Expanding the application of the Eu‐oxybarometer to the lherzolitic shergottites and nakhlites: Implications for the oxidation state heterogeneity of the Martian interior

Abstract— Experimentally rehomogenized melt inclusions from the nakhlite Miller Range 03346 (MIL 03346) and the lherzolitic shergottite Allan Hills 77005 (ALH 77005) have been analyzed for their rare earth element (REE) concentrations in order to characterize the early melt compositions of these Martian meteorites and to calculate the oxygen fugacity conditions they crystallized under. D(Eu/Sm)_{pyroxene/melt} values were measured at 0.77 and 1.05 for ALH 77005 and MIL 03346, respectively. These melts and their associated whole rock compositions have similar REE patterns, suggesting that whole rock REE values are representative of those of the early melts and can be used as input into the pyroxene Eu‐oxybarometer for the nakhlites and lherzolitic shergottites. Crystallization fO₂ values of IW + 1.1 (ALH 77005) and IW + 3.2 (MIL 03346) were calculated. Whole rock data from other nakhlites and lherzolitic shergottites was input into the Eu‐oxybarometer to determine their crystallization fO₂ values. The lherzolitic shergottites and nakhlites have fO₂ values that range from IW + 0.4 to 1.6 and from IW + 1.1 to 3.2, respectively. These values are consistent with some previously determined fO₂ estimates and expand the known range of fO₂ values of the Martian interior to four orders of magnitude. The origins of this range are not well constrained. Possible mechanisms for producing this spread in fO₂ values include mineral/melt fractionation, assimilation, shock effects, and magma ocean crystallization processes. Mineral/melt partitioning can result in changes in fO₂ from the start to the finish of crystallization of 2 orders of magnitude. In addition, crystallization of a Martian magma ocean with reasonable initial water content results in oxidized, water‐rich, late‐stage cumulates. Sampling of these oxidized cumulates or interactions between reduced melts and the oxidized material can potentially account for the range of fO₂ values observed in the Martian meteorites.     

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 ).     

Two‐stage polybaric formation of the new enriched,pyroxene‐oikocrystic,lherzolitic shergottite,NWA 7397

Northwest Africa (NWA) 7397 is a newly discovered, enriched, lherzolitic shergottite, the third described example of this group. This meteorite consists of two distinct textural lithologies (1) poikilitic—comprised of zoned pyroxene oikocrysts, with chadacrysts of chromite and olivine, and (2) nonpoikilitic—comprised of olivine, low‐Ca and high‐Ca pyroxene, maskelynite, and minor abundances of merrillite, spinel, ilmenite, and pyrrhotite. The constant Ti/Al ratios of pyroxene oikocrysts suggests initial crystallization of the poikilitic lithology at depth (equivalent to pressures of approximately 10 kbar), followed by crystallization of the nonpoikilitic lithology at shallower levels. Oxygen fugacity conditions become more oxidizing during crystallization ranging from fO₂ conditions of approximately QFM‐2 to QFM‐0.7. Magma calculated to be in equilibrium with the major rock‐forming minerals is LREE‐enriched relative to depleted or intermediate shergottites and has flat overall profiles. Therefore, we suggest that the parental magma for NWA 7397 had sampled an enriched, oxidized, Martian geochemical source, similar to that of other enriched basaltic and olivine‐phyric shergottites. We present a polybaric formation model for the lherzolitic shergottite NWA 7397, to account for the petrologic constraints. Three successive stages in the development of NWA 7397 are discussed (1) formation of a REE‐enriched parental magma from a distinct Martian mantle reservoir; (2) magma ponding and development of a staging chamber concomitant with initial crystallization of the poikilitic lithology; and (3) magma ascent to the near surface, with entrainment of cumulates from the staging chamber and subsequent crystallization of the nonpoikilitic lithology en route to the surface.     

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.     

Constraints on the structure of the martian interior determined from the chemical and isotopic systematics of SNC meteorites

Abstract— The crystallization ages of martian (SNC) meteorites give evidence that martian volcanism has continued until recent times‐perhaps until the present. These meteorites also indicate that the mantle source regions of this volcanism are modestly to extremely depleted by terrestrial standards. These 2 observations produce a conundrum. How is it that such depleted source regions have produced basaltic magma for such a long time? This contribution attempts to quantify the radiogenic heat production in 2 distinct martian mantle source regions: those of the shergottites and nakhlites. Compared to the depleted upper mantle of the Earth (MORB), the nakhlite source region is depleted by about a factor of 2, and the shergottite source region is depleted by a factor of 6. According to current geophysical models, the nakhlite source contains the minimum amount of radioactive heat production to sustain whole‐mantle convection and basalt generation over geologic time. A corollary of this conclusion is that the shergottite source contains much too little radioactivity to produce recent (<200 Ma) basalts. A model martian interior with a deep nakhlite mantle that is insulated by a shallow shergottite mantle may allow basalt production from both source regions if the divide between the nakhlite‐shergottite mantles acts as a thermal boundary layer. Similarities between lunar and martian isotopic reservoirs indicate that the Moon and Mars may have experienced similar styles of differentiation.     

Detailed mineralogy and petrology of highly shocked poikilitic shergottite Northwest Africa 6342

Northwest Africa (NWA) 6342 is an intermediate, poikilitic shergottite, found in Algeria in 2010. It is comprised of two distinct petrographic areas; poikilitic domains with rounded Mg‐rich olivine chadacrysts enclosed by large low‐Ca pyroxene oikocrysts, and a nonpoikilitic domain mainly comprised of subhedral olivine and vesicular recrystallized plagioclase. Oxygen fugacity conditions become more oxidizing during crystallization from the poikilitic to the nonpoikilitic domain (QFM?3.0 to QFM?2.2). As such, it is likely that NWA 6342 experienced a two‐stage (polybaric) crystallization history similar to that of the enriched poikilitic shergottites. NWA 6342 also experienced relatively high levels of shock metamorphism in comparison to most other poikilitic shergottites as evidenced by the fine‐grained recrystallization texture in olivine, as well as melting and subsequent crystallization of plagioclase. The recrystallization of plagioclase requires an extended period of postshock thermal metamorphism for NWA 6342 and similarly shocked intermediate poikilitic shergottites NWA 4797 and Grove Mountains 99027 most likely due to launch from Mars. The similarities in petrology, chemistry, and shock features between these three meteorites indicate that they have similar crystallization and shock histories; possibly originating from the same source area on Mars.     

Melting in the martian mantle: Shergottite formation and implications for present‐day mantle convection on Mars

Abstract— Radiometric age dating of the shergottite meteorites and cratering studies of lava flows in Tharsis and Elysium both demonstrate that volcanic activity has occurred on Mars in the geologically recent past. This implies that adiabatic decompression melting and upwelling convective flow in the mantle remains important on Mars at present. I present a series of numerical simulations of mantle convection and magma generation on Mars. These models test the effects of the total radioactive heating budget and of the partitioning of radioactivity between crust and mantle on the production of magma. In these models, melting is restricted to the heads of hot mantle plumes that rise from the core‐mantle boundary, consistent with the spatially localized distribution of recent volcanism on Mars. For magma production to occur on present‐day Mars, the minimum average radioactive heating rate in the martian mantle is 1.6 times 10^?12 W/kg, which corresponds to 39% of the Wanke and Dreibus (1994) radioactivity abundance. If the mantle heating rate is lower than this, the mean mantle temperature is low, and the mantle plumes experience large amounts of cooling as they rise from the base of the mantle to the surface and are, thus, unable to melt. Models with mantle radioactive heating rates of 1.8 to 2.1 times 10 ^?12 W/kg can satisfy both the present‐day volcanic resurfacing rate on Mars and the typical melt fraction observed in the shergottites. This corresponds to 43–50% of the Wanke and Dreibus radioactivity remaining in the mantle, which is geochemically reasonable for a 50 km thick crust formed by about 10% partial melting. Plausible changes to either the assumed solidus temperature or to the assumed core‐mantle boundary temperature would require a larger amount of mantle radioactivity to permit present‐day magmatism. These heating rates are slightly higher than inferred for the nakhlite source region and significantly higher than inferred from depleted shergottites such as QUE 94201. The geophysical estimate of mantle radioactivity inferred here is a global average value, while values inferred from the martian meteorites are for particular points in the martian mantle. Evidently, the martian mantle has several isotopically distinct compositions, possibly including a radioactively enriched source that has not yet been sampled by the martian meteorites. The minimum mantle heating rate corresponds to a minimum thermal Rayleigh number of 2 times 10⁶, implying that mantle convection remains moderately vigorous on present‐day Mars. The basic convective pattern on Mars appears to have been stable for most of martian history, which has prevented the mantle flow from destroying the isotopic heterogeneity.     

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.     

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.     

Siderophile and chalcophile element abundances in shergottites: Implications for Martian core formation

Elemental abundances for volatile siderophile and chalcophile elements for Mars inform us about processes of accretion and core formation. Such data are few for Martian meteorites, and are often lacking in the growing number of desert finds. In this study, we employed laser ablation inductively coupled plasma–mass spectrometry (LA‐ICP‐MS) to analyze polished slabs of 15 Martian meteorites for the abundances of about 70 elements. This technique has high sensitivity, excellent precision, and is generally accurate as determined by comparisons of elements for which literature abundances are known. However, in some meteorites, the analyzed surface is not representative of the bulk composition due to the over‐ or underrepresentation of a key host mineral, e.g., phosphate for rare earth elements (REE). For other meteorites, the range of variation in bulk rastered analyses of REE is within the range of variation reported among bulk REE analyses in the literature. An unexpected benefit has been the determination of the abundances of Ir and Os with a precision and accuracy comparable to the isotope dilution technique. Overall, the speed and small sample consumption afforded by this technique makes it an important tool widely applicable to small or rare meteorites for which a polished sample was prepared. The new volatile siderophile and chalcophile element abundances have been employed to determine Ge and Sb abundances, and revise Zn, As, and Bi abundances for the Martian mantle. The new estimates of Martian mantle composition support core formation at intermediate pressures (14 ± 3 GPa) in a magma ocean on Mars.     

Petrology and shock history of the first depleted-like poikilitic shergottite Asuka 12325

Asuka (A) 12325 is the first poikilitic shergottite having a depleted pattern in light rare earth elements (REE). Compared with known poikilitic shergottites, A 12325 has smaller but more abundant pyroxene oikocrysts with remarkable Fe-rich pigeonite rims, indicating that A 12325 cooled relatively faster at a shallower part of the crust. The redox condition (logfO₂ = IW + 0.6-IW + 1.7) and Fe-rich chemical compositions of each mineral in A 12325 are close to enriched shergottites. The intermediate shergottites could not form by a simple mixing between parent magmas of A 12325 and enriched shergottites. Although A 12325 contains various high-pressure minerals such as majorite and ringwoodite, plagioclase is only partly maskelynitized. Therefore, the maximum shock pressure may be within 17–22 GPa. Thermal conduction and ringwoodite growth calculation around a shock vein revealed that the shock dwell time of A 12325 is at least 40 ms. The weaker shock pressure and longer shock dwell time in A 12325 may be attained by an impact event similar to those of nakhlites and Northwest Africa (NWA) 8159. Such a weak shock ejection event may be as common on Mars as a severe shock event recorded in shergottites. Alteration of sulfide observed in A 12325 may imply the presence of magmatic fluid in its reservoir on Mars. A 12325 expands a chemical variety of Martian rocks and has a unique shock history among poikilitic shergottites while A 12325 also implies that poikilitic shergottites are common rocks on Mars regardless of their sources.     

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.     

Ejection of Martian meteorites

Abstract— We investigated the transfer of meteorites from Mars to Earth with a combined mineralogical and numerical approach. We used quantitative shock pressure barometry and thermodynamic calculations of post‐shock temperatures to constrain the pressure/temperature conditions for the ejection of Martian meteorites. The results show that shock pressures allowing the ejection of Martian meteorites range from 5 to 55 GPa, with corresponding post‐shock temperature elevations of 10 to about 1000 °C. With respect to shock pressures and post‐shock temperatures, an ejection of potentially viable organisms in Martian surface rocks seems possible. A calculation of the cooling time in space for the most highly shocked Martian meteorite Allan Hills (ALH) 77005 was performed and yielded a best‐fit for a post‐shock temperature of 1000 °C and a meteoroid size of 0.4 to 0.6 m. The final burial depths of the sub‐volcanic to volcanic Martian rocks as indicated by textures and mineral compositions of meteorites are in good agreement with the postulated size of the potential source region for Martian meteorites during the impact of a small projectile (200 m), as defined by numerical modeling (Artemieva and Ivanov 2004). A comparison of shock pressures and ejection and terrestrial ages indicates that, on average, highly shocked fragments reach Earth‐crossing orbits faster than weakly shocked fragments. If climatic changes on Mars have a significant influence on the atmospheric pressure, they could account for the increase of recorded ejection events of Martian meteorites in the last 5 Ma.     

Shock experiments in support of the Lithopanspermia theory: The influence of host rock composition,temperature, and shock pressure on the survival rate of endolithic and epilithic microorganisms

Abstract– Shock recovery experiments were performed with an explosive set‐up in which three types of microorganisms embedded in various types of host rocks were exposed to strong shock waves with pressure pulse lengths of lower than 0.5 μs: spores of the bacterium Bacillus subtilis, Xanthoria elegans lichens, and cells of the cyanobacterium Chroococcidiopsis sp. 029. In these experiments, three fundamental parameters were systematically varied (1) shock pressures ranging from 5 to 50 GPa, (2) preshock ambient temperature of 293, 233 and 193 K, and (3) the type of host rock, including nonporous igneous rocks (gabbro and dunite as analogs for the Martian shergottites and chassignites, respectively), porous sandstone, rock salt (halite), and a clay‐rich mineral mixture as porous analogs for dry and water‐saturated Martian regolith. The results show that the three parameters have a strong influence on the survival rates of the microorganisms. The most favorable conditions for the impact ejection from Mars for microorganisms would be (1) low porosity host rocks, (2) pressures <10–20 GPa, and (3) low ambient temperature of target rocks during impact. All tested microorganisms were capable of surviving to a certain extent impact ejection in different geological materials under distinct conditions.     

The chlorine isotopic composition of Martian meteorites 1: Chlorine isotope composition of Martian mantle and crustal reservoirs and their interactions

The Martian meteorites record a wide diversity of environments, processes, and ages. Much work has been done to decipher potential mantle sources for Martian magmas and their interactions with crustal and surface environments. Chlorine isotopes provide a unique opportunity to assess interactions between Martian mantle‐derived magmas and the crust. We have measured the Cl‐isotopic composition of 17 samples that span the range of known ages, Martian environments, and mantle reservoirs. The ³⁷Cl of the Martian mantle, as represented by the olivine‐phyric shergottites, NWA 2737 (chassignite), and Shergotty (basaltic shergottite), has a low value of approximately ?3.8‰. This value is lower than that of all other planetary bodies measured thus far. The Martian crust, as represented by regolith breccia NWA 7034, is variably enriched in the heavy isotope of Cl. This enrichment is reflective of preferential loss of ³⁵Cl to space. Most basaltic shergottites (less Shergotty), nakhlites, Chassigny, and Allan Hills 84001 lie on a continuum between the Martian mantle and crust. This intermediate range is explained by mechanical mixing through impact, fluid interaction, and assimilation‐fractional crystallization.     

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.     

Highly siderophile element (HSE) abundances in the mantle of Mars are due to core formation at high pressure and temperature

Highly siderophile elements (HSEs) can be used to understand accretion and core formation in differentiated bodies, due to their strong affinity for FeNi metal and sulfides. Coupling experimental studies of metal–silicate partitioning with analyses of HSE contents of Martian meteorites can thus offer important constraints on the early history of Mars. Here, we report new metal–silicate partitioning data for the PGEs and Au and Re across a wide range of pressure and temperature space, with three series designed to complement existing experimental data sets for HSE. The first series examines temperature effects for D(HSE) in two metallic liquid compositions—C‐bearing and C‐free. The second series examines temperature effects for D(Re) in FeO‐bearing silicate melts and FeNi‐rich alloys. The third series presents the first systematic study of high pressure and temperature effects for D(Au). We then combine our data with previously published partitioning data to derive predictive expressions for metal–silicate partitioning of the HSE, which are subsequently used to calculate HSE concentrations of the Martian mantle during continuous accretion of Mars. Our results show that at midmantle depths in an early magma ocean (equivalent to approximately 14 GPa, 2100 °C), the HSE contents of the silicate fraction are similar to those observed in the Martian meteorite suite. This is in concert with previous studies on moderately siderophile elements. We then consider model calculations that examine the role of melting, fractional crystallization, and sulfide saturation/undersaturation in establishing the range of HSE contents in Martian meteorites derived from melting of the postcore formation mantle. The core formation modeling indicates that the HSE contents can be established by metal–silicate equilibrium early in the history of Mars, thus obviating the need for a late veneer for HSE, and by extension volatile siderophile elements, or volatiles in general.     

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

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

Chemical layering in the upper mantle of Mars: Evidence from olivine‐hosted melt inclusions in Tissint

Melting of Martian mantle, formation, and evolution of primary magma from the depleted mantle were previously modeled from experimental petrology and geochemical studies of Martian meteorites. Based on in situ major and trace element study of a range of olivine‐hosted melt inclusions in various stages of crystallization of Tissint, a depleted olivine–phyric shergottite, we further constrain different stages of depletion and enrichment in the depleted mantle source of the shergottite suite. Two types of melt inclusions were petrographically recognized. Type I melt inclusions occur in the megacrystic olivine core (Fo_76‐70), while type II melt inclusions are hosted by the outer mantle of the olivine (Fo_66‐55). REE‐plot indicates type I melt inclusions, which are unique because they represent the most depleted trace element data from the parent magmas of all the depleted shergottites, are an order of magnitude depleted compared to the type II melt inclusions. The absolute REE content of type II displays parallel trend but somewhat lower value than the Tissint whole‐rock. Model calculations indicate two‐stage mantle melting events followed by enrichment through mixing with a hypothetical residual melt from solidifying magma ocean. This resulted in ~10 times enrichment of incompatible trace elements from parent magma stage to the remaining melt after 45% crystallization, simulating the whole‐rock of Tissint. We rule out any assimilation due to crustal recycling into the upper mantle, as proposed by a recent study. Rather, we propose the presence of Al, Ca, Na, P, and REE‐rich layer at the shallower upper mantle above the depleted mantle source region during the geologic evolution of Mars.     

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.