Hydrous olivine alteration on Mars and Earth

Hydrous alteration of olivine macrocrysts in a Martian olivine phyric basalt, NWA 10416, and a terrestrial basalt from southern Colorado are examined using SEM, EPMA, TEM, and µXRD techniques. The olivines in the meteorite contain linear nanotubes of hydrous material, amorphous areas, and fluid dissolution textures quite distinct from alteration identified in other Martian meteorites. Instead, they bear resemblance to terrestrial deuteric alteration features. The presence of the hydrous alteration phase Mg‐laihunite within the olivines has been confirmed by µXRD analysis. The cores of the olivines in both Martian and terrestrial samples are overgrown by unaltered rims whose compositions match those of a separate population of groundmass olivines, suggesting that the core olivines are xenocrysts whose alteration preceded crystallization of the groundmass. The terrestrial sample is linked to deep crustal metasomatism and the “ignimbrite flare‐up” of the Oligocene epoch. The comparison of the two samples suggests the existence of an analogous relatively water‐rich magmatic reservoir on Mars.     

Evidence for silicate dissolution on Mars from the Nakhla meteorite

Veins containing carbonates, hydrous silicates, and sulfates that occur within and between grains of augite and olivine in the Nakhla meteorite are good evidence for the former presence of liquid water in the Martian crust. Aqueous solutions gained access to grain interiors via narrow fractures, and those fractures within olivine whose walls were oriented close to (001) were preferentially widened by etching along [001]. This orientation selective dissolution may have been due to the presence within olivine of shock‐formed [001](100) and [001]{110} screw dislocations. The duration of etching is likely to have been brief, possibly less than a year, and the solutions responsible were sufficiently cool and reducing that laihunite did not form and Fe liberated from the olivine was not immediately oxidized. The pores within olivine were mineralized in sequence by siderite, nanocrystalline smectite, a Fe‐Mg phyllosilicate, and then gypsum, whereas only the smectite occurs within augite. The nanocrystalline smectite was deposited as submicrometer thick layers on etched vein walls, and solution compositions varied substantially between and sometimes during precipitation of each layer. Together with microcrystalline gypsum the Fe‐Mg phyllosilicate crystallized as water briefly returned to some of the veins following desiccation fracturing of the smectite. These results show that etching of olivine enhanced the porosity and permeability of the nakhlite parent rock and that dissolution and secondary mineralization took place within the same near‐static aqueous system.     

Alteration assemblages in the nakhlites: Variation with depth on Mars

Secondary mineral assemblages in the nakhlite meteorites, Lafayette, Governador Valadares (GV), Nakhla, Yamato (Y)‐000593/Y‐000749 have been studied using scanning electron microscopy, transmission electron microscopy, and electron probe micro analysis. The different nakhlites have distinctive secondary assemblages in their olivine grains and mesostases, showing compositional fractionation correlated with their relative depths below the Martian surface. Fracture‐filled veins in Lafayette at the bottom of the pile consist of a siderite‐phyllosilicate‐Fe oxide‐hydrated silicate gel assemblage. Corresponding veins in Nakhla and GV further up the pile are predominantly a siderite‐gel assemblage, with additional evaporites including gypsum. Y‐000593/Y‐000749 veins are dominated by gel. The gel’s Mg/(Mg + Fe) ratio decreases from Lafayette (0.37) to GV (0.32), Nakhla (0.24), and Y‐000593 (0.15). We suggest that hydrothermal fluid flowed up this depth profile, initiated by melting of buried H₂O–CO₂ ice. Our results show a complex mix of Fe‐rich phyllosilicate within the veins and mesostasis of Lafayette with d‐spacings of 0.7–1.1 nm suggesting a mixture of smectite and serpentine. The phyllosilicate formed at close to neutral pH, ≤150 °C. We also suggest that water rock ratios (W/R) of 1–10 occurred in Lafayette with smaller values for the other nakhlites. This is reflected in the volume of alteration minerals: 10% of olivine in Lafayette to 3% in Nakhla. Textural evidence of rapid cooling, together with the W/R and likely fluid velocities, suggest that the secondary assemblages formed quickly, e.g., within months. A model is proposed in which the secondary assemblages formed in an impact‐induced hydrothermal system terminated by precipitation of the gel and evaporation of soluble salts.     

A New Martian Meteorite: the Dhofar 019 Shergottite with an Exposure Age of 20 Million Years

The isotopic composition of the noble gases of the new Martian meteorite, the Dhofar 019 shergottite, found in the desert in the territory of the Sultanate of Oman on January 24, 2001, was investigated. Stepwise thermal annealing with isotopic analysis of each of the noble-gas temperature fractions was employed to determine the component composition. The concentration of the trapped noble gases in the new Martian meteorite Dhofar 019 is relatively high, although it lies within the range of concentrations in known SNC meteorites. A characteristic feature of all the trapped noble gases is the presence of two main components: a low-temperature, probably terrestrial atmospheric, component, trapped during the weathering of the meteorite on Earth, and a high-temperature trapped Martian component. Owing to the different ratios of the quantities of the two components, the trapped neon, argon, krypton, and xenon differ markedly in the kinetics of their release. The isotopic composition of the noble gases varies accordingly. The trapped xenon was found to contain two Martian components. One of them, with typical ratios of ¹²⁹Xe/¹³²Xe and ¹³²Xe/⁸⁴Kr, is representative of xenon and krypton of the Martian atmosphere; the other, of gases of the Martian mantle. Variations of the isotopic compositions of helium, neon, and argon (and also, to a lesser extent, of krypton and xenon) during the thermal annealing of the Dhofar 019 meteorite clearly point to a large proportion of cosmogenic as well as trapped components. The concentration of cosmogenic neon and argon in the meteorite is unusually high. This corresponds to a maximum exposure age among other SNC meteorites: 20 million years. Estimates of the potassium–argon age (gas-retention age) yielded the figure of 560 million years, which is within the range of values obtained for SNC meteorites by other authors, who used the rubidium–strontium and the potassium–argon technique.     

Shergottites Dhofar 019, SaU 005, Shergotty,and Zagami: 40Ar‐39Ar chronology and trapped Martian atmospheric and interior argon

Abstract— We report a high‐resolution ⁴⁰Ar‐³⁹Ar study of mineral separates and whole‐rock samples of olivine‐phyric (Dhofar 019, Sayh al Uhaymir [SaU] 005) and basaltic (Shergotty, Zagami) shergottites. Excess argon is present in all samples. The highest (⁴⁰Ar/³⁶Ar)_trapped ratios are found for argon in pyroxene melt inclusions (?1500), maskelynite (?1200), impact glass (?1800) of Shergotty and impact glass of SaU 005 (?1200). A high (⁴⁰Ar/³⁶Ar)_trapped component‐usually uniquely ascribed to Martian atmosphere‐can also originate from the Martian interior, indicating a heterogeneous Martian mantle composition. As additional explanation of variable high (⁴⁰Ar/³⁶Ar)_trapped ratios in shocked shergottites, we suggest argon implantation from a “transient atmosphere” during impact induced degassing. The best ⁴⁰Ar‐³⁹Ar age estimate for Dhofar 019 is 642 ± 72 Ma (maskelynite). SaU 005 samples are between 700–900 Ma old. Relatively high ⁴⁰Ar‐³⁹Ar ages of melt inclusions within Dhofar 019 (1086 ± 252 Ma) and SaU 005 olivine (885 ± 66 Ma) could date entrapment of a magmatic liquid during early olivine crystallization, or reflect unrecognized excess ⁴⁰Ar components. The youngest ⁴⁰Ar‐³⁹Ar age of Shergotty separates (maskelynite) is ?370 Ma, that of Zagami is ?200 Ma. The ⁴⁰Ar‐³⁹Ar chronology of Dhofar 019 and SaU 005 indicate >1 Ga ages. Apparent ages uncorrected for trapped (e.g., Martian atmosphere, mantle) argon components approach 4.5 Ga, but are not caused by inherited ⁴⁰Ar, because excess ⁴⁰Ar is supported by ³⁶Ar_trapped. Young ages obtained by ⁴⁰Ar‐³⁹Ar and other chronometers argue for primary rather than secondary events. The cosmic ray exposure ages calculated from cosmogenic argon are 15.7 ± 0.7 Ma (Dhofar 019), 1.0–1.6 Ma (SaU 005), 2.1–2.5 Ma (Shergotty) and 2.2–3.0 Ma (Zagami).     

Opal‐A in the Nakhla meteorite: A tracer of ephemeral liquid water in the Amazonian crust of Mars

The nakhlite meteorites are clinopyroxenites that are derived from a ~1300 million year old sill or lava flow on Mars. Most members of the group contain veins of iddingsite whose main component is a fine‐grained and hydrous Fe‐ and Mg‐rich silicate. Siderite is present in the majority of veins, where it straddles or cross‐cuts the Fe‐Mg silicate. This carbonate also contains patches of ferric (oxy)hydroxide. Despite 40 years of investigation, the mineralogy and origins of the Fe‐Mg silicate is poorly understood, as is the paragenesis of the iddingsite veins. Nanometer‐scale analysis of Fe‐Mg silicate in the Nakhla meteorite by electron and X‐ray imaging and spectroscopy reveals that its principal constituents are nanoparticles of opal‐A. This hydrous and amorphous phase precipitated from acidic solutions that had become supersaturated with respect to silica by dissolution of olivine. Each opal‐A nanoparticle is enclosed within a ferrihydrite shell that formed by oxidation of iron that had also been liberated from the olivine. Siderite crystallized subsequently and from solutions that were alkaline and reducing, and replaced both the nanoparticles and olivine. The fluids that formed both the opal‐A/ferrihydrite and the siderite were sourced from one or more reservoirs in contact with the Martian atmosphere. The last event recorded by the veins was alteration of the carbonate to a ferric (oxy)hydroxide that probably took place on Mars, although a terrestrial origin remains possible. These results support findings from orbiter‐ and rover‐based spectroscopy that opaline silica was a common product of aqueous alteration of the Martian crust.     

Martian meteorite Dhofar 019: A new shergottite

Abstract— Dhofar 019 is a new martian meteorite found in the desert of Oman. In texture, mineralogy, and major and trace element chemistry, this meteorite is classified as a basaltic shergottite. Olivine megacrysts are set within a groundmass composed of finer grained olivine, pyroxene (pigeonite and augite), and maskelynite. Minor phases are chromite‐ulvöspinel, ilmenite, silica, K‐rich feldspar, merrillite, chlorapatite, and pyrrhotite. Secondary phases of terrestrial origin include calcite, gypsum, celestite, Fe hydroxides, and smectite. Dhofar 019 is most similar to the Elephant Moraine (EETA) 79001 lithology A and Dar al Gani (DaG) 476/489 shergottites. The main features that distinguish Dhofar 019 from other shergottites are lack of orthopyroxene; lower Ni contents of olivine; the heaviest oxygen‐isotopic bulk composition; and larger compositional ranges for olivine, maskelynite, and spinel, as well as a wide range for pyroxenes. The large compositional ranges of the minerals are indicative of relatively rapid crystallization. Modeling of olivine chemical zonations yield minimum cooling rates of 0.5‐0.8 °C/h. Spinel chemistry suggests that crystallization took place under one of the most reduced conditions for martian meteorites, at an fO₂ 3 log units below the quartz‐fayalite‐magnetite (QFM) buffer. The olivine megacrysts are heterogeneously distributed in the rock. Crystal size distribution analysis suggests that they constitute a population formed under steady‐state conditions of nucleation and growth, although a few grains may be cumulates. The parent melt is thought to have been derived from partial melting of a light rare earth element‐ and platinum group element‐depleted mantle source. Shergottites, EETA79001 lithology A, DaG 476/489, and Dhofar 019, although of different ages, comprise a particular type of martian rocks. Such rocks could have formed from chemically similar source(s) and parent melt(s), with their bulk compositions affected by olivine accumulation.     

Type 1 aqueous alteration in CM carbonaceous chondrites: Implications for the evolution of water‐rich asteroids

The CM carbonaceous chondrite meteorites experienced aqueous alteration in the early solar system. They range from mildly altered type 2 to almost completely hydrated type 1 chondrites, and offer a record of geochemical conditions on water‐rich asteroids. We show that CM1 chondrites contain abundant (84–91 vol%) phyllosilicate, plus olivine (4–8 vol%), magnetite (2–3 vol%), Fe‐sulfide (<5 vol%), and calcite (<2 vol%). The CM1/2 chondrites contain phyllosilicate (71–88 vol%), olivine (4–20 vol%), enstatite (2–6 vol%), magnetite (2–3 vol%), Fe‐sulfides (1–2 vol%), and calcite (~1 vol%). As aqueous alteration progressed, the abundance of Mg‐serpentine and magnetite in the CM chondrites increased. In contrast, calcite abundances in the CM1/2 and CM1 chondrites are often depleted relative to the CM2s. The modal data support the model, whereby metal and Fe‐rich matrix were the first components to be altered on the CM parent body(ies), before further hydration attacked the coarser Mg‐rich silicates found in chondrules and fragments. Based on the absence of tochilinite, we suggest that CM1 chondrites experienced increased alteration due to elevated temperatures (>120 °C), although higher water/rock ratios may also have played a role. The modal data provide constraints for interpreting the composition of asteroids and the mineralogy of samples returned from these bodies. We predict that “CM1‐like” asteroids, as has been proposed for Bennu—target for the OSIRIS‐REx mission—will have a high abundance of Mg‐rich phyllosilicates and Fe‐oxides, but be depleted in calcite.     

Replacement of glass in the Nakhla meteorite by berthierine: Implications for understanding the origins of aluminum‐rich phyllosilicates on Mars

A scanning and transmission electron microscope study of aluminosilicate glasses within melt inclusions from the Martian meteorite Nakhla shows that they have been replaced by berthierine, an aluminum‐iron serpentine mineral. This alteration reaction was mediated by liquid water that gained access to the glasses along fractures within enclosing augite and olivine grains. Water/rock ratios were low, and the aqueous solutions were circumneutral and reducing. They introduced magnesium and iron that were sourced from the dissolution of olivine, and exported alkalis. Berthierine was identified using X‐ray microanalysis and electron diffraction. It is restricted in its occurrence to parts of the melt inclusions that were formerly glass, thus showing that under the ambient physico‐chemical conditions, the mobility of aluminum and silicon were low. This discovery of serpentine adds to the suite of postmagmatic hydrous silicates in Nakhla that include saponite and opal‐A. Such a variety of secondary silicates indicates that during aqueous alteration compositionally distinct microenvironments developed on sub‐millimeter length scales. The scarcity of berthierine in Nakhla is consistent with results from orbital remote sensing of the Martian crust showing very low abundances of aluminum‐rich phyllosilicates.     

The survivability of phyllosilicates and carbonates impacting Stardust Al foils: Facilitating the search for cometary water

Comet 81P/Wild 2 samples returned by NASA's Stardust mission provide an unequalled opportunity to study the contents of, and hence conditions and processes operating on, comets. They can potentially validate contentious interpretations of cometary infrared spectra and in situ mass spectrometry data: specifically the identification of phyllosilicates and carbonates. However, Wild 2 dust was collected via impact into capture media at ~6 km s^?1, leading to uncertainty as to whether these minerals were captured intact, and, if subjected to alteration, whether they remain recognizable. We simulated Stardust Al foil capture conditions using a two‐stage light‐gas gun, and directly compared transmission electron microscope analyses of pre‐ and postimpact samples to investigate survivability of lizardite and cronstedtite (phyllosilicates) and calcite (carbonate). We find the phyllosilicates do not survive impact as intact crystalline materials but as moderately to highly vesiculated amorphous residues lining resultant impact craters, whose bulk cation to Si ratios remain close to that of the impacting grain. Closer inspection reveals variation in these elements on a submicron scale, where impact‐induced melting accompanied by reducing conditions (due to the production of oxygen scavenging molten Al from the target foils) has resulted in the production of native silicon and Fe‐ and Fe‐Si‐rich phases. In contrast, large areas of crystalline calcite are preserved within the calcite residue, with smaller regions of vesiculated, Al‐bearing calcic glass. Unambiguous identification of calcite impactors on Stardust Al foil is therefore possible, while phyllosilicate impactors may be inferred from vesiculated residues with appropriate bulk cation to Si ratios. Finally, we demonstrate that the characteristic textures and elemental distributions identifying phyllosilicates and carbonates by transmission electron microscopy can also be observed by state‐of‐the‐art scanning electron microscopy providing rapid, nondestructive initial mineral identifications in Stardust residues.     

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.     

Petrography of refractory inclusions in CM2.6 QUE 97990 and the origin of melilite‐free spinel inclusions in CM chondrites

Abstract— Queen Alexandra Range (QUE) 97990 (CM2.6) is among the least‐altered CM chondrites known. It contains 1.8 vol% refractory inclusions; 40 were studied from a single thin section. Inclusion varieties include simple, banded and nodular structures as well as simple and complex distended objects. The inclusions range in mean size from 30 to 530 μm and average 130 ± 90 μm. Many inclusions contain 25 ± 15 vol% phyllosilicate (predominantly Mg‐Fe serpentine); several contain small grains of perovskite. In addition to phyllosilicate, the most abundant inclusions in QUE 97990 consist mainly of spinel‐pyroxene (35%), followed by spinel (20%), spinel‐pyroxene‐olivine (18%), pyroxene (12%), pyroxene‐olivine (8%) and hibonite ± spinel (8%). Four pyroxene phases occur: diopside, Al‐rich diopside (with ≥ 8.0 wt% Al₂O₃), Al‐Ti diopside (i.e., fassaite), and (in two inclusions) enstatite. No inclusions contain melilite. Aqueous alteration of refractory inclusions transforms some phases (particularly melilite) into phyllosilicate; some inclusions broke apart during alteration. Melilite‐free, phyllosilicate‐bearing, spinel inclusions probably formed from pristine, phyllosilicate‐free inclusions containing both melilite and spinel. Sixty‐five percent of the refractory inclusions in QUE 97990 appear to be largely intact; the major exception is the group of spinel inclusions, all of which are fragments. Whereas QUE 97990 contains about 50 largely intact refractory inclusions/cm², estimates from literature data imply that more‐altered CM chondrites have lower modal abundances (and lower number densities) of refractory inclusions: Mighei (CM ? 2.3) contains roughly 0.3–0.6 vol% inclusions (?10 largely intact inclusions/cm²); Cold Bokkeveld (CM2.2) contains ?0.01 vol% inclusions (on the order of 6 largely intact inclusions/cm²).     

“New” lunar meteorites: Impact melt and regolith breccias and large‐scale heterogeneities of the upper lunar crust

Abstract— We have analyzed nine highland lunar meteorites (lunaites) using mainly INAA. Several of these rocks are difficult to classify. Dhofar 081 is basically a fragmental breccia, but much of its groundmass features a glassy‐fluidized texture that is indicative of localized shock melting. Also, much of the matrix glass is swirly‐brown, suggesting a possible regolith derivation. We interpret Dar al Gani (DaG) 400 as an extremely immature regolith breccia consisting mainly of impact‐melt breccia clasts; we interpret Dhofar 026 as an unusually complex anorthositic impact‐melt breccia with scattered ovoid globules that formed as clasts of mafic, subophitic impact melt. The presence of mafic crystalline globules in a lunar material, even one so clearly impact‐heated, suggests that it may have originated as a regolith. Our new data and a synthesis of literature data suggest a contrast in Al₂O₃‐incompatible element systematics between impact melts from the central nearside highlands, where Apollo sampling occurred, and those from the general highland surface of the Moon. Impact melts from the general highland surface tend to have systematically lower incompatible element concentration at any given Al₂O₃ concentration than those from Apollo 16. In the case of Dhofar 026, both the bulk rock and a comparatively Al‐poor composition (14 wt% Al₂O₃, 7 μg/g Sm) extrapolated for the globules, manifest incompatible element contents well below the Apollo 16 trend. Impact melts from Luna 20 (57°E) distribute more along the general highland trend than along the Apollo 16 trend. Siderophile elements also show a distinctive composition for Apollo 16 impact melts: Ni/Ir averaging ?1.8x chondritic. In contrast, lunaite impact‐melt breccias have consistently chondritic Ni/Ir. Impact melts from Luna 20 and other Apollo sites show average Ni/Ir almost as high as those from Apollo 16. The prevalence of this distinctive Ni/Ir ratio at such widely separated nearside sites suggests that debris from one extraordinarily large impact may dominate the megaregolith siderophile component of a nearside region 2300 km or more across. Highland polymict breccia lunaites and other KREEP‐poor highland regolith samples manifest a strong anticorrelation between Al₂O₃ and mg. The magnesian component probably represents the chemical signature of the Mg‐suite of pristine nonmare rocks in its most “pure” form, unaltered by the major KREEP‐assimilation that is so common among Apollo Mg‐suite samples. The average composition of the ferroan anorthositic component is now well constrained at Al₂O₃ ?29–30 wt% (implying about 17–19 wt% modal mafic silicates), in good agreement with the composition predicted for flotation crust over a “ferroan” magma ocean (Warren 1990).     

Phyllosilicates in the matrix of the unique carbonaceous chondrite Lewis Cliff 85332 and possible implications for the aqueous alteration of CI chondrites

Abstract— The fine-grained matrix of the unique, unequilibrated carbonaceous chondrite Lewis Cliff (LEW) 85332 has been studied by scanning electron microscopy (SEM), electron probe microanalysis (EPMA) and transmission electron microscopy (TEM). Compositionally, LEW 85332 has a matrix that is more Fe-rich than typical CI chondrites but has elemental abundance ratios that appear to be closer to CI matrices than to CM or CR chondrites. The mineralogy of the matrix is dominated by phyllosilicate phases that are predominantly interlayered Fe-rich serpentine/saponite; anhydrous silicate phases such as olivine and pyroxene are rare. Minor magnetite, troilite and ferrihydrite also occur associated with the phyllosilicates. Despite the high degree of weathering in LEW 85332, the phyllosilicates appear to have an extraterrestrial origin, but the highly variable Mg/Fe ratios of saponite may be the result of partial terrestrial oxidation of Fe-rich saponite to a more Mg-rich saponite and ferrihydrite. Alternatively, some of the ferrihydrite may have formed as a result of terrestrial weathering of Fe-Ni metal. The compositional and mineralogical data suggest that the matrix of LEW 85332 may represent a very early stage in the type of aqueous alteration experienced by the CI chondrites, although it is improbable that LEW 85332 was a precursor to the CI chondrites because of its high abundance of chondrules. The absence of carbonates, the high-Fe content of the matrix and phyllosilicate phases and relatively low abundance of magnetite all indicate that the degree of oxidation and leaching of LEW 85332 matrix was significantly less than that experienced by the CI chondrites. The absence of clear evidence for alteration of chondrules suggests that either the formation of the hydrous phases in the matrix occurred prior to accretion or that alteration occurred on a parent body and involved limited amounts of fluid, such that the reactions took place preferentially and exclusively within the fine-grained (anhydrous?) matrix materials.     

The petrography,mineralogy and origins of calcium sulphate within the Cold Bokkeveld CM carbonaceous chondrite

Abstract— A detailed scanning and transmission electron microscopy study of Cold Bokkeveld has shown that calcium sulphate is widespread, occluding ～30 μm wide matrix-cutting fractures in addition to μm-sized veins and irregular dissolution pores within calcitized chondrules, matrix calcite grains and Ca- and Al-rich inclusions (CAI). The majority of calcium sulphate crystals have fibrous habits, especially those which have grown within straight-sided fractures and veins. Mineralogically, the calcium sulphate is composed of a fine-scale mixture of hemihydrate and anhydrite which have probably formed by the dehydration of primary gypsum during sample preparation. In all contexts, calcium sulphate precipitation was the last identifiable diagenetic event in the pre-terrestrial history of Cold Bokkeveld and followed pervasive aqueous alteration of the meteorite matrix to phyllosilicates. The fibrous fracture- and vein-filling calcium sulphates are morphologically similar to a terrestrial form of gypsum termed “satinspar” and so may have formed in a similar manner by precipitation from supersaturated aqueous solutions during fracture and vein dilation. The aqueous solutions were most probably generated by melting of water ice due to internal heating and/or post-accretional impact heating of the parent body. Although impact-produced fractures and veins may have provided conduits for fluid advection, the dissolution of calcite, alteration of metal sulphides and precipitation of gypsum probably took place when aqueous solutions were more-or-less static. Despite their similarity to late-stage mineralized fractures in CI meteorites, the calcium sulphate-filled fractures in Cold Bokkeveld probably do not have any significance regarding a shared CM-CI parent body.     

Linking mineralogy and spectroscopy of highly aqueously altered CM and CI carbonaceous chondrites in preparation for primitive asteroid sample return

The highly hydrated, petrologic type 1 CM and CI carbonaceous chondrites likely derived from primitive, water‐rich asteroids, two of which are the targets for JAXA's Hayabusa2 and NASA's OSIRIS‐REx missions. We have collected visible and near‐infrared (VNIR) and mid infrared (MIR) reflectance spectra from well‐characterized CM1/2, CM1, and CI1 chondrites and identified trends related to their mineralogy and degree of secondary processing. The spectral slope between 0.65 and 1.05 μm decreases with increasing total phyllosilicate abundance and increasing magnetite abundance, both of which are associated with more extensive aqueous alteration. Furthermore, features at ~3 μm shift from centers near 2.80 μm in the intermediately altered CM1/2 chondrites to near 2.73 μm in the highly altered CM1 chondrites. The Christiansen features (CF) and the transparency features shift to shorter wavelengths as the phyllosilicate composition of the meteorites becomes more Mg‐rich, which occurs as aqueous alteration proceeds. Spectra also show a feature near 6 μm, which is related to the presence of phyllosilicates, but is not a reliable parameter for estimating the degree of aqueous alteration. The observed trends can be used to estimate the surface mineralogy and the degree of aqueous alteration in remote observations of asteroids. For example, (1) Ceres has a sharp feature near 2.72 μm, which is similar in both position and shape to the same feature in the spectra of the highly altered CM1 MIL 05137, suggesting abundant Mg‐rich phyllosilicates on the surface. Notably, both OSIRIS‐REx and Hayabusa2 have onboard instruments which cover the VNIR and MIR wavelength ranges, so the results presented here will help in corroborating initial results from Bennu and Ryugu.     

Aqueous alteration of chondrules from the Murchison CM carbonaceous chondrite: Replacement,pore filling,and the genesis of polyhedral serpentine

Forsterite and clinoenstatite in type IAB chondrules from the Murchison CM carbonaceous chondrite have been partially serpentinized, and the mechanisms of their alteration reveal crystallographic and microstructural controls on the reaction of silicate minerals with parent body aqueous solutions. Grains of forsterite were altered in two stages. Narrow veinlets of Fe‐rich serpentine formed first and by the filling of sheet pores. Most of these pores were oriented parallel to (010) and (001) and had been produced by earlier fracturing and/or congruent dissolution. In the second stage, the subset of veinlets that were oriented parallel to (001) was widened accompanying the replacement of forsterite by Mg‐Fe serpentine. This reaction proceeded most rapidly parallel to [001], and crystallographic controls on the trajectory of retreating vein walls created fine‐scale serrations. Murchison clinoenstatite grains have a skeletal appearance due to the presence of abundant veinlets and patches of phyllosilicate. Two alteration stages can again be recognized, with initial water–mineral interaction producing tochilinite‐rich veinlets by the filling of (001)‐parallel contraction cracks. Pores then formed by congruent dissolution that was guided principally by orthopyroxene lamellae, and they were subsequently filled by submicrometer‐sized crystals of polyhedral serpentine. This finding that Murchison forsterite and clinoenstatite grains have been altered demonstrates that aqueous processing of magnesium silicate minerals started much earlier in CM parent body history than previously believed. Our results also show that the occurrence of polyhedral serpentine can be used to locate former pore spaces within the parent body.     

Lead and Mg isotopic age constraints on the evolution of the HED parent body

The large collection of howardite‐eucrite‐diogenite (HED) meteorites allows us to study the initial magmatic differentiation of a planetesimal. We report Pb‐Pb ages of the unequilibrated North West Africa (NWA) 4215 and Dhofar 700 diogenite meteorites and their mass‐independent ²⁶Mg isotope compositions (²⁶Mg*) to better understand the timing of differentiation and crystallization of their source reservoir(s). NWA 4215 defines a Pb‐Pb age of 4484.5 ± 7.9 Myr and has a ²⁶Mg* excess of +2.3 ± 1.6 ppm whereas Dhofar 700 has a Pb‐Pb age of 4546.4 ± 4.7 Myr and a ²⁶Mg* excess of +25.5 ± 1.9 ppm. We interpret the young age of NWA 4215 as a thermal overprint, but the age of Dhofar 700 is interpreted to represent a primary crystallization age. Combining our new data with published Mg isotope and trace element data suggests that approximately half of the diogenites for which such data are available crystallized within the first 1–2 Myr of our solar system, consistent with a short‐lived, early‐formed magma ocean undergoing convective cooling. The other half of the diogenites, including both NWA 4215 and Dhofar 700, are best explained by their crystallization in slowly cooled isolated magma chambers lasting over at least ~20 Myr.     

Amorphous silicates as a record of solar nebular and parent body processes—A transmission electron microscope study of fine‐grained rims and matrix in three Antarctic CR chondrites

Renazzo‐type (CR) carbonaceous chondrites belong to one of the most pristine meteorite groups containing various early solar system components such as matrix and fine‐grained rims (FGRs), whose formation mechanisms are still debated. Here, we have investigated FGRs of three Antarctic CR chondrites (GRA 95229, MIL 07525, and EET 92161) by electron microscopy techniques. We specifically focused on the abundances and chemical compositions of the amorphous silicates within the rims and matrix by analytical transmission electron microscopy. Comparison of the amorphous silicate composition to a matrix area of GRA 95229 clearly shows a compositional relationship between the matrix and the fine‐grained rim, such as similar Mg/Si and Fe/Si ratios. This relationship and the abundance of the amorphous silicates in the rims strengthen a solar nebular origin and rule out a primary formation mechanism by parent body processes such as chondrule erosion. Moreover, our chemical analyses of the amorphous silicates and their abundance indicate that the CR rims experienced progressive alteration stages. According to our analyses, the GRA 95229 sample is the least altered one based on its high modal abundance of amorphous silicates (31%) and close‐to‐chondritic Fe/Si ratios, followed by MIL 07525 and finally EET 92161 with lesser amounts of amorphous silicates (12% and 5%, respectively) and higher Fe/Si ratios. Abundances and chemical compositions of amorphous silicates within matrix and rims are therefore suitable recorders to track different alteration stages on a submicron scale within variably altered CR chondrites.     

Spinels and oxygen fugacity in olivine‐phyric and lherzolitic shergottites

Abstract— We examine the occurrences, textures, and compositional patterns of spinels in the olivine‐phyric shergottites Sayh al Uhaymir (SaU) 005, lithology A of Elephant Moraine A79001 (EET‐A), Dhofar 019, and Northwest Africa (NWA) 1110, as well as the Iherzolitic shergottite Allan Hills (ALH) A77005, in order to identify spinel‐olivine‐pyroxene assemblages for the determination of oxygen fugacity (using the oxybarometer of Wood [1991]) at several stages of crystallization. In all of these basaltic martian rocks, chromite was the earliest phase and crystallized along a trend of strict Cr‐Al variation. Spinel (chromite) crystallization was terminated by the appearance of pyroxene but resumed later with the appearance of ulvöspinel. Ulvöspinel formed overgrowths on early chromites (except those shielded as inclusions in olivine or pyroxene), retaining the evidence of the spinel stability gap in the form of a sharp core/rim boundary (except in ALH A77005, where subsolidus reequilibration diffused this boundary). Secondary effects seen in chromites include reaction with melt before ulvöspinel overgrowth, reaction with melt inclusions, reaction with olivine hosts (in ALH A77005), and exsolution of ulvöspinel or ilmenite. All chromites experienced subsolidus Fe/Mg reequilibration. Spinel‐olivine‐pyroxene assemblages representing the earliest stages of crystallization in each rock essentially consist of the highest‐Cr#, lowest‐fe# chromites not showing secondary effects plus the most magnesian olivine and equilibrium low‐Ca pyroxene. Assemblages representing the onset of ulvöspinel crystallization consist of the lowest‐Ti ulvöspinel, the most magnesian olivine in which ulvöspinel occurs as inclusions, and equilibrium low‐Ca pyroxene. The results show that, for early crystallization conditions, oxygen fugacity (fO₂) increases from SaU 005 and Dhofar 019 (?QFM ‐3.8), to EET‐A (QFM ‐2.8) and ALH A77005 (QFM ‐2.6), to NWA 1110 (QFM ‐1.7). Estimates for later conditions indicate that in SaU 005 and Dhofar 019 oxidation state did not change during crystallization. In EET‐A, there was an increase in fO₂ that may have been due to mixing of reduced material with a more oxidized magma. In NWA 1110, there was a dramatic increase, indicating a non‐buffered system, possibly related to its high oxidation state. Differences in fO₂ among shergottites are not primarily due to igneous fractionation but, rather, to derivation from (and possibly mixing of) different reservoirs.