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NASA NTRS2020

Mineralogy and Geochemistry of Sedimentary Rocks and Eolian Sediments in Gale Crater, Mars: A Review After Six Earth Years of Exploration with Curiosity

The Mars Science Laboratory Curiosity rover arrived at Mars in August 2012 with a primary goal of characterizing the habitability of ancient and modern environments. Curiosity was sent to Gale crater to study a sequence of ∼3.5 Ga old sedimentary rocks that, based on orbital visible and near- to short-wave infrared reflectance spectra, contain secondary minerals that suggest deposition and/or alteration in liquid water. The sedimentary sequence in the lower slopes of Mount Sharp in Gale crater preserves a dramatic shift on early Mars from a relatively warm and wet climate to a cold and dry climate, based on a transition from smectite-bearing strata to sulfate-bearing strata. The rover is equipped with instruments to examine the sedimentology and identify compositional changes in the stratigraphy. The Chemistry and Mineralogy (CheMin) instrument is one of two internal laboratories on Curiosity and includes a transmission X-ray diffractometer (XRD) and X-ray fluorescence (XRF) spectrometer. CheMin measures loose sediment samples scooped from the surface and drilled rock powders, and the XRD provides quantitative mineralogy to a detection limit of ∼1 wt.% for crystalline phases. Curiosity has traversed>20 km since landing and has primarily been exploring an ancient lake environment fed by streams and groundwater. Of the 19 drilled rock samples analyzed by CheMin as of sol 2300 (January 2019), 15 are from fluvio-lacustrine deposits that comprise the Bradbury and Murray formations. Most of these samples were drilled from units that did not have a clear mineralogical signature from orbit. Results from CheMin demonstrate an astounding diversity in the mineralogy of these rocks that signifies geochemical variations in source rocks, transportation mechanisms, and depositional and diagenetic fluids. Most detrital igneous minerals are basaltic, but the discovery in a few samples of abundant silicate minerals that usually crystallize from evolved magmas on Earth remains enigmatic. Trioctahedral smectite and magnetite at the base of the section may have formed from low-salinity pore waters with a circumneutral pH in lake sediments. A transition to dioctahedral smectite, hematite, and Ca-sulfate going up section suggests a change to more saline and oxidative aqueous conditions in the lake waters themselves and/or in diagenetic fluids. Perhaps one of the biggest mysteries revealed by CheMin is the high abundance of X-ray amorphous materials (15–73 wt.%) in all samples drilled or scooped to date. CheMin has analyzed three modern eolian sands, which have helped constrain sediment transport and mineral segregation across the active Bagnold Dune Field. Ancient eolian sandstones drilled from the Stimson formation differ from modern eolian sands in that they contain abundant magnetite but no olivine, suggesting that diagenetic processes led to the alteration of olivine to release Fe(II) and precipitate magnetite. Fracture-associated halos in the Stimson and the Murray formations are evidence for complex aqueous processes long after the streams and lakes vanished from Gale crater. The sedimentology and composition of the rocks analyzed by Curiosity demonstrate that habitable environments persisted intermittently on the surface or in the subsurface of Gale crater for perhaps more than a billion years.

E.B. Rampe↗
NASA NTRS2020

Dust and gas absorption in the High Mass X-ray Binary IGR J16318−4848

Context. With an absorption column density on the order of 10(exp 24)per sq. cm, IGR J16318-4848 is one of the most extreme cases of a highly obscured High Mass X-ray Binary. Besides the overall continuum absorption, the source spectrum exhibits a strong iron and nickel fluorescence line complex at 6.4 keV. Previous empirical modeling of these features and comparison with radiative transfer simulations raised questions about the structure and covering fraction of the absorber and the profile of the fluorescence lines. Aims. We aim at a self-consistent description of the continuum absorption, the absorption edges and the fluorescent lines to constrain properties of the absorbing material, such as ionization structure and geometry. We further investigate the effects of dust absorption on the observed spectra and the possibility of fluorescent emission from dust grains. Methods. We use XMM-Newton and NuSTAR spectra to first constrain empirically the incident continuum and fluorescence lines. Next, we use XSTAR to construct a customized photoionization model where we vary the ionization parameter, column density, and covering fraction. In a third step, we model the absorption and fluorescence in a dusty olivine absorber and employ both, a simple analytical model for the fluorescent line emission and Monte Carlo radiative transfer, spectral shapes and line fluxes that are very close to the data are generated. Results. Our empirical spectral modeling is in agreement with previous works. Our second model, the single gas absorber does not describe the observational data. In particular, irrespective of the ionization state or column density of the absorber, a much higher covering fraction than previously estimated is needed to produce the strong fluorescence lines and the large continuum absorption. A dusty, spherical absorber (modeled as consisting of olivine dust, although the nature of dust cannot be constrained) is well able to produce the observed continuum absorption and edges. Conclusions. A dense, dusty absorber in the direct vicinity of the source consisting of dust offers a consistent description of both the strong continuum absorption and the strong emission features in the X-ray spectrum of IGR J16318􀀀4848. In particular, for low optical depth of individual grains the dust will contribute significantly to the fluorescent emission, which is the case for typical densities and grain size distribution models.

Ralf Ballhausen↗
NASA NTRSDate not supplied

Mineralogy of the Greenheugh Pediment and Underlying Murray Formation from the Mars Science Laboratory CheMin Instrument

The Mars Science Laboratory Curiosity rover has been investigating a sequence of ancient fluvio-lacustrine and eolian units in Gale crater. For much of the mission, Curiosity has studied the fluvio-lacustrine deposits of the Murray formation. Curiosity has also studied the ancient eolian Stimson formation in a few locations, which unconformably overlies the Murray fm. The Stimson formation was previously studied at the Naukluft and Emerson Plateaus and recently studied at the Greenheugh pediment capping unit. The Curiosity science team also investigated the Murray formation directly underlying the pediment. Curiosity drilled the “Edinburgh” target within the pediment capping unit and the “Hutton” target in the Murray formation near the contact with the pediment and delivered these materials to the CheMin X-ray diffractometer to characterize bulk mineralogy. Edinburgh contains abundant plagioclase, pyroxene, magnetite, olivine, and X-ray amorphous materials, with 10 wt.% smectite and minor sanidine. The mineralogy of the Stimson at Greenheugh is distinct from the mineralogy of the Stimson at Naukluft and Emerson because previous Stimson targets did not contain olivine or clay minerals. This suggests sediments in the pediment may have a different source and/or different aqueous alteration history than those from Naukluft and Emerson. Hutton contains abundant plagioclase, pyroxene, magnetite, and X-ray amorphous materials, 6 wt.% smectite, and minor cristobalite, opal-CT, sanidine, hematite, fluorapatite, and anhydrite. Other Murray targets in the surrounding Glen Torridon region that are farther from the pediment contact contain ~30 wt.% smectite and lack cristobalite and opal-CT. Cristobalite and/or opal-CT are present in a few other targets elsewhere along the traverse, including the top of the nearby Vera Rubin ridge and the top of the Pahrump Hills outcrop. Stimson overlies the Pahrump Hills, and, based on projections of the pediment slope, the Stimson may have overlain Vera Rubin ridge. The proximity of the low-smectite and cristobalite- and/or opal-CT-bearing outcrops to the contact between the Murray and Stimson suggests the contact provided a conduit for diagenetic fluids that altered clay minerals and formed crystalline and paracrystalline silica.

E. B. Rampe↗
NASA NTRSDate not supplied

Carbonatite metasomatism and water systematics of peridotite xenoliths from Lanzarote, Canaries

Water in Earth’s mantle, present as structural hydrogen in minerals, influences large scale processes like mantle deformation, plate tectonics, and melting. To better understand the processes controlling water concentrations in the Earth’s upper mantle, we analyzed hydrogen (calculated as ppm wt. H2O), major, and trace element concentrations in minerals from harzburgite xenoliths of Lanzarote, Canaries. Previous studies have shown evidence for carbonatite metasomatism in Lanzarote peridotites and carbonatite magmas have erupted in the Canaries. Thus, the Canaries offer a rare opportunity to examine the role of metasomatism and carbonatitic magmas in rehydrating the oceanic lithosphere during plume-lithosphere interaction. Major element data (obtained by electron microprobe) show that these peridotites are highly depleted compared to the primitive mantle, with a high average olivine Mg# (91.1 ± 0.5), low bulk rock Al2O3 (0.4 to 1.4 wt.%), high spinel Cr# (40 to 72) from which high degrees of melting were estimated (15 to 21%). There is no evidence of hydrous phases (e.g., amphibole and phlogopite), thus water in these peridotites is thought to be stored only in nominally anhydrous minerals and melt inclusions. Water concentrations (determined by polarized FTIR spectroscopy), in the peridotite silicate minerals range from 2.7 to 13 ppm in olivine, 42 to 265 ppm in orthopyroxene (Opx), and 76 to 470 ppm in clinopyroxene (Cpx). Reconstructed bulk rock water concentrations range from 5 to 115 ppm, generally lower than estimates for the depleted mantle (DM, 50-200 ppm). Trace element data in Opx, Cpx, and bulk rock frequently show high La/Yb ratios (up to 12.2, 71.5, 45.2; respectively) and strong negative Zr, Hf, and Ti anomalies relative to REE, consistent with carbonatite metasomatism. With decreasing Ti/Eucpx ratios, a proxy for carbonatite metasomatism, the bulk water increases. The calculated trace element compositions of melts in equilibrium with Cpx strongly resemble those of carbonatites. However, the bulk rock water concentrations are two magnitudes lower than what is expected by equilibrium with a carbonatite melt. Evidently, carbonatitic metasomatism did rehydrate of the Lanzarote mantle lithosphere but less so than expected, implying lower partitioning of H in the presence of CO2than a silicate melt.

S. Patterson↗
NASA NTRS2021

Petrology, Geochemistry, and Pairing of Lunar Meteorites from the Dominion Range

Introduction: During the 2018-2019 Antarctic Search for Meteorites (ANSMET) field season in the Dominion Range (DOM), 7 lunar meteorite stones were collected: DOM 18242 (15.1 g), DOM 18244 (25.1 g), DOM 18262 (6.8 g), DOM 18509 (16.5 g), DOM 18543 (13.6 g), DOM 18666 (45.9 g), and DOM 18678 (11.6 g). Here we present the initial results of electron microprobe and X-ray computed tomography (XCT) studies of these stones and look at the details of their petrography and mineral chemistry, as well as investigate possible pairing relationships, both with each other and with previously described lunar meteorites. Most of the work presented here is on the DOM 18509, 18543, and 18678 stones; subsamples of the other stones are in hand and similar measurements will be made on them by the time of the meeting. Methods: Textures in DOM 18509, DOM 18543, and DOM 18678 were characterized in 2D by optical microscopy, backscattered electron (BSE) imaging and elemental X-ray images on thin sections, as well as in 3D by X-ray computed tomography (XCT) on sample chips. Mineral compositions were assessed through a combination of wavelength dispersive spectroscopy EPMA (electron probe microanalysis) and x-ray mapping on the JEOL 8530 at NASA JSC. The bulk composition of all three meteorites was determined based on analyses of the fusion crust glass. XCT analyses were done on the Nikon XTH 320 at NASA JSC. ICP-MS data on bulk rock subsamples for each meteorite will be carried out in the near future. Results: The stones are all similar in macroscopic appearance with a dark aphanitic matrix hosting a variety of small- to medium-sized angular mineral and lithic fragments (often light colored in nature) [1,2]. Based on EPMA and XCT results, the three meteorites are polymict regolith breccias comprised of mineral, glass, and lithic clasts ranging up to several mm in length. Melt veins run through all three meteorite samples. Mineral clasts in all 3 stones are dominated by pyroxene and plagioclase (An82-96), with minor amounts of SiO2, olivine (Fo1-52), and FeTi-oxides. Pyroxene grains are mostly Fe-rich pigeonite and augite, and larger clasts are normally zoned and have fine exsolution lamellae. The lithic clasts in all stones consists of: (1) basalt clasts that contain zoned pyroxene, plagioclase laths, and ilmenite, with minor silica and Fe-rich olivine; (2) granulitic clasts; (3) anorthosite clasts; (4) Si-rich clasts that also contain ilmenite, troilite, high-Ca pyroxene, fayalite, and K-feldspar likely mesostasis from late stage basalts). All three meteorites contain glassy fusion crust that is highly vesicular, high in FeO and Al2O3 (15-17 wt% each), ferroan (Mg# of 23-24), and moderately rich in TiO2 (1.4-1.8 wt%). The composition of the fusion crust can serve as a proxy for the bulk meteorite composition and is identical within error for all three meteorites. Implications: The lithic and mineral clasts in all three stones are similar in clast population and assemblages as well as mineral chemistry. In addition, the fusion crust composition, a proxy for bulk composition, is within error of each other for all three stones. Thus DOM 18509, DOM 18543, and DOM 18678 are almost certainly paired. Based on similarities in macroscopic description as well as preliminary classification data [1,2], all 7 lunar stones from DOM are likely paired, though additional quantitative analyses are needed to confirm this. The presence of spherules and vesicular fusion crusts indicates that the DOM pairing group is a regolith breccia. The presence of basaltic and gabbroic clasts as well as more feldspathic materials, suggest that the regolith from which these meteorites formed contained a mixture of feldspathic highland material and mare material, suggesting a possible provenance near a marehighlands boundary. No evidence of KREEPy lithologies have been observed so far in these meteorites, however, future ICP-MS data on bulk rock chips for the stones will reveal any KREEP component if present. The DOM pairing group has many similarities to previously described lunar breccia meteorite MET 01210, however more detailed compositional data will be needed to make a definitive comparison.

R.A. Zeigler↗
NASA NTRSDate not supplied

Microstructural Constraints on the Formation of Diamond in Ureilites, the Case from the Kenna Meteorite

The origin of diamonds in ureilitic meteorites, a major family of ultramafic achondrites, has long been debated, with various formation mechanisms inferred, including: 1) shock conversion of preexisting graphite due to a hypervelocity impact on the ureilite parent body; 2) vapor deposition during condensation of the solar nebula; or 3) static transformation in the mantle of a large planetesimal (>1000 km in diameter). The Kenna ureilite is a 10.9 kg stone that was found in Kansas in 1972 and is dominantly composed of olivine and pigeonite (68% and 22% modal abundance, respectively), together with minor metal and carbon-rich regions. Within the carbon-rich domains researchers have identified microdiamonds up to ~10 µm in size. Due to the proximity of the extremely hard microdiamonds with soft graphite and moderately hard silicates, achieving an appropriately flat surface for electron backscatter diffraction (EBSD) analysis has proved challenging. We have, therefore, employed a Hitachi ArBlade 5000 broad beam Ar ion milling system to prepare a sample with an adequate surface uniformity. The ion milling dramatically improved indexing of the EBSD patterns and facilitated high-resolution microstructural analysis of the carbon-rich domains. The carbon-bearing regions occur as tabular domains between polygonal olivine and pigeonite, and are composed of aggregates of micrometer-scale diamond with intermediate graphite, oxides and metal grains. Within the microdiamonds, {111} twins are abundant, many of which form ragged lamellae consistent with mechanical twinning. The microdiamond assemblages appear to pseudomorph tabular graphite habits, which together with the abundant deformation twins, supports a shock transformation mechanism for microdiamond formation within the Kenna meteorite. To compliment the EBSD microstructural analyses, coordinated laser Raman, focused ion beam/transmission electron microscopy imaging and diffraction data, and NanoSIMS N and C tomographic isotopic imaging will be collected. These data will provide further constraints on the formation of diamonds within ureilites.

Timmons M Erickson↗
NASA NTRSDate not supplied

Development of New Lunar Highland Regolith Simulant, NUW-LHT-5M

Introduction: NASA has a need for large quantities of lunar simulants that closely match future manned lunar missions at landing sites near the Lunar South Pole. The current simulant was designed to approximate NU-LHT-2M, and -4M, except using natural minerals and a fully synthetic, non-basaltic, high calcium glass. Washington Mills in Niagara Falls, NY was contracted to produce this new simulant due to their electric arc furnace (EAF) fusion technology and capabilities for crushing and sizing ceramics. The primary objectives of this work were: (1) to create a commercially produced simulant that contains a high fidelity, high calcium (An90+), low Mg/Fe glass without basaltic constituents; (2) to create a simulant that uses existing, terrestrially mined, and readily available minerals blended with a synthetic glass, and (3) accomplish objectives (1) and (2) using conventional processing methods capable of production levels that can meet substantial current and future demands of NASA projects. Another consideration was that highland simulants closest to meeting these requirements, NU-LHT-2M and -4M types, are out of production and largely out of stock. Design: The design chosen for development and production for this work is NU-LHT-2M, de-signed by Doug Stoeser and Douglas Rickman, which uses Stillwater anorthosite and norite rocks and synthetic glass. The composition targeted the average composition, glass content and particle size distribution of Apollo 16 samples [1]. The design utilizes two Stillwater minerals, anorthosite (37.7 wt.%), norite (17.6 wt.%), a commercially sourced olivine (4.7 wt.%), and a synthetic glass (40 wt.%). Processing: Stillwater rocks were hand collected and initially crushed by the USGS. Further crushing and milling was performed at Washing-ton Mills. For the glass, oxides were blended in the ap-propriate ratios, blended in a v-blender, and placed in a graphite lined, water cooled pot. The mixture was fused in Washington Mills’ pilot scale, 500 kW EAF. The molten glass was then poured into water and quenched to inhibit crystallization. Several pour/quench cycles were required to produce the total quantity of glass needed. Anorthosite, norite and olivine were milled together to the target particle size in a ball mill. The glass was ball milled separately. The complete simulant was produced by blending the milled materials. Particle size distribution, phase and chemical analyses of the materials was were per-formed at Washington Mills. Results: The glass composition was found to match the Apollo 16 oxide content average [1] quite well, with the exception of SiO2 and Fe2O3. The deviation of SiO2 and Fe2O3 from batched content was believed to be due to limitations inherent in the use of the arc furnace technique for these types of materials. A particle size distribution of the full simulant formulation closely matching the average for the Apollo 16 samples was also achieved. Fig. 1 shows the morphology of the final simulant particles. The size distribution is compared to the target in Fig. 2. Conclusions: A new lunar highlands type simulant containing a high-quality synthetic glass, closely matching an average composition of the Apollo 16 regolith was produced. Processing utilized easily scalable mineral and glass making methods.

simulant↗
NASA NTRSDate not supplied

Comparing Analysis of Hydrogen Concentration in Astromaterials Nominally Anhydrous Minerals by Multiple SIMS

Secondary Ion Mass Spectrometry (SIMS) is utilized to determine hydrogen (H) concentration in astromaterials nominally anhydrous minerals (NAMs) and their inclusions [e.g., 1]. This data is interpreted to refine the volatile history of planetary bodies. Four instruments are being used to compare H concentration analysis: a large geometry SIMS (The University of Hawaiʻi Cameca IMS 1280), a compact SIMS (Arizona State University (ASU) Cameca IMS 6f), and two Cameca NanoSIMS 50L at ASU and NASA-Johnson Space Center (JSC). Results on the first three instruments are available. Although fundamentally similar, SIMS instruments and their modifications [2] may produce different values or pose advantages for H analysis, especially for shocked samples that are susceptible to contamination filling their fractures. New data from the IMS 1280 is reported, using its microchannel plate (MCP) to image high H signals in grain fractures during pre-sputtering to avoid them as much as possible. Between fractures, 16 OH/ 30 Si was measured with a Cs + 4 nA primary beam, 30 micron spot size, and central ~5x5 micron collection area. First order comparison of H concentration (reported in ppm H 2 O) is achieved on a terrestrial gem quality clinopyroxene (SLP114, 162±12 ppm H 2 O [3]), with 157±7 and 215±40 ppm H 2 O by the IMS 1280 and 6f respectively. SIMS comparison is then extended to analysis of two Martian shergottites: RBT 04262 and NWA 5789. Due to a dense fracture network (< 20 micron) in RBT 04262, only one clinopyroxene hosted glassy inclusion was analyzed (n=6, ≤1 ppm H 2 O), while six olivine grains in NWA 5789 (n=12, ≤ 2 ppm H 2 O) (1s ±0.21) were analyzed. Higher concentrations were obtained for RBT 04262 olivine by the ASU NanoSIMS 50L (up to 350 ppm H 2 O [4]), and IMS 6f (300+ ppm H 2 O, [5]), for which contamination in fractures could not be avoided. Work on the JSC NanoSIMS 50L will further develop the SIMS comparison.

J.-M. Dudley↗
NASA NTRSDate not supplied

Coordinated Microstructural and Isotopic Characterization of Diamond Inclusions within the Kenna Ureilite

Introduction: The origin of diamonds in ureilitic meteorites, a major family of ultramafic achondrites, has long been debated, with various formation mechanisms inferred, including: 1) shock conversion of preexisting graphite due to a hypervelocity impact on the ureilite parent body [e.g., 1]; 2) vapor deposition during condensation of the solar nebula [e.g., 2]; or 3) static transformation in the mantle of a large planetesimal (>1000 km in diameter) [e.g., 3]. The Kenna ureilite is a 10.9 kg stone that was found in Kansas in 1972 and is dominantly composed of olivine and pigeonite (68% and 22% modal abundance, respectively), together with minor metal and carbon-rich regions. Within the carbon-rich domains researchers have identified microdiamonds up to ~10 µm in size [4]. Methods: Due to the proximity of the extremely hard microdiamonds with soft graphite and moderately hard silicates, achieving an appropriately flat surface for electron backscatter diffraction (EBSD) analysis has proven challenging. We have, therefore, employed a Hitachi ArBlade 5000 broad beam Ar ion milling system to prepare a sample with an adequately uniform surface flatness across the various minerals. The ion milling dramatically im-proved indexing of the EBSD patterns and facilitated high-resolution microstructural analysis of the carbon-rich domains. After microstructural EBSD analyses using an Oxford Symmetry detector we collected coordinated hy-perspectral cathodoluminescence (CL) analyses using a Gatan Monarc system mounted on a JEOL 7900F field emission (FE) scanning electron microscope at NASA Johnson Space Center. A focused ion beam (FIB) foil was extracted from a region of interest and analyzed using a JEOL 2500 FE scanning transmission electron microscope (STEM). In situ carbon and nitrogen isotopic analyses were collected from diamond-bearing domains using a Cameca NanoSIMS 50L at NASA JSC. Results: The carbon rich regions occur as tabular domains between polygonal olivine and pigeonite, and are composed of aggregates of micrometer-scale diamond with intermediate graphite, oxides and metal grains. Within the microdiamonds, {111} twins are abundant, many of which form ragged lamellae consistent with mechanical twinning. The microdiamond assemblages appear to pseudomorph tabular graphite habits, which together with the abundant deformation twins, support a shock transformation mechanism for microdiamond formation within the Kenna meteorite. Further supporting this observation, the diamond laths show close alignment of <111> and <110> between domains, consistent with a solid-state transformation from graphite along <0001> and <1-210>, respec-tively [5]. A FIB foil was extracted from a region with mechanical twins, and high resolution STEM analyses reveal cross-cutting veins of graphite and oriented kamacite crystals together with additional sets of {111} nano-twins formed in at least three orientations. Isotopic analyses of C and N reveal sector zoning patterns [cf. 3] that are unre-lated to the diamond substructure identified by EBSD yet consistent with hyperspectral CL images. Conclusions: These data provide new constraints on microdiamond formation within ureilites. The microdia-monds exhibit orientation variants defined by aligned <111> and <110> axes consistent with inherited crystallo-graphic orientations from transformation of a single hexagonal graphite parent crystal [5]. Crosscutting the micro-diamonds are veins of graphite and kamacite, together with additional {111} nanotwins. Taken together these data suggest that microdiamonds from ureilites formed from a solid state, diffusionless transformation from graphite, likely associated with a major shock event, which was subject to subsequent reversion either during decompression or a later deformation event. The N and C isotopic sector zoning is unrelated to diamond microstructures and likely reflects inheritance from the parent graphite crystal.

Ureilite↗
NASA NTRS2022

Geological, Multispectral, and Meteorological Imaging Results from the Mars 2020 Perseverance Rover in Jezero Crater

Perseverance’s Mastcam-Z instrument provides high-resolution stereo and multispectral images with a unique combination of spatial resolution, spatial coverage, and wavelength coverage along the rover’s traverse in Jezero crater, Mars. Images reveal rocks consistent with an igneous (including volcanic and/or volcaniclastic) and/or impactite origin and limited aqueous alteration, including polygonally fractured rocks with weathered coatings; massive boulder-forming bedrock consisting of mafic silicates, ferric oxides, and/or iron-bearing alteration minerals; and coarsely layered outcrops dominated by olivine. Pyroxene dominates the iron-bearing mineralogy in the fine-grained regolith, while olivine dominates the coarse-grained regolith. Solar and atmospheric imaging observations show significant intra- and intersol variations in dust optical depth and water ice clouds, as well as unique examples of boundary layer vortex action from both natural (dust devil) and Ingenuity helicopter–induced dust lifting. High-resolution stereo imaging also provides geologic context for rover operations, other instrument observations, and sample selection, characterization, and confirmation.

Mars 2020↗
NASA NTRS2024

The H-poor nature of incompletely melted planetesimals: The view from acapulcoites and lodranites

The abundance of H in planetary building blocks is of fundamental importance for constraining the evolution of the terrestrial planets. It is commonly assumed that chondrites are the principal sources of Earth’s H; however, recent studies have suggested that primitive achondrites and achondrites may retain a small complement of H. There are few constraints on the H budgets of primitive achondrites, which represent the transition from unmelted to melted planetesimals, but prior work suggests that bulk parent body H contents are several orders of magnitude lower than typical chondritic values. Therefore, to provide further constraints on H retention during the transition from unmelted to melted planetesimals, we have measured the H contents of olivine, orthopyroxene, clinopyroxene, and plagioclase from a suite of acapulcoite-lodranite clan meteorites. Acapulcoite-lodranite clan meteorites represent the “prototypical” primitive achondrite parent body and have bulk major element compositions more akin to the Earth than previously studied primitive achondrites (e.g., the ureilites). We find that the H 2 O contents of olivine (∼5–12 µg/g H 2 O), orthopyroxene (∼3–10 µg/g H 2 O), and clinopyroxene (∼5–8 µg/g H 2 O) are broadly similar, while plagioclase (∼2.5–5 µg/g H 2 O) tends to be offset to lower values. Using a simple, single-stage batch-melting model, we calculate a preferred maximum acapulcoite-lodranite parent body H 2 O content of 38 µg/g, which is similar to other estimates for primitive achondritic and achondritic parent bodies. Furthermore, assuming chondrite-like precursor materials, our data are consistent with efficient loss of H prior to or during the onset of melting of early-formed planetesimals. This requires that Earth’s H-budget was dominated by building blocks that underwent minimal thermal processing.

Primitive achondrite↗
NASA NTRS2024

Revisiting the petrogenesis of pyroclastic glass bead deposits at the Apollo 15 and 17 sites

The Apollo 15 low-titanium and Apollo 17 high-titanium pyroclastic glass beads are amongst the most primitive magmatically derived samples obtained from the Moon. Two key samples, the low-Ti Apollo 15426 green glass clod and the high-Ti Apollo 74220 orange glass are morphologically distinct, where the Apollo 15 beads are larger (~ 107 μm along maximum axis) and more fractured, and the Apollo 17 are smaller (~42 μm) and less fractured. In this study, holohyaline beads as well as crystallized beads were examined from both samples. Crystallized beads show compositional variability in major, minor, and trace elements and enable examination of magmatic mineral fractionation processes during cooling of both deposits. The Apollo 15426 beads experienced variable olivine crystallization, whereas the Apollo 74220 beads experienced both olivine and ilmenite crystallization. Holohyaline beads from both deposits show more limited major, minor, and trace element variability than their crystallized counterparts. Trace element abundance data for individual holohyaline beads show that in Apollo 74220, they are tightly clustered at ~30 × Carbonaceous Ivuna chondrite [CI] with negative Eu anomalies and subchondritic Nb/Ta, and interpreted to reflect the presence of late-stage magma ocean cumulate overturned into an otherwise primitive mantle source. Incompatible trace element abundances for holohyaline beads in 15426 are supra-chondritic from ~8 × CI, to >80 × CI, with pronounced relative depletions in Sr and Eu for the most incompatible element enriched beads, which represent a distinct bead group within the deposit. Apollo 15426 beads have elevated Ni and Co abundances at the edges of the beads compared to their centers. These data are interpreted to reflect a more complex magmatic evolution of the 15426 deposit, beginning with: (i) initial magma generation, storage and assimilation within shallower low-Ca and high-Ca pyroxene bearing magma ocean cumulates (15B,C); (ii) mobilization of the earlier magmas by more recently generated primitive magmas (15A); (iii) eruption and crystallization of some beads (15D,E), and (iv) later jumbling of the deposit, possible impact contamination and addition of exotic bead components (J Group). In contrast, the 74220 data shows no discernable difference between Ni and Co abundances at the edges and centers supporting prior observations for limited melt fractionation and an absence of meteoritic components. It is further suggested that both deposits are likely to have been formed in the presence of a transient atmosphere. Using 74220 melt compositions from this study, post-entrapment crystallization abundances range from 266 to 1130 micrograms/g for H 2 O, 36 to 68 micrograms/g for F, 441 to 832 micrograms/g for S, and zero to 2.31 micrograms/g for Cl, consistent with prior studies and suggesting up to ~0.1 wt.% H 2 O in the melt, with considerably less in the source. The role that late-stage magma ocean cumulates rich in ilmenite, apatite and high-Ca pyroxene might play in modifying this volatile element estimate, however, casts remaining doubt on the volatile element abundance and evolution of the primitive Moon.

Moon↗
NASA NTRS2024

Volatiles in melt inclusions from lunar mare basalts: Bridging the gap in the H 2 O/Ce ratio between melt Inclusions in lunar pyroclastic sample 74220 and other mare samples

The H2O concentration and H 2 O/Ce ratio in olivine-hosted melt inclusions are high in lunar pyroclastic sample 74220 (H 2 O up to 1410 ppmw; H 2 O/Ce up to 77) but lower (H2O 10 to 430 ppmw; H 2 O/Ce 0.3 to 9.4) in all other lunar samples studied before this work. The difference in H 2 O concentration and in H 2 O/Ce ratio is absent for other volatile elements (F, S, and Cl) in melt inclusions in 74220 and other lunar samples. Because H 2 O (or H) is a critical volatile component with significant ramifications on the origin and evolution of the Moon, it is important to understand what causes such a large gap in H 2 O/Ce ratio between 74220 and other lunar samples. Two explanations have been advanced. One is that volcanic product in sample 74220 has the highest cooling rate and thus best preserved H 2 O in melt inclusions compared to melt inclusions in other samples. The other explanation is that sample 74220 comes from a localized heterogeneity enriched in some volatiles. To distinguish these two possibilities, here we present new data from two rapidly cooled lunar samples with glassy melt inclusions: olivine-hosted melt inclusions (OHMIs) in 79135 regolith breccia (unknown cooling rate but with glassy MIs similar in texture with those in 74220), and pyroxene-hosted melt inclusions (PHMIs) in 15597 pigeonite basalts (known high cooling rate, second only to 74220 and 15421). In addition, we also investigated new OHMIs in sample 74220. If the gap is due to the difference in cooling rates, samples with cooling rates between those of 74220 and other studied lunar samples should have preserved intermediate H2O concentrations and H 2 O/Ce ratios. Our results show that melt inclusions in 79135 and 15597 contain high H 2 O concentrations (up to 969 ppmw in 79135 and up to 793 ppmw in 15597) and high H 2 O/Ce ratios (up to 21 in 79135 and up to 13 in 15997), bridging the big gap in H 2 O/Ce ratio among 74220 and other lunar samples. Combined with literature data, we confirm that H 2 O/Ce ratios of different lunar samples are positively correlated to the cooling rates and independent of the type of mare basalts. We hence reinforce the interpretation that the lunar sample with the highest cooling rate best represents pre-eruptive volatiles in lunar basalts due to the least degassing. Based on Ce concentration in the primitive lunar mantle, we estimate that H 2 O concentration in the primitive lunar mantle (meaning bulk silicate Moon) is 121 ± 15 ppmw. Our new data also further constrain F/P, S/Dy and Cl/Ba ratios in lunar basalts and the lunar mantle. Estimated F, P, and S concentrations in the lunar primitive mantle are 4.4 ± 1.1 ppmw, 22 ± 8 ppmw, and 67 +67 −33 ppmw, respectively.

Xue Su↗
DOE OSTI2022

Visualizing the Distribution of Water in Nominally Anhydrous Minerals at the Atomic Scale: Insights From Atom Probe Tomography on Fayalite

Olivine is an important reservoir for hydrogen in the Earth’s upper mantle, and the presence of OH in this nominally anhydrous mineral can play an important role in determining the physical properties of the host phase. Here we report on the 3-D distribution of the hydrated region at atomic scale in fayalite using atom probe tomography. Site-specific analysis reveals regions that are either compositionally homogenous or contain interlayers that are consistent with hydrated dislocations. Elemental distributions of the minor elements within the hydrated interlayers show enrichment of Na, indicating the formation of equilibrium environment is associated with Na geochemically, as well as depletion of Mn and Mg, the result of incompatibility of OH. This direct observation of hydrated region distribution in 3-D at the nanometer scale, can provide insight into the material properties of these nominally anhydrous minerals and possible rheology of upper mantle minerals and geodynamics.

58 GEOSCIENCES↗
DOE OSTI2022

Electrochemically-Induced Phase Transformations in Battery Storage Compounds (Final Technical Report)

Compounds of interest for ion storage in advanced batteries frequently exhibit phase transformations as the working ion concentration varies. Under large electrochemical driving forces inherent to practical use, systems are often driven far from equilibrium. This program combines experiments and theory to understand the phase transition behavior of ion insertion compounds when electrochemically driven far from equilibrium. As model systems, we focus on alkaline metal phosphates AMPO4 (A = alkali; M = first row transition metal) of olivine structure, which are both technologically interesting and ideally suited for fundamental study due to the ability to systematically tune transformation strain, and along with it, the phase transformation pathway. Behavior in compositions having large transformation strains (~15 vol%) requiring plasticity for strain accommodation is emphasized. Experimental techniques include operando characterization of structure while simultaneously varying electrokinetic parameters, and high resolution microscopy of nanoscale and interfacial phenomena. Phase-field modeling is used to model the thermodynamics and kinetics of competing transformation pathways, extended to include the effects of plasticity, and integrated with porous electrode kinetic theory to treat multi-particle effects. Success in this project will lead to an ability to design ion storage compounds with predictable transformation pathways, electrochemical kinetics, capacity utilization, and durability. New technologically important compounds may also be discovered.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Ferrotorryweiserite, Rh 5 Fe 10 S 16 , a New Mineral Species from the Sisim Placer Zone, Eastern Sayans, Russia, and the Torryweiserite–Ferrotorryweiserite Series

Ferrotorryweiserite, Rh 5 Fe 10 S 16 , occurs as small grains (≤20 µm) among droplet-like inclusions (up to 50 μm in diameter) of platinum-group minerals (PGM), in association with oberthürite or Rh-bearing pentlandite, laurite, and a Pt-Pd-Fe alloy (likely isoferroplatinum and Fe-Pd-enriched platinum), hosted by placer grains of Os-Ir alloy (≤0.5 mm) in the River Ko deposit. The latter is a part of the Sisim placer zone, which is likely derived from ultramafic units of the Lysanskiy layered complex, southern Krasnoyarskiy kray, Russia. The mineral is opaque, gray to brownish gray in reflected light, very weakly bireflectant, not pleochroic to weakly pleochroic (grayish to light brown tints), and weakly anisotropic. The calculated density is 5.93 g·cm –3 . Mean results (and ranges) of four WDS analyses are: Ir 18.68 (15.55–21.96), Rh 18.34 (16.32–20.32), Pt 0.64 (0.19–1.14), Ru 0.03 (0.00–0.13), Os 0.07 (0.02–0.17), Fe 14.14 (13.63–14.64), Ni 13.63 (12.58–14.66), Cu 4.97 (3.42–6.41), Co 0.09 (0.07–0.11), S 29.06 (28.48–29.44), and total 99.66 wt.%. They correspond to the following formula calculated for a total of 31 atoms per formula unit: (Rh 3.16 Ir 1.72 Pt 0.06 Ru 0.01 Os 0.01 ) Σ 4.95 (Fe 4.48 Ni 4.11 Cu 1.38 Co 0.03 ) Σ10.00 S 16.05 . The results of synchrotron micro-Laue diffraction studies indicate that ferrotorryweiserite is trigonal; its probable space group is $R\bar{3}m$ (#166) based on its Ni-analog, torryweiserite. The unit-cell parameters refined from 177 reflections are a = 7.069 (2) Å, c = 34.286 (11) Å, V = 1484 (1) Å 3 , and Z = 3. The c:a ratio is 4.8502. The strongest eight peaks in the X-ray diffraction pattern derived from results of micro-Laue diffraction study [d in Å(hkil)(I)] are 2.7950 ($20\bar{2}5$) (100); 5.7143 (0006) (60); 1.7671 ($22\bar{4}0$) (44.4); 3.0486 ($20\bar{2}1$) (39.4); 5.7650 ($10\bar{1}2$) (38.6); 2.5956 ($20\bar{2}7$) (37.8); 3.0058 ($11\bar{2}6$) (36.5); and 1.5029 ($4\bar{2}\bar{2}12$) (35.3). Ferrotorryweiserite and the associated PGM crystallized from microvolumes of residual melt at late stages of crystallization of grains of Os- and Ir-dominant alloys occurred in lode zones of chromitites of the Lysanskiy layered complex. In a particular case, the residual melt is disposed peripherally around a core containing a disequilibrium association of magnesian olivine (Fo 72.9–75.6 ) and albite (Ab 81.6–86.4 ), with the development of skeletal crystals of titaniferous augite: Wo 40.8–43.2 En 26.5–29.3 Fs 20.3–22.6 Aeg 6.9–9.5 (2.82–3.12 wt.% TiO 2 ). Ferrotorryweiserite represents the Fe-dominant analog of torryweiserite. We also report occurrences of ferrotorryweiserite in the Marathon deposit, Coldwell Complex, Ontario, Canada, and infer the existence of the torryweiserite–ferrotorryweiserite solid solution in other deposits and complexes.

58 GEOSCIENCES↗