The composition and thickness of the crust of Mars estimated from rare earth elements and neodymium-isotopic compositions of Martian meteorites

Abstract— Isotopic and trace element compositions of Martian meteorites show that early differentiation of Mars produced complementary crustal and mantle reservoirs that were sampled by later magmatic events. This paper describes a mass balance model that estimates the rare earth element (REE) content and thickness of the crust of Mars from the compositions of shergottites. The diverse REE and Nd isotopic compositions of shergottites are most easily explained by variable addition of light rare earth element (LREE)–enriched crust to basaltic magmas derived from LREE-depleted mantle source regions. Antarctic shergottites EET 79001, ALH 77005, LEW 88516, and QUE 94201 all have strongly LREE-depleted patterns and positive initial ¹⁴³Nd isotopic compositions, which is consistent with the generation of these magmas from depleted mantle sources and little or no interaction with enriched crust. In contrast, Shergotty and Zagami have negative initial ¹⁴³Nd isotopic compositions and less pronounced depletions of the LREE, which have been explained by incorporation of enriched crustal components into mantle-derived magmas (Jones, 1989; Longhi, 1991; Borg et al., 1997). The mass balance model presented here derives the REE composition of the crustal component in Shergotty by assuming it represents a mixture between a mantle-derived magma similar in composition to EET 79001A and a LREE-enriched crustal component. The amount of crust in Shergotty is constrained by mixing relations based on Nd-isotopic compositions, which allows the REE pattern of the crustal component to be calculated by mass balance. The effectiveness of this model is demonstrated by the successful recovery of important characteristics of the Earth's continental crust from terrestrial Columbia River basalts. Self-consistent results for Nd-isotopic compositions and REE abundances are obtained if Shergotty contains ～10–30% of LREE-enriched crust with >10 ppm Nd. This crustal component would have moderately enriched LREE (Sm/Nd = 0.25–0.27; ¹⁴⁷Sm/¹⁴⁴Nd = 0.15–0.17; La/Yb = 2.7–3.8), relatively unfractionated heavy rare earth elements (HREE), and no Eu anomaly. Crust with these characteristics can be produced from a primitive lherzolitic Martian mantle by modest amounts (2–8%) of partial melting, and it would have a globally averaged thickness of <45 km, which is consistent with geophysical estimates. Mars may serve as a laboratory to investigate planetary differentiation by extraction of a primary basaltic crust.     

The chlorine isotope composition of Martian meteorites 2. Implications for the early solar system and the formation of Mars

We determined the chlorine isotope composition of 16 Martian meteorites using gas source mass spectrometry on bulk samples and in situ secondary ion microprobe analysis on apatite grains. Measured δ³⁷Cl values range from ?3.8 to +8.6‰. The olivine‐phyric shergottites are the isotopically lightest samples, with δ³⁷Cl mostly ranging from ?4 to ?2‰. Samples with evidence for a crustal component have positive δ³⁷Cl values, with an extreme value of 8.6‰. Most of the basaltic shergottites have intermediate δ³⁷Cl values of ?1 to 0‰, except for Shergotty, which is similar to the olivine‐phyric shergottites. We interpret these data as due to mixing of a two‐component system. The first component is the mantle value of ?4 to ?3‰. This most likely represents the original bulk Martian Cl isotope value. The other endmember is a ³⁷Cl‐enriched crustal component. We speculate that preferential loss of ³⁵Cl to space has resulted in a high δ³⁷Cl value for the Martian surface, similar to what is seen in other volatile systems. The basaltic shergottites are a mixture of the other two endmembers. The low δ³⁷Cl value of primitive Mars is different from Earth and most chondrites, both of which are close to 0‰. We are not aware of any parent‐body process that could lower the δ³⁷Cl value of the Martian mantle to ?4 to ?3‰. Instead, we propose that this low δ³⁷Cl value represents the primordial bulk composition of Mars inherited during accretion. The higher δ³⁷Cl values seen in many chondrites are explained by later incorporation of ³⁷Cl‐enriched HCl‐hydrate.     

Geochemistry of intermediate olivine‐phyric shergottite Northwest Africa 6234, with similarities to basaltic shergottite Northwest Africa 480 and olivine‐phyric shergottite Northwest Africa 2990

Abstract— The newly found meteorite Northwest Africa 6234 (NWA 6234) is an olivine (ol)‐phyric shergottite that is thought, based on texture and mineralogy, to be paired with Martian shergottite meteorites NWA 2990, 5960, and 6710. We report bulk‐rock major‐ and trace‐element abundances (including Li), abundances of highly siderophile elements, Re‐Os isotope systematics, oxygen isotope ratios, and the lithium isotope ratio for NWA 6234. NWA 6234 is classified as a Martian shergottite, based on its oxygen isotope ratios, bulk composition, and bulk element abundance ratios, Fe/Mn, Al/Ti, and Na/Al. The Li concentration and δ⁷Li value of NWA 6234 are similar to that of basaltic shergottites Zagami and Shergotty. The rare earth element (REE) pattern for NWA 6234 shows a depletion in the light REE (La‐Nd) compared with the heavy REE (Sm‐Lu), but not as extreme as the known “depleted” shergottites. Thus, NWA 6234 is suggested to belong to a new category of shergottite that is geochemically “intermediate” in incompatible elements. The only other basaltic or ol‐phyric shergottite with a similar “intermediate” character is the basaltic shergottite NWA 480. Rhenium‐osmium isotope systematics are consistent with this intermediate character, assuming a crystallization age of 180 Ma. We conclude that NWA 6234 represents an intermediate compositional group between enriched and depleted shergottites and offers new insights into the nature of mantle differentiation and mixing among mantle reservoirs in Mars.     

Petrography and geochemistry of the enriched basaltic shergottite Northwest Africa 2975

We present a study of the petrology and geochemistry of basaltic shergottite Northwest Africa 2975 (NWA 2975). NWA 2975 is a medium‐grained basalt with subophitic to granular texture. Electron microprobe (EMP) analyses show two distinct pyroxene compositional trends and patchy compositional zoning patterns distinct from those observed in other meteorites such as Shergotty or QUE 94201. As no bulk sample was available to us for whole rock measurements, we characterized the fusion crust and its variability by secondary ion mass spectrometer (SIMS) measurements and laser ablation inductively coupled plasma spectroscopy (LA‐ICP‐MS) analyses as a best‐available proxy for the bulk rock composition. The fusion crust major element composition is comparable to the bulk composition of other enriched basaltic shergottites, placing NWA 2975 within that sample group. The CI‐normalized REE (rare earth element) patterns are flat and also parallel to those of other enriched basaltic shergottites. Merrillite is the major REE carrier and has a flat REE pattern with slight depletion of Eu, parallel to REE patterns of merrillites from other basaltic shergottites. The oxidation state of NWA 2975 calculated from Fe‐Ti oxide pairs is NNO‐1.86, close to the QFM buffer. NWA 2975 represents a sample from the oxidized and enriched shergottite group, and our measurements and constraints on its origin are consistent with the hypothesis of two distinct Martian mantle reservoirs: a reduced, LREE‐depleted reservoir and an oxidized, LREE‐enriched reservoir. Stishovite, possibly seifertite, and dense SiO₂ glass were also identified in the meteorite, allowing us to infer that NWA 2975 experienced a realistic shock pressure of ~30 GPa.     

Noble gases in the Martian meteorite Northwest Africa 2737: A new chassignite signature

Abstract— We report noble gas data for the second chassignite, Northwest Africa (NWA) 2737, which was recently found in the Moroccan desert. The cosmic ray exposure (CRE) age based on cosmogenic ³He, ²¹Ne, and ³⁸Ar around 10–11 Ma is comparable to the CRE ages of Chassigny and the nakhlites and indicates ejection of meteorites belonging to these two families during a discrete event, or a suite of discrete events having occurred in a restricted interval of time. In contrast, U‐Th/He and K/Ar ages <0.5 Ga are in the range of radiometric ages of shergottites, despite a Sm‐Nd signature comparable to that of Chassigny and the nakhlites (Misawa et al. 2005). Overall, the noble gas signature of NWA 2737 resembles that of shergottites rather than that of Chassigny and the nakhlites: NWA 2737 does not contain, in detectable amount, the solar‐like xenon found in Chassigny and thought to characterize the Martian mantle nor apparently fission xenon from ²⁴⁴Pu, which is abundant in Chassigny and some of the nakhlites. In contrast, NWA 2737 contains Martian atmospheric noble gases trapped in amounts comparable to those found in shergottite impact glasses. The loss of Martian mantle noble gases, together with the trapping of Martian atmospheric gases, could have occurred during assimilation of Martian surface components, or more likely during shock metamorphism, which is recorded in the petrology of this meteorite.     

Various aspects of the petrogenesis of the Martian shergottite meteorites

Several controversies are associated with the age and origin of the shergottite meteorites, a suite of basaltic samples from Mars. Here, it will be argued that (1) the shergottites have a young igneous age, ≤600 Myr, (2) their parent magmas were relatively dry, (3) the range of initial isotopic compositions in shergottites is most likely due to assimilation of crustal materials by mantle‐derived basaltic magmas, and (4) the intercumulus liquid compositions of shergottites such as Shergotty and Zagami are relatively well constrained.     

Matching Martian crustal magnetization and magnetic properties of Martian meteorites

Abstract— Magnetic properties of 26 (of 32) unpaired Martian meteorites (SNCs) are synthesized to further constrain the lithology carrying Martian magnetic crustal sources. Magnetic properties of ultramafic cumulates (i.e., Chassigny, Allan Hills [ALH] 84001) and lherzolitic shergottites (ALH 77005, Lewis Cliff [LEW] 88516) are one or two orders of magnitude too weak to account for the crustal magnetizations, assuming magnetization in an Earth‐like field. Nakhlites and some basaltic shergottites, which are the most magnetic SNCs, show the right intensity. Titanomagnetite is the magnetic carrier in the nakhlites (7 meteorites), whereas in most basaltic shergottites (11 meteorites) it is pyrrhotite. Dhofar (Dho) 378, Los Angeles, and NWA 480/1460 and 2046 are anomalous basaltic shergottites, as their magnetism is mainly due to titanomagnetite. Pyrrhotite should be among the candidate minerals for the magnetized Noachian crust.     

Petrography,mineral chemistry,and crystallization history of olivine‐phyric shergottite NWA 6234: A new melt composition

Knowledge of Martian igneous and mantle compositions is crucial for understanding Mars' mantle evolution, including early differentiation, mantle convection, and the chemical alteration at the surface. Primitive magmas provide the most direct information about their mantle source regions, but most Martian meteorites either contain cumulate olivine or crystallized from fractionated melts. The new Martian meteorite Northwest Africa (NWA) 6234 is an olivine‐phyric shergottite. Its most magnesian olivine cores (Fo₇₈) are in Mg‐Fe equilibrium with a magma of the bulk rock composition, suggesting that it represents a melt composition. Thermochemical calculations show that NWA 6234 not only represents a melt composition but is a primitive melt derived from an approximately Fo₈₀ mantle. Thus, NWA 6234 is similar to NWA 5789 and Y 980459 in the sense that all three are olivine‐phyric shergottites and represent primitive magma compositions. However, NWA 6234 is of special significance because it represents the first olivine‐phyric shergottite from a primitive ferroan magma. On the basis of Al/Ti ratio of pyroxenes in NWA 6234, the minor components in olivine and merrillite, and phosphorus zoning of olivine, we infer that the rock crystallized completely at pressures consistent with conditions in Mars' upper crust. The textural intergrowths of the two phosphates (merrillite and apatite) indicate that at a very last stage of crystallization, merrillite reacted with an OH‐Cl‐F‐rich melt to form apatite. As this meteorite crystallized completely at depth and never erupted, it is likely that its apatite compositions represent snapshots of the volatile ratios of the source region without being affected by degassing processes, which contain high OH‐F content.     

Shergottites Dhofar 019, SaU 005, Shergotty,and Zagami: 40Ar‐39Ar chronology and trapped Martian atmospheric and interior argon

Abstract— We report a high‐resolution ⁴⁰Ar‐³⁹Ar study of mineral separates and whole‐rock samples of olivine‐phyric (Dhofar 019, Sayh al Uhaymir [SaU] 005) and basaltic (Shergotty, Zagami) shergottites. Excess argon is present in all samples. The highest (⁴⁰Ar/³⁶Ar)_trapped ratios are found for argon in pyroxene melt inclusions (?1500), maskelynite (?1200), impact glass (?1800) of Shergotty and impact glass of SaU 005 (?1200). A high (⁴⁰Ar/³⁶Ar)_trapped component‐usually uniquely ascribed to Martian atmosphere‐can also originate from the Martian interior, indicating a heterogeneous Martian mantle composition. As additional explanation of variable high (⁴⁰Ar/³⁶Ar)_trapped ratios in shocked shergottites, we suggest argon implantation from a “transient atmosphere” during impact induced degassing. The best ⁴⁰Ar‐³⁹Ar age estimate for Dhofar 019 is 642 ± 72 Ma (maskelynite). SaU 005 samples are between 700–900 Ma old. Relatively high ⁴⁰Ar‐³⁹Ar ages of melt inclusions within Dhofar 019 (1086 ± 252 Ma) and SaU 005 olivine (885 ± 66 Ma) could date entrapment of a magmatic liquid during early olivine crystallization, or reflect unrecognized excess ⁴⁰Ar components. The youngest ⁴⁰Ar‐³⁹Ar age of Shergotty separates (maskelynite) is ?370 Ma, that of Zagami is ?200 Ma. The ⁴⁰Ar‐³⁹Ar chronology of Dhofar 019 and SaU 005 indicate >1 Ga ages. Apparent ages uncorrected for trapped (e.g., Martian atmosphere, mantle) argon components approach 4.5 Ga, but are not caused by inherited ⁴⁰Ar, because excess ⁴⁰Ar is supported by ³⁶Ar_trapped. Young ages obtained by ⁴⁰Ar‐³⁹Ar and other chronometers argue for primary rather than secondary events. The cosmic ray exposure ages calculated from cosmogenic argon are 15.7 ± 0.7 Ma (Dhofar 019), 1.0–1.6 Ma (SaU 005), 2.1–2.5 Ma (Shergotty) and 2.2–3.0 Ma (Zagami).     

Trace elements in olivine and the petrogenesis of the intermediate,olivine‐phyric shergottite NWA 10170

Olivine‐phyric shergottites represent primitive basaltic to picritic rocks, spanning a large range of Mg# and olivine abundances. As primitive olivine‐bearing magmas are commonly representative of their mantle source on Earth, understanding the petrology and evolution of olivine‐phyric shergottites is critical in our understanding of Martian mantle compositions. We present data for the olivine‐phyric shergottite Northwest Africa (NWA) 10170 to constrain the petrology with specific implications for magma plumbing‐system dynamics. The calculated oxygen fugacity and bulk‐rock REE concentrations (based on modal abundance) are consistent with a geochemically intermediate classification for NWA 10170, and overall similarity with NWA 6234. In addition, we present trace element data using laser ablation ICP‐MS for coarse‐grained olivine cores, and compare these data with terrestrial and Martian data sets. The olivines in NWA 10170 contain cores with compositions of Fo₇₇ that evolve to rims with composition of Fo₅₈, and are characterized by cores with low Ni contents (400–600 ppm). Nickel is compatible in olivine and such low Ni content for olivine cores in NWA 10170 suggests either early‐stage fractionation and loss of olivine from the magma in a staging chamber at depth, or that Martian magmas have lower Ni than terrestrial magmas. We suggest that both are true in this case. Therefore, the magma does not represent a primary mantle melt, but rather has undergone 10–15% fractionation in a staging chamber prior to extrusion/intrusion at the surface of Mars. This further implies that careful evaluation of not only the Mg# but also the trace element concentrations of olivine needs to be conducted to evaluate pristine mantle melts versus those that have fractionated olivine (±pyroxene and oxide minerals) in staging chambers.     

Experimental petrology,crystallization history,and parental magma characteristics of olivine‐phyric shergottite NWA 1068: Implications for the petrogenesis of “enriched” olivine‐phyric shergottites

Abstract– Northwest Africa (NWA) 1068 is one of the few olivine‐phyric shergottites (e.g., NWA 1068, Larkman Nunatak [LAR] 06319, and Roberts Massif [RBT] 04262) that is not depleted in light rare earth elements (LREE). Its REE pattern is similar to that of the basaltic shergottite Shergotty, suggesting a possible connection between the olivine‐phyric and the basaltic shergottites. To test this possible link, we have investigated the high‐pressure near‐liquidus phase equilibria for the NWA 1068 meteorite bulk composition. Our results show that the NWA 1068 bulk composition does not represent an unmodified mantle‐derived melt; the olivine and pyroxene in our near‐liquidus experiments are more magnesian than in the rock itself, which suggests that NWA 1068 contains cumulate minerals (extra olivine). We have then used these experimental results combined with the pyroxene compositions in NWA 1068 to constrain the possible high‐pressure crystallization history of the parental magma. These results suggest that NWA 1068 had a complex polybaric history. Finally, we have calculated a model parental magma composition for the NWA 1068 meteorite. The calculated parental magma is an evolved basaltic composition which is too ferroan to be a primitive melt directly derived from the mantle. We suggest that it ponded and crystallized at approximately the base of the crust. This provided an opportunity for the magma to become contaminated by an “enriched” crustal component prior to crystallization. The results and modeling from these experiments are applicable not only to the NWA 1068 meteorite, but also to LAR 06319 and possibly any other enriched olivine‐phyric shergottite.     

The noble gas concentrations of the Martian meteorites GRV 99027 and paired NWA 7906/NWA 7907

Here we present the isotopic concentrations of He, Ne, Ar, Kr, and Xe for the three Martian meteorites, namely Grove Mountains 99027 (GRV 99027), Northwest Africa 7906 (NWA 7906), and Northwest Africa 7907 (NWA 7907). The cosmic ray exposure (CRE) age for GRV 99027 of 5.7 ± 0.4 Ma (1σ) is consistent with CRE ages for other poikilitic basaltic shergottites and suggests that all were ejected in a single event ~5.6 Ma ago. After correcting for an estimated variable sodium concentration, the CRE ages for NWA 7906 and NWA 7907 of 5.4 ± 0.4 and 4.9 ± 0.4 Ma (1σ), respectively, are in good agreement with the CRE age of ~5 Ma favored by Cartwright et al. ( 2014 ) for NWA 7034. The data, therefore, support the conclusion that all three basaltic regolith breccias are paired. The ⁴⁰Ar gas retention age for NWA 7907 of ~1.3 Ga is in accord with Cartwright et al. ( 2014 ). For NWA 7906, we were unable to determine a ⁴⁰Ar gas retention age. The ⁴He gas retention ages for NWA 7906 and 7907 are in the range of 200 Ma and are much shorter than the ⁴⁰Ar gas retention age of NWA 7907, indicating that about 86–88% of the radiogenic ⁴He has been lost. The Kr and Xe isotopic concentrations in GRV 99027 are composed almost exclusively of Martian interior (MI) gases, while for NWA 7906 and NWA 7907, they indicate gases from the MI, elementally fractionated air, and possibly Martian atmosphere.     

Heterogeneous distribution of H2O in the Martian interior: Implications for the abundance of H2O in depleted and enriched mantle sources

We conducted a petrologic study of apatite within 12 Martian meteorites, including 11 shergottites and one basaltic regolith breccia. These data were combined with previously published data to gain a better understanding of the abundance and distribution of volatiles in the Martian interior. Apatites in individual Martian meteorites span a wide range of compositions, indicating they did not form by equilibrium crystallization. In fact, the intrasample variation in apatite is best described by either fractional crystallization or crustal contamination with a Cl‐rich crustal component. We determined that most Martian meteorites investigated here have been affected by crustal contamination and hence cannot be used to estimate volatile abundances of the Martian mantle. Using the subset of samples that did not exhibit crustal contamination, we determined that the enriched shergottite source has 36–73 ppm H₂O and the depleted source has 14–23 ppm H₂O. This result is consistent with other observed geochemical differences between enriched and depleted shergottites and supports the idea that there are at least two geochemically distinct reservoirs in the Martian mantle. We also estimated the H₂O, Cl, and F content of the Martian crust using known crust‐mantle distributions for incompatible lithophile elements. We determined that the bulk Martian crust has ~1410 ppm H₂O, 450 ppm Cl, and 106 ppm F, and Cl and H₂O are preferentially distributed toward the Martian surface. The estimate of crustal H₂O results in a global equivalent surface layer (GEL) of ~229 m, which can account for at least some of the surface features on Mars attributed to flowing water and may be sufficient to support the past presence of a shallow sea on Mars' surface.     

A review of volatiles in the Martian interior

Multiple observations from missions to Mars have revealed compelling evidence for a volatile‐rich Martian crust. A leading theory contends that eruption of basaltic magmas was the ultimate mechanism of transfer of volatiles from the mantle toward the surface after an initial outgassing related to the crystallization of a magma ocean. However, the concentrations of volatile species in ascending magmas and in their mantle source regions are highly uncertain. This work and this special issue of Meteoritics & Planetary Science summarize the key findings of the workshop on Volatiles in the Martian Interior (Nov. 3–4, 2014), the primary open questions related to volatiles in Martian magmas and their source regions, and the suggestions of the community at the workshop to address these open questions.     

Noble gases and chemical composition of Shergotty mineral fractions,Chassigny, and Yamato 793605: The trapped argon-40/argon-36 ratio and ejection times of Martian meteorites

Abstract— We report the elemental and isotopic composition of the noble gases as well as the chemical abundances in pyroxene, maskelynite/mesostasis glass, and bulk material of Shergotty and of bulk samples from Chassigny and Yamato 793605. The ⁴⁰K-⁴⁰Ar isochron for the Shergotty minerals yields a gas retention age of 196 Ma, which is, within errors, in agreement with previously determined Rb-Sr internal isochron ages. Argon that was trapped at this time has a ⁴⁰Ar/³⁶Ar ratio of 1100. For Chassigny and Y-793605, we obtain trapped ⁴⁰Ar/³⁶Ar ratios of 1380 and 950, respectively. Using these results and literature data, we show that the three shergottites, Shergotty, Zagami, and QUE 94001; the lherzolites ALH 77005, LEW 88516, and Y-793605; as well as Chassigny and ALH 84001 contain a mixture of Martian mantle and atmospheric Ar; whereas, the trapped ⁴⁰Ar/³⁶Ar ratio of the nakhlites, Nakhla, Lafayette, and Governador Valadares cannot be determined with the present data. We show that Martian atmospheric trapped Ar in Martian meteorites is correlated with the shock pressure that they experienced. Hence, we conclude that the Martian atmospheric gases were introduced by shock into the meteoritic material. For the Shergotty minerals, we obtain ³He-, ²¹Ne-, and ³⁸Ar-based cosmic-ray exposure ages of 3.0 Ma, and for the lherzolite Y-793605, 4.0 Ma, which confirms our earlier conclusion that the lherzolites were ejected from Mars ～1 Ma before the shergottites. Chassigny yields the previously known ejection age of 11.6 Ma.     

Primitive olivine‐phyric shergottite NWA 5789: Petrography,mineral chemistry,and cooling history imply a magma similar to Yamato‐980459

Knowledge of Martian igneous basaltic compositions is crucial for constraining mantle evolution, including early differentiation and mantle convection. Primitive magmas provide direct information about their mantle source regions, but most Martian meteorites either contain cumulate olivine or crystallized from fractionated melts. The recently discovered Martian meteorite Northwest Africa (NWA) 5789 is an olivine‐phyric shergottite. NWA 5789 has special significance among the Martian meteorites because it appears to represent one of the most magnesian Martian magmas known, other than Yamato (Y) 980459. Its most magnesian olivine cores (Fo₈₅) are in Mg‐Fe equilibrium with a magma of the bulk rock composition, suggesting that the bulk represents a magma composition. Based on the Al/Ti ratio of its pyroxenes, we infer that the rock began to crystallize at a high pressure consistent with conditions in Mars’ lower crust/upper mantle. It continued and completed its crystallization closer to the surface, where cooling was rapid and produced a mesostasis of radiating sprays of plagioclase and pyroxene. The mineralogy, petrology, mineral chemistry, and bulk rock composition of NWA 5789 are very similar to those of Y‐980459. The similarities between the two meteorites suggest that NWA 5789 (like Y‐980459) represents a primitive, mantle‐derived magma composition. They also suggest the possibility that NWA 5789 and Y‐980459 formed in the same lava flow. However, based on the mineralogy and texture of its mesostasis, NWA 5789 must have cooled more slowly than Y‐980459. NWA 5789 will help elucidate the igneous geology and geochemistry of Mars.     

High oxidation state during formation of Martian nakhlites

Abstract– The oxygen fugacities recorded in the nakhlites Nakhla, Yamato‐000593 (Y‐000593), Lafayette, and NWA998 were studied by applying the Fe,Ti‐oxide oxybarometer. Oxygen fugacities obtained cluster closely around the FMQ (Fayalite–Magnetite–Quartz) buffer (NWA998 = FMQ ? 0.8; Y‐000593 = FMQ ? 0.7; Nakhla = FMQ; Lafayette = FMQ + 0.1). The corresponding equilibration temperatures are 810 °C for Nakhla and Y‐000593, 780 °C for Lafayette and 710 °C for NWA998. All nakhlites record oxygen fugacities significantly higher and with a tighter range than those determined for Martian basalts, i.e., shergottites whose oxygen fugacities vary from FMQ ? 1 to FMQ ? 4. It has been known for some time that nakhlites are different from other Martian meteorites in chemistry, mineralogy, and crystallization age. The present study adds oxygen fugacity to this list of differences. The comparatively large variation in fO₂ recorded by shergottites was interpreted by Herd et al. (2002) as reflecting variable degrees of contamination with crustal fluids that would also carry a light rare earth element (REE)‐enriched component. The high oxygen fugacities and the large light REE enrichment of nakhlites fit qualitatively in this model. In detail, however, it is found that the inferred contaminating phase in nakhlites must have been different from those in shergottites. This is supported by unique ¹⁸²W/¹⁸⁴W and ¹⁴²Nd/¹⁴⁴Nd ratios in nakhlites, which are distinct from other Martian meteorites. It is likely that the differences in fO₂ between nakhlites and other Martian meteorites were established very early in the history of Mars. Parental trace element rich and trace element poor regions (reservoirs) of Mars mantle ( Brandon et al. 2000 ) must have been kept isolated throughout Martian history. Our results further show significant differences in closure temperature among the different nakhlites. The observed range in equilibration temperatures together with similar fO₂ values is attributable to crystallization of nakhlites in the same cumulate pile or lava layer at different burial depths from 0.5 to 30 m below the Martian surface in agreement with Mikouchi et al. (2003) and is further confirmed by similar crystallization ages of about 1.3 Ga ago (e.g., Misawa et al. 2003 ).     

Isotopic composition of trapped and cosmogenic noble gases in several Martian meteorites

Abstract— Isotopic abundances of the noble gases were measured in the following Martian meteorites: two shock glass inclusions from Elephant Moraine (EET) 79001, shock vein glass from Shergotty and Yamato (Y) 793605, and whole-rock samples of Allan Hills (ALH) 84001 and Queen Alexandra Range (QUE) 94201. These glass samples, when combined with literature data on a separate single glass inclusion from EET 79001 and a glass vein from Zagami, permit examination in greater detail of the isotopic composition of Ne, Ar, Kr, and Xe trapped from the Martian atmosphere. The isotopic composition of Martian Ne, if actually present in these glasses, remains poorly defined. The ⁴⁰Ar/³⁶Ar ratio of trapped Martian atmospheric Ar is probably considerably lower than the nominal ratio of 3000 measured by Viking, and data on impact glasses suggest a value of ～1900. The atmospheric ³⁶Ar/³⁸Ar ratio is ≤4.0. Martian atmospheric Kr may be enriched in lighter isotopes by ～0.5%/amu compared to both solar-wind Kr and to the Martian composition previously reported. The isotopic composition of Xe in these glasses agrees with that previously reported in the literature. The Martian atmospheric ³⁶Ar/¹³²Xe and ⁸⁴Kr/¹³²Xe elemental ratios are higher than those reported by Viking by factors of ～2.5–1.6 (depending on the ⁴⁰Ar/³⁶Ar ratio adopted) and ～1.8, respectively, and are discussed in a separate paper. Cosmogenic gases indicate space exposure ages of 2.7 ± 0.6 Ma for QUE 94201 and Shergotty and 14 ± 1 Ma for ALH 84001. Small amounts of ²¹Ne produced by energetic solar protons may be present in QUE 94201 but are not present in ALH 84001 or Y-793605. The space exposure age for Y-793605 is 4.9 ± 0.6 Ma and appears to be distinctly older than the ages for basaltic shergottites. However, uncertainties in cosmogenic production rates still makes somewhat uncertain the number of Martian impact events required to produce the exposure ages of Martian meteorites.     

Noble gases in 18 Martian meteorites and angrite Northwest Africa 7812—Exposure ages,trapped gases,and a re‐evaluation of the evidence for solar cosmic ray‐produced neon in shergottites and other achondrites

We present noble gas data for 16 shergottites, 2 nakhlites (NWA 5790, NWA 10153), and 1 angrite (NWA 7812). Noble gas exposure ages of the shergottites fall in the 1–6 Ma range found in previous studies. Three depleted olivine‐phyric shergottites (Tissint, NWA 6162, NWA 7635) have exposure ages of ~1 Ma, in agreement with published data for similar specimens. The exposure age of NWA 10153 (~12.2 Ma) falls in the range of 9–13 Ma reported for other nakhlites. Our preferred age of ~7.3 Ma for NWA 5790 is lower than this range, and it is possible that NWA 5790 represents a distinct ejection event. A Tissint glass sample contains Xe from the Martian atmosphere. Several samples show a remarkably low (²¹Ne/²²Ne)_cos ratio < 0.80, as previously observed in a many shergottites and in various other rare achondrites. This was explained by solar cosmic ray‐produced Ne (SCR Ne) in addition to the commonly found galactic cosmic ray‐produced Ne, implying very low preatmospheric shielding and ablation loss. We revisit this by comparing measured (²¹Ne/²²Ne)_cos ratios with predictions by cosmogenic nuclide production models. Indeed, several shergottites, acalpulcoites/lodranites, angrites (including NWA 7812), and the Brachina‐like meteorite LEW 88763 likely contain SCR Ne, as previously postulated for many of them. The SCR contribution may influence the calculation of exposure ages. One likely reason that SCR nuclides are predominantly detected in meteorites from rare classes is because they usually are analyzed for cosmogenic nuclides even if they had a very small (preatmospheric) mass and hence low ablation loss.     

39Ar‐40Ar “ages” and origin of excess 40Ar in Martian shergottites

Abstract— We report new ³⁹Ar‐⁴⁰Ar measurements on 15 plagioclase, pyroxene, and/or whole rock samples of 8 Martian shergottites. All age spectra suggest ages older than the meteorite formation ages, as defined by Sm‐Nd and Rb‐Sr isochrons. Employing isochron plots, only Los Angeles plagioclase and possibly Northwest Africa (NWA) 3171 plagioclase give ages in agreement with their formation ages. Isochrons for all shergottite samples reveal the presence of trapped Martian ⁴⁰Ar (⁴⁰Ar_xs), which exists in variable amounts in different lattice locations. Some ⁴⁰Ar_xs is uniformly distributed throughout the lattice, resulting in a positive isochron intercept, and other ⁴⁰Ar_xs occurs in association with K‐bearing minerals and increases the isochron slope. These samples demonstrate situations where linear Ar isochrons give false ages that are too old. After subtracting ⁴⁰Ar*that would accumulate by ⁴⁰K decay since meteorite formation and small amounts of terrestrial ⁴⁰Ar, all young age samples give similar ⁴⁰Ar_xs concentrations of ?1–2 × 10^?6cm³/g, but a variation in K content by a factor of ?80. Previously reported NASA Johnson Space Center data for Zagami, Shergotty, Yamato (Y‐) 000097, Y‐793605, and Queen Alexandra Range (QUE) 94201 shergottites show similar concentrations of ⁴⁰Ar_xs to the new meteorite data reported here. Similar ⁴⁰Ar_xs in different minerals and meteorites cannot be explained as arising from Martian atmosphere carried in strongly shocked phases such as melt veins. We invoke the explanation given by Bogard and Park (2008) for Zagami, that this ⁴⁰Ar_xs in shergottites was acquired from the magma. Similarity in ⁴⁰Ar_xs among shergottites may reveal common magma sources and/or similar magma generation and emplacement processes.