Precursors of Mars: Constraints from nitrogen and oxygen isotopic compositions of martian meteorites

Abstract— We present an approach to assess the nature of materials involved in the accretion of Mars by the planet's nitrogen (δ¹⁵N) and oxygen (Δ¹⁷O) isotopic compositions as derived from data on martian meteorites. δ¹⁵N for Mars has been derived from nitrogen and xenon systematics, while Δ¹⁷O has been taken from the literature data. These signatures indicate that Mars has most probably accreted from enstatite and ordinary chondritic materials in a ratio of 74:26 and may not have a significant contribution from the carbonaceous (CI, CM, or CV) chondrites. This is consistent with the chromium isotopic (?⁵³Cr) signatures of martian meteorites and the bulk planet Fe/Si ratio for Mars as suggested by the moment of inertia factor (I/MR²) obtained from the Mars Pathfinder data. Further, a simple homogeneous accretion from the above two types of materials is found to be consistent with the planet's moment of inertia factor and the bulk composition of the mantle. But, it requires a core with 6.7 wt% Si, which is consistent with the new results from the high pressure and temperature melting experiments and chemical data on the opaque minerals in enstatite 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.     

Thermal and impact histories of reheated group IVA,IVB, and ungrouped iron meteorites and their parent asteroids

Abstract– The microstructures of six reheated iron meteorites—two IVA irons, Maria Elena (1935), Fuzzy Creek; one IVB iron, Ternera; and three ungrouped irons, Hammond, Babb’s Mill (Blake’s Iron), and Babb’s Mill (Troost’s Iron)—were characterized using scanning and transmission electron microscopy, electron‐probe microanalysis, and electron backscatter diffraction techniques to determine their thermal and shock history and that of their parent asteroids. Maria Elena and Hammond were heated below approximately 700–750 °C, so that kamacite was recrystallized and taenite was exsolved in kamacite and was spheroidized in plessite. Both meteorites retained a record of the original Widmanstätten pattern. The other four, which show no trace of their original microstructure, were heated above 600–700 °C and recrystallized to form 10–20 μm wide homogeneous taenite grains. On cooling, kamacite formed on taenite grain boundaries with their close‐packed planes aligned. Formation of homogeneous 20 μm wide taenite grains with diverse orientations would have required as long as approximately 800 yr at 600 °C or approximately 1 h at 1300 °C. All six irons contain approximately 5–10 μm wide taenite grains with internal microprecipitates of kamacite and nanometer‐scale M‐shaped Ni profiles that reach approximately 40% Ni indicating cooling over 100–10,000 yr. Un‐decomposed high‐Ni martensite (α₂) in taenite—the first occurrence in irons—appears to be a characteristic of strongly reheated irons. From our studies and published work, we identified four progressive stages of shock and reheating in IVA irons using these criteria: cloudy taenite, M‐shaped Ni profiles in taenite, Neumann twin lamellae, martensite, shock‐hatched kamacite, recrystallization, microprecipitates of taenite, and shock‐melted troilite. Maria Elena and Fuzzy Creek represent stages 3 and 4, respectively. Although not all reheated irons contain evidence for shock, it was probably the main cause of reheating. Cooling over years rather than hours precludes shock during the impacts that exposed the irons to cosmic rays. If the reheated irons that we studied are representative, the IVA irons may have been shocked soon after they cooled below 200 °C at 4.5 Gyr in an impact that created a rubblepile asteroid with fragments from diverse depths. The primary cooling rates of the IVA irons and the proposed early history are remarkably consistent with the Pb‐Pb ages of troilite inclusions in two IVA irons including the oldest known differentiated meteorite ( Blichert‐Toft et al. 2010 ).     

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).     

The abundance and isotopic composition of Cd in iron meteorites

Cadmium is a highly volatile element and its abundance in meteorites may help better understand volatility‐controlled processes in the solar nebula and on meteorite parent bodies. The large thermal neutron capture cross section of ¹¹³Cd suggests that Cd isotopes might be well suited to quantify neutron fluences in extraterrestrial materials. The aims of this study were (1) to evaluate the range and magnitude of Cd concentrations in magmatic iron meteorites, and (2) to assess the potential of Cd isotopes as a neutron dosimeter for iron meteorites. Our new Cd concentration data determined by isotope dilution demonstrate that Cd concentrations in iron meteorites are significantly lower than in some previous studies. In contrast to large systematic variations in the concentration of moderately volatile elements like Ga and Ge, there is neither systematic variation in Cd concentration amongst troilites, nor amongst metal phases of different iron meteorite groups. Instead, Cd is strongly depleted in all iron meteorite groups, implying that the parent bodies accreted well above the condensation temperature of Cd (i.e., ≈650 K) and thus incorporated only minimal amounts of highly volatile elements. No Cd isotope anomalies were found, whereas Pt and W isotope anomalies for the same iron meteorite samples indicate a significant fluence of epithermal and higher energetic neutrons. This observation demonstrates that owing to the high Fe concentrations in iron meteorites, neutron capture mainly occurs at epithermal and higher energies. The combined Cd‐Pt‐W isotope results from this study thus demonstrate that the relative magnitude of neutron capture‐induced isotope anomalies is strongly affected by the chemical composition of the irradiated material. The resulting low fluence of thermal neutrons in iron meteorites and their very low Cd concentrations make Cd isotopes unsuitable as a neutron dosimeter for iron meteorites.     

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.     

A molecular and isotopic study of the macromolecular organic matter of the ungrouped C2 WIS 91600 and its relationship to Tagish Lake and PCA 91008

Abstract– Insight into the chemical history of an ungrouped type 2 carbonaceous chondrite meteorite, Wisconsin Range (WIS) 91600, is gained through molecular analyses of insoluble organic matter (IOM) using solid‐state ¹³C nuclear magnetic resonance (NMR) spectroscopy, X‐ray absorption near edge structure spectroscopy (XANES), and pyrolysis‐gas chromatography coupled with mass spectrometry (pyr‐GC/MS), and our previous bulk elemental and isotopic data. The IOM from WIS 91600 exhibits similarities in its abundance and bulk δ¹⁵N value with IOM from another ungrouped carbonaceous chondrite Tagish Lake, while it exhibits H/C, δ¹³C, and δD values that are more similar to IOM from the heated CM, Pecora Escarpment (PCA) 91008. The ¹³C NMR spectra of IOM of WIS 91600 and Tagish Lake are similar, except for a greater abundance of CH_xO species in the latter and sharper carbonyl absorption in the former. Unusual cross‐polarization (CP) dynamics is observed for WIS 91600 that indicate the presence of two physically distinct organic domains, in which the degrees of aromatic condensation are distinctly different. The presence of two different organic domains in WIS 91600 is consistent with its brecciated nature. The formation of more condensed aromatics is the likely result of short duration thermal excursions during impacts. The fact that both WIS 91600 and PCA 91008 were subjected to short duration heating that is distinct from the thermal history of type 3 chondrites is confirmed by Carbon‐XANES. Finally, after being briefly heated (400 °C for 10 s), the pyrolysis behavior of Tagish Lake IOM is similar to that of WIS 91600 and PCA 91008. We conclude that WIS 91600 experienced very moderate, short duration heating at low temperatures (<500 °C) after an episode of aqueous alteration under conditions that were similar to those experienced by Tagish Lake.     

A theory of local formation of isotopic anomalies in meteorites

The consequences of a postulated collision between planets in the early solar system have been investigated. At least one of the planets has been taken with a D/H ratio similar to that of Venus (0.016) and the temperature of the collision interface (3 × 10⁶ K) triggers chain reactions in near-surface material beginning with D-D reactions. The initial composition of the reacting material is consistent with a silicate + ices surface and a hydrogen-helium-inert gas atmosphere. The reaction chain contains 284 reactions, plus reverse reactions, and 40 radioactive decay processes. When the pressure in the reacting region is sufficiently high the colliding planets are blown apart and the highly-processed material at the heart of the explosion mixes with less processed and unprocessed material from cooler parts of the system. Mixtures of materials are found to explain isotopic anomalies associated with oxygen, magnesium, neon, silicon, carbon and nitrogen. The local production of isotopic anomalies avoids the problems associated with other suggested explanations - in particular the observation of neon E, almost pure²²Ne, assumed as the product of the decay of²²Na with a half-life of 2.6 years.     

Prebiotic carbon in clays from Orgueil and Ivuna (CI), and Tagish Lake (C2 ungrouped) meteorites

Abstract— Transmission electron microscopic (TEM) and electron energy‐loss spectroscopic (EELS) study of the Ivuna and Orgueil (CI), and Tagish Lake (C2 ungrouped) carbonaceous chondrite meteorites shows two types of C‐clay assemblages. The first is coarser‐grained (to 1 μm) clay flakes that show an intense O K edge from the silicate together with a prominent C K edge, but without discrete C particles. Nitrogen is common in some clay flakes. Individual Orgueil and Tagish Lake meteorite clay flakes contain up to 6 and 8 at% C, respectively. The C K‐edge spectra from the clays show fine structure revealing aromatic, aliphatic, carboxylic, and carbonate C. The EELS data shows that this C is intercalated with the clay flakes. The second C‐clay association occurs as poorly crystalline to amorphous material occurring as nanometer aggregates of C, clay, and Fe‐O‐rich material. Some aggregates are dominated by carbonaceous particles that are structurally and chemically similar to the acid insoluble organic matter. The C K‐edge shape from this C resembles that of amorphous C, but lacking the distinct peaks corresponding to aliphatic, carboxylic, and carbonate C groups. Nanodiamonds are locally abundant in some carbonaceous particles. The abundance of C in the clays suggest that molecular speciation in the carbonaceous chondrites is partly determined by the effects of aqueous processing on the meteorite parent bodies, and that clays played an important role. This intricate C‐clay association lends credence to the proposal that minerals were important in the prebiotic chemical evolution of the early solar system.     

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.     

Atmospheric odd oxygen production due to the photodissociation of ordinary and isotopic molecular oxygen

Through a line by line calculation, the contributions of the Schumann-Runge bands of the ordinary and isotopic oxygen to the photodissociation of these molecules at different altitudes have been calculated. The photodissociation rates are expressed analytically. Contribution of the satellite lines has been taken into account. Due to the broadening of the SR lines, this contribution is insignificant. Similarly, it is shown that the first and higher vibrational states of the initial molecular states contribute insignificantly to the dissociation rates. It is also shown that the main contribution to the odd oxygen production in the important ozone producing altitudes is from the low vibrational and high rotational quantum numbers. The effect of the temperature on dissociation rates has similarly been studied.Due to its selective absorption, the isotopic oxygen ¹⁶O¹⁸O produces at 70 km 10 times as much odd oxygen as would be produced if the isotope did not have selective absorption. At this altitude 6% of the odd oxygen produced is due to this isotope. Also, 1.45% of the odd oxygen produced per second in an atmospheric column is due to ¹⁶O¹⁸O. However, the excess odd oxygen produced is not enough to explain the excess amount of ozone observed in the atmosphere which cannot be accounted for in the photochemical models.The calculated dissociation rates for the isotope are in moderate agreement with similar rates obtained by Blake et al. (1984, J. geophys. Res.89, 7277), but are by an order of magnitude smaller than similar rates given by Cicerone and McCrumb (1980, Geophys. Res. Lett.7, 251).     

Mn‐Cr chronology of five IIIAB iron meteorites

Abstract— Mn‐Cr systematics in phosphates (sarcopside, graftonite, beusite, galileiite, and johnsomervilleite) in IIIAB iron meteorites were investigated by secondary ion mass spectrometry (SIMS). In most cases, excesses in ⁵³Cr are found and δ⁵³Cr is well correlated with Mn/Cr ratios, suggesting that ⁵³Mn was alive at the time of IIIAB iron formation. The inferred Mn‐Cr “ages” are different for different phosphate minerals. This is presumably due to a combined effect of the slow cooling rates of IIIAB iron meteorites and the difference in the diffusion properties of Cr and Mn in the phosphates. The ages of sarcopside are the same for the IIIAB iron meteorites. Johnsomervilleite shows apparent old ages, probably because of a gain of Cr enriched in ⁵³Cr during the closure process. Apparently, old Mn‐Cr ages reported in previous studies can also be explained in a similar way. Therefore, the IIIAB iron meteorites probably experienced identical thermal histories and thus derived from the core of a parent body. Thermal histories of the parent body of IIIAB iron meteorites that satisfy the Mn‐Cr chronology and metallographic cooling rates were constructed by computer simulation. The thermal history at an early stage (<10 Ma after CAI formation) is well determined, though later history may be more model‐dependent. It is suggested that relative timing of various events in the IIIAB parent body may be estimated with the aid of the thermal history. There is a systematic difference in Mn and Cr concentrations in various minerals (phosphates, sulfide, etc.) among the IIIAB iron meteorites, which seems to be mainly controlled by redox conditions.     

Noble gases,bulk chemistry,and petrography of olivine-rich achondrites Eagles Nest and Lewis Cliff 88763: Comparison to brachinites

Abstract— Eagles Nest and Lewis Cliff (LEW) 88763 are olivine-rich achondrites that have been suggested to be related to Brachina and ALH 84025. Both are ultramafic, although LEW 88763 has ～10% plagioclase, which Eagles Nest lacks. Olivine in Eagles Nest (Fo₆₈) is virtually identical in composition to that in Brachina (Fo_68–70), and that in LEW 88763 is only slightly different (Fo_63–64). The meteorites' cosmic-ray exposure ages differ from each other and from Brachina and ALH 84025. Like Brachina, Eagles Nest has a substantial amount of radiogenic ¹²⁹Xe and an apparent K-Ar age of <4.5 Ga. Lewis Cliff 88763, on the other hand, has no detectable radiogenic ¹²⁹Xe, an apparent K-Ar age of ～4.5 Ga, and a substantial amount of trapped Xe. The chemical composition of LEW 88763 is within a factor of two of chondritic for virtually every element analyzed, including siderophiles, which suggests that it was melted (or at least heated and recrystallized) in a closed system. Analyses of the chemical composition of Eagles Nest are hampered by extensive terrestrial weathering; but it appears to be broadly chondritic also, although it, like Brachina, is depleted in siderophiles. Our data suggest that Eagles Nest is genetically related to Brachina but that LEW 88763 is not, which is a conclusion that is consistent with the O isotopic data of Clayton and Mayeda (1996).     

Comets, meteorites and atmospheres

The relatively low value of Xe/Kr in the atmospheres of Earth and Mars seems to rule out meteorites as the major carriers of noble gases to the inner planets. Laboratory experiments on the trapping of gases in ice forming at low temperatures suggest that comets may be a better choice. It is then possible to develop a model for the origin of inner planet atmospheres based on volatiles delivered by comets added to volatiles originally trapped in planetary rocks. The model will be tested by results from the Galileo Entry Probe.     

Populations of nanodiamond grains in meteorites from the data on isotopic composition and content of nitrogen

The present study has shown that the dependence of the isotopic composition of nitrogen on the N/C ratio, revealed from the data for bulk samples of meteoritic nanodiamond, can be obtained within the framework of the following model of the composition of populations of nanodiamond grains: (a) initial nanodiamond, i.e., the nanodiamond in the protoplanetary cloud before the accretion of the meteorite parent bodies, was composed mainly of grains of two populations (denoted as C_N and C_F), the ratio of which changed in meteorites depending on the degree of hydrothermal metamorphism; (b) only the grains of one of these populations (C_N) contain volume-bound nitrogen with δ¹⁵N = ?350‰; (c) the grains of both populations contain surface-bound nitrogen (δ¹⁵N ≡ 0). The calculations revealed the following properties of population grains in this model. (1) The grains of the C_N and C_F populations are most likely the same in isotopic composition of carbon and heterogeneous in distribution of its isotopes: the central part of grains is enriched with the δ¹²C isotope relative to the remainder of the grain. While the value of δ¹³C is ?37.3 ± 1.1‰ for carbon in the central part, it is ?32.8 ± 1.5‰ for the whole volume of the grains. (2) The noble gases of the HL component, specifically Xe-HL, are anomalous in isotopic composition and are most likely contained in the third population of nanodiamond grains (denoted as C_HL), the mass fraction of which is negligible relative to that for other grain populations. Only the grains of the C_HL population have an undoubtedly presolar origin, while the grains of the other nanodiamond populations could have formed at the early stages of the evolution of the protoplanetary cloud material before the accretion of the meteoritic parent bodies.     

Comets, meteorites and atmospheres

The relatively low value of Xe/Kr in the atmospheres of Earth and Mars seems to rule out meteorites as the major carriers of noble gases to the inner planets. Laboratory experiments on the trapping of gases in ice forming at low temperatures suggest that comets may be a better choice. It is then possible to develop a model for the origin of inner planet atmospheres based on volatiles delivered by comets added to volatiles originally trapped in planetary rocks. The model will be tested by results from the Galileo Entry Probe.     

In search of the Earth‐forming reservoir: Mineralogical,chemical, and isotopic characterizations of the ungrouped achondrite NWA 5363/NWA 5400 and selected chondrites

High‐precision isotope data of meteorites show that the long‐standing notion of a “chondritic uniform reservoir” is not always applicable for describing the isotopic composition of the bulk Earth and other planetary bodies. To mitigate the effects of this “isotopic crisis” and to better understand the genetic relations of meteorites and the Earth‐forming reservoir, we performed a comprehensive petrographic, elemental, and multi‐isotopic (O, Ca, Ti, Cr, Ni, Mo, Ru, and W) study of the ungrouped achondrites NWA 5363 and NWA 5400, for both of which terrestrial O isotope signatures were previously reported. Also, we obtained isotope data for the chondrites Pillistfer (EL6), Allegan (H6), and Allende (CV3), and compiled available anomaly data for undifferentiated and differentiated meteorites. The chemical compositions of NWA 5363 and NWA 5400 are strikingly similar, except for fluid mobile elements tracing desert weathering. We show that NWA 5363 and NWA 5400 are paired samples from a primitive achondrite parent‐body and interpret these rocks as restite assemblages after silicate melt extraction and siderophile element addition. Hafnium‐tungsten chronology yields a model age of 2.2 ± 0.8 Myr after CAI, which probably dates both of these events within uncertainty. We confirm the terrestrial O isotope signature of NWA 5363/NWA 5400; however, the discovery of nucleosynthetic anomalies in Ca, Ti, Cr, Mo, and Ru reveals that the NWA5363/NWA 5400 parent‐body is not the “missing link” that could explain the composition of the Earth by the mixing of known meteorites. Until this “missing link” or a direct sample of the terrestrial reservoir is identified, guidelines are provided of how to use chondrites for estimating the isotopic composition of the bulk Earth.     

An experimental study of silver and palladium partitioning between solid and liquid metal,with applications to iron meteorites

Abstract— Solid metal/liquid metal partition coefficients for Ag and Pd were determined experimentally as a function of the S concentration of the metallic liquid. Silver is incompatible in solid metal and strongly sensitive to the S content of the metallic liquid; partition coefficients for Ag decrease more than an order of magnitude with increasing S content of the metallic liquid and can be expressed as: where k(Ag) is the molar solid metal/liquid metal partition coefficient and X_S is the molar S content of the metallic liquid. The partition coefficient of Pd is less variable but changes from modestly incompatible to modestly compatible in solid metal with increasing S content of the metallic liquid: With these new partition coefficients for Pd and a fractional crystallization model, Pd abundance trends recorded in iron meteorite groups are modeled successfully. Measured Ag distribution between troilite-rich nodules and adjacent metal in iron meteorites also agree well with experimental solid metal/liquid metal equilibrium values. However, observed Pd metal/nodule distributions do not agree with experimentally determined partition coefficients, which suggests a more complex history than simple solid metal/liquid metal equilibrium.     

History of lunar meteorites Queen Alexandra Range 93069, Asuka 881757, and Yamato 793169 based on noble gas isotopic abundances,radionuclide concentrations,and chemical composition

Abstract— We investigated the characteristics and history of lunar meteorites Queen Alexandra Range 93069, Yamato 793169 and Asuka 881757 based on the abundances of all stable noble gas isotopes, the concentrations of the radionuclides ¹⁰Be, ²⁶Al, ³⁶Cl, and ⁸¹Kr, and the abundances of Mg, Al, K, Ca, Fe, Cl, Sr, Y, Zr, Ba, and La. Based on the solar wind and cosmic-ray irradiations, QUE 93069 is the most mature lunar meteorite studied up to now. The ⁴⁰Ar/³⁶Ar ratio of the trapped component is 1.87 ± 0.16. This ratio corresponds to a time when the material was exposed to solar and lunar atmospheric volatiles ～400 Ma ago. On the other hand, Yamato 793169 and Asuka 881757 contain very little or no solar noble gases, which indicates that these materials resided in the top layer of the lunar regolith only briefly or not at all. For all lunar meteorites, we observe a positive correlation of the concentrations of cosmic-ray produced with trapped solar noble gases. The duration of lunar regolith residence for the lunar meteorites was calculated based on cosmic-ray produced ²¹Ne, ³⁸Ar, ⁷⁸Kr, ⁸³Kr, and ¹²⁶Xe and appropriate production rates that were derived based on the target element abundances and the shielding indicator ¹³¹Xe/¹²⁶Xe. For QUE 93069, Yamato 793169, and Asuka 881757, we obtained 1000 ± 400 Ma, 50 ± 10 Ma, and <1 Ma, respectively. Both Asuka 881757 and Yamato 793169 show losses of radiogenic ⁴He from U and Th decay and Yamato 793169 also ⁴⁰Ar loss from K-decay. For Asuka 881757, we calculate a K-Ar gas retention age of 3100 ± 600 Ma and a ²⁴⁴Pu-¹³⁶Xe fission age of 4240 ± 170 Ma. This age is one of the oldest formation ages ever observed for a lunar basalt. The exposure history of QUE 93069 after ejection from the Moon was derived from the radionuclide concentrations: ejection 0.16 ± 0.03 Ma ago, duration of Moon-Earth transit 0.15 ± 0.02 Ma and fall on Earth <0.015 Ma ago. This ejection event is distinguished temporally from those which produced the other lunar meteorites. We conclude that six to eight events are necessary to eject all the known lunar meteorites.