Disturbance of isotope systematics during experimental shock and thermal metamorphism of a lunar basalt with implications for Martian meteorite chronology

Abstract– To better determine the effects of impact‐related processes on radiometric chronometers in meteorites, we undertook an isotopic study of experimentally shocked and heated samples of lunar basalt 10017. Shock experiments at 55 GPa were completed on one subsample, and a second subsample was heated in an evacuated quartz tube at 1000 °C for 170 h. A third subsample was maintained as a control. Samarium‐neodymium, Rb‐Sr, ²³⁸U‐²⁰⁶Pb, and ²⁰⁶Pb‐²⁰⁷Pb isotopic analyses were completed on mineral fractions (leached and unleached), leached whole rocks, and complementary acid leachates. Disturbance in the shocked and heated samples was evaluated through comparison of their isochron diagrams with those of the control sample. The Sm‐Nd isotope system was the least disturbed, the Rb‐Sr isotope system was more disturbed, and the ²³⁸U‐²⁰⁶Pb and ²⁰⁶Pb‐²⁰⁷Pb isotope systems were the most disturbed by shock and annealing. Samples that experienced extended heating demonstrated greater isotopic disturbances than shocked samples. In some cases, the true crystallization age was preserved, and in others, age information was degraded or destroyed. In no case did the experiments generate isochrons that maintained linearity while being rotated or completely reset. Although our results show that neither experimental shock nor thermal metamorphism alone can account for the discordant ages represented by different isotope systems in some Martian meteorites, we postulate that shock metamorphism may render a meteorite more susceptible than its unshocked counterpart to subsequent disturbance during extended impact‐related heating or aqueous alteration. The combination of these processes may result in the disparate chronometric information preserved in some meteorites.     

Zinc isotopic composition of iron meteorites: Absence of isotopic anomalies and origin of the volatile element depletion

High‐precision Zn isotopic compositions measured by MC‐ICP‐MS are documented for 32 iron meteorites from various fractionally crystallized and silicate‐bearing groups. The δ⁶⁶Zn values range from ?0.59‰ up to +5.61‰ with most samples being slightly enriched in the heavier isotopes compared with carbonaceous chondrites (0 < δ⁶⁶Zn < 0.5). The δ⁶⁶Zn versus δ⁶⁸Zn plot of all samples defines a common linear fractionation line, which supports the hypothesis that Zn was derived from a single reservoir or from multiple reservoirs linked by mass‐dependent fractionation processes. Our data for Redfields fall on a mass fractionation line and therefore refute a previous claim of it having an anomalous isotopic composition due to nonmixing of nucleosynthetic products. The negative correlation between δ⁶⁶Zn and the Zn concentration of IAB and IIE is consistent with mass‐dependent isotopic fractionation due to evaporation with preferential loss of lighter isotopes in the vapor phase. Data for the Zn concentrations and isotopic compositions of two IVA samples demonstrate that volatile depletion in the IVA parent body is not likely the result of evaporation. This is important evidence that favors the incomplete condensation origin for the volatile depletion of the IVA parent body.     

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.     

Ion microprobe U‐Th‐Pb dating of phosphates in martian meteorite ALH 84001

Abstract— Phosphates in martian meteorites are important carriers of trace elements, although, they are volumetrically minor minerals. PO₄ also has potential as a biomarker for life on Mars. Here, we report measurements of the U‐Th‐Pb systematics of phosphates in the martian meteorite ALH 84001 using the Sensitive High Resolution Ion MicroProbe (SHRIMP) installed at Hiroshima University, Japan. Eleven analyses of whitlockites and 1 analysis of apatite resulted in a total Pb/U isochron age of 4018 ± 81 Ma in the ²³⁸U/²⁰⁶Pb‐²⁰⁷Pb/²⁰⁶Pb‐²⁰⁴Pb/²⁰⁶ Pb 3‐D space, and a ²³²Th‐²⁰⁸Pb age of 3971 ± 860 Ma. These ages are consistent within a 95% confidence limit. This result is in agreement with the previously published Ar‐Ar shock age of 4.0 ± 0.1 Ga from maskelynite and other results of 3.8–4.3 Ga but are significantly different from the Sm‐Nd age of 4.50 ± 0.13 Ga based on the whole rock and pyroxene. Taking into account recent studies on textural and chemical evidence of phosphate, our result suggests that the shock metamorphic event defines the phosphate formation age of 4018 ± 81 Ma, and that since then, ALH 84001 has not experienced a long duration thermal metamorphism, which would reset the U‐Pb system in phosphates.     

40Ar‐39Ar age determinations of lunar basalt meteorites Asuka 881757, Yamato 793169, Miller Range 05035, La Paz Icefield 02205, Northwest Africa 479, and basaltic breccia Elephant Moraine 96008

Abstract— ⁴⁰Ar‐³⁹Ar data are presented for the unbrecciated lunar basaltic meteorites Asuka (A‐) 881757, Yamato (Y‐) 793169, Miller Range (MIL) 05035, LaPaz Icefield (LAP) 02205, Northwest Africa (NWA) 479 (paired with NWA 032), and basaltic fragmental breccia Elephant Moraine (EET) 96008. Stepped heating ⁴⁰Ar‐³⁹Ar analyses of several bulk fragments of related meteorites A‐881757, Y‐793169 and MIL 05035 give crystallization ages of 3.763 ± 0.046 Ga, 3.811 ± 0.098 Ga and 3.845 ± 0.014 Ga, which are comparable with previous age determinations by Sm‐Nd, U‐Pb Th‐Pb, Pb‐Pb, and Rb‐Sr methods. These three meteorites differ in the degree of secondary ⁴⁰Ar loss with Y‐793169 showing relatively high Ar loss probably during an impact event ?200 Ma ago, lower Ar loss in MIL 05035 and no loss in A‐881757. Bulk and impact melt glass‐bearing samples of LAP 02205 gave similar ages (2.985 ± 0.016 Ga and 2.874 ± 0.056 Ga) and are consistent with ages previously determined using other isotope pairs. The basaltic portion of EET 96008 gives an age of 2.650 ± 0.086 Ga which is considered to be the crystallization age of the basalt in this meteorite. The Ar release for fragmental basaltic breccia EET 96008 shows evidence of an impact event at 631 ± 20 Ma. The crystallization age of 2.721 ± 0.040 Ga determined for NWA 479 is indistinguishable from the weighted mean age obtained from three samples of NWA 032 supporting the proposal that these meteorites are paired. The similarity of ⁴⁰Ar‐³⁹Ar ages with ages determined by other isotopic systems for multiple meteorites suggests that the K‐Ar isotopic system is robust for meteorites that have experienced a significant shock event and not a prolonged heating regime.     

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.     

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 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.     

The oxygen-isotopic composition of Earth and Mars

Abstract— The small difference between the O-isotopic mass fractionation lines of the Earth and Mars has been measured precisely using a laser fluorination system. The precision achieved from the two sample sets is better than ±0.014‰, with the offset (Δ¹⁷O) between Mars and Earth measured as +0.321‰. This result shows that all the Shergotty—Nakhla—Chassigny (SNC) meteorites define a high level of isotopic homogeneity, comparable to that of crustal material on the Earth, indicating that these meteorites originate, unequivocally, from a single, common parent body (Mars). Allan Hills 84001, with its ancient age (4.56 Ga), shows that any initial heterogeneity imparted into Mars from the nebula was homogenised very early in the formation history of the planet.     

Intermineral oxygen three‐isotope systematics of silicate minerals in equilibrated ordinary chondrites

High‐precision oxygen three‐isotope ratios were measured for four mineral phases (olivine, low‐Ca and high‐Ca pyroxene, and plagioclase) in equilibrated ordinary chondrites (EOCs) using a secondary ion mass spectrometer. Eleven EOCs were studied that cover all groups (H, L, LL) and petrologic types (4, 5, 6), including S1–S4 shock stages, as well as unbrecciated and brecciated meteorites. SIMS analyses of multiple minerals were made in close proximity (mostly <100 μm) from several areas in each meteorite thin section, to evaluate isotope exchange among minerals. Oxygen isotope ratios in each mineral become more homogenized as petrologic type increases with the notable exception of brecciated samples. In type 4 chondrites, oxygen isotope ratios of olivine and low‐Ca pyroxene are heterogeneous in both δ¹⁸O and Δ¹⁷O, showing similar systematics to those in type 3 chondrites. In type 5 and 6 chondrites, oxygen isotope ratios of the four mineral phases plot along mass‐dependent fractionation lines that are consistent with the bulk average Δ¹⁷O of each chondrite group. The δ¹⁸O of three minerals, low‐Ca and high‐Ca pyroxene and plagioclase, are consistent with equilibrium fractionation at temperatures of 700–1000 °C. In most cases the δ¹⁸O values of olivine are higher than those expected from pyroxene and plagioclase, suggesting partial retention of premetamorphic values due to slower oxygen isotope diffusion in olivine than pyroxene during thermal metamorphism in ordinary chondrite parent bodies.     

Helium loss from Martian meteorites mainly induced by shock metamorphism: Evidence from new data and a literature compilation

Abstract— Noble gas data from Martian meteorites have provided key constraints about their origin and evolution, and their parent body. These meteorites have witnessed varying shock metamorphic overprinting (at least 5 to 14 GPa for the nakhlites and up to 45–55 GPa (e.g., the lherzolitic shergottite Allan Hills [ALH] A77005), solar heating, cosmic‐ray exposure, and weathering both on Mars and Earth. Influences on the helium budgets of Martian meteorites were evaluated by using a new data set and literature data. Concentrations of ³He, ⁴He, U, and Th are measured and shock pressures for same sample aliquots of 13 Martian meteorites were determined to asses a possible relationship between shock pressure and helium concentration. Partitioning of ⁴He into cosmogenic and radiogenic components was performed using the lowest ⁴He/³He ratio we measured on mineral separates (⁴He/³He = 4.1, pyroxene of ALHA77005). Our study revealed significant losses of radiogenic ⁴He. Systematics of cosmogenic ³He and neon led to the conclusion that solar radiation heating during transfer from Mars to Earth and terrestrial weathering can be ruled out as major causes of the observed losses of radiogenic helium in bulk meteorites. For bulk rock we observed a correlation of shock pressure and radiogenic ⁴He loss, ranging between ?20% for Chassigny and other moderately shocked Martian meteorites up to total loss for meteorites shocked above 40 GPa. A steep increase of loss occurs around 30 GPa, the pressure at which plagioclase transforms to maskelynite. This correlation suggests significant ⁴He loss induced by shock metamorphism. Noble gas loss in rocks is seen as diffusion due to (1) the temperature increase during shock loading (shock temperature) and (2) the remaining waste heat after adiabatic unloading (post shock temperature). Modeling of ⁴He diffusion in the main U, Th carrier phase apatite showed that post‐shock temperatures of ?300 °C are necessary to explain observed losses. This temperature corresponds to the post‐shock temperature calculated for bulk rocks shocked at about 40 GPa. From our investigation, data survey, and modeling, we conclude that the shock event during launch of the meteorites is the principal cause for ⁴He loss.     

The formation of Ca‐, Fe‐rich silicates in reduced and oxidized CV chondrites: The roles of impact‐modified porosity and permeability,and heterogeneous distribution of water ices

CV (Vigarano type) carbonaceous chondrites, comprising Allende‐like (CV_oxA) and Bali‐like (CV_oxB) oxidized and reduced (CV_red) subgroups, experienced differing degrees of fluid‐assisted thermal and shock metamorphism. The abundance and speciation of secondary minerals produced during asteroidal alteration differ among the subgroups: (1) ferroan olivine and diopside–hedenbergite solid solution pyroxenes are common in all CVs; (2) nepheline and sodalite are abundant in CV_oxA, rare in CV_red, and absent in CV_oxB; (3) phyllosilicates and nearly pure fayalite are common in CV_oxB, rare in CV_red, and virtually absent in CV_oxA; (4) andradite, magnetite, and Fe‐Ni‐sulfides are common in oxidized CVs, but rare in reduced CVs; the latter contain kirschsteinite instead. Thus, a previously unrecognized correlation exists between meteorite bulk permeabilities and porosities with the speciation of the Ca‐, Fe‐rich silicates (pyroxenes, andradite, kirschsteinite) among the CVox and CVred meteorites. The extent of secondary mineralization was controlled by the distribution of water ices, permeability, and porosity, which in turn were controlled by impacts on the asteroidal parent body. More intense shock metamorphism in the region where the reduced CVs originated decreased their porosity and permeability while simultaneously expelling intergranular ices and fluids. The mineralogy, petrography, and bulk chemical compositions of both the reduced and oxidized CV chondrites indicate that mobile elements were redistributed between Ca,Al‐rich inclusions, dark inclusions, chondrules, and matrices only locally; there is no evidence for large‐scale (>several cm) fluid transport. Published ⁵³Mn‐⁵³Cr ages of secondary fayalite in CV, CO, and unequilibrated ordinary chondrites, and carbonates in CI, CM, and CR chondrites are consistent with aqueous alteration initiated by heating of water ice‐bearing asteroids by decay of ²⁶Al, not shock metamorphism.     

Isotope fractionation and concentration measurements of Zn in meteorites determined by the double spike,IDMS‐TIMS techniques

Abstract– The isotope fractionation of Zn in meteorites has been measured for the first time using thermal ionization mass spectrometry and a double spiking technique. The magnitude of δZn ranged from ?0.29 to +0.38‰ amu^?1 for five stone meteorites whereas the iron meteorite Canyon Diablo displays δZn of 1.11 ± 0.11‰ amu^?1. The results for chondrites in this work can be divided into positive and negative δZn, supporting a previous proposal that chondrites are a mixture of materials from two different temperature sources. The Zn isotope fractionation present in meteorites may represent a primordial heterogeneity formed in the early solar system. An anomalous isotopic composition of Zn obtained for the Redfields iron meteorite suggests large‐scale inherited isotope heterogeneity of the protosolar nebula, or the presence of a parent body that has formed within its own isotopically anomalous reservoir. These anomalies are in the same direction but smaller than nuclear field shift effects observed in chemical exchange reactions. The isotope dilution mass spectrometry (IDMS) technique was used to measure Zn concentration, yielding a range from 20.1 μg g^?1 to 302 μg g^?1 in five stone meteorites and from 0.019 to 26 μg g^?1 in seven iron meteorites. The IDMS‐measured abundance of Zn in Orgueil is 302 ± 14 μg g^?1 and should be considered for future compilations of the abundance of Zn in the solar system.     

Petrology and oxygen isotopic compositions of calcium‐aluminum‐rich inclusions in primitive CO3.0‐3.1 chondrites

The petrologic and oxygen isotopic characteristics of calcium‐aluminum‐rich inclusions (CAIs) in CO chondrites were further constrained by studying CAIs from six primitive CO3.0‐3.1 chondrites, including two Antarctic meteorites (DOM 08006 and MIL 090010), three hot desert meteorites (NWA 10493, NWA 10498, and NWA 7892), and the Colony meteorite. The CAIs can be divided into hibonite‐bearing inclusions (spinel‐hibonite spherules, monomineralic grains, hibonite‐pyroxene microspherules, and irregular/nodular objects), grossite‐bearing inclusions (monomineralic grains, grossite‐melilite microspherules, and irregular/nodular objects), melilite‐rich inclusions (fluffy Type A, compact type A, monomineralic grains, and igneous fragments), spinel‐pyroxene inclusions (fluffy objects resembling fine‐grained spinel‐rich inclusions in CV chondrites and nodular/banded objects resembling those in CM chondrites), and pyroxene‐anorthite inclusions. They are typically small (98.4 ± 54.4 µm, 1SD) and comprise 1.54 ± 0.43 (1SD) area% of the host chondrites. Melilite in the hot desert and Colony meteorites was extensively replaced by a hydrated Ca‐Al‐silicate during terrestrial weathering and converted melilite‐rich inclusions into spinel‐pyroxene inclusions. The CAI populations of the weathered COs are very similar to those in CM chondrites, suggesting that complete replacement of melilite by terrestrial weathering, and possibly parent body aqueous alteration, would make the CO CAIs CM‐like, supporting the hypothesis that CO and CM chondrites derive from similar nebular materials. Within the CO3.0‐3.1 chondrites, asteroidal alteration significantly resets oxygen isotopic compositions of CAIs in CO3.1 chondrites (?¹⁷O: ?25 to ?2‰) but left those in CO3.0‐3.05 chondrites mostly unchanged (?¹⁷O: ?25 to ?20‰), further supporting the model whereby thermal metamorphism became evident in CO chondrites of petrologic type ≥3.1. The resistance of CAI minerals to oxygen isotope exchange during thermal metamorphism follows in the order: melilite + grossite < hibonite + anorthite < spinel + diopside + forsterite. Meanwhile, terrestrial weathering destroys melilite without changing the chemical and isotopic compositions of melilite and other CAI minerals.     

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).     

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%.     

Search for isotopic anomalies in oldhamite (CaS) from unequilibrated (E3) enstatite chondrites

Abstract— The Ca isotopic compositions of 32 oldhamite (CaS) grains from the Qingzhen (EH3), MAC88136 (EL3), and Indarch (EH4) enstatite chondrites were determined by ion microprobe mass spectrometry. Also measured were the S isotopic compositions of eight oldhamite, two niningerite (MgS), and seven troilite (FeS) grains. The S isotopic compositions of all minerals are normal, but oldhamite grains of the first two meteorites exhibit apparent small ⁴⁸Ca excesses and deficits that are correlated with isotopic mass fractionation as determined from the ⁴⁰Ca-⁴⁴Ca pair. The interpretation of these results is complicated by the fact that none of the established mass fractionation laws can account for the data in the Norton County oldhamite standard. The method of analysis is carefully scrutinized for experimental artifacts. Neither interferences nor any known mass fractionation effect can satisfactorily explain the observed small deviations from normal isotopic composition. If these are truly isotopic anomalies, they are much smaller than those observed in hibonite. The nucleosynthetic origin of Ca isotopes is discussed.     

Extraterrestrial amino acids and L‐enantiomeric excesses in the CM2 carbonaceous chondrites Aguas Zarcas and Murchison

The abundances, distributions, enantiomeric ratios, and carbon isotopic compositions of amino acids in two fragments of the Aguas Zarcas CM2 type carbonaceous chondrite fall and a fragment of the CM2 Murchison meteorite were determined via liquid chromatography time‐of‐flight mass spectrometry and gas chromatography isotope ratio mass spectrometry. A suite of two‐ to six‐carbon aliphatic primary amino acids was identified in the Aguas Zarcas and Murchison meteorites with abundances ranging from ~0.1 to 158 nmol/g. The high relative abundances of α‐amino acids found in these meteorites are consistent with a Strecker‐cyanohydrin synthesis on these meteorite parent bodies. Amino acid enantiomeric and carbon isotopic measurements in both fragments of the Aguas Zarcas meteorites indicate that both samples experienced some terrestrial protein amino acid contamination after their fall to Earth. In contrast, similar measurements of alanine in Murchison revealed that this common protein amino acid was both racemic (D ≈ L) and heavily enriched in ¹³C, indicating no measurable terrestrial alanine contamination of this meteorite. Carbon isotope measurements of two rare non‐proteinogenic amino acids in the Aguas Zarcas and Murchison meteorites, α‐aminoisobutyric acid and D‐ and L‐isovaline, also fall well outside the typical terrestrial range, confirming they are extraterrestrial in origin. The detections of non‐terrestrial L‐isovaline excesses of ~10–15% in both the Aguas Zarcas and Murchison meteorites, and non‐terrestrial L‐glutamic acid excesses in Murchison of ~16–40% are consistent with preferential enrichment of circularly polarized light generated L‐amino acid excesses of conglomerate enantiopure crystals during parent body aqueous alteration and provide evidence of an early solar system formation bias toward L‐amino acids prior to the origin of life.     

The Kumtag 016 L5 strewn field,Xinjiang Province,China

The Kumtag 016 strewn field was found in the eastern part of the Kumtag desert, Xinjiang Province, China. In this study, 24 recovered meteorites have been characterized by a suite of different analytical techniques to investigate their petrography, mineralogy, bulk trace elements, noble gas isotopic composition, density, and porosity. We attribute to the strewn field 22 L5 chondrites with shock stage S4 and weathering grade W2–W3. Two different meteorites, Kumtag 021, an L4 chondrite and Kumtag 032, an L6 chondrite, were recognized within the strewn field area. Moreover, Kumtag 003, an H5 chondrite, was previously found in the same area. We infer that the Kumtag 016 strewn field most likely consists of at least four distinct meteorite falls. The effects of terrestrial weathering on the studied meteorites involve sulfide/metal alteration, chemical changes (Sr, Ba, Pb, and U enrichments and depletion in Cr, Co, Ni, and Cs abundances), and physical modifications (decrease of grain density and porosity). Measurements of the light noble gases indicate that the analyzed Kumtag L5 samples contain solar wind-implanted noble gases with a ²⁰Ne/²²Ne ratio of ~12.345. The cosmic-ray exposure (CRE) ages of the L5 chondrites are in a narrow range (3.6 ± 1.4 Ma to 5.2 ± 0.4 Ma). For L4 chondrite Kumtag 021 and L6 chondrite Kumtag 032, the CRE ages are 5.9 ± 0.4 Ma and 4.7 ± 0.8 Ma, respectively.     

Noble gas study of the Saratov L4 chondrite

Abstract– We have determined the elemental abundances and the isotopic compositions of noble gases in a bulk sample and an HF/HCl residue of the Saratov (L4) chondrite using stepwise heating. The Ar, Kr, and Xe concentrations in the HF/HCl residue are two orders of magnitude higher than those in the bulk sample, while He and Ne concentrations from both are comparable. The residue contains only a portion of the trapped heavy noble gases in Saratov; 40 ± 9% for ³⁶Ar, 58 ± 12% for ⁸⁴Kr, and 48 ± 10% for ¹³²Xe, respectively. The heavy noble gas elemental pattern in the dissolved fraction is similar to that in the residue but has high release temperatures. Xenon isotopic ratios of the HF/HCl residue indicate that there is no Xe‐HL in Saratov, but Ne isotopic ratios in the HF/HCl residue lie on a straight line connecting the cosmogenic component and a composition between Ne‐Q and Ne‐HL. This implies that the Ne isotopic composition of Q has been changed by incorporating Ne‐HL (Huss et al. 1996) or by being mass fractionated during the thermal metamorphism. However, it is most likely that the Ne‐Q in Saratov is intrinsically different from this component in other meteorites. The evidence of this is a lack of correlation between the isotopic ratio of Ne‐Q and petrologic types of meteorites (Busemann et al. 2000). A neutron capture effect was observed in the Kr isotopes, and this process also affected the ¹²⁸Xe/¹³²Xe ratio. The ³He and ²¹Ne exposure ages for the bulk sample are 33 and 35 Ma, respectively.