Ar-Ar ages of martian nakhlites

We report ³⁹Ar-⁴⁰Ar ages of whole rock (WR) and plagioclase and pyroxene mineral separates of nakhlites MIL 03346 and Y-000593, and of WR samples of nakhlites NWA 998 and Nakhla. All age spectra are complex and indicate variable degrees of ³⁹Ar recoil and variable amounts of trapped ⁴⁰Ar in the samples. Thus, we examine possible Ar-Ar ages in several ways. From consideration of both limited plateau ages and isochron ages, we prefer Ar-Ar ages of NWA 998 = 1334 ± 11 Ma, MIL 03346 = 1368 ± 83 Ma (mesostasis) and 1334 ± 54 Ma (pyroxene), Y-000593 = 1367 ± 7 Ma, and Nakhla = 1357 ± 11 Ma, (2σ errors). For NWA 998 and MIL 03346 the Ar-Ar ages are within uncertainties of preliminary Rb-Sr isochron ages reported in the literature. These Ar-Ar ages for Y-000593 and Nakhla are several Ma older than Sm-Nd ages reported in the literature. We conclude that the major factor in producing Ar-Ar ages slightly too old is the presence of small amounts of trapped martian or terrestrial ⁴⁰Ar on weathered grain surfaces that was degassed along with the first several percent of ³⁹Ar. A total K-⁴⁰Ar isochron for WR and mineral data from five nakhlites analyzed by us, plus Lafayette data in the literature, gives an isochron age of 1325 ± 18 Ma (2σ). We emphasize the precision of this isochron over the value of the isochron age. Our Ar-Ar data are consistent with a common formation age for nakhlites. The cosmic-ray exposure (CRE) age for NWA 998 of ∼12 Ma is also similar to CRE ages for other nakhlites.     

Experimental study of polybaric REE partitioning between olivine, pyroxene and melt of the Yamato 980459 composition: Insights into the petrogenesis of depleted shergottites

A synthetic composition representing the Yamato 980459 martian basalt (shergottite) has been used to carry out phase relation, and rare earth element (REE) olivine and pyroxene partitioning experiments. Yamato 980459 is a sample of primitive basalt derived from a reduced end-member among martian mantle sources. Experiments carried out between 1-2 GPa and 1350-1650 °C simulate the estimated pressure-temperature conditions of basaltic melt generation in the martian mantle. Olivine-melt and orthopyroxene-melt partition coefficients for La, Nd, Sm, Eu, Gd and Yb (D_REE values) were determined by LA-ICPMS, and are similar to the published values for terrestrial basaltic systems. We have not detected significant variation in D-values with pressure over the range investigated, and by comparison with previous studies carried out at lower pressure.We apply the experimentally obtained olivine-melt and orthopyroxene-melt D_REE values to fractional crystallization and partial melting models to develop a three-stage geochemical model for the evolution of martian meteorites. In our model we propose two ancient (∼4.535 Ga) sources: the Nakhlite Source, located in the shallow mantle, and the Deep Mantle Source, located close to the martian core-mantle boundary. These two sources evolved distinctly on the ε¹⁴³Nd evolution curve due to their different Sm/Nd ratios. By partially melting the Nakhlite Source at ∼1.3 Ga, we are able to produce a slightly depleted residue (Nakhlite Residue). The Nakhlite Residue is left undisturbed until ∼500 Ma, at which point the depleted Deep Mantle Source is brought up by a plume mechanism carrying with it high heat flow, melts and isotopic signatures of the deep mantle (e.g., ε¹⁸²W, ε¹⁴²Nd, etc.). The plume-derived Deep Mantle Source combines with the Nakhlite Residue producing a mixture that becomes a mantle source (herein referred to as “the Y98 source”) for Yamato 980459 and the other depleted shergottites with the characteristic range of Sm/Nd ratios of these meteorites. The same hot plume provides a heat source for the formation of enriched and intermediate shergottites. Our model reproduces the REE patterns of nakhlites and depleted shergottites and can explain high ε¹⁴³Nd in depleted shergottites. Furthermore, the model results can be used to interpret whole rock Rb-Sr and Sm-Nd ages of shergottites.     

Shock implantation of Martian atmospheric argon in four basaltic shergottites: A laser probe Ar/Ar investigation

Spatially resolved argon isotope measurements have been performed on neutron-irradiated samples of two Martian basalts (Los Angeles and Zagami) and two Martian olivine-phyric basalts (Dar al Gani (DaG) 476 and North West Africa (NWA) 1068). With a ∼50 μm diameter focused infrared laser beam, it has been possible to distinguish between argon isotopic signatures from host rock (matrix) minerals and localized shock melt products (pockets and veins). The concentrations of argon in analyzed phases from all four meteorites have been quantified using the measured J values, ⁴⁰Ar/³⁹Ar ratios and K₂O wt% in each phase. Melt pockets contain, on average, 10 times more gas (7-24 ppb ⁴⁰Ar) than shock veins and matrix minerals (0.3-3 ppb ⁴⁰Ar). The ⁴⁰Ar/³⁶Ar ratio of the Martian atmosphere, estimated from melt pocket argon extractions corrected for cosmogenic ³⁶Ar, is: Los Angeles (∼1852), Zagami (∼1744) and NWA 1068 (∼1403). In addition, Los Angeles shows evidence for variable mixing of two distinct trapped noble gas reservoirs: (1) Martian atmosphere in melt pockets, and (2) a trapped component, possibly Martian interior (⁴⁰Ar/³⁶Ar: 480-490) in matrix minerals. Average apparent ⁴⁰Ar/³⁹Ar ages determined for matrix minerals in the four analyzed meteorites are 1290 Ma (Los Angeles), 692 Ma (Zagami), 515 Ma (NWA 1068) and 1427 Ma (DaG 476). These ⁴⁰Ar/³⁹Ar apparent ages are substantially older than the ∼170-474 Ma radiometric ages given by other isotope dating techniques and reveal the presence of trapped ⁴⁰Ar. Cosmic ray exposure (CRE) ages were measured using spallogenic ³⁶Ar and ³⁸Ar production. Los Angeles (3.1 ± 0.2 Ma), Zagami (2.9 ± 0.4 Ma) and NWA 1068 (2.0 ± 0.5 Ma) yielded ages within the range of previous determinations. DaG 476, however, yielded a young CRE age (0.7 ± 0.25 Ma), attributed to terrestrial alteration. The high spatial variation of argon indicates that the incorporation of Martian atmospheric argon into near-surface rocks is controlled by localized glass-bearing melts produced by shock processes. In particular, the larger (mm-size) melt pockets contain near end-member Martian atmospheric argon. Based on petrography, composition and argon isotopic data we conclude that the investigated melt pockets formed by localized in situ shock melting associated with ejection. Three processes may have led to atmosphere incorporation: (1) argon implantation due to atmospheric shock front collision with the Martian surface, (2) transformation of an atmosphere-filled cavity into a localized melt zone, and (3) shock implantation of atmosphere trapped in cracks, pores and fissures.     

Li isotopic variations in single pyroxenes from the Northwest Africa 480 shergottite (NWA 480): a record of degassing of Martian magmas?

Lithium abundances and isotopic compositions were measured by ion microprobe in individual grains of pyroxene, and in a few maskelynites and Ca-phosphates grains, from the Martian meteorite Northwest Africa 480 (NWA 480).In pyroxenes Li abundances are nearly constant from core to rim with concentrations ranging between 3 and 4 μg/g. In contrast, a significant isotopic zoning is observed with δ⁷Li values increasing within single crystals from ∼ −17‰ in the core to ∼ +10‰ in the rim, most of the variability being observed in the core. Plagioclase (now maskelynite) and phosphate crystals, which co-crystallized with the pyroxene rims, display similar δ⁷Li values. Because of the incompatible behavior of Li, the present constancy of Li concentrations within zoned pyroxenes rules out any simple crystallization model in a closed system for Li. The large Li isotopic variations observed within pyroxenes support this conclusion. There is no evidence in support of secondary alteration of NWA 480 to explain the Li isotopic variations, which thus most likely reflect magmatic processes on Mars. Degassing might explain the Li systematics observed in NWA 480 pyroxenes. Because Li has a strong affinity with water-rich fluids, a significant loss of Li from NWA 480 parental melt can happen upon melt emplacement and cooling. Such a Li loss could compensate the effect of crystal fractionation and thus help to maintain constant the Li content of the melt. Li isotopic fractionation is anticipated to accompany this process, ⁷Li being depleted relative to ⁶Li in the volatile phase. The magnitude of the isotopic change of the fractionating melts is difficult to predict because it depends on the value of the Li isotopic fractionation and on the amount of Li loss, but at first glance it seems consistent with the increase of δ⁷Li values observed in NWA 480 pyroxenes with increasing fractionation. The present data suggest that degassing prevailed not only during the crystallization of shergottites like Zagami and Shergotty, but also during the crystallization of the other types of basaltic shergottites.     

A Rb-Sr and Sm-Nd isotope geochronology and trace element study of lunar meteorite LaPaz Icefield 02205

Rubidium-strontium and samarium-neodymium isotopes of lunar meteorite LaPaz Icefield (LAP) 02205 are consistent with derivation of the parent magma from a source region similar to that which produced the Apollo 12 low-Ti olivine basalts followed by mixing of the magma with small amounts (1-2 wt%) of trace element-enriched material similar to lunar KREEP-rich sample SaU 169. The crystallization age of LAP 02205 is most precisely dated by an internal Rb-Sr isochron of 2991 ± 14 Ma, with an initial ⁸⁷Sr/⁸⁸Sr at the time of crystallization of 0.699836 ± 0.000010. Leachable REE-rich phosphate phases of LAP 02205 do not plot on a Sm-Nd mineral isochron, indicating contamination or open system behavior of the phosphates. Excluding anomalous phases from the calculation of a Sm-Nd isochron yields a crystallization age of 2992 ± 85 (initial ε¹⁴³Nd = +2.9 ± 0.8) that is within error of the Rb-Sr age, and in agreement with other independent age determinations for LAP 02205 from Ar-Ar and U-Pb methods. The calculated ¹⁴⁷Sm/¹⁴⁴Nd source ratios for LAP 02205, various Apollo 12 and 15 basalts, and samples with strong affinities to KREEP (SaU 169, NWA 773, 15386) are uncorrelated with their crystallization ages. This finding does not support the involvement of a common KREEP component as a heat source for lunar melting events that occurred after crystallization of the lunar magma ocean.     

A combined Sm-Nd, Rb-Sr, and U-Pb isotopic study of Mg-suite norite 78238: Further evidence for early differentiation of the Moon

Lunar Mg-suite norite 78238 was dated using the Sm-Nd, Rb-Sr, and U-Pb isotopic systems in order to constrain the age of lunar magma ocean solidification and the beginning of Mg-suite magmatism, as well as to provide a direct comparison between the three isotopic systems. The Sm-Nd isotopic system yields a crystallization age for 78238 of 4334 ± 37 Ma and an initial value of −0.27 ± 0.74. The age-initial (T-I) systematics of a variety of KREEP-rich samples, including 78238 and other Mg-suite rocks, KREEP basalts, and olivine cumulate NWA 773, suggest that lunar differentiation was completed by 4492 ± 61 Ma assuming a Chondritic Uniform Reservoir bulk composition for the Moon. The Rb-Sr isotopic systematics of 78238 were disturbed by post-crystallization processes. Nevertheless, selected data points yield two Rb-Sr isochrons. One is concordant with the Sm-Nd crystallization age, 4366 ± 53 Ma. The other is 4003 ± 95 Ma and is concordant with an Ar-Ar age for 78236. The ²⁰⁷Pb-²⁰⁶Pb age of 4333 ± 59 Ma is concordant with the Sm-Nd age. The U-Pb isotopic systematics of 78238 yield linear arrays equivalent to younger ages than the Pb-Pb system, and may reflect fractionation of U and Pb during sample handling. Despite the disturbed nature of the U-Pb systems, a time-averaged μ (²³⁸U/²⁰⁴Pb) value of the source can be estimated at 27 ± 30 from the Pb-Pb isotopic systematics. Because KREEP-rich samples are likely to be derived from source regions with the highest U/Pb ratios, the relatively low μ value calculated for the 78238 source suggests the bulk Moon does not have an exceedingly high μ value.     

The origin of geochemical diversity of lunar mantle sources inferred from the combined U-Pb, Rb-Sr, and Sm-Nd isotope systematics of mare basalt 10017

The results of our combined U-Pb, Rb-Sr, and Sm-Nd isotope study of mare basalt 10017 contribute to the understanding of the petrogenetic processes involved in the origin of geochemical diversity in lunar mare basalt sources, as well as the U-Pb isotope systematics of the Moon. The Rb-Sr, Sm-Nd, and ²³⁸U-²⁰⁶Pb isotope systems yield concordant crystallization ages of 3.633 ± 0.057 Ga, 3.678 ± 0.069 Ga, and 3.616 ± 0.098 Ga, respectively. The ²³⁵U-²⁰⁷Pb isochron yields an older, though still concordant, age of 3.80 ± 0.12 Ga. Neither the ²⁰⁶Pb-²⁰⁷Pb system nor U-Pb concordia system yields an age for 10017 that is concordant with the age determined from the Sm-Nd, Rb-Sr, and ²³⁸U-²⁰⁶Pb systems. The initial ⁸⁷Sr/⁸⁶Sr of 10017 is 0.69941 ± 7 and the initial ε_Nd is +3.2 ± 0.4. Initial Pb isotopic compositions, determined from the U-Pb isochrons, are ²⁰⁶Pb/²⁰⁴Pb_i = 31 ± 11 and ²⁰⁷Pb/²⁰⁴Pb_i = 34 ± 15. Together, these initial Pb compositions constrain the μ value of the 10017 source to be 70 ± 30, assuming a single-stage Pb growth model. This is considerably lower than μ values typically estimated for mare basalt sources (∼100-600). Regardless, the μ values calculated for the sources of mare basalts, as well as other lunar samples, show a range that is larger than can be explained by fractionation of U from Pb solely by crystallization of silicate phases and ilmenite during magma ocean solidification and formation of lunar mantle sources. The U-Pb isotope systematics may reflect late-stage formation of a sulfide phase, which strongly fractionates Pb from U but has minimal effect on Rb/Sr or Sm/Nd compositions, during crystallization of the lunar magma ocean.     

Isotopic and petrographic evidence for young Martian basalts

Radiometric age data for shergottites yield ages of 4.0 Ga and 180-575 Ma; the interpretation of these ages has been, and remains, a subject of debate. Here, we present new ³⁹Ar-⁴⁰Ar laser probe data on lherzolitic shergottites Allan Hills (ALH) 77005 and Northwest Africa (NWA) 1950. These two meteorites are genetically related, but display very different degrees of shock damage. On a plot of ⁴⁰Ar/³⁶Ar versus ³⁹Ar/³⁶Ar, the more strongly shocked ALH 77005 (45-55 GPa) does not yield an array of values indicating an isochron, but the data are highly scattered with the shock melts yielding ⁴⁰Ar/³⁶Ar ratios of 1600-2026. Apparent ages calculated from these extractions range from 374-8183 Ma, with 50% of the data, particularly from the shock melts, yielding impossibly old ages (>4.567 Ga). On the same plot, extractions from igneous minerals in the less shocked NWA 1950 (30-44 GPa) yield a fitted age of 382 ± 36 Ma. Argon extractions from the shock melts are well distinguished from minerals, with the melts exhibiting the highest ⁴⁰Ar/³⁶Ar ratios (1260-1488) and the oldest apparent ages. Laser step heating was also performed on maskelynite separates from NWA 1950 yielding ages of 1000 Ma at the lowest release temperatures, and ages of 360 and 362 Ma at higher temperature steps. Stepped heating data from previous studies have yielded ages of 500 and 700 Ma to 1.7 Ga for ALH 77005 maskelynite separates. If the ages obtained from igneous minerals represent undegassed argon from an ancient (4.0 Ga) rock, then the ages are expected to anticorrelate with the degree of shock heating. The data do not support this inference. Our data support young crystallization ages for minerals and Martian atmosphere as the origin of excess ⁴⁰Ar in the shock melts.The shock features of shergottites are also reviewed in the context of what is known of the geologic history of the Martian surface through remote observation. The oldest, most heavily cratered surfaces of Mars are thought to be ?4.0 Ga; we contend that ancient rocks from Mars (Noachian >3.5 Ga) are likely to record multiple impact events reflecting megaregolith formation and the cumulative effects of erosion and aqueous alteration occurring during or since that era. Young rocks (Late Amazonian, <0.6 Ga) should record a relatively simple history of emplacement and ejection from the near surface. We show that although shergottites are strongly shocked, they are relatively pristine crystalline igneous rocks and not pervasively altered breccias. The petrography of shergottites is at odds with an ancient age interpretation. A model in which young coherent rocks are preferentially sampled by hypervelocity impact because of material strength is considered highly plausible.     

Constraints on the petrogenesis of Martian meteorites from the Rb-Sr and Sm-Nd isotopic systematics of the lherzolitic shergottites ALH77005 and LEW88516

Detailed Rb-Sr and Sm-Nd isotopic analyses have been completed on the lherzolitic shergottites ALH77005 and LEW88516. ALH77005 yields a Rb-Sr age of 185 ± 11 Ma and a Sm-Nd age of 173 ± 6 Ma, whereas the Rb-Sr and Sm-Nd ages of LEW88516 are 183 ± 10 and 166 ± 16 Ma, respectively. The initial Sr isotopic composition of ALH77005 is 0.71026 ± 4, and the initial ε_Nd value is +11.1 ± 0.2. These values are distinct from those of LEW88516, which has an initial Sr isotopic composition of 0.71052 ± 4 and an initial ε_Nd value of +8.2 ± 0.6. Several of the mineral and whole rock leachates lie off the Rb-Sr and Sm-Nd isochrons, indicating that the isotopic systematics of the meteorites have been disturbed. The Sm-Nd isotopic compositions of the leachates appear to be mixtures of primary igneous phosphates and an alteration component with a low ¹⁴³Nd/¹⁴⁴Nd ratio that was probably added to the meteorites on Mars. Tie lines between leachate-residue pairs from LEW88516 mineral fractions and whole rocks have nearly identical slopes that correspond to Rb-Sr ages of 90 ± 1 Ma. This age may record a major shock event that fractionated Rb/Sr from lattice sites located on mineral grain boundaries. On the other hand, the leachates could contain secondary alteration products, and the parallel slopes of the tie lines could be coincidental.Nearly identical mineral modes, compositions, and ages suggest that these meteorites are very closely related. Nevertheless, their initial Sr and Nd isotopic compositions differ outside analytical uncertainty, requiring derivation from unique sources. Assimilation-fractional-crystallization models indicate that these two lherzolitic meteorites can only be related to a common parental magma, if the assimilant has a Sr/Nd ratio near 1 and a radiogenic Sr isotopic composition. Further constraints placed on the evolved component by the geochemical and isotopic systematics of the shergottite meteorite suite suggest that it (a) formed at ∼4.5 Ga, (b) has a high La/Yb ratio, (c) is an oxidant, and (d) is basaltic in composition or is strongly enriched in incompatible elements. The composition and isotopic systematics of the evolved component are unlike any evolved lunar or terrestrial igneous rocks. Its unusual geochemical and isotopic characteristics could reflect hydrous alteration of an evolved Martian crustal component or hydrous metasomatism within the Martian mantle.     

New constraints on early Solar System chronology from Al-Mg and U-Pb isotope systematics in the unique basaltic achondrite Northwest Africa 2976

We report elemental abundances and the isotopic systematics of the short-lived ²⁶Al-²⁶Mg (half-life of ∼0.73 Ma) and long-lived U-Pb radiochronometers in the ungrouped basaltic meteorite Northwest Africa (NWA) 2976. The bulk geochemical composition of NWA 2976 is clearly distinct from that of the eucrites and angrites, but shows broad similarities to that of the paired NWA 001 and 2400 ungrouped achondrites indicating that it is likely to also be paired with these two samples. The major and trace element abundances in NWA 2976 further indicate that it formed by extensive melting and magmatic fractionation processes on its parent body. The Al-Mg and Pb-Pb isotope systematics indicate that this meteorite represents the earliest stages of crust formation on a differentiated parent body in the early Solar System. The absolute Pb-Pb internal isochron age of NWA 2976, obtained from acid leaching residues of three whole-rock samples and two pyroxene separates, is 4562.89 ± 0.59 Ma (MSWD = 0.02). This Pb-Pb age is calculated using the measured ²³⁸U/²³⁵U ratio of a NWA 2976 whole-rock of 137.751 ± 0.018 (2σ) which was determined relative to the recently revised value of 137.840 ± 0.008 for the SRM 950a U isotope standard. The Al-Mg systematics reveal the presence of ²⁶Mg isotopic anomalies produced by the decay of ²⁶Al with an (²⁶Al/²⁷Al)₀ of (3.94 ± 0.16) × 10⁻⁷, and indicate a time of formation of 0.26 ± 0.18 Ma after the D’Orbigny angrite. Using the revised Pb-Pb age of 4563.36 ± 0.34 Ma for the D’Orbigny anchor (corrected for its U isotopic composition), we deduce an Al-Mg model age of 4563.10 ± 0.38 Ma for NWA 2976, which is consistent with its Pb-Pb internal isochron age.The concordance of the Pb-Pb and Al-Mg chronometers, when taking into account the differences in the U isotopic compositions of the D’Orbigny and NWA 2976 achondrites (whose parent bodies likely formed in distinct regions of early Solar System as indicated by their different oxygen isotopic compositions), implies that ²⁶Al was homogeneously distributed in the early Solar System. It also suggests that igneous processes on planetesimals, as represented by the formation of various basaltic meteorite groups that likely originated on distinct parent bodies (e.g., eucrites and angrites, as well as ungrouped achondrites), were widespread throughout the protoplanetary disk within the first ∼5 Ma of the history of the Solar System.     

Mechanisms for incompatible-element enrichment on the Moon deduced from the lunar basaltic meteorite Northwest Africa 032

The lunar meteorite Northwest Africa (NWA) 032 is a low-Ti basalt that has incompatible-element abundances and Th/Sm ratios characteristic of the involvement of late stage magma ocean crystallization products (urKREEP) in its petrogenesis. This sample is very fine-grained and contains terrestrial weather products. A progressive leaching procedure was therefore developed and applied to magnetic separates and whole rock fractions to obtain Rb-Sr and Sm-Nd ages. Although many of the leachates, as well as the unleached mineral and whole rock fractions contain terrestrial alteration products, selected residue fractions yield concordant Rb-Sr and Sm-Nd ages. Rubidium-Sr isotopic analyses yield an age of 2947 ± 16 Ma with an initial ⁸⁷Sr/⁸⁶Sr of 0.700057 ± 17. These characteristics indicate NWA 032 is derived from a source region with an ⁸⁷Rb/⁸⁶Sr ratio of 0.044 ± 0.001. This value is higher than all but those determined for KREEP basalts, and suggests that NWA 032 is derived from a source region that has higher incompatible-element abundances than other low-Ti basalts. Samarium-neodymium isotopic analysis yield a concordant age of 2931 ± 92 Ma and an initial ε_Nd of +9.71 ± 0.74 corresponding to a source region with ¹⁴⁷Sm/¹⁴⁴Nd ratio of 0.246 ± 0.004. The initial Nd isotopic composition stands in contrast to the initial Sr isotopic composition by requiring NWA 032 to be derived from a source with lower incompatible-element abundances than most low-Ti basalts. The source of NWA 032 is therefore unlike those of other lunar basalts.Modeling of magma ocean cumulate formation demonstrates that unlike other low-Ti basalt source regions the NWA 032 source is a mixture of olivine, pigeonite, and clinopyroxene bearing cumulates and only a small amount of urKREEP. Furthermore, unlike other mare basalt sources, the NWA 032 source does not contain appreciable quantities of plagioclase. Partial melting models demonstrate that the incompatible-element characteristics of the NWA 032 result from formation by smaller degrees of partial melting than other mare basalts. Thus, the incompatible-element geochemical signature that is observed in NWA 032 appears to reflect the combined effects of generation from an unusual plagioclase-free incompatible-element-depleted source region by very small degrees of partial melting. This study demonstrates that both the presence of urKREEP in the source region and small degrees of partial melting generate magmas with similar, but not identical, incompatible-element characteristics. In addition, it underscores the fact that there is significantly more geochemical diversity on the Moon than is represented by samples collected by the American and Soviet lunar missions.     

The early differentiation history of Mars from W-Nd isotope systematics in the SNC meteorites

We report here the results of an investigation of W and Nd isotopes in the SNC (Shergottite-Nakhlite-Chassignite (martian)) meteorites. We have determined that ε¹⁸²W values in the nakhlites are uniform within analytical uncertainties and have an average value of ∼3. Also, while ε¹⁸²W values in the shergottites have a limited range (from 0.3-0.7), their ε¹⁴²Nd values vary considerably (from −0.2-0.9). There appears to be no correlation between ε¹⁸²W and ε¹⁴²Nd in the nakhlites and shergottites. These results shed new light on early differentiation processes on Mars, particularly on the timing and nature of fractionation in silicate reservoirs. Assuming a two-stage model, the metallic core is estimated to have formed at ∼12 Myr after the beginning of the solar system. Major silicate differentiation established the nakhlite source reservoir before ∼4542 Ma and the shergottite source reservoirs at 4525 Ma. These ages imply that, within the uncertainties afforded by the ¹⁸²Hf-¹⁸²W and ¹⁴⁶Sm-¹⁴²Nd chronometers, the silicate differentiation events that established the source reservoirs of the nakhlites and shergottites may have occurred contemporaneously, possibly during crystallization of a global magma ocean. The distinct ¹⁸²W-¹⁴²Nd isotope systematics in the nakhlites and the shergottites imply the presence of at least three isotopically distinct silicate reservoirs on Mars, two of which are depleted in incompatible lithophile elements relative to chondrites, and the third is enriched. The two depleted silicate reservoirs most likely reside in the Martian mantle, while the enriched reservoir could be either in the crust or the mantle. Therefore, the ¹⁸²W-¹⁴²Nd isotope systematics indicate that the nakhlites and the shergottites originated from distinct source reservoirs and cannot be petrogenetically related. A further implication is that the source reservoirs of the nakhlites and shergottites on Mars have been isolated since their establishment before ∼4.5 Ga. Therefore, there has been no giant impact or efficient global mantle convection to thoroughly homogenize the Martian mantle following the establishment of the SNC source reservoirs.     

The origin of enriched mantle beneath São Miguel, Azores

Lavas from the island of São Miguel, Azores Archipelago have long been known to display large radiogenic isotopic variability, that ranges from “depleted” isotopic signatures (e.g. high ε_Nd ∼ +5) in the west, typical of many ocean island basalts, to more “enriched” compositions (e.g. low ε_Nd ∼ +1) in the east. Here, we further characterise the geochemistry of lavas from this remarkable locality, focussing on the nature and origin of the enriched source. Our new isotope data define a striking, linear array in Nd and Hf isotope space that points towards an unusual, enriched composition below the mantle array. This distinctive Hf-Nd isotope signature is associated with elevated values of all three radiogenic Pb isotope ratios. Although the enriched component has certain geochemical similarities to both terrigenous sediments and some samples of the continental mantle lithosphere, such comparisons do not stand closer examination. In the absence of a clear, modern analogue we explore the isotope evolution of some simple, model melt compositions to investigate plausible means of producing an appropriate enriched component. Nd-Hf isotope characteristics provide the tightest constraints and can be reproduced by an ancient (∼3 Ga), modest-degree melt (∼2%) from a garnet peridotite source. Currently, modest-degree melts from garnet-bearing sources are found forming some major oceanic islands. Subduction, isolation and later mixing of small amounts (<5%) of such basaltic material with more ubiquitous ambient mantle can account for the isotopic characteristics of the enriched São Miguel source. Yet the incompatible element ratios of the enriched São Miguel lavas do not show “recycled” signatures of near-surface alteration nor subduction zone dehydration. Thus, we infer that the enriched component was originally under-plated basalt, intruded into oceanic mantle lithosphere rather than forming the island edifice itself. Since the extreme isotope compositions of São Miguel reflect unextraordinary, albeit ancient, magmatic fractionation, the general rarity of such signatures indicates the efficiency of mantle processes in homogenising or hiding similar sources.     

Pt-Re-Os and Sm-Nd isotope and HSE and REE systematics of the 2.7 Ga Belingwe and Abitibi komatiites

High-precision Pt-Re-Os and Sm-Nd isotope and highly siderophile element (HSE) and rare earth element (REE) abundance data are reported for two 2.7 b.y. old komatiite lava flows, Tony’s flow (TN) from the Belingwe greenstone belt, Zimbabwe, and the PH-II flow (PH) from Munro Township in the Abitibi greenstone belt, Canada. The emplaced lavas are calculated to have contained ∼25% (TN) and ∼28% (PH) MgO. These lavas were derived from mantle sources characterized by strong depletions in highly incompatible lithophile trace elements, such as light REE (Ce/Sm_N = 0.64 ± 0.02 (TN) and 0.52 ± 0.01 (PH), ε¹⁴³Nd(T) = +2.9 ± 0.2 in both sources). ¹⁹⁰Pt-¹⁸⁶Os and ¹⁸⁷Re-¹⁸⁷Os isochrons generated for each flow yield ages consistent with respective emplacement ages obtained using other chronometers. The calculated precise initial ¹⁸⁶Os/¹⁸⁸Os = 0.1198318 ± 3 (TN) and 0.1198316 ± 5 (PH) and ¹⁸⁷Os/¹⁸⁸Os = 0.10875 ± 17 (TN) and 0.10873 ± 15 (PH) require time-integrated ¹⁹⁰Pt/¹⁸⁸Os and ¹⁸⁷Re/¹⁸⁸Os of 0.00178 ± 11 and 0.407 ± 8 (TN) and 0.00174 ± 18 and 0.415 ± 5 (PH). These parameters, which by far represent the most precise and accurate estimates of time-integrated Pt/Os and Re/Os of the Archean mantle, are best matched by those of enstatite chondrites. The data also provide evidence for a remarkable similarity in the composition of the sources of these komatiites with respect to both REE and HSE. The calculated absolute HSE abundances in the TN and PH komatiite sources are within or slightly below the range of estimates for the terrestrial Primitive Upper Mantle (PUM). Assuming a chondritic composition of the bulk silicate Earth, the strong depletions in LREE, yet chondritic Re/Os in the komatiite sources are apparently problematic because early Earth processes capable of fractionating the LREE might also be expected to fractionate Re/Os. This apparent discrepancy could be reconciled via a two-stage model, whereby the moderate LREE depletion in the sources of the komatiites initially occurred within the first 100 Ma of Earth’s history as a result of either global magma ocean differentiation or extraction and subsequent long-term isolation of early crust, whereas HSE were largely added subsequently via late accretion. The komatiite formation, preceded by derivation of basaltic magmas, was a result of second-stage, large-degree dynamic melting in mantle plumes.     

Mineralogy, geochemistry, and Ar-Ar geochronology of lunar granulitic breccia Northwest Africa 3163 and paired stones: Comparisons with Apollo samples

The lunar meteorites Northwest Africa (NWA) 3163, 4881, and 4483 are paired stones classified as granulitic breccias. At 2.4 kg, these three stones constitute one of the largest known lunar meteorite masses. Here we describe the petrography, mineralogy, and chemistry of NWA 3163, 4881, and 4483, and present ⁴⁰Ar-³⁹Ar data for two of the meteorites. Two-pyroxene thermometry indicates that the rocks equilibrated at 1050 ± 50 °C, which represents the high-temperature, low-pressure event that generated their characteristic recrystallization textures and reset their Ar systematics. Stepped-heating, in situ infrared laser microprobe ⁴⁰Ar-³⁹Ar geochronology yields a mean age of 3327 ± 29 Ma for NWA 3163, and a more disturbed release spectrum for NWA 4881. NWA 4881 shows an upward-trending pattern, suggesting that it may have had a ⁴⁰Ar-³⁹Ar age of >3.0 Ga, but that it was partially reset at ∼2.6 Ga. NWA 3163 et al. exhibit shock effects, including maskelynitized plagioclase, shock veins, and melt pockets, which are absent in the Apollo granulitic breccias. Although the Apollo and meteorite samples are texturally similar and have comparable bulk compositions and equilibration temperatures, their trace and siderophile element contents point to distinct parental lithologies derived from different regions of the Moon. Based on mineralogical and geochemical differences between the Apollo and meteorite samples, we conclude that the parent rock(s) of the paired NWA meteorites came from an area outside the Imbrium region and that they underwent high-temperature (granulite event) metamorphism long after the Late Heavy Bombardment.     

Petrogenesis of olivine-phyric shergottite Larkman Nunatak 06319: Implications for enriched components in martian basalts

We report on the petrography and geochemistry of the newly discovered olivine-phyric shergottite Larkman Nunatak (LAR) 06319. The meteorite is porphyritic, consisting of megacrysts of olivine (?2.5 mm in length, Fo_77-52) and prismatic zoned pyroxene crystals with Wo₃En₇₁ in the cores to Wo_8-30En_23-45 at the rims. The groundmass is composed of finer grained olivine (<0.25 mm, Fo_62-46), Fe-rich augite and pigeonite, maskelynite and minor quantities of chromite, ulvöspinel, magnetite, ilmenite, phosphates, sulfides and glass. Oxygen fugacity estimates, derived from the olivine-pyroxene-spinel geo-barometer, indicate that LAR 06319 formed under more oxidizing conditions (QFM -1.7) than for depleted shergottites. The whole-rock composition of LAR 06319 is also enriched in incompatible trace elements relative to depleted shergottites, with a trace-element pattern that is nearly identical to that of olivine-phyric shergottite NWA 1068. The oxygen isotope composition of LAR 06319 (Δ¹⁷O = 0.29 ±0.03) confirms its martian origin.Olivine megacrysts in LAR 06319 are phenocrystic, with the most Mg-rich megacryst olivine being close to equilibrium with the bulk rock. A notable feature of LAR 06319 is that its olivine megacryst grains contain abundant melt inclusions hosted within the forsterite cores. These early-trapped melt inclusions have similar trace element abundances and patterns to that of the whole-rock, providing powerful evidence for closed-system magmatic behavior for LAR 06319. Calculation of the parental melt trace element composition indicates a whole-rock composition for LAR 06319 that was controlled by pigeonite and augite during the earliest stages of crystallization and by apatite in the latest stages. Crystal size distribution and spatial distribution pattern analyses of olivine indicate at least two different crystal populations. This is most simply interpreted as crystallization of megacryst olivine in magma conduits, followed by eruption and subsequent crystallization of groundmass olivine.LAR 06319 shows close affinity in mineral and whole-rock chemistry to olivine-phyric shergottite, NWA 1068 and the basaltic shergottite NWA 4468. The remarkable features of these meteorites are that they have relatively similar quantities of mafic minerals compared with olivine-phyric shergottites (e.g., Y-980459, Dho 019), but flat and elevated rare earth element patterns more consistent with the LREE-enriched basaltic shergottites (e.g., Shergotty, Los Angeles). This relationship can be interpreted as arising from partial melting of an enriched mantle source and subsequent crystal-liquid fractionation to form the enriched olivine-phyric and basaltic shergottites, or by assimilation of incompatible-element enriched martian crust. The similarity in the composition of early-trapped melt inclusions and the whole-rock for LAR 06319 indicates that any crustal assimilation must have occurred prior to crystallization of megacryst olivine, restricting such processes to the deeper portions of the crust. Thus, we favor LAR06319 forming from partial melting of an “enriched” and oxidized mantle reservoir, with fractional crystallization of the parent melt upon leaving the mantle.     

Ar-Ar and I-Xe ages and thermal histories of three unusual metal-rich meteorites

Portales Valley, Sombrerete, and Northwest Africa (NWA) 176 are three unrelated meteorites, which consist of silicate mixed with substantial amounts of metal and which likely formed at elevated temperatures as a consequence of early impacts on their parent bodies. Measured ³⁹Ar-⁴⁰Ar ages of these meteorites are 4477 ± 11 Ma and 4458 ± 16 Ma (two samples of Portales Valley), 4541 ± 12 Ma, and 4524 ± 13 Ma, respectively (Ma = million years; all one-sigma errors). The Ar-Ar data for Portales Valley show no evidence of later open system behavior suggested by some other chronometers. Measured ¹²⁹I-¹²⁹Xe ages of these three meteorites are 4559.9 ± 0.5 Ma, 4561.9 ± 1.0 Ma, and ∼4544 Ma, respectively (relative to Shallowater = 4562.3 ± 0.4 Ma). From stepwise temperature release data, we determined the diffusion characteristics for Ar and Xe in our samples and calculated approximate closure temperatures for the K-Ar and I-Xe chronometers. Adopting results and interpretations about these meteorites from some previous workers, we evaluated all these data against various thermal cooling models. We conclude that Portales Valley formed 4560 Ma ago, cooled quickly to below the I-Xe closure temperature, then cooled deep within the parent body at a rate of ∼4 °C/Ma through K-Ar closure. We conclude that Sombrerete formed 4562 Ma ago and cooled relatively quickly. NWA 176 likely formed and cooled quickly ∼4544 Ma ago, or later than formation times of most meteorite parent bodies. For all three meteorites, the Ar-Ar ages are in better agreement with I-Xe ages and preferred thermal models if we increase these Ar-Ar ages by ∼20 Ma. Such age corrections would be consistent with probable errors in ⁴⁰K decay parameters in current use, as suggested by others. The role of impact heating and possible disruption and partial reassembly of meteorite parent bodies to form some meteorites likely was an important process in the early solar system.     

Diffusion induced Li isotopic fractionation during the cooling of magmatic rocks: The case of pyroxene phenocrysts from nakhlite meteorites

Ion-microprobe was used to measure Li abundances and isotopic compositions in pyroxenes from three Martian meteorites belonging to the nakhlite family. The profiles performed across augite crystals from Northwest Africa 817 show a large isotopic zoning from crystal cores (δ⁷Li ∼ 0‰) to rims (δ⁷Li ∼ +20‰) while Li abundances are almost constant (∼9.2 μg/g). Unlike NWA 817, the pyroxene studied in the Miller Range 03346 nakhlite shows a zoning in Li abundance, with concentrations increasing from ∼2.5 μg/g in the core to ∼9 μg/g in the rim. The augite rim (δ⁷Li = +7‰) is slightly enriched in ⁷Li with regard to the core (δ⁷Li = +4‰), but most of the isotopic variations observed occur at an intermediate position along the profile, where δ⁷Li falls down to ∼−11‰. In the case of Nakhla, Li concentrations in augite increase from cores (∼3.5 μg/g) to rims (∼6.5 μg/g), while the δ⁷Li variation is restricted (i.e., between δ⁷Li = +6.0 and +12.6‰). For the three meteorites the Li abundances were also measured in the groundmass, which was found to be enriched in lithium (∼10 μg/g). Conventional magmatic and post-magmatic processes such as alteration and fractional crystallization, fail to explain the dataset obtained on nakhlites. Degassing processes, which were previously proposed to explain the Li distribution in shergottite crystals, cannot result in the strong decoupling between Li abundances and isotopic composition observed in nakhlites. We suggest that the original magmatic Li distributions (concentrations and isotopic compositions) in nakhlites have been modified by diffusion of Li from the Li-rich groundmass towards the pyroxene crystals during sub-solidus cooling. Diffusion appears to have been efficient for NWA 817 and MIL 03346 but, apparently, did not produce a significant migration of Li in Nakhla, possibly because of the lower abundance of groundmass in the latter. Diffusion induced Li redistributions may also affect terrestrial porphyric rocks but very specific cooling rates are required to quench the diffusion profiles as observed in two of the present nakhlites.     

Lithium isotopes in Guatemalan and Franciscan HP-LT rocks: Insights into the role of sediment-derived fluids during subduction

High-pressure, low-temperature (HP-LT) rocks from a Cretaceous age subduction complex occur as tectonic blocks in serpentinite mélange along the Motagua Fault (MF) in central Guatemala. Eclogite and jadeitite among these are characterized by trace element patterns with enrichments in fluid mobile elements, similar to arc lavas. Eclogite is recrystallized from MORB-like altered oceanic crust, presumably at the boundary between the down-going plate and overlying mantle wedge. Eclogite geochemistry, mineralogy and petrography suggest a two step petrogenesis of (1) dehydration during prograde metamorphism at low temperatures (<500 °C) followed by (2) partial rehydration/fertilization at even lower T during exhumation. In contrast, Guatemalan jadeitites are crystallized directly from low-T aqueous fluid as veins in serpentinizing mantle during both subduction and exhumation. The overall chemistry and mineralogy of Guatemalan eclogites are similar to those from the Franciscan Complex, California, implying similar P-T-x paths.Li concentrations (?90 ppm) in mineral separates and whole rocks (WR) from Guatemalan and Franciscan HP-LT rocks are significantly higher than MORB (4-6 ppm), but similar to HP-LT rocks globally. Li isotopic compositions range from −5‰ to +5‰ for Guatemalan HP-LT rocks, and −4‰ to +1‰ for Franciscan eclogites, overlapping previous findings for other HP-LT suites. The combination of Li concentrations greater than MORB, and Li isotopic values lighter than MORB are inconsistent with a simple dehydration model. We prefer a model in which Li systematics in Guatemalan and Franciscan eclogites reflect reequilibration with subduction fluids during exhumation. Roughly 5-10% of the Li in these fluids is derived from sediments.Model results predict that the dehydrated bulk ocean crust is isotopically lighter (δ⁷Li ? +1 ± 3‰) than the depleted mantle (∼+3.5 ± 0.5‰), while the mantle wedge beneath the arc is the isotopic complement of the bulk crust. A subduction fluid with an AOC-GLOSS composition over the full range of model temperatures (50-600 °C) gives an average fluid δ⁷Li (∼+7 ± 5‰ 1σ) that is isotopically heavier than the depleted mantle. If the lowest temperature steps are excluded (50-260 °C) as too cold to participate in circulation of the mantle wedge, then the average subduction fluid (δ⁷Li = +4 ± 2.3‰ 1σ, is indistinguishable from depleted mantle. Because of the relatively compatible nature of Li in metamorphic minerals, the most altered part of the crust (uppermost extrusives), may retain a Li isotopic signature (∼+5 ± 3‰) heavier than the bulk crust. The range of Li isotopic values for OIB, IAB and MORB overlap, making it is difficult to resolve which of these components may contribute to the recycled component in the mantle using δ⁷Li alone.     

Petrology, geochemistry, and age of low-Ti mare-basalt meteorite Northeast Africa 003-A: A possible member of the Apollo 15 mare basaltic suite

Northeast Africa 003 (NEA 003) is a lunar meteorite found as a two paired stones (6 and 118 g) in Libya, 2000 and 2001. The main portion (∼75 vol%) of the 118 g meteorite, used for this study, (NEA 003-A) consists of mare-basalt and a smaller adjacent portion (∼25 vol%) is a basaltic breccia (NEA 003-B). NEA 003-A has a coarse-grained magmatic texture consisting mainly of olivine, pyroxene and plagioclase. The late-stage mineral association is composed mainly of elongated plagioclase, ilmenite, troilite, fayalite, Si-K-rich glass, apatite, and a rare SiO₂ phase. Other accessory minerals include ulvöspinel, chromite, and trace Fe-Ni metal. Olivine and pyroxene contain shock-induced fractures, and plagioclase is completely converted into maskelynite.The Fe/Mn values of the whole rock, olivines and pyroxenes, and the bulk-rock oxygen isotopic composition provide evidence for the lunar origin of NEA 003-A meteorite. This is further supported by the presence of Fe-Ni metal and the anhydrous mineral association.NEA 003-A is geochemically and petrographically distinct from previously described mare-basalt meteorites and is not paired with any of them. The petrography and major element composition of NEA 003-A is similar to the composition of low-Ti olivine mare basalts from Apollo 12 and olivine-normative basalts from Apollo 15. The NEA 003-A meteorite shows obvious geochemical similarities in trace elements contents with Apollo 15 olivine-normative basalts and could represent a yet unknown geochemically primitive member of the olivine-normative basalt series. The meteorite is depleted in rare earth elements (REE) and incompatible trace elements indicating a primitive character of the parental magma. The bulk-rock chemical composition demonstrates that the parent melt of NEA 003-A was not contaminated with KREEP components as a result of magma mixing or assimilation processes. Results of crystallization modelling and low minimum cooling rate estimates (∼0.07 °C/h) suggest that the parent melt of NEA 003-A crystallized in the lower part of a lava flow containing cumulate olivine (∼10%) and was probably derived from more primitive picritic magma by fractional crystallization processes.Sm-Nd dating yields an age of 3.09 ± 0.06 Ga which corresponds to the period of lower Eratosthenian lunar volcanic activity, and the near-chondritic ε_Nd value of −0.4 ± 0.3 indicates that the meteorite could be derived from a slightly enriched mantle source similar to the Apollo 15 green glasses. Ar-Ar step release results are inconsistent with Sm-Nd ages suggesting that NEA 003-A was exposed to one or more impact events. The most extensive event took place at 1.8 Ga and the shock intensity was likely between 28 and 45 GPa. The absence of solar Ar suggests that NEA 003-A has not been directly exposed at the lunar surface but the cosmic ray exposure age of 209 ± 6 Ma suggests that NEA 003-A resided in the upper regolith for part of its history.