Petrology and chemistry of MIL 03346 and its significance in understanding the petrogenesis of nakhlites on Mars

Abstract— Antarctic meteorite Miller Range (MIL) 03346 is a nakhlite composed of 79% clinopyroxene, ?1% olivine, and 20% vitrophyric intercumulus material. We have performed a petrological and geochemical study of MIL 03346, demonstrating a petrogenetic history similar to previously discovered nakhlites. Quantitative textural study of MIL 03346 indicates long (>1 × 10¹ yr) residence times for the cumulus augite, whereas the skeletal Fe‐Ti oxide, fayalite, and sulfide in the vitrophyric intercumulus matrix suggest rapid cooling, probably as a lava flow. From the relatively high forsterite contents of olivine (up to Fo₄₃) compared with other nakhlites and compositions of augite cores (Wo_38–42En_35–40Fs_22–28) and their hedenbergite rims, we suggest that MIL 03346 is part of the same or a similar Martian cumulate‐rich lava flow as other nakhlites. However, MIL 03346 has experienced less equilibration and faster cooling than other nakhlites discovered to date. Calculated trace element concentrations based upon modal abundances of MIL 03346 and its constituent minerals are identical to whole rock trace element abundances. Parental melts for augite have REE patterns that are approximately parallel with whole rock and intercumulus melt using experimentally defined partition coefficients. This parallelism reflects closed‐system crystallization for MIL 03346, where the only significant petrogenetic process between formation of augite and eruption and emplacement of the nakhlite flow has been fractional crystallization. A model for the petrogenesis of MIL 03346 and the nakhlites (Nakhla, Governador Valadares, Lafayette, Yamato‐000593, Northwest Africa (NWA) 817, NWA 998) would include: 1) partial melting and ascent of melt generated from a long‐term LREE depleted mantle source, 2) crystallization of cumulus augite (± olivine, ± magnetite) in a shallow‐level Martian magma chamber, 3) eruption of the crystal‐laden nakhlite magma onto the surface of Mars, 4) cooling, crystal settling, overgrowth, and partial equilibration to different extents within the flow, 5) secondary alteration through hydrothermal processes, possibly immediately succeeding or during emplacement of the flow. This model might apply to single—or multiple—flow models for the nakhlites. Ultimately, MIL 03346 and the other nakhlites preserve a record of magmatic processes in volcanic rocks on Mars with analogous petrogenetic histories to pyroxene‐rich terrestrial lava flows and to komatiites.     

Northwest Africa 5790: A previously unsampled portion of the upper part of the nakhlite pile

We present a geochemical study of recently discovered Martian meteorite Northwest Africa (NWA) 5790 and use our results to constrain its origin and relationship with the other nakhlites. This nakhlite is a clinopyroxene cumulate composed of phenocrysts of augite, olivine, and rare oxides surrounded by a mesostasis composed of vitrophyric glass, feldspars, oxides, phosphates, and fine‐grained olivines and augite. Petrography, and major and trace element compositions of the phases present are consistent with derivation of NWA 5790 from a parental magma common to all the nakhlites. Olivine cores grew from a distinct, incompatible‐element enriched magma and are surrounded by rims containing augite inclusions that grew from the nakhlite parental liquid, supporting previous arguments for xenocrystic olivine cores in nakhlites. Rare earth element microdistributions suggest derivation of NWA 5790 augites from an evolved, relatively oxidized magma, produced by augite fractionation from the common nakhlite parental liquid. Augite grain shapes and CSD patterns are consistent with rapid cooling and derivation near the top of the nakhlite cumulate pile, but patterns are distinct from other nakhlites thought to have formed near the stratigraphic top. The high mesostasis abundance (~44 vol%) indicates solidification near the top of the nakhlite pile close to locations suggested for nakhlites NWA 817 and Miller Range (MIL) 03346. However, the geochemical and petrographic characteristics of these three samples do not permit their placement in a simple stratigraphic order as would occur in a single lava flow. This lack of simple ordering suggests that the nakhlite lava flow split into multiple sections as would occur during breakouts from a single lava flow. Finally we note that NWA 5790 is unique among currently available nakhlites in having phenocryst abundances low enough to allow it to flow.     

Caleta el Cobre 022 Martian meteorite: Increasing nakhlite diversity

Caleta el Cobre (CeC) 022 is a Martian meteorite of the nakhlite group, showing an unbrecciated cumulate texture, composed mainly of clinopyroxene and olivine. Augite shows irregular core zoning, euhedral rims, and thin overgrowths enriched in Fe relative to the core. Low‐Ca pyroxene is found adjacent to olivine. Phenocrysts of Fe‐Ti oxides are titanomagnetite with exsolutions of ilmenite/ulvöspinel. Intercumulus material consists of both coarse plagioclase and fine‐grained mesostasis, comprising K‐feldspars, pyroxene, apatite, ilmenite, Fe‐Ti oxides, and silica. CeC 022 shows a high proportion of Martian aqueous alteration products (iddingsite) in olivine (45.1 vol% of olivine) and mesostasis. This meteorite is the youngest nakhlite with a distinct Sm/Nd crystallization age of 1.215 ± 0.067 Ga. Its ejection age of 11.8 ± 1.8 Ma is similar to other nakhlites. CeC 022 reveals contrasted cooling rates with similarities with faster cooled nakhlites, such as Northwest Africa (NWA) 817, NWA 5790, or Miller Range 03346 nakhlites: augite irregular cores, Fe‐rich overgrowths, fine‐grained K‐feldspars, quenched oxides, and high rare earth element content. CeC 022 also shares similarities with slower cooled nakhlites, including Nakhla and NWA 10153: pyroxene modal abundance, pyroxenes crystal size distribution, average pyroxene size, phenocryst mineral compositions, unzoned olivine, and abundant coarse plagioclase. Moreover, CeC 022 is the most magnetic nakhlite and represents an analog source lithology for the strong magnetization of the Martian crust. With its particular features, CeC 022 must originate from a previously unsampled sill or flow in the same volcanic system as the other nakhlites, increasing Martian sample diversity and our knowledge of nakhlites.     

Comparisons of the four Miller Range nakhlites,MIL 03346, 090030, 090032 and 090136: Textural and compositional observations of primary and secondary mineral assemblages

Abstract– Petrological and geochemical analyses of Miller Range (MIL) 03346 indicate that this meteorite originated from the same augitic cumulate layer(s) as the nakhlite Martian meteorites, but underwent rapid cooling prior to complete crystallization. As with the other nakhlites, MIL 03346 contains a secondary alteration assemblage, in this case consisting of iddingsite‐like alteration veins in olivine phenocrysts, Fe‐oxide alteration veins associated with the mesostasis, and Ca‐ and K,Fe‐sulfate veins. We compared the textural and mineralogical compositions of MIL 090030, 090032, and 090136 with MIL 03346, focusing on the composition and Raman spectra of the alteration assemblages. These observations indicate that the meteorites are paired, and that the preterrestrial olivine‐bound alteration assemblages were produced by weakly acidic brine. Although these alteration assemblages resemble similar assemblages in Nakhla, the absence of siderite and halite in the Miller Range nakhlites indicates that the parental alteration brine was comparatively HCO₃^? depleted, and less concentrated, than that which altered Nakhla. This indicates that the Miller Range nakhlite alteration brine experienced a separate evolutionary pathway to that which altered Nakhla, and therefore represents a separate branch of the Lafayette‐Nakhla evaporation sequence. Thin‐sections cut from the internal portions of these meteorites (away from any fusion crust or terrestrially exposed edge), contain little Ca‐sulfate (identified as gypsum), and no jarosite, whereas thin‐sections with terrestrially exposed edges have much higher sulfate abundances. These observations suggest that at least the majority of sulfate within the Miller Range nakhlites is terrestrially derived.     

Igneous and shock processes affecting chassignite amphibole evaluated using chlorine/water partitioning and hydrogen isotopes

Amphibole in chassignite melt inclusions provides valuable information about the volatile content of the original interstitial magma, but also shock and postshock processes. We have analyzed amphibole and other phases from NWA 2737 melt inclusions, and we evaluate these data along with published values to constrain the crystallization Cl and H₂O content of phases in chassignite melt inclusions and the effects of shock on these amphibole grains. Using a model for the Cl/OH exchange between amphibole and melt, we estimate primary crystallization OH contents of chassignite amphiboles. SIMS analysis shows that amphibole from NWA 2737 currently has 0.15 wt% H₂O. It has lost ~0.6 wt% H₂O from an initial 0.7–0.8 wt% H₂O due to intense shock. Chassigny amphibole had on average 0.3–0.4 wt% H₂O and suffered little net loss of H₂O due to shock. NWA 2737 amphibole has δD ≈ +3700‰; it absorbed Martian atmosphere‐derived heavy H in the aftermath of shock. Chassigny amphibole, with δD ≤ +1900‰, incorporated less heavy H. Low H₂O/Cl ratios are inferred for the primitive chassignite magma, which had significant effects on melting and crystallization. Volatiles released by the degassing of Martian magma were more Cl‐rich than on Earth, resulting in the high Cl content of Martian surface materials.     

Modal abundances of pyroxene,olivine, and mesostasis in nakhlites: Heterogeneity,variation, and implications for nakhlite emplacement

Nakhlites, clinopyroxenite meteorites from Mars, share common crystallization and ejection ages, suggesting that they might have been ejected from the same place on Mars by the same ejection event (impact) and are different samples of the same thick volcanic flow unit or shallow sill. Mean modal abundances and abundance ranges of pyroxene, olivine, and mesostasis vary widely among different thin‐sections of an individual nakhlite. Lithologic heterogeneity is the main factor contributing to the observed modal‐abundance variations measured in thin‐sections prepared from different fragments of the same stone. Two groups of nakhlites are distinguished from one another by which major constituent varies the least and the abundance of that constituent. The group consisting of Nakhla, Lafayette, Governador Valadares, and the Yamato nakhlite pairing group is characterized by low modal mesostasis and pyroxene‐olivine covariance, whereas the group consisting of the Miller Range nakhlite pairing group and Northwest Africa 5790 is characterized by low modal olivine and pyroxene‐mesostasis covariance. These two groups sample the slowest‐cooled interior portion and the chilled margin, respectively, of the nakhlite emplacement body as presently understood, and appear to be also related to recently proposed nakhlite groups independently established using compositional rather than petrographic observations. Phenocryst modal abundances vary with inferred depth in the nakhlite igneous body in a manner consistent with solidification of the nakhlite stack from dynamically sorted phenocryst‐rich magmatic crystal‐liquid mush.     

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.     

Density,porosity, and magnetic susceptibility of achondritic meteorites

As part of a large‐scale survey of meteorite bulk and grain densities, porosities, and magnetic susceptibilities, we measured these properties for 174 stones from 106 achondritic meteorites. These include four lunar meteorites, 15 stones from 10 shergottites, nakhlites, and chassignites (SNCs), 96 stones from 56 howardites, eucrites, and diogenites (HEDs), 17 stones from nine aubrites, two angrites, and 16 stones from 10 ureilites, four stones of three acapulcoites, as well as four stones of three lodranites, and 15 stones from eight primitive achondrites. Those meteorites derived from basalts and crustal material of differentiated parent bodies have lower densities and magnetic susceptibilities, on an average, than the more primitive achondrites, which have a higher percentage metal. A notable exception is the one chassignite in the study (Chassigny), which has a high grain density of 3.73 ± 0.04 g cm^?3. Ureilites have magnetic susceptibilities consistent with primitive achondrites, but lower grain densities. Porosities do not vary considerably between most of the groups, with most stones 5–14% porous, although on an average, ureilites and brachinites have lower porosities, with most stones less than 7% porous. For primitive achondrites, the higher metal content causes finds to exhibit weathering effects similar to what is observed in ordinary chondrites, with a reduction in grain density, magnetic susceptibility, and porosity as compared with unweathered falls. For lunites, SNCs, and HEDs, no such effect is observed. We also observe that grain density and magnetic susceptibility used in conjunction distinguish shergottites, nakhlites, and chassignites from each other. Shergottites and nakhlites have low grain densities (averaging 3.31 and 3.41 g cm^?3, respectively) whereas Chassigny is 3.7 g cm^?3. In magnetic susceptibility, shergottities and chassignites are similar (averaging 2.85 and 2.98 in log units of 10^?9 m³ kg^?1, respectively) with nakhlites averaging higher at 3.42.     

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.     

Petrology of the Miller Range 03346 nakhlite in comparison with the Yamato‐000593 nakhlite

Abstract— We petrologically examined the Miller Range (MIL) 03346 nakhlite. The main‐phase modal abundances are 67.7 vol% augite, 0.8 vol% olivine, and 31.5 vol% mesostasis. Among all known nakhlites, MIL 03346's modal abundance of olivine is the smallest and of mesostasis is the largest. Augite occurs as cumulus phenocrysts having a homogeneous core composition (En_36–38Fs_24–22Wo₄₀), which is identical with other nakhlites. They accompany thin ferroan rims divided into inner and outer rims with a compositional gap at the boundary between the two rims. Olivine grains have magnesian cores (Fa ≥ 55) and show normal zoning toward ferroan rims (Fa ≤ 84). Mesostasis consists mostly of glass (26.0 vol%) with minor skeletal fayalites, skeletal titanomagnetites, acicular phosphate, massive cristobalite, and sulfides. We conclude that MIL 03346 is the most rapidly cooled nakhlite among all known nakhlites based on the petrography. We obtain the intercumulus melt composition for MIL 03346 from the mass balance calculation using the modal abundances and discuss the crystallization sequence of MIL 03346 in comparison with that of Yamato (Y‐) 000593. Although magnesian olivines of Y‐000593 are phenocrystic, magnesian olivine grains of MIL 03346 seem to have texturally crystallized from the intercumulus melt. After the MIL 03346 magma intruded upward to the Martian surficial zone, the magnesian olivine crystallized, and then the ferroan inner rim formed on phenocrystic core augite. The outer rim of phenocrystic augites formed after the crystallization of skeletal fayalites and skeletal titanomagnetites, resulting in a compositional gap between the inner and outer rims. Finally, glassy mesostasis formed from the residual melt. This crystallization sequence of MIL 03346 is different from those of other nakhlites, including Y‐000593.     

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.     

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.     

Paired nakhlites MIL 090030, 090032, 090136, and 03346: Insights into the Miller Range parent meteorite

Abstract– Miller Range (MIL) 03346 is the most oxidized and least equilibrated nakhlite known and displays the highest amount of intercumulus phase. The discovery of three new nakhlites, MIL 090030, MIL 090032, and MIL 090136, in the Miller Range, Antarctica, geographically close to the location of MIL 03346, suggests that they may come from the same parent meteorite. In this study, we investigate the mineralogy and texture of cumulus and intercumulus phases, in situ major and trace element compositions for the cumulus phases, as well as pyroxene crystal size distribution patterns and spatial distribution patterns of MIL 090030, 090032, and 090136. Using these combined results, we conclude that the three nakhlites studied here are paired with MIL 03346. However, modal mineral abundances of MIL 090030, 090032, 090136, and 03346 exhibit variations indicating that a single sample of a Miller Range nakhlite is not modally representative of the parent meteorite and that analyses of multiple samples for a single nakhlite may be necessary to obtain representative modal data for placement in the cumulate pile. Our calculated parental melt composition based on all the paired samples confirms a previous study suggesting that the nakhlite parent melt crystallized as a closed system.     

Melt inclusions in augite from the nakhlite meteorites: A reassessment of nakhlite parental melt and implications for petrogenesis

Abstract– The nakhlites, a subgroup of eight clinopyroxenites thought to come from a single geological unit at the Martian surface, show melt inclusions in augite and olivine. In contrast to olivine‐hosted melt inclusions, augite‐hosted melt inclusions are not surrounded by fractures, and are thus considered preferential candidates for reconstructing parent liquid compositions. Furthermore, two types of augite‐hosted melt inclusion have been defined and characterized in four different nakhlites (Northwest Africa [NWA] 817, Nakhla, Governador Valadares, and NWA 998): Type‐I isolated inclusions in augite cores that contain euhedral to subhedral augite, Ti‐magnetite, and pigeonite plus silica‐rich glass and a gas bubble; Type‐II microinclusions that form trails crosscutting host augite crystals. Fast‐heating experiments were performed on selected pristine primary augite‐hosted melt inclusions from these four samples. Of these, only data from Nakhla were considered robust for reconstruction of a nakhlite parental magma composition (NPM). Based upon careful petrographic selection and consideration of iron‐magnesium ratios, our data are used to propose an NPM, which is basaltic (49.1 wt% SiO₂), of high Ca/Al (1.95), and K₂O‐poor (0.32 wt%). Thermodynamic modeling at an oxygen fugacity one log unit below the QFM buffer using the MELTS and PETROLOG programs implies that Mg‐rich olivine was not a liquidus phase for this composition. Our analysis is used to suggest that olivine megacrysts found in the nakhlites are unlikely to have coprecipitated with augite, and thus may have been introduced during or subsequent to accumulation in the magma chamber, possibly from more evolved portions of the same chamber.     

Alteration assemblages in the Miller Range and Elephant Moraine regions of Antarctica: Comparisons between terrestrial igneous rocks and Martian meteorites

The weathering products present in igneous terrestrial Antarctic samples were analyzed, and compared with those found in the four Miller Range nakhlite Martian meteorites. The aim of these comparisons was to determine which of the alteration phases in the Miller Range nakhlites are produced by terrestrial weathering, and what effect rock composition has on these phases. Antarctic terrestrial samples MIL 05031 and EET 96400, along with the Miller Range nakhlites MIL 03346 and 090032, were found to contain secondary alteration assemblages at their externally exposed surfaces. Despite the difference in primary mineralogy, the assemblages of these rocks consist mostly of sulfates (jarosite in MIL 05031, jarosite and gypsum in EET 96400) and iddingsite‐like Fe‐clay. As neither of the terrestrial samples contains sulfur‐bearing primary minerals, and these minerals are rare in the Miller Range nakhlites, it appears that SO₄^2?, possibly along with some of the Na⁺, K⁺, and Ca⁺ in these phases, was sourced from wind‐blown sea spray and biogenic emissions from the southern ocean. Cl enrichment in the terrestrially derived “iddingsite” of MIL 05031 and MIL 03346, and the presence of halite at the exterior edge of MIL 090032, can also be explained by this process. However, jarosite within and around the olivine‐bound melt inclusions of MIL 090136 is present in the interior of the meteorite and, therefore, is probably the product of preterrestrial weathering on Mars.     

Alkalic parental magmas for chassignites?

Abstract Detailed analysis of cumulate and melt inclusion assemblages in the chassignites provide important constraints on the nature of the melt trapped as inclusions in cumulus olivine (and, by extension, parental magma compositions), the pressures of crystallization, and magmatic volatile contents. These mineral assemblages show strong similarities to the experimental fractionation assemblages that produce the sodic silica‐saturated alkalic lavas on Earth (e.g., Ascension Island, Azores, the Nandewar volcano of Australia). The experimental assemblages were produced from silica‐saturated hawaiite at pressures above 4.3 kbar with dissolved water contents above 0.5 wt%. Such pressures are consistent with Ti:Al ratios of the melt‐inclusion pyroxenes in the Chassigny meteorite. Pyroxene compositions suggest early high crystallization temperatures and thus relatively low initial water and F contents. Feldspars indicate that melt evolution proceeded to rhyolite compositions both within the interstices of the cumulate olivine and within the melt inclusions, even though rhyolitic glass is only found within olivine‐hosted polyphase melt inclusions. The observed rhyolite glass is compositionally similar to the alkali‐rich rhyolite of Ascension Island which is produced experimentally by crystallization of hawaiite. It is proposed that the melt trapped in cumulus olivine of the Chassigny dunite was similar to a terrestrial silica‐saturated hawaiite, while that trapped in olivine of the Northwest Africa (NWA) 2727 dunite was less evolved, perhaps mildly alkalic basalt. Melts similar to terrestrial intra‐plate tholeiite could be parental to the cumulus minerals and evolve upon crystallization at pressures above 4.3 kbar and water contents above ?0.4 wt% to mildly alkalic basalt, silica‐saturated hawaiite, and alkali‐rich rhyolite. The melt inclusion assemblages are inconsistent with either crystallization of a low‐Al, high‐Fe basalt, or low‐pressure crystallization of a terrestrial‐like tholeiite.     

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.     

The variability of ruthenium in chromite from chassignite and olivine‐phyric shergottite meteorites: New insights into the behavior of PGE and sulfur in Martian magmatic systems

The Martian meteorites comprise mantle‐derived mafic to ultramafic rocks that formed in shallow intrusions and/or lava flows. This study reports the first in situ platinum‐group element data on chromite and ulvöspinel from a series of dunitic chassignites and olivine‐phyric shergottites, determined using laser‐ablation ICP‐MS. As recent studies have shown that Ru has strongly contrasting affinities for coexisting sulfide and spinel phases, the precise in situ analysis of this element in spinel can provide important insights into the sulfide saturation history of Martian mantle‐derived melts. The new data reveal distinctive differences between the two meteorite groups. Chromite from the chassignites Northwest Africa 2737 (NWA 2737) and Chassigny contained detectable concentrations of Ru (up to ~160 ppb Ru) in solid solution, whereas chromite and ulvöspinel from the olivine‐phyric shergottites Yamato‐980459 (Y‐980459), Tissint, and Dhofar 019 displayed Ru concentrations consistently below detection limit (<42 ppb). The relatively elevated Ru signatures of chromite from the chassignites suggest a Ru‐rich (~1–4 ppb) parental melt for this meteorite group, which presumably did not experience segregation of immiscible sulfide liquids over the interval of mantle melting, melt ascent, and chromite crystallization. The relatively Ru‐depleted signature of chromite and ulvöspinel from the olivine‐phyric shergottites may be the consequence of relatively lower Ru contents (<1 ppb) in the parental melts, and/or the presence of sulfides during the crystallization of the spinel phases. The results of this study illustrate the significance of platinum‐group element in situ analysis on spinel phases to decipher the sulfide saturation history of magmatic systems.     

Crystallization experiments of intercumulus melts for nakhlites under QFM ± 2 at 1 bar

Abstract— Crystallization of parent melts for nakhlites was experimentally studied under QFM ± 2 at one bar. Isothermal experiments suggest that melts having parent magma composition for nakhlites crystallize both augites and titanomagnetites at liquidus temperatures of 1144–1154 °C. Compositions of the augites are identical to those of phenocrystic core augites (En_36–38Fs_22–25Wo_39–40) in nakhlites. No olivines crystallize from the isothermal runs, and solidus temperature is about 1000 °C. Linear‐cooling experiments were carried out at various cooling rates (1–17 °C/h) ranging from liquidus to solidus temperatures under similar pressure conditions to the isothermal runs. Augites, titanomagnetites, and fayalites crystallized in the cooling runs, but magnesian olivines never crystallized there. Magnesian core augite in the cooling runs has the same composition as those of nakhlites. Rims of augite crystals from the cooling runs of 1–4 °C/h consist of two layers, ferroan augite inner rim and hedenbergite outer rim, which are very similar to those in the Miller Range (MIL) 03346 nakhlite. Small amounts of pyroxferroite crystallized in mesostasis and augite rims from two cooling runs. Titanomagnetites from cooling runs never accompany ilmenite lamellae as seen in nakhlites, suggesting that the subsolidus cooling rate of the cooling runs was much more rapid than those of nakhlite intercumulus melts. The cooling experiments reproduce the crystallization processes of pyroxenes and the compositional change of residual melt for a rapidly cooled magma such as MIL 03346.     

K2O‐rich trapped melt in olivine in the Nakhla meteorite: Implications for petrogenesis of nakhlites and evolution of the Martian mantle

We used new analytical and theoretical methods to determine the major and minor element compositions of the primary trapped liquid (PTLs) represented by melt inclusions in olivine and augite in the Martian clinopyroxenite, Nakhla, for comparison with previously proposed compositions for the Nakhla (or nakhlite) parent magma. We particularly focused on obtaining accurate K₂O contents, and on testing whether high K₂O contents and K₂O/Na₂O ratios obtained in previous studies of melt inclusions in olivine in Nakhla could have been due to unrepresentative sampling, systematic errors arising from electron microprobe techniques, late alteration of the inclusions, and/or boundary layer effects. Based on analyses of 35 melt inclusions in olivine cores, the PTL in olivine, PTL_oliv, contained (by wt) approximately 47% SiO₂, 6.3% Al₂O₃, 9.6% CaO, 1.8% K₂O, and 0.9% Na₂O, with K₂O/Na₂O = 2.0. We infer that the high K₂O content of PTL_oliv is not due to boundary layer effects and represents a real property of the melt from which the host olivine crystallized. This melt was cosaturated with olivine and augite. Its mg# is model‐dependent and is constrained only to be ≥19 (equilibrium Fo = 40). Based on analyses of 91 melt inclusions in augite cores, the PTL in augite, PTL_aug, contained (by wt) 53–54% SiO₂, 7–8% Al₂O₃, 0.8–1.1% K₂O, and 1.1–1.4% Na₂O, with K₂O/Na₂O = 0.7–0.8. This K₂O content and K₂O/Na₂O ratio are significantly higher than inferred in studies of melt inclusions in augite in Nakhla by experimental rehomogenization. PTL_aug was saturated only with augite, and in equilibrium with augite cores of mg# 62. PTL_aug represents the Nakhla parent magma, and does not evolve to PTL_oliv by fractional crystallization. We therefore conclude that olivine cores in Nakhla (and, by extension, other nakhlites) are xenocrystic. We propose that PTL_oliv and PTL_aug were generated from the same source region. PTL_oliv was generated first and emplaced to form olivine‐rich cumulate rocks. Shortly thereafter, PTL_aug was generated and ascended through these olivine‐rich cumulates, incorporating fragments of wallrock that became the xenocrystic olivine cores in Nakhla. The Nakhla (nakhlite) mantle source region was pyroxenitic with some olivine, and could have become enriched in K relative to Na via metasomatism. A high degree of melting of this source produced the silica‐poor, alkali‐rich magma PTL_oliv. Further ascension and decompression of the source led to generation of the silica‐rich, relatively alkali‐poor magma PTL_aug. Potassium‐rich magmas like those involved in the formation of the nakhlites represent an important part of the diversity of Martian igneous rocks.