re isotopic difference between IVBs and other irons or chondritic metal remains unexplained.     

The Cu isotopic composition of iron meteorites

Abstract– High‐precision Cu isotopic compositions have been measured for the metal phase of 29 iron meteorites from various groups and for four terrestrial standards. The data are reported as the δ⁶⁵Cu permil deviation of the ⁶⁵Cu/⁶³Cu ratio relative to the NIST SRM 976 standard. Terrestrial mantle rocks have a very narrow range of variations and scatter around zero. In contrast, iron meteorites show δ⁶⁵Cu approximately 2.3‰ variations. Different groups of iron meteorites have distinct δ⁶⁵Cu values. Nonmagmatic IAB‐IIICD iron meteorites have similar δ⁶⁵Cu (0.03 ± 0.08 and 0.12 ± 0.10, respectively), close to terrestrial values (approximately 0). The other group of nonmagmatic irons, IIE, is isotopically distinct (?0.69 ± 0.15). IVB is the iron meteorite group with the strongest elemental depletion in Cu and samples in this group are enriched in the lighter isotope (δ⁶⁵Cu down to ?2.26‰). Evaporation should have produced an enrichment in ⁶⁵Cu over ⁶³Cu (δ⁶⁵Cu >0) and can therefore be ruled out as a mechanism for volatile loss in IVB meteorites. In silicate‐bearing iron meteorites, Δ¹⁷O correlates with δ⁶⁵Cu. This correlation between nonmass‐dependent and mass‐dependent parameters suggests that the Cu isotopic composition of iron meteorites has not been modified by planetary differentiation to a large extent. Therefore, Cu isotopic ratios can be used to confirm genetic links. Cu isotopes thus confirm genetic relationships between groups of iron meteorites (e.g., IAB and IIICD; IIIE and IIIAB); and between iron meteorites and chondrites (e.g., IIE and H chondrites). Several genetic connections between iron meteorites groups are confirmed by Cu isotopes, (e.g., IAB and IIICD; IIIE and IIIAB); and between iron meteorites and chondrites (e.g., IIE and H chondrites).     

Potassium isotopic compositions of enstatite meteorites

Enstatite chondrites and aubrites are meteorites that show the closest similarities to the Earth in many isotope systems that undergo mass‐independent and mass‐dependent isotopic fractionations. Due to the analytical challenges to obtain high‐precision K isotopic compositions in the past, potential differences in K isotopic compositions between enstatite meteorites and the Earth remained uncertain. We report the first high‐precision K isotopic compositions of eight enstatite chondrites and four aubrites and find that there is a significant variation of K isotopic compositions among enstatite meteorites (from ?2.34‰ to ?0.18‰). However, K isotopic compositions of nearly all enstatite meteorites scatter around the bulk silicate earth (BSE) value. The average K isotopic composition of the eight enstatite chondrites (?0.47 ± 0.57‰) is indistinguishable from the BSE value (?0.48 ± 0.03‰), thus further corroborating the isotopic similarity between Earth's building blocks and enstatite meteorite precursors. We found no correlation of K isotopic compositions with the chemical groups, petrological types, shock degrees, and terrestrial weathering conditions; however, the variation of K isotopes among enstatite meteorite can be attributed to the parent‐body processing. Our sample of the main‐group aubrite MIL 13004 is exceptional and has an extremely light K isotopic composition (δ⁴¹K = ?2.34 ± 0.12‰). We attribute this unique K isotopic feature to the presence of abundant djerfisherite inclusions in our sample because this K‐bearing sulfide mineral is predicted to be enriched in ³⁹K during equilibrium exchange with silicates.     

Mass‐dependent fractionation of nickel isotopes in meteoritic metal

Abstract— We measured nickel isotopes via multicollector inductively coupled plasma mass spectrometry (MC‐ICPMS) in the bulk metal from 36 meteorites, including chondrites, pallasites, and irons (magmatic and non‐magmatic). The Ni isotopes in these meteorites are mass fractionated; the fractionation spans an overall range of ～0.4‰ amu^?1. The ranges of Ni isotopic compositions (relative to the SRM 986 Ni isotopic standard) in metal from iron meteorites (～0.0 to ～0.3‰ amu^?1) and chondrites (～0.0 to ～0.2‰ amu^?1) are similar, whereas the range in pallasite metal (～–0.1 to 0.0‰ amu^?1) appears distinct. The fractionation of Ni isotopes within a suite of fourteen IIIAB irons (～0.0 to ～0.3‰ amu^?1) spans the entire range measured in all magmatic irons. However, the degree of Ni isotopic fractionation in these samples does not correlate with their Ni content, suggesting that core crystallization did not fractionate Ni isotopes in a systematic way. We also measured the Ni and Fe isotopes in adjacent kamacite and taenite from the Toluca IAB iron meteorite. Nickel isotopes show clearly resolvable fractionation between these two phases; kamacite is heavier relative to taenite by ～0.4‰ amu^?1. In contrast, the Fe isotopes do not show a resolvable fractionation between kamacite and taenite. The observed isotopic compositions of kamacite and taenite can be understood in terms of kinetic fractionation due to diffusion of Ni during cooling of the Fe‐Ni alloy and the development of the Widmanstätten pattern.     

Sulfur isotopic composition of Fe‐Ni sulfide grains in CI and CM carbonaceous chondrites

Abstract– In situ secondary ion mass spectrometry analyses of ³²S, ³³S, and ³⁴S in iron‐nickel sulfide grains in two CI1 chondrites and six CM chondrites were performed. The results show a wider range of both enrichment and depletion in δ³⁴S relative to troilite from the Canyon Diablo meteorite (CDT) than has been observed in previous studies. All data points lie within error of a single mass dependent fractionation line. Sulfides from CI1 chondrites show δ³⁴S_CDT from ?0.7 to 6.8‰, while sulfide grains in the CM1 chondrite are generally depleted in heavy sulfur relative to CDT (δ³⁴S from ?2.9 to 1.8‰). CM2 chondrites contain sulfide grains that show enrichment and depletion in ³⁴S (δ³⁴S_CDT from ?7.0 to 6.8‰). Sulfates forming from sulfide grains during aqueous alteration on the chondrite parent body are suggested to concentrate light sulfur, leaving the remaining sulfide grains enriched in the heavy isotopes of sulfur. The average degree of enrichment in ³⁴S in CM chondrite sulfides is broadly consistent with previously suggested alteration sequences.     

Early solar system aqueous activity: K isotope evidence from Allende

The alkali element K is moderately volatile and fluid mobile; thus, it can be influenced by both primary processes (evaporation and recondensation) in the solar nebula and secondary processes (thermal and aqueous alteration) in the parent body. Since these primary and secondary processes would induce different isotopic fractionations, K isotopes could become a potential tracer to distinguish them. Using recently developed methods with improved precision (0.05‰, 95% confidence interval), we systematically measured the K isotopic compositions and major/trace elemental compositions of chondritic components (18 chondrules, 3 CAIs, 2 matrices, and 5 bulks) in the carbonaceous chondrite fall Allende. Among all the components analyzed in this study, CAIs, which formed initially under high‐temperature conditions in the solar nebula and were dominated by nominally K‐free refractory minerals, have the highest K₂O content (average 0.53 wt%) and have K isotope compositions most enriched in heavy isotopes (δ⁴¹K: ?0.30 to ?0.25‰). Such an observation is consistent with previous petrologic studies that show CAIs in Allende have undergone alkali enrichment during metasomatism. In contrast, chondrules contain lower K₂O content (0.003–0.17 wt%) and generally lighter K isotope compositions (δ⁴¹K: ?0.87‰ to ?0.24‰). The matrix and bulks are nearly identical in K₂O content and K isotope compositions (0.02–0.05 wt%; δ⁴¹K: ?0.62 to ? 0.46‰), which are, as expected, right in the middle of CAIs and chondrules. This strongly indicates that most of the chondritic components of Allende suffered aqueous alteration and their K isotopic compositions are the ramification of Allende parent‐body processing instead of primary nebular signatures. Nevertheless, we propose the small K isotope fractionations observed (< 1‰) among Allende components are likely similar to the overall range of K isotopic fractionation that occurred in nebular environment. Furthermore, the K isotope compositions seen in the components of Allende in this study are consistent with MC‐ICP‐MS analyses of the components in ordinary chondrites, which also show an absence of large (10‰) isotope fractionations. This is not expected as evaporation experiments in nebular conditions suggest there should be large K isotopic fractionations. Nevertheless, possible nebular processes such as chondrules back exchanging with ambient gas when they formed could explain this lack of large K isotopic variation.     

The chlorine isotope composition of iron meteorites: Evidence for the Cl isotope composition of the solar nebula and implications for extensive devolatilization during planet formation

The bulk chlorine concentrations and isotopic compositions of a suite of non‐carbonaceous (NC) and carbonaceous (CC) iron meteorites were measured using gas source mass spectrometry. The δ³⁷Cl values of magmatic irons range from ?7.2 to 18.0‰ versus standard mean ocean chloride and are unrelated to their chlorine concentrations, which range from 0.3 to 161 ppm. Nonmagmatic IAB irons are comparatively Cl‐rich containing >161 ppm with δ³⁷Cl values ranging from ?6.1 to ?3.2‰. The anomalously high and low δ³⁷Cl values are inconsistent with a terrestrial source, and as Cl contents in magmatic irons are largely consistent with derivation from a chondrite‐like silicate complement, we suggest that Cl is indigenous to iron meteorites. Two NC irons, Cape York and Gibeon, have high cooling rates with anomalously high δ³⁷Cl values of 13.4 and 18.0‰. We interpret these high isotopic compositions to result from Cl degassing during the disruption of their parent bodies, consistent with their low volatile contents (Ga, Ge, Ag). As no relevant mechanisms in iron meteorite parent bodies are expected to decrease δ³⁷Cl values, whereas volatilization is known to increase δ³⁷Cl values by the preferential loss of light isotopes, we interpret the low isotope values of <?5‰ and down to ?7.2‰ to most closely represent the primordial isotopic composition of Cl in the solar nebula. Similar conclusions have been derived from low δ³⁷Cl values down to ?6, and ?3.8‰ measured in Martian and Vestan meteorites, respectively. These low δ³⁷Cl values are in contrast to those of chondrites which average around 0‰ previously explained by the incorporation of isotopically heavy HCl clathrate into chondrite parent bodies. The poor retention of low δ³⁷Cl values in many differentiated planetary materials suggest that extensive devolatilization occurred during planet formation, which can explain Earth's high δ³⁷Cl value by the loss of approximately 60% of the initial Cl content.     

The oxygen‐isotopic record in enstatite meteorites

Abstract— Oxygen‐isotopic compositions were determined for a suite of enstatite chondrites and aubrites. In agreement with previous work (Clayton et al., 1984), most samples have O‐isotopic compositions close to the terrestrial fractionation line (TFL), and there appear to be no significant differences in O‐isotopic compositions between individual EH and EL chondrites and aubrites. Five enstatite meteorites have O‐isotopic compositions that are significantly different from the other samples and >0.2% away from the TFL. Two of these have petrographic evidence of brecciation and interaction between other meteorite types; for the other three, similar scenarios are suggested. There appears to be a systematic increase in δ¹⁸O from enstatite chondrites (both EH and EL) of petrologic type 3 to those of type 6. There is also good evidence that the EH meteorites do not fall along a mass fractionation line but along a line slope 0.66. At the present time, detailed understanding of the origin of these O‐isotopic systematics remain elusive but clearly point to a complex accretion history, parent‐body evolution, or both.     

Chemical and oxygen isotopic properties of ordinary chondrites (H5, L6) from Oman: Signs of isotopic equilibrium during thermal metamorphism

Mean bulk chemical data of recently found H5 and L6 ordinary chondrites from the deserts of Oman generally reflect isochemical features which are consistent with the progressive thermal metamorphism of a common, unequilibrated starting material. Relative differences in abundances range from 0.5–10% in REE (Eu = 14%), 6–13% in siderophile elements (Co = 48%), and >10% in lithophile elements (exceptions are Ba, Sr, Zr, Hf, U = >30%) between H5 and L6 groups. These differences may have accounted for variable temperature conditions during metamorphism on their parent bodies. The CI/Mg‐normalized mean abundances of refractory lithophile elements (Al, Ca, Sm, Yb, Lu, V) show no resolvable differences between H5 and L6 suggesting that both groups have experienced the same fractionation. The REE diagram shows subtle enrichment in LREE with a flat HREE pattern. Furthermore, overall mean REE abundances are ~0.6 × CI with enriched La abundance (~0.9 × CI) in both groups. Precise oxygen isotope compositions demonstrate the attainment of isotopic equilibrium by progressive thermal metamorphism following a mass‐dependent isotope fractionation trend. Both groups show a ~slope‐1/2 line on a three‐isotope plot with subtle negative deviation in ?¹⁷O associated with δ¹⁸O enrichment relative to δ¹⁷O. These deviations are interpreted as the result of liberation of water from phyllosilicates and evaporation of a fraction of the water during thermal metamorphism. The resultant isotope fractionations caused by the water loss are analogous to those occurring between silicate melt and gas phase during CAI and chondrule formation in chondrites and are controlled by cooling rates and exchange efficiency.     

Oxygen isotopic and chemical composition of chromites in micrometeorites: Evidence of ordinary chondrite precursors

We identified 66 chromite grains from 42 of ~5000 micrometeorites collected from Indian Ocean deep‐sea sediments and the South Pole water well. To determine the chromite grains precursors and their contribution to the micrometeorite flux, we combined quantitative electron microprobe analyses and oxygen isotopic analyses by high‐resolution secondary ion mass spectrometry. Micrometeorite chromite grains show variable O isotopic compositions with δ¹⁸O values ranging from ?0.8 to 6.0‰, δ¹⁷O values from 0.3 to 3.6‰, and Δ¹⁷O values from ?0.9 to 1.6‰, most of them being similar to those of chromites from ordinary chondrites. The oxygen isotopic compositions of olivine, considered as a proxy of chromite in chromite‐bearing micrometeorites where chromite is too small to be measured in ion microprobe have Δ¹⁷O values suggesting a principal relationship to ordinary chondrites with some having carbonaceous chondrite precursors. Furthermore, the chemical compositions of chromites in micrometeorites are close to those reported for ordinary chondrite chromites, but some contribution from carbonaceous chondrites cannot be ruled out. Consequently, carbonaceous chondrites cannot be a major contributor of chromite‐bearing micrometeorites. Based on their oxygen isotopic and elemental compositions, we thus conclude with no ambiguity that chromite‐bearing micrometeorites are largely related to fragments of ordinary chondrites with a small fraction from carbonaceous chondrites, unlike other micrometeorites deriving largely from carbonaceous chondrites.     

The lack of potassium‐isotopic fractionation in Bishunpur chondrules

Abstract— In a search for evidence of evaporation during chondrule formation, the mesostases of 11 Bishunpur chondrules and melt inclusions in olivine phenocrysts in 7 of them have been analyzed for their alkali element abundances and K‐isotopic compositions. Except for six points, all areas of the chondrules that were analyzed had δ⁴¹K compositions that were normal within error (typically ±3%, 2s?). The six “anomalous” points are probably all artifacts. Experiments have shown that free evaporation of K leads to large ⁴¹K enrichments in the evaporation residues, consistent with Rayleigh fractionation. Under Rayleigh conditions, a 3% enrichment in δ⁴¹K is produced by ～12% loss of K. The range of L‐chondrite‐normalized K/Al ratios (a measure of the K‐elemental fractionation) in the areas analyzed vary by almost three orders of magnitude. If all chondrules started out with L‐chondrite‐like K abundances and the K loss occurred via Rayleigh fractionation, the most K‐depleted chondrules would have had compositions of up to δ⁴¹K ? 200%. Clearly, K fractionation did not occur by evaporation under Rayleigh conditions. Yet experiments and modeling indicate that K should have been lost during chondrule formation under currently accepted formation conditions (peak temperature, cooling rate, etc.). Invoking precursors with variable alkali abundances to produce the range of K/Al fractionation in chondrules does not explain the K‐isotopic data because any K that was present should still have experienced sufficient loss during melting for there to have been a measurable isotopic fractionation. If K loss and isotopic fractionation was inevitable during chondrule formation, the absence of K‐isotopic fractionation in Bishunpur chondrules requires that they exchanged K with an isotopically normal reservoir during or after formation. There is evidence for alkali exchange between chondrules and rim‐matrix in all unequilibrated ordinary chondrites. However, melt inclusions can have alkali abundances that are much lower than the mesostases of the host chondrules, which suggests that they at least remained closed since formation. If it is correct that some or all melt inclusions remained closed since formation, the absence of K‐isotopic fractionation in them requires that the K‐isotopic exchange took place during chondrule formation, which would probably require gas‐chondrule exchange. Potassium evaporated from fine‐grained dust and chondrules during chondrule formation may have produced sufficient K‐vapor pressure for gas‐chondrule isotopic exchange to be complete on the timescales of chondrule formation. Alternatively, our understanding of chondrule formation conditions based on synthesis experiments needs some reevaluation.     

Hydrogen isotopic composition of the Martian mantle inferred from the newest Martian meteorite fall,Tissint

The hydrogen isotopic composition of planetary reservoirs can provide key constraints on the origin and history of water on planets. The sources of water and the hydrological evolution of Mars may be inferred from the hydrogen isotopic compositions of mineral phases in Martian meteorites, which are currently the only samples of Mars available for Earth‐based laboratory investigations. Previous studies have shown that δD values in minerals in the Martian meteorites span a large range of ?250 to +6000‰. The highest hydrogen isotope ratios likely represent a Martian atmospheric component: either interaction with a reservoir in equilibrium with the Martian atmosphere (such as crustal water), or direct incorporation of the Martian atmosphere due to shock processes. The lowest δD values may represent those of the Martian mantle, but it has also been suggested that these values may represent terrestrial contamination in Martian meteorites. Here we report the hydrogen isotopic compositions and water contents of a variety of phases (merrillites, maskelynites, olivines, and an olivine‐hosted melt inclusion) in Tissint, the latest Martian meteorite fall that was minimally exposed to the terrestrial environment. We compared traditional sample preparation techniques with anhydrous sample preparation methods, to evaluate their effects on hydrogen isotopes, and find that for severely shocked meteorites like Tissint, the traditional sample preparation techniques increase water content and alter the D/H ratios toward more terrestrial‐like values. In the anhydrously prepared Tissint sample, we see a large range of δD values, most likely resulting from a combination of processes including magmatic degassing, secondary alteration by crustal fluids, shock‐related fractionation, and implantation of Martian atmosphere. Based on these data, our best estimate of the δD value for the Martian depleted mantle is ?116 ± 94‰, which is the lowest value measured in a phase in the anhydrously prepared section of Tissint. This value is similar to that of the terrestrial upper mantle, suggesting that water on Mars and Earth was derived from similar sources. The water contents of phases in Tissint are highly variable, and have been affected by secondary processes. Considering the H₂O abundances reported here in the driest phases (most likely representing primary igneous compositions) and appropriate partition coefficients, we estimate the H₂O content of the Tissint parent magma to be ≤0.2 wt%.     

Isotopic composition of carbon and nitrogen in ureilitic fragments of the Almahata Sitta meteorite

This study characterizes carbon and nitrogen abundances and isotopic compositions in ureilitic fragments of Almahata Sitta. Ureilites are carbon‐rich (containing up to 7 wt% C) and were formed early in solar system history, thus the origin of carbon in ureilites has significance for the origin of solar system carbon. These samples were collected soon after they fell, so they are among the freshest ureilite samples available and were analyzed using stepped combustion mass spectrometry. They contained 1.2–2.3 wt% carbon; most showed the major carbon release at temperatures of 600–700 °C with peak values of δ¹³C from ?7.3 to +0.4‰, similar to literature values for unbrecciated (“monomict”) ureilites. They also contained a minor low temperature (≤500 °C) component (δ¹³C = ca ?25‰). Bulk nitrogen contents (9.4–27 ppm) resemble those of unbrecciated ureilites, with major releases mostly occurring at 600–750 °C. A significant lower temperature release of nitrogen occurred in all samples. Main release δ¹⁵N values of ?53 to ?94‰ fall within the range reported for diamond separates and acid residues from ureilites, and identify an isotopically primordial nitrogen component. However, they differ from common polymict ureilites which are more nitrogen‐rich and isotopically heavier. Thus, although the parent asteroid 2008TC₃ was undoubtedly a polymict ureilite breccia, this cannot be deduced from an isotopic study of individual ureilite fragments. The combined main release δ¹³C and δ¹⁵N values do not overlap the fields for carbonaceous or enstatite chondrites, suggesting that carbon in ureilites was not derived from these sources.     

Stable isotope analysis of carbon and nitrogen in angrites

Angrites are a small group of ancient basaltic achondrites, notable for their unusual chemistry and extreme volatile depletion. No comprehensive study of indigenous light elements currently exists for the group. Measurement of the abundances and isotopic composition of carbon and nitrogen could provide information pertaining to the evolution of the angrite parent body. Bulk‐sample stepped combustion analyses of five angrites and a glass separate from D'Orbigny were combined with earlier data and acid dissolution experiments of carbonates found in D'Orbigny to compile an inventory of indigenous carbon and nitrogen. Indigenous carbon combusted between 700 °C and 1200 °C, with abundances of 10–140 ppm and a mass‐weighted δ¹³C of ?25 to ?20‰ with the exception of D'Orbigny (δ¹³C approximately ?5‰). Nitrogen was released at 850–1200 ºC, 1–20 ppm with a δ¹⁵N ?3‰ to +4‰; again, D'Orbigny (δ¹⁵N approximately +20 to +25‰) was an exception. We interpret these components as largely indigenous and decoupled; the carbon in graphitic or amorphous form, while the nitrogen is present as a dissolved component in the silicates. No relationship with the textural sub‐classification of angrites is apparent. We suggest that the angrite parent body contains a reservoir of reduced carbon and thus may have undergone a change in redox conditions, although the timing and mechanism for this remain unclear.     

Oxygen isotopes in magnetite and fayalite in CV chondrites Kaba and Mokoia

Abstract— We report in situ measurements of O‐isotopic compositions of magnetite and primary and secondary olivine in the highly unequilibrated oxidized CV chondrites Kaba and Mokoia. In both meteorites, the magnetite and the secondary olivine (fayalite, Fa_90–100) have O‐isotopic compositions near the terrestrial fractionation (TF) line; the mean Δ¹⁷O (= δ¹⁷O‐0.52 × δ¹⁸O) value is about ?1%‰. In contrast, the compositions of nearby primary (chondrule), low‐FeO olivines (Fa_1–2) are well below the TF line; Δ¹⁷O values range from ?3 to ?9%‰. Krot et al. (1998) summarized evidence indicating that the secondary phases in these chondrites formed by aqueous alteration in an asteroidal setting. The compositions of magnetite and fayalite in Kaba and Mokoia imply that the O‐isotopic composition of the oxidant was near or somewhat above the TF line. In Mokoia the fayalite and magnetite differ in δ¹⁸O by ～20%‰, whereas these same materials in Kaba have virtually identical compositions. The difference between Mokoia magnetite and fayalite may indicate formation in isotopic equilibrium in a water‐rich environment at low temperatures, ～300 K. In contrast, the similar compositions of these phases in Kaba may indicate formation of the fayalite by replacement of preexisting magnetite in dry environment, with the O coming entirely from the precursor magnetite and silica. The Δ¹⁷O of the oxidant incorporated into the CV parent body (as phyllosilicates or H₂O) appears to have been much (7–8%‰) lower than that in that incorporated into the LL parent body (Choi et al, 1998), which suggests that the O‐isotopic composition of the nebular gas was spatially or temporally variable.     

Evidence for high‐temperature fractionation of lithium isotopes during differentiation of the Moon

Lithium isotope and abundance data are reported for Apollo 15 and 17 mare basalts and the LaPaz low‐Ti mare basalt meteorites, along with lithium isotope data for carbonaceous, ordinary, and enstatite chondrites, and chondrules from the Allende CV3 meteorite. Apollo 15 low‐Ti mare basalts have lower Li contents and lower δ⁷Li (3.8 ± 1.2‰; all uncertainties are 2 standard deviations) than Apollo 17 high‐Ti mare basalts (δ⁷Li = 5.2 ± 1.2‰), with evolved LaPaz mare basalts having high Li contents, but similar low δ⁷Li (3.7 ± 0.5‰) to Apollo 15 mare basalts. In low‐Ti mare basalt 15555, the highest concentrations of Li occur in late‐stage tridymite (>20 ppm) and plagioclase (11 ± 3 ppm), with olivine (6.1 ± 3.8 ppm), pyroxene (4.2 ± 1.6 ppm), and ilmenite (0.8 ± 0.7 ppm) having lower Li concentrations. Values of δ⁷Li in low‐ and high‐Ti mare basalt sources broadly correlate negatively with ¹⁸O/¹⁶O and positively with ⁵⁶Fe/⁵⁴Fe (low‐Ti: δ⁷Li ≤4‰; δ⁵⁶Fe ≤0.04‰; δ¹⁸O ≥5.7‰; high‐Ti: δ⁷Li >6‰; δ⁵⁶Fe >0.18‰; δ¹⁸O <5.4‰). Lithium does not appear to have acted as a volatile element during planetary formation, with subequal Li contents in mare basalts compared with terrestrial, martian, or vestan basaltic rocks. Observed Li isotopic fractionations in mare basalts can potentially be explained through large‐degree, high‐temperature igneous differentiation of their source regions. Progressive magma ocean crystallization led to enrichment in Li and δ⁷Li in late‐stage liquids, probably as a consequence of preferential retention of ⁷Li and Li in the melt relative to crystallizing solids. Lithium isotopic fractionation has not been observed during extensive differentiation in terrestrial magmatic systems and may only be recognizable during extensive planetary magmatic differentiation under volatile‐poor conditions, as expected for the lunar magma ocean. Our new analyses of chondrites show that they have δ⁷Li ranging between ?2.5‰ and 4‰. The higher δ⁷Li in planetary basalts than in the compilation of chondrites (2.1 ± 1.3‰) demonstrates that differentiated planetary basalts are, on average, isotopically heavier than most chondrites.     

Oxygen isotopic compositions and origins of calcium‐aluminum‐rich inclusions and chondrules

Abstract— Primary minerals in calcium‐aluminum‐rich inclusions (CAIs), Al‐rich and ferromagnesian chondrules in each chondrite group have δ¹⁸O values that typically range from ?50 to +5%0. Neglecting effects due to minor mass fractionations, the oxygen isotopic data for each chondrite group and for micrometeorites define lines on the three‐isotope plot with slopes of 1.01 ± 0.06 and intercepts of ?2 ± 1. This suggests that the same kind of nebular process produced the ¹⁶O variations among chondrules and CAIs in all groups. Chemical and isotopic properties of some CAIs and chondrules strongly suggest that they formed from solar nebula condensates. This is incompatible with the existing two‐component model for oxygen isotopes in which chondrules and CAIs were derived from heated and melted ¹⁶O‐rich presolar dust that exchanged oxygen with ¹⁶O‐poor nebular gas. Some FUN CAIs (inclusions with isotope anomalies due to fractionation and unknown nuclear effects) have chemical and isotopic compositions indicating they are evaporative residues of presolar material, which is incompatible with ¹⁶O fractionation during mass‐independent gas phase reactions in the solar nebula. There is only one plausible reason why solar nebula condensates and evaporative residues of presolar materials are both enriched in ¹⁶O. Condensation must have occurred in a nebular region where the oxygen was largely derived from evaporated ¹⁶O‐rich dust. A simple model suggests that dust was enriched (or gas was depleted) relative to cosmic proportions by factors of ～10 to >50 prior to condensation for most CAIs and factors of 1–5 for chondrule precursor material. We infer that dust‐gas fractionation prior to evaporation and condensation was more important in establishing the oxygen isotopic composition of CAIs and chondrules than any subsequent exchange with nebular gases. Dust‐gas fractionation may have occurred near the inner edge of the disk where nebular gases accreted into the protosun and Shu and colleagues suggest that CAIs formed.