The water content and parental magma of the second chassignite NWA 2737: Clues from trapped melt inclusions in olivine

NWA 2737, the second known chassignite, mainly consists of cumulate olivine crystals of homogeneous composition (Fo = 78.7 ± 0.9). These brown colored olivine grains exhibit two sets of perpendicular planar defects due to shock. Two forms of trapped liquids, interstitial melts and magmatic inclusions, have been examined. Mineral assemblages within the olivine‐hosted magmatic inclusions include low‐Ca pyroxene, augite, kaersutite, fluorapatite, biotite, chromite, sulfide, and feldspathic glass. The reconstructed parental magma composition (A^#) of the NWA 2737 is basaltic and resembles both the experimentally constrained parental melt composition of chassiginites and the Gusev basalt Humphrey, albeit with lower Al contents. A^# also broadly resembles the average of shergottite parent magmas or LAR 06319. However, we suggest that the mantle source for the chassignite parental magmas was distinct from that of the shergottite meteorites, particularly in CaO/Al₂O₃ ratio. In addition, based on the analysis of the volatile contents of kaersutite, we derived a water content of 0.48–0.67 wt% for the parental melt. Finally, our MELTS calculations suggest that moderate pressure (approximately 6.8 kb) came closest to reproducing the crystallized melt‐inclusion assemblages.     

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.     

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.     

Mineralogical study of brown olivine in Northwest Africa 1950 shergottite and implications for the formation mechanism of iron nanoparticles

Martian meteorites, in particular shergottites, contain darkened olivine (so‐called “brown olivine”) whose color is induced by iron nanoparticles formed in olivine during a shock event. The formation process and conditions of brown olivine have been discussed in the Northwest Africa 2737 (NWA 2737) chassignite. However, formation conditions of brown olivine in NWA 2737 cannot be applied to shergottites because NWA 2737 has a different shock history from that of shergottites. Therefore, this study observed brown olivine in the NWA 1950 shergottite and discusses the general formation process and conditions of brown olivine in shergottites. Our observation of NWA 1950 revealed that olivine is heterogeneously darkened between and within grains different from brown olivine in NWA 2737. XANES analysis showed that brown olivine contains small amounts of Fe³⁺ and TEM/STEM observation revealed that there is no SiO‐rich phase around iron metal nanoparticles. These observations indicate that iron nanoparticles were formed by a disproportionation reaction of olivine (3Fe²⁺_olivine → Fe⁰_metal + 2Fe³⁺_olivine + V_olivine, where V_olivine means a vacancy in olivine). Some parts of brown olivine show lamellar textures in SEM observation and Raman peaks in addition to those expected for olivine, implying that brown olivine experienced a phase transition (to e.g., ringwoodite). In order to induce heterogeneous darkening, heterogeneous high temperature of about 1500–1700 K and shock duration of at least ~90 ms are required. This heterogeneous high temperature resulted in high postshock temperature (>900 K) inducing back‐transformation of most high‐pressure phases. Therefore, in spite of lack of high‐pressure phases, NWA 1950 (= Martian meteorites with brown olivine) experienced higher pressure and temperature compared to other highly shocked meteorite groups.     

Determination of volatile concentrations in fluorapatite of Martian shergottite NWA 2975 by combining synchrotron FTIR,Raman spectroscopy,EMPA, and TEM,and inferences on the volatile budget of the apatite host‐magma

We combined the focused ion beam sample preparation technique with polarized synchrotron‐based FTIR (Fourier transform infrared) spectroscopy, laser‐Raman spectroscopy, electron microprobe analysis (EMPA), and transmission electron microscope (TEM) analysis to identify and quantify structurally bound OH, F, Cl, and CO₃ groups in fluorapatite from the Northwest Africa 2975 (NWA 2975) shergottite. In this study, the first FTIR spectra of the OH‐stretching region from a Martian apatite are presented that show characteristic OH‐bands of a F‐rich, hydroxyl‐bearing apatite. Depending on the method of apatite‐formula calculation and whether charge balance is assumed or not, the FTIR‐based quantification of the incorporated OH, expressed as wt% H₂O, is in variably good agreement with the H₂O concentration calculated from electron microprobe data. EMP analyses yielded between 0.35 and 0.54 wt% H₂O, and IR data yielded an average H₂O content of 0.31 ± 0.03 wt%, consistent with the lower range determined from EMP analyses. The TEM observations implied that the volatiles budget of fluorapatite is magmatic. The water content and the relative volatile ratios calculated for the NWA 2975 magma are similar to those established for other enriched or intermediate shergottites. It is difficult to define the source of enrichment: either Martian wet mantle or crustal assimilation. Comparing the environment of parental magma generation for NWA 2975 with the terrestrial mantle in terms of water content, it displays a composition intermediate between enriched and depleted MORB.     

Metal‐saturated sulfide assemblages in NWA 2737: Evidence for impact‐related sulfur devolatilization in Martian meteorites

NWA 2737, a Martian meteorite from the Chassignite subclass, contains minute amounts (0.010 ± 0.005 vol%) of metal‐saturated Fe‐Ni sulfides. These latter bear evidence of the strong shock effects documented by abundant Fe nanoparticles and planar defects in Northwest Africa (NWA) 2737 olivine. A Ni‐poor troilite (Fe/S = 1.0 ± 0.01), sometimes Cr‐bearing (up to 1 wt%), coexists with micrometer‐sized taenite/tetrataenite‐type native Ni‐Fe alloys (Ni/Fe = 1) and Fe‐Os‐Ir‐(Ru) alloys a few hundreds of nanometers across. The troilite has exsolved flame‐like pentlandite (Fe/Fe + Ni = 0.5–0.6). Chalcopyrite is almost lacking, and no pyrite has been found. As a hot desert find, NWA 2737 shows astonishingly fresh sulfides. The composition of troilite coexisting with Ni‐Fe alloys is completely at odds with Chassigny and Nahkla sulfides (pyrite + metal‐deficient monoclinic‐type pyrrhotite). It indicates strongly reducing crystallization conditions (close to IW), several log units below the fO₂ conditions inferred from chromites compositions and accepted for Chassignites (FMQ‐1 log unit). It is proposed that reduction in sulfides into base and precious metal alloys is operated via sulfur degassing, which is supported by the highly resorbed and denticulated shape of sulfide blebs and their spongy textures. Shock‐related S degassing may be responsible for considerable damages in magmatic sulfide structures and sulfide assemblages, with concomitant loss of magnetic properties as documented in some other Martian meteorites.     

A petrogenetic model for the comagmatic origin of chassignites and nakhlites: Inferences from chlorine‐rich minerals,petrology, and geochemistry

Twelve samples belonging to the chassignite and nakhlite subgroups of Martian meteorites were investigated using a variety of micro‐beam analytical techniques to gain insight into the petrogenesis of these two meteorite classes. There are a striking number of geochemical similarities between the chassignites and nakhlites, including mineralogy and petrology, crystallization age, cosmic‐ray exposure age, and radiogenic isotopic compositions. However, there are also geochemical differences, namely in trace element systematics of pyroxenes, that have led some authors to conclude that the nakhlites are comagmatic with each other, but not comagmatic with the chassignites. On the basis of data presented here, we propose a model in which these differences can be reconciled by the addition of an exogenous Cl‐rich fluid to the chassignite‐nakhlite magma body shortly after the formation of the cumulate horizon that was sampled by the Chassigny meteorite. This model is supported by the textural and chemical associations of the volatile‐bearing minerals apatite, amphibole, and biotite, which record a history starting with the addition of a Cl‐ and LREE‐enriched fluid to the magma body. As the magma continued to crystallize, it eventually reached chloride saturation and degassed a Cl‐rich fluid phase. Depending on the provenance of the Cl‐rich fluid, this model could explain how the chassignites and nakhlites originated from an LREE‐depleted source, yet all exhibit LREE‐enriched bulk‐rock patterns. Additionally, the model explains the range in oxygen fugacity that is recorded by the chassignites and nakhlites because eventual exsolution and loss of Cl‐rich fluid phases near the end of crystallization of the nakhlite sequence leads to auto‐oxidation of the magma body due to the preferential partitioning of Fe²⁺ into the fluid phase.     

Effect of chlorine on near‐liquidus crystallization of olivine‐phyric shergottite NWA 6234 at 1 GPa: Implication for volatile‐induced melting of the Martian mantle

Martian magmas are thought to be rich in chlorine compared with their terrestrial counterparts. Here, we experimentally investigate the effect of chlorine on liquidus depression and near‐liquidus crystallization of olivine‐phyric shergottite NWA 6234 and compare these results with previous experimental results on the effect of chlorine on near‐liquidus crystallization of the surface basalts Humphrey and Fastball. Previous experimental results showed that the change in liquidus temperature is dependent on the bulk composition of the basalt. The effect of chlorine on liquidus depression is greater for lower SiO₂ and higher Al₂O₃ magmas than for higher SiO₂ and lower Al₂O₃ magmas. The bulk composition for this study has lower Al₂O₃ and higher FeO contents than previous work; therefore, we provide additional constraints on the effect of the bulk composition on the influence of chlorine on near‐liquidus crystallization. High pressure and temperature crystallization experiments were performed at 1 GPa on a synthetic basalt, of the bulk composition of NWA 6234, with 0–4 wt% Cl added to the sample as AgCl. The results are consistent with previous notions that with increasing wt% Cl in the melt, the crystallization temperature decreases. Importantly, our results have a liquidus depression ?T (°C) from added chlorine that is consistent with the difference in bulk composition and suggest a dependence on both the bulk Al₂O₃ and FeO content. Our results suggest that the addition of chlorine to the Martian mantle may lower magma genesis temperatures and potentially aid in the petrogenesis of Martian magmas.     

Petrogenesis of basaltic shergottite Northwest Africa 8657: Implications for fO2 correlations and element redistribution during shock melting in shergottites

Northwest Africa (NWA) 8657 is an incompatible trace element-enriched, low-Al basaltic shergottite, similar in texture and chemistry to Shergotty, Zagami, and NWA 5298. It is composed of zoned pyroxene, maskelynite, merrillite, and Ti-oxide minerals with minor apatite, silica, and pyrrhotite. Pyroxene grains are characterized by patchy zoning, with pigeonite or augite cores zoned to Fe-rich pigeonite mantles. The cores have rounded morphologies and irregular margins. Combined with the low Ti/Al of the cores, the morphology and chemistry of the pyroxene grains are consistent with initial crystallization at depth (30–70 km) followed by partial resorption en route to the surface. Enriched rare earth element (REE) equilibrium melt compositions and calculated oxygen fugacities (fO₂) conditions for pigeonite cores indicate that the original parent melts were enriched shergottite magmas that staged in chambers at depth within the Martian crust. NWA 8657 does not represent a liquid but rather entrained a proportion of pyroxene crystals from magma chambers where fractional crystallization was occurring at depth. Variation between fO₂ and bulk-rock (La/Yb)_N of the enriched and intermediate shergottites suggests that oxidation conditions and degree of incompatible element enrichment in the source may not be correlated, as thought previously. Shock melt pockets are characterized by an absence of phosphates and oxide minerals. It is likely that these phases were melted during shock. REEs were redistributed during this process into maskelynite and to a lesser extent the shock melt; however, the overall normalized REE profile of the shock melt is like that of the bulk-rock, but at lower absolute concentrations. Overall, shock melting has had a significant effect on the mineralogy of NWA 8657, especially the distribution of phosphates, which may be significant for geochronological applications of this meteorite and other Martian meteorites with extensive shock melt.     

Ancient geologic events on Mars revealed by zircons and apatites from the Martian regolith breccia NWA 7034

Zircons and apatites in clasts and matrix from the Martian breccia NWA 7034 are well documented, timing ancient geologic events on Mars. Furthermore, in this study, zircon trace elemental content, apatite volatile content, and apatite volatile isotopic compositions measured in situ could constrain the evolution of those geologic events. The U‐Pb dates of zircons in basalt, basaltic andesite, trachyandesite igneous clasts, and the matrix are similar (4.4 Ga) suggesting intense volcanism on ancient Mars. However, two metamict zircon grains found in the matrix have an upper intercept date of ~4465 Ma in crystalline, whereas amorphous areas have a lower intercept date of 1634 ± 93 Ma. The younger date is consistent with the date of apatites (1530 ± 65 Ma), suggesting a metamorphic event that completely reset the U‐Pb system in both the amorphous areas of zircon and all apatites. δD values in all apatites negatively correlate with water content in a two‐endmember mixing trend. The D (δD up to 2459‰) and ³⁷Cl heavy core (3.8‰) of a large apatite grain suggest a D‐, ³⁷Cl‐rich fluid during the metamorphic event ~1.6 Ga ago, consistent with the trace elements Y, Hf and Ti and P in zircons. The fluid was also therefore P‐rich. The D‐, ³⁷Cl‐poor H₂O‐rich rim (<313‰) suggests the degassing of water from the Martian Cl‐poor interior at a later time. This D‐, ³⁷Cl‐poor Martian mantle reservoir could have derived from volcanic intrusions postdating the younger metamorphic event recorded in NWA 7034.     

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.     

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.     

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.     

Carbonates and sulfates in the Chassigny meteorite: Further evidence for aqueous chemistry on the SNC parent planet

Abstract— Scanning electron microscopy and energy-dispersive X-ray spectrometry of untreated interior chips from three different specimens of the Chassigny meteorite confirm the presence of discrete grains of Ca-carbonate, Mg-carbonate, and Ca-sulfate. Morphologies of these salt grains suggest that the Ca-carbonate is calcite (CaCO₃) and that the Ca-sulfate is gypsum (CaSO₄·2H₂O) or bassanite (CaSO₄·1/2H₂O). The morphologic identification of the Mg-carbonate is equivocal, but rhombohedral and acicular crystal habits suggest magnesite and hydromagnesite, respectively. The salts in Chassigny occur as discontinuous veins in primary igneous minerals and are similar to those previously documented in the nakhlites, Nakhla and Lafayette, and in shergottite EETA79001. Unlike those in nakhlites, however, the Chassigny salts occur alone, without associated ferric oxides or aluminosilicate clays. Traces of Cl and P in Chassigny salts are consistent with precipitation of the salts from short-lived, saline, aqueous solutions that postdated igneous crystallization. In contrast with the clear case for nakhlites, stratigraphic evidence for a preterrestrial origin of the salts in Chassigny is ambiguous; however, a preterrestrial origin of the Chassigny salts best explains all available evidence. The water-precipitated salts provide clear physical evidence for the hypothesis, proposed by other workers, that the igneous amphiboles in Chassigny might have experienced isotope-exchange reactions with near-surface water, thereby compromising the original stable-isotope signature of any magmatic water in melt inclusions.     

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.     

H and Cl isotope systematics of apatite in brecciated lunar meteorites Northwest Africa 4472, Northwest Africa 773, Sayh al Uhaymir 169, and Kalahari 009

We have investigated the H and Cl systematics in apatite from four brecciated lunar meteorites. In Northwest Africa (NWA) 4472, most of the apatites contain ～2000–6000 ppm H₂O with δD between ?200 and 0‰, except for one grain isolated in the matrix, which contains ～6000 ppm H₂O with δD of ～500–900‰. This low‐δD apatite contains ～2500–7500 ppm Cl associated with δ³⁷Cl of ～15–20‰, while the high‐δD grain contains ～2500 ppm Cl with δ³⁷Cl of ～7–15‰. In NWA 773, apatites in a first group contain ～700–2500 ppm H₂O with δD values averaging around ～0 ± 100‰, while apatites in a second group contain ～5500–16500 ppm H₂O with δD ～250 ± 50‰. In Sayh al Uhaymir (SaU) 169 and Kalahari (Kal) 009, apatites are similar in terms of their H₂O contents (～600–3000 ppm) and δD values (?100 to 200‰). In SaU 169, apatites contain ～6000–10,000 ppm Cl, characterized by δ³⁷Cl of ～5–12‰. Overall, most of the analyzed apatite grains have δD within the range reported for carbonaceous chondrites, similar to apatite analyzed in ancient (>3.9 Ga) lunar magmatic. One grain in NWA 4472 has H and Cl isotope compositions similar to apatite from mare basalts. With an age of 4.35 Ga, this grain could be a representative of the oldest known lunar volcanic activity. Finally, since numerous evolved clasts in NWA 773 formed through silicate liquid immiscibility, the apatite grains with extremely high H₂O contents, reaching pure hydroxylapatite composition, could provide insights into the effects of such process on the evolution of volatiles in lunar magmas.     

Petrogenesis of lunar meteorite Northwest Africa 2977: Constraints from in situ microprobe results

Abstract– Northwest Africa (NWA) 2977 is an olivine‐gabbro lunar meteorite that has a distinctly different petrographic texture from other lunar basalts. We studied this rock with a series of in situ analytical methods. NWA 2977 consists mainly of olivine and pyroxene with minor plagioclase. It shows evidence of intense shock metamorphism, locally as high as shock‐stage S6. Olivine adjacent to a melt vein has been partially transformed into ringwoodite and Al,Ti‐rich chromite grains have partially transformed into their high‐pressure polymorph (possibly CaTi₂O₄‐structure). Olivine in NWA 2977 contains two types of lithic inclusions. One type is present as Si,Al‐rich melt inclusions that are composed of glass and, in most cases, dendritic pyroxene. The other type is mafic and composed of relatively coarse‐grained augite with accessory chromite, RE‐merrillite, and baddeleyite. Two Si,Al‐rich melt inclusions are heavy rare earth elements (REE) enriched, whereas the mafic inclusion has high REE concentrations and a KREEP‐like pattern. The mafic inclusion could be a relict fragment captured during the ascent of the parent magma of NWA 2977, whereas the Si,Al‐rich inclusions may represent the original NWA 2977 melt. The calculated whole‐rock composition has a KREEP‐like REE pattern, suggesting that NWA 2977 has an affinity to KREEP rocks. Baddeleyite has recorded a young crystallization age of 3123 ± 7 Ma (2σ), which is consistent with results from previous whole‐rock and mineral Sm‐Nd and Rb‐Sr studies. The petrography, mineralogy, trace element geochemistry, and young crystallization age of NWA 2977 support the possibility of pairing between NWA 2977 and the olivine‐gabbro portion of NWA 773.     

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.     

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.     

The formation environment of potassic‐chloro‐hastingsite in the nakhlites MIL 03346 and pairs and NWA 5790: Insights from terrestrial chloro‐amphibole

Potassic‐chloro‐hastingsite has been found in melt inclusions in MIL 03346, its paired stones, and NWA 5790. It is some of the most chlorine‐rich amphibole ever analyzed. In this article, we evaluate what crystal chemistry, terrestrial analogs, and experiments have shown about how chlorine‐dominant amphibole (chloro‐amphibole) forms and apply these insights to the nakhlites. Chloro‐amphibole is rare, with about a dozen identified localities on Earth. It is always rich in potassium and iron and poor in titanium. In terrestrial settings, its presence has been interpreted to result from medium to high‐grade alteration (>400 °C) of a protolith by an alkali and/or iron chloride‐rich aqueous fluid. Ferrous chloride fluids exsolved from mafic magmas can cause such alteration, as can crustal fluids that have reacted with rock and lost H₂O in preference to chloride, resulting in concentrated alkali chloride fluids. In the case of the nakhlites, an aqueous alkali‐ferrous chloride fluid was exsolved from the parental melt as it crystallized. This aqueous chloride fluid itself likely unmixed into chloride‐dominant and water‐dominant fluids. Chloride‐dominant fluid was trapped in some melt inclusions and reacted with the silicate contents of the inclusion to form potassic‐chloro‐hastingsite.