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© 2015 by Walter de Gruyter. The Mars Science Laboratory (MSL) rover Curiosity has documented a section of fluvio-lacustrine strata at Yellowknife Bay (YKB), an embayment on the floor of Gale crater, approximately 500 m east of the Bradbury landing site. X-ray diffraction (XRD) data and evolved gas analysis (EGA) data from the CheMin and SAM instruments show that two powdered mudstone samples (named John Klein and Cumberland) drilled from the Sheepbed member of this succession contain up to ∼20 wt% clay minerals. A trioctahedral smectite, likely a ferrian saponite, is the only clay mineral phase detected in these samples. Smectites of the two samples exhibit different 001 spacing under the low partial pressures of H2O inside the CheMin instrument (relative humidity 2+ in olivine to Fe3+ in magnetite, and perhaps in smectites provided a potential energy source for organisms.

Among the lunar samples that were returned by the Apollo missions are many cumulate plutonic rocks with high Mg# [molar Mg/(Mg+Fe) in %] and abundances of KREEP elements (potassium, rare earth elements, phosphorus, U, Th, etc.) that imply KREEP-rich parental magmas. These rocks, collectively called the magnesian suite, are nearly absent from sampling sites distant from Imbrium basin ejecta, including those of lunar highlands meteorites. This absence has significant implications for the early differentiation of the Moon and its distribution of heat-producing elements (K, Th, U). Here, we analyze a unique fragment of basalt with the mineralogy and mineral chemistry of a magnesian suite rock, in the lunar highlands meteorite Allan Hills (ALH) A81005. In thin section, the fragment is 700 × 300 μm, and has a sub-ophitic texture with olivine phenocrysts, euhedral plagioclase grains (An97-70),and interstitial pyroxenes. Its minerals are chemically equilibrated. Olivine has Fe/Mn ~ 70 (consistent with a lunar origin), and Mg# ~80, which is consistent with rocks of the magnesian suite and far higher than in mare basalts. It has a rich suite of minor minerals: fluorapatite, ilmenite, Zr-armalcolite, chromite, troilite, silica, and Fe metal (Ni = 3.8%, Co = 0.17%). The metal is comparable to that in chondrite meteorites, which suggests that the fragment is from an impact melt. The fragment itself is not a piece of magnesian suite rock (which are plutonic), but its mineralogy and mineral chemistry suggest that its protolith (which was melted by impact) was related to the magnesian suite. However, the fragment’s mineral chemistry and minor minerals are not identical to those of known magnesian suite rocks, suggesting that the suite may be more varied than apparent in the Apollo samples. Although ALHA81005 is from the lunar highlands (and likely from the farside), Clast U need not have formed in the highlands. It could have formed in an impact melt pool on the nearside and been transported by meteoroid impact. Lunar highlands meteorites should be searched for rock fragments related to the magnesian-suite rocks, but the fragments are rare and may have mineral compositions similar to some meteoritic (impactor) materials.

Ferrian saponite from the eastern Santa Monica Mountain, near Griffith Park (Los Angeles, California), was investigated as a mineralogical analog to smectites discovered on Mars by the CheMin X-ray diffraction instrument onboard the Mars Science Laboratory (MSL) rover. The martian clay minerals occur in sediment of basaltic composition and have 02 l diffraction bands peaking at 4.59 A, consistent with tri-octahedral smectites. The Griffith saponite occurs in basalts as pseudomorphs after olivine and mesostasis glass and as fillings of vesicles and cracks and has 02 l diffraction bands at that same position. We obtained chemical compositions (by electron microprobe), X-ray diffraction patterns with a lab version of the CheMin instrument, Mossbauer spectra, and visible and near-IR reflectance (VNIR) spectra on several samples from that locality. The Griffith saponite is magnesian, Mg/(Mg+∑Fe) = 65–70%, lacks tetrahedral Fe 3+ and octahedral Al 3+ , and has Fe 3+ /∑Fe from 64 to 93%. Its chemical composition is consistent with a fully tri-octahedral smectite, but the abundance of Fe 3+ gives a nominal excess charge of +1 to +2 per formula unit. The excess charge is likely compensated by substitution of O 2− for OH − , causing distortion of octahedral sites as inferred from Mossbauer spectra. We hypothesize that the Griffith saponite was initially deposited with all its iron as Fe 2+ and was oxidized later. X-ray diffraction shows a sharp 001 peak at 15 A, 00 l peaks, and a 02 l diffraction band at the same position (4.59 A) and shape as those of the martian samples, indicating that the martian saponite is not fully oxidized. VNIR spectra of the Griffith saponite show distinct absorptions at 1.40, 1.90, 2.30–2.32, and 2.40 μm, arising from H 2 O and hydroxyl groups in various settings. The position of the ~2.31 μm spectral feature varies systematically with the redox state of the octahedrally coordinated Fe. This correlation may permit surface oxidation state to be inferred (in some cases) from VNIR spectra of Mars obtained from orbit, and, in any case, ferrian saponite is a viable assignment for spectral detections in the range 2.30–2.32 μm.

Mg-Al spinel is rare in lunar rocks (Apollo and meteorite collections), and occurs mostly in troctolites and troctolitic cataclastites. Recently, a new lunar lithology, rich in spinel and plagioclase, and lacking abundant olivine and pyroxene, was recognized in visible to near-infrared (VNIR) reflectance spectra by the Moon Mineralogy Mapper (M3) instrument on the Chandrayaan-1 spacecraft at the Moscoviense basin. These outcrop-scale areas are inferred to contain 20–30% Mg-Al spinel. Possible explanations for the petrogenesis of spinel-bearing and spinel-rich lithology(s) range from low-pressure near-surface crystallization to a deep-seated origin in the lower lunar crust or upper mantle. Here, we describe 1-bar crystallization experiments conducted on rock compositions rich in olivine and plagioclase that crystallize spinel. This would be equivalent to impact-melting, which is moderately common among lunar plutonic rocks and granulites. To explore possible precursor materials and the maximum amount of spinel that could be crystallized, a lunar troctolitic composition similar to Apollo pink spinel troctolite 65785, and a composition similar to ALHA81005 as analog to the source region of this meteorite have been chosen. The crystallization experiments on the composition of AHLA 81005 did not yield any spinel; experiments on the composition similar to Apollo 65785 crystallized a maximum of ~8 wt% spinel, much less than the suggested 20–30% spinel of the new lithology detected by M3. However, our VNIR spectral reflectance analyses of the experimental run products indicate that the spinel composition of the experimental run products not only appears to be similar to the composition of the spinel lithology detected by M3 (characteristics of the spinel absorption), but also that the modal abundances of coexisting phases (e.g., mafic glass) influence the spectral reflectance properties. Thus, the spinel-rich deposits detected by M3 might not be as spinel-rich as previously thought and could contain as little as 4–5 wt% spinel. However, the effect of space weathering on spinel is unknown and could significantly weaken its 2 μm absorptions. If this occurs, weathered lunar rocks could contain more spinel than a comparison with our unweathered experimental charges would suggest.

A suite of Hawaiian basalts that were variably altered in the presence of SO 2 -rich gases during the current summit eruptive episode at Halemaumau crater, Kilauea, were studied to determine their alteration phase assemblage and reactive pathways using electron microscopy, Mossbauer spectroscopy, and X-ray diffraction. The alteration conditions represent an acid fog environment. Alteration rinds on the basalts vary in thickness from tens of micrometers to the entirety of the rock and are composed of amorphous silica rims (85–95 wt% SiO 2 ) overlain by sulfates. Sulfate mineralogy consisted of gypsum, anhydrite, and natroalunite-jarosite. No phyllosilicates were observed in any alteration assemblages. Phenocrysts and glass were both observed to be extensively reacted during alteration. The Halemaumau samples may provide good analogs for basalt alteration on other rocky planetary bodies, i.e., Mars, Venus, and Mercury, where S is ubiquitous and low fluid/rock ratios are common.

Trace element mineral-magma partitioning models are important in understanding processes by which basaltic magmas are generated. Partitioning models for nickel have been extrapolated from their original applicability for the Earth’s mantle to compositions appropriate for other planets, notably the Moon and Mars. Before partitioning models can be extrapolated to explain nickel concentrations in planetary rocks, these models need to be verified thermodynamically and experimentally using planetary basaltic compositions. Experiments conducted in this study on the Martian Gusev Adirondack-class basalt, Humphrey, with 1 wt% nickel in the magma have shown that Ni affects its liquidus phase relations. By stabilizing olivine to higher temperatures, Ni increases the liquidus temperature. These experiments have shown that the Hart and Davis (1978) model based on iron-free systems cannot be extrapolated to planetary, iron-rich, basaltic systems. This work verifies the independence of the Jones (1984, 1995) and Beattie et al. (1991) models from temperature and pressure effects and suggests extrapolation to planetary compositions is justified but needs further verification. Furthermore, these experiments support the Longhi and Walker (2006) hypothesis that at high temperature nickel may be incompatible.

Grains ofrhonite have been discovered in magmatic inclusions in augite grains of the lunar regolith from Mare Crisium, returned to Earth by the Russian Luna 24 spacecraft. These rhonite grains are up to 8 μm long, pleochroic from tan to dark brown, and associated with ulvospinel and silica-rich glass. Electron microprobe analysis gives a composition near end-member ferroan rhonite: (Ca 1.9 Mn 0.0 Na 0.1 ) (Fe 2+ 4.5 Mg 0.1 Al 0.3 Cr 0.0 )Ti 1.0 (Si 4 . 0 Al 2.0 )O 20 . The Raman spectrum of these grains is like those of terrestrial rhonites, and distinct from titanian amphiboles. Compositionally, rhonite plus silica plus water or halogens (F, Cl) is equivalent to titanian amphibole plus pyroxene, so the presence ofrhonite in lunar basaltic rock is consistent with the known low abundance of volatiles in the Moon. When calibrated, mineral reactions involving rhonite and titanian amphibole may provide quantitative constraints on fugacities of water, F, and Cl in basaltic magmas from the Moon and other planetary bodies.

The mineral proportions of rocks or rock fragments in thin section can be retrieved from electron microprobe element X-ray maps using multispectral image classification software. However, different image classification algorithms can yield different inferred mineral proportions and thus deviate from the true modal mineralogy. Several image classification algorithms (implemented in the programs Erdas Imagine and Multispec) were evaluated on a very simple rock—a fragment of noritic anorthositic granulite in a thin section of lunar meteorite ALHA81005. This fragment contains only plagioclase, orthopyroxene, olivine, clinopyroxene, and chromite; each has a constant composition across the fragment. The true (reference) mineral proportions of the fragment were measured manually from the X-ray maps. Results of classification algorithms varied widely in accuracy—from ~1% to more than 15% misclassified pixels compared to the reference. The best match for this fragment comes from an unsupervised classification using the ISODATA algorithm (most minerals were placed into multiple classes, which had to be manually recombined), and the second closest match was a supervised classification using a Euclidean distance classifier. The results of supervised classifications depend strongly on the user’s selection of training areas, and small errors in defined training areas (e.g., a training area for one phase contains an inclusion of another) can produce large errors. The most common source of misclassification is “mixed pixels”—those that contain signatures from multiple phases. In this example, pixels including both plagioclase and olivine tend to be classified as clinopyroxene. Thus, mineral proportions calculated from classification of X-ray maps must be considered critically, even for simple rocks. In more complex samples, like those with more phases or with chemically zoned phases, mineral classification of X-ray maps are likely to require care and may be difficult to validate.

Magnetite crystals produced by terrestrial magnetotactic bacterium MV-1 are elongated on a [111] crystallographic axis, in a so-called truncated hexa-Octahedral shape. This morphology has been proposed to constitute a biomarker (i.e., formed only in biogenic processes). A subpopulation of magnetite crystals associated with carbonate globules in Martian meteorite ALH84001 is reported to have this morphology, and the observation has been taken as evidence for biological activity on Mars. In this study, we present evidence for the exclusively inorganic origin of [111]-elongated magnetite crystals in ALH84001. We report three-dimensional(3-D) morphologies for approx.1000 magnetite crystals extracted from: (1) thermal decomposition products of Fe-rich carbonate produced by inorganic hydrothermal precipitation in laboratory experiments; (2) carbonate globules in Martian meteoriteeALH84001; and (3) cells of magnetotactic bacterial strain MV-1. The 3-D morphologies were derived by fitting 3-D shape models to two-dimensional bright-field transmission-electron microscope (TEAM) images obtained at a series of viewing angles. The view down the {110} axes closest to the [111] elongation axis of magnetite crystals ([111]x{110) not equal to 0) provides a 2-D projection that uniquely discriminates among the three [111]-elongated magnetite morphologies found in these samples: [111]-elongated truncated hexaoctahedron ([111]-THO), [111]-elongated cubo-octahedron ([111]-ECO), and [111]-elongated simple octahedron ([111]-ESO). All [111] -elongated morphologies are present in the three types of sample, but in different proportions. In the ALH84001 Martian meteorite and in our inorganic laboratory products, the most common [111]-elongated magnetite crystal morphology is [111]-ECO. In contrast, the most common morphology for magnetotactic bacterial strain MV-1 is [111]-THO. These results show that: (1) the morphology of [111]-elongated magnetite crystals associated with the carbonate globules in Martian meteorite ALH84001 is replicated by an inorganic process; and (2) the most common crystal morphology for biogenic (MV-1) magnetite is distinctly different from that in both ALH84001 and our inorganic laboratory products. Therefore, [111]-elongated magnetite crystals in ALH84001 do not constitute, as previously claimed, a robust biosignature and, in fact, an exclusively inorganic origin for the magnetite is fully consistent with our results. Furthermore, the inorganic synthesis method, i.e., the thermal decomposition of hydrothermally precipitated Fe-rich carbonate, is a process analogue for formation of the magnetite on Mars. Namely, precipitation of carbonate globules from carbonate-rich hydrothermal solutions followed at some later time by a thermal pulse, perhaps in association with meteoritic impact or volcanic processes on the Martian surface.

Light-lithophile-element zoning patterns in pyroxene in the Shergotty and Zagami martian basaltic meteorites have previously been presented as evidence for pre-eruptive martian water. We investigate the partitioning of Li and B in martian igneous minerals experimentally, using a composition approximating that of the Queen Alexandria Range (QUE) 94201 martian basalt in one-atmosphere gas-mixing furnaces. Partition coefficients obtained for pyroxene( D Li = 0.2, D B = 0.023), plagioclase ( D Li = 0.37, D B = 0.024), olivine ( D Li = 0.27, D B = 0.007) and merrillite ( D Li = 0.7, D B = 0.03), measured using Secondary Ion Mass Spectrometry of experimental charges, demonstrate that Li and B are incompatible in these minerals. As a test of our experimentally determined, anhydrous partition coefficients, we analyzed pyroxene in the Pasamonte eucrite, an asteroidal basalt with an anhydrous petrogenesis. Coupling of the partition coefficients with Pasamonte pyroxene analyses gives B parental melt concentrations in relative agreement with bulk rock analyses; however, Li parental melt concentrations and bulk analyses do not agree, suggestive of post-crystallization modification of Li zoning trends. Our results demonstrate that Li and B zoning patterns in pyroxene in martian basalts cannot be explained by the uptake of Li and B by co-crystallizing plagioclase, olivine, or merrillite, and suggest that the petrogeneses of Shergotty and Zagami involved something other than simple, one-atmosphere, anhydrous crystallization.

A thermochemical model of the activities of species in carbonate-rich melts would be useful in quantifying chemical equilibria between carbonatite magmas and vapors and in extrapolating liquidus equilibria to unexplored PTX. A regular-solution model of Ca-rich carbonate melts is developed here, using the fact that they are ionic liquids, and can be treated (to a first approximation) as interpenetrating regular solutions of cations and of anions. Thermochemical data on systems of alkali metal cations with carbonate and other anions are drawn from the literature; data on systems with alkaline earth (and other) cations and carbonate (and other) anions are derived here from liquidus phase equilibria. The model is validated in that all available data (at 1 kbar) are consistent with single values for the melting temperature and heat of fusion for calcite, and all liquidi are consistent with the liquids acting as regular solutions. At 1 kbar, the metastable congruent melting temperature of calcite (CaCO3) is inferred to be 1596 K, with (Delta)bar-H(sub fus)(calcite) = 31.5 +/- 1 kJ/mol. Regular solution interaction parameters (W) for Ca(2+) and alkali metal cations are in the range -3 to -12 kJ/sq mol; W for Ca(2+)-Ba(2+) is approximately -11 kJ/sq mol; W for Ca(2+)-Mg(2+) is approximately -40 kJ/sq mol, and W for Ca(2+)-La(3+) is approximately +85 kJ/sq mol. Solutions of carbonate and most anions (including OH(-), F(-), and SO4(2-)) are nearly ideal, with W between 0(ideal) and -2.5 kJ/sq mol. The interaction of carbonate and phosphate ions is strongly nonideal, which is consistent with the suggestion of carbonate-phosphate liquid immiscibility. Interaction of carbonate and sulfide ions is also nonideal and suggestive of carbonate-sulfide liquid immiscibility. Solution of H2O, for all but the most H2O-rich compositions, can be modeled as a disproportionation to hydronium (H3O(+)) and hydroxyl (OH(-)) ions with W for Ca(2+)-H3O(+) (approximately) equals 33 kJ/sq mol. The regular-solution model of carbonate melts can be applied to problems of carbonatite magma + vapor equilibria and of extrapolating liquidus equilibria to unstudied systems. Calculations on one carbonatite (the Husereau dike, Oka complex, Quebec, Canada) show that the anion solution of its magma contained an OH mole fraction of (approximately) 0.07, although the vapor in equilibrium with the magma had P(H2O) = 8.5 x P(CO2). F in carbonatite systems is calculated to be strongly partitioned into the magma (as F(-)) relative to coexisting vapor. In the Husereau carbonatite magma, the anion solution contained an F(-) mole fraction of (approximately) 6 x 10(exp -5).