Valence of Ti,V, and Cr in Apollo 14 aluminous basalts 14053 and 14072

The valences of Ti, V, and Cr in olivine and pyroxene, important indicators of the fO₂ of the source region of their host rocks, can be readily measured nondestructively by XANES (X‐ray absorption near edge structure) spectroscopy, but little such work has been done on lunar rocks, and there is some uncertainty regarding the presence of Ti³⁺ in lunar silicates and the redox state of the lunar mantle. This is the first study involving direct XANES measurement of valences of multivalent cations in lunar rocks. Because high alumina activity facilitates substitution of Ti cations into octahedral rather than tetrahedral sites in pyroxene and Ti³⁺ only enters octahedral sites, two aluminous basalts from Apollo 14, 14053 and 14072, were studied. Most pyroxene contains little or no detectable Ti³⁺, but in both samples relatively early, magnesian pyroxene was found that has Ti valences that are not within error of 4; in 14053, this component has an average Ti valence of 3.81 ± 0.06 (i.e., Ti³⁺/[Ti³⁺ + Ti⁴⁺ = 0.19]). This pyroxene has relatively low atomic Ti/Al ratios (<0.4) due to crystallization before plagioclase, contrary to the long‐held belief that lunar pyroxene with Ti/Al > 0.5 contains Ti³⁺ and pyroxene with lower ratios does not. Later pyroxene, with lower Mg/Fe and higher Ti/Al ratios, has higher proportions of Ti (all Ti⁴⁺) in tetrahedral sites. All pyroxene analyzed contains divalent Cr, ranging from 15 to 30% of the Cr present, and all but one analysis spot contains divalent V, accounting for 0 to 40% (typically 20–30%) of the V present. Three analyses of olivine in 14053 do not show any Ti³⁺, but Ti valences in 14072 olivine range from 4 down to 3.70 ± 0.10. In 14053 olivine, ~50% of the Cr and 60% of the V are divalent. In 14072 olivine, the divalent percentages are ~20% for Cr and 20–60% for V. These results indicate significant proportions of divalent Cr and V and limited amounts of trivalent Ti in the parental melts, especially when crystal/liquid partitioning preferences are taken into account. These features are consistent with an fO₂ closer to IW ? 2 than to IW ? 1. Apollo 15 basalt 15555, analyzed for comparison with A‐14 materials, has olivine with strongly reduced Cr (Cr²⁺/(Cr²⁺ + Cr³⁺) ~0.9). Basalts from different sites may record redox differences between source regions.     

Valences of Ti,Cr, and V in Apollo 17 high-Ti and very low-Ti basalts and implications for their formation

To assess the variability of redox states among mare basalt source regions, investigation of the valence of Ti, Cr, and V and the coordination environment of Ti in pyroxene and olivine in lunar rocks via XANES (X-ray absorption near-edge structure) spectroscopy has been extended to Apollo 17 basalts: two high-Ti (70017 and 74275) hand samples, and three very low-Ti (70006,371, 70007,289B, and 70007,296) basalt fragments from the Apollo 17 deep drill core. Valences of Ti in pyroxene of both suites range from 3.6 to 4, or from 40% to 0% Ti³⁺, averaging 15–20% Ti³⁺. Assuming Ti³⁺ is more compatible in pyroxene than Ti⁴⁺, then even lower Ti³⁺ proportions are indicated for the parental melts. The VLT pyroxene exhibits a slightly wider range of V valences (2.57–2.96) than the high-Ti pyroxene (2.65–2.86) and a much wider range of Cr valences (2.32–2.80 versus 2.68–2.86); Cr is generally reduced in VLT pyroxene compared to high-Ti pyroxene. Valences of Ti and Cr in VLT pyroxene become less reduced with increasing FeO contents, possibly indicating change in oxygen fugacity during crystallization. Olivine in all samples has very low (<20%) proportions of Ti³⁺, with no Ti³⁺ and higher proportions of Ti in tetrahedral coordination in the VLTs than in the high-Ti basalts. Olivine in 74275, including that in a dunite clast, has much higher proportions of Cr²⁺ than the pyroxene in that sample, consistent with previous studies indicating that the olivine grains in this sample are xenocrysts and possibly indicating oxidation just prior to pyroxene crystallization. Results for this sample, the VLTs, and previously studied Apollo 14 and 15 basalts all indicate that mare magmas were in reducing environments at depth, as recorded in early crystallization products, and that later, presumably shallower environments, were relatively oxidizing; single, characteristic fO₂s of formation cannot be assigned to these samples. A process likely to account for this feature seen in multiple samples is loss by degassing of a reducing, H-rich vapor (probably H₂) during ascent and/or eruption, causing oxidation of the residual melt, recorded in relatively late-crystallized pyroxene.     

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.     

Incremental melting in the ureilite parent body: Initial composition,melting temperatures,and melt compositions

Ureilites are carbon‐rich ultramafic achondrites that have been heated above the silicate solidus, do not contain plagioclase, and represent the melting residues of an unknown planetesimal (i.e., the ureilite parent body, UPB). Melting residues identical to pigeonite‐olivine ureilites (representing 80% of ureilites) have been produced in batch melting experiments of chondritic materials not depleted in alkali elements relative to the Sun’s photosphere (e.g., CI, H, LL chondrites), but only in a relatively narrow range of temperature (1120 ºC–1180 ºC). However, many ureilites are thought to have formed at higher temperature (1200 ºC–1280 ºC). New experiments, described in this study, show that pigeonite can persist at higher temperature (up to 1280 ºC) when CI and LL chondrites are melted incrementally and while partial melts are progressively extracted. The melt productivity decreases dramatically after the exhaustion of plagioclase with only 5–9 wt% melt being generated between 1120 ºC and 1280 ºC. The relative proportion of pyroxene and olivine in experiments is compared to 12 ureilites, analyzed for this study, together with ureilites described in the literature to constrain the initial Mg/Si ratio of the UPB (0.98–1.05). Experiments are also used to develop a new thermometer based on the partitioning of Cr between olivine and low‐Ca pyroxene that is applicable to all ureilites. The equilibration temperature of ureilites increases with decreasing Al₂O₃ and Wo contents of pyroxene and decreasing bulk REE concentrations. The UPB melted incrementally, at different fO₂, and did not cool significantly (0 ºC–30 ºC) prior to its disruption. It remained isotopically heterogenous, but the initial concentration of major elements (SiO₂, MgO, CaO, Al₂O₃, alkali elements) was similar in the different mantle reservoirs.     

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.     

Mineralogy of Antarctic basaltic shergottite Queen Alexandra Range 94201: Similarities to Elephant Moraine A79001 (Lithology B) martian meteorite

Abstract— Antarctic meteorite QUE 94201 is a new basaltic shergottite that is mainly composed of subequal amounts of maskelynite and pyroxenes (pigeonite and augite) plus abundant merrillite and accessory phases. It also contains impact melt. Complex zoning patterns in QUE 94201 pyroxenes revealed by elemental map analyses using an electron microprobe suggest a crystallization sequence from Mg-rich pigeonite (En₆₂Fss₃₀Wo_g) to extremely Fe-rich pigeonite (En₅Fs₈₁Wo₁₄) via {110} Mg-rich augite bands (En₄₄Fs₂₀Wo₃₆) in a single crystal. These textures, along with the abundant plagioclase (maskelynite), indicates single-stage rapid cooling (>5 °C/year) of this rock from a supercooled magma. Transition from Mg-rich augite to Fe-rich pigeonite reflects the onset of plagioclase crystallization. Enrichment of late-stage phases in QUE 94201 implies crystallization from an evolved magma and suggests a different parent magma composition from the other basaltic shergottites. Lithology B of EETA79001 basaltic shergottite contains pyroxenes that show complex zoning with augite bands similar to those in QUE 94201 pyroxene, which suggests similar one-stage rapid cooling. Lithology B of EETA79001 also resembles QUE 94201 in its coarse-grained texture of silicates and its high abundance of maskelynite, although QUE 94201 probably crystallized from a more fractionated magma. We also note that some Apollo lunar mare basalts (e.g., 12020 and 12021) have similar mineralogy and petrology to QUE 94201, especially in pyroxene zoning. All these basaltic rocks with complex pyroxene zoning suggest rapid metastable crystallization from supercooled magmas.     

Detection of ferric iron in an exsolved lunar pyroxene using electron energy loss spectroscopy (EELS): Implications for space weathering and redox conditions on the Moon

To shed light on the mechanism of formation of nanophase iron particles (npFe) in space-weathered materials from airless bodies, we analyzed exsolved and unexsolved space-weathered lunar pyroxenes from Apollo 17 sample 71501. The exsolved pyroxene allowed for the observation of the effects of space weathering on similar mineral phases with variable composition. Using coordinated scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy (EELS), we determined that two coexisting pyroxenes in the exsolved grain showed systematic variations in response to space weathering, despite equivalent exposure conditions. The npFe in the space-weathered rim of augite lamellae were smaller and fewer than the npFe in the rim of pigeonite lamellae. EELS spectrum imaging revealed the presence and heterogeneous distribution of Fe⁰, Fe²⁺, and Fe³⁺ in the exsolved pyroxene. Metallic iron occurred in the npFe, a mixture of Fe²⁺ and Fe³⁺ occurred in the pigeonite lamellae, and the augite lamellae contained virtually all Fe³⁺. Approximately 50% of the total Fe measured in the exsolved pyroxene grain was ferric. Partitioning of Fe²⁺ and Fe³⁺ among the lamellae is invoked to explain the difference in npFe development in pigeonite and augite. The results of this study, the first to identify Fe³⁺ in a crystalline lunar ferromagnesian silicate, have implications for our understanding of how space weathering might proceed in oxidized phases. Furthermore, the discovery of an Fe³⁺-rich pyroxene also supports attribution of the 0.7 μm absorption feature observed in Galileo Solid State Imager data to oxidized Fe in clinopyroxenes.     

Trace ferric ion in lunar and meteoritic titanaugites

Evidence for presence of Fe³⁺ in lunar rocks is furnished by heating them in air to 200-225°C for two hours. This causes a large decrease in the same charge transfer bands attributed to Fe³⁺ that can be enhanced by heating the same rocks in air at 500°C. This data is interpreted as evidence that the Fe³⁺ was not in equilibrium in the melt but was produced by cosmic radiation subsequent to the rock formation. The decrease of the Fe³⁺ charge-transfer bands is accompanied by decrease in intensity of spin-allowed Fe²⁺ bands attributed toM ₁ sites in the pyroxene in rock 12018. This decrease in the Fe²⁺ bands is attributed to decrease in the Fe²⁺ Fe³⁺ charge-transfer intensification of these Fe²⁺ spin-allowed transitions when radiation-produced Fe³⁺ is partially-reduced by the low-temperature heating.The reaction of Fe³⁺ on heating to 200-225°C is probably Fe³⁺ + Ti³⁺ Fe²⁺ + Ti⁴⁺.This is the reverse of the reaction caused by cosmic ray bombardment of the rock on the lunar surface. Possible tetrahedrally coordinated Fe³⁺ is present in the meteoritic and lunar augites as suggested by comparison of their spectra to that of terrestrial augite high in Fe³⁺. This would have been present in the original melt and is distinct from radiation produced Fe³⁺ in theM-sites.The polarized absorption spectra of single crystal pigeonite and augite from rock 12021 before heating, and augite from 12018 after heating are compared to that of meteoritic titanaugite in the Angra dos Reis meteorite and terrestrial titanaugite from Maui, Hawaii. The absorption spectrum of meteoritic hypersthene (Tatahouine) is also included for comparison to the pigeonite.     

Pyroxene microstructure in the Northwest Africa 856 martian meteorite

Abstract— Transmission electron microscopy was used to examine pyroxene microstructure in the Northwest Africa (NWA) 856 martian meteorite to construct its cooling and shock histories. All pyroxenes contain strained coherent pigeonite/augite exsolution lamellae on (001). The average width and periodicity of lamellae are 80 and 400 nm, respectively, indicating a cooling rate below 0.1 °C/hr for the parent rock. Pigeonite and augite are topotactic, with strained coherent interfaces parallel to (001). The closure temperature for Ca‐Fe, Mg interdiffusion, estimated from the composition at the augite pigeonite interface, is about 700 °C. Tweed texture in augite reveals that a spinodal decomposition occurred. Locally, tweed evolved toward secondary pigeonite exsolutions on (001). Due to the decreasing diffusion rate with decreasing temperature, “M‐shaped” concentration profiles developed in augite lamellae. Pigeonite contains antiphase boundaries resulting from the C2/c to P2₁/c space group transition that occurred during cooling. The reconstructive phase transition from P2₁/c clinopyroxene to orthopyroxene did not occur. The deformation (shock) history of the meteorites is revealed by the presence of dislocations and mechanical twins. Dislocations are found in glide configuration, with the [001](100) glide system preferentially activated. They exhibit strong interaction with the strained augite/pigeonite interfaces and did not propagate over large distances. Twins are found to be almost all parallel to (100) and show moderate interaction with the augite/pigeonite interfaces. These twins are responsible for the plastic deformation of the pyroxene grains. Comparison with microstructure of shocked clinopyroxene (experimentally or naturally shocked) suggests that NWA 856 pyroxenes are not strongly shocked.     

Thermal history of the Ibitira noncumulate eucrite as inferred from pyroxene exsolution lamella: Evidence for reheating and rapid cooling

Abstract— Ibitira is a strongly recrystallized and unbrecciated noncumulate eucrite. We measured Ca compositional profiles of Ibitira pyroxene by electron microprobe and computed the cooling rate and burial depth from pyroxene exsolution profiles to gain information on early thermal history of Ibitira. Pyroxene begins to exsolve at 1082 °C and cools down to 550 °C at a rate of 0.02 °C/year, forming an augite lamella about 7.0 μm in width. A notable characteristic of the Ca profile of augite lamellae in Ibitira pyroxene is a gradient near the interface between augite and low‐Ca pyroxene (pigeonite). This profile suggests that after thermal metamorphism Ibitira pyroxene experienced a sudden temperature rise to above solidus temperature of pyroxene (～1082 °C), and subsequent rapid cooling. The ³⁹Ar‐⁴⁰Ar age of 4.485 Ga for Ibitira, which is the oldest ³⁹Ar‐⁴⁰Ar age for noncumulate eucrites, may date this reheating event.     

An experimental and petrographic investigation of Elephant Moraine 79001 lithology A: Implications for its petrogenesis and the partitioning of chromium and vanadium in a martian basalt

Abstract— A composition approximating the lithology A groundmass of the Elephant Moraine (EET) 79001 martian basalt (Eg; McSween and Jarosewich, 1983) has been used to investigate the petrogenesis of the meteorite and the behavior of Cr and V at different oxygen fugacities. Crystallization experiments were carried out over a range of temperatures, and oxygen fugacities of either iron‐wüstite (IW) or IW + 2 (i.e., 1.5 log units below the quartz‐fayalite‐magnetite (QFM) buffer). Comparison of trace element concentrations (obtained by secondary ion mass spectrometry (SIMS) analysis) in experimental silicates with those of natural silicates supports the Fe‐Ti oxide‐derived oxygen fugacity of QFM ?1.8 ± 0.3 for this basalt (Herd et al., 2001). Experimental distribution coefficients, in conjunction with SIMS analyses of rims from the olivine and pyroxene xenocrysts in lithology A, as well as analyses of lithology A groundmass pigeonite cores, are used to calculate coexisting liquid concentrations of V and Cr. Liquid compositions derived from pigeonite xenocryst rims and groundmass pigeonite cores are similar, suggesting that the rims of orthopyroxene xenocrysts are overgrowths, which have not previously been accounted for when reconstructing the groundmass composition. This implies that the Eg composition requires modification. A similar exercise for the ferroan rims on olivine xenocrysts yields very different liquid compositions, indicating that these rims are not overgrowths but are part of the xenocryst assemblage. These results are shown to be consistent with the petrography of lithology A xenocrysts.     

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 Gao‐Guenie impact melt breccia—Sampling a rapidly cooled impact melt dike on an H chondrite asteroid?

The Gao‐Guenie H5 chondrite that fell on Burkina Faso (March 1960) has portions that were impact‐melted on an H chondrite asteroid at ~300 Ma and, through later impact events in space, sent into an Earth‐crossing orbit. This article presents a petrographic and electron microprobe analysis of a representative sample of the Gao‐Guenie impact melt breccia consisting of a chondritic clast domain, quenched melt in contact with chondritic clasts, and an igneous‐textured impact melt domain. Olivine is predominantly Fo_80–82. The clast domain contains low‐Ca pyroxene. Impact melt‐grown pyroxene is commonly zoned from low‐Ca pyroxene in cores to pigeonite and augite in rims. Metal–troilite orbs in the impact melt domain measure up to ~2 mm across. The cores of metal orbs in the impact melt domain contain ~7.9 wt% of Ni and are typically surrounded by taenite and Ni‐rich troilite. The metallography of metal–troilite droplets suggest a stage I cooling rate of order 10 °C s^?1 for the superheated impact melt. The subsolidus stage II cooling rate for the impact melt breccia could not be determined directly, but was presumably fast. An analogy between the Ni rim gradients in metal of the Gao‐Guenie impact melt breccia and the impact‐melted H6 chondrite Orvinio suggests similar cooling rates, probably on the order of ~5000–40,000 °C yr^?1. A simple model of conductive heat transfer shows that the Gao‐Guenie impact melt breccia may have formed in a melt injection dike ~0.5–5 m in width, generated during a sizeable impact event on the H chondrite parent asteroid.     

Pervasive shock melting at >65 GPa in a Martian basalt,the shergottite Northwest Africa 14672

Shergottites have provided abundant information on the volcanic and impact history of Mars. Northwest Africa (NWA) 14672 contributes to both of these aspects. It is a vesicular ophitic depleted olivine–phyric shergottite, with average plagioclase An₆₁Ab₃₉Or_0.2. It is highly ferroan, with pigeonite compositions En_49-25Fs_41-61Wo_10-14 like those of basaltic shergottites, for example, NWA 12335. Olivine (Fo_53-15) has discrete ferroan overgrowths, more ferroan when in contact with plagioclase than when enclosed by pyroxene. The pyroxene (a continuum of augite, subcalcic augite, and pigeonite) is patchy, with ragged “cores” enveloped or invaded by ferroan pyroxene. Magma mixing may be responsible for capture of olivine and formation of pyroxene mantles. The plagioclase is maskelynite-like in appearance, but the original laths were (congruently) melted and the melt partly crystallized as fine dendrites. Most of the 14% vesicles occur within plagioclase. Olivine, pyroxene, and ilmenite occur in part as fine aggregates crystallized after congruent melting with limited subsequent liquid mixing. There are two fine-grained melt components, barred plagioclase with interstitial Fe-bearing phases, and glass with olivine dendrites, derived by melting of mainly plagioclase and mainly pyroxene, respectively. Rare silica particles contain coesite and/or quartz, and silica glass. The rock has experienced >50% melting, compatible with peak pressure >~65 GPa. It is the most highly shocked shergottite so far, at shock stage S6/7. It may belong to the group of depleted shergottites ejected at ~1 Myr from Tooting Crater.     

Remelting of refractory inclusions in the chondrule‐forming regions: Evidence from chondrule‐bearing type C calcium‐aluminum‐rich inclusions from Allende

Abstract— We describe the mineralogy, petrology, oxygen, and magnesium isotope compositions of three coarse‐grained, igneous, anorthite‐rich (type C) Ca‐Al‐rich inclusions (CAIs) (ABC, TS26, and 93) that are associated with ferromagnesian chondrule‐like silicate materials from the CV carbonaceous chondrite Allende. The CAIs consist of lath‐shaped anorthite (An₉₉), Cr‐bearing Al‐Ti‐diopside (Al and Ti contents are highly variable), spinel, and highly åkermanitic and Na‐rich melilite (Åk_63–74, 0.4–0.6 wt% Na₂O). TS26 and 93 lack Wark‐Lovering rim layers; ABC is a CAI fragment missing the outermost part. The peripheral portions of TS26 and ABC are enriched in SiO₂ and depleted in TiO₂ and Al₂O₃ compared to their cores and contain relict ferromagnesian chondrule fragments composed of forsteritic olivine (Fa_6–8) and low‐Ca pyroxene/pigeonite (Fs₁Wo_1–9). The relict grains are corroded by Al‐Ti‐diopside of the host CAIs and surrounded by haloes of augite (Fs_0.5Wo_30–42). The outer portion of CAI 93 enriched in spinel is overgrown by coarse‐grained pigeonite (Fs_0.5–2Wo_5–17), augite (Fs_0.5Wo_38–42), and anorthitic plagioclase (An₈₄). Relict olivine and low‐Ca pyroxene/pigeonite in ABC and TS26, and the pigeonite‐augite rim around 93 are ¹⁶O‐poor (Δ17O ～ ?1‰ to ?8‰). Spinel and Al‐Ti‐diopside in cores of CAIs ABC, TS26, and 93 are ¹⁶O‐enriched (Δ17O down to ?20‰), whereas Al‐Ti‐diopside in the outer zones, as well as melilite and anorthite, are ¹⁶O‐depleted to various degrees (Δ17O = ?11‰ to 2‰). In contrast to typical Allende CAIs that have the canonical initial ²⁶Al/²⁷Al ratio of ～5 × 10^?5 ABC, 93, and TS26 are ²⁶Al‐poor with (²⁶Al/²⁷Al)₀ ratios of (4.7 ± 1.4) × 10^?6 (1.5 ± 1.8) × 10^?6 <1.2 × 10^?6 respectively. We conclude that ABC, TS26, and 93 experienced remelting with addition of ferromagnesian chondrule silicates and incomplete oxygen isotopic exchange in an ¹⁶O‐poor gaseous reservoir, probably in the chondrule‐forming region. This melting episode could have reset the ²⁶Al‐²⁶Mg systematics of the host CAIs, suggesting it occurred ～2 Myr after formation of most CAIs. These observations and the common presence of relict CAIs inside chondrules suggest that CAIs predated formation of chondrules.     

Regolith breccia Northwest Africa 7533: Mineralogy and petrology with implications for early Mars

Northwest Africa 7533, a polymict Martian breccia, consists of fine‐grained clast‐laden melt particles and microcrystalline matrix. While both melt and matrix contain medium‐grained noritic‐monzonitic material and crystal clasts, the matrix also contains lithic clasts with zoned pigeonite and augite plus two feldspars, microbasaltic clasts, vitrophyric and microcrystalline spherules, and shards. The clast‐laden melt rocks contain clump‐like aggregates of orthopyroxene surrounded by aureoles of plagioclase. Some shards of vesicular melt rocks resemble the pyroxene‐plagioclase clump‐aureole structures. Submicron size matrix grains show some triple junctions, but most are irregular with high intergranular porosity. The noritic‐monzonitic rocks contain exsolved pyroxenes and perthitic intergrowths, and cooled more slowly than rocks with zoned‐pyroxene or fine grain size. Noritic material contains orthopyroxene or inverted pigeonite, augite, calcic to intermediate plagioclase, and chromite to Cr‐bearing magnetite; monzonitic clasts contain augite, sodic plagioclase, K feldspar, Ti‐bearing magnetite, ilmenite, chlorapatite, and zircon. These feldspathic rocks show similarities to some rocks at Gale Crater like Black Trout, Mara, and Jake M. The most magnesian orthopyroxene clasts are close to ALH 84001 orthopyroxene in composition. All these materials are enriched in siderophile elements, indicating impact melting and incorporation of a projectile component, except for Ni‐poor pyroxene clasts which are from pristine rocks. Clast‐laden melt rocks, spherules, shards, and siderophile element contents indicate formation of NWA 7533 as a regolith breccia. The zircons, mainly derived from monzonitic (melt) rocks, crystallized at 4.43 ± 0.03 Ga (Humayun et al. 2013 ) and a ¹⁴⁷Sm‐¹⁴³Nd isochron for NWA 7034 yielding 4.42 ± 0.07 Ga (Nyquist et al. 2016 ) defines the crystallization age of all its igneous portions. The zircon from the monzonitic rocks has a higher Δ¹⁷O than other Martian meteorites explained in part by assimilation of regolith materials enriched during surface alteration (Nemchin et al. 2014 ). This record of protolith interaction with atmosphere‐hydrosphere during regolith formation before melting demonstrates a thin atmosphere, a wet early surface environment on Mars, and an evolved crust likely to have contaminated younger extrusive rocks. The latest events recorded when the breccia was on Mars are resetting of apatite, much feldspar and some zircons at 1.35–1.4 Ga (Bellucci et al. 2015 ), and formation of Ni‐bearing pyrite veins during or shortly after this disturbance (Lorand et al. 2015 ).     

Impact‐related thermal effects on the redox state of Ca‐pyroxene

Oxidation is observed in Ca‐pyroxene subjected to a range of shock pressures (21–59 GPa). Changes in the pyroxene redox ratio as measured by the changes in %Fe³⁺ ranged from 2–6 times the starting composition. Mössbauer and reflectance spectroscopy record the changing Fe³⁺ concentration as a preferential oxidation of Fe²⁺ in the M2 crystallographic site. The oxidation is also accompanied by mechanical changes in the pyroxene crystals including fracturing, linear defects, and twinning. As oxygen fugacity is often calculated using mineral redox ratios and thought to represent the prevailing fO₂ during crystallization, it is imperative to recognize that the fO₂ values measured in impact‐derived materials may represent that of the impact and not the magma source region.     

A review of the chondrite–achondrite transition,and a metamorphic facies series for equilibrated primitive stony meteorites

Here, the petrological features of numerous primitive achondrites and highly equilibrated chondrites are evaluated to review and expand upon our knowledge of the chondrite–achondrite transition, and primitive achondrites in general. A thermodynamic model for the initial silicate melting temperature and progressive melting for nearly the entire known range of oxidation states is provided, which can be expressed as T_m = 0.035Fa²?3.51Fa + 1109 (in °C, where Fa is the proportion of fayalite in olivine). This model is then used to frame a discussion of textural and mineralogical evolution of stony meteorites with increasing temperature. We suggest that the metamorphic petrology of these meteorites should be based on diffusive equilibration among the silicate minerals, and as such, the chondrite–achondrite transition should be defined by the initial point of silicate melting, not by metal–troilite melting. Evidence of silicate melting is preserved by a distinctive texture of interconnected interstitial plagioclase ± pyroxene networks among rounded olivine and/or pyroxene (depending on ?O₂), which pseudomorph the former silicate melt network. Indirectly, the presence of exsolution lamellae in augite in slowly cooled achondrites also implies that silicate melting occurred because of the high temperatures required, and because silicate melt enhances diffusion. A metamorphic facies series is defined: the Plagioclase Facies is equivalent to petrologic types 5 and 6, the Sub‐calcic Augite Facies is bounded at lower temperatures by the initiation of silicate melting and at higher temperatures by the appearance of pigeonite, which marks the transition to the Pigeonite Facies.     

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.     

Ferric iron in SNC meteorites as determined by Mössbauer spectroscopy: Implications for martian landers and martian oxygen fugacity

Abstract— Mössbauer spectra of martian meteorites are currently of great interest due to the Mössbauer spectrometers on the Athena mission MER rovers as well as the European Space Agency Mars Express mission, with its Beagle 2 payload. Also, considerable current effort is being made to understand the oxygen fugacity of martian magmas because of the effect of fO₂ on mineral chemistry and crystallization processes. For these 2 reasons, the present study was conceived to acquire room temperature Mössbauer spectra of mineral separates and whole rock samples of 10 SNC meteorites. The results suggest that mineral identification using remote application of this technique will be most useful when the phases present have distinctive parameters arising from Fe in very different coordination polyhedra; for example, pyroxene coexisting with olivine can be discriminated easily, but opx versus cpx cannot. The MER goal of using Mössbauer spectroscopy to quantify the relative amounts of individual mineral species present will be difficult to satisfy if silicates are present because the lack of constraints on wt% FeO contents of individual silicate phases present will make modal calculations impossible. The remote Mössbauer spectroscopy will be most advantageous if the rocks analyzed are predominantly oxides with known stoichiometries, though these phases are not present in the SNCs. As for the detection of martian oxygen fugacity, no evidence exists in the SNC samples studied of a relationship between Fe³⁺ content and fO₂ as calculated by independent methods. Possibly, all of the Fe³⁺ observed in olivine is the result of dehydrogenation rather than oxidation, and this process may also be the source of all the Fe³⁺ observed in pyroxene. The observed Fe³⁺ in pyroxene also likely records an equilibrium between pyroxene and melt at such low fO₂ that little or no Fe³⁺ would be expected.