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.     

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.     

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.     

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.     

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.     

Magmatic cristobalite and quartz in the NWA 856 Martian meteorite

Abstract— Silica‐rich late‐stage crystallization pockets in the Martian meteorite Northwest Africa (NWA) 856 were investigated by transmission electron microscopy (TEM). The pockets occur as wedges between maskelynite laths or between maskelynite and pyroxene. They consist of elongated grains of cristobalite and quartz embedded in a silica‐rich glass. Interstitial to the amorphous phase and silica minerals, a number of small accessory minerals have been identified, typical for late‐stage crystallization products. They are ilmenite, tranquillityite, fayalite, troilite, baddeleyite, apatite, and chloroapatite. Cristobalite and quartz are shocked, as revealed by the occurrence of numerous amorphous lamellae. This assemblage suggests metastable dendritic crystallization under hydrous conditions. Cristobalite crystallization was probably facilitated by the presence of impurities such as Na or H₂O. Our observations show that silica minerals can be formed under magmatic conditions on Mars.     

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.     

The volatile content of Vesta: Clues from apatite in eucrites

Apatite was analyzed by electron microprobe in 3 cumulate and 10 basaltic eucrites. Eucritic apatite is fluorine‐rich with minor chlorine and hydroxyl (calculated by difference). We confirmed the hydroxyl content by measuring hydroxyl directly in apatites from three representative eucrites using secondary ionization mass spectroscopy. Overall, most eucritic apatites resemble fluorine‐rich lunar mare apatites, but intriguing OH‐ and Cl‐rich apatites suggest a role for water and/or hydrothermal fluids in the Vestan interior or on other related differentiated asteroids. Most late‐stage apatite found in mesostasis has little hydroxyl or chlorine and is thought to have crystallized from a degassed magma; however, several apatites exhibit atypical compositions and/or textural characteristics. For example, the isotopically anomalous basaltic eucrite Pasamonte has apatite in the mesostasis with significant OH. Apatites in Juvinas also have significant OH and occur as veinlets crosscutting silicates. Euhedral apatites in the Moore County cumulate eucrite occur as inclusions in pyroxene and are also hydroxyl‐rich (0.62 wt% OH). The OH was confirmed by SIMS analysis and this apatite clearly points to the presence of water, at least locally, in the Vestan interior. Portions of Elephant Moraine (EET) 90020 have large and abundant apatites, which may be the product of apatite accumulation in a zone of melt‐rock reaction. Relatively chlorine‐rich apatites occur in basaltic eucrite Graves Nunataks (GRA) 98098 (approximately 1 wt% Cl). Particularly striking is the compositional similarity between apatite in GRA 98098 and apatites in lunar KREEP, which may indicate the presence of residual magmas from an asteroid‐wide magma ocean on Vesta.     

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.     

Constraints on the water,chlorine, and fluorine content of the Martian mantle

Previous estimates of the volatile contents of Martian basalts, and hence their source regions, ranged from nearly volatile‐free through estimates similar to those found in terrestrial subduction zones. Here, we use the bulk chemistry of Martian meteorites, along with Martian apatite and amphibole chemistry, to constrain the volatile contents of the Martian interior. Our estimates show that the volatile content of the source region for the Martian meteorites is similar to the terrestrial Mid‐Ocean‐Ridge Mantle source. Chlorine is enriched compared with the depleted terrestrial mantle but is similar to the terrestrial enriched source region; fluorine is similar to the terrestrial primitive mantle; and water is consistent with the terrestrial mantle. Our results show that Martian magmas were not volatile saturated; had water/chlorine and water/fluorine ratios ~0.4–18; and are most similar, in terms of volatiles, to terrestrial MORBs. Presumably, there are variations in volatile content in the Martian interior as suggested by apatite compositions, but more bulk chemical data, especially for fluorine and water, are required to investigate these variations. Finally, the Noachian Martian interior, as exemplified by surface basalts and NWA 7034, may have had higher volatile contents.     

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.     

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.     

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%.     

火星陨石NWA 8716的岩矿学特征及粗粒橄榄石斑晶的来源

火星陨石可以为研究火星岩浆演化过程提供直接证据并限制其源区特征.通常认为含粗粒橄榄石斑晶辉玻无球粒陨石携带有火星原始地幔的信息,因此选取该类样品Northwest Africa (NWA) 8716为研究对象,进行岩相结构及矿物成分分析. NWA8716由橄榄石、辉石、填隙状熔长石以及其他次要矿物组成.其中橄榄石颗粒有两种级别的粒径,长轴分别约为0.5–1.8 mm和50–400μm.较小橄榄石斑晶内部的熔体包裹体和NWA 8716全岩成分(计算值)均显示明显的轻稀土元素亏损([La/Yb]CI值为0.06–0.1),说明NWA 8716源于一个亏损的火星岩浆池.粗粒橄榄石斑晶的来源对衡量该样品是否能够代表原始熔体成分非常重要.对橄榄石晶体的粒径统计分析发现,粗粒橄榄石斑晶应为堆晶.进一步对铁-镁以及稀土元素分配特征的计算表明NWA 8716并非形成于一个封闭系统,但是计算所得原始熔体成分与全岩成分差异不大,因此粗粒橄榄石斑晶应当来源于与母岩浆成分相似的熔体.总的看来, NWA 8716应当来源于亏损型火星幔源区且演化程度较低.     

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.     

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.     

Fluids on differentiated asteroids: Evidence from phosphates in differentiated meteorites GRA 06128 and GRA 06129

Abstract– Paired meteorites Graves Nunatak 06128 and 06129 (GRA) represent an ancient cumulate lithology (4565.9 Ma ± 0.3) containing high abundances of sodic plagioclase. Textures and stable isotope compositions of GRA indicate that superimposed on the igneous lithology is a complex history of subsolidus reequilibration and low‐temperature alteration that may have extended over a period of 150 Myr. In GRA, apatite is halogen‐rich with Cl between 4.5 and 5.5 wt% and F between 0.3 and 0.9 wt%. The Cl/(Cl+F+OH) ratio of the apatite is between 0.65 and 0.82. The Cl and F are negatively correlated and are heterogeneously distributed in the apatite. Merrillite is low in halogens with substantial Na in the 6‐fold coordinated Na‐site (≈2.5%) and Mg in the smaller octahedral site. The merrillite has a negative Eu anomaly, whereas the apatite has a positive Eu anomaly. The chlorine isotope composition of the bulk GRA leachate is +1.2‰ relative to standard mean ocean chloride (SMOC). Ion microprobe chlorine isotope analyses of the apatite range between ?0.5 and +1.2‰. Textural relationships between the merrillite and apatite, and the high‐Cl content of the apatite, suggest that the merrillite is magmatic in origin, whereas the apatite is a product of the interaction between merrillite and a Cl‐rich fluid. If the replacement of merrillite by apatite occurred at approximately 800 °C, the fluid composition is f(HCl)/f(H₂O) = 0.0383 and a HCl molality of 2.13 and f(HCl)/f(HF) = 50–100. It is anticipated that the calculated f(HCl)/f(H₂O) and a HCl molality are minimum values due to assumptions made on the OH component in apatite and basing the calculations on the apatite with the lowest X_Cl. The bulk δ³⁷Cl of GRA is a >2σ outlier from chondritic meteorites and suggests that parent body processes resulted in fractionation of the Cl isotopes.     

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.     

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.     

Phase equilibria of the Shergotty meteorite: Constraints on pre‐eruptive water contents of martian magmas and fractional crystallization under hydrous conditions

Abstract— An experimental investigation of the Shergotty meteorite was performed at 0.1 MPa under anhydrous conditions at the quartz‐fayalite‐magnetite buffer and at 100 and 200 MPa under H₂O‐saturated conditions at the nickel‐nickel oxide buffer. The results of these experiments are used to infer magmatic conditions recorded by co‐crystallization of augite and pigeonite phenocrysts found in Shergotty and to investigate the effect of H₂O on fractional crystallization paths followed by shergottite magmas. The phase relations and compositions of the homogeneous magnesian pyroxene cores in Shergotty are most closely approximated by crystallization under H₂O‐saturated conditions at 1120 °C (± 10 °C) and 56 MPa (± 18 MPa), corresponding to dissolved H₂O contents of 1.8 wt% (± 0.6 wt%) and a depth of 5 km (± 1.5 km) in the martian crust (uncertainties are 2s? values). The Shergotty magma then lost this water during ascent and eruption. Fractional crystallization of the Shergotty magma under anhydrous conditions produces liquids that follow a strong Fe‐enrichment trend at nearly constant SiO₂. Crystallization under H₂O‐saturated conditions generates derivative liquids, depleted in FeO and Al₂O₃ and enriched in SiO₂, that are compositionally similar to the Mars Pathfinder andesite rock composition. The presence of ～1.8 wt% water in Shergotty parental magmas could result from assimilation of hydrated crustal materials or from dehydration of hydrous phases in the mantle source region.